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WO2000037595A1 - Compactat contenant des agents renforçateurs a base de silicates - Google Patents

Compactat contenant des agents renforçateurs a base de silicates Download PDF

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Publication number
WO2000037595A1
WO2000037595A1 PCT/EP1999/009736 EP9909736W WO0037595A1 WO 2000037595 A1 WO2000037595 A1 WO 2000037595A1 EP 9909736 W EP9909736 W EP 9909736W WO 0037595 A1 WO0037595 A1 WO 0037595A1
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WO
WIPO (PCT)
Prior art keywords
weight
washing
acid
cleaning agent
mol
Prior art date
Application number
PCT/EP1999/009736
Other languages
German (de)
English (en)
Inventor
Rene-Andres Artiga Gonzalez
Monika Böcker
Beatrix Kottwitz
Maria Liphard
Katrin Schnepp-Hentrich
Berthold Schreck
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO2000037595A1 publication Critical patent/WO2000037595A1/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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the invention relates to a method for producing detergent and cleaning agent compactates which contain a silicate builder.
  • the builders or builder systems perform a variety of tasks in detergents and cleaning agents, which have also changed considerably in recent years and decades with the constant change in the composition, the form of supply and the production of detergents.
  • Modern detergents today contain approx. 20 to 50% by weight builder substances. These are among the most important classes of substances for the construction of detergents and cleaning agents.
  • zeolite NaA As a builder, it was proposed to use selected water-soluble amorphous sodium silicate compounds as builders in washing and cleaning agents.
  • Amorphous sodium silicate compounds are described here as builder substances, which are produced by spray drying aqueous water glass solutions, subsequent grinding and subsequent compression and rounding with additional removal of water from the ground material, cf. see, for example, FIG. 3 of US 3,912,649.
  • the water content of the products used is approx. 18 to 20% by weight with bulk densities well above 500 g / l.
  • detergents with 5 to 50% by weight of at least one surfactant, 0.5 to 60% by weight of a builder and conventional washing aids are proposed, the characteristic being that an amorphous as builder low-water sodium disilicate with a water content of 0.3 to 6% by weight is used.
  • the amorphous sodium disilicate should preferably contain 0.5 to 2% by weight of water.
  • These highly dehydrated amorphous disilicates are produced in a multi-stage process which initially provides for the production of a powdery amorphous sodium silicate with a water content of 15 to 23% by weight. This material is treated in a rotary tube furnace with flue gas at temperatures of 250 to 500 ° C in countercurrent.
  • the amorphous sodium disilicate emerging from the rotary kiln is comminuted to a particle size of 0.1 to 12 mm with the aid of a mechanical crusher and then ground to a particle size of 2 to 400 ⁇ m using a mill.
  • EP-A-0 542 131 discloses a process for the production of alkali silicates in granular form in a turbo dryer, alkali silicate solutions with a defined solids content being introduced into a heated drum, in the longitudinal axis of which a shaft with a plurality of close to the inner surface of the drum reaching arms rotates.
  • granular silicates with free water contents between 5 and 12% by weight and high bulk densities between 500 and 1200 g / l can be produced.
  • Other granular alkali silicates with secondary washing ability are from the European Patent applications EP-A-0 561 656 and EP-A-0 488 868 are known. These are compounds of alkali silicates with certain Q distributions and alkali carbonates.
  • Patent application WO 96/20269 describes an amorphous alkali silicate with secondary washability and a molar ratio of M 2 O: SiO 2 between 1: 1, 5 and 1: 3.3, which is impregnated with detergent ingredients and a bulk density of 300 g / l.
  • the silicate carrier grain to be impregnated is preferably in granular form and / or as a compound with alkali carbonates and can be produced by spray drying, granulation and / or compacting, for example roller compaction.
  • the silicate is impregnated with surfactants and in particular with nonionic surfactants. By absorbing the impregnating agent, the flowability of the silicate material is reduced, but this can be restored if the impregnated material is subsequently treated with an aqueous solution.
  • Granular amorphous alkali silicates with bulk densities of at least 700 g / l which have a high absorbency, i.e. which are sufficiently free-flowing even after impregnation with detergent or cleaning agent ingredients that are liquid or flowable at processing temperature, can be 34977 described process that starts from the spray drying and includes the compression of the spray-dried beads.
  • the spray-dried bead is ground and granulated at the same time or subsequently with the addition of a liquid granulation aid, bulk densities of at least 700 g / l - up to above 1000 g / l - being set.
  • Such granules are particularly suitable for use in compact and surfactant-rich detergents or cleaners with bulk densities above 700 g / l, because they prevent or at least greatly reduce gel formation when the agent dissolves in water.
  • the patent application WO 97/07194 describes the production of spray-dried amorphous silicates which are impregnated with liquid to wax-like ingredients of detergents or cleaning agents under customary processing conditions, the free-flowing properties not significantly diminishing. It is carried out by a process in which an aqueous batch essentially containing the active substance an amorphous alkali silicate, spray-dried and then impregnated with an aqueous dispersion of ingredients of washing or cleaning agents, one ingredient of this dispersion being an organic cobuilder, and optionally dried.
  • amorphous sodium silicates can be processed together with other washing or cleaning agent ingredients to form washing and / or cleaning agent compactates with a bulk density above 700 g / l if certain polymeric polycarboxylates are used at the same time.
  • detergents resulting from the process are superior to detergents containing zeolite and the classic acrylic acid-maleic acid copolymers in the secondary washing behavior, in particular in the graying-inhibiting effect and in the residue behavior (ash).
  • the amorphous sodium silicates used with preference include those with a modulus Na 2 O: Si0 2 of 1: 2 to 1: 2.8, preferably of 1: 2 to 1: 2.6.
  • the processing according to the invention results in a delay in dissolution and the silicates have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates occurs on the one hand through the compaction / compression, but on the other hand can also be caused by overdrying, for example on drying water contents below 15% by weight.
  • Amorphous is also understood to mean so-called X-ray amorphous silicates, which do not provide any sharp X-ray reflections in the X-ray diffraction spectrum, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle, but on the other hand at
  • Electron diffraction experiments provide washed-out or even sharp diffraction maxima.
  • X-ray amorphous silicates of this type have microcrystalline regions of the size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • X-ray amorphous silicates of this type are described, for example, in German patent application DE-A-44 00 024. It is believed that the release delay increases the secondary washing ability of amorphous silicates.
  • amorphous sodium silicates of the specified module including commercially available granular silicates or carbonate-silicate compounds, are suitable starting materials for the purposes of this invention.
  • These silicates can themselves have been produced by spray drying, granulation and / or compacting, for example by roller compacting, if such a preparation of the silicate starting products is also not always expedient, since these products have to be dissolved again in an aqueous batch.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 10,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
  • the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • polyacrylates which preferably have a molecular weight of 2000 to 6000 and particularly preferably 3000 to 5000 g / mol, have proven to be particularly suitable according to the invention.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and acrylic or methacrylic acid with maleic acid, copolymers of acrylic acid with maleic acid containing 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid being particularly suitable have proven suitable.
  • the drying device into which the aqueous preparation is sprayed can be any drying apparatus.
  • the drying is carried out as spray drying in a drying tower.
  • the aqueous preparations are exposed to a drying gas stream in finely divided form in a known manner.
  • the applicant describes this working principle of spray drying with superheated steam, in particular of valuable substances and mixtures of substances from the field of wetting agents, detergents and cleaning agents, in a number of published documents and older applications.
  • the working principle disclosed there is hereby expressly made the subject of the present disclosure of the invention.
  • the drying is carried out simultaneously with a granulation in a fluidized bed granulation system.
  • a fluidized bed granulation system This can be a fluidized bed running batchwise or continuously. It is particularly preferred to carry out the process continuously in the fluidized bed, as described, for example, in EP-B-0 603 207.
  • the liquid preparations are introduced into the fluidized bed via disposable or reusable nozzles or via several nozzles. Any solids present are either dusted pneumatically via blow lines, the addition either taking place before the atomization of the liquid components or simultaneously with them, or as a solution or suspension in a mixture with the liquids.
  • the liquid components are mixed either before spraying or directly in the nozzle.
  • Fluidized bed apparatuses which are preferably used have base plates with dimensions of at least 0.4 m.
  • fluidized bed apparatuses are preferred which have a base plate with a diameter between 0.4 and 5 m, for example 1, 2 m or 2.5 m.
  • fluidized bed apparatuses are also suitable which have a base plate with a diameter greater than 5 m.
  • a perforated base plate or a Conidur plate (commercial product from Hein & Lehmann, Federal Republic of Germany) is preferably used as the base plate.
  • the process according to the invention is preferably carried out at fluidized air speeds between 1 and 8 m / s and in particular between 1.5 and 5.5 m / s.
  • the granules are discharged from the fluidized bed advantageously by means of a size classification of the granules.
  • This classification can take place, for example, with a sieve device or by means of an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed.
  • the inflowing air is composed of the heated or unheated classifier air and the heated soil air.
  • the soil air temperature is preferably between 80 and 400 ° C, in particular between 90 and 350 ° C.
  • the fluidized air cools down due to heat losses and the heat of vaporization of the constituents of the solvent.
  • the temperature of the fluidizing air is about 5 cm above the bottom plate 60 to 120 ° C, preferably 70 to 100 ° C.
  • the air outlet temperature is preferably between 60 and 120 ° C, in particular below 100 ° C. If the discharge from the fluidized bed takes place against a classifier air flow, as described in EP-B-0 603 207, dust-free granules are obtained by this classification, ie the particle sizes of the particles are above 0.2 mm.
  • Granules preferred according to the invention have ad 50 values between 0.4 and 2.0 mm.
  • the grain fraction that is greater than 2.0 mm is returned. This coarse grain fraction can either be added as a solid component after grinding the fluidized bed or it is dissolved again and sprayed into the fluidized bed.
  • the first basic detergent resulting from the drying step has a water content of 3 to 30% by weight. If no further drying is to take place after the subsequent compacting, the water content is preferably below 20% by weight, in particular below 10% by weight.
  • Drying is followed by compaction of the dried basic detergent, with further detergent and cleaning agent ingredients, such as bleach or enzyme granules, and compacting aids, such as binders, being able to be mixed in before the compacting.
  • compaction is understood to mean any process in which the bulk density of the compact is increased.
  • this compacting of the basic detergent takes place in a press agglomeration process.
  • the press agglomeration process to which the solid premix (dried basic detergent) is subjected can be carried out in various apparatuses. Different press agglomeration processes are distinguished depending on the type of agglomerator used.
  • the four most common press agglomeration processes preferred in the context of the present invention are extrusion, roll pressing or compacting, hole pressing (pelletizing) and tableting, so that preferred press agglomeration processes within the scope of the present invention are extrusion, roll compacting, pelletizing or Tableting processes are.
  • a binder can be used as an aid to compaction.
  • only one or the binder will be mentioned for the sake of simplicity.
  • a binder is used which is already completely present as a melt at temperatures of up to 130 ° C., preferably up to 100 ° C. and in particular up to 90 ° C.
  • the binder must therefore be selected depending on the process and process conditions, or the process conditions, in particular the process temperature, must - if a particular binder is desired - be adapted to the binder.
  • the actual compression process is preferably carried out at processing temperatures which, at least in the compression step, correspond at least to the temperature of the softening point, if not even the temperature of the melting point of the binder.
  • the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt.
  • the process temperature in the compression step is not more than 20 ° C. above the melting temperature or the upper limit of the melting range of the binder. It is technically possible to set even higher temperatures; however, it has been shown that a temperature difference of 20 ° C. from the melting temperature or softening temperature of the binder is generally sufficient and even higher temperatures do not bring any additional advantages.
  • Such temperature control has the further advantage that thermally sensitive raw materials, for example peroxygen bleaching agents such as perborate and / or percarbonate, but also enzymes, can be processed increasingly without serious loss of active substance.
  • thermally sensitive raw materials for example peroxygen bleaching agents such as perborate and / or percarbonate, but also enzymes.
  • the possibility of precise temperature control of the binder especially in the decisive step of compression, i.e. between the mixing / homogenization of the premix and the shaping, allows an energetically very economical and extremely gentle process control for the temperature-sensitive components of the premix, since the premix only lasts for a short time exposed to higher temperatures.
  • the work tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (s) of the pellet press) have a temperature of at most 150 ° C., preferably at most 100 ° C. and in particular at most 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the temperature effect in the compression range of the press agglomerators is preferably a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
  • Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and also modified polyethylene glycols and polypropylene glycols.
  • the modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12000 and in particular between 1000 and 4000.
  • Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights have between 600 and 6000, preferably between 1000 and 4000.
  • polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C 3 -C 5 glycols and glycerol and mixtures of these as starting molecules. Also included are ethoxylated derivatives such as trimethylol propane with 5 to 30 EO.
  • the preferably used polyethylene glycols can have a linear or branched structure, wherein linear polyethylene glycols in particular are preferred.
  • the particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12000, advantageously around 4000, polyethylene glycols with relative molecular weights below 3500 and above 5000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4000, can be used, and such combinations advantageously more than 50 wt .-%, based on the total amount of polyethylene glycols, have polyethylene glycols with a relative molecular weight between 3500 and 5000.
  • polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; Here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600.
  • these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C.
  • binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000 are preferred. Polyvinylpyrrolidones are preferably not used as sole binders, but in combination with others, in particular in combination with Polyethylene glycols used.
  • binders have been found to be raw materials which have wash- or cleaning-active properties, for example nonionic surfactants with melting points of at least 45 ° C. or mixtures of nonionic surfactants and other binders.
  • the preferred nonionic surfactants include alkoxylated fatty or oxo alcohols, in particular C 12 -C 18 alcohols. Degrees of alkoxylation, in particular degrees of ethoxylation, of on average 18 to 80 AO, in particular EO per mole of alcohol and mixtures thereof have proven to be particularly advantageous.
  • fatty alcohols with an average of 18 to 35 EO, in particular with an average of 20 to 25 EO show advantageous binder properties in the sense of the present invention.
  • Binder mixtures may also contain ethoxylated alcohols with an average of fewer EO units per mole of alcohol, for example tallow fatty alcohol with 14 EO. However, it is preferred to use these relatively low ethoxylated alcohols only in a mixture with higher ethoxylated alcohols.
  • the content of these relatively low ethoxylated alcohols in the binders is less than 50% by weight, in particular less than 40% by weight, based on the total amount of binder used.
  • nonionic surfactants such as C 12 -C 18 alcohols with an average of 3 to 7 EO, which are usually used in washing or cleaning agents and which are liquid per se at room temperature, are preferably only present in the binder mixtures in such an amount that less than 2 % By weight of these nonionic surfactants, based on the end product of the process, are provided. As already described above, however, it is less preferred to use nonionic surfactants which are liquid at room temperature in the binder mixtures.
  • nonionic surfactants are not a component of the binder mixture, since they not only lower the softening point of the mixture, but can also contribute to the stickiness of the end product and also, due to their tendency to cause gelling when they come into contact with water The requirement for rapid dissolution of the binder / partition in the end product is not sufficient to the desired extent.
  • anionic surfactants or their precursors, the anionic surfactant acids, used in washing or cleaning agents are contained in the binder mixture.
  • nonionic surfactants which are suitable as binders are the fatty acid methyl ester ethoxylates which do not tend to gel, in particular those with an average of 10 to 25 EO (for a more detailed description of this group of substances, see below).
  • Particularly preferred representatives of this group of substances are predominantly methyl esters based on C 16 -C 18 fatty acids, for example hardened beef tallow methyl esters with an average of 12 EO or with an average of 20 EO.
  • a mixture is used as the binder which uses C 12 -C 18 fatty alcohol based on coconut or tallow with an average of 20 EO and polyethylene glycol with a relative molecular weight of 400 to 4000.
  • a mixture is used as the binder which is predominantly methyl ester-based C 16 -C 18 fatty acids with an average of 10 to 25 EO, in particular hardened beef tallow methyl ester with an average of 12 EO or an average of 20 EO, and a C 12 - Contains C 18 fatty alcohol based on coconut or tallow with an average of 20 EO and / or polyethylene glycol with a relative molecular weight of 400 to 4000.
  • binders have proven to be based either solely on polyethylene glycols with a relative molecular weight around 4000 or on a mixture of C 12 -C 18 fatty alcohol based on coconut or tallow with an average of 20 EO and one of the fatty acid methyl ester ethoxylates described above or on a mixture of C 12 -C 18 fatty alcohol based on coconut or tallow with an average of 20 EO , one of the fatty acid methyl ester ethoxylates described above and a polyethylene glycol, in particular with a molecular weight around 4000, are based.
  • the compressed material preferably has temperatures not above 90 ° C., temperatures between 35 and 85 ° C. being particularly preferred. It has been found that exit temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.
  • the method according to the invention is carried out by means of an extrusion, as described, for example, in European patent EP-B-486592 or international patent applications WO 93/02176 and WO 94/09111 or WO 98/12299.
  • a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device.
  • the homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work.
  • Preferred plasticizers and / or lubricants are surfactants and / or polymers.
  • the premix is preferably fed continuously to a planetary roller extruder or a 2-screw extruder or 2-screw extruder with co-rotating or counter-rotating screw guide, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature.
  • the premix is under the shear action of the extruder screws under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used, compacted, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally preferably the extrudate by means of a rotating knife reduced in size from spherical to cylindrical granules.
  • the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension.
  • the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use.
  • Particle diameters of up to at most 0.8 cm are generally preferred.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
  • the length / diameter ratio of the chopped-off primary granules is in the range from about 1: 1 to about 3: 1.
  • small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this step.
  • extrusion / blackmailing can also be carried out in low-pressure extruders, in the Kahl press (Amandus Kahl) or in the Bepex extruder.
  • the invention provides that the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is designed such that the melting temperature of the binder or the upper limit of the melting range of the binder at least reaches, preferably but is exceeded.
  • the duration of the temperature influence in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.
  • the method according to the invention is carried out by means of roller compaction.
  • the premix is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rollers smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later detergent or cleaning agent particles can be specified.
  • the sliver belt is subsequently broken down into smaller pieces by a knocking-off and crushing process and can be processed into granules in this way, which can be refined by further surface treatment processes known per se, in particular in an approximately spherical shape.
  • the temperature of the pressing tools is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C.
  • Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the temperature effect in the compression area of the smooth rollers or with depressions of a defined shape is a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
  • the method according to the invention is carried out by means of pelleting.
  • the premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization.
  • Pellet presses compress the premix under pressure, plasticize it, press it through a perforated surface in the form of fine strands using a rotating roller and finally crush it to form granules using a knock-off device.
  • pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers.
  • the press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.
  • An apparatus suitable for carrying out the method according to the invention is described, for example, in German laid-open specification DE 38 16 842.
  • the ring die press disclosed in this document consists of a rotating ring die penetrated by press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
  • the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
  • the temperature of the pressing tools is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at most 75 ° C.
  • Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
  • Another press agglomeration process that can be used according to the invention is tableting. Due to the size of the tablets produced, it may be useful for tableting to add conventional disintegration aids, for example cellulose and its derivatives, in particular in coarser form, or cross-linked PVP in addition to the binder described above, which facilitate the disintegration of the compacts in the wash liquor.
  • the particulate press agglomerates obtained can either be used directly as detergents or cleaning agents or aftertreated and / or prepared beforehand by customary methods.
  • the usual aftertreatments include, for example, powdering with finely divided ingredients from washing or cleaning agents, which generally further increases the bulk density.
  • a preferred aftertreatment is also the procedure according to German patent applications DE-A-195 24 287 and DE-A-195 47 457, dusty or at least finely divided ingredients (the so-called fine fractions) of the particulate end products of the process, which are the core serve, be glued and thus funds are created which have these so-called fines as an outer shell.
  • melt agglomeration of the fine fractions of the base granules according to the invention and produced according to the invention reference is expressly made to the disclosure in German patent applications DE-A-195 24 287 and DE-A-195 47 457.
  • the resulting detergent and / or cleaning agent compacts are preferably understood to mean those detergents and cleaning agents which have a bulk density above 700 g / l, preferably above 800 g / l.
  • Agents which do not have any dust-like components and in particular have no particle sizes below 200 ⁇ m can furthermore be preferred.
  • particle size distributions are preferred which have at least 90% by weight of particles with a diameter of at least 400 ⁇ m.
  • the washing or cleaning agents produced consist of at least 70% by weight, advantageously at least 80% by weight and, with particular preference, up to 100% by weight of spherical (pearl-shaped) particles with a particle size distribution which has at least 80% by weight of particles between 0.8 and 2.0 mm.
  • the detergent and / or cleaning agent compactates preferably consist of at least 50% by weight, in particular at least 60% by weight, of the basic detergent which is produced by the process according to the invention.
  • make up the basic detergent less than 90% by weight of the finished product, the rest being 100% by weight of admixed components, such as, for example, thermally sensitive ingredients.
  • the basic detergent can even make up less than 80% by weight of the finished product. It is then preferred, however, if the remaining constituents have approximately the same pourability, bulk density, size and particle size distribution as the basic detergent.
  • a second subject of the invention are detergent and / or cleaning agent compactates with a bulk density above 700 g / l, which contain 10-50% by weight of surfactants and are characterized in that they contain 5-40% by weight.
  • % amorphous sodium silicate with a module Na 2 0: Si0 2 from 1: 2 to 1: 3.3 and 0.05-10% by weight polymeric polycarboxylate with M 500-10,000 g / mol, and 0-10% by weight.
  • -% contains aluminosilicate and / or crystalline layered silicate and 0-5% by weight polymeric polycarboxylate with M> 20,000 g / mol, the amorphous sodium silicate and the polymeric polycarboxylate being processed together with other washing and / or cleaning agent ingredients.
  • the agents preferably contain at least 10% by weight of amorphous sodium silicates, but in special embodiments up to a maximum of 30% by weight, and it may even be preferred if a maximum of 20% by weight of the sodium silicates are contained.
  • These polymers are preferably present in the compositions in amounts of less than 7% by weight, but at least 0.5% by weight.
  • Agents which are particularly effective according to the invention contain between 2 and 5% by weight of these polymers.
  • the compositions can also contain polymeric polycarboxylates which have a molecular weight greater than 20,000 g / mol (as already explained above, these molecular weights are GPC against an external polyacrylic acid -Standard measured).
  • suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 20,000 to 120,000 g / mol.
  • 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 weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol (measured against the polyacrylic acid standard). In preferred embodiments of the invention, however, these polymers are only present in small amounts (about 1% by weight) or not at all.
  • finely crystalline, synthetic and bound water-containing zeolite preferably zeolite A, X, Y and / or P, and crystalline layered silicates can be used, which are likewise preferably only present in small amounts.
  • Suitable zeolites are also mixtures of A, X, Y and / or P.
  • zeolite P for example, zeolite MAP (for example Doucil A24®; commercial product from Crosfield) is particularly preferred.
  • zeolite MAP for example Doucil A24®; commercial product from Crosfield
  • zeolite MAP for example Doucil A24®; commercial product from Crosfield
  • cocrystallized sodium / potassium aluminum silicate from zeolite A and zeolite X, which is commercially available as VEGOBOND AX® (commercial product from Condea Augusta SpA).
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 10 to 22% by weight, in particular 15 to 22% by weight, of bound water.
  • crystalline, layered sodium silicates corresponding to the general formula NaMSi x 0 2x + 1 yH 2 0, 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 are preferred Values for x 2, 3 or 4 are to be included in the means.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 0 5 yH 2 0 are preferred.
  • both zeolites and crystalline layered silicates are only of minor importance in the agents according to the invention. In preferred embodiments of the invention, less than 5% by weight of these substances are contained in total. It may even be preferred if they are completely absent, with zeolites in particular also frequently being used as powdering agents on admixed granules, and thus being able to be present in a small proportion in the agents, although their use as a builder was not intended.
  • the agents according to the invention also contain alkali carbonates, in particular sodium carbonate. It is advantageous for the implementation of the invention if the weight ratio of alkali carbonate to amorphous sodium silicate is in the range 1: 100 to 10: 1, preferably 1:50 to 5: 1. In embodiments of the invention it can be particularly advantageous if the weight ratio of alkali carbonate to amorphous sodium silicate is less than 1.
  • organic builder substances can be contained in the agents according to the invention.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nithlotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value for detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.
  • a preferred dextrin is described in British patent application 94 19 091.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known.
  • An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous his.
  • Ethylene diamine N, N'-disuccinate (EDDS) the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93/339896 become.
  • Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • cobuilders are described, for example, in international patent application WO 95/20029.
  • Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals.
  • the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.
  • Such organic cobuilders can be contained in the agents according to the invention in total in a proportion of up to 10% by weight, but preferably not more than 5% by weight.
  • the washing and cleaning agents according to the invention can, in principle, contain all known ingredients which are customary in such agents.
  • the compositions contain 10-50% by weight, preferably 15-35% by weight, of surfactants, these surfactants being selected from the following groups:
  • a first group are the anionic surfactants, which should be present in the agents according to the invention or agents according to the invention at least in amounts of 0.5% by weight. These include in particular sulfonates and sulfates, but also soaps.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C- Atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered.
  • esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and Butyl ester.
  • MES ⁇ -sulfofatty acids
  • saponified disalts are used with particular advantage.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol be preserved.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are particularly preferred.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN (R) , are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl branches with an average of 3.5 moles of ethylene oxide (EO) or C 12 -C 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (see description below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Fatty acid derivatives of amino acids for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.2 to 5% by weight.
  • Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the known alkenyl succinic acid salts can also be used together with these soaps or as a substitute for soaps.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the anionic surfactants are contained or used in the agents according to the invention or in the method according to the invention preferably in amounts of 1 to 30% by weight and in particular in amounts of 5 to 25% by weight.
  • nonionic surfactants are particularly preferred.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 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 are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, 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 averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used, as described above. Examples of these are (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 denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G for one Glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G for one Glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (I) in which R 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups: R 2
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • [Z] is also preferably obtained here 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-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO 95/07331, 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 which are used either as the sole nonionic surfactant or in combination with other 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 with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • C 12 -C 18 - are nonionic surfactants
  • Fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO are preferred, while, as described above, higher ethoxylated fatty acid methyl esters are particularly advantageous as binders.
  • C 12 -C 18 fatty acid methyl esters with 10 to 12 EO can be used both as surfactants and as binders.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are generally separated from one another by a so-called “spacer”. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another. Such surfactants are distinguished generally by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water, but in exceptional cases the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis- and trimeral alcohol tris-sulfates and ether sulfates according to German patent application DE-A-195 03 061.
  • End group-blocked dimeric and trimeric mixed ethers According to German patent application DE-A-195 13 391, they are particularly characterized by their bi- and multifunctionality.
  • the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides, as described in the international patent applications WO-A-95/1953, WO-A-95/19954 and WO95-A- / 19955, can also be used.
  • bleaching agents are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 0 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is 0 to 30% by weight and in particular 5 to 25% by weight, advantageously using perborate monohydrate, tetrahydrate or percarbonate.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H 2 0 2 , preferably multiply acylated alkylenediamines such as N, N'-tetraacylated diamines, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles , Triazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid esters such as p- (alkanoyloxy) benzenesulfonate, in particular sodium isononanoyloxybenzenesulfonate, and the p- (alkenoyloxy) benzenesulfonate, furthermore caprolactam derivatives,
  • Carboxylic anhydrides such as phthalic anhydride and esters of polyols such as glucose pentaacetate.
  • Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described for example in European patent application EP-A-0 525 239, and acetylated pentaerythritol.
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • the bleach activator can be used in a known manner Shell substances have been coated or, if appropriate using auxiliaries, in particular methyl celluloses and / or carboxymethyl celluloses, have been granulated or extruded / pelletized and, if desired, contain further additives, for example dye. Such granules preferably contain more than 70% by weight, in particular 90 to 99% by weight, of bleach activator.
  • a bleach activator is preferably used which forms peracetic acid under washing conditions.
  • Transition metal salts or transition metal complexes may be included as so-called bleaching catalysts.
  • the transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, which consist of the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium described in German patent application DE 196 05 688 -, Vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20 411, the manganese described in German patent application DE 44 16 438, Copper and cobalt complexes, the cobalt complexes described in European
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.
  • the enzymes optionally contained in agents according to the invention include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP ® , Optimase ® , Opticlean ® , Maxacal ® , Maxapem ® , Durazym ® , Purafect ® OxP, Esperase ® and / or Savinase ®, amylases such as Termamyl ®, amylase LT ®, Maxamyl ®, Duramyl ®, Purafect ® OxAm, cellulases as Celluzyme ®, Carezyme ®, KAC® and / or the international patent applications WO 96/34108 from and WO 96/34092 known cellulases and / or lipases such as Lipolase ® , Lipomax ® , Lumafast ® and / or Lipozym ®
  • the enzymes used can, as described, for example, in international patent applications WO 92/11347 or WO 94/23005, be adsorbed on carriers and / or be embedded in coating substances in order to protect them against premature inactivation. They are contained in washing and cleaning agents according to the invention preferably in amounts of up to 10% by weight, in particular from 0.05% by weight to 5% by weight, particular preference being given to enzymes stabilized against oxidative degradation, such as, for example known from international patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350.
  • the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like 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 or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • 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 bistearylethylenediamides are particularly preferred.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches etc.
  • polyvinylpyrrolidone in particular in the form of PVP granules, is preferred in the agents according to the invention.
  • Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are also preferred.
  • Graying inhibitors, such as PVP are usually used in amounts of 0.1 to 5% by weight, based on the composition.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group one diethanolamino group, one Carry a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Healers of the substituted diphenyl styrene type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • the agents can also contain other known additives which are usually used in detergents, dishwashing detergents or cleaning agents, for example small amounts of neutral filler salts as well as colorants and fragrances, opacifiers or pearlescent agents.
  • Another object of the invention is a builder system as contained in the agents according to the invention.
  • a basic detergent was produced by spray drying and from this basic detergent, C 12 -C 18 fatty alkyl sulfate, citrate, nathumperborate monohydrate and polyethylene glycol as a binder with a relative molecular weight of 4000 creates a homogeneous premix.
  • C 12 -C 18 fatty alcohol with an average of 7 EO was sprayed into the powder stream.
  • the premix was then extruded. After the extrusion, 7% by weight of TAED granules were added.
  • the resulting detergents had bulk densities between 770 and 850 g / l.
  • the resulting detergents contained, in addition to the constituents listed in Table 1, enzyme granules and other washing auxiliaries, as well as water and salts.
  • Table 1 Composition of the detergent (in% by weight based on the total detergent and anhydrous substance).
  • Sokalan CP5 ® Acrylic acid-maleic acid copolymer; M w «35000 g / mol; Commercial product from BASF
  • Norasol LMW 45N ® Polyacrylic acid, sodium salt; M w * 4500 g / mol; Commercial product of
  • Citrate was added as citrate or citric acid depending on the pH to be set.
  • the detergents were tested under practical conditions in household washing machines. For this purpose, the machines were loaded with 3.0 kg of clean laundry and 0.5 kg of test fabric, some of the test fabric being impregnated with the usual test soiling and partially consisting of white fabric for testing the secondary washing ability. strips of standardized cotton fabric (Krefeld laundry research institute; WFK), nettle (BN), knitwear (cotton jersey; B) and terry toweling fabric (FT) were used as the white test fabric.
  • Washing conditions Tap water of 23 ° d (equivalent to 230 mg CaO / l), amount of detergent used per detergent and machine: 76 g, 90 ° C washing program (including heating phase), liquor ratio (kg of washing: liters of washing solution in the main wash) 1: 5, 7, rinse three times with tap water, spin off and dry.
  • the combustion of organic constituents usually results in a lower value than the actual incrustation.
  • the total incrustation was therefore determined for E3-5 and V3 (1st weighing of the untreated fabric, 2nd weighing of the fabric after 25 washing cycles, 3rd weighing of the fabric after extraction with EDTA, 4th determination of the so-called "soluble ash” from the difference between the weighings 2nd and 3rd, 5th ashing of the extracted tissue to determine the residual ash, 6. determination of the total incrustation (sum of soluble ash and residual ash)).
  • L-test To determine the residue behavior or the solubility behavior, 8 g of the agent to be tested were sprinkled into a 2 l beaker while stirring (800 rpm with laboratory stirrer / propeller stirring head centered 1.5 cm from the beaker bottom) and 1 , 5 minutes at 30 ° C. The test was carried out with water with a hardness of 16 ° d. The wash liquor was then poured off through a sieve (80 ⁇ m). The beaker was rinsed over the sieve with very little cold water. A double determination was carried out.
  • Grade 1 flawless, no recognizable residues Grade 2 tolerable, isolated, not yet disturbing residues Grade 3 recognizable residues, which in the case of a critical assessment are already disturbing, grade 4 clearly recognizable and disturbing residues in increasing number and quantity; gelling when water is added
  • R-Test 30 l of water were first introduced into a tub washing machine (TYPE Arcelik), 76 g of the agent were added and dissolved by stirring.
  • the laundry consisting of various dark-colored, easy-care delicate items made of wool, cotton, polyamide and polyacrylonitrile, was then inserted and the machine heated to a temperature of 30 ° C. After this temperature had been reached, the laundry was washed for 10 minutes by actuating the agitator, then the washing liquor was drained off, rinsed three times with 30 l of water each time and the laundry was Flung for seconds.
  • the laundry was dried with an infrared heater and graded by 5 trained people according to the following scheme (averaging):
  • Grade 1 flawless, no recognizable residues Grade 2 tolerable, isolated, not yet disturbing residues Grade 3 recognizable residues, which in the case of a critical assessment are already disturbing, grade 4 clearly recognizable and disturbing residues in increasing number and quantity
  • E-test In order to determine the induction behavior of the extrudates, the extrudates were tested in household drum washing machines with an induction drawer at a water pressure of 0.5 bar. Test machines were Miele W918 and Jo Privileg 1100. 5 determinations were carried out in each machine. The mean value given below was then formed from the 10 results. For this purpose, 80 g of the extrudates were added to the induction chamber per wash. The tap water, with which the extrudates were flushed into the respective machine, which was loaded with 3.5 kg of dry laundry, had a water hardness of 16 ° d.

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Abstract

Les silicates de sodium amorphes font office de renforçateurs dans les agents de lavage et de nettoyage. S'ils sont traités, comme dans les procédés actuels, en même temps que d'autres constituants d'agents de lavage et de nettoyage, leur utilisation augmente la quantité de résidus. L'invention propose donc un procédé qui permet de traiter les silicates de sodium amorphes en même temps que les autres composants. Selon ledit procédé permettant de produire des compactats d'agents de lavage et/ou de nettoyage ayant une densité en vrac supérieure à 700 g/l, on pulvérise des préparations aqueuses de silicate de sodium amorphe, comprenant un module Na2O:SiO2 dont le rapport est compris entre 1:2 et 1:3,3 et un polycarboxylate polymère dont la masse moléculaire M est comprise entre 500 et 10000 g/mol, en même temps que d'autres composants d'agents de lavage et/ou de nettoyage dans un dispositif de séchage, dans lequel la granulation se fait en même temps que le séchage. L'agent de lavage basique obtenu est ensuite compacté, éventuellement après ajout d'autres composants. Par rapport aux agents de lavage et de nettoyage existants, les agents ainsi obtenus possèdent un comportement de lavage primaire comparable et une capacité de lavage secondaire améliorée.
PCT/EP1999/009736 1998-12-19 1999-12-10 Compactat contenant des agents renforçateurs a base de silicates WO2000037595A1 (fr)

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DE1998158887 DE19858887A1 (de) 1998-12-19 1998-12-19 Kompaktat mit silicatischem Builder
DE19858887.9 1998-12-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7928054B2 (en) 2007-05-17 2011-04-19 The Procter & Gamble Company Detergent additive extrudates containing alkyl benzene sulphonate

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19936613B4 (de) 1999-08-04 2010-09-02 Henkel Ag & Co. Kgaa Verfahren zur Herstellung eines Waschmittels mit löslichem Buildersystem
DE10242222A1 (de) * 2002-09-12 2004-03-25 Henkel Kgaa Unter Druck kompaktiertes Wasch- oder Reinigungsmittel
US7709437B2 (en) * 2006-04-27 2010-05-04 Oci Chemical Corp. Co-granulates of bleach activator-peroxide compounds

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0220024A2 (fr) * 1985-10-09 1987-04-29 The Procter & Gamble Company Compositions détergentes granulées à solubilité
EP0561656A1 (fr) * 1992-03-20 1993-09-22 Rhone-Poulenc Chimie Agent "builder" à base de silicate et d'un produit minéral
DE4320358A1 (de) * 1993-06-21 1994-12-22 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate
WO1995012651A1 (fr) * 1993-11-01 1995-05-11 The Procter & Gamble Company Procede de sechage par pulverisation destine a produire une composition detergente pour lave-vaisselle, contenant tres peu ou pas de phosphates
DE4400024A1 (de) * 1994-01-03 1995-07-06 Henkel Kgaa Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet
DE19611012A1 (de) * 1996-03-21 1997-09-25 Henkel Kgaa Verfahren zur Herstellung von granularen Silikaten mit hohem Schüttgewicht

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19624415A1 (de) * 1996-06-19 1998-01-02 Henkel Kgaa Verfahren zur Herstellung von festen Wasch- oder Reinigungsmitteln
DE19638599A1 (de) * 1996-09-20 1998-03-26 Henkel Kgaa Verfahren zur Herstellung eines teilchenförmigen Wasch- oder Reinigungsmittels

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0220024A2 (fr) * 1985-10-09 1987-04-29 The Procter & Gamble Company Compositions détergentes granulées à solubilité
EP0561656A1 (fr) * 1992-03-20 1993-09-22 Rhone-Poulenc Chimie Agent "builder" à base de silicate et d'un produit minéral
DE4320358A1 (de) * 1993-06-21 1994-12-22 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate
WO1995012651A1 (fr) * 1993-11-01 1995-05-11 The Procter & Gamble Company Procede de sechage par pulverisation destine a produire une composition detergente pour lave-vaisselle, contenant tres peu ou pas de phosphates
DE4400024A1 (de) * 1994-01-03 1995-07-06 Henkel Kgaa Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet
DE19611012A1 (de) * 1996-03-21 1997-09-25 Henkel Kgaa Verfahren zur Herstellung von granularen Silikaten mit hohem Schüttgewicht

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7928054B2 (en) 2007-05-17 2011-04-19 The Procter & Gamble Company Detergent additive extrudates containing alkyl benzene sulphonate

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