EP0566583B1 - Produits concentres secs facilement solubles, contenant des substances de produits de lavage - Google Patents

Produits concentres secs facilement solubles, contenant des substances de produits de lavage Download PDF

Info

Publication number
EP0566583B1
EP0566583B1 EP92900156A EP92900156A EP0566583B1 EP 0566583 B1 EP0566583 B1 EP 0566583B1 EP 92900156 A EP92900156 A EP 92900156A EP 92900156 A EP92900156 A EP 92900156A EP 0566583 B1 EP0566583 B1 EP 0566583B1
Authority
EP
European Patent Office
Prior art keywords
compacts
components
adhesive
press
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP92900156A
Other languages
German (de)
English (en)
Other versions
EP0566583A1 (fr
Inventor
Christiane Zeise
Wilfried Rähse
Jochen Jacobs
Jürgen HOFFMEISTER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6422660&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0566583(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0566583A1 publication Critical patent/EP0566583A1/fr
Application granted granted Critical
Publication of EP0566583B1 publication Critical patent/EP0566583B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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

Definitions

  • the invention relates to a new form of offer for ingredients of detergents and / or cleaning agents, in particular textile detergents, as well as correspondingly designed detergents and / or cleaning agents and the novel method for their production. It describes in particular the production of a comparatively coarse-grained and storage-stable, free-flowing material which, on the one hand, is compressed to increased bulk densities, but on the other hand, due to its special structure, is capable of rapid interaction with, in particular, aqueous liquid phases with destruction of the grain structure.
  • detergent mixtures in granular form with a bulk density of at least 650 g / l which are obtained by predetermined mixing ratios of selected non-soap-like surface-active agents - at least partially corresponding anionic surfactants - with predetermined amounts of crystalline or amorphous sodium aluminum silicate.
  • the granules are to be produced in a high-speed mixer / granulator, which ensures the process elements of the mixing and comminution.
  • the process is carried out in the presence of a liquid binder, with water being the preferred binder which, if necessary, can be added before or during the granulation step.
  • the particle size of the agglomerates obtained in this way is clearly below 1 mm and generally in the range from about 400 to a maximum of 600 ⁇ m.
  • German patent application DE 39 26 253 a new way of producing solid and free-flowing granules of detergents and / or cleaning agents, in particular corresponding textile detergents.
  • These granules are characterized by bulk densities of at least about 700 g / l, in particular those in the range from about 850 to 1,000 g / l.
  • the granules are produced by extrusion using the smallest possible amounts of liquid phase, in particular water, and are preferably subsequently additionally dried by dehydration. A dry granulate of high density and high strength is obtained in this process, which has good storage stability compared to the ambient conditions in practice.
  • a characteristic of the manufacturing process from this earlier application is an intensive mixing of the the respective mixture of substances when using high shear forces and processing pressures in screw extruders while plasticizing the mixture.
  • the mass homogenized in this form is extruded in the form of strands through perforated molds, the emerging compacted material strands are cut to the predetermined granulate dimension and, if desired, rounded off before the granulate grains formed are loaded with other active ingredients and / or dried to the granular, free-flowing material, if necessary.
  • EP-A-0 273 334 describes platelets which have a large empty space between the individual particles.
  • EP-A-0 273 334 neither discloses nor suggests that a microporous basic structure, in which the highest possible internal surface of the particles is associated with a microdisperse distribution of air in the particles, is known.
  • the teaching of the invention is based on the object of allowing targeted modifications in the specific design of such granular granules while maintaining the form of compacted comparatively coarse granules.
  • the invention aims to create the possibility of controlling the grain internal structure and in particular the microporosity of the grain.
  • the teaching of the invention is intended to make it possible to influence the inner surface of the granulate, preferably in such a way that the largest possible inner surface can be ensured in spite of a high compression of the mixture of substances in the granulate.
  • the object of the invention is based on the objective of achieving good and rapid dissolving power in the washing or cleaning bath despite the high bulk densities of the granular concentrates. It is obvious that an increase in the inner grain surface, in particular by inclusion and protection of the proportion of the finest microdisperse air inclusions, can influence the redissolvability of the granulate.
  • Another important determining element for the manufacturing process of the concentrates with the new structure is aimed in the same direction: the compacting and pressing of the material should be possible with the greatest possible restriction of shear forces to the respective substance mixture.
  • smearing of the individual solid particles with one another should be prevented as far as possible, as is the case, for example when processing the corresponding solid mixtures in screw extruders due to their strong shear effect.
  • this aspect can be of particular importance because, as a rule, highly lubricious components such as surfactants, polymeric builder substances and other mixture components which can be deformed or even spreadable under pressure are also used.
  • the invention aims to enable compacts of the type described to be obtained as immediate process products without the need for an intermediate drying step.
  • the invention provides a plurality of structural elements for the grain or compact structure on the one hand and for the process parameters in the production of such compressed concentrates from the at least predominantly powdery feedstocks.
  • the subject of the invention is a process for producing these granular compacts, this process being characterized in that components (a) and adhesive component (b) are mixed as fine-grained material under conditions, at least largely homogeneously, to form a loose bulk material , under which there is no distinctly solidifying adhesive function.
  • components (a) and adhesive component (b) are mixed as fine-grained material under conditions, at least largely homogeneously, to form a loose bulk material , under which there is no distinctly solidifying adhesive function.
  • liquid components to be used in the process which are only used in a very limited amount, as will be described in detail below, are mixed in here.
  • the bulk material prepared in this way is then pressed to form compacts with the exclusion of shear forces as much as possible - at least to its main mass - with the inclusion of microdispersed air.
  • these processing conditions are achieved by pressing using a die press, the bulk material being pressed onto a surface of a rotating, Bore-containing die applied and rolled into a compacted shape by means of a pressing tool rotating on or slightly above the die surface and pressed through it to form the granules.
  • a ring die press which essentially consists of a rotating hollow roll into which radial bores are made is particularly suitable for carrying out the method according to the invention.
  • a press roll is arranged eccentrically and rotatably mounted.
  • the mixture is introduced into the inside of the ring die, drawn into the nip between the press roll and the ring die and extruded.
  • a targeted control or adjustment of the temperature of the mixture within the ring die press in particular by means of temperature regulation via the coolable and / or heatable pressing tool, can take place.
  • Such a temperature control by varying the nip height between the pressing tool and the die surface and by the operating parameters of the ring die press, which are described in detail below, make it possible to control both the desired degree of compaction and the internal porosity of the granulate.
  • the dry concentrates according to the invention are produced in two successive steps: In the first step, solid fine-grained ingredients of detergents and cleaning agents, which preferably have no particles with diameters above 100 »m, are essentially in dry form and can be assigned to two different classes of material, are mixed as homogeneously as possible.
  • the first class of substances are ingredients without pronounced adhesive properties, which are referred to here as “components (a)”.
  • the second class of substances are fine-grained ingredients with adhesive or adhesive properties, which are referred to in the description of the invention as "adhesive components (b)".
  • Detergent and / or cleaning agent concentrates in dry form generally contain a large number of representatives of the two classes of substances mentioned here.
  • Fine-particle powders of this type which are solid at room temperature are either available as commercial products or can be prepared in a manner known per se, for example by spray drying.
  • Adhesive components (b) in the sense of the invention are, in particular, those representatives of the ingredients of detergents and cleaning agents which are present as a solid at room temperature, but at least superficially soften by increasing the temperature and / or by adding very limited amounts of liquid additives and / or under pressure - And the effect of temperature with subsequent cooling towards the neighboring solid particles form a certain adhesive and adhesive strength.
  • Typical examples of compounds of this type are finely divided surfactant compounds which are solid at room temperature and are generally used in detergents and cleaners. The particular type of surfactant is largely insignificant for the achievement of the object according to the invention as long as the selected surfactant compound can correspond to its function as adhesive and adhesive component (b).
  • Nonionic surfactant compounds can also be assigned to substance class (b), provided that they form a solid phase at room temperature.
  • substance class (b) The fact that liquid auxiliary components, in particular nonionic surfactants which are liquid at room temperature, can also play an important auxiliary role in the development of the compacts according to the invention for strengthening the adhesive components (b) is described below.
  • Typical representatives for such adhesive components are polymer compounds of synthetic and / or natural origin, examples being the polymers or copolymers of acrylic acid, which are known today as so-called Co-builders are usually used to inactivate water hardness in the washing process.
  • Co-builders are usually used to inactivate water hardness in the washing process.
  • other organic components, in particular organic polymer compounds can also have the appropriate adhesive and adhesive function.
  • Starch and starch derivatives, cellulose or cellulose derivatives and the like, which are used, for example, to improve the dirt-carrying capacity of the wash liquor, may be mentioned here merely by way of example.
  • Nonionic surfactants that are liquid at room temperature are now regular active ingredient constituents in detergent and cleaning agent mixtures and, accordingly, are also important mixture constituents within the framework of the teaching according to the invention. They take on an important additional function as an activating agent for the adhesive components (b) in the context of the teaching according to the invention.
  • aqueous pastes of anionic surfactants and / or of non-adhesive active ingredients according to (a), such as finely divided sodium zeolite, can also be used in the preparation of the mixture to be pressed.
  • Possible oil phases for use in the mixtures according to the invention are, for example, limited amounts of paraffin oils, of ester oils, but also low-volatile mono- and / or polyfunctional alcohols, corresponding ethers and the like.
  • Fine-grained ingredients of washing and / or cleaning agents without pronounced adhesive or adhesive properties ie the components (a) are a regular component of active ingredient mixtures of the type concerned here. As a rule, these are water-soluble or moderately soluble to insoluble components of inorganic origin or else organic mixture components with a comparatively high softening or melting point.
  • the representatives can be assigned to the most diverse classes of active ingredients, for example the builders or builder substances, for example of the zeolite NaA type, bleaching agents, bleach activators, textile-softening auxiliaries such as the swellable fine-particle sheet silicates and inorganic alkaline or neutral to slightly acidic salts, for example sodium silicate, sodium carbonate, sodium hydrogen carbonate, sodium sulfate Sodium bisulfate and perborate.
  • the builders or builder substances for example of the zeolite NaA type
  • bleaching agents bleach activators
  • textile-softening auxiliaries such as the swellable fine-particle sheet silicates and inorganic alkaline or neutral to slightly acidic salts, for example sodium silicate, sodium carbonate, sodium hydrogen carbonate, sodium sulfate Sodium bisulfate and perborate.
  • textile-softening auxiliaries such as the swellable fine-particle sheet silicates and inorganic alkaline or neutral to slightly acidic salts
  • the granulation or pressing process according to the invention proceeds in two stages.
  • the fine-grained components from (a) and (b), which are mostly solid at room temperature, are intimately mixed with one another.
  • All the slow to fast mixer types that are common in practice are suitable here, ploughshare mixers, segment screw mixers, paddle mixers, pin mixers, Eirich mixers, vortex mixers, horizontal high-speed mixers, multi-flow fluid mixers and the like being mentioned only as examples.
  • any liquid components that are used are homogeneously incorporated into the mixture of substances. This is possible, for example, by spraying on corresponding liquid constituents before or during this premixing stage or by adding aqueous pastes of active ingredients to this mixing stage.
  • the choice and coordination of the mixture components with one another in the subsequent second stage of the process according to the invention enables the desired microporous grain structure to be built up, which combines high bulk densities with a comparatively large inner surface of the granulate.
  • the respective mixing ratios of the components to one another can be optimized within the framework of general specialist knowledge.
  • the following working rules generally serve as guidelines:
  • the solid dry powder components (a) and (b) together make up at least about 90% by weight, preferably at least about 94% by weight, of the mixture to be produced in the first working step.
  • liquid components are preferably present in a maximum of about 10% by weight, preferably in amounts of about 1-8% by weight and in particular in amounts of about 2-6% by weight.
  • the premix is generally present as a dry-appearing powder at the beginning of the second stage of the process.
  • a particularly advantageous embodiment of the invention uses the following control element for the correct coordination of the active ingredient components in the mixture to be pressed:
  • the finely divided solids with and without adhesive or adhesive properties and the liquid constituents which may be used are used in such mixing ratios that under the conditions of the pressing in the second process stage as the primary product of extrusion, in addition to the desired compacts, just the first traces or small amounts of powdery material that has not yet solidified are pressed out.
  • the stickiness of the mixtures in the second Processing level is so coordinated here that the mass is under the working conditions used just in the border area of the compressibility to firm strands or granules to be obtained therefrom.
  • This border area can easily be left on both sides.
  • this boundary region is extended in the direction of the insufficient adhesion, ie in the direction of the coextrusion of small powdery residual fractions.
  • the powder-co-extruded proportions can make up, for example, up to 10% by weight, preferably up to about 5% by weight, based on the total extrudate.
  • the portion which has penetrated in powder form takes over the function of an auxiliary for powdering the primary extrudates, the stickiness of which is due in particular to their slightly elevated processing temperature.
  • the homogenized premix from the first stage of the process is compressed in the subsequent second stage of work to give a strand shape, which strands are expediently cut to the grain shape immediately after leaving the die.
  • a ring die press with a rotating ring die interspersed with press channels and at least one press roller connected to its inner surface, which presses the material supplied to the die press space through the press channels into a material discharge.
  • Both the ring die and the press roller (s) are related to the outer surfaces that come into operation can be driven in the same direction.
  • the rotational speeds of the ring die and press roll can be coordinated and adjusted to one another in such a way that no or practically no shear forces are exerted on the mixture introduced into the interior of the ring die.
  • the objective of the invention is thereby favored in several ways.
  • the mixture containing microdisperse air is only subjected to pressure in the direction of the extrusion pressure and thus compressed, without destroying the primarily predetermined structure of high microporosity.
  • the desired result is the comparatively high values of the inner surface of the compacts, which can be, for example, in the range from 2 to 5 m2 / g, in particular in the range from about 3 to 5 m2 / g. Values of this size can only be set by keeping the percentage of micropores with a diameter below 1 »m, preferably below 0.1» m or even below 0.01 »m, comparatively high.
  • the processing of the mixture homogenized in the first step with the exclusion of significant shear forces also leads to further advantages.
  • the individual constituents of the mixture lie next to one another in an individualized manner as in a bed, there is no smearing of plastic and / or thermoplastic good fractions over larger areas of adjacent surfaces of solid particles. This can mean substantial help for the rapid redissolvability of the compact. Easily water-soluble mixture components, for example corresponding proportions of neutral salts and / or washing alkalis, are accessible to direct interaction with the water when water enters; there is no need for detachment, for example, of a surfactant layer smeared on the fine crystalline material.
  • the exclusion of shear forces on the bulk material when compacting it also has an effect on restricting the temperature increase, which is always associated with the introduction of considerable mechanical forces into the bulk material to be compressed.
  • the pressure roller is designed to be temperature-controllable by means of a heating or cooling medium.
  • the method according to the invention makes use of it in the second working stage. Material temperatures of approximately 80 ° C., preferably approximately 70 ° C., are not exceeded within the ring matrix. Lower limit values for the temperature of the material in the processing step are usually in the temperature range from approximately 30 to 40 ° C., whereby working temperatures for compressing the bulk material in the range from approximately 45 to 60 ° C. can be particularly suitable.
  • the temperature conditions described here can in turn determine the selection of the adhesive components (b) and / or the use of liquid components in the first mixing stage.
  • adhesive components (b) in a finely particulate and essentially homogeneously distributed form in the substance mixture may be preferred which - if appropriate with the participation of the mixture components which are liquid at room temperature - soften to such an extent in the temperature range above 40 ° C. and in particular in the temperature range from approximately 45 to 70 ° C. that they form an adhesive effect under the working conditions according to the invention and subsequently in the cooled, granular extrudate.
  • the possibility of temperature control in the second processing step also determines, among other things, the mixing ratios of the dry components (a) to the adhesive components (b) in the multicomponent mixtures used.
  • the adhesive component (s) (b) it is preferred to use the adhesive component (s) (b) at most approximately at the same quantity as the components (a), although usually smaller mixture fractions (b), based on mixture fractions (a), can be preferred.
  • Suitable mixtures of substances for the purposes of the invention contain the adhesive components (b) in amounts in the range from about 15 to 40% by weight, based on the compacts.
  • the ring die press can then be used Bulk weights of the extrudates extruded in the form of strands and preferably immediately thereafter cut to the grain shape of at least 500 g / l are set.
  • the bulk densities of the granular compacts described according to the invention are preferably at or above about 600 g / l, with significantly higher values being set, for example those in the range up to about 900 g / l, or even more, depending on the working conditions and the choice and coordination of the mixture components can be.
  • Particularly suitable bulk weights can be, for example, in the range from about 550 to 850 g / l.
  • Suitable grain sizes for the compacts described according to the invention are, for example, in the range from about 1 to 3 mm, it being possible for the compacts to be of rod-shaped or spherical design in a manner known per se.
  • the material is pressed into bores with a diameter of approximately 0.8 to 1.5 mm and is preferably cut to lengths in the range of approximately 1 to 2 mm.
  • the freshly extruded compacts can be rounded off in a subsequent process step, the rounding expediently taking place before the material to be solidified by lowering the temperature.
  • auxiliary measures for stabilizing the primarily occurring compacts are, for example, shock cooling the primarily emerging product strands and the granules obtained therefrom, for example by means of a doctor blade, if desired drying these granules, for example in a fluidized bed dryer , and / or powdering the primary granulate with finely divided powder.
  • shock cooling the primarily emerging product strands and the granules obtained therefrom for example by means of a doctor blade, if desired drying these granules, for example in a fluidized bed dryer , and / or powdering the primary granulate with finely divided powder.
  • shock cooling the primarily emerging product strands and the granules obtained therefrom for example by means of a doctor blade, if desired drying these granules, for example in a fluidized bed dryer , and / or powdering the primary granulate with finely divided powder.
  • the appropriate choice of the mixture components used according to the invention in terms of type and / or quantity also makes
  • the compacts produced in this way can be processed further in a further process step, as a result of which the desired form of supply is obtained.
  • the compacts can be mixed with other detergent ingredients Granulation, spray drying, pelleting or extrusion were mixed.
  • the compacts are preferably packaged separately, it being particularly preferred to pack the compacts, which are either complete detergents or detergent additives, in portions, one portion usually being sufficient for one washing operation.
  • anionic surfactants e.g. Soaps from natural or synthetic
  • preferably saturated fatty acids can be used.
  • Natural fatty acids e.g. Soap mixtures derived from coconut, palm kernel or tallow fatty acids. Preferred are those which are composed of 50 to 100% of saturated C12 ⁇ 18 fatty acid soaps and 0 to 50% of oleic acid soap.
  • Further suitable synthetic anionic surfactants are those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are alkylbenzenesulfonates, preferably C9-C13-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C12 ⁇ 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent sulfonates or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which can be obtained from C12 ⁇ 18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins are, and in particular the esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Suitable sulfate-type surfactants are the sulfuric acid monoesters of primary alcohols of natural and synthetic origin, i.e. from fatty alcohols, e.g. Coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C10 ⁇ 20 oxo alcohols, and those of secondary alcohols of this chain length.
  • the sulfuric acid monoesters of alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9 ⁇ 11 alcohols with an average of 3.5 moles of ethylene oxide, are suitable.
  • Sulfated fatty acid monoglycerides are also suitable.
  • anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the detergent content according to the invention of anionic surfactants or of anionic surfactant mixtures is preferably 5 to 40, in particular 8 to 30,% by weight.
  • Addition products of 1 to 40, preferably 2 to 20 moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides or alkanesulfonamides can be used as nonionic surfactants.
  • polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule which are not or not completely water-soluble, are also of interest, in particular if they are used together with water-soluble, nonionic or anionic surfactants.
  • alkyl glycosides of the general formula RO- (G) x can also be used as nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18 C atoms, methyl-branched in the 2-position, G is a symbol which stands for a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x between 1 and 10, preferably between 1 and 2 and in particular significantly less than 1.5, for example between 1.1 and 1.4, lies.
  • Suitable and, in particular, ecologically harmless builder substances such as finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g, are preferably used.
  • Their particle size is usually in the range from 1 to 10 »m.
  • Their content in the compositions is generally 0 to 60, preferably 10 to 45,% by weight, based on the anhydrous substance.
  • co-builder constituents which can be used in particular together with the zeolites are (co) polymeric polycarboxylates, such as polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50% to 10% maleic acid.
  • the molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 200 and 200,000, preferably 50,000 to 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, in which the proportion of acid is at least 50%.
  • vinyl ethers such as vinyl methyl ether
  • polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, and polymeric acid, which are obtained by polymerizing acrolein and subsequent disproportionation using alkalis and are composed of acrylic acid units and vinyl alcohol units or acrolein units.
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid and nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons.
  • NTA nitrilotriacetic acid
  • phosphates can also be used, in particular pentasodium triphosphate, optionally also pyrophosphates and orthophosphates, which act primarily as precipitants for lime salts.
  • the phosphate content based on pentasodium triphosphate, is below 30% by weight. However, agents without a phosphate content are preferably used.
  • Suitable inorganic, non-complexing salts are the bicarbonates, carbonates, borates or silicates of the alkalis, which are also referred to as "washing alkalis"; Of the alkali silicates, especially the sodium silicates with a Na2O: SiO2 ratio of 1: 1 to 1: 3.5 can be used.
  • the other detergent ingredients include graying inhibitors (dirt carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents, dyes and fragrances as well as neutral salts.
  • Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying.
  • water-soluble colloids of mostly organic nature are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • Carboxymethyl cellulose (Na salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone are preferably used, in particular in amounts of 0.1 to 5 wt .-%, based on the agent.
  • the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like organic substances.
  • a reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, e.g. of sulfates and / or sulfonates with nonionics and / or with soaps.
  • soaps the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid residue. Soaps of natural and synthetic origin that have a high proportion of C18 ⁇ 2 auf Struktur fatty acids are therefore suitable as foam-inhibiting soaps.
  • Suitable non-surfactant-like foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica.
  • Bisacylamides derived from C12 ⁇ 20 alkylamines and C2 ⁇ 6 dicarboxylic acids are also useful.
  • Mixtures of different foam inhibitors are also advantageously used, e.g. those made of silicone and paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • bleaching agents which supply H2O2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxycarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-delivering peracid salts or peracids, such as perbenzoates, peroxaphthalates, diperazelaic acid or diperdodecanedioic acid.
  • bleach activators can be incorporated into the agents.
  • these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'tetraacylated diamines such as N, N, N ', N'-tetraacetylethylenediamine, also carboxylic anhydrides and esters of polyols, such as glucose pentaacetate.
  • the detergents can contain derivatives of di-aminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2 'disulfonic acid or compounds of the same structure which instead of the morpholino group have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present; e.g. the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Enzymes from the class of prostheses, lipases and amylases or their mixtures are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the salts of polyphosphonic acids in particular the sodium salts of 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriamine-pentamethylenephosphonic acid (DTPMP or DETPMP) come into consideration as stabilizers, in particular for per-compounds and enzymes.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriamine-pentamethylenephosphonic acid
  • the teaching according to the invention is suitable both for the production of washing and / or cleaning agent mixtures, in particular textile detergents in the form of readily water-soluble storage-stable granules, and for the production of active substance concentrates from the field of these working materials, in particular for incorporation into textile detergents, the granules of different active substances contain predetermined mixing ratios.
  • perborates and bleach activators are separate from one another to be provided in different granules, which are then mixed in predetermined proportions.
  • Both grain types can be produced or formed separately from one another according to the invention and then be mixed with one another in a storage-stable manner.
  • the process according to the invention can be used advantageously for the production of bleach activator granules, as described, for example, in the older German patent application DE 4024759.
  • the components (A) to (K), of which only the components (B) are in liquid form - all other components are solid - in the mixing ratios specified in the table in a ploughshare mixer (Fa Lödige, Germany) mixed thoroughly for one minute.
  • the premix obtained in this way was then fed continuously to a ring die press (pellet press, embodiment DE 3816842, from Schlueter, Germany), the temperable roller (press roll) of which was cooled to 20.degree. Since the temperature generally rises in the product while the process is being carried out, cooling of the pan is necessary. In this way, a maximum product temperature of 50 ° C could be ensured.
  • the diameter of the press channels in the ring die was 1 - 1.5 mm (see Table 1).
  • the distance between the press roller and the ring die was 1.8 - 2 mm (see Table 1).
  • the emerging strand was cut to a length of 1.2-1.5 mm by a knife attached to the outside of the ring die.
  • the cut granules were rounded off in a Marumerizer-type rounding machine.
  • the stickiness of the particle surface was prevented by powdering by means of the proportion of fine dust produced during the process, so that a separate addition of a further solid was not necessary.
  • the products 1 - 6 thus produced were sieved: fine fraction (smaller than 0.6 mm) and oversize fraction (larger than 1.6 mm) were separated off.
  • the fine fraction of the granules was below 5% in all cases, the oversize fraction was below 1%.
  • the bulk density of the screened products varied between 650 g / l and 770 g / l.
  • the concentrates produced in Examples 1 to 6 can be mixed directly as detergents or - if desired - with non-pelleted or pelleted but separately prepared formulation components.
  • the compacts according to Example 4, as well as compacts of a number of other recipe combinations designed according to the invention were measured by means of mercury porosimetry. The following parameters were determined: Total internal volume in mm3 / g Total porosity in vol .-% Average pore radius in micrometers Specific surface area in m2 / g The relative volume distribution in mm3 / g within the following ranges of the respective pore radius (in »m): 0.001 to 0.01; 0.01 to 0.1; 0.1 to 1; 1 to 10 and 10 to 100
  • the compacts examined were produced as previously given for Examples 1 to 6 and correspond to the following overall formulations:
  • Bleach activator granules from the following components: 80 wt% TAED 8.0% by weight sodium dodecylbenzenesulfonate (96%) 4.0% by weight of C16 ⁇ 1 Tal tallow alcohol sulfate 6.0% by weight of C12 ⁇ 18 fatty alcohol with 5 EO 2.0 wt% zeolite NaA
  • the recipes for the granules or compacts according to Examples 9 to 15 are summarized in Table 2 below.
  • the materials of Examples 11 to 15 in the sense of the invention are molded articles produced by means of the pellet press.
  • the granules according to Examples 9 and 10 are extrudates which have been produced by extrusion in a screw extruder with a downstream perforated plate in accordance with the teaching of German patent application DE 39 26 253.
  • Example 5 summarizes the formulations of Examples 22-28, all of which deal with universal detergents (UWM).
  • UWM universal detergents
  • two representatives are processed by means of extrusion via a screw extruder with a downstream perforated plate in the manner given above (Examples 22 and 23).
  • the same starting recipes are then processed again into pellets via the pellet press in the sense of the invention, the recipe of example 22 corresponding to example 28 according to the invention and the recipe of example 23 corresponding to example 27 according to the invention.
  • pelletized mixtures according to the invention consistently show a dissolving time below 100 seconds, the solubility time of the two extrudates is above 200 seconds.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Glanulating (AREA)

Claims (21)

  1. Comprimés compactés à grains grossiers aptes à l'écoulement et stables au stockage contenant des ingrédients d'agents de lavage et/ou de nettoyage sous forme concentrée, produites par compactage donnant la forme, d'un prémélange à grains fins au moins largement homogénéisé des ingrédients, auquel des composants liquides à température ambiante peuvent aussi être ajoutés en petites quantités, caractérisées en ce qu'elles renferment des mélanges séchés liés d'une manière adhérente, ayant des densités apparentes d'au moins 500 g/l, composés :
    a) des ingrédients à grains fins sans propriétés marquées d'adhérence ou d'encollage avec
    b) des ingrédients à grains fins, ayant des propriétés d'adhérence ou d'encollage, ont été produites sur le matériau à grains fins par compactage procurant la forme, à des températures modérément élevées, des températures de matériau de 80°C n'étant pas dépassées, sans intervention de forces de cisaillement importantes, qui pourraient conduire à un empâtement substantiel des constituants du mélange en principe aptes au graissage, et
    c) de l'air en distribution microdispersée dans la particule compactée
    et possèdent une surface interne -déterminée par porosimétrie au mercure- d'au moins 1 m²/g.
  2. Comprimés compactés selon la revendication 1, caractérisées en ce qu'elles possèdent des densités apparentes à ou au-dessus d'environ 600 g/l, par exemple dans la zone allant jusqu'à 850 g/l.
  3. Comprimés compactés selon l'une des revendications 1 ou 2, caractérisées en ce qu'elles possèdent une surface interne à, ou au-dessus de 1,5 -2 m²/g qui peut se situer en particulier dans la zone d'environ 3 à 5 m²/g.
  4. Comprimés compactés selon l'une des revendications 1 à 3, caractérisées en ce que leur proportion en micropores d'un diamètre en-dessous de 1 »m représente au moins environ 30 % en volume, de préférence au moins 50 % en volume de la porosité totale.
  5. Comprimés compactés selon l'une des revendications 1 à 4, caractérisées en ce qu'elles renferment les composants (a) par rapport aux composants d'encollage (b) dans des rapports quantitatifs, qui conduisent dans les conditions opératoires du compactage à une zone limite de la formation de comprimés compactés stables quant à la forme, en préférant les rapports de mélange qui conduisent dans l'étape de façonnage donnant la forme, outre aux comprimés compactés, à de faibles quantités de matériau pulvérulent.
  6. Comprimés compactés selon l'une des revendications 1 à 5, caractérisées en ce qu'elles renferment en vue de la formation de matériau composite adhérent, dans la particule compactée conjointement avec les composants d'encollage b) finement divisés solides, des quantités limitées de constituants de mélange liquides à température ambiante, ayant ou n'ayant pas d'action propre sur les agents de lavage et/ou de nettoyage qui sont présents, répartis de préférence de manière largement homogène dans les particules, sans porter substantiellement préjudice à la microporosité.
  7. Comprimés compactés selon l'une des revendications 1 à 6, caractérisés en ce qu'elles renferment comme composants d'encollage b) des constituants de mélange ayant une action propre dans les agents de lavage et/ou de nettoyage et en particulier des composants correspondants de nature organique parmi lesquels ici, on préfère des composés tensioactifs solides à température ambiante et/ou des composés polymères correspondants d'origine naturelle et/ou synthétique, qui peuvent être activés par utilisation conjointe de petites quantités de constituants liquides à température ambiante, dans leur fonction de colle.
  8. Comprimés compactés selon l'une des revendications 1 à 7, caractérisées en ce qu'elles renferment des composants d'encollage b) sous forme divisée en fines particules et essentiellement homogène dans le mélange de substances qui, le cas échéant, avec interaction des constituants de mélange liquides à température ambiante, se ramollissent dans la zone de températures au-dessus de 40°C en particulier à des températures d'environ 45-80°C.
  9. Comprimés compactés selon l'une des revendications 1 à 8, caractérisées en ce qu'elles renferment les composants d'encollage b) au maximum en quantités environ égales aux composants a), tandis que cependant des proportions de mélange b) plus faibles sont préférées, qui se situent par exemple dans la zone d'environ 15 à 40 % en poids rapporté aux comprimés compactés.
  10. Comprimés compactés selon l'une des revendications 1 à 9, caractérisées en ce que leur teneur en constituants de mélange liquides à température ambiante ne représente pas plus qu'environ 10 % en poids et de préférence se situe dans la zone d'environ 2 à 8 % en poids, parmi lesquels comme composants correspondants, viennent en considération des niotensides liquides à température ambiante, des huiles et/ou des quantités limitées d'eau.
  11. Comprimés compactés selon l'une des revendications 1 à 10, caractérisées en ce que sont présents comme composants (a), des composants de mélange minéraux et/ou organiques, solides finement divisés ayant une action propre dans les agents de lavage et/ou de nettoyage comme des adjuvants ou des substances de squelette, des sels minéraux alcalins et neutres à faiblement acides, des agents de blanchiment, des activateurs de blanchiment et des silicates lamellaires aptes au gonflement.
  12. Comprimés compactés selon l'une des revendications 1 à 11, caractérisées en ce que comme composants (a), on utilise conjointement des constituants qui sont aptes pour la liaison interne à l'eau, par exemple sous la forme d'eau de cristallisation.
  13. Procédé de production des comprimés compactés selon l'une des revendications 1 à 12, caractérisé en ce que l'on mélange les composants (a) et les composants d'encollage (b) dans des conditions telles, d'une manière au moins largement homogène en un pré-mélange lâche, dans lequel encore aucune fonction de colle notablement durcissante ne survient, de cette façon on introduit les composants de liquide utilisés conjointement si désiré par mélange et on compacte le pré-mélange en excluant le plus largement possible les forces de cisaillement sur leur masse principale avec inclusion d'air microdispersé, en comprimés compactés, pour lesquels une surface interne - déterminée à l'aide de porosimétrie au mercure- d'au moins 1 m²/g est générée et des densités apparentes d'au moins 500 g/l sont ajustées.
  14. Procédé selon la revendication 13, caractérisé en ce que le compactage est effectué à une température de produit en vrac légèrement accrue, qui se situe de préférence dans la zone d'environ 40°C à 80°C, en particulier à environ 45 à 60°C.
  15. Procédé selon l'une des revendications 13 ou 14, caractérisé en ce que le compactage s'effectue au moyen d'une presse à matrice, en particulier dans une presse à matrice circulaire, dans laquelle le produit en vrac est appliqué sur une surface d'une matrice possédant des orifices, tournante et engagée à l'aide d'un outil de pressage qui tourne sur ou légèrement au-dessus de la surface de la matrice, en le compactant dans les orifices et à travers ceux-ci, il est comprimé sous forme de filaments et est allongé en granulés, tandis qu'en particulier par le contrôle de la température du matériau et par la variation de la hauteur de l'espace, de laminage entre l'outil de pressage et la surface de la matrice, le degré de compactage ainsi que la porosité interne du granulé peuvent être ajustés d'une manière influençable.
  16. Procédé selon l'une des revendications 13 à 15 caractérisé en ce que la matrice et l'outil de pressage sont actionnés avec un même sens de rotation, l'ajustement de vitesses d'enveloppe essentiellement identiques étant préféré.
  17. Procédé selon l'une des revendications 13 à 16 , caractérisé en ce que l'outil de pressage est refroidi et de cette façon la température du produit en vrac à compacter est régulée.
  18. Procédé selon l'une des revendications 13 à 17, caractérisé en ce que les masses compactées directement après la sortie des orifices de la matrice, sont coupées en longueur de préférence à l'aide d'un couteau de raclage.
  19. Procédé selon l'une des revendications 13 à 18 caractérisé en ce que les comprimés compactés continuent à être traitées si désiré après un séchage par exemple dans un séchoir à lit fluidifié, de préférence sans séchage additionnel, le cas échéant par un saupoudrage léger, et en particulier sont emballées par portions.
  20. Procédé selon l'une des revendications 13 à 19, caractérisé en ce que l'on travaille avec de tels rapports de mélange des composants (a) par rapport aux composants d'encollage (b), que par compactage donnant la forme simultanément avec les comprimés compactés, de petites quantités de poudres non liées se produisent qui représentent, de préférence, pas plus d'environ 10 % en poids et, en particulier, pas plus d'environ 5 % de l'évacuation du matériau en dehors de la presse.
  21. Procédé selon l'une des revendications 13 à 20, caractérisé en ce que le matériau est compacté dans des orifices ayant un diamètre d'environ 0,8 à 1,5 mm et est découpé en long de préférence à des longueurs dans la gamme d'environ 1 à 2 mm.
EP92900156A 1991-01-08 1991-12-10 Produits concentres secs facilement solubles, contenant des substances de produits de lavage Revoked EP0566583B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4100306A DE4100306A1 (de) 1991-01-08 1991-01-08 Kornfoermige, leicht loesliche trockenkonzentrate von inhaltsstoffen aus wasch- und/oder reinigungsmitteln und verfahren zu ihrer herstellung
DE4100306 1991-01-08
PCT/EP1991/002366 WO1992012229A1 (fr) 1991-01-08 1991-12-10 Produits concentres secs facilement solubles, contenant des substances de produits de lavage

Publications (2)

Publication Number Publication Date
EP0566583A1 EP0566583A1 (fr) 1993-10-27
EP0566583B1 true EP0566583B1 (fr) 1995-06-28

Family

ID=6422660

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92900156A Revoked EP0566583B1 (fr) 1991-01-08 1991-12-10 Produits concentres secs facilement solubles, contenant des substances de produits de lavage

Country Status (8)

Country Link
US (1) US5587104A (fr)
EP (1) EP0566583B1 (fr)
JP (1) JPH06504303A (fr)
KR (1) KR100200025B1 (fr)
AT (1) ATE124448T1 (fr)
DE (2) DE4100306A1 (fr)
ES (1) ES2073907T3 (fr)
WO (1) WO1992012229A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19531690A1 (de) * 1995-08-29 1997-03-06 Henkel Kgaa Figurenhaft ausgestaltete feste und verdichtete Mehrkomponentengemische aus dem Bereich der Wasch- und Reinigungsmittel sowie Verfahren zu ihrer Herstellung
GB9606913D0 (en) * 1996-04-02 1996-06-05 Unilever Plc Surfactant blends processes for preparing them and particulate detergent compositions containing them
DE19959002C2 (de) * 1999-12-08 2002-12-05 Henkel Kgaa Verfahren zur Herstellung von verdichteten Teilchen
DE10242222A1 (de) * 2002-09-12 2004-03-25 Henkel Kgaa Unter Druck kompaktiertes Wasch- oder Reinigungsmittel
US20050187132A1 (en) * 2002-09-12 2005-08-25 Volker Blank Detergent composition which has been compacted under pressure
US20150182960A1 (en) * 2013-12-31 2015-07-02 Ecowater Systems Llc Zeolite regeneration
KR101715275B1 (ko) * 2016-07-06 2017-03-17 (주) 대은글로벌솔루션 세제기능을 가지는 세라믹볼 및 이의 제조방법

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT915806A (fr) * 1970-12-22
GB1517713A (en) * 1974-10-31 1978-07-12 Unilever Ltd Preparation of detergent formulations
JPS51126974A (en) * 1975-04-30 1976-11-05 Kao Corp A process for producing granules containing viscous substances at high concentration
US4146495A (en) * 1977-08-22 1979-03-27 Monsanto Company Detergent compositions comprising polyacetal carboxylates
US4144226A (en) * 1977-08-22 1979-03-13 Monsanto Company Polymeric acetal carboxylates
DE3048641A1 (de) * 1980-12-23 1982-07-15 Hoechst Ag, 6000 Frankfurt "tensidhaltiges gemisch zur reinigung harter oberflaechen"
US5362413A (en) * 1984-03-23 1994-11-08 The Clorox Company Low-temperature-effective detergent compositions and delivery systems therefor
CA1275019A (fr) * 1985-10-09 1990-10-09 The Procter & Gamble Company Compositions detergentes granulees a solubilite accrue
GB8525269D0 (en) * 1985-10-14 1985-11-20 Unilever Plc Detergent composition
DE3768509D1 (de) * 1986-01-17 1991-04-18 Kao Corp Granuliertes reinigungsmittel von hoher dichte.
GB8626082D0 (en) * 1986-10-31 1986-12-03 Unilever Plc Detergent powders
DE3644564A1 (de) * 1986-12-27 1988-07-07 Henkel Kgaa Verfahren zur herstellung von rieselfaehigen, stabilen persaeure-konzentraten durch kompaktierende granulation
JPH01221497A (ja) * 1988-02-29 1989-09-04 Lion Corp 浴室用洗浄剤組成物
GB8810193D0 (en) * 1988-04-29 1988-06-02 Unilever Plc Detergent compositions & process for preparing them
DE3816842A1 (de) * 1988-05-18 1989-11-23 Schlueter Gmbh U Co Kg H Ringmatrizenpresse
DE68925938T2 (de) * 1988-11-02 1996-08-08 Unilever Nv Verfahren zur Herstellung einer körnigen Reinigungsmittelzusammensetzung mit hoher Schüttdichte
JPH05500076A (ja) * 1989-08-09 1993-01-14 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン 洗剤中で使用する高密度顆粒の製造方法
DE3926253A1 (de) * 1989-08-09 1991-02-14 Henkel Kgaa Verdichtete wasch- und reinigungsmittel in granulatform, verfahren zu ihrer herstellung und anwendung des verfahrens zur gewinnung lagerstabil rieselfaehiger waschmittel-konzentrate
GB9015503D0 (en) * 1990-07-13 1990-08-29 Unilever Plc Detergent composition
DE4024759A1 (de) * 1990-08-03 1992-02-06 Henkel Kgaa Bleichaktivatoren in granulatform
DE4112075A1 (de) * 1991-04-12 1992-10-15 Henkel Kgaa Verfahren zur herstellung stabiler, bifunktioneller, phospat- und metasilikatfreier niederalkalischer reinigungsmitteltabletten fuer das maschinelle geschirrspuelen

Also Published As

Publication number Publication date
KR100200025B1 (ko) 1999-06-15
EP0566583A1 (fr) 1993-10-27
DE4100306A1 (de) 1992-07-09
DE59105893D1 (de) 1995-08-03
US5587104A (en) 1996-12-24
WO1992012229A1 (fr) 1992-07-23
ES2073907T3 (es) 1995-08-16
JPH06504303A (ja) 1994-05-19
KR930703428A (ko) 1993-11-30
ATE124448T1 (de) 1995-07-15

Similar Documents

Publication Publication Date Title
EP0486592B1 (fr) Fabrication de granules comprimes pour produits de lavage
EP0595946B1 (fr) Procede de fabrication de produits de lavage a densite apparente elevee et a vitesse de dissolution amelioree
EP0642576B1 (fr) Procede de fabrication continue d'un detergent et/ou d'un nettoyant granulaire
DE69014186T2 (de) Verfahren zur Herstellung von Detergenszubereitungen mit hoher Schüttdichte.
DE69019574T2 (de) Detergens-Zusammensetzungen und Verfahren zu ihrer Herstellung.
DE4010533A1 (de) Tablettierte wasch- und/oder reinigungsmittel fuer haushalt und gewerbe und verfahren zu ihrer herstellung
EP0665879B1 (fr) Procede de preparation d'extrudats a action lavante et nettoyante
DE4203031A1 (de) Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
EP0663005B1 (fr) Procede de fabrication de granules tensioactifs
EP0566583B1 (fr) Produits concentres secs facilement solubles, contenant des substances de produits de lavage
EP1167509B1 (fr) Granules d'agent tensio-actif a vitesse de decomposition amelioree
WO1984003708A1 (fr) Composition detersive en granule d'ecoulement facile et procede de sa preparation
EP0804535B1 (fr) Detergents et nettoyants de blanchiment sous forme de granulats
EP0605436B1 (fr) Procede de preparation de granules de zeolithe
WO1996017045A1 (fr) Agents de lavage ou de nettoyage contenant des adjuvants de lavage hydrosolubles
DE4304475A1 (de) Granuliertes Wasch- und Reinigungsmittel
EP0674703B1 (fr) Procede de fabrication d'un detergent et nettoyant granule
DE19542570A1 (de) Verfahren zur Herstellung von granularen Wasch- oder Reinigungsmitteln oder Komponenten hierfür
DE19546465A1 (de) Verfahren zur Herstellung von granularen Wasch- oder Reinigungsmitteln oder Komponenten hierfür
WO1995004129A1 (fr) Procede de fabrication d'un produit extrude a activite detergente ou nettoyante
DE19548346A1 (de) Verfahren zum Herstellen granularer Wasch- und/oder Reinigungsmittel und zur Durchführung geeignete Vorrichtung
DE4435742A1 (de) Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19930630

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR IT LI NL

17Q First examination report despatched

Effective date: 19940325

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR IT LI NL

REF Corresponds to:

Ref document number: 124448

Country of ref document: AT

Date of ref document: 19950715

Kind code of ref document: T

ET Fr: translation filed
REF Corresponds to:

Ref document number: 59105893

Country of ref document: DE

Date of ref document: 19950803

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2073907

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19951231

Ref country code: CH

Effective date: 19951231

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 19960328

NLR1 Nl: opposition has been filed with the epo

Opponent name: THE PROCTER & GAMBLE COMPANY

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN

RDAH Patent revoked

Free format text: ORIGINAL CODE: EPIDOS REVO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20001204

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20010315

Year of fee payment: 10

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20011212

Year of fee payment: 11

Ref country code: AT

Payment date: 20011212

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20011228

Year of fee payment: 11

Ref country code: ES

Payment date: 20011228

Year of fee payment: 11

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20011120

NLR2 Nl: decision of opposition
NLR2 Nl: decision of opposition

Effective date: 20011120

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO