EP1025198B1 - 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 Download PDF

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Publication number
EP1025198B1
EP1025198B1 EP98955451A EP98955451A EP1025198B1 EP 1025198 B1 EP1025198 B1 EP 1025198B1 EP 98955451 A EP98955451 A EP 98955451A EP 98955451 A EP98955451 A EP 98955451A EP 1025198 B1 EP1025198 B1 EP 1025198B1
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EP
European Patent Office
Prior art keywords
premix
weight
perfume
process according
binder
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Revoked
Application number
EP98955451A
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German (de)
English (en)
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EP1025198A1 (fr
Inventor
Kathleen Paatz
Wolfgang Lahn
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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 Detergents or cleaning agents.
  • the invention relates to a method of manufacture fragrance-reinforced washing or cleaning agents with bulk densities above 600 g / l by press agglomeration of a substantially water-free premix.
  • the perfume is mostly incorporated in the way that the finished solid granules are sprayed with perfume, which if necessary is fixed with powdering components on the surface of the solid agent.
  • This The procedure has the disadvantage that the fragrances are not homogeneous over the whole Means are distributed and additionally in any subsequent drying steps partially removed again. Also the fragrance impression of the agents or the treated ones Objects are often not intense enough with this type of perfuming and only through to make increased use of fragrance satisfactory.
  • the present invention is based on the object of providing a method with which fragrance-reinforced detergents or cleaning agents or components therefor Can produce not only dry laundry, but also wet laundry give a stronger fragrance and as a medium itself more clearly perceptible smell as the traditionally scented means.
  • the invention relates to a method for producing fragrance-reinforced washing or Detergents or components therefor with bulk densities above 600 g / l, with a solid and essentially water-free premix of detergent or cleaning agent compounds and / or raw materials is produced which contains at least 0.1% by weight Perfume, based on the premix, and this premix contains a press agglomeration subjects, where the premix contains binders already at Temperatures up to a maximum of 150 ° C completely as a melt are present and the incorporation of the binder at temperatures takes place in which the binder is in the form of a melt is present.
  • a condition is "substantially water-free" understand, where the content of liquid, i.e. not in the form of water of hydration and / or Constitutional water 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. Accordingly, water can essentially only be chemically and / or physically bound form or as part of the raw materials or compounds present as a solid, but not as a liquid, solution or dispersion in the manufacturing process of the Vorgemtsches are introduced.
  • the premix as a whole a water content of not more than 15 wt .-%, so this water not in liquid free form, but chemically and / or physically bound, and it is particularly preferred that the content of not zeolite and / or silicates bound water in the solid premix not more than 10 wt .-% and in particular is not more than 7% by weight.
  • Detergents or cleaning agents are understood to mean such compositions that can be used for washing or cleaning, without usually more Ingredients must be added.
  • a component for detergents or cleaning agents on the other hand consists of at least 2 usually in detergents or cleaning agents used components; Components or so-called compounds are usually but only in a mixture with other ingredients, preferably together with others Compounds used.
  • the ingredients used in the process according to the invention can - with the exception the possibly existing at temperatures below 45 ° C and a Pressure of 1 bar liquid non-ionic surfactants - separately manufactured compounds, however also be raw materials that are available in powder or particulate form (fine to coarse). Beads produced by spray drying, for example, can be used as particulate particles or (fluidized bed) granules etc. can be used.
  • the composition of the compounds in itself is immaterial to the invention with the exception of the water content, which must be such that the premix is essentially anhydrous as defined above is and preferably not more than 10% by weight of water of hydration and / or water of constitution contains. In a preferred embodiment, they are over-dried Compounds used in the premix.
  • Such compounds can, for example can be obtained by spray drying, the temperature control being regulated so that the tower outlet temperatures above 70 ° C, for example at 85 ° C or above lie.
  • solid compounds are used in the premix as a carrier of liquids, for example liquid nonionic surfactants or silicone oil and / or paraffins.
  • These compounds can contain water in the above Frame included, the compounds are free-flowing and even at higher Temperatures of at least 45 ° C remain free-flowing or at least conveyable.
  • Free water that is water that is not in any form a solid is bound and is therefore "in liquid form" is preferably done not included in the premix because very small amounts, e.g. around 0.2 or 0.5% by weight, based on the premix, are sufficient to be water-soluble per se To loosen components. This would have the consequence that the melting point or softening point reduced and the end product both in flowability and bulk density would lose.
  • the essentially water-free premixes contain perfume, with at least 0.1% by weight of perfume, based on the premix, being added.
  • fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, Benzyl acetate, ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, Benzyl salicylate, cyclohexyl salicylate, floramate, melusate and jasmine cyclate.
  • DMBCA dimethylbenzylcarbinylacetate
  • ethers include, for example, benzyl ethyl ether and ambroxan, the aldehydes e.g. the linear alkanals with 8 - 18 C atoms, citral, citronellal, citronellyloxy-acetaldehyde, Cyclamenaldehyde, Lilial and Bourgeonal, to the ketones e.g.
  • mixtures are preferred different fragrances, which together make an appealing Generate fragrance.
  • perfume oils can also contain natural fragrance mixtures such as those from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or Ylang-ylang oil.
  • natural fragrance mixtures such as those from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or Ylang-ylang oil.
  • muscatel sage oil chamomile oil, clove oil, lemon balm oil, Mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, Galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and Sandalwood oil.
  • the essentially water-free premix which reaches the press agglomeration, has preferably no dust-like components and in particular no particles with particle sizes less than 200 ⁇ m.
  • Such particle size distributions are particularly preferred, which at least 90 wt .-% particles with a diameter of at least 400 ⁇ m.
  • the washing or cleaning agents or components produced by press agglomeration at least 70% by weight, advantageously at least 80% by weight and with particular preference up to 100% by weight of spherical or almost spherical (pearl-shaped) particles with a particle size distribution, which has at least 60 wt .-% particles between 0.8 and 2.0 mm.
  • the solid and essentially water-free premix contains conventional solid washing and Detergent ingredients such as builders, solid surfactants, bleach, Bleach activators, polymers and other common 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 are.
  • Pre-mixtures are preferably used in the context of the present invention, the individual raw materials and / or compounds that are at room temperature and one Pressure of 1 bar as a solid and not a melting or softening point Have below 45 ° C and optionally up to 20 wt .-%, preferably up to 15 % By weight and in particular up to 10% by weight, based on the premix, at temperatures Contain liquid nonionic surfactants below 45 ° C and a pressure of 1 bar.
  • the premix can be a raw material or contain a compound that as a binding and disintegration aid acts.
  • binding and disintegration aids serve as press agglomeration Lubricants and adhesives that glue the solid components of the premix together and the passage of the premix through the pressure zone of the press agglomeration apparatus facilitate.
  • water-soluble binders they also facilitate redissolution the press agglomerates, since they act as disintegrants in aqueous liquors.
  • this contains Premix at least one raw material or compound that at a pressure of 1 bar and temperatures below 45 ° C in solid form in the press agglomeration but is in the form of a melt, this melt being a polyfunctional, in Water soluble binder serves both function in the preparation of the agents a lubricant as well as an adhesive function for the solid detergent or cleaning agent compounds exercises or raw materials when redissolving the agent in aqueous Fleet has a disintegrating effect.
  • Binders suitable for use in the method according to the invention are available in one Pressure of 1 bar and temperatures below 45 ° C, but are within the process conditions the press agglomeration as a melt. Incorporation of the binders in the premix can be done in such a way that a melt of the binder or binder mixture sprayed onto the premix or the premix is added dropwise.
  • the binder (mixture) can also as a fine solid in the Be premixed.
  • the type of suitable binder and the temperature in the compression step in press agglomeration are interdependent. Since it turned out to be beneficial if the binder in the compression step is as homogeneous as is possible distributed in the material to be compacted, the Compression temperatures are present, at which the binder at least softens, preferably but completely and not only partially in the molten form. Becomes So a binder with a high melting point or high softening point is selected, see above a temperature must be set in the compression step, which ensures the melting of the binder. In addition, depending on the desired composition of the end product also temperature-sensitive raw materials should be able to be processed.
  • the upper temperature limit is determined by the decomposition temperature given the sensitive raw material, it being preferred, significant to work below the decomposition temperature of this raw material.
  • the lower one Limit for the melting point or softening point is therefore of such great importance as a rule at melting points or softening points below 45 ° C an end product is obtained that is already at room temperature and slightly elevated temperatures around 30 ° C, i.e. at summer temperatures and under storage or transport conditions tends to stick. It has proven to be particularly advantageous if a few degrees, for example 2 to 20 ° C, above the melting point or above the Softening point is worked
  • the applicant is of the opinion that due to the homogeneous distribution of the binder within the premix Process conditions of compression of the solid compounds and, if necessary existing individual raw materials in this way enclosed by the binder and then are glued together that the finished end products almost exactly from these many small individual particles that are built up by the binder that the Takes on the role of a preferably thin partition between these individual particles, be held together.
  • the idealized form it can be of a honeycomb-like Structure are assumed, these honeycombs with solids (compounds or individual raw materials) are filled.
  • Binder used, which in a test procedure as described below in a Concentration of 8 g binder in 1 l water at 30 ° C almost within 90 seconds let it solve completely.
  • the binder or binders must therefore be of the type that the adhesive properties even at temperatures that are significantly above the melting point or the softening point lie, still remain. On the other hand, it is also essential for that Choice of the type and amount of the binder (s) used, that the binding Properties are not lost after re-cooling within the end product, the cohesion of the end product is thus assured, but the end product not glued even under normal storage and transport conditions.
  • a binder which is already completely in the form of a melt at temperatures up to a maximum of 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 specific 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 modified polyethylene glycols and polypropylene glycols.
  • the modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12000 and in particular between 1000 and 4000.
  • Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights have between 600 and 6000, preferably between 1000 and 4000.
  • polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C 3 -C 5 glycols and glycerol and mixtures of these as starting molecules. Also included are ethoxylated derivatives such as trimethylol propane with 5 to 30 EO.
  • the preferably used polyethylene glycols can be linear or branched Have structure, with linear polyethylene glycols being preferred in particular.
  • the particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12000, advantageously around 4000, with polyethylene glycols with relative molecular weights below 3500 and above 5000 especially in Combination with polyethylene glycols with a molecular weight around 4000 used and such combinations advantageously to more than 50 wt .-%, based on the total amount of polyethylene glycols, polyethylene glycols with a have molecular weights between 3500 and 5000.
  • a binder also polyethylene glycols are used, which per se at room temperature and a pressure of 1 bar in the liquid state; here is mostly from polyethylene glycol with a relative molecular mass of 200, 400 and 600. Indeed These per se liquid polyethylene glycols should only be mixed with at least another binder can be used, this mixture again according to the invention Requirements must meet, i.e. a melting point or softening point must be 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 12 -alkyl chains which can be linear or branched.
  • the end groups have the alkyl chains between C 1 and C 6 , especially between C 1 and C 4 , 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 initially at room temperature to slightly elevated temperatures, preferably below the melting temperature or the softening point of the binder and in particular at temperatures to 35 ° C mixed together in a conventional mixing and / or granulating.
  • the binders are preferably added as the last component.
  • Your offer can, as already explained above, as a solid, that is at a processing temperature that is below its melting point or softening point, or as a melt respectively.
  • the admixture is advantageous under such conditions carried out that a uniform, homogeneous distribution of the binder in the solid mixture is reached. With very finely divided binders, this can occur at temperatures below 40 ° C, for example at temperatures of the binder between 15 and 30 ° C.
  • the binder advantageously has temperatures where it is already in the form of a melt, i.e. above the softening point, in particular in the form of a complete melt.
  • the melt is at 60 to 150 ° C with particular preference for the temperature range from 80 to 120 ° C.
  • the mixing process which takes up to room temperature slightly elevated temperature, but below the softening point or melting point of the binder occurs, the melt solidifies almost immediately, and the premix according to the invention is in solid, free-flowing form.
  • the mixing process will in any case advantageously continued until the melt has solidified and that Premix is in solid, free-flowing form.
  • the proportion of binder (s) can be reduced. Since the fragrances act as lubricants and, due to 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 premix 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.
  • Incorporation of the perfume into the premix can be done in almost every stage of the premix respectively. So it is possible, for example, part or all of the amount the solids as described above at room temperature in a conventional mixing and / or Submit pelletizer and put the perfume on the moving solid bed or spray on.
  • the perfume can also be combined with the binder as above described to be added to the solids.
  • all of the above Incorporation methods can be combined with one another of the perfume is introduced into the premix in different ways. If in Non-ionic surfactants are used according to the invention, the addition is carried out of the perfume preferably as a mixture with the nonionic surfactants, where Mixtures of binder, nonionic surfactant and perfume can also be produced and used can.
  • the agglomeration of the press By compressing the particle aggregate (premix), the agglomeration of the press on the one hand the porosity is reduced, on the other hand the plastic deformation of the Contact zones reinforce the particle adhesion, which is why materials that are largely plastic let deform, deliver compacts with high strength, while elastically deformable Particles with brittle behavior are more difficult to compress.
  • the compressibility of binders can be improved.
  • the press agglomeration process to which the solid and essentially water-free premix is subjected, can be realized in different devices. Depending on the type of used A distinction is made between agglomerators and different press agglomeration processes.
  • the four most common press agglomeration processes preferred in the context of the present invention are extrusion, roll pressing or compacting, the Hole pressing (pelleting) and tableting, so that in the context of the present invention preferred press agglomeration processes extrusion, roll compacting, pelletizing or tableting processes.
  • the premix compresses and plastifies under pressure and the individual particles are pressed together while reducing the porosity become and stick together.
  • the tools can be heated to higher temperatures or removed cool the heat generated by shear forces.
  • the actual compression process takes place at processing temperatures that are at least in the compression step at least the temperature of the softening point, if not the temperature of the Correspond to 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 be no more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder lies.
  • thermoly sensitive raw materials for example peroxy bleach such as perborate and / or percarbonate, but also enzymes, increasingly without serious Active substance losses can be processed.
  • a temperature of a maximum of 150 ° C preferably a maximum of 100 ° C and especially a maximum 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the temperature effect is preferably in the compression range the press agglomerators a maximum of 2 minutes and is especially in a range between 30 seconds and 1 minute.
  • the compressed material preferably points directly after it leaves the production apparatus Temperatures not above 90 ° C, with temperatures between 35 and 85 ° C are particularly preferred. It has been found that outlet temperatures - before especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, particularly advantageous are.
  • 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 extruded under pressure and the strand is cut to the predeterminable size of the granulate by means of a cutting device after it has emerged from the hole shape.
  • 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.
  • plasticizers and / or lubricants are surfactants and / or polymers which, in the context of the present invention, with the exception of the nonionic surfactants mentioned above, are not introduced into the premix in liquid and in particular not in aqueous, but in solid form.
  • the premix is preferably continuously one Planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guide supplied, its housing and whose extruder pelletizing head must be heated to the predetermined extrusion temperature can.
  • the premix is mixed in under the shear of the extruder screws Pressure, which is preferably at least 25 bar, depending on extremely high throughputs of the apparatus used but can also be below it, compressed, plasticized, in the form of fine strands through the perforated nozzle plate in the extruder head and finally, preferably the extrudate by means of a rotating knock-off knife reduced spherical to cylindrical granules.
  • the hole diameter of the Perforated nozzle plate and the strand cut length are based on the selected granule dimension Voted.
  • the production of granules is successful an essentially uniformly predeterminable particle size, in particular the absolute particle sizes can be adapted to the intended application. In general, particle diameters up to at most 0.8 cm are preferred.
  • granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from about 0.8 to 3 mm.
  • the length / diameter ratio of the chipped primary In an important embodiment, granules are in the range from about 1: 1 to about 3: 1.
  • the still plastic primary granulate to another to supply shaping processing step; the raw extrudate is present Rounded edges so that ultimately spherical to approximately spherical extrudate grains can be obtained.
  • small amounts of can be added at this stage
  • Dry powder for example zeolite powder such as zeolite NaA powder, can also be used. This shape can be done in standard rounding machines.
  • extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (Amandus Kahl) or in the Bepex extruder.
  • the invention now provides that the Temperature control in the transition area of the screw, the pre-distributor and the nozzle plate is designed such that the melting temperature of the binder or the upper one Limit of the melting range of the binder is at least reached, but preferably exceeded becomes.
  • the duration of the temperature influence is in the compression range the extrusion preferably less than 2 minutes and in particular in one area 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. Under these process conditions, in addition to the previously mentioned modes of action, 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 to processing in continuously operating mixers / granulators or rollers, for example.
  • a further shaping processing step supply in particular a rounding
  • the particle size distribution of the premix is much broader than that of the invention manufactured and end product according to the invention.
  • the premix can be essential Larger fractions of fine grains, even dust, possibly also coarser grains Contain proportions, but it is preferred that a premix with relatively broad Particle size distribution and relatively high proportions of fine grain in an end product transferred relatively narrow particle size distribution and relatively small proportions of fine grain becomes.
  • the process of the invention is essentially anhydrous - i.e. with the exception water-free ("impurities") of the solid raw materials used - is carried out is not only the risk of gelling the surfactant raw materials already minimized to excluded in the manufacturing process, in addition also an ecologically valuable process is provided because by omitting a subsequent one Drying step not only saves energy but also emissions, such as they mainly occur with conventional types of drying, can be avoided. In addition, the omission of subsequent drying steps enables the Incorporation of the fragrances into the premix and thus the production of fragrance-reinforced Detergents or cleaning agents or components therefor.
  • the invention Process carried out by means of roller compaction.
  • the fragrance-containing solid and essentially water-free premix between metered in two smooth rollers or with recesses of a defined shape and between the two rollers under pressure to form a leaf-shaped compact, the so-called Schülpe, rolled out.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rollers you get smooth, unstructured coulter bands while correspondingly structured slugs are produced by using structured rollers can be in which, for example, certain forms of the later detergent or cleaning agent particles can be specified.
  • the cuff band is below broken down into smaller pieces by a knock-off and crushing process and can processed in this way to granules, which are known by others Surface treatment processes refined, especially in an approximately spherical shape can be brought.
  • the temperature of the pressing tools is also in the case of roller compacting the rollers, preferably at a maximum of 150 ° C, preferably at a maximum of 100 ° C and in particular at a maximum of 75 ° C.
  • Particularly preferred manufacturing processes work for Roll compacting with process temperatures that 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 exposure in the compression area of the smooth or with depressions of defined Molded rollers is a maximum of 2 minutes and especially in one area is 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. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers.
  • the press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.
  • An apparatus suitable for carrying out the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH).
  • the ring die press disclosed in this document consists of a rotating ring die interspersed with 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 pelleting temperature is also the temperature of the pressing tools Pressure rollers or press rolls, preferably at a maximum of 150 ° C, preferably at a maximum 100 ° C and especially at a maximum of 75 ° C.
  • Particularly preferred manufacturing processes work in roller compacting with process temperatures that are 10 ° C, in particular maximum 5 ° C above the melting temperature or the upper temperature limit of the Melting range of the binder.
  • Another press agglomeration process which can be used according to the invention is the tableting. Due to the size of the molded body, it can be Tableting may be useful, in addition to the binder, customary disintegration aids, for example to add cellulose and its derivatives or cross-linked PVP, which the Ease disintegration of the compacts in the wash liquor.
  • a fragrance-reinforced extruded, roller-compacted or pelletized detergent which is at least 80 % By weight of compounds and / or treated raw materials produced according to the invention consists.
  • the remaining ingredients can be made by any known method and have been mixed. However, it is preferred that these remaining constituents, which compounds and / or treated raw materials can be, according to the invention Processes were made. In particular, this enables Basic granules and remaining components 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 washing or cleaning agents, which generally further increases the bulk density.
  • a preferred aftertreatment is also the procedure according to German patent applications DE-A-195 24 287 and DE-A-195 47 457 , dusty or at least finely divided ingredients (the so-called fine fractions) of the particulate end products of the process, which are the core serve, be glued and thus arise means that have these so-called fine particles as an outer shell.
  • For melt agglomeration of the fine fractions of the base granules according to the invention and produced according to the invention reference is expressly made to the disclosure in German patent applications DE-A-195 24 287 and DE-A-195 47 457
  • 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, ie powdering and spraying with perfume, can also 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 introduced into the agents via the manufacturing method according to the invention, ie into Press agglomerates incorporated, while the remaining 70 wt .-%, preferably 60 wt .-% and in particular 50 wt .-% of the total perfume contained on the press agglomerates, which can optionally be surface-treated, sprayed or otherwise applied.
  • fragrances should be volatile, in addition to the nature of the functional groups and the Structure of the chemical compound also the molecular weight plays an important role. So most fragrances have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Because of the different Volatility of fragrances changes the smell of one of several fragrances composite perfume or fragrance during evaporation, wherein the smell impressions in "top note” (top note), “heart or middle note” (middle note or body) and “base note” (end note or dry out).
  • the top note is largely based on the smell intensity of a perfume or fragrance not only from volatile compounds, while the Base note for the most part from less volatile, i.e. adherent refractories.
  • perfumes for example, more volatile fragrances certain fixatives are bound, which prevents them from evaporating too quickly becomes.
  • the above-described embodiment of the present invention in which the more volatile fragrances or fragrances are incorporated into the press agglomerate, is such a method for fragrance fixation.
  • classification of Fragrance in "more volatile” or "sticky” fragrance is so about the odor impression and whether the corresponding fragrance is perceived as a top or heart note nothing is said.
  • Adhesive fragrances 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, champaca flower oil, noble fir oil, noble pine cone oil, elemi oil, Eucalyptus oil, fennel oil, spruce oil, galbanum oil, geranium oil, ginger grass oil, Guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, kajeput oil, calamus oil, Chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copaiva balsam oil, Coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, Lime oil, mandarin oil, lemon balm oil, musk seed oil, myrrh oil, clove oil, Neroli oil, ni
  • fragrances can be used in the context of the present invention as adhesive odoriferous substances or Fragrance mixtures, i.e. fragrances.
  • These connections include the compounds mentioned below and mixtures of these: ambrettolide, ⁇ -amylcinnamaldehyde, Anethole, anisaldehyde, anis alcohol, anisole, anthranilic acid methyl ester, Acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, Benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol, bornyl acetate, ⁇ -bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl
  • the more volatile fragrances include in particular the lower-boiling fragrances natural or synthetic origin, used alone or in mixtures can be.
  • 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 especially anionic surfactants, at least in amounts of 0.5% by weight in the agents according to the invention or according to the invention manufactured means should be included.
  • surfactants especially anionic surfactants, at least in amounts of 0.5% by weight in the agents according to the invention or according to the invention manufactured means should be included.
  • anionic surfactants include in particular sulfonates and sulfates, but also soaps.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12 -C 18 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 obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated Methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which by ⁇ -sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble Mono salts are made into consideration.
  • ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids also sulfonation products of unsaturated fatty acids, for example Oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight, can be present.
  • ⁇ -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 methyl esters of ⁇ -sulfofatty acids
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures as they are produced by esterification by a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of Triglycerides with 0.3 to 2 moles of glycerol can be obtained.
  • the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are particularly preferred from the point of view of washing technology.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat . Nos . 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN (R) , are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 -C 18 -Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are fatty acid derivatives of amino acids, for example of N-methyl taurine (tauride) and / or of N-methyl glycine (sarcoside).
  • the sarcosides or sarcosinates are particularly preferred, and above all Sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate.
  • anionic surfactants include, in particular, soaps, preferably in quantities from 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.
  • these soaps or the known alkenyl succinic acid salts can also be used as a substitute for soaps be used.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or triethanolamine, available.
  • the anionic surfactants are preferably in the form of their sodium or Potassium salts, especially in the form of the sodium salts.
  • the anionic surfactants are in the agents according to the invention or are in the agents according to the invention Process preferably in amounts of 1 to 30 wt .-% and in particular contained or used in amounts of 5 to 25 wt .-%.
  • nonionic surfactants are 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 residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used, as described above. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x , in which R 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.
  • polyhydroxy fatty acid amides of the formula (I) in which R 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, especially from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 is a linear, branched or cyclic alkyl radical or an aryl radical is 2 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 is a linear, branched or cyclic alkyl radical or an
  • [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 12 -C 18 fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are preferred as nonionic surfactants, while, as described above, especially higher ethoxylated fatty acid methyl esters are advantageous as binders.
  • C 12 -C 18 fatty acid methyl esters with 10 to 12 EO can be used both as surfactants and as binders.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amide can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.
  • gemini surfactants can be considered as further surfactants.
  • the two hydrophilic groups and two have hydrophobic groups per molecule. These groups are usually by one so-called “spacers” separated from each other. This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient Distance so that they can act independently of each other.
  • Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water.
  • Gemini surfactants does not only refer to dimeric, but also understood trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis- and trimeral alcohol tris-sulfates and ether sulfates according to German patent application DE-A-195 03 061.
  • End group-blocked dimeric and trimeric mixed ethers according to German patent application DE-A-195 13 391 is particularly characterized by its 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 belong above all on the most important ingredients of washing 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 in the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 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. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .y H 2 O are preferred.
  • the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release 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” also means “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 provide 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 are also used as builder substances possible, provided that such use is not avoided for ecological reasons should be.
  • the sodium salts of orthophosphates, pyrophosphates are particularly suitable and especially the tripolyphosphates.
  • Your salary in general is not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished funds.
  • tripolyphosphates in particular even in small quantities up to a maximum of 10% by weight, based on the finished agent, in Combination with other builder substances to a synergistic improvement of the Secondary washing power.
  • 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. However, smectites, in particular bentonites, are preferred here.
  • Suitable sheet 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 from 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.
  • Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if 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 from these.
  • the acids themselves can also be used.
  • the acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents.
  • succinic acid succinic acid
  • glutaric acid glutaric acid
  • Adipic acid Adipic acid
  • gluconic acid any mixtures of these.
  • these acids if they are used in the premix according to the invention and not are subsequently added, used anhydrous.
  • 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 methods, for example acid or enzyme catalysis. 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 and 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 are known.
  • 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 are 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 . Suitable amounts used in formulations containing zeolite and / or silicate are from 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • 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 from 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been particularly suitable Maleic acid proved to be 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
  • Their relative molecular weight, based on free acids is in general 5000 to 200000, preferably 10000 to 120000 and in particular 50000 to 100000.
  • the content of (co) polymeric polycarboxylates in the compositions is in 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 which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • 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 that make the oil and fat washable made of textiles. This effect is particularly evident if a textile is soiled, which has previously been repeatedly with an inventive Detergent containing this oil and fat-dissolving component has been washed.
  • the preferred oil- and fat-dissolving components include, for example, non-ionic ones Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and that from the Polymers of phthalic acid and / or terephthalic acid known from the prior art or of their derivatives, 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 acid and the terephthalic acid polymers.
  • Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on
  • 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 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 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, bleaches 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.
  • Acid can also be used to reduce the pH of detergents or cleaning agents
  • Salts or slightly alkaline salts can be used.
  • Acidifying components Bisulfates and / or bicarbonates or the above-mentioned organic polycarboxylic acids, which can also be used as builder substances at the same time.
  • citric acid which is either added subsequently (usual procedure) or - in anhydrous form - in a solid premix is used.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid 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.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-diacetyloxy, 2,5-ethylene glycol 2,5-dihydrofuran and the enol esters known from German patent
  • 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 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • the salts of polyphosphonic acids are preferably the neutral sodium salts for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5 wt .-% used.
  • enzymes from the hydrolase class such as proteases, Lipases or lipolytically active enzymes, amylases, cellulases or mixtures thereof in question.
  • Oxireductases are also suitable.
  • Bacterial strains or fungi such as Bacillus subtilis and Bacillus are particularly suitable licheniformis, Streptomyces griseus and Humicola insolens Agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic acting enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytically acting enzymes and cellulase, in particular, however, mixtures or mixtures containing protease and / or lipase with lipolytic enzymes of particular interest.
  • the well-known cutinases are lipolytic enzymes. Also peroxidases or oxidases have proven to be suitable in some cases.
  • amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases that also called cellobiases, or mixtures of these are used. Because the different Distinguish cellulase types by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases become.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
  • 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.
  • calcium salts 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 H 2 B 4 O 7 ), is particularly advantageous.
  • Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, 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 cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Soluble starch preparations can also be used and use starch products other than the above, e.g. degraded starch, Aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methyl carboxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone for example in amounts of 0.1 to 5 wt .-%, based on the agent used.
  • the agents can be derivatives of diaminostilbenedisulfonic acid or whose alkali metal salts contain. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which, instead of the morpholino group, have a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
  • 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.
  • the perfume oil was dissolved in the liquid C 12-18 fatty alcohol with 7 EO before being added to the mixer. After leaving the mixer, the free-flowing premix had a bulk density of 450 g / l and was placed in a twin-screw extruder from Lihotzky and plasticized and extruded under pressure.
  • the plasticized premix left the extruder at a pressure of 85 bar Perforated plate with 1.4 mm diameter holes.
  • the extruded strands were measured with a rotating knives to a length / diameter ratio of cut off approx. 1 and rounded in a Marumerizer®.
  • extrudates E1 and E2 produced according to the invention which differed in the perfume oils used, were now compared with extrudates V1 and V2 of the same composition, in which the perfume oils in question were sprayed onto the extruded and rounded particles, which were powdered with finely divided zeolite, in a customary procedure 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 extrudate 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 as well as of 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". Since 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 The results of the smell tests are summarized in Table 4.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Claims (26)

  1. Procédé de préparation d'un produit lessiviel au parfum renforcé, ou de ses composants, ayant à cet effet une densité apparente supérieure à 600 g/l, caractérisé en ce que l'on prépare un pré-mélange solide, dont la teneur en eau liquide - c'est-à-dire ne se trouvant pas sous forme d'eau d'hydratation et/ou d'eau de constitution - est inférieure à 2 % en poids, à partir de compounds (mélanges de composants) et/ou de matières premières de produits lessiviels, qui contient au moins 0,1 % en poids de parfum par rapport au pré-mélange, on soumet ensuite ce pré-mélange à une agglomération par pressage, le pré-mélange contenant des liants qui se présentent sous forme de masse fondue déjà à des températures allant au maximum jusqu'à 130°C et l'incorporation des liants s'effectuant à des températures auxquelles les liants se présentent sous forme de masse fondue.
  2. Procédé selon la revendication 1, caractérisé en ce que le pré-mélange présente une teneur totale en eau qui n'est pas supérieure à 15 % en poids, cette eau n'étant pas sous forme libre, et de préférence, la teneur en eau non liée à des zéolithes et/ou à des silicates n'est pas supérieure à 10 % en poids et en particulier, n'est pas supérieure à 7 % en poids.
  3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que l'on met en oeuvre un pré-mélange qui contient des matières premières individuelles et/ou des compounds qui sont solides à la température ambiante sous une pression de 1 bar et présentent un point de fusion ou de ramollissement qui n'est pas inférieur à 45°C, et éventuellement, une proportion allant jusqu'à 20 % en poids, de préférence jusqu'à 15 % en poids et en particulier, jusqu'à 10 % en poids, par rapport au pré-mélange, de tensioactifs non ioniques liquides à une température inférieure à 45°C et sous une pression de 1 bar.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'en plus des constituants solides, le pré-mélange contient une proportion allant jusqu'à 20 % en poids, de préférence jusqu'à 15 % en poids et en particulier, jusqu'à 10 % en poids, de tensioactifs non ioniques liquides à une température inférieure à 45°C sous une pression de 1 bar, en particulier des alcools alcoxylés mis en oeuvre habituellement dans les produits lessiviels, tels que les alcools gras ou les alcools oxo ayant une longueur de chaíne carbonée qui comprend de 8 à 20 atomes de carbone et en particulier en moyenne, de 3 à 7 unités oxyde d'éthylène par molécule d'alcool, l'adjonction des tensioactifs non ioniques liquides s'effectuant de préférence en mélange avec le parfum.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le pré-mélange contient au moins une matière première ou un compound qui se présente sous forme solide sous une pression de 1 bar et à une température inférieure à 45°C, mais qui, lors de l'agglomération par pressage, se présente sous forme de masse fondue, cette masse fondue servant de liant polyfonctionnel hydrosoluble lequel, lors de la préparation, remplit la fonction d'un agent lubrifiant et également une fonction d'adhérence pour les compounds ou les matières premières du produit lessiviel solides, mais se désintègre lors de la re-dissolution du produit lessiviel dans un bain aqueux.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le pré-mélange contient un ou plusieurs liants qui, à une concentration de 8 g dans 1 litre d'eau à 30°C, se dissolvent presque complètement en 90 secondes.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le liant est introduit en dernier dans le pré-mélange, son incorporation s'effectuant dans des conditions qui permettent d'obtenir une répartition aussi uniforme, homogène que possible - sous forme de masse fondue solidifiée ou sous forme de poudre - dans le mélange de substances solides.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que l'incorporation du liant s'effectue à une température à laquelle celui-ci se présente sous la forme d'une masse fondue, la température de cette masse fondue étant comprise entre 60 et 150°C, en particulier dans la gamme de température de 80 à 120°C.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que l'opération de brassage est poursuivie aussi longtemps que la masse fondue se solidifie et que le pré-mélange se présente sous forme solide s'écoulant librement.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que l'on met en oeuvre un pré-mélange dont la teneur en liant ou liants est d'au moins 1 % en poids, mais inférieure à 10 % en poids, de préférence inférieure à 8 % en poids, et en particulier de 2 à 4 % en poids, toujours par rapport au pré-mélange.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que le produit compacté présente, immédiatement après sa sortie du dispositif de préparation, une température qui n'est pas supérieure à 90°C, de préférence comprise entre 35 et 85°C et en particulier, entre 40 et 80°C, par exemple une température ne dépassant pas 70°C.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que le pré-mélange contient une proportion de parfum supérieure à 0,15 % en poids, de préférence supérieure à 0,2 % en poids et en particulier, supérieure à 0,3 % en poids.
  13. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce qu'une partie ou la totalité des substances solides à la température ambiante est disposée dans un mélangeur et/ou granulateur usuel, et que le parfum est répandu sur le lit fluidisé de substances solides, ou pulvérisé sur celui-ci.
  14. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que le parfum est ajouté aux substances solides conjointement avec le liant.
  15. Procédé selon l'une quelconque des revendications 1 à 14, caractérisé en ce que l'opération d'agglomération par pressage est une opération d'extrusion, de compactage par laminage, de pelletisation ou de pastillage.
  16. Procédé selon la revendication 15, caractérisé en ce que les outils de travail du dispositif d'agglomération par pressage (la ou les vis de l'extrudeuse, le ou les cylindres du compacteur ainsi que le ou les cylindres de pressage du pelletiseur) sont à une température maximale de 150°C, de préférence à une température maximale de 100°C et en particulier, à une température maximale de 75°C, et que la température du procédé est supérieure au plus de 30°C et en particulier au plus de 20°C au dessus de la température de fusion, respectivement de la limite de température supérieure de la zone de fusion du liant.
  17. Procédé selon la revendication 15, caractérisé en ce que la durée de l'application de la température dans la zone de compression du dispositif d'agglomération par pressage est de 2 minutes au maximum et en particulier, comprise dans une plage allant de 30 secondes à 1 minute.
  18. Procédé selon l'une quelconque des revendications 1 à 17, caractérisé en ce que la préparation s'effectue par extrusion, le pré-mélange étant compacté, plastifié, extrudé sous pression en un boudin à travers la plaque de buses perforée d'une tête d'extrudeuse et enfin, réduit en granules de forme sphérique (perles) à cylindrique au moyen d'un couteau et que le réglage de la température dans la zone de transition de la vis d'extrudeuse, du pré-répartiteur et de la plaque de buses est ajusté de telle façon, que la température de fusion du liant ou la limite supérieure de la zone de fusion du liant soit au moins atteinte, mais de préférence dépassée.
  19. Procédé selon l'une quelconque des revendications 1 à 17, caractérisé en ce que la préparation s'effectue par compactage par laminage, le pré-mélange étant, sous pression, compacté, plastifié, pressé entre les cylindres sous la forme d'une feuille compacte ("bande") et enfin, réduit en granulé à l'aide d'un dispositif de découpage et de broyage.
  20. Procédé selon l'une quelconque des revendications 1 à 17, caractérisé en ce que la préparation s'effectue par pelletisation, le pré-mélange étant, sous pression, compacté, plastifié, pressé à travers une plaque perforée à l'aide d'un cylindre rotatif, sous la forme d'un boudin fin, et enfin, réduit en granulé à l'aide d'un dispositif de découpage.
  21. Produit lessiviel au parfum renforcé, caractérisé en ce qu'il est constitué d'au moins 80 % en poids d'un composant préparé selon l'invention, les autres constituants étant, de façon particulièrement avantageuse, également des compounds ou des matières premières traitées qui ont été préparés selon l'une quelconque des revendications 1 à 20.
  22. Produit lessiviel au parfum renforcé selon la revendication 21, caractérisé en ce qu'il présente, en tant que gaine extérieure, des constituants pulvérulents ou au moins finement divisés (appelés fines) qui ont été encollés par agglomération par fusion.
  23. Produit lessiviel au parfum renforcé selon la revendication 21 ou 22, caractérisé en ce que le parfum est aspergé ultérieurement sur le produit.
  24. Produit lessiviel au parfum renforcé selon la revendication 23, caractérisé en ce qu'une proportion d'au moins 30 % en poids, de préférence d'au moins 40 % en poids et en particulier d'au moins 50 % en poids du parfum contenu en totalité dans le produit a été introduite au cours du procédé de préparation selon l'une quelconque des revendications 1 à 20.
  25. Produit lessiviel au parfum renforcé selon la revendication 24, caractérisé en ce que la fraction du parfum qui a été introduite dans le produit au cours du procédé de préparation selon l'une quelconque des revendications 1 à 20 est principalement constituée de matières odorantes adhérentes.
  26. Produit lessiviel au parfum renforcé selon la revendication 24, caractérisé en ce que la fraction du parfum qui a été introduite dans le produit au cours du procédé de préparation selon l'une quelconque des revendications 1 à 20 est principalement constituée de matières odorantes volatiles.
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

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EP1025198B1 true EP1025198B1 (fr) 2003-08-06

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EP (1) EP1025198B1 (fr)
JP (1) JP2001521060A (fr)
CN (1) CN1276829A (fr)
AT (1) ATE246727T1 (fr)
DE (2) DE19746781A1 (fr)
ES (1) ES2205570T3 (fr)
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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
WO2003097723A1 (fr) * 2002-05-14 2003-11-27 E.I. Du Pont De Nemours And Company Emballage et conteneurs fabriques a partir de polyamides solubles dans l'eau et procedes de fabrication de ceux-ci
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
JP2012502173A (ja) * 2008-09-10 2012-01-26 ダニスコ・ユーエス・インク 酵素性繊維品漂白組成物及びその使用方法
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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ES2205570T3 (es) 2004-05-01
DE19746781A1 (de) 1999-04-29
WO1999021955A1 (fr) 1999-05-06
EP1025198A1 (fr) 2000-08-09
CN1276829A (zh) 2000-12-13
PL340036A1 (en) 2001-01-15
DE59809226D1 (de) 2003-09-11
ATE246727T1 (de) 2003-08-15
US6228833B1 (en) 2001-05-08
JP2001521060A (ja) 2001-11-06

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