EP1382665A1 - Utilisation des composés de phosphate - Google Patents
Utilisation des composés de phosphate Download PDFInfo
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- EP1382665A1 EP1382665A1 EP03019563A EP03019563A EP1382665A1 EP 1382665 A1 EP1382665 A1 EP 1382665A1 EP 03019563 A EP03019563 A EP 03019563A EP 03019563 A EP03019563 A EP 03019563A EP 1382665 A1 EP1382665 A1 EP 1382665A1
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- Prior art keywords
- weight
- phosphate
- agents
- compounds
- phosphate compounds
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Classifications
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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
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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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
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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
- 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 which are suitable for incorporation into Detergent tablets are suitable, and detergent tablets, which contain such compounds. Next is a manufacturing process for specified such phosphate compounds.
- Alkali phosphates are generally suitable as phosphorus-containing builder substances for Detergents and cleaning agents.
- STP pentasodium triphosphate
- Spray drying a slurry from a water-soluble inorganic phosphate with a polymeric polycarboxylate is in patent application DE 38 18 660 described.
- the resulting hollow spheres serve as carriers for nonionic surfactant, which the balls are sprayed on in amounts of 2 to 40% by weight.
- Document GB-A-1466868 relates to a process for the production of porous granular Materials and granules produced by the process, which in a Detergent formulation can be installed.
- the powder used for granulation contains alkali metal tripolyphosphates and a binder, e.g. Water.
- This binder that is necessary to bring about the granulation is added after the powdered tripolyphosphate has been formed into an annular bed; the Granulated product is then kept in motion and z. B. in a fluidized bed dried.
- the German patent application DE-A-29 25 137 discloses homogeneous, dust-free and free-flowing detergent and cleaning agent granules based on Pentasodium tripolyphosphate, which is practically free of hydrolysis products from Are polyphosphate, and a process for their continuous production.
- This Granules contain, among other components, 50 to 80% by weight Pentasodium tripolyphosphate and 10 to 25% by weight, in particular 9 to 19% by weight Water.
- the ratio of ortho- and sodium pyrophosphate to total phosphate is 0.005 to 0.08% by weight.
- a granular composition that contains a hydrate-forming phosphate, preferably Pentasodium triphosphate, 0.1-23 wt .-% water and 2 to 125 ppm surfactant is described in European patent EP-B-259 291.
- This is made 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 hydrate water in the product in favor of Hydrate water shifts.
- the degree of conservation of the pentasodium triphosphate is also this process between 84 and 94% of the phosphate content. Such a low one Degree of phosphate conservation and the associated high pyrophosphate content leads to the Use of such granules when washing dishes to undesirably strong Glass corrosion.
- phosphate compounds which contain little pyrophosphate i.e. have a high degree of phosphate retention and are present as agglomerates, are excellent for incorporation into moldings of detergents and cleaning agents are suitable and even improve the dissolution behavior of these moldings.
- a first object of the invention are phosphate compounds for Use in detergents or cleaning agents that contain at least 50% by weight Pentasodium triphosphate, less than 5% by weight sodium pyrophosphate and maximum Contain 18 wt .-% water and exist as agglomerates of primary particles.
- 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% by weight of the total compounds.
- the content of the compounds should increase other phosphates, especially ortho-, meta- and pyrophosphates. Less than 5% by weight, in particular even less than 3% by weight, of these are preferred Phosphates contained in the compound.
- the proportion of these phosphates is expressed about the degree of conservation of the pentasodium triphosphate in the compound (STP degree of conservation). It is preferably at least 95%, particularly preferably even at least 97%.
- a high pyrophosphate content leads to the use of such Compounds in dishwashing detergents to undesirably reinforce the Glass corrosion.
- the inventive compounds avoid such disadvantages, in which contain less than 5% by weight of sodium pyrophosphate, it being preferred if the sodium pyrophosphate content is even less than 3% by weight or less.
- the compound contains a proportion of water that is a maximum of 18% by weight. can be. However, preferred compounds contain a maximum of 15% by weight of water, a water content of at most 13% by weight can also be preferred. If particularly phosphate-rich compounds are to be produced, one can even Water content of at most 11 wt .-% may be preferred.
- the water is in the Compounds for the most part as hydrate water.
- the content is Pentasodium triphosphate hexahydrate preferably between 20 and 70 wt .-% of the content of total pentasodium triphosphate.
- the free water content of the compounds, i.e. water not bound as hydrate water should be as low as possible.
- He is preferably at most 5% by weight, with free water contents of at most 3% by weight can be particularly preferred. In a special, preferred embodiment the free water content should even be below 1.5% by weight. The free water is already released below 100 ° C and can therefore at this temperature be determined.
- the compounds can contain other ingredients of washing and / or Detergents included. These can preferably be substances that Have cobuilder properties. Here are primarily polycarboxylates, to name in particular polymeric polycarboxylates, and phosphonates.
- 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 70,000 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.
- 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 with molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn 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 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.
- Such polymeric polycarboxylates are preferably contained in the compounds since they are not only effective as cobuilders but can also serve as agglomeration aids.
- the (co) polymeric polycarboxylate content of the compounds is preferably 0.5 to 20% by weight, in particular 3 to 15% by weight.
- the polymers can also allylsulfonic acids, such as for example in EP-B-727448 allyloxybenzenesulfonic acid and methallylsulfonic acid, included as a monomer.
- Biodegradable are also particularly preferred Polymers made up of more than two different monomer units, for example those which according to DE-A-43 00 772 as monomer salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as in DE-C-42 21 381 Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.
- copolymers are those described in the 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 Have vinyl acetate.
- Hydroxyalkane and aminoalkane phosphonates in particular can be used as phosphonates be included.
- hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder.
- HEDP 1-hydroxyethane-1,1-diphosphonate
- Preferred aminoalkane phosphonates are Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. You will prefer in the form of neutral sodium salts, e.g. B.
- the class of phosphonates preferably uses HEDP, and is accordingly also then preferably contained in the compounds if these compounds as Builder compounds are designed, i.e. as a predominant or sole builder in laundry or cleaning agents 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 aminoalkane phosphonates, especially DTPMP, or Mixtures of the aforementioned phosphonates are included.
- the salary of the Compounds of total phosphonates are preferably 0.3 to 20% by weight.
- the compounds are designed as builder compounds, it is preferred that these compounds contain no silicates, especially no sodium silicates, or insoluble ones Contain aluminosilicates. Accordingly, the compounds are primarily suitable for use in agents that contain phosphate as the main builder. Should be in the middle other inorganic builders are included, they are preferably separated from the Phosphate compounds introduced. Other ingredients of washing and Cleaning agents, in particular surfactants, can be contained in the compounds, however, they are preferably only present in small amounts or not at all. In particular, the nonionic surfactants frequently used as granulation aids are in the Compounds preferably not included.
- the middle Particle size of the agglomerates is included preferably in the range of 0.2 to 1.0 mm, in particular in the range of 0.3 up to 0.8 mm.
- the average diameter of the primary particles is preferred Embodiments here by a factor of 5, preferably even by a factor 10, less than the average particle size of the agglomerates. Because of this special In terms of structure, the compounds themselves are easily and quickly soluble.
- the compounds show usually has a bulk density in the range 600 to 1000 g / l, the Bulk weight of the compounds is preferably between 700 and 900 g / l. This The special form of the compounds also places special demands on Manufacturing process for such compounds.
- a second subject of the invention is accordingly a method for the production of such phosphate compounds, which is characterized in that anhydrous, powdered pentasodium triphosphate in a high speed mixer with 12 up to 28% by weight of water, based on the pentasodium triphosphate, and if appropriate other ingredients of washing and / or cleaning agents is agglomerated and the agglomerate immediately afterwards in a fluid bed dryer at a Product temperature below 50 ° C to a free water content of below 5% by weight is dried.
- anhydrous pentasodium triphosphate commercial pentasodium triphosphate qualities understood, the maximum 1 wt .-% May contain moisture.
- STP anhydrous pentasodium triphosphate
- Phase I anhydrous pentasodium triphosphate
- Phase II stable at room temperature
- the two phases also differ in terms of their rate of hydration.
- Phase I absorbs water much faster than Phase II
- the heat released during the hydration process heats up pentasodium triphosphate may become so strong during this process that it may decompose the Triphosphate is coming. Because this decomposition is undesirable, most do Hydration procedure for STP a certain ratio of phase I to phase II required to avoid overheating.
- Phase II Phase II
- the present procedure is largely independent of the share of two phases, it can be with any ratio of phase I to phase II be performed. Particularly high levels of triphosphate should be achieved However, it is also advantageous with 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 free-fall mixer.
- the term "high speed” in this context means that such mixer with a speed of several revolutions per second, preferably than 1500 rpm -1, mix.
- the residence time of the phosphate in the mixer is 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, 12 to 28% by weight, preferably 15 to 20% by weight, of the phosphate weight being applied as water. In a special variant of the method, less than 18% by weight of water is applied.
- phosphate other ingredients already described above Detergents and / or cleaning agents are mixed, so these 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 the Ingredients used for spraying in the high-speed mixer You can other ingredients have already been dry mixed with the phosphate.
- the mixer turns the wet compound into one without wasting time Drying device, which is designed as a fluid bed drying, transferred.
- Drying in the fluidized bed takes place under mild conditions, whereby the product temperature during the entire process is preferably below 60 ° C is below 45 ° C.
- the supply air temperature It is the optimal supply air temperature depending on the dimension of the fluid bed and the amount of air supplied. However, it has been shown that in general with a Supply air temperature of maximum 130 ° C overheating of the product can be avoided can. However, the supply air temperature is preferably a maximum of 100 ° C.
- the embodiment releases the heat of hydration of the triphosphate Drying used and the supply air is not preheated. But also if preheated supply air supplied, the process always has the advantage of the heat of hydration to use at the same time for drying and accordingly with compared to others Processes with little additional energy. Through this mild Conditions, especially the low product temperature, will cause decomposition of the Triphosphate largely prevented. After drying, preferably still lie at least 95% by weight of the phosphate as triphosphate. The drying takes place until the free water content is at most 5% by weight, preferably at maximum 3% by weight. As a rule, the required length of stay is Agglomerates in the fluid bed dryer between 30 and 60 minutes.
- a return can follow the fluid bed drying. Fine fractions can if necessary together with the filter dusts from the fluid bed dryer be fed to the agglomeration stage, while coarse grain before recycling is preferably ground in a hammer mill and after the fluid bed drying at least a third of the distance, preferably after more than two thirds of the Distance, is fed again.
- the phosphate compound described above is ideal for Incorporation in detergent tablets such as Detergent tablets for washing textiles, detergent tablets for machine dishwashing or cleaning hard surfaces, Bleach tablets for use in washing machines or dishwashers, Water softening tablets or stain tablets.
- Another object of the present invention is therefore the use of Phosphate compounds after mixing with finely divided processing components pressed into detergent tablets in a manner known per se to improve the stability and solubility of washing and Detergent tablets.
- the phosphate compounds according to the invention which after mixing with other components to wash and Detergent tablets are pressed, the physical properties the molded body, in particular the mechanical stability and the solubility behavior, be significantly improved.
- This allows washing and low pressure pressures Manufacture detergent tablets that have sufficient mechanical stability Have packaging, transport and handling, compared to use In this way, conventional phosphates can add equally stable tablets lower pressures are produced, so that the wear on the Tableting machines significantly reduced and their lifespan extended.
- Another object of the present invention are washing and Detergent tablets made of compressed particulate washing, and Detergents which contain a phosphate compound according to the invention.
- the phosphate compounds according to the invention can be used in a mixture with conventional and commercially available phosphates.
- the majority of the phosphate contained in the shaped bodies preferably originates from the phosphate compounds according to the invention. Washing and Detergent tablets which have at least 80% by weight, preferably at least 90 % By weight and particularly preferably the total amount contained in the shaped body Amount of phosphate in the form of phosphate compounds according to the invention are included therefore preferred.
- the phosphate compounds can be those of the invention Detergent tablets in varying amounts in the tablets be included.
- detergent tablets are preferred which, based on the weight of the molded body, 10 to 90 wt .-%, preferably 20 to 80 % By weight and in particular 25 to 70% by weight of the phosphate compound.
- disintegration aids so-called tablet disintegrants
- tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in resorbable form.
- Disintegration aids are, for example, carbonate / citric acid systems, wherein other organic acids can also 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 do not contain any disintegration aids. You are alone the incorporation of the phosphate compound according to the invention is sufficiently high Dissolution speed.
- the washing and Detergent tablets 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the weight of the molded body.
- Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
- Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, viewed formally, is a ⁇ -1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
- Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
- Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
- Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
- celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
- the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
- the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
- the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
- the cellulose used as disintegration aid is preferably not in finely divided form used, but before mixing to the to be pressed Premixes are converted into a coarser form, for example granulated or compacted.
- Detergent tablets, the disintegrants in granular or optionally contain cogranulated form are in the German Patent applications DE 197 09 991 and DE 197 10 254 as well as international Patent application WO98 / 40463 described. These writings are also closer Information on the production of granulated, compacted or cogranulated To remove cellulose disintegrant.
- the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
- Disintegration aids based on cellulose are within the scope of the present invention preferably used as a disintegration aid and commercially, for example, at the name Arbocel® TF-30-HG available from Rettenmaier.
- microcrystalline cellulose As another disintegrant based on cellulose or as part of it Component can be used microcrystalline cellulose.
- This microcrystalline Cellulose is made by partial hydrolysis of celluloses under such conditions receive that only the amorphous areas (about 30% of the total cellulose mass) of the Attack and completely dissolve celluloses, but the crystalline areas (approx. 70%) leave undamaged.
- a subsequent disaggregation by hydrolysis emerging microfine celluloses delivers the microcrystalline celluloses that Have primary particle sizes of approx. 5 ⁇ m and, for example, granules with a average particle size of 200 microns are compactible.
- Preferred washing and Detergent tablets additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.
- a disintegration aid preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.
- phosphate compound and disintegration aid can the detergent tablets according to the invention additionally one or several substances from the groups of bleaching agents, bleach activators, enzymes, pH regulators, Fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, Color transfer inhibitors, corrosion inhibitors and silver preservatives included. These substances are described below.
- bleaching agents sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are of particular importance.
- Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid 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.
- bleaching agents from the group of organic bleaching agents can also be used.
- Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
- Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
- 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, ⁇ -phthalimidoperoxyaloacidoperoxycaproic acid (P ⁇ ) )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxydiperoxybiperyldoxybiperyldiacyldiperoxy-diper
- Chlorine or. Can also be used as bleaching agents in moldings for automatic dishwashing
- Bromine-releasing substances are used.
- appropriate chlorine or bromine releasing materials come, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered.
- Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
- bleach activators can be used in the detergent tablets according to the invention are incorporated.
- Bleach activators can be compounds that are aliphatic under perhydrolysis conditions Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid become. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups.
- polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
- TAED tetraacetylethylenediamine
- bleaching catalysts can be incorporated into the moldings.
- these Fabrics are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo salt 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 amine complexes can be used as bleaching catalysts.
- Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question.
- Bacterial strains are particularly suitable or mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus-derived enzymatic agents.
- Proteases are preferably from Subtilisin type and in particular proteases derived from Bacillus lentus, used.
- enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, in particular, however, cellulase-containing mixtures of particular interest.
- Peroxidases or oxidases have proven to be suitable in some cases.
- the Enzymes can be adsorbed on carriers and / or embedded in coating substances, to protect them against premature decomposition.
- the proportion of enzymes, enzyme mixtures or enzyme granules in the moldings according to the invention for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
- enzymes include lipases, amylases, cellulases and Proteases.
- Preferred proteases are e.g. B. BLAP®140 from 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 Novo Nordisk.
- Duramyl® and Termamyl® are particularly used as amylases 60 T, and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades. Other enzymes can also be used become.
- the detergent tablets can also contain components contain, which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is soiled, which has previously been repeatedly with an inventive Detergent containing this oil and fat-dissolving component has been washed.
- the preferred oil- and fat-dissolving components include, for example, nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of Methoxyl groups from 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15 %
- nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of Methoxyl groups from 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15 %
- nonionic cellulose ether and those from the prior art known polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these.
- the sulfonated derivatives of are particularly preferred Phthalic acid and terephthalic acid polymers.
- the moldings can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid 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 Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
- Dyes and fragrances are the detergent tablets according to the invention added to improve the aesthetic impression of the products and to the consumer, in addition to the softness performance, a visually and sensory "typical and to provide a distinctive "product.
- perfume oils or fragrances individual fragrance compounds, e.g. synthetic products of the type Esters, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g.
- benzyl acetate Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
- ethers include, for example, benzyl ethyl ether, the aldehydes e.g.
- the linear alkanals with 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal
- ketones e.g. the Jonone, ⁇ -isomethylionon and methyl cedryl ketone
- the alcohols anethole citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol
- to the hydrocarbons mainly include the terpenes such as limes and pinene.
- Mixtures of different fragrances are used, which together make an appealing Generate fragrance.
- perfume oils can also contain natural fragrance mixtures included as they are 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, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.
- the content of the detergent tablets according to the invention is usually in the range of dyes below 0.01% by weight, while fragrances up to 2% by weight of the can make up the entire wording.
- the fragrances can be incorporated directly into the agents according to the invention but it can also be advantageous to apply the fragrances to the carrier, which have the liability of the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles.
- carrier materials have become
- cyclodextrins have proven to be the cyclodextrin-perfume complexes can also be coated with other auxiliaries.
- the agents according to the invention can be dyed with suitable dyes.
- Preferred dyes their selection the expert has no difficulty, have a high storage stability and Insensitivity to the other ingredients of the agent and to light as well no pronounced substantivity towards textile fibers in order not to dye them.
- Dishwasher detergent tablets according to the invention can be used to protect the dishes or the machine contain corrosion inhibitors, especially silver protection agents have a special meaning in the field of automatic dishwashing.
- silver protection agents 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 to benzotriazole and / or alkylaminotriazole are used.
- detergent formulations often contain active chlorine agents that corrode significantly reduce the silver surface.
- chlorine-free cleaners especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B.
- salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
- The are preferred here Transition metafl salts selected from the group of manganese and / or Cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes; the chlorides of cobalt or Manganese and manganese sulfate.
- Zinc compounds can also be used for prevention corrosion on the wash ware.
- soil release compounds Special ingredients that can be used in moldings according to the invention for machine dishwashing or cleaning hard surfaces are substances which prevent surfaces from being soiled again and / or facilitate the detachment of dirt after a single use (so-called “soil release compounds”).
- the soil release connections that can be used include all connections known in the prior art.
- Cationic polymers such as, for example, hydroxypropyltrimethylammonium guar, are particularly suitable; 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 of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or -acrylamide; Dialkyldiallyldiammoniumsalze; polymeranalogous Reaction products of ethers or esters of polysaccharides with ammonium side 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.
- natural ones are also exceptionally preferred Polyuronic acids and related substances, as well as polyampholytes and hydrophobized Polyampholytes, or mixtures of these substances.
- To water-insoluble builders include the zeolites, which can also be used as well as mixtures of the aforementioned builder substances.
- phosphate compounds of trisodium citrate and / or Sodium carbonate and / or sodium bicarbonate and / or gluconate and / or silicate Builder from the class of disilicates and / or metasilicates or layered silicates used.
- Alkali carriers can be present as further constituents.
- a phosphate compound is produced.
- the person skilled in the art can fall back on machines and apparatuses known from the literature 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.
- the washing and Detergent tablets according to the phosphate compounds according to the invention Intended use in varying amounts.
- the invention is also completely analogous Processes preferred in which the phosphate compound produced in step a) 10 to 90% by weight, preferably 20 to 80% by weight and in particular 25 to 70% by weight of the compressing premix.
- the phosphate compound according to the invention is used in step b) mixed with other ingredients of detergents and cleaning agents and for Molded body pressed.
- Methods according to the invention are preferred here, which thereby are characterized in that the phosphate compound produced 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 bleaches in question were described above.
- the invention Preferred processes in which the phosphate compound produced in step a) with at least one bleaching agent selected from the group of trichlorocyanuric acids, the Dichloro- or Monochlorcyanurate, the hypochlorite, and other common chlorine-containing Bleach is mixed.
- the bleaching performance of moldings containing bleach is preferably such as Detergent tablets, detergent tablets or bleach tablets by the Use of bleach activators increased.
- a bleach activator preferably from the group of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), the N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, 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 the manganese and
- Foam inhibitor granules in step b) with at least one surfactant-containing granulate a premix to be pressed with a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l. in the Preferred methods within the scope of the present invention therefore include the Pressing a particulate premix of at least one phosphate compound, at least one surfactant-containing granulate and at least one admixed powdery component.
- the production of granules containing surfactants can be carried out using conventional technical granulation processes such as compacting, Extrusion, mixer granulation, pelleting or fluidized bed granulation take
- the granules containing surfactant are sufficient Colour deskstandnkriterien.
- Methods according to the invention are preferred in which the Granules containing surfactants Particle sizes between 100 and 2000 microns, preferably between 200 and 1800 ⁇ m, particularly preferably between 400 and 1600 ⁇ m and in particular between 600 and 1400 ⁇ m.
- anionic and / or nonionic and / or cationic and / or amphoteric surfactants preferably also contain the surfactant granules Carriers that particularly preferably come from the group of builders.
- Particularly advantageous processes are characterized in that the surfactant Granules contain anionic and / or nonionic surfactants and builders and Total surfactant contents of at least 10% by weight, preferably at least 20% by weight has in particular at least 25% by weight.
- the Surfactant content of detergent tablets between 10 and 40 wt .-%, preferably between 12.5 and 30% by weight and in particular between 15 and 25% by weight, while Detergent tablets for automatic dishwashing between 0.1 and 10% by weight, 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.
- anionic surfactants come from the group of anionic, nonionic, zwitterionic or cationic surfactants, with anionic surfactants clearly preferred for economic reasons and due to their range of services are.
- Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
- the surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
- alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
- Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
- Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved.
- Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 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.
- the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of 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. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
- 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®, are also suitable anionic surfactants.
- the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
- Suitable 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.
- alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see 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.
- Soaps are particularly suitable as further anionic surfactants.
- 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 the soaps 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, especially in the form of the sodium salts.
- Preferred surfactant granules have However, a soap content of 0.2 wt .-%, based on the total weight of the Detergent tablets produced in step d) exceeds.
- Anionic surfactants to be used are the alkylbenzenesulfonates and Fatty alcohol sulfates, preferred detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s), each 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 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 can 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 fat 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 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol 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 thereof, 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 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. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- nonionic surfactants which either as sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the Alkyl chain, especially fatty acid methyl esters, such as those found in Japanese Patent application JP 58/217598 are described or which are preferably according to the in the international patent application WO-A-90/13533 become.
- alkyl polyglycosides are the alkyl polyglycosides (APG).
- APG alkyl polyglycosides
- Alkylpolyglycosides satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for 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.
- Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
- the surfactant granules can preferably contain alkyl polyglycosides, with levels of APG over 0.2 wt .-%, based on the entire molded body, are preferred.
- Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10 % By weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.
- nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can 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.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 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 which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, 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 rest.
- R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 1 represents a linear, branched or cyclic alkyl radical or an aryl
- [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 can then, for example according to the teaching of international application WO-A-95/07331 by implementation with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.
- the surfactant granules used are preferred according to the method of the invention which the surfactant content of the surfactant-containing granules is 5 to 60% by weight, preferably 10 up to 50 wt .-% and in particular 15 to 40 wt .-%, each based on the Granules of surfactant. moldings
- step b) further builder substances; the preferably contain at least one aluminosilicate and / or a layered silicate with which Phosphate compound are mixed.
- 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.
- 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 as an undried stabilized suspension that is still moist from its production.
- the zeolite in the event that the zeolite is used as a suspension, it can contain small 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 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 layered 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 represents sodium and x assumes the values 2 or 3. In particular, 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 cleaning agents included, so that preferred process variants are to be carried out analogously.
- An im Process preferred in the context of the present invention is characterized in that that the premix additionally a disintegration aid, preferably a Disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 % By weight and in particular from 4 to 6% by weight, in each case based on the weight of the Premix contains, it being additionally preferred that the premix additionally one or more substances from the group of enzymes, pH adjusting agents, fragrances, Perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, Anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors, Contains corrosion inhibitors and silver protection agents.
- the premix Before the particulate premix is pressed into detergent tablets, the premix can be "powdered” with finely divided surface treatment agents. This can be advantageous for the nature and physical properties of both the premix (storage, pressing) and the finished detergent tablets. Fine-particle powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the premix is preferably “powdered” with finely divided zeolite, 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 structure group 4 (compare Donald W.
- zeolite Y and faujasite and mixtures of these compounds can also be used, pure zeolite X being preferred.
- Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites which do not necessarily have to belong to structure group 4 of the zeolite can also be used as powdering agents, it being advantageous if at least 50% by weight of the powdering agent from a zeolite of faujasite -Type exist.
- the moldings according to the invention are first produced by dry Mixing the components, which can be partially or completely pre-granulated, and then Inform, in particular pressing to tablets, taking on conventional methods can be used.
- the premix in a so-called die compacted between two stamps to form a solid compact. This process, which takes place in The following, briefly referred to as tableting, is divided into four sections: Dosage, compression (elastic deformation), plastic deformation and ejection.
- the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molding being formed being determined by the position of the lower punch and the shape of the pressing tool.
- the constant metering, even at high molding throughputs, is preferably achieved by volumetric metering of the premix.
- the upper punch touches the premix and lowers further towards the lower punch.
- the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed.
- the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.). Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down.
- Eccentric tablet presses are preferred for small production quantities used, in which the stamp or stamps are attached to an eccentric, the in turn is mounted on an axis with a certain rotational speed.
- the Movement of this ram is with the operation of a standard four-stroke engine comparable.
- the pressing can be done with an upper and lower stamp
- several stamps can also be attached to an eccentric disc, the Number of die holes has been expanded accordingly.
- the throughputs of Eccentric presses vary from a few hundred to a maximum of 3000 tablets depending on the type per hour.
- rotary tablet presses are selected in which a larger number of matrices 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 also commercially available.
- Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps.
- the die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation.
- these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
- the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix.
- the pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.
- Rotary presses can also be provided with two filling shoes to increase the throughput, only a semicircle having to be run through to produce a tablet.
- Suitable tableting machines are within the scope of the present invention for example available from the Apparatebau company.
- Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy N.V., Halle (BE / LU).
- the hydraulic one is particularly suitable Double printing press HPF 630 from LAEIS, D.
- the moldings can be in a predetermined spatial shape and a predetermined size are manufactured. Practically all sensibly manageable come as a room shape Configurations into consideration, for example, the training as a board, the staff or Bar shape, cubes, cuboids and corresponding room elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross section.
- This last embodiment covers the presentation form 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 one another Individual elements can be formed, the predetermined dosage of the washing and / or Detergent corresponds. However, it is also possible to form compacts, which connect a plurality of such mass units in one compact, wherein the easy separability in portions by predetermined predetermined breaking points smaller units is provided.
- a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred is.
- Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices in particular for the production of such pressing pieces.
- the spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the moldings can be dosed directly into the induction bowl without a dosing aid, where it dissolves during the induction process.
- a dosing aid where it dissolves during the induction process.
- the detergent tablets can be used without any problems using a dosing aid Preferred within the scope of the present invention.
- Another preferred molded body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, see above that individual segments of this "bolt" at the predetermined breaking points, the short display thin segments, can be canceled and entered into the machine can.
- This principle of the "bar-shaped" molded article detergent can also be used in other geometric shapes, such as vertical triangles, the are connected to each other only on one of their sides, can be realized.
- the different components do not become one uniform tablet are pressed, but that molded bodies are obtained, the have multiple layers, i.e. at least two layers. It is also there possible that these different layers have different dissolving speeds exhibit. This can result in advantageous application properties of the Moldings result. If, for example, components are contained in the moldings are, which mutually influence each other negatively, it is possible that one component to integrate in the faster soluble layer and the other component in one incorporate slower soluble layer so that the first component already has reacted when the second goes into solution.
- the layer structure of the moldings can this is done both in stacks, with the inner layer (s) dissolving the edges of the molded body already occurs when the outer layers are still are not completely solved, but it can also be a complete wrapping of the inner Layer (s) can be achieved through the layer (s) further out, what to prevent early release of components of the inner layer (s) leads.
- a molded body consists of at least three layers, i.e. two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and the envelope-shaped molded body, however, the outermost layers free of peroxy bleach are.
- peroxy bleach and any present Bleach activators and / or enzymes spatially in a molded body separate.
- Such multilayered moldings have the advantage that they are not only via a detergent dispenser or a dosing device which is added to the wash liquor given, can be used; rather, in such cases it is also possible to put the molded body in direct contact with the textiles in the machine without Stains from bleach and the like would be feared.
- Similar effects can also be achieved by coating individual components the detergent composition to be pressed or the reach the entire molded body.
- the body to be coated can do this be sprayed with aqueous solutions or emulsions, for example, or over the process of melt coating received a coating.
- ⁇ stands for diametral fracture stress (DFS) in Pa
- P is the force in N which leads to the pressure exerted on the molded body, which is the Breakage of the molded body causes
- D is the molded body diameter in meters
- t is the height of the moldings.
- Pentasodium triphosphate powder was used to produce the phosphate compounds a pure substance content of 98.3% and 0.3% by weight of 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 fell from the mixer into a fluidized bed and was at one Product temperature of 40 ° C within 45 minutes to a total water content dried by 13 wt .-%.
- the granules obtained had a raspberry shape Structure, the average particle diameter of the agglomerate particles around 550 microns was, but the primary particles forming the agglomerate almost smaller by a factor of 10 were than the average particle diameter of the agglomerates.
- the dates of the Granules obtained are given in Table 1.
- the phosphate content in Table 1 was determined from the total phosphorus content (in the case of C4, the phosphorus contained in the phosphonate was subtracted 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 stated crystal water content is the difference between the two values.
- a crystal water content of 8.1% by weight was determined for C1 using thermoanalytical methods (DTA-TG; heating rate: 10 K / min).
- Shaped bodies were produced with Compound C1.
- the phosphate compound was mixed with further processing components and pressed on an eccentric tablet press according to Table 3.
- the composition of the premix to be pressed (and thus the composition of the moldings) can be found in Table 2.
- the moldings contained auxiliaries such as binders, disintegration aids, colorants and fragrances, fillers and water.
- Comparative Example V had the same formulation, but here phosphate and copolymer were used separately from one another, the phosphate being used in the form of a commercially available granulate with a free water content of more than 7% by weight. In the comparative example, considerably higher compression pressures were required to produce tablets of comparable hardness (see Table 3).
- Premix [wt%] phosphate 49 copolymer 3 phosphonate 1
- the hardness of the tablets was measured by deforming the tablet until it broke, where the force applied to the side surfaces of the tablet and the maximum force that the tablet withstood, was determined. The measurement was carried out on a hardness tester CT5 (Holland) with punch diameters of 8 mm.
- the dissolution time of the tablets was determined in a household dishwasher.
- the tablets were placed in the machine basket before the main rinse began placed, with the basket in the same place in all tests Machine.
- a 50 ° C program was used and the time until complete dissolution of the tablet is determined by tracking conductivity.
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- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19859807A DE19859807A1 (de) | 1998-12-23 | 1998-12-23 | Phosphat-Compounds |
DE19859807 | 1998-12-23 | ||
EP99963522A EP1141191B1 (fr) | 1998-12-23 | 1999-12-14 | Composes phosphates |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99963522A Division EP1141191B1 (fr) | 1998-12-23 | 1999-12-14 | Composes phosphates |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1382665A1 true EP1382665A1 (fr) | 2004-01-21 |
Family
ID=7892500
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03019563A Withdrawn EP1382665A1 (fr) | 1998-12-23 | 1999-12-14 | Utilisation des composés de phosphate |
EP99963522A Expired - Lifetime EP1141191B1 (fr) | 1998-12-23 | 1999-12-14 | Composes phosphates |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99963522A Expired - Lifetime EP1141191B1 (fr) | 1998-12-23 | 1999-12-14 | Composes phosphates |
Country Status (5)
Country | Link |
---|---|
EP (2) | EP1382665A1 (fr) |
AT (1) | ATE290581T1 (fr) |
DE (2) | DE19859807A1 (fr) |
ES (1) | ES2239473T3 (fr) |
WO (1) | WO2000039260A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004020010A1 (de) * | 2004-04-21 | 2005-11-17 | Henkel Kgaa | Verfahren zur Herstellung von Polymer-Granulaten |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1048831A (en) * | 1963-02-04 | 1966-11-23 | Unilever Ltd | 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 |
DE4435743A1 (de) * | 1994-02-17 | 1995-08-24 | Chemolux Sarl | Verfahren zur Herstellung eines Mehrkomponenten-Granulates |
DE19502774A1 (de) * | 1995-01-27 | 1996-08-01 | Henkel Kgaa | Verfahren zur Herstellung von bruchstabilen Reinigungstabletten |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3624336A1 (de) * | 1986-07-18 | 1988-01-28 | Henkel Kgaa | Verfahren zur herstellung von rieselfaehigen alkalischen reinigungsmitteln durch kompaktierende granulation |
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 |
GB9706083D0 (en) * | 1997-03-24 | 1997-05-14 | Unilever Plc | Detergent compositions |
-
1998
- 1998-12-23 DE DE19859807A patent/DE19859807A1/de not_active Withdrawn
-
1999
- 1999-12-14 ES ES99963522T patent/ES2239473T3/es not_active Expired - Lifetime
- 1999-12-14 EP EP03019563A patent/EP1382665A1/fr not_active Withdrawn
- 1999-12-14 AT AT99963522T patent/ATE290581T1/de active
- 1999-12-14 EP EP99963522A patent/EP1141191B1/fr not_active Expired - Lifetime
- 1999-12-14 DE DE59911739T patent/DE59911739D1/de not_active Expired - Lifetime
- 1999-12-14 WO PCT/EP1999/009892 patent/WO2000039260A1/fr active IP Right Grant
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1048831A (en) * | 1963-02-04 | 1966-11-23 | Unilever Ltd | 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 |
DE4435743A1 (de) * | 1994-02-17 | 1995-08-24 | Chemolux Sarl | Verfahren zur Herstellung eines Mehrkomponenten-Granulates |
DE19502774A1 (de) * | 1995-01-27 | 1996-08-01 | Henkel Kgaa | Verfahren zur Herstellung von bruchstabilen Reinigungstabletten |
Also Published As
Publication number | Publication date |
---|---|
DE19859807A1 (de) | 2000-06-29 |
EP1141191B1 (fr) | 2005-03-09 |
EP1141191A1 (fr) | 2001-10-10 |
WO2000039260A1 (fr) | 2000-07-06 |
ES2239473T3 (es) | 2005-09-16 |
DE59911739D1 (en) | 2005-04-14 |
ATE290581T1 (de) | 2005-03-15 |
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