EP0888449A1 - Detergent et nettoyant solide a masse volumique apparente elevee contenant des tensioactifs et des adjuvants, et compose approprie - Google Patents

Detergent et nettoyant solide a masse volumique apparente elevee contenant des tensioactifs et des adjuvants, et compose approprie

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Publication number
EP0888449A1
EP0888449A1 EP97907093A EP97907093A EP0888449A1 EP 0888449 A1 EP0888449 A1 EP 0888449A1 EP 97907093 A EP97907093 A EP 97907093A EP 97907093 A EP97907093 A EP 97907093A EP 0888449 A1 EP0888449 A1 EP 0888449A1
Authority
EP
European Patent Office
Prior art keywords
weight
detergent
builder
zeolite
cleaning agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97907093A
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German (de)
English (en)
Other versions
EP0888449B1 (fr
Inventor
Katrin Burmeister
Hubert Pawelczyk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065High-density particulate detergent compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/37Mixtures of compounds all of which are anionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/08Silicates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/128Aluminium silicates, e.g. zeolites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to a solid detergent and builder-containing detergent and cleaning agent with a high bulk density or compound therefor, which contains water-soluble silicate and zeolite as a builder and C 9 -Ci 3 -alkylbenzenesulfonates and C 8 -C 22 -alkyl sulfates as anionic surfactants.
  • inorganic zeolite in particular zeolite NaA and zeolite P, and alkali silicates are used as inorganic builder substances.
  • alkali silicates are used as inorganic builder substances.
  • EP-A-0 291 869 describes builder combinations of zeolite, aminoalkane polyphosphonate and / or polymeric polycarboxylate and 1-hydroxyethane-1,1-diphosphonate (HEDP), certain weight ratios of the last three components being a synergism with regard to the change in Show formation of fiber incrustations.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • crystalline, layered sodium silicates as a builder is described, for example, in European patent application EP-A-164 514, which discloses a builder combination which mainly comprises crystalline sheet silicates of the formula (I) NaMSi ⁇ O 2 ⁇ + ⁇ .yH 2 Contains O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • These layered silicates can be used as water softeners both separately and in detergents and cleaning agents together with other builders such as phosphates, zeolite, other silicates, phosphonates and polycarboxylates.
  • European patent application EP-A-0 405 122 describes a builder combination for a textile detergent which contains a mixture of zeolite and crystalline sodium phyllosilicate in a ratio of 4: 1 to 1: 4.
  • builder systems based on zeolite as described in the above-mentioned publications, no ecologically disadvantageous effects are known, but modern household washing machines require less and less water per wash cycle, so that there is a risk that the relatively poorly soluble builder systems will not be completely dissolve and incrustations can form.
  • the zeolites In addition to the Ca binding capacity of the zeolites, their absorbency, i.e. the adsorption capacity, as a carrier material for some surfactants, e.g. nonionic surfactants.
  • zeolites are replaced by the water-soluble silicates in products containing large amounts of sticky substances, for example alkylbenzenesulfonates, this leads to increased stickiness.
  • the alkyl benzene sulfonates can be replaced, for example, by the fatty alkyl sulfates.
  • the fatty alkyl sulfates have the disadvantage that they have a lower solubility than the alkylbenzenesulfonates and in particular the C 2 -C 4 fatty alkyl sulfates foam very strongly.
  • zeolite is necessary to be able to process the surfactants in the spray tower.
  • solid matter is removed from the tower powder, so that correspondingly smaller amounts of surfactant can be incorporated.
  • the object of the present invention was to provide a powdered washing and cleaning agent which is easy to produce and has good manageability, ie good powder properties, such as low tack and good solubility, the zeolite can be at least partially replaced by a water-soluble silicate
  • the present invention relates to a solid detergent and builder-containing washing and cleaning agent with a high bulk density or compound therefor, this agent being an anionic surfactant of 0.1% by weight to 10% by weight of C 9 -C 13 -alkylbenzenesulfonates and 10 % By weight to 50% by weight of C 8 -C 2 z-alkyl sulfates and as a builder contains 10% by weight to 45% by weight of water-soluble silicates and up to 30% by weight of zeolite
  • the weight percentages given here relate to the total composition.
  • the total of the ingredients adds up to 100% by weight.
  • the water-soluble alkali metal silicates contained according to the invention can be amorphous, X-ray amorphous or crystalline.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na 2 0 SiO 2 of 1 1.8 to 1 3.5 as crystalline silicates, which can be present alone or in a mixture with amorphous silicates, crystalline sheet silicates of the formula (I) NaMS ⁇ x ⁇ 2X + 1 + yH 2 O, in which M represents sodium, x is a number from 1.9 to 4, are preferably used and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application 164 514.
  • Preferred stable layered silicates of the formula (I) are those in which where M stands for Natnum and x assumes the values 2 or 3
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si2 ⁇ 5 'yH 2 O are preferred, wherein ⁇ -sodium disodium can be obtained, for example, by the process which can be obtained in the international patent application WO-A-91/08171.
  • the content of water-soluble alkali silicates in the compositions is preferably 10% by weight to 40% by weight and in particular 10% by weight to 35% by weight, based on anhydrous active substance
  • the agents according to the invention contain C 8 -C 22 alkyl sulfates as further substances, which are preferably contained in an amount of 12% to 30% by weight in the agent according to the invention
  • Suitable C 8 -C 2 alkyl sulfates are, in particular, the sulfuric acid monoesters of fatty alcohols, in particular Ce-C ⁇ fatty alcohols, such as lauryl, mynstyl, cetyl or stearyl alcohol or the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil which may additionally contain proportions of unsaturated alcohols, for example oleyl alcohol.
  • Preferred mixtures are those in which the proportion of the alkyl radicals is 15 to 40% by weight on d 2 , 5 to 15% by weight on C and to 15 to 25 wt -% are distributed to C 1 0 -% to C ⁇ 6 to 30 to 60 weight -% to C ⁇ 8 and below 1 wt
  • alkylbenzenesulfonates are preferably in an amount of 0.5% by weight to 5% by weight in the invention ⁇ agents according to the invention.
  • alkylbenzenesulfonates preference is given to cuts which contain large amounts of C 2 -alkylbenzenesulfonate
  • the C 8 -C 22 alkyl sulfates and the C 9 -C 3 alkylbenzenesulfonates are preferably in a weight ratio of 20 1 to 2 1, in particular 10 1 to 2 1, in the inventive composition
  • the detergents and cleaning agents according to the invention can contain further builder substances and surfactants as well as other substances usually contained in such agents as further ingredients.
  • the agent according to the invention can also contain zeolites as optional builder substances.
  • zeolites as optional builder substances.
  • Zeolite A is suitable, for example, but also zeolite X and zeolite P and mixtures of A, X and / or P.
  • A-type zeolite is preferably used in detergent quality.
  • Mixtures of zeolite NaA and NaX are also suitable, the proportion of the zeolite NaX in such mixtures advantageously being less than 30%. They have practically no particles larger than 30 ⁇ m and preferably consist at least 80% of particles smaller than 10 ⁇ m.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (measurement method: Eisenhofer diffraction; mean volume distribution), preferably between 1.5 and 4.5 ⁇ m, in particular between 2.0 and 4.0 ⁇ m.
  • Their calcium binding capacity which is determined according to the information in German patent application 24 12 837, is in the range from 100 to 200 mg CaO / g.
  • the zeolite generally has a water content of 17 to 25% by weight, preferably 18 to 22, in particular 20 to 22% by weight.
  • the content of finely divided, in particular crystalline, hydrated zeolite in the agents is preferably 0.5 to 30% by weight, based on the anhydrous active substance.
  • the weight ratio of the water-soluble silicates to zeolite is between 1: 0.01 and 1: 1.5.
  • Polymeric carboxylates or polymeric carboxylic acids may also be present as further builders. These polymeric carboxylates or carboxylic acids can be present in the detergent according to the invention in an amount of 1 to 15% by weight.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 1 to 12% by weight, in particular 2 to 10% by weight.
  • biodegradable terpolymers for example those which, according to DE-A-43 00 772, are monomers, salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those which are described in German patent applications DE-A-43 03 320 and P 44 17 734.8 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid, aminocarboxylic acid, nitrilotriacetic acid (NTA), provided that such use is unobjectionable for ecological reasons , and mixtures of these.
  • Preferred salts are the salts of polycarbonic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the agent according to the invention C e -C 8 alkyl polyglycol ether sulfonates, Ce-Ci ⁇ fatty acid ester sulfonates, C ⁇ -C 18 fatty alkyl ether sulfates, olefin sulfonates, glycerol ether sulfonates, glycerol ether sulfates, alkenyl sulfates, hydroxymischlycerol sulfides, monoglysyl sulfate sulfates, monoglysyl sulfate sulfates, monoglysyl sulfate sulfates, monoglysyl sulfate sulfates, monoglysulfate sulfates, monoglysulfide sulfates, monoglysulfide sulfates, monoglysulfate sulfates, monoglysulfate
  • soaps can be contained in the agents according to the invention, in which case saturated fatty acid soaps, the salts of launic acid, mynstic acid, palmitic acid or steanic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids, are suitable
  • the further surfactants and the soaps can be present in total in an amount of 1 to 15% by weight, in particular 1 to 10% by weight, alone or in any mixtures in the composition according to the invention.
  • the total surfactant content in the compositions according to the invention is preferably above 20% by weight.
  • the agent according to the invention can also contain nonionic surfactants in an amount of 1 to 25% by weight, preferably 2% by weight to 20% by weight.
  • the nonionic surfactants used are preferably liquid, alkoxylated, preferably ethoxylated, especially primary alcohols with preferably 8 to 18 ° C.
  • alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms are preferred, for example from coconut oil, tallow fat or oleyl alcohol, which can have an average of 2 to 8 EO units per mole of alcohol ethoxylated alcohols include, for example, Ci 2 -C 14 alcohols with 3 EO units or 7 EO units, C 9 -Cn alcohols with 3 EO units, 5 EO units or 7 EO units and mixtures of these, such as mixtures of C 2 -C 4 alcohol with 3 EO units and C 2 -C 8 alcohol with 5 EO units, the specified degrees of ethoxylation represent
  • the agent according to the invention can contain alkyl polyglycosides, fatty acid alkyl esters, amine oxides and polyhydroxy fatty acid amides as further nonionic surfactants
  • Structure breakers can be used as further components. Structure breakers are usually used to improve the processability of the agents Structure breakers are particularly suitable for ethoxylated C 8 -C 18 fatty alcohols with 20 to 45 EO, preferably tallow fatty alcohols with 30 and 40 EO, polyethylene glycol or polypropylene glycol, sulfates and / or disulfates of polyethylene glycol or polypropylene glycol, sulfosuccinates and / or disulfosuccmates from Polyethylene glycol or polypropylene glycol or mixtures of these.
  • the nonionic surfactants and the structure breakers can be used in a ratio of nonionic surfactant to structure breaker of 1 1 to 15 1
  • the detergents produced in accordance with the invention preferably contain peroxy bleaching agents and in particular peroxy bleaching agents in combination with bleach activators.
  • peroxy bleaching agents include sodium piperborate tetrahydrate, the sodium perborate monohydrate and sodium pipercarbonate are of particular importance.
  • Other useful bleaching agents are, for example, peroxy pyrophosphates , Citrate perhydrates and H 2 O 2 providing peracidic salts or peracids such as perbenzoates, peroxophthalates, diperoxyazelamic acid or diperoxydodecanedioic acid.
  • the detergents preferably contain 5 to 25% by weight and in particular 10 to 20% by weight of bleaching agents, preference being given to sodium pipercarbonate and / or sodium piperborate monohydrate be used
  • bleach activators can be incorporated into the preparations which form organic peracids with H 2 O 2.
  • these are N- or O-acyl compounds, for example several times acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolunle, especially tetraacetylglycolu ⁇ l, N-acylated hydantoins, hydrazides, t ⁇ azoles, t ⁇ azines, urazoles, diketopiperazines, sulfurylamides and cyanuronate, especially phtalsulfanoyl anoxides, especially phthalsolanoyl anonate, carboxylic acid, benzylsulfonate,
  • the bleach activator can be coated with shell substances in a known manner or, if necessary with the aid of auxiliaries, granulated or extruded / pelletized and
  • a bleach activator is preferably used which forms peracetic acid under the washing conditions.
  • TAED carboxymethyl cellulose Granulated tetraacetylethylenediamine
  • DADHT granulated 1,5-diacetyl-2,4 -dioxohexahydro-1,3,5-triazine
  • Extruded TAED can also be used, which contains> 70% by weight TAED, 15 to 25% by weight Ci ⁇ .is fatty alcohol sulfate and 2 to 6% by weight soda.
  • the content of bleach activators in the detergents containing bleach is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Suitable ingredients of the agents according to the invention are water-soluble inorganic salts such as bicarbonates, carbonates or mixtures thereof; in particular alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously 5 and 15% by weight.
  • the other detergent components include foam inhibitors, optical brighteners, enzymes, textile-softening substances, colorants and fragrances.
  • Neutral salts can also be present in an amount of up to 20% by weight, the proportion of which is preferably ⁇ 10% by weight.
  • the agent can contain additional graying inhibitors in an amount of 0.1 to 5% by weight, based on the agent.
  • Water-soluble colloids of mostly organic nature are suitable as additional graying inhibitors, for example soluble starch preparations and z.
  • Suitable enzymes are those from the class of proteases, lipases or lipolytically active enzymes, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic Enzymes or protease, lipase or lipolytically acting enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytically acting enzymes of particular interest. Examples of such lipolytically acting enzymes are the known cutmases.
  • Peroxidases or oxidases have also been found in some Traps proven to be suitable
  • the enzymes can be adsorbed on carrier substances and / or embedded in shell substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2 wt -%
  • Suitable stabilizers in particular for peroxygen compounds and enzymes, are the salts, such as neutral sodium salts, of polyphosphonic acids, in particular of 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid. These compounds also come into consideration as water-soluble complexing agents
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DETPMP diethylenetriaminepentamethylenephosphonic acid
  • ethylenediaminetetramethylenephosphonic acid ethylenediaminetetramethylenephosphonic acid.
  • the agents can contain enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight of sodium formate can be used. It is also possible to use proteases stabilized with soluble calcium seeds and a calcium content of preferably about 1.2% by weight, based on the enzyme
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, is particularly advantageous
  • Suitable foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of different foam inhibitors can also be used with advantage, for example those made from silicon konöl, paraffin oil or waxing.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • the powdered detergents can contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, which can be incorporated well into dispersions (see below).
  • optical brighteners for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, which can be incorporated well into dispersions (see below).
  • the maximum content of brighteners in the agents according to the invention is 0.5% by weight, preferably from 0.02 to 0.25% by weight.
  • Another object of the present invention relates to the production of detergents and cleaning agents containing surfactants and builders which contain 0.1% by weight to 10% by weight of C 9 -C 13 alkylbenzenesulfonate and 10% by weight to 50 % By weight of C 8 -C 22 alkyl sulfate as anionic surfactants and 10 to 45% by weight of water-soluble silicates and 0 to 30% by weight of zeolite as a builder, in which a premix is prepared from solid and liquid detergent constituents and this Premix is then pressed.
  • Liquid non-ionic surfactants are particularly suitable as liquid detergent components.
  • the joining of the solid and liquid detergent raw materials with simultaneous or subsequent shaping and, if desired, drying can be carried out by all known processes in which detergents and cleaning agents have a high bulk density, ie a bulk density above 500 g / l, preferably above 600 g / l and in particular between 700 and 1,000 g / l, are carried out.
  • Examples of such known and preferred processes are granulation processes in which either the solid ingredients of a washing and cleaning agent or a spray-dried washing and cleaning agent or a mixture of spray-dried and non-spray-dried ingredients of washing and cleaning agents, optionally including the additive, in a rapid manner running mixer is compacted and simultaneously mixed or acted upon in this mixer or subsequently in a further device, for example in a fluidized bed, with the liquid constituents.
  • granules and tablets in particular can be obtained.
  • a method for the production of granules, a method is preferred in which a premix of detergent components is first prepared.
  • This solid, preferably homogeneous premix is extruded in the form of a strand with the addition of a plasticizer and / or lubricant via hole shapes with opening widths of the predetermined granule dimension at high pressures between 25 and 200 bar.
  • the strand is cut to the predetermined pellet dimension immediately after exiting the hole shape by means of a cutting device.
  • the application of the high working pressure causes the premix to be plasticized during the formation of the granulate and ensures the cutting ability of the freshly extruded strands.
  • the premix consists, at least in part, of solid, preferably finely divided, usual ingredients of detergents and cleaning agents, to which liquid constituents may have been added.
  • the solid ingredients can be tower powders obtained by spray drying, but also agglomerates, the mixture components selected in each case as pure substances which are mixed with one another in the finely divided state, and mixtures of these.
  • the liquid ingredients are optionally added and then the plasticizer and / or lubricant selected according to the invention is mixed in.
  • Preferred plasticizers and / or lubricants are aqueous solutions of polymeric polycarboxylates, as well as highly concentrated anionic surfactant pastes and nonionic surfactants.
  • liquid nonionic surfactants can also be added to the solid premix as a liquid constituent or as a plasticizer and / or lubricant, or they are part of a solid mixture component of the premix, whereby this solid mixture component can consist of a carrier bead that has been exposed to a solution or dispersion.
  • the addition of the liquid component can be carried out at any point in the process, for example in the preparation of the premix, but also in the processing of the plasticized premix, but before it passes through the perforated mold (perforated nozzle plate ) Kneaders of any configuration, for example 2-screw kneaders, can preferably be selected as the homogenizing device.
  • the intensive mixing process can in itself lead to a desired temperature increase. Moderately elevated temperatures of, for example, 60 to 70 ° C.
  • the premix is preferably fed continuously to a 2-screw kneader (extruder), the housing and the extruder pelletizing head of which are heated to the predetermined extrusion temperature, for example heated to 40 to 60 ° C.
  • the premix is subjected to the shear action of the extruder screws plasticized at pressures of 25 to 200 bar, extruded in the form of fine strands through the perforated die plate in the extruder head and finally the extrudate is reduced, preferably in spherical to cylindrical granule cores by means of a rotating knives esser in the perforated nozzle plate and the strand cut length are matched to the selected granule dimension.
  • granules of a substantially uniformly predeterminable particle size can be produced, and in particular the absolute particle sizes can be adapted to the intended use.
  • particle diameters become up to at most 0 .8 cm preferred.
  • Important embodiments see the production of uniform granules with diameters in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from 0.8 to 3 mm.
  • the length / diameter ratio of the chopped-off primary granules In an important embodiment, it lies in the range from 1 1 to about 3 1.
  • edges present on the raw granulate are rounded off, so that ultimately spherical or at least approximately spherical granules can be obtained.
  • small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this step.
  • This shaping can be done in commercially available rounding machines, for example in Rondiergeraten with rotating bottom disk, preferably the granules are then fed to a drying step, for example a fluidized bed dryer
  • Tablets can, for example, be prepared in such a way that the builder substances, in particular the water-soluble alkali metal silicates and, if appropriate, all other constituents are mixed together in a mixer and the mixture is mixed using Conventional tablet presses, for example eccentric presses, hydraulic presses or rotary presses, with compression pressures in the range from 1 to 300 bar, advantageously in the range from about 5 to 200 bar and in particular between 10 and 150 bar.
  • the pressing takes place without the addition of water.
  • the premixes provided for compression can be produced by mixing the individual ingredients, which are at least partially present in a pre-assembled form as a granular compound.
  • a tablet produced in this way preferably has a weight of 10 to 120 g, in particular 20 to 100 g, the diameter of the tablets usually being less than 100 mm.
  • Preferred detergent tablets have a maximum diameter of 80 mm and in particular from 30 to 80 mm.
  • the diameter / height ratio of the tablets should be optimized so that the least possible abrasion on the vertical walls of the tabletting apparatus (higher Diameter / narrow height) with sufficient stability and a surface that is not too large (small diameter / large height) is guaranteed.
  • Preferred diameter / high ratios of the cylindrical compacts are around 0.5 1 to 10 1, in particular 1 1 to 8 1
  • the dried granulocytes late optionally once again with feinteilgen dry powdersSWpudern
  • dry powders are Zeohth NaA powder, but also precipitated or pyrogenic silicic acid, such as for example as Aerosil ® or Sipernat ® (products from Degussa) are commercially available.
  • Highly concentrated, at least 90% by weight alcohol sulfate powder which essentially, ie at least 90%, consists of particles with a particle size of less than 100 ⁇ m are particularly preferred mixtures of zeolite and alcohol sulfate powder are preferred
  • the detergents and cleaning agents can be produced uniformly from extrudates which have the abovementioned ingredients.
  • the finished agents can also be obtained from a mixture of several different solids, in particular several different granules, of which, for example, the powdered detergents and cleaning agents according to the invention Forming the main constituent
  • the bleach, the bleach activator, the enzymes, and colorants and fragrances can be subsequently added to the extrudates.
  • the bleach, the bleach activator and the enzymes are each in compacted granular form, for example as extrudates produced separately , which are obtained by means of a kneader of the configuration described above or via a pellet press
  • a solid premix was prepared from the solid constituents listed in the table below in a batch mixer equipped with a cutter head chopper.
  • the mixture was homogenized for 2 minutes and then fed to a twin-screw extruder, the housing of which, including the extruder granulating head, was heated to 45 ° C.
  • the premix was plasticized and then extruded at a pressure of 120 bar through the extruder perforated die plates into fine strands with a diameter of 1.2 mm, which were chopped into approximately spherical granules by means of a knock-out knife . (Length / diameter ratio about 1, hot cut).
  • the resulting product was rounded about 1 minute in a commercially available spheronizer type Marumerizer ® under low addition amounts of zeolite NaA and subsequently dried at an inlet air temperature of 70 ° C in a fluidized bed dryer until reaching an exhaust air temperature of 53 ° C.
  • the extruded and dried granules obtained had the compositions shown in Table 1.
  • solubility of the agents can be increased significantly by adding small amounts of alkylbenzenesulfonate if large amounts of alkyl sulfates are present.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP97907093A 1996-03-21 1997-03-12 Detergent et nettoyant solide a masse volumique apparente elevee contenant des tensioactifs et des adjuvants, et compose approprie Revoked EP0888449B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19611013A DE19611013A1 (de) 1996-03-21 1996-03-21 Festes Tensid- und Builder-haltiges Wasch- oder Reinigungsmittel mit hohem Schüttgewicht oder Compound hierfür
DE19611013 1996-03-21
PCT/EP1997/001241 WO1997034994A1 (fr) 1996-03-21 1997-03-12 Detergent et nettoyant solide a masse volumique apparente elevee contenant des tensioactifs et des adjuvants, et compose approprie

Publications (2)

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EP0888449A1 true EP0888449A1 (fr) 1999-01-07
EP0888449B1 EP0888449B1 (fr) 2001-12-05

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EP (1) EP0888449B1 (fr)
AT (1) ATE210179T1 (fr)
DE (2) DE19611013A1 (fr)
ES (1) ES2169357T3 (fr)
WO (1) WO1997034994A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009149276A1 (fr) * 2008-06-04 2009-12-10 The Procter & Gamble Company Composition détergente

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Publication number Priority date Publication date Assignee Title
US5961663A (en) * 1997-05-29 1999-10-05 Colgate-Palmolive Co. Microwave-dried amorphous alkali metal silicate powders and their use as builders in detergent compositions
EP0971028A1 (fr) * 1998-07-10 2000-01-12 The Procter & Gamble Company Comprimé détergent à caractéristiques de dissolution et mécaniques améliorées
DE69829044T2 (de) * 1998-07-10 2006-02-09 The Procter & Gamble Company, Cincinnati Waschmitteltablette mit hohen mechanischen und Lösungs-Eigenschaften
US6559115B1 (en) * 1998-07-10 2003-05-06 The Procter & Gamble Company Detergent tablet with high mechanical and dissolution characteristics
DE19903290A1 (de) * 1999-01-28 2000-08-03 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit definiertem Aniontensidverhalten
DE19911570A1 (de) * 1999-03-16 2000-09-28 Henkel Kgaa Aniontensid-Granulate
AU6288999A (en) * 1999-10-06 2001-05-10 Procter & Gamble Company, The Detergent tablet with high dissolution and mechanical characteristics
DE10031619A1 (de) * 2000-06-29 2002-01-10 Cognis Deutschland Gmbh Tensidgranulate mit verbesserter Auflösegeschwindigkeit
DE102015002877B4 (de) * 2015-03-09 2024-09-12 Henkel Ag & Co. Kgaa Wasch- oder reinigungsaktive Extrudate, deren Herstellung und Verwendung in granularen Wasch- oder Reinigungsmitteln
US11767495B2 (en) * 2020-03-13 2023-09-26 YFY Consumer Products, Co. Systems and methods for manufacturing solid granules

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JPH0436398A (ja) * 1990-06-01 1992-02-06 Lion Corp 高嵩密度粒状洗剤組成物
DE4125178A1 (de) * 1991-07-30 1993-02-04 Henkel Kgaa Pulverfoermige aniontensidzubereitung
DE19525378A1 (de) * 1995-07-12 1997-01-16 Henkel Kgaa Amorphes Alkalisilicat-Compound

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009149276A1 (fr) * 2008-06-04 2009-12-10 The Procter & Gamble Company Composition détergente

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ES2169357T3 (es) 2002-07-01
EP0888449B1 (fr) 2001-12-05
DE59705671D1 (de) 2002-01-17
DE19611013A1 (de) 1997-09-25
ATE210179T1 (de) 2001-12-15
WO1997034994A1 (fr) 1997-09-25

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