EP1025198A1 - Procede servant a preparer un produit lavant ou detergent au parfum renforce - Google Patents

Procede servant a preparer un produit lavant ou detergent au parfum renforce

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Publication number
EP1025198A1
EP1025198A1 EP98955451A EP98955451A EP1025198A1 EP 1025198 A1 EP1025198 A1 EP 1025198A1 EP 98955451 A EP98955451 A EP 98955451A EP 98955451 A EP98955451 A EP 98955451A EP 1025198 A1 EP1025198 A1 EP 1025198A1
Authority
EP
European Patent Office
Prior art keywords
premix
weight
perfume
binder
fragrance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP98955451A
Other languages
German (de)
English (en)
Other versions
EP1025198B1 (fr
Inventor
Kathleen Paatz
Wolfgang Lahn
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
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1025198A1 publication Critical patent/EP1025198A1/fr
Application granted granted Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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

Definitions

  • the present invention relates to a method for producing solid, fragrance-reinforced washing or cleaning agents.
  • the invention relates to a method for producing fragrance-reinforced detergents or cleaning agents with bulk densities above 600 g / 1 by press agglomeration of an essentially water-free premix.
  • fragrances should lead to the objects treated with the agents, in particular textiles , are given a long-lasting fragrance, which is rated by the consumer as a performance of the agent in question.
  • auxiliaries that do not act directly in the washing or cleaning process are added last to the washing and cleaning agents. This procedure particularly affects the "aesthetic" Components such as colors and fragrances.
  • the perfume is usually incorporated in such a way that the finished solid granules are sprayed with perfume, which is optionally fixed to the surface of the solid composition with powdering components.
  • the disadvantage of this procedure is that the fragrances are not distributed homogeneously over the entire composition and are additionally partially removed in the case of any subsequent drying steps.
  • the fragrance impression of the agents or the treated objects is often not intense enough with this type of perfuming and can only be made satisfactory by using more fragrance.
  • the present invention is based on the object of providing a method with which fragrance-reinforced detergents or cleaning agents or components therefor can be produced which not only impart a stronger fragrance to dry laundry, but also to moist laundry, and also as an agent per se smell more clearly than the traditionally scented agents.
  • the invention relates to a process for the production of fragrance-reinforced detergents or cleaning agents or components therefor with bulk densities above 600 g / 1, a solid and essentially water-free premix made from detergent or cleaning agent compounds and / or raw materials being produced contains at least 0.1% by weight of perfume, based on the premix, and subjecting this premix to press agglomeration.
  • essentially water-free is understood to mean a state in which the content of liquid water, ie water not present in the form of hydrated water and / or constitutional water, is below 2% by weight, preferably below 1% by weight. and in particular even less than 0.5% by weight, based in each case on the premix.
  • the premix has a total water content of not more than 15% by weight, this water therefore not in liquid free form, but chemically and / or is physically bound, and it is particularly preferred that the content of not zeolite and / or silicates bound water in the solid premix is not more than 10% by weight and in particular not more than 7% by weight.
  • Detergents or cleaning agents are understood to mean compositions of this type which can be used for washing or cleaning without usually having to add further ingredients.
  • a component for detergents or cleaning agents on the other hand, consists of at least 2 components usually used in detergents or cleaning agents; However, components or so-called compounds are normally only used in a mixture with other constituents, preferably together with other compounds.
  • ingredients used in the process according to the invention with the exception of any nonionic surfactants which are liquid at temperatures below 45 ° C. and a pressure of 1 bar - can be separately prepared compounds, but also raw materials which are in powder or particulate form (fine to coarse) .
  • beads or (fluidized bed) granules etc. produced by spray drying can be used as particulate particles.
  • the composition of the compounds per se is insignificant for the invention with the exception of the water content, which must be such that the premix is essentially water-free as defined above and preferably contains no more than 10% by weight of water of hydration and / or constitutional water .
  • over-dried compounds are used in the premix.
  • Such compounds can be obtained, for example, by spray drying, the temperature control being regulated in such a way that the tower outlet temperatures are above 70 ° C., for example 85 ° C. or above.
  • solid compounds in the premix which serve as carriers for liquids, for example liquid nonionic surfactants or silicone oil and / or paraffins.
  • These compounds can contain water within the scope specified above, the compounds being free-flowing and remaining free-flowing or at least conveyable even at higher temperatures of at least 45 ° C.
  • Free water that is water that is not in any form a solid is bound and is therefore "in liquid form" is preferably not contained in the premix at all, since very small amounts, for example around 0.2 or 0.5% by weight, based on the premix, are sufficient to absorb This would result in the melting point or softening point being lowered and the end product losing both its flowability and bulk density.
  • the water that is bound to builder substances such as zeolite or silicates (for a description of the substances see below), in particular if the water is bound to zeolite A, zeolite P or MAP and / or zeolite X, is to be regarded as less critical.
  • water which is bound to solid constituents other than the builder substances mentioned is preferably present in the premix in amounts of less than 3% by weight. It is particularly advantageous if the premix contains no water that is not bound to the builder substances. However, this is difficult to achieve from a technical point of view, since traces of water are usually always brought in by the raw materials and compounds.
  • the essentially water-free premixes contain perfume, at least 0.1% by weight of perfume, based on the premix, being added.
  • fragrances By incorporating the perfume into the premix and the subsequent press agglomeration step, a homogeneous distribution of the fragrances is achieved over the entire detergent or cleaning agent or the component therefor. Since an essentially water-free premix is used, there is no need for subsequent drying steps in which perfume could evaporate in whole or in part.
  • the targeted incorporation of the perfume into the agents or components also results in a significantly reduced loss of fragrance during transport or storage. Compared to conventionally scented agents, not only is the perfume distributed much more evenly, but also a more intense fragrance impression of the product. In this way, products with the same olfactory impression can be scented with less perfume or with the same Perfume amount significantly improved fragrance impressions can be achieved.
  • the improvement in the fragrance impression not only comes to light on the scented product, but also on the treated objects, preferably textiles. Both on damp and on dry laundry, the agents leave an increased fragrance impression compared to conventionally scented press agglomerates.
  • the fact that the fragrances are homogeneously distributed over the entire press agglomerate also avoids problems associated with conventional scenting: since the suction of the agglomerates for sprayed-on perfume is low and decreases with increasing degree of compaction, most of the perfume adheres to Powdering agent.
  • the conventionally scented product which is inevitably moved during transport, loses part of the powdering agent, which carries most of the perfume, due to friction.
  • fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, benzyl acetate, ethyl methylphenylglycinate, allyl cyclohexylate, methylateylateylate, styrallyl methylylateylate, styrallyl amylateylate, styrallyl methylateylate,
  • the ethers include, for example, benzylethyl ether and ambroxan, the aldehydes, for example,
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel sage oil, chamomile oil, clove oil, melissa 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 essentially water-free premix which is pressed agglomerated preferably has no dust-like components and in particular no particles with particle sizes below 200 ⁇ m.
  • those particle size distributions are preferred which have at least 90% by weight of particles with a diameter of at least 400 ⁇ m.
  • the washing or cleaning agents or components produced by press agglomeration consist of at least 70% by weight, advantageously at least 80% by weight and, with particular preference, up to 100% by weight spherical or almost spherical (pearl-shaped) particles with a particle size distribution which has at least 60% by weight of particles between 0.8 and 2.0 mm.
  • the solid and essentially water-free premix contains conventional solid detergent and cleaning agent ingredients such as builders, solid surfactants, bleaches, bleach activators, polymers and other conventional ingredients.
  • the ingredients can be used individually or in the form of compounds, as described above, optionally with liquid to pasty detergent and cleaning agent ingredients such as silicone oils, paraffins or liquid nonionic surfactants.
  • Pre-mixtures are preferably used in the context of the present invention, the individual raw materials and / or compounds which are present as a solid at room temperature and a pressure of 1 bar and have a melting or softening point not below 45 ° C. and optionally up to 20% by weight.
  • % preferably up to 15% by weight and in particular up to 10% by weight, based on the premix, contain liquid nonionic surfactants at temperatures below 45 ° C. and a pressure of 1 bar.
  • alkoxylated alcohols such as fatty or oxo alcohols, which are usually used in washing and cleaning agents is preferred, so that one is preferred Process is designed in such a way that the premix in addition to the solid constituents up to 20% by weight, preferably up to 15% by weight and in particular up to 10% by weight at temperatures below 45 ° C.
  • liquid nonionic surfactants in particular the alkoxylated alcohols usually used in detergents or cleaning agents, such as fatty alcohols or oxo alcohols with a carbon chain length between 8 and 20 and in particular an average of 3 to 7 ethylene oxide units per mole of alcohol, the addition of the liquid nonionic surfactants preferably in Mix with the perfume.
  • the premix can contain a raw material or a compound which functions as a binding and disintegration aid.
  • these binding and disintegration aids serve as lubricants and adhesives which adhere the solid components of the premix to one another and facilitate the passage of the premix through the pressure zone of the press agglomeration apparatus.
  • water-soluble binders they also facilitate the redissolution of the press agglomerates, since they act as disintegrants in aqueous liquors.
  • the premix contains at least one raw material or a compound which is present in solid form at a pressure of 1 bar and temperatures below 45 ° C., but is present as a melt in the press agglomeration, where this melt serves as a polyfunctional, water-soluble binder which, in the preparation of the compositions, performs both the function of a lubricant and an adhesive function for the solid detergent or cleaning agent compounds or raw materials, but disintegrates when the composition is redissolved in an aqueous liquor works.
  • Binders suitable for use in the process according to the invention are solid at a pressure of 1 bar and temperatures below 45 ° C., but are present as a melt under the process conditions of the press agglomeration.
  • the binders can be incorporated into the premix in such a way that a melt of the binder or binder mixture is sprayed onto the premix or the premix is added dropwise.
  • the binder (mixture) can also be incorporated into the premix as a finely divided solid.
  • the type of suitable binder and the temperature in the compression step of the press agglomeration are dependent on one another. Since it has proven to be advantageous if the binder is distributed as homogeneously as possible in the material to be compacted in the compression step, temperatures must be present in the compression step at which the binder at least softens, but preferably completely and not only partially is in molten form. If a binder with a high melting point or high softening point is selected, then a temperature must be set in the compression process step, which ensures that the binder melts. In addition, depending on the desired composition of the end product, temperature-sensitive raw materials should also be able to be processed.
  • the upper temperature limit is given by the decomposition temperature of the sensitive raw material, it being preferred to work significantly below the decomposition temperature of this raw material.
  • the lower limit for the melting point or softening point is of such great importance, since at melting points or softening points below 45 ° C, an end product is usually obtained which is already at room temperature and slightly elevated temperatures of 30 ° C, tends to stick at summer temperatures and under storage or transport conditions. It has proven to be particularly advantageous if a few degrees, for example 2 to 20 ° C., are used above the melting point or above the softening point
  • the applicant is of the opinion that the homogeneous distribution of the binder within the premix under the process conditions of compression compresses the solid compounds and any individual raw materials that may be present in the binder and subsequently glues them together the finished end products are made almost exactly from these many small individual particles, which are held together by the binder, which takes over the function of a preferably thin partition between these individual particles.
  • a honeycomb Similar structure can be assumed, these honeycombs are filled with solids (compounds or individual raw materials).
  • these thin partitions dissolve or disintegrate almost immediately; Surprisingly, this is also the case if the binder itself is not readily soluble in water at room temperature, for example due to a crystal structure.
  • binders are preferably used, which can be almost completely dissolved within 90 seconds in a test method as described below in a concentration of 8 g of binder in 1 liter of water at 30 ° C.
  • the binder or binders must therefore be such that the adhesive properties are retained even at temperatures which are significantly above the melting point or the softening point.
  • a binder which is already completely present as a melt at temperatures of up to 130 ° C., preferably up to 100 ° C. and in particular up to 90 ° C.
  • the binder must therefore be selected depending on the process and process conditions, or the process conditions, in particular the process temperature, must - if a particular binder is desired - be adapted to the binder.
  • Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and also modified polyethylene glycols and polypropylene glycols.
  • the modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or poly- lypropylene glycols with a relative molecular weight between 600 and 12000 and in particular between 1000 and 4000.
  • Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights between 600 and 6000, preferably between 1000 and 4000.
  • polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C -C 5 glycols and glycerol and mixtures of these as starting molecules. Also included are ethoxylated derivatives such as trimethylol propane with 5 to 30 EO.
  • the polyethylene glycols preferably used can have a linear or branched structure, linear polyethylene glycols being particularly preferred.
  • the particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12000, advantageously around 4000, polyethylene glycols with relative molecular weights below 3500 and above 5000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4000, and such combinations advantageously to more than 50% by weight, based on the total amount of polyethylene glycols, have polyethylene glycols with a relative molecular weight between 3500 and 5000.
  • polyethylene glycols which are in the liquid state at room temperature and a pressure of 1 bar can also be used as binders;
  • polyethylene glycol with a relative molecular mass of 200, 400 and 600 can also be used as binders;
  • these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C.
  • the modified polyethylene glycols also include polyethylene glycols which are end-group-capped on one or more sides, the end groups preferably being C 1 -C 2 -alkyl chains which can be linear or branched.
  • the End groups on the alkyl chains between Ci and C 6 especially between Ci and C, with isopropyl and isobutyl or tert-butyl also being possible alternatives.
  • the binder or binder content in the premix is preferably at least 2% by weight, but less than 15% by weight, in particular less than 10% by weight, with particular preference given to 3 up to 6 wt .-%, each based on the premix.
  • the water-swollen polymers are used in amounts below 10% by weight, advantageously in amounts of 4 to 8% by weight, with preference of 5 to 6% by weight.
  • the solids for the preparation of the solid and free-flowing premix are firstly at room temperature to slightly elevated temperatures, which are preferably below the melting temperature or the softening point of the binder and in particular at temperatures up to 35 ° C. in a customary mixture. and / or pelletizer mixed together.
  • the binders are preferably added as the last component. As already stated above, they can be added as a solid, ie at a processing temperature which is below their melting point or their softening point, or as a melt respectively. However, the admixture is advantageously carried out under conditions such that the most homogeneous possible distribution of the binder in the solid mixture is achieved. In the case of very finely divided binders, this can be accomplished at temperatures below 40 ° C., for example at temperatures of the binder between 15 and 30 ° C. However, the binder advantageously has temperatures at which it is already in the form of a melt, that is to say above the softening point, in particular in the form of a complete melt.
  • Preferred temperatures of the melt are 60 to 150 ° C with particular preference for the temperature range of 80 to 120 ° C.
  • the melt solidifies almost instantaneously, and the premix is, according to the invention, in solid, free-flowing form.
  • the mixing process is advantageously continued until the melt has solidified and the premix is in a solid, free-flowing form.
  • the proportion of binder (s) can be reduced by incorporating the perfume into the premix. Since the fragrances act as lubricants and, because of their homogeneous distribution in the finished press agglomerate, do not hinder redissolution despite their mostly hydrophobic character, it is possible to adjust the content of the premix of binders mentioned in the earlier German patent application 196.38.599.7 (over 2 to under 15 wt %, preferably less than 10% by weight and in particular from 3 to 6% by weight), so that binder contents of 1 to 5% by weight, preferably 2 to 4% by weight, are used can.
  • a premix is used, the content of binder or binders of which is at least 1% by weight, but less than 10% by weight, preferably less than 8% by weight and, with particular preference, 2 to 4% by weight. , each based on the premix.
  • the premix preferably contains significantly more than the minimum amount of 0.1% by weight of perfume. Methods according to the invention are preferred in which the mix contains more than 0.15% by weight, preferably more than 0.2% by weight and in particular more than 0.3% by weight of perfume.
  • the perfume can be incorporated into the premix in almost every stage of the premix production. It is thus possible, for example, to place some or all of the solids, as described above, at room temperature in a conventional mixing and / or granulating device and to apply or spray the perfume onto the moving bed of solids.
  • the perfume can also be added to the solids together with the binder as described above. Here it is possible to mix perfume with solid binder as well as to incorporate the perfume into a separately produced melt of the binder and to add the paste-like to liquid binder-perfume mixture to the solids.
  • all of the above-mentioned incorporation methods can also be combined with one another, with each part of the perfume being introduced into the premix in different ways. If nonionic surfactants are used in the process according to the invention, the perfume is preferably added as a mixture with the nonionic surfactants, it also being possible to prepare and use mixtures of binder, nonionic surfactant and perfume.
  • the essentially water-free procedure enables the perfume to be incorporated into the premix, since subsequent drying steps in which fragrance losses could occur are not necessary.
  • this procedure has the advantage that peroxy bleaching agents can be processed without loss of activity, and it also makes it possible to process peroxy bleaching agents and bleach activators (see description below exactly) without having to fear serious loss of activity.
  • the porosity is reduced during the press agglomeration, on the other hand, the particle adhesion is increased by the plastic deformation of the contact zones, which is why materials that can be largely plastically deformed, deliver compacts with high strengths, while elastically deformed malleable particles with brittle behavior are more difficult to compress.
  • the compressibility can be improved by adding binders.
  • the press agglomeration process to which the solid and essentially water-free premix is subjected can be carried out in various apparatuses. Different press agglomeration processes are distinguished depending on the type of agglomerator used.
  • the four most common press agglomeration processes preferred in the context of the present invention are extrusion, roll pressing or compacting, hole pressing (pelletizing) and tableting, so that preferred press agglomeration processes within the scope of the present invention include extrusion, roll compacting. , Pelleting or tableting processes.
  • the premix is compressed and plasticized under pressure and that the individual particles are pressed against one another while reducing the porosity and adhere to one another.
  • the tools can be heated to higher temperatures or cooled to dissipate the heat generated by shear forces.
  • the actual compression process takes place at processing temperatures which, at least in the compression step, correspond at least to the temperature of the softening point, if not even the temperature of the melting point of the binder.
  • the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt.
  • the process temperature in the compression step is not more than 20 ° C.
  • thermoly sensitive raw materials for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, increasingly without grave four loss of active substance can be processed.
  • the working tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (s) of the pellet press) have a temperature of at most 150 ° C., preferably at most 100 ° C., and in particular to a maximum of 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the temperature exposure in the compression range of the press agglomerators is preferably a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
  • the compressed material preferably has temperatures not above 90 ° C., temperatures between 35 and 85 ° C. being particularly preferred. It has been found that exit temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.
  • the method according to the invention is carried out by means of an extrusion, as described, for example, in European patent EP-B-0 486 592 (Henkel KGaA) or international patent applications WO-A-93/02176 (Henkel KGaA) and WO -A-94/09111 (Henkel KGaA).
  • a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device.
  • the homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work.
  • Preferred plasticizers and / or lubricants are surfactants and / or polymers, which are now within the scope of present invention with the exception of the above-mentioned nonionic surfactants, however, not in liquid and in particular not in aqueous, but in solid form in the premix.
  • the premix is preferably fed continuously to a planetary roller extruder or a 2-screw extruder or 2-screw extruder with co-rotating or counter-rotating screw guide, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature.
  • the premix is compressed, plastified and extruded in the form of fine strands through the perforated die plate in the extruder head under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used and finally the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knife.
  • the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension.
  • the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use.
  • particle diameters up to at most 0.8 cm are preferred.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
  • the length / diameter ratio of the chopped-off primary granules is in the range from about 1: 1 to about 3: 1.
  • small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this step.
  • extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder.
  • the invention now provides that the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded.
  • the duration of the temperature influence in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.
  • the binder used has a melting temperature or a melting range of up to 75 ° C .; Process temperatures which are at most 10 ° C. and in particular at most 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder have then proven to be particularly favorable.
  • the binder also functions as a lubricant and at least prevents or at least reduces sticking to apparatus walls and compaction tools. This applies not only to processing in the extruder, but also equally to processing, for example in continuously operating mixers / granulators or rollers. Just as in the extrusion process, it is also preferred in the other production processes to feed the resulting primary granules / compactates to a further shaping processing step, in particular to round them, so that ultimately spherical to approximately spherical (pearl-shaped) grains can be obtained.
  • the particle size distribution of the premix is designed to be substantially wider than that of the end product produced according to the invention and according to the invention.
  • the premix can contain much larger fine-grained fractions, even dust, and possibly also coarser-grained fractions, although it is preferred that a premix with a relatively broad particle size distribution and relatively high fractions of fine-grained material in an end product with a relatively narrow particle size distribution and relatively small fractions of fine-grain is transferred.
  • the method of the invention is essentially anhydrous - i.e. with the exception of water contents ("impurities") of the solid raw materials used, water-free, not only is the risk of gelling of the surfactant raw materials minimized to ruled out in the manufacturing process, in addition, an ecologically valuable process is also provided, since by dispensing with one subsequent drying step not only saves energy but also emissions, as they occur predominantly with conventional drying methods, can be avoided. In addition, the omission of subsequent drying steps only allows the fragrances to be incorporated into the premix and thus the production of fragrance-enhanced detergents or cleaning agents or Components for this.
  • the method according to the invention is carried out by means of roller compaction.
  • the fragrance-containing solid and essentially water-free premix is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe.
  • the rollers practice a high linear pressure and can be additionally heated or cooled as required.
  • smooth rollers smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later detergent or cleaning agent particles can be specified.
  • the sliver belt is subsequently broken up into smaller pieces by a knocking-off and comminution process and can be processed in this way into granules which can be refined, in particular in an approximately spherical shape, by further known surface treatment processes.
  • the temperature of the pressing tools is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C.
  • Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the temperature effect in the compression area of the smooth rollers or with depressions of a defined shape is a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
  • the method according to the invention is carried out by means of pelleting.
  • the fragrance-containing, solid and essentially water-free premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization.
  • the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device.
  • the most varied configurations of the pressure roller and perforated die are conceivable here.
  • the press rolls can with the plate devices also be conical, in the ring-shaped devices the dies and press roller (s) can have the same or opposite direction of rotation.
  • An apparatus suitable for carrying out the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH).
  • the ring die press disclosed in this document consists of a rotating ring die penetrated by press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
  • the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
  • the temperature of the pressing tools is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at most 75 ° C.
  • Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
  • Another press agglomeration process that can be used according to the invention is tableting. Because of the size of the molded articles produced, it may be useful for tableting to add customary disintegration aids, for example cellulose and its derivatives or crosslinked PVP, in addition to the binder, which facilitate the disintegration of the compacts in the wash liquor.
  • customary disintegration aids for example cellulose and its derivatives or crosslinked PVP
  • a fragrance-reinforced extruded, roller-compacted or pelletized detergent which consists of at least 80% by weight of compounds and / or treated raw materials produced according to the invention.
  • an extruded, roller-compacted or pelletized detergent consists of at least 80% by weight of a base agent produced according to the invention. glomerate.
  • the remaining ingredients can be prepared and admixed by any known method. However, it is preferred that these remaining constituents, which may be compounds and / or treated raw materials, were also produced by the process according to the invention. In particular, this enables basic granules and remaining constituents to be produced with approximately the same pourability, bulk density, size and particle size distribution.
  • the particulate press agglomerates obtained can either be used directly as detergents or cleaning agents or can be aftertreated and / or prepared beforehand by customary methods.
  • the usual aftertreatments include, for example, powdering with finely divided ingredients from detergents or cleaning agents, which generally further increases the bulk density.
  • a preferred aftertreatment is also the procedure according to German patent applications DE-A-195 24 287 and DE-A-195 47 457, dusty or at least finely divided ingredients (the so-called fine fractions) of the particulate end products of the process, which are the core serve, be glued and thus funds are created which have these so-called fines as an outer shell.
  • melt agglomeration of the fine fractions of the basic granules according to the invention and produced according to the invention reference is expressly made to the disclosure in German patent applications DE-A-195 24 287 and DE-A-195 47 4
  • Both the fragrance-reinforced detergents which consist of at least 80% by weight of press agglomerates produced according to the invention, and the press agglomerates themselves can additionally be subsequently sprayed with perfume.
  • the conventional fragrance variant i.e. powdering and spraying with perfume can be carried out with the press agglomerates according to the invention.
  • At least 30% by weight, preferably at least 40% by weight and in particular at least 50% by weight of the total perfume contained in the agent is Manufacturing processes according to the invention introduced into the agents, ie incorporated into the press agglomerates, while the remaining 70% by weight, preferably 60% by weight and in particular 50% by weight of the total perfume contained in the agent onto the press agglomerates, which can optionally be surface-treated , sprayed on or otherwise applied.
  • fragrance in order to be perceptible, a fragrance must be volatile, with the molecular weight also playing an important role in addition to the nature of the functional groups and the structure of the chemical compound . Most odoriferous substances have molecular weights of up to about 200 daltons, while molecular weights of 300 daltons and more are an exception.
  • the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less volatile
  • more volatile fragrances can be bound, for example, to certain fixatives, which prevents them from evaporating too quickly.
  • the embodiment of the present invention described above, in which the more volatile fragrances or fragrances are incorporated into the press agglomerate be incorporated, i is such a method for fragrance fixation.
  • the subsequent classification of the fragrances into “more volatile” or “adhesive” fragrances nothing is said about the odor impression and whether the corresponding fragrance is perceived as a top or heart note.
  • Non-stick odoriferous substances that can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champagne flower oil, noble fir oil, noble pine cone oil, elem oil, eucalyptus oil, fennel oil, galbane oil, spruce oil.
  • the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champagne flower oil, noble fir oil, noble pine cone oil, elem oil, eucalyptus oil, fennel oil, galbane oil, spruce oil.
  • fragrances can also be used in the context of the present invention as adhesive fragrances or fragrance mixtures, that is to say fragrances.
  • These compounds include the compounds mentioned below and mixtures of these: ambrettolide, ⁇ -amyl cinnamaldehyde, anethole, anisaldehyde, anis alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate benzate ,
  • the more volatile fragrances include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures.
  • Examples of more volatile fragrances are alkyisothiocyanates (alkyl mustards), butanedione, limonene, linalool, Linaylacetate and propionate, menthol, Menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinylacetate, citral, citronellal.
  • surfactants in particular anionic surfactants, which should be present in the agents according to the invention or agents according to the invention at least in amounts of 0.5% by weight.
  • anionic surfactants include in particular sulfonates and sulfates, but also soaps.
  • Preferred surfactants of the sulfonate type are C 9 -C 8 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 1 -C 2 monoolefins with an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates the 2 -C ⁇ 8 alkanes or chlorination of C, for example by sulfo sulfoxidation be recovered and subsequent hydrolysis or neutralization.
  • esters of sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts.
  • esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
  • MES ⁇ -sulfofatty acids
  • saponified disalts are used with particular advantage.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol be preserved.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid semiesters of C 1 -C 8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 1 -C 2 o- Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 2 -C 6 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 4 -C 5 alkyl sulfates are particularly preferred.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN (R) , are also suitable anitone surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 2 -alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl branched C 9 -C 2 -alcohols with an average of 3.5 mol of ethylene oxide (EO) or C] 2 -C ⁇ 8 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and represent in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 - to C 8 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).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Fatty acid derivatives of amino acids for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.2 to 5% by weight.
  • Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • anionic surfactants are contained or used in the agents according to the invention or in the method according to the invention preferably in amounts of 1 to 30% by weight and in particular in amounts of 5 to 25% by weight.
  • nonionic surfactants are particularly preferred.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • 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 2 -C 4 alcohols with 3 EO or 4 EO, C 9 -C 1 -alcohols with 7 EO, d 3 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 -C] 8 - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 2 -C 4 alcohol with 3 EO and C 2 -C 8 - alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used, as described above. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched 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 oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4. 1
  • polyhydroxy fatty acid amides of the formula (I) in which R * CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 5 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, dC 4 - alkyl or phenyl radicals being preferred
  • [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • C] 2 -C 8 fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are preferred, while, as described above, higher ethoxylated fatty acid methyl esters are particularly advantageous as binders.
  • Ci 2 -C] 8 fatty acid methyl esters with 10 to 12 EO can be used both as surfactants and as binders.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are generally separated from one another by a so-called “spacer”. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another. Such surfactants are distinguished generally due to an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water, but in exceptional cases the term gemini surfactants means not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis and trimeral alcohol tris-sulfates and ether sulfates according to German patent application DE-A-195 03 061. Dimer and trimer mixed ethers which are capped by end groups According to German patent application DE-A-195 13 391, they are distinguished in particular by their bi- and multifunctionality. The end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides can also be used.
  • the inorganic and organic builder substances are among the most important ingredients of detergents or cleaning agents.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P for example, zeolite MAP (R) (commercial product from Crosfield) is used.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
  • the zeolite may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 2 -C 8 fatty alcohols with 2 to 5 ethylene oxide groups , -C 2 -C-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.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x ⁇ 2X + ⁇ 'yH 2 ⁇ , where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4.
  • 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.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 0 5 ' y H 2 O are preferred.
  • the preferred builder substances also include amorphous sodium silicates with a Na2 ⁇ : Si ⁇ 2 modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which are delayed in dissolving and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • phosphates As builders, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished funds. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability.
  • Suitable substitutes or partial substitutes for the zeolite are layer silicates of natural and synthetic origin.
  • Layered silicates of this type are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405.
  • Their usability is not limited to a special composition or structural formula.
  • smectites, in particular bentonites, are preferred here.
  • Suitable layered silicates which belong to the group of water-swellable smectites, are, for example, montmorrilonite, hectorite or saponite.
  • small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas.
  • the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca 2+ .
  • the amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing.
  • Useful sheet silicates are known, for example, from US-A-3,966,629, EP-A-0 026 529 and EP-A-0 028 432.
  • Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and serve thus also for setting a lower and milder pH value of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular. If they are used in the premix according to the invention and are not subsequently added, these acids are preferably used in anhydrous form.
  • Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used.
  • a preferred dextrin is described in British patent application 94 19 091.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Also particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93/339896 - be written. Suitable amounts used are 3 to 15% by weight in formulations containing zeolite and / or silicate.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO-A-95/20029.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • the content of (co) polymeric polycarboxylates in the compositions is within the usual range and is preferably 1 to 10% by weight.
  • biodegradable polymers composed of more than two different monomer units, for example those which, according to DE-A-43 00 772, are salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C -42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • Other suitable builder substances are oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110 .
  • Oxidized oligosaccharides according to German patent application DE-A-196 00 018 are also suitable.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the agents can also contain components which have a positive effect on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Of these, the sulfonated derivatives of phthalic and terephthalic acid polymers are particularly preferred.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates such as the above-mentioned dissolving-delayed silicates or mixtures thereof; in particular, alkali carbonate and amorphous alkali silicate, especially sodium silicate with a molar ratio Na 2 0: SiO 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the content of sodium silicate in the agents is - if it is not to be used as builder substance - generally up to 10% by weight and preferably between 2 and 8% by weight, otherwise more.
  • 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 such as sulfates and chlorides in the form of their sodium or potassium salts.
  • Acidic salts or slightly alkaline salts can also be used to reduce the pH of detergents or cleaning agents.
  • Preferred acidifying components are bisulfates and / or bicarbonates or the above-mentioned organic polycarboxylic acids, which can also be used as builder substances at the same time.
  • Particular preference is given to the use of citric acid, which is either added subsequently (customary procedure) or - in anhydrous form - in the solid premix.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.
  • aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used as bleach activators.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • hydrophilically substituted acylacetals known from German patent application DE-A-196 16 769 and the acyl lactams described in German patent application DE-A-196 16 770 and international patent application WO-A-95/14075 are also preferably used.
  • the combinations of conventional bleach activators known from German patent application DE-A-44 43 177 can also be used.
  • Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 8 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffm-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylene diamides are particularly preferred.
  • the salts of polyphosphonic acids which are preferably used are the neutral sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5% by weight.
  • Particularly suitable enzymes are those from the class of hydrolases, such as proteases, lipases or lipolytically active enzymes, amylases, cellulases or mixtures thereof. Oxireductases are also suitable.
  • Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxi in some cases, these have proven to be suitable.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the agents can also contain further enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • magnesium salts also serve as stabilizers.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid HBO), is particularly advantageous.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyal- kylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-mo ⁇ holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the Mo ⁇ holino- Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Spray drying produced granules with the composition given in Table 1, which were mixed with further components according to Table 2 and processed into a premix in a Lödige mixer.
  • Table 1 Composition of the spray-dried granules [% by weight]:
  • the perfume oil was in the liquid before adding to the mixer solved with 7 EO.
  • the free-flowing premix had a bulk density of 450 g / l after leaving the mixer and was placed in a twin-screw extruder from Lihotzky and plasticized and extinguished under pressure.
  • the plasticized premix left the extrader at a pressure of 85 bar through a perforated plate with exit holes of 1.4 mm in diameter.
  • the extruded strands were chopped to a length / diameter ratio of approx. 1 with a rotating knife and rounded in a MarumerizeA. After the fine parts ( ⁇ 0.4 mm) and the coarse parts (> 2.0 mm) had been sieved, the extrudate had a bulk density of 810 g / l.
  • extrudates E1 and E2 produced according to the invention which differed in the perfume oils used, were now compared with extrudates VI and V2 with an analog composition, in which the perfume oils in question were sprayed onto the extruded and rounded particles, which had been powdered with finely divided zeolite, in a conventional manner has been.
  • an extrudate E3 was also produced which contained part of the perfume and was also sprayed with the rest of the perfume. This agent was compared with a comparative sex trudate V3, in which the total amount of the perfume was applied by spraying.
  • the composition of the perfume oils is given in Table 3.
  • the fragrance of the product and treated textiles was assessed as a subjective smell impression by perfumers.
  • the numerical values in the evaluation table (Table 4) indicate the number of perfumers who rated the respective products or the textiles treated with the respective agent as “more fragrant”. Because a different number of perfumers was present in the different smell tests , the values in the "Perfumers" columns do not always add up to the same value.
  • the first block of the first column (product) should therefore be read in such a way that 5 out of 7 perfumers rated the extrudates produced according to the invention as more fragrant.
  • Table 4 Composition of the perfume oils [% by weight]:

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Fats And Perfumes (AREA)
EP98955451A 1997-10-23 1998-10-14 Procede servant a preparer un produit lavant ou detergent au parfum renforce Revoked EP1025198B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19746781 1997-10-23
DE19746781A DE19746781A1 (de) 1997-10-23 1997-10-23 Verfahren zur Herstellung duftverstärkter Wasch- oder Reinigungsmittel
PCT/EP1998/006513 WO1999021955A1 (fr) 1997-10-23 1998-10-14 Procede servant a preparer un produit lavant ou detergent au parfum renforce

Publications (2)

Publication Number Publication Date
EP1025198A1 true EP1025198A1 (fr) 2000-08-09
EP1025198B1 EP1025198B1 (fr) 2003-08-06

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EP98955451A Revoked EP1025198B1 (fr) 1997-10-23 1998-10-14 Procede servant a preparer un produit lavant ou detergent au parfum renforce

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US (1) US6228833B1 (fr)
EP (1) EP1025198B1 (fr)
JP (1) JP2001521060A (fr)
CN (1) CN1276829A (fr)
AT (1) ATE246727T1 (fr)
DE (2) DE19746781A1 (fr)
ES (1) ES2205570T3 (fr)
PL (1) PL188261B1 (fr)
WO (1) WO1999021955A1 (fr)

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EP1149144A1 (fr) * 1999-02-05 2001-10-31 Unilever Plc Procede utilise pour laver la vaisselle et compositions connexes
US6786223B2 (en) * 2001-10-11 2004-09-07 S. C. Johnson & Son, Inc. Hard surface cleaners which provide improved fragrance retention properties to hard surfaces
GB0130498D0 (en) * 2001-12-20 2002-02-06 Unilever Plc Process for production of detergent tablets
GB0201300D0 (en) * 2002-01-21 2002-03-06 Unilever Plc Detergent composition in tablet form
CN1649942A (zh) * 2002-05-14 2005-08-03 纳幕尔杜邦公司 由水溶性聚酰胺制造的包装和容器及其制造方法
US6689342B1 (en) * 2002-07-29 2004-02-10 Warner-Lambert Company Oral care compositions comprising tropolone compounds and essential oils and methods of using the same
EP1627036B2 (fr) 2003-05-28 2015-06-17 Kao Corporation Composition de parfum
EP1657298A1 (fr) * 2004-11-12 2006-05-17 Cognis IP Management GmbH Compositions solides
DE102005062008B3 (de) * 2005-12-22 2007-08-30 Henkel Kgaa Geruchsreduktion hypochlorithaltiger Mittel
DE102006040103A1 (de) * 2006-08-28 2008-03-06 Henkel Kgaa Schmelzgranulate für Wasch- und Reinigungsmittel
KR20110073439A (ko) * 2008-09-10 2011-06-29 다니스코 유에스 인크. 효소적 직물 표백 조성물 및 이의 사용 방법
CN104479912A (zh) * 2014-12-13 2015-04-01 张慧娜 一种柠檬油复合清洗剂及其制备方法
CN106422978B (zh) * 2016-12-20 2019-03-05 上海试四赫维化工有限公司 水溶性引发剂的造粒方法
EP3642319B1 (fr) * 2017-06-20 2020-12-30 Unilever N.V. Compositions de détergents particulaires comprenant un parfum
CN108531298B (zh) * 2018-04-10 2020-06-23 上海应用技术大学 一种含有金佛手精油微胶囊的洗衣粉及其制备方法
CN111286414B (zh) * 2019-11-28 2021-04-27 纳爱斯浙江科技有限公司 一种衣物留香珠及其制备方法
CN116507708A (zh) * 2020-11-19 2023-07-28 宝洁公司 制备包含香料的洗涤剂组合物的方法
CN115073287B (zh) * 2021-03-11 2024-06-25 万华化学(四川)有限公司 一种高品质乙酸芳樟酯及其制备方法
CN113712421B (zh) * 2021-09-23 2022-10-21 涟源市宝福香业有限公司 一种中药檀香的加工工艺
CN115108751B (zh) 2022-07-14 2023-03-21 武汉工程大学 一种预拌流态固化土用分散剂及其制备方法和应用

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Publication number Publication date
CN1276829A (zh) 2000-12-13
DE59809226D1 (de) 2003-09-11
WO1999021955A1 (fr) 1999-05-06
ATE246727T1 (de) 2003-08-15
ES2205570T3 (es) 2004-05-01
EP1025198B1 (fr) 2003-08-06
DE19746781A1 (de) 1999-04-29
PL340036A1 (en) 2001-01-15
JP2001521060A (ja) 2001-11-06
PL188261B1 (pl) 2005-01-31
US6228833B1 (en) 2001-05-08

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