EP1141191B1 - Composes phosphates - Google Patents

Composes phosphates Download PDF

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Publication number
EP1141191B1
EP1141191B1 EP99963522A EP99963522A EP1141191B1 EP 1141191 B1 EP1141191 B1 EP 1141191B1 EP 99963522 A EP99963522 A EP 99963522A EP 99963522 A EP99963522 A EP 99963522A EP 1141191 B1 EP1141191 B1 EP 1141191B1
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EP
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Prior art keywords
weight
phosphate
phosphate compound
detergent
water
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EP99963522A
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German (de)
English (en)
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EP1141191A1 (fr
Inventor
Manfred Greger
Christian Nitsch
Peter Jeschke
Christiane Kaell
Jürgen Härer
Harald Volk
Mike PÜTZ
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to EP03019563A priority Critical patent/EP1382665A1/fr
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    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates

Definitions

  • the present invention relates to phosphate compounds suitable for incorporation in Washing or cleaning product tablets are suitable, and detergent tablets, containing such compounds.
  • Next is a manufacturing method for stated such phosphate compounds.
  • alkali phosphates are suitable as phosphorus-containing builders for Detergents and cleaners.
  • trisodium phosphate, tetrasodium diphosphate, Disodium dihydrogen diphosphate, pentasodium triphosphate, so-called Sodium hexametaphosphate, oligomeric trisodium phosphate with Oligomermaschines grade in the range of 5 to 1000, in particular 5 to 50, and mixtures used from sodium and potassium salts. The most common of these is pentasodium triphosphate used.
  • STP pentasodium triphosphate
  • Spray-drying a slurries from a water-soluble inorganic phosphate with a polymeric polycarboxylate is described in the patent application DE 38 18 660.
  • the resulting hollow spheres serve as a carrier for nonionic surfactant, which acts on the spheres in amounts of 2 to 40 wt .-% is sprayed.
  • Pentasodium triphosphate is included one of the suitable phosphates.
  • Document GB-A-1466868 relates to a process for the preparation of porous granulated Materials and granules made by the process which are incorporated in a detergent formulation to be built in.
  • the powder used for granulation contains alkali metal tripolyphosphates and a binder, e.g. Water. This binder, the cause the granulation is required is added after the powdered tripolyphosphate has been formed into a circular bed; the granulated Product is then kept in motion and z. B. dried in a fluidized bed.
  • the German patent application DE-A-29 25 137 discloses homogeneous, dust-free and free-flowing Washing and cleaning agent granules based on pentasodium tripolyphosphate, which are virtually free of hydrolysis products of the polyphosphate, as well as a Process for their continuous production. These granules contain, among others Components, 50 to 80% by weight of pentasodium tripolyphosphate and 10 to 25% by weight, in particular 9 to 19 wt .-% water. The ratio of ortho and sodium pyrophosphate to the total phosphate is 0.005 to 0.08 wt .-%.
  • a granular composition containing a hydrate-forming phosphate, preferably Pentasodium triphosphate, 0.1 to 23 wt .-% water and 2 to 125 ppm of surfactant is described in European patent EP-B-259 291.
  • This is manufactured Granules, for example, in a mixer in which an aqueous solution of the surfactant the phosphate is given.
  • Essential to the invention is the surfactant content which leads to that the proportion of free water to water of hydration in the product in favor of the water of hydration shifts.
  • the degree of preservation of the pentasodium triphosphate is with this Method between 84 and 94% of the phosphate content.
  • Such a low phosphate balance and associated high pyrophosphate content results in use such granules when washing dishes to undesirably strong glass corrosion.
  • phosphate compounds which contain little pyrophosphate, i. have a high degree of phosphate retention, and are present as agglomerates ideal for incorporation in moldings of detergents and cleaners and even improve the dissolution behavior of these moldings.
  • a first subject of the invention are accordingly phosphate compounds for Use in detergents or cleaners containing at least 50% by weight Pentasodium triphosphate, less than 5 wt .-% sodium pyrophosphate and maximum Contain 18% by weight of water and are present as agglomerates of primary particles, characterized in that the content of the compounds in free water at most 5% by weight, preferably at most 3% by weight, and the content of pentasodium triphosphate hexahydrate between 20 and 70% by weight of Total content of pentasodium triphosphate is.
  • STP pentasodium triphosphate
  • STP pentasodium triphosphate
  • the content of STP is at least 50% by weight, preferably over 70% by weight, and especially preferably even more than 80 wt .-% of the total compounds.
  • STP content of the compounds should other phosphates, especially ortho-, meta- and pyrophosphates be low. Preference is given to less than 5% by weight, in particular even less than 3% by weight, of these Phosphates contained in the compound. Expressed is the proportion of these phosphates on the degree of retention of the pentasodium triphosphate in the compound (STP preservation level). It is preferably at least 95%, more preferably even at least 97%.
  • a high pyrophosphate content leads to the use of such Compounds in dishwashing agents to an unwanted reinforcement of Glass corrosion.
  • Such disadvantages avoid the compounds according to the invention, in containing less than 5% by weight of sodium pyrophosphate, it being preferred that when the sodium pyrophosphate content is even less than 3% by weight or lower.
  • the compound contains a proportion of water which is not more than 18% by weight. can amount. However, preferred compounds contain water too much 15 wt .-%, wherein a water content of at most 13 wt .-% also be preferred can. If particularly phosphate-rich compounds are to be produced, then it is even possible a water content of at most 11 wt .-% may be preferred.
  • the water is in the Compounds for the most part as water of hydration ago.
  • the content is Pentasodium triphosphate hexahydrate between 20 and 70 wt .-% of the content of pentasodium triphosphate in total.
  • the content of the compounds in free water i.e.
  • water of hydration bound water should be as low as possible. He is not more than 5% by weight, with a maximum free water content of 3% by weight may be preferred. In a special, preferred Embodiment, the content of free water should be less than 1.5 wt .-%.
  • the free water is released already below 100 ° C and can therefore at This temperature can be determined.
  • the compounds may contain other ingredients of laundry and / or Detergents included. These may preferably be substances which Cobuildereigenschaften have. Here are primarily polycarboxylates, in particular polymeric polycarboxylates, and to call phosphonates.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molar masses 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 with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group. Also suitable are copolymeric polycarboxylates, 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 from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • Such polymeric polycarboxylates are preferably included in the compounds because they are not only effective as co-builders but can also serve as agglomeration aids.
  • the content of (co) polymeric polycarboxylates in the compounds is preferably 0.5 to 20% by weight, in particular 3 to 15% by weight.
  • the polymers may also be allyl sulfonic acids, for example, in EP-B-727448 allyloxybenzenesulfonic acid and Methallylsulfonic acid, as a monomer.
  • allyl sulfonic acids for example, in EP-B-727448 allyloxybenzenesulfonic acid and Methallylsulfonic acid, as a monomer.
  • biodegradable polymers from more than two different monomer units for example, those according to DE-A-43 00 772 as monomers salts of Acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and as monomers preferably acrolein and Acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • hydroxyalkane and Aminoalkanphosphonate be included.
  • hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt is neutral and the tetrasodium salt alkaline (pH 9) reacts.
  • Aminoalkanphosphonate are preferably Ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, e.g. B.
  • the class of phosphonates preferably uses HEDP, and is accordingly then preferably included in the compounds, if these compounds as Builder compounds are designed, i. as predominant or sole builder in wash or Detergents are suitable.
  • the aminoalkanephosphonates have a clear lower calcium binding capacity than HEDP, however, due to their Heavy metal binding capacity used for bleach stabilization. Accordingly It can, especially if the compounds are used together with bleach should also be preferred that Aminoalkanphosphonate, in particular DTPMP, or Mixtures of the mentioned phosphonates are included.
  • the salary of Compounds of total phosphonates is preferably 0.3 to 20 wt .-%.
  • the compounds. are designed as builder compounds, it is preferred that these compounds do not contain silicates, especially no sodium silicates, or insoluble A-luminosilicates contain. Accordingly, the compounds are mainly for Use in agents that contain phosphate as the main builder. Should-in the means more inorganic builders are included, they are preferably separated from the Introduced phosphate compounds. Other ingredients of detergents and cleaners, especially surfactants, may be included in the compounds, wherein they but preferably only in small amounts or not at all. especially the Frequently used as granulating aids nonionic surfactants are preferred in the compounds not included.
  • the compounds are their form. she are present as agglomerates, which are formed from primary particles.
  • the mean particle size The agglomerates, as it emerges from a sieve analysis, is preferably in the range of 0.2 to 1.0 mm, especially in the range of 0.3 to 0.8 mm.
  • the mean diameter of the primary particles is in preferred embodiments about a factor of 5, preferably even a factor of 10, less than the mean particle size of the agglomerates. Because of this special structure are the Compounds themselves easily and quickly soluble.
  • the compounds usually have one Bulk density in the range 600 to 1000 g / l, wherein the bulk density of the compounds preferably between 700 and 900 g / l. This particular form of compounds also places special demands on a manufacturing process for such compounds.
  • a second subject of the invention is accordingly a process for the preparation
  • Such phosphate compounds which is characterized in that anhydrous, powdery Pentasodium triphosphate in a high speed mixer with 12 to 28 wt .-% water, based on the pentasodium triphosphate, and optionally further Ingredients of detergents and / or cleaning agents is agglomerated and the Agglomerate immediately afterwards in a fluidized bed drying at a product temperature dried below 60 ° C to a content of free water of less than 5 wt .-%.
  • anhydrous pentasodium triphosphate (STP) are thereby understood commercial pentasodium triphosphate qualities, the maximum 1 wt .-% May contain moisture.
  • STP anhydrous pentasodium triphosphate
  • Phase I metastable at room temperature High temperature modification
  • Phase II stable at room temperature phase II. This Both phases also differ in their rate of hydration.
  • Phase I absorbs water much faster than Phase II Hydration process liberated heat heats pentasodium triphosphate during this process may be so strong that it may decompose the Triphosphate is coming. Since this decomposition is undesirable, is at most Hydration method for STP a specific ratio of phase I to phase II necessary to avoid overheating.
  • Phase II In general, must be predominantly Phase II to prevent decomposition of the STP during hydration can be.
  • the present method is largely independent of the proportion of both phases, it can with any ratio of phase I to phase II be performed. Are particularly high Triphosphaterariasgrade achieved However, it is also advantageous in this method, if more than 50% by weight of the phosphate is present as phase II.
  • the phosphate powder is placed in a high speed mixer, which is preferably designed as a tumbler mixer.
  • the term "high speed” means that such mixers at a speed of several revolutions per second, preferably above 1500 Umin -1 , mix.
  • the residence time of the phosphate is in the mixer only a short time, preferably less than 20 seconds; if a free-fall mixer is used as the mixer, preferably even less than 2 seconds, in particular less than 1.5 seconds.
  • the phosphate powder is sprayed with water or an aqueous solution, wherein 12 to 28 wt .-%, preferably 15 to 20 wt .-%, of the phosphate weight is applied as water. In a specific variant of the process, less than 18% by weight of water is applied.
  • phosphate even more, already described above ingredients of Blended with detergents and / or cleaning agents they are in one Embodiment of the invention in dry form with the anhydrous phosphate powder mixed and then introduced into the high-speed mixer.
  • an aqueous solution of at least one of Ingredients used for spraying in high-speed mixer It can other ingredients have already been mixed dry with the phosphate.
  • the wet compound without loss of time in a drying device, which is designed as a fluidized bed drying, transferred.
  • a drying device which is designed as a fluidized bed drying
  • the compound falls directly from the mixer to the fluidized bed.
  • the drying in the fluidized bed is carried out under mild conditions, the product temperature preferably even below 60 ° C during the entire process 45 ° C.
  • the supply air temperature optimum supply air temperature depending on the size of the fluidized bed and the supplied Air volume.
  • the supply air temperature is a maximum of 100 ° C.
  • the process becomes the released heat of hydration of the triphosphate for drying used and the supply air not preheated. But even if preheated supply air supplied However, the process still has the advantage, the heat of hydration simultaneously to use for drying and accordingly with compared to other methods little additional energy supplied. Through these mild conditions, especially the low product temperature, a decomposition of the triphosphate largely prevented.
  • After drying preferably still at least 95 wt .-% of the phosphate as a triphosphate ago. The drying takes place until, until the content of free water is not more than 5% by weight, preferably not more than 3% by weight, lies.
  • the required residence time of the agglomerate is in the Fluid bed dryer between 10 and 60 minutes.
  • Fine parts can optionally together with the filter dusts from the fluid bed dryer turn the Grobkom preferred before recycling is ground in a hammer mill and the fluidized bed drying after at least one third of the route, preferably after more than two thirds of the route, again is supplied.
  • the above - described phosphate compound is excellent for Incorporation in detergent tablets, such as Detergent tablets for washing textiles, detergent tablets for automatic dishwashing or cleaning of hard surfaces, Bleach moldings for use in washing machines or dishwashers, Water softening tablets or patch salt tablets.
  • detergent tablets such as Detergent tablets for washing textiles, detergent tablets for automatic dishwashing or cleaning of hard surfaces, Bleach moldings for use in washing machines or dishwashers, Water softening tablets or patch salt tablets.
  • Another object of the present invention is therefore the use of Phosphate compounds, which after mixing with finely divided treatment components pressed in a conventional manner to washing and makesmittefformkörpem be used to improve the stability and solubility of washing and makesmittelformkörpem.
  • the phosphate compounds according to the invention after mixing with other components to washing and Cleaning agent molding can be pressed, the physical properties the shaped body, in particular the mechanical stability and the solubility behavior, be significantly improved. This can be washed and pressed with low pressures Prepare detergent tablets which have sufficient mechanical stability in packaging, transport and handling. Opposite the insert Conventional phosphates can in this way equal stable tablets lower pressing pressures are produced, so that the wear on the Tabletting significantly reduced and their life is extended.
  • Another object of the present invention are also washing and Detergent shaped body of compacted particulate washing and Detergents containing a phosphate compound according to the invention.
  • the phosphate compounds of the invention in mixture with conventional and commercially available phosphates.
  • the majority of the phosphate contained in the moldings comes from the phosphate compounds according to the invention. Washing and makesmitteiform stresses which at least 80 wt .-%, preferably at least 90th Wt .-% and particularly preferably the total amount contained in the molding Phosphate amount in the form of phosphate compounds according to the invention are included therefore preferred.
  • the phosphate compounds can be used according to the invention Detergents and cleaning agent tablets in varying amounts in the Formkörpem be included. In this case, washing and cleaning agent tablets are preferred which, based on the weight of the molding, 10 to 90 wt .-%, preferably 20 to 80 Wt .-% and in particular 25 to 70 wt .-% of the phosphate compound.
  • excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.
  • Disintegration aids are, for example, carbonate / citric acid systems, wherein also other organic acids can be used.
  • overflowing Disintegration aids are, for example, synthetic polymers such as Polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as Cellulose and starch and their derivatives, alginates or casein derivatives.
  • the washing and Detergent tablets no disintegration aids. They show alone the incorporation of the phosphate compound according to the invention a sufficiently high Dissolution speed up.
  • washing and Detergent tablets 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% of one or more Cesintegrationstosstoff, respectively based on the molding body weight.
  • cellulose-based disintegrating agents are used in the present invention, so that preferred washing and takesmittelform stresses- such disintegrating agent based on cellulose in amounts of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% included.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and formally represents a ⁇ -1,4-polyacetate of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
  • the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of
  • the cellulose used as disintegration aid is preferably not in used finely divided form, but before admixing to be pressed Premixes converted into a coarser form, for example, granulated or compacted.
  • Detergents and cleaning agents, the disintegrators in granular or optionally cogranulated form are in the German Patent applications DE 197 09 991 and DE 197 10 254 and the international Patent Application WO98 / 40463. These writings are also closer Information on the production of granulated, compacted or cogranulated Remove cellulose explosives.
  • the particle sizes of such disintegrating agents are usually above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90 wt .-% between 400 and 1200 microns.
  • the coarser ones mentioned above and described in more detail in the cited documents Cellulosic disintegration aids are within the scope of the present invention preferably used as a disintegration aid and in the trade, for example, under the name Arbocel® TF-30-HG of the company Rettenmaier available.
  • microcrystalline cellulose Another disintegrating agent based on cellulose or as part of this Component may be used microcrystalline cellulose.
  • This microcrystalline Cellulose is produced by partial hydrolysis of celluloses under such conditions containing only the amorphous regions (30% of the total cellulose mass) of the Celluloses attack and completely dissolve, but the crystalline areas (70%) leave undamaged. Subsequent deaggregation by hydrolysis resulting micro-fine celluloses provides the microcrystalline celluloses, the Primary particle sizes of about 5 microns and, for example, with granules a mean particle size of 200 microns are compacted.
  • preferred washing and Detergent tablets also contain a disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, respectively based on the molding body weight ,.
  • a disintegration aid preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, respectively based on the molding body weight ,.
  • the detergent tablets according to the invention additionally one or more substances from the groups of bleaches, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, Foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, Grayness inhibitors, color transfer inhibitors, corrosion inhibitors and Contain silver protectants. These substances are described below.
  • the sodium perborate tetrahydrate, the sodium perborate monohydrate and the sodium percarbonate have particular significance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced.
  • bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, irrespective of which further ingredients are contained in the shaped bodies.
  • bleaching agents from the group of organic bleaching agents.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP ), o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyl
  • chlorine may also be used or bromine-releasing substances are used.
  • bromine-releasing materials include, for example, heterocyclic N-bromo and N-chloroamides, for example, trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with Cations such as potassium and sodium into consideration.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable
  • bleach activators can be incorporated into the Detergent tablets according to the invention are incorporated.
  • Bleach activators may be compounds that are under perhydrolysis conditions aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, be used. Suitable substances are the O- and / or N-acyl groups of bear C-atomic number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (N- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED Tetraacetylethylenediamine
  • bleach catalysts are incorporated into the moldings.
  • bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.
  • Enzymes are those from the class of proteases, lipases, amylases, Cellulases or mixtures thereof in question. Particularly suitable are from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, proteases are from Subtilisin type and in particular proteases derived from Bacillus lentus, used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or protease, amylase and lipase or protease, lipase and cellulase, but especially cellulase-containing mixtures of particular interest.
  • Peroxidases or oxidases have proven to be suitable in some cases.
  • the Enzymes can be adsorbed to carriers and / or embedded in encapsulating substances be to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the moldings of the invention can for example, 0.1 to 5 wt .-%, preferably 0.1 to 2 wt .-% amount.
  • the most commonly used enzymes include lipases, amylases, cellulases and proteases.
  • Preferred proteases are, for. B. BLAP®140 Fa. Biozym, Optimase® M-440 and Opticlean® M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo.
  • Especially suitable cellulases and lipases are Celluzym® 0.7 T and Lipolase® 30 T from the company.
  • amylases are found in Duramyl® and Termamyl® 60 T, and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades. Other enzymes can be used become.
  • the detergent tablets may also contain components which positively influence the oil and Fettauswaschles from textiles (so-called soil repellents). This effect becomes particularly apparent when a textile is contaminated, which previously several times with an inventive Detergent containing this oil and fat dissolving component was washed.
  • nonionic Cellulose ethers such as methylcellulose and methylhydroxy-propylcellulose with a proportion at methoxyl groups from 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ether, and from the State of the art known polymers of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionic and / or nonionic modified Derivatives of these. Particularly preferred of these are the sulfonated derivatives of Phthalic acid and the terephthalic acid polymers.
  • the moldings can be used as optical brighteners derivatives of Diaminostilbendisulfonklare or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which, instead of the morpholino group, a diethanolamino group, a Methylamino group, an anilino group or a 2-Methoxyethylaminoè carry. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g.
  • Dyes and fragrances are the washing and makesmittelformkörpem invention added to improve the aesthetic appearance of the products and the consumer in addition to the softness a visually and sensory "typical and unmistakable "product as perfume oils or fragrances
  • individual perfume compounds e.g. the synthetic products of the type Esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are known e.g.
  • benzyl acetate Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • Ethem include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 carbon atoms.
  • perfume oils can also be natural fragrance mixtures as available from plant sources, e.g. Pine, Citrus, Jasmine, Patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, Vetiver oil, Olibanum oil, Galbanum oil and Labdanum oil and Orange blossom oil, Neroliol, Orange peel oil and sandalwood oil.
  • the content of the detergent tablets according to the invention is Dyes below 0.01 wt .-%, while perfumes up to 2 wt .-% of entire formulation can make.
  • the fragrances can be incorporated directly into the compositions according to the invention However, it may also be advantageous to apply the fragrances to carriers, the adhesion of the perfume on the lingerie and by a slower release of fragrance for long-lasting fragrance of the textiles.
  • carrier materials have become
  • cyclodextrins have proven useful, with the cyclodextrin-perfume complexes additionally can be coated with other excipients.
  • the agents according to the invention can dyed with suitable dyes.
  • Preferred dyes their selection the expert no difficulty, have a high storage stability and Insensitivity to the other ingredients of the agent and against light as well no pronounced substantivity to textile fibers so as not to stain them.
  • Dishwashing agent shaped bodies according to the invention can be used to protect the items to be washed or the machine contain corrosion inhibitors, with particular silver protectants have special significance in the field of automatic dishwashing.
  • silver protectants selected from the group of triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used.
  • Particularly preferred too use are benzotriazole and / or alkylaminotriazole.
  • cleaner formulations often include active chlorine containing agents Corrosion of the silver surface can significantly reduce.
  • oxygen- and nitrogen-containing organic redox-active Compounds such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, Hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these Classes of compounds.
  • organic redox-active Compounds such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, Hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these Classes of compounds.
  • salt and complex inorganic compounds such as Salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are frequently used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds be used to prevent corrosion of items to be washed.
  • cationic polymers such as for example, hydroxypropyltrimethylammonium guar; Copolymers of Aminoethyl methacrylate and acrylamide and copolymers of dimethyldiallylammonium chloride and acrylamide, polymers with imino groups, cationic Cellulose derivatives, cationic homo- and / or copolymers (monomer units: quaternized ammonium alkyl methacrylate groups).
  • the cationic polymers are particularly preferably selected from cationic polymers Polymers of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or -acrylamide; Dialkyldiallyldiammoniumsalze; polymeranalogous Reaction products of ethers or esters of polysaccharides with pendant ammonium groups, in particular guar, cellulose and starch derivatives; Polyadducts of Ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and Polyamides with quaternary side groups as soil release compounds. Exceptionally preferred in the context of this application are also natural Polyuronic acids and related substances, as well as polyampholytes and hydrophobized Polyampholytes, or mixtures of these substances.
  • Water-insoluble buildem include the zeolites, which also can be used, as well as mixtures of the aforementioned builders. Preference is given in addition to the phosphate compounds according to the invention Trisodium citrate and / or sodium carbonate and / or sodium bicarbonate and / or Gluconates and / or silicatic builders from the class of disilicates and / or Metasilicates or the layered silicates used.
  • alkali carriers may be present.
  • Alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, Alkatimetallsesquicarbonate, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances preference being given in the context of this invention to the alkali metal carbonates, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate be used.
  • a phosphate compound is produced.
  • the person skilled in the art can use literature-known machines and apparatus as well as process engineering operations, as described, for example, in W. Pietsch, "Size Enlargement by Agglomeration", Verlag Wiley, 1991 , and the literature cited therein are.
  • inventive washing and Detergent tablets the phosphate compounds of the invention depending on Intended use in varying quantities.
  • Completely analogous are also inventive Preferred method in which the prepared in step a) phosphate compound 10 bis 90 wt .-%, preferably 20 to 80 wt .-% and in particular 25 to 70 wt .-% of the constituting the compressing premix.
  • the phosphate compound according to the invention in step b) mixed with other ingredients of detergents and cleaners and for Molded body pressed.
  • methods according to the invention are preferred which are characterized characterized in that the phosphate compound prepared in step a) in step b) with at least one oxygen bleach selected from the group of Alkali perborates, alkali percarbonates, organic peracids and hydrogen peroxide is mixed.
  • the bleaching agents in question were described above.
  • inventive Preferred method in which the phosphate compound prepared in step a) with at least one bleaching agent selected from the group of trichlorocyanuric acids, dichloro- or monochlorocyanurates, hypochlorites, and other usual ones chlorine-containing bleaching agent is mixed.
  • the bleaching performance of bleach-containing Formkörpem as Detergent tablets, detergent tablets or bleach tablets through the Use of bleach activators increased.
  • a bleach activator preferably from the group of the multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED).
  • the N-acylimides especially N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and / or the bleach-enhancing Transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and / or the manganese sulfate is mixed.
  • NOSI N-nonanoylsuccinimide
  • preferred methods of the present invention include the Pressing a particulate premix of at least one phosphate compound, at least one surfactant-containing granules and at least one admixed powdered component.
  • the preparation of surfactant-containing granules can by conventional technical Granulationsverfähren such as compaction, Extrusion, mixer granulation, pelleting or fluidized bed granulation done.
  • the surfactant-containing granules are sufficient in preferred process variants Molchen relienkriterien.
  • methods according to the invention are preferred in which the surfactant-containing granules particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, more preferably between 400 and 1600 microns and especially between 600 and 1400 ⁇ m, has.
  • anionic and / or nonionic and / or cationic and / or amphoteric surfactants preferably still contain the surfactant granules Carriers which more preferably originate from the group of builders.
  • Particularly advantageous methods are characterized in that the surfactant-containing Granules containing anionic and / or nonionic surfactants and builders and Total surfactant contents of at least 10% by weight, preferably at least 20% by weight in particular at least 25% by weight.
  • it is Tenside content of detergent tablets between 10 and 40 wt .-%, preferably between 12.5 and 30% by weight and especially between 15 and 25% by weight while Detergent tablets for automatic dishwashing between 0.1 and 10 wt .-%, preferably between 0.5 and 7.5% by weight and in particular between 1 and 5 Wt .-% surfactants.
  • Bleach tablets and water softener tablets are usually free of surfactants.
  • surfactants come from the group of anionic, nonionic, zwitterionic or cationic surfactants, with anionic surfactants for economic reasons and because of their range of services clearly preferred are.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 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 are suitable.
  • sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
  • Fatty acid glycerol esters are the mono-, di- and triesters and mixtures thereof as understood in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example the Caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. They are used in detergents due to their high Schaumverhattens only in relatively small amounts, for example in amounts of 1 to 5 wt .-%.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • suitable saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants including soaps may 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 in the form their sodium or potassium salts, in particular in the form of the sodium salts.
  • Preferred surfactant granules have However, a content of soap, which is 0.2 wt .-%, based on the total weight of In step d) produced detergent and cleaner molding exceeds.
  • Preferred anionic surfactants are the alkylbenzenesulfonates and Fatty alcohol sulfates, preferred detergent tablets being from 2 to 20% by weight, preferably from 2.5 to 15% by weight and in particular from 5 to 10% by weight of fatty alcohol sulphate (e), in each case based on the weight of the detergent tablets
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants used either as sole nonionic surfactant or in combination with other nonionic surfactants
  • Surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 Carbon atoms in the alkyl chain, especially fatty acid methyl esters, as they
  • JP 58/217598 are described or preferably according to the method described in International Patent Application WO-A-90/13533 be prepared described methods.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable alkylpolyglycosides satisfy the general formula RO (G) z , in which R is a linear or branched, in particular in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Preference is given to using linear alkyl polyglucosides that is to say alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
  • the surfactant granules may preferably contain alkylpolyglycosides, wherein contents of APG over 0.2 wt .-%, based on the total molding, are preferred.
  • Particularly preferred detergent tablets contain APG in amounts of from 0.2 to 10 Wt .-%, preferably 0.2 to 5 wt .-% and in particular from 0.5 to 3 wt .-%.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides may 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 it.
  • polyhydroxy fatty acid amides of the formula (I) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical
  • [Z] is preferably obtained by reductive amination of a reduced sugar, For example, glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar For example, glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds may then be, for example according to the teaching of international application WO-A-95/07331 by reaction with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxyfatty acid amides are transferred.
  • anionic or nonionic surfactants or mixtures of These surfactant classes and optionally amphoteric or cationic surfactants in Tensidgranulat are used, methods of the invention are preferred in the surfactant content of the surfactant-containing granules 5 to 60 wt .-%, preferably 10 to 50 wt .-% and in particular 15 to 40 wt .-%, each based on the Surfactant granules, is.
  • step b) more Builders, preferably at least one aluminosilicate and / or a Layered silicate, are mixed with the phosphate compound.
  • the aluminosilicate is preferably finely crystalline, synthetic and bound water-containing zeolites, in particular zeolite A, X and / or P.
  • zeolite P for example, zeolite MAP (R) (commercial product from Crosfield) is used.
  • zeolite Y and mixtures of A, X, Y and / or P are also suitable, however, are zeolite Y and mixtures of A, X, Y and / or P.
  • Such a mixture of zeolite A and zeolite X is commercially available, for example, under the name Vegobond AX® (from Condea Augusta SpA).
  • the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • layered silicates are preferably crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 ⁇ yH 2 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 are understood.
  • Such crystalline sheet silicates are described, for example, in European Patent Application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • the washing and Detergent tablets further ingredients of detergents and cleaners included, so that preferred variants of the method are analog.
  • An im Under the present invention preferred method is characterized in that that the premix additionally a disintegration aid, preferably a Cellulosic disintegration aids, preferably granular, co-granulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7 Wt .-% and in particular from 4 to 6 wt .-%, each based on the weight of Premix, it being additionally preferred that the premix additionally one or more substances from the group of enzymes, pH adjusters, fragrances, Perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, Anti redeposition agents, optical brighteners, grayness inhibitors, color transfer inhibitors, Contains corrosion inhibitors and silver protectants.
  • a disintegration aid preferably a Cellulosic disintegration aids, preferably granular, co-granulated or compacted form,
  • the premix Prior to compression of the particulate premix into detergent tablets, the premix may be "powdered” with finely divided surface treatment agents. This may be advantageous for the nature and physical properties of both the premix (storage, compression) and the finished detergent tablets. Fine particulate powdering agents are well known in the art, with mostly zeolites, silicates or other inorganic salts are used. Preferably, however, the premix is "powdered” with finely divided zeolite, with faujasite-type zeolites being preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structural group 4 (cf. Donald W.
  • the production of the shaped body according to the invention is initially carried out by the dry Mixing the ingredients, which may be pre-granulated in whole or in part, and subsequent Informing, in particular pressing into tablets, wherein conventional methods can be used.
  • Shaped body according to the invention is the premix in a so-called template compressed between two stamps to a fixed compressed. This process, in the hereinafter referred to as tableting, is divided into four sections: Dosing, compaction (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix.
  • the upper punch contacts the pre-mix and continues to descend toward the lower punch.
  • the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding.
  • the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the shaped body is finally determined because the compacts due to physical processes (re-expansion, crystallographic effects, cooling) can change their shape and size.
  • the tableting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches.
  • eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed.
  • the movement of these punches is comparable to the operation of a conventional four-stroke engine.
  • the compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohritch is extended accordingly.
  • the throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies are arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available.
  • Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp.
  • the die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection.
  • suitable tabletting machines are available, for example, from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Keil am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Berne (CH) and Courtoy N.V., Halle (BE / LU).
  • the hydraulic is particularly suitable Double printing press HPF 630 of the company LAEIS, D.
  • the moldings can be in a predetermined spatial form and predetermined size be made.
  • the training as a blackboard the rod or Barrel shape, cubes, cuboids and corresponding room elements with flat side surfaces and in particular cylindrical embodiments with circular or oval cross-section.
  • This last embodiment detects the Darbletungsform of the Tablet up to compact cylinder pieces with a ratio of height to Diameter above 1.
  • the portioned compacts can each be separated from each other Be formed individual elements that the predetermined dosage of the washing and / or Cleaning agent corresponds.
  • textile detergents in machines of the type common in Europe with horizontally arranged mechanics may be the training the portioned compacts as tablets, in cylindrical or cuboid form be expedient a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred is.
  • Commercially available hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for producing such compacts.
  • the spatial form of another embodiment of the moldings is in their dimensions the Ein Honeycet adapted from commercial household washing machines, so that the moldings can be metered directly into the dispensing chamber without dosing aid, where it dissolves during the flushing process.
  • the moldings can be metered directly into the dispensing chamber without dosing aid, where it dissolves during the flushing process.
  • Another preferred molded article which can be produced has a plate or tabular structure with alternately thick long and thin short segments, see above that individual segments of this "bar" at the predetermined breaking points, the short thin segments, aborted and entered into the machine can.
  • This principle of the "bar-shaped" molding detergent can also in other geometric shapes, such as vertical triangles, the are connected together only on one of their sides, realized become.
  • the various components not one uniform tablet be pressed, but that moldings are obtained, the several layers, so at least two layers have. And that's it possible that these different layers have different dissolution rates exhibit. From this, advantageous application properties of the Shaped bodies result. For example, if components are contained in the moldings are mutually negatively affecting, so it is possible that one component integrate into the faster soluble layer and the other component into one incorporate slower soluble layer, so that the first component already abreacted when the second goes into solution.
  • the layer structure of the molded body can doing both stacked, with a solution process of the inner layer (s) on The edges of the shaped body already takes place when the outer layers are still not completely solved, but it can also be a complete covering of the inner Layer (s) are achieved by the respective outer layer (s), which to prevent premature dissolution of constituents of the inner layer (s) leads.
  • a shaped body is made at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the stack-shaped molded body, the two outer layers and the shell-shaped moldings, the outermost layers, however, free of peroxy bleach are.
  • Such multilayer molded articles have the advantage that they not only via a dispenser or via a metering device, which in the wash liquor given can be used; rather, it is also possible in such cases to give the shaped body in direct contact with the textiles in the machine, without that stains caused by bleach and the like are to be feared.
  • the body to be coated For example, be sprayed with aqueous solutions or emulsions, or over the process of melt coating obtained a coating.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • ⁇ stands for the diametrical fracture stress (DFS) in Pa
  • P is the force in N which leads to the pressure exerted on the molding, which is the pressure Fraction of the molded body caused
  • D is the molding diameter in meters
  • t is the height of the moldings.
  • phosphate compounds were pentasodium triphosphate powder with a pure substance content of 98.3% and 0.3 wt .-% water in a free fall mixer (Flexomix®, company Schugi), which ran at a speed of 2600 rpm, with a 10% solution of a polyacrylate-maleate copolymer (Sokalan CP5®, BASF) sprayed.
  • the agglomerate dropped from the mixer into a fluidized bed and became at one Product temperature of 40 ° C within 45 minutes to a total water content dried by 13 wt .-%.
  • the resulting granules had a raspberry-shaped Structure, wherein the average particle diameter of the agglomerate particles by 550 .mu.m However, the primary particles forming the agglomerate are almost a factor of 10 smaller were as the average particle diameter of the agglomerates.
  • the data of obtained granules are given in Table 1.
  • the phosphate content in Table 1 was determined from the total phosphorus content (in C4, the phosphorus contained in the phosphonate was removed here) and the total water content was measured at 160 ° C. Free water is the moisture that is split off up to 100 ° C, the specified water content is the difference between the two values.
  • DTA-TG heating rate: 10 K / min
  • a crystallized water content of 8.1% by weight was determined for C1.
  • Moldings were produced with compound C1.
  • the phosphate compound was mixed with further treatment components and pressed on an eccentric tablet press according to Table 3.
  • the composition of the premix to be compressed can be found in Table 2.
  • the moldings contained auxiliaries, such as binders, disintegration aids, dyes and fragrances, fillers and water.
  • Comparative Example V had the same formulation, but here phosphate and copolymer were used separately, the phosphate was used in the form of a commercial granules with a free water content of about 7 wt .-%.
  • significantly higher pressing pressures were required in the comparative example (see Table 3).
  • Premix [% by weight] phosphate 49 copolymer 3 phosphonate 1
  • Sodium hydroxide monohydrate 9 enzymes 4 surfactants 2 silicate 4 TAED 2
  • the hardness of the tablets was measured by deformation of the tablet until fracture, the force acting on the side surfaces of the tablet and the maximum force, the the tablet withstood, was detected.
  • the measurement was carried out on a hardness tester CT5 (Holland) with punch diameter of 8 mm.
  • the determination of the dissolution time of the tablets was carried out in a household dishwasher.
  • the tablets were placed in the basket of the machine before starting the main wash cycle
  • the basket is in all attempts in the same place in the Machine was. It was used a 50 ° C program and the time until the completely dissolving the tablet over the pursuit of conductivity.

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Claims (28)

  1. Compounds phosphatés destinés à être utilisés dans des agents de lavage et de nettoyage, contenant au moins 50% en poids de triphosphate pentasodique, moins de 5% en poids de pyrophosphate de sodium ainsi qu'au maximum 18% en poids d'eau, les compounds se trouvant sous forme d'agglomérats de particules primaires, caractérisés en ce que la teneur du compounds en eau libre est d'au maximum 5% en poids, de préférence d'au maximum 3% en poids et la teneur en triphosphate pentasodique hexahydraté est compris entre 20 et 70% en poids de la teneur en triphosphate pentasodique totale.
  2. Compounds phosphatés selon la revendication 1, caractérisés en ce que les compounds contiennent 0,5 à 20 % en poids d'un polycarboxylate polymère.
  3. Compounds phosphatés selon l'une quelconque des revendications 1 ou 2, caractérisés en ce que les compounds contiennent 0,3 à 20% en poids de phosphonate.
  4. Compounds phosphatés selon l'une quelconque des revendications 1 à 3, caractérisés en ce que les compounds ne contiennent pas d'agent tensioactif non ionique ni de silicate.
  5. Compounds phosphatés selon l'une quelconque des revendications 1 à 4, caractérisés en ce que les compounds présentent une densité apparente dans la plage de 600 à 1000 g/l et les agglomérats présentent une grosseur moyenne des particules dans la plage de 0,2 à 1,0 mm, de préférence dans la plage de 0,3 à 0,8 mm.
  6. Procédé pour la préparation de compounds phosphatés selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'on agglomère du triphosphate pentasodique anhydre sous forme de poudre dans un mélangeur à vitesse élevée avec 12 à 28% en poids d'eau par rapport au triphosphate pentasodique et le cas échéant d'autres constituants d'agents de lavage et/ou de nettoyage et l'agglomérat est séché de manière immédiatement consécutive dans un séchage en lit fluidisé à une température de produit inférieure à 60°C jusqu'à une teneur en eau libre inférieure à 5% en poids.
  7. Procédé pour la préparation de compounds phosphatés selon la revendication 6, caractérisé en ce que la durée de séjour du phosphate dans le mélangeur à haute vitesse est inférieure à 20 secondes et l'agglomération est réalisée avec 15 à 20% en poids d'eau.
  8. Procédé pour la préparation de compounds phosphatés selon l'une quelconque des revendications 6 ou 7, caractérisé en ce que la durée de séjour de l'agglomérat dans le sécheur à lit fluidisé est comprise entre 10 et 60 minutes et la température de l'air alimenté est inférieure à 130°C, de préférence inférieure à 100°C.
  9. Procédé pour la préparation de compounds phosphatés selon l'une quelconque des revendications 6 à 8, caractérisé en ce que d'autres constituants des agents de lavage et/ou de nettoyage sont mélangés sous forme sèche avec la poudre de phosphate et le mélange est ensuite aggloméré.
  10. Procédé pour la préparation de compounds phosphatés selon l'une quelconque des revendications 6 à 9, caractérisé en ce que l'eau est utilisée sous forme d'une solution aqueuse d'autres constituants d'agents de lavage et/ou de nettoyage et la durée de séjour du phosphate dans le mélangeur à haute vitesse est inférieure à 2 secondes.
  11. Utilisation de compounds phosphatés selon l'une quelconque des revendications 1 à 5 pour améliorer la solubilité de corps façonnés d'agents de lavage et de nettoyage, exprimée par un meilleur facteur de corrélation dureté/temps de dissolution, qui est obtenu en ce que la valeur de la dureté des comprimés est divisée par la valeur obtenue pour le temps de dissolution au moment correspondant et en multipliant ce facteur par 10.
  12. Utilisation de compounds phosphatés selon l'une quelconque des revendications 1 à 5 pour améliorer la stabilité mécanique de corps façonnés d'agents de lavage et de nettoyage.
  13. Corps façonnés d'agents de lavage et de nettoyage réalisés à partir d'agents de lavage et de nettoyage en forme de particules compactées, caractérisés en ce qu'ils contiennent un compound phosphaté selon l'une quelconque des revendications 1 à 5 ou un produit du procédé selon l'une quelconque des revendications 6 à 10.
  14. Corps façonnés d'agents de lavage et de nettoyage selon la revendication 13, caractérisés en ce qu'ils contiennent au moins 80% en poids, de préférence au moins 90% en poids et de manière particulièrement préférée la quantité totale de la quantité de phosphate contenue dans le corps façonné sous forme de compound phosphatés selon l'une quelconque des revendications 1 à 5 ou d'un produit du procédé selon l'une quelconque des revendications 6 à 10.
  15. Corps façonnés d'agents de lavage et de nettoyage selon l'une quelconque des revendications 13 ou 14, caractérisés en ce qu'ils contiennent, par rapport au poids du corps façonné, 10 à 90% en poids, de préférence 20 à 80% en poids et en particulier 25 à 70% en poids du compound phosphaté.
  16. Corps façonnés d'agents de lavage et de nettoyage selon l'une quelconque des revendications 13 à 15, caractérisés en ce qu'ils contiennent en outre un adjuvant de désintégration, de préférence un adjuvant de désintégration à base de cellulose, de préférence sous forme granulée, co-granulée ou compactée, en des quantités de 0,5 à 10% en poids, de préférence de 3 à 7% en poids et en particulier de 4 à 6% en poids, à chaque fois par rapport au poids du corps façonné.
  17. Corps façonnés d'agents de lavage et de nettoyage selon l'une quelconque des revendications 13 à 16, caractérisés en ce qu'ils contiennent en outre une ou plusieurs substances des groupes constitués par les agents de blanchiment, les activateurs de blanchiment, les enzymes, les agents de réglage du pH, les parfums, les supports de parfum, les agents de fluorescence, les colorants, les inhibiteurs de mousse, les huiles de silicone, les agents anti-redépôt, les azurants optiques, les inhibiteurs de jaunissement, les inhibiteurs de transfert de couleur, les inhibiteurs de corrosion et les agents de protection de l'argent.
  18. Procédé pour la préparation de corps façonnés d'agents de lavage et de nettoyage, caractérisé par les étapes
    a) préparation d'un compound phosphaté selon un procédé selon l'une ou plusieurs des revendications 6 à 10,
    b) mélange du compound préparé dans l'étape a) avec d'autres constituants d'agents de lavage et de nettoyage en un prémélange à comprimer,
    c) compression en corps façonnés.
  19. Procédé selon la revendication 18, caractérisé en ce que le compound phosphaté préparé dans l'étape a) représente 10 à 90% en poids, de préférence 20 à 80% en poids et en particulier 25 à 70% en poids du prémélange à comprimer.
  20. Procédé selon l'une quelconque des revendications 18 ou 19, caractérisé en ce que le compound phosphaté préparé dans l'étape a) est mélangé dans l'étape b) avec au moins un agent de blanchiment oxygéné choisi dans le groupe constitué par les perborates alcalins, les percarbonates alcalins, les peracides organiques et le peroxyde d'hydrogène.
  21. Procédé selon l'une quelconque des revendications 18 à 20, caractérisé en ce que le compound phosphaté préparé dans l'étape a) est mélangé avec au moins un agent de blanchiment, choisi dans le groupe constitué par les acides trichlorocyanuriques, les dichlorocyanurates ou les monochlorocyanurates, les hypochlorites et les autres agents de blanchiment usuels contenant du chlore.
  22. Procédé selon l'une quelconque des revendications 18 à 21, caractérisé en ce que le compound phosphaté préparé dans l'étape a) est mélangé avec au moins un activateur de blanchiment, provenant de préférence du groupe constitué par les alkylènediamines polyacylées, en particulier la tétraacétyléthylènediamine (TAED), les N-acylimides, en particulier le N-nonanoylsuccinimide (NOSI), les phénolsulfonates acylés, en particulier le n-nonanoyloxybenzènesulfonate ou l'isononanoyloxybenzènesulfonate (n-NOBS ou iso-NOBS), le n-méthyl-morpholinium-acétonitrile-méthylsulfate (MMA) et/ou les complexes de métaux de transition renforçant le blanchiment, en particulier avec les atomes centraux Mn, Fe, Co, Cu, Mo, V, Ti et/ou Ru, de préférence du groupe constitué par les sels et/ou les complexes de manganèse et/ou de cobalt, de manière particulièrement préférée les complexes de cobalt(ammine), les complexes de cobalt(acétate), les complexes de cobalt(carbonyle), les chlorures de cobalt ou du manganèse et/ou le sulfate de manganèse.
  23. Procédé selon l'une quelconque des revendications 18 à 22, caractérisé en ce que le compound phosphaté préparé dans l'étape a) est assemblé avec au moins un granulat contenant un ou des agents tensioactifs en un prémélange à comprimer présentant une densité apparente d'au moins 500 g/l, de préférence d'au moins 600 g/l et en particulier d'au moins 700 g/l.
  24. Procédé selon la revendication 23, caractérisé en ce que le granulat contenant un ou des agents tensioactifs présente des grosseurs de particules entre 100 et 2000 µm, de préférence entre 200 et 1800 µm, de manière particulièrement préférée entre 400 et 1600 µm et en particulier entre 600 et 1400 µm.
  25. Procédé selon l'une quelconque des revendications 23 ou 24, caractérisé en ce que le granulat contenant un ou des agents tensioactifs contient des agents tensioactifs anioniques et/ou non ioniques ainsi que des adjuvants et présente des teneurs totales en agent(s) tensioactif(s) d'au moins 10% en poids, de préférence d'au moins 20% en poids et en particulier d'au moins 25% en poids.
  26. Procédé selon l'une quelconque des revendications 18 à 25, caractérisé en ce qu'on mélange dans l'étape b), avec le compound phosphaté, d'autres substances builder qui contiennent de préférence au moins un aluminosilicate et/ou un silicate à couches.
  27. Procédé selon l'une quelconque des revendications 18 à 26, caractérisé en ce que le prémélange contient en outre un agent de désintégration, de préférence un adjuvant de désintégration à base de cellulose, de préférence sous forme granulée, co-granulée ou compactée, en des quantités de 0,5 à 10% en poids, de préférence de 3 à 7% en poids et en particulier de 4 à 6% en poids, à chaque fois par rapport au poids du prémélange.
  28. Procédé selon l'une quelconque des revendications 18 à 27, caractérisé en ce que le prémélange contient en outre une ou plusieurs substances du groupe constitué par les enzymes, les agents de réglage du pH, les parfums, les supports de parfum, les agents de fluorescence, les colorants, les inhibiteurs de mousse, les huiles de silicone, les agents d'anti-redépôt, les azurants optiques, les inhibiteurs de jaunissement, les inhibiteurs de transfert de couleur, les inhibiteurs de corrosion et les agents de protection de l'argent.
EP99963522A 1998-12-23 1999-12-14 Composes phosphates Expired - Lifetime EP1141191B1 (fr)

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DE19859807A DE19859807A1 (de) 1998-12-23 1998-12-23 Phosphat-Compounds
DE19859807 1998-12-23
PCT/EP1999/009892 WO2000039260A1 (fr) 1998-12-23 1999-12-14 Composes phosphates

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CA717943A (en) * 1963-02-04 1965-09-14 Unilever Limited Detergent compositions
GB1466868A (en) * 1973-04-19 1977-03-09 Unilever Ltd Granulation of materials
DE2925137A1 (de) * 1979-06-22 1981-01-08 Keri Dipl Ing Karoly Homogene, staubfreie und rieselfaehige wasch- und reinigungsmittelgranulate, sowie verfahren zu deren herstellung
DE3624336A1 (de) * 1986-07-18 1988-01-28 Henkel Kgaa Verfahren zur herstellung von rieselfaehigen alkalischen reinigungsmitteln durch kompaktierende granulation
DE4435743C2 (de) * 1994-02-17 1998-11-26 Chemolux Sarl Verfahren zur Herstellung eines Mehrkomponenten-Granulates
DE19502774A1 (de) * 1995-01-27 1996-08-01 Henkel Kgaa Verfahren zur Herstellung von bruchstabilen Reinigungstabletten
GB2318800A (en) * 1996-11-01 1998-05-06 Unilever Plc Detergent composition
JPH10204500A (ja) * 1997-01-20 1998-08-04 Soft Kyukyu Corp:Kk 発泡錠剤洗浄剤
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DE19859807A1 (de) 2000-06-29
EP1141191A1 (fr) 2001-10-10
DE59911739D1 (en) 2005-04-14

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