EP1807498B1 - Procede de preparation des granules / agglomerats pour compositions detergentes - Google Patents

Procede de preparation des granules / agglomerats pour compositions detergentes Download PDF

Info

Publication number
EP1807498B1
EP1807498B1 EP05800573A EP05800573A EP1807498B1 EP 1807498 B1 EP1807498 B1 EP 1807498B1 EP 05800573 A EP05800573 A EP 05800573A EP 05800573 A EP05800573 A EP 05800573A EP 1807498 B1 EP1807498 B1 EP 1807498B1
Authority
EP
European Patent Office
Prior art keywords
particles
advantageously
admixable
granules
chargeable
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.)
Not-in-force
Application number
EP05800573A
Other languages
German (de)
English (en)
Other versions
EP1807498B2 (fr
EP1807498A2 (fr
Inventor
Wilfried Rähse
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=35520649&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1807498(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from DE200410053385 external-priority patent/DE102004053385A1/de
Priority claimed from DE200510036346 external-priority patent/DE102005036346A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL05800573T priority Critical patent/PL1807498T3/pl
Publication of EP1807498A2 publication Critical patent/EP1807498A2/fr
Application granted granted Critical
Publication of EP1807498B1 publication Critical patent/EP1807498B1/fr
Publication of EP1807498B2 publication Critical patent/EP1807498B2/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • 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
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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 process for the preparation of granules or agglomerates for detergents or cleaners.
  • the respective aggregates / agglomerates / granules can be used and used advantageously in the washing or cleaning agent industry.
  • so-called pouches have been developed. These are offer forms in which the actual washing or cleaning agent, wrapped in films, in such an amount, the so-called disposable portions are present.
  • the consumer can now take such a pouch and place it in the washing drum and is the manual dosing of the detergent or cleaning agent unbound. This ensures that the consumer can not contaminate with the detergent or cleaning agent, for example, in which he pours it as a result of an unfortunate skill on the hands.
  • a significant disadvantage of such a technology is that the individual dosability with the use of pouches is more or less lost.
  • the consumer can only think about whether he wants to give 1 or 2 pouches for washing, but a fine adjustment of the dosage is not possible. For this reason, consumers often avoid the use of the pouches to keep the dosing sovereignty.
  • EP 179 264 A1 relates to a process for the preparation of a granular detergent component containing (a) alkoxylated nonionic surfactants, (b) inorganic carriers, (c) other organic detergents and (d) adsorptively or hydrate bound water, whereby to obtain the detergent component sprayed aqueous approach using nozzles under a pressure in a drying tower. The procedure described there results in a spray-dried powder.
  • EP 1 186 652 A1 describes the preparation of pellets wherein a slurry is dried using a countercurrent spray dryer and the resulting powder is then fed along with other ingredients to a continuous kneader and then pelletized. The resulting pellets have no core-shell nature. These pellets are then subjected to a pulverization and granulation process and further treated in other ways.
  • sucrose particles are sprayed with an aqueous protease solution, which further comprises sucrose and corn starch, resulting in coated sucrose particles. These particles are then further sprayed with an aqueous solution of magnesium sulfate and then further sprayed with an aqueous solution comprising titanium dioxide, methyl cellulose and other ingredients. The resulting particles have more than 5% by weight of enzymes.
  • the object of the present invention was to provide a form of supply in the field of detergents which satisfies the consumer need for increased safety comfort in the application.
  • the advantage of the invention lies in the increased safety comfort for the consumer in the application.
  • Powdered detergents and cleaners may be like other particulate solid systems in their handling, such as during storage or filling, release dust.
  • dusts released in this way may jeopardize or impair human health, for example by inadvertently inhaling larger quantities of dust.
  • Um colllvorêtn Even with simple Um colllvorticiann it can namely come to an undesirable dust release.
  • the dusting tendency of the washing or cleaning agent is minimized, so that, for example, the danger of inhaling dust tends to zero.
  • this invention is of great importance, as it realizes the concept to combat dust even before the emergence. This is the safest way to consistently prevent a human health hazard associated with dust.
  • the air flow through the granules / agglomerates causes them to be whirled up.
  • the resulting dust is carried away by the air stream and collected on a filter (filter Whatman, type: glass fiber microfilter GF / C Circles, pore size 1.2 ⁇ m: 150mm diameter).
  • the dust mass can then be determined gravimetrically quantitatively.
  • the dust determination with the elution method is always carried out as a multiple determination, at least as a triple determination, preferably as a quadruple, quintuple or sixfold determination, whereby the mean value from the multiple determinations serves as measured value (dust value). This gives the dust value (synonym: dust content) in mg based on 60 g of granules / agglomerate.
  • the statement that the dust value (dust content) "on average" is smaller than eg 2000 mg / 60 g should indicate that the dust value (dust content) is the result of a multiple determination, ie that the elutriation method was used several times to determine the dust value ( Dust content).
  • the Elutriationsmethode simulates the dust formation of granules / agglomerates, as it occurs during light use, eg during transfer.
  • the elutriation method is therefore the method of choice to capture those stresses and conditions that are usually present in the consumer budget.
  • a further advantage of the article according to the invention is an improved stability and improved shelf life of the granules / agglomerates compared with conventional products.
  • This process allows the production of largely spherical and very low-dust or dust-free and abrasion-resistant granules.
  • this process according to the invention is characterized in that the resulting granules have a dust content (according to the elutriation method described here). of on average less than 2500 mg / 60g, preferably on average less than 2000 mg / 60g with bulk densities of the coated core-shell aggregate ⁇ 500 g / l, or of on average less than 2000 mg / 60g.
  • the coated core-shell aggregate of 501 to 700 g / l Preferably, on average less than 1500 mg / 60 g at bulk densities of the coated core-shell aggregate of 501 to 700 g / l, or of on average less than 1500 mg / 60g, preferably on average less than 1200 mg / 60 g in bulk densities of the coated core-shell aggregate of from 701 to 850 g / l, or of on average less than 700 mg / 60 g, preferably on average less than 600 mg / 60 g at bulk densities of the coated core-shell aggregate of> 851 g / l, depending on the bulk density of the granules.
  • the specific power of the mixer / granulator less than 8 kW / m 3 , advantageously less than 5 kW / m 3 , preferably less than 3 kW / m 3 , in particular is less than 1.5 kW / m 3 , which corresponds to a preferred embodiment of the invention.
  • low energy introduction means an economic advantage over the energy consumption, but in particular a particularly gentle agglomeration without appreciable destruction of already formed granules takes place in this way.
  • mixer / granulator preferably drum and plate mixers and / or fluidized bed granulators, but also single- and two-shaft mixers with fast to slow rotating shafts and Zig-Zag mixers, especially discontinuous machines with low specific energy input.
  • the particles in the mixer preferably move over the free fall or by introducing a thrust, throw or centrifugal force. Free-fall mixers are preferably used.
  • mixer / granulator means any apparatus suitable for mixing / granulating.
  • granulation or granulation foam can be used. It should be noted at this point that a granulation foam is not granulation liquid.
  • a foam is a complex structure or agglomerate of gas-filled, spherical or polyhedron-shaped cells or bubbles which are bounded by liquid, semi-liquid, highly viscous or solid cell webs, but it is not a liquid.
  • foams usually have a much lower density than liquids and, for example, react quite differently than fluids to compression or mechanical stress.
  • granulation liquids preferably water or aqueous solutions can be used, but advantageously also other granulation aids than water, for example liquid nonionic surfactants, polyethylene glycols or other organic solvents.
  • aqueous granulation liquids for example, salts, water glass, alkyl polyglycosides, carbohydrates, natural polymers, synthetic polymers, eg. Cellulose ethers, starch, polyethylene glycol, polyvinyl alcohol and / or biopolymers such as e.g. Containing xanthan gum.
  • water-containing organic solvents with swollen polymers it is also possible to melt suitable substances
  • the granules produced by this process are free-flowing, nearly spherical and therefore aesthetically very attractive.
  • the granules are well pourable and pourable even after long storage and show no tendency to clumping.
  • the contact area between the individual particles is significantly minimized.
  • This minimization of the contact area between the respective particulate particles is very advantageous because it prevents the particles from intensely contacting each other and thereby interacting by, for example, sticking together. The likelihood of sticking or baking is thus significantly reduced here.
  • the process according to the invention leads only to a negligible extent to granules whose diameters are so small that they fit into the spaces formed by the other particulate particles.
  • the most extensive absence of relatively small granules in relation to the other particles, which in particular have a diameter of less than 0.16 ⁇ d 90 is advantageous because the incorporation of small granules in the cavities formed causes an undesirable significant increase in contact area between the particles What would be associated with increased interaction of the individual granules, which should be avoided.
  • the diameter d 50 of the particles to be prepared is in the range of 0.15 to 5 mm, preferably in the range of 0.2 to 2 mm, in particular in the range of 0.3 to 1 mm.
  • the granules resulting from the process have, in particular, a comparatively large diameter if the particles to be present already have a large diameter, while in particular smaller granules result, if the particles to be present already have a rather small diameter.
  • the process according to the invention is suitable both with regard to granules with particularly large particle diameters, for example with diameters of above 2 to 5 or 10 mm or greater, and also with smaller particulate particles in the range of 0.3 and 2 mm or smaller is advantageous.
  • the resulting advantages are substantially independent of the diameter of the particulate particles, since the contact area between the individual particulate particles is very low, so that undesirable interactions and interactions between the individual particles are minimized ,
  • the particle size distribution is thus freely adjustable, which is an important advantage of the method according to the invention.
  • the particles resulting from the process according to the invention it may be preferable to obtain rather small particulate particles.
  • the particles to be submitted rather small may have a particle size in the range of 0.1 to 0.4 mm.
  • Particulate particles of smaller diameters have the advantage that the means consisting of them usually have a high bulk density. This in turn leads advantageously to a significant reduction in the packaging volume.
  • particulate particles having a relatively small particle size are also advantageous if they are to dissolve as quickly as possible, as is often desired, for example with regard to detergents and / or cleaning agents.
  • rather small particulate particles according to the invention advantageously combine high bulk densities on the one hand and, if appropriate, good dispersibility and solubility - for example in the flushing phase of a washing powder in conventional household washing machines.
  • the inventive concept also offers advantages in terms of very large granules with a particle size of, for example, up to 5 mm in diameter or up to 10 mm in diameter or even beyond, such.
  • the user has the opportunity to specifically pick out, assemble and use the granules of defined composition, which may be colored differently.
  • the ratio of d 50 to d 90 of the particles to be submitted is at least 0.5, preferably at least 0.6, advantageously at least 0.75 and in particular 0.8, where d 50 represents the median value.
  • the median value is defined as the particle size below and above which 50% of the particle quantity is located.
  • 90% of the particle quantity is below the value, ie 10% higher.
  • the ratio d 50 / d 90 approaches the value of 1 at very narrow particle size distributions, or is well below 0.5 for broad distributions.
  • the granulation aid is a granulation foam.
  • express reference is made to the German Offenlegungsschrift DE 101 24 430 A1 Henkel KGaA.
  • a granulation process is described in which a flowable component is charged with a gaseous medium and thereby foamed and the resulting foam is subsequently added to a charged in a mixer solid bed.
  • the foam generation takes place under a pressure which is above the pressure in the granulation plant.
  • the particles of the process according to the invention to be added have a particle diameter d 50 which is at most 1/12, preferably at most 1/14, advantageously at most 1/16, in a further advantageous manner at most 1/18, more preferably at most 1/20, in more preferably, a maximum of 1/22, most preferably a maximum of 1/24 and in particular a maximum of 1/26 of the particle diameter d 50 of the particles to be submitted is again a preferred embodiment of the invention.
  • the reduction of the particle diameter d 50 in the manner described results in that particularly spherical granules / agglomerates are formed.
  • the particles to be added of the process according to the invention have a particle diameter d 50 which is in the range 3 to 50 ⁇ m, preferably 4 to 30 ⁇ m, advantageously 5 to 20 ⁇ m, in particular 6 to 12 ⁇ m, then a particularly preferred embodiment of the invention is present.
  • the reduction of the particle diameter d 50 does not go so far that the particles to be added would be equivalent to a powder.
  • the particles to be added are advantageously not powder.
  • powder is a kind of flour, ie an accumulation of solid particles having a particle size preferably below 100 nm. It is also advantageous for process-technical reasons, if the particles do not fall below a certain minimum size.
  • the particles to be added have a particle diameter d 50 which is preferably at least 1/100, advantageously at least 1/80, more preferably at least 1/70, more preferably at least 1/60, even more advantageous Way is at least 1/50, in an extremely advantageous manner at least 1/40 and in particular at least 1/35 of the particle diameter d 50 of the particles to be submitted.
  • the particles to be present are less than 50% by weight, preferably less than 45% by weight, advantageously less than 40% by weight, more preferably from 15 to 35% by weight, in particular from 20 to 30% by weight, and the particles to be added more than 50 wt .-%, preferably more than 55 wt .-%, more preferably more than 60 wt .-%, more preferably 65 to 85 wt .-%, in particular 70 to 80 wt. - Make up% of the solids involved in the granulation process, then there is a further preferred embodiment of the invention.
  • the particles to be prepared may also constitute 5 to 25% by weight and the particles to be added 75 to 95% by weight of the solids involved in the granulation process.
  • the particles to be prepared and the particles to be added are obtained by screening out a starting material, preferably a single starting material, whereby the particles to be added are obtained by grinding the coarse and fine material sieved from this starting material, so that the particle diameter criterion is satisfied according to claim 53, wherein the particle diameter d 50 of the particles to be added is preferably in the range of 3 to 50 microns.
  • the particles to be submitted and a part of the particles to be added are obtained by screening out a powdery or crystalline base material or a granular finished product, preferably a single material, wherein the particles to be added by grinding the sifted out of this material coarse and fine material and optionally other substances are obtained, so that the particle diameter criterion is satisfied according to claim 53, wherein the particle diameter d 50 of the particles to be added so preferably in the range of 3 to 50 microns.
  • Another preferred embodiment is when the granulation process is such that the particles to be added and the granulation aids over a period of a maximum of 5 minutes, advantageously of a maximum of 3 minutes, more advantageously of a maximum of 2 minutes, more preferably of a maximum of 1 minute and in particular of a maximum of 30 seconds are added and granulated.
  • the granulate is dried and / or cooled in a further process step, preferably in a fluidized bed, and advantageously powdered before or after this process step.
  • the particles to be added have a largely uniform particle size, wherein the particle size distribution of these particles is such that the ratio of d 50 to d 90 of the particles to be added at least 0.5, preferably at least 0.6, in particular is at least 0.75, where d 50 is the median value.
  • the original process end product consists of good grain, oversize and undersize (fines), although the oversize and undersize fractions are negligible.
  • good grain refers to the granulated material whose size or diameter is desired. This size range is an individual range, which is oriented to the needs of the user and can be selected according to the respective requirements.
  • the oversize is the built-up granulate, which in contrast is too coarse, i. is too big.
  • the undersize (fines) is that granulate which in turn is too fine or too small. It is an advantage of the method according to the invention that oversize and undersize already occupy only a negligible proportion in the original end product of the process.
  • the granules to be presented, the granules to be added and / or the granulation aids comprise ingredients from the field of detergents and / or cleaning agents.
  • the granules and / or granules to be added are tower powder products (spray drying products) and / or (raw) products resulting from non-tower technologies (ie products which are not direct spray drying products), preferably resulting from granulation in drum, dish -, mixer and fluidized bed granulators are, or have emerged from these, preferably originate from the same process, then again there is a further preferred embodiment of the invention.
  • the particles to be prepared and / or the particles to be added can preferably also be produced by means of extrusion, particularly preferably using a two-shaft extruder.
  • the raw materials intended for the respective particulate particles are first mixed and then homogenized and plasticized in the extruder.
  • preformed particles can be obtained by cutting the extruded mass at the extruder head. Extrusion processes suitable according to the invention are known in the art.
  • the preparation of the particles to be submitted and / or the particles to be added, preferably with a defined composition, can in the broadest sense be carried out quite generally according to methods known per se, ie. H.
  • the particles to be used can be obtained, for example, as needed by spraying and subsequent dry compaction, by granulation, spray agglomeration or by extrusion.
  • the particles to be submitted and / or the particles to be added can be rounded in a method step which precedes the method according to the invention.
  • the particles to be prepared and / or the particles to be added are rounded with the aid of a so-called spheronizer, a rotary drum, a coating drum or a coating pan.
  • the particles to be prepared and / or the particles to be added are those which have been prepared by the so-called spray agglomeration method.
  • the particles to be used are simultaneously agglomerated in a fluidized bed and dried.
  • the onion-like application of the substances and the movement of the particles give rise to very dense and round particles, which can be processed very advantageously in the method according to the invention.
  • the granules (constructed as process end products of the process according to the invention) essentially have an average form factor of at least 0.77, preferably of at least 0.79, advantageously of at least 0.81, more preferably of at least zero , 83, more preferably at least 0.85, in particular at least 0.87.
  • Substantially means here in particular that at least 80%, preferably at least 90% and more preferably at least 95% of the built-up granules have the aforementioned form factor.
  • the built-up granules are the whole of good grain, oversize and undersize (fines), which proves that oversize and undersize (fines) are negligible.
  • the shape factor in the sense of the present invention can be precisely determined by modern particle-measuring techniques with digital image processing.
  • a typical particle shape analysis as for example with the Camsizer® system by Retsch Technology or with the KeSizer® Kemira is feasible, based on the fact that the particles or the bulk material are irradiated with a light source and detects the particles as projection surfaces , digitized and processed by computer technology.
  • the determination of the surface curvature is made by an optical measuring method in which the "shadow" of the parts to be examined is determined and converted into a corresponding form factor.
  • the measurement limits of this optical analysis method are 15 ⁇ m and 90 mm, respectively.
  • the numerical values for d 50 and d 90 are also available via the aforementioned measuring method.
  • a further preferred embodiment of the invention is when the granules constructed as process end product are present in a particle size distribution which is as uniform as possible, ie the ratio of d 50 to d 90 is as high as possible.
  • the ratio of d 50 to d 90 is at least 0.5, preferably at least 0.6, advantageously at least 0.75, more preferably at least 0.8.
  • a preferred embodiment is a process in which the first process end product resulting from the process is again used as a particle to be prepared in the granulation stage in order to produce a larger and / or rounder granulate.
  • the granules built up are provided with a partial or complete, optionally multi-layered coating of an at least partially water-soluble polymer material for additional stabilization.
  • Inorganic compounds are also suitable. Suitable polymers are well known in the art, as are suitable inorganic compounds.
  • the method is characterized in that it is carried out at elevated temperatures, at least partially, preferably over all stages, which are in particular in the range of 15 to 75 ° C, but preferably ⁇ 20 ° C, advantageously ⁇ 25 ° C, in particular in the range 28-40 ° C are.
  • a very suitable temperature range for granulation / agglomeration is 25-35 ° C, for milling operations at 40-50 ° C, achievable by introducing tempered air.
  • the method is characterized in that enzyme-free is used, which means in the context of the invention that the resulting granules / agglomerate contains less than 5 wt .-% of enzymes, based on the total granules / agglomerate.
  • enzyme-free means in the context of the invention that the resulting granules / agglomerate contains less than 5 wt .-% of enzymes, based on the total granules / agglomerate.
  • all enzyme-free work is carried out, so that the resulting granules / agglomerate is also completely enzyme-free, ie 0 wt .-% enzyme, based on the total granules / agglomerate.
  • the granules it is furthermore advantageous to surround the granules with a coating of fine solids, ie to remove them, for example in order to achieve protection.
  • a coating of fine solids ie to remove them, for example in order to achieve protection.
  • the choice of these fine solids depends on the nature of the granules and their intended use.
  • powdering agents are suitable which preferably contain very finely divided zeolite and / or silica, in particular hydrophobic silica.
  • the process according to the invention is outstandingly suitable for the preparation of corresponding detergents and / or cleaning agents.
  • the granules may preferably contain all the ingredients required or commonly used for a washing and / or cleaning process, so that such granules are in themselves an independent, complete and functional washing and / or cleaning agent.
  • An inventively constructed detergent and / or detergent granules is therefore preferably a complete washing and / or cleaning agent.
  • the granules contain only a certain or several specific detergent and / or detergent ingredients.
  • Such a granulate constructed in accordance with the invention would then not be an independent, complete and functional washing and / or cleaning agent, but rather a detergent and / or detergent component.
  • Such granules would then be with the other customary components, which are necessary to form a complete washing and / or cleaning agent to mix. It is preferred in such a case if at least two or more granules constructed according to the invention are mixed to form a washing and / or cleaning agent and the resulting fully-fledged washing and / or cleaning agent consists only of these granules constructed according to the invention, the different granules preferably having different colors exhibit.
  • washing and / or cleaning agent granules is to be understood as meaning both complete washing and / or cleaning agents and also washing and / or cleaning agent components.
  • the washing and / or cleaning agent granules produced in the preparation according to the invention contain constituents which are preferably selected from the group comprising surfactants, fragrances, dyes, enzymes, enzyme stabilizers, builders, pH adjusters, bleaching agents, bleach activators, stain-repellent substances, optical agents Brightener, grayness inhibitors, disintegration aids, customary ingredients and / or mixtures thereof.
  • constituents which are preferably selected from the group comprising surfactants, fragrances, dyes, enzymes, enzyme stabilizers, builders, pH adjusters, bleaching agents, bleach activators, stain-repellent substances, optical agents Brightener, grayness inhibitors, disintegration aids, customary ingredients and / or mixtures thereof.
  • all other detergents and / or cleaning agent ingredients known to the person skilled in the art from the prior art may also be present in conventional amounts as constituents of the detergent and / or detergent granules to be produced according to the invention.
  • detergent and / or cleaning agent components are explained in greater detail. These ingredients may be included in the detergent and / or detergent granules themselves and / or in appropriate admixtures which may optionally be added to the laundry and / or detergent granules, if required, to provide a full wash and / or detergent receive.
  • surfactants anion, cation, ampho- and / or nonionic surfactants can be used for the preparation according to the invention of the washing and / or cleaning agent granules.
  • anionic surfactants of the sulfonate and sulfates type can be used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-8 -monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example, the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids suitable.
  • sulfonation of unsaturated fatty acids for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt .-%.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester.
  • methyl esters of ⁇ -sulfo fatty acids (MES), but also their saponified disalts are used.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or tri-ethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the anionic surfactants are present in the detergent and / or detergent granules to be produced according to the invention preferably in amounts of from 1 to 30% by weight and in particular in amounts of from 5 to 25% by weight.
  • alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.
  • Preferred nonionic surfactants are C 12 -C 18 fatty acid methyl esters having an average of from 3 to 15 EO, in particular having an average of from 5 to 12 EO.
  • C 12 -C 18 fatty acid methyl esters with 10 to 12 EO can be used as surfactants.
  • alkylpolyglycosides Another class of nonionic surfactants which can be used to advantage for the preparation according to the invention of detergent granules and / or detergent granules are the alkylpolyglycosides (APG).
  • APG alkylpolyglycosides
  • Usable Alkypolyglycoside meet the general formula RO (G) z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable for the preparation according to the invention of the detergents and / or detergent granules.
  • Suitable further surfactants for the preparation according to the invention of the washing and / or cleaning agent granules are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is usually a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to 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. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.
  • Gemini surfactants for the preparation according to the invention of detergent granules and / or detergent granules are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimeralcohol tris-sulfates and ether sulfates.
  • End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality. So possess the mentioned end disabilityver stricten Surfactants good wetting properties and are low in foam, so that they are particularly suitable for use in machine washing and / or cleaning methods.
  • the washing and / or cleaning agent granules which can be prepared according to the invention may contain as builder or builder all builders customarily used in detergents and / or cleaning agents, in particular detergents, in particular zeolites, silicates, carbonates, soda, organic cobuilders and also the phosphates. To avoid particulate residues on textiles, it is particularly advantageous to use builders which are completely water-soluble, such as soda or the like.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of 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.
  • a useful fine crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P zeolite MAP ® commercial product from Crosfield
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by Condea Augusta SpA under the brand name VEGOBOND AX ® and the formula: nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2 - 2.5) SiO 2 • (3.5-5.5) H 2 O, equivalent.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the content of zeolite granules obtainable according to the invention is up to 60% by weight, advantageously up to 40% by weight and more advantageously up to 30% by weight, although it may be even more advantageous maximum 15 Wt .-%, preferably at most 12 wt .-%, in particular at most 10 wt .-%, in each case based on the anhydrous active substance, for example 1 to 8 wt .-% or 0 to 5 wt .-% are included.
  • the granules which can be prepared according to the invention are free of zeolite.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.
  • the granules according to the invention are preferably not only zeolite but also low in phosphate.
  • the phosphate content is advantageously at most 15 wt .-%, preferably at most 12 wt .-%, in particular at most 10 wt .-%, for example 1 to 8 wt .-% or 0 to 5 wt .-%.
  • Very particular preference is given to granules which are both free of zeolite and of phosphate.
  • the detergent and / or cleaning agent granules according to the invention may contain, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and also phosphonates. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric 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 thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents and / or cleaning agents.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • GPC gel permeation chromatography
  • the measurement was carried out against an external standard of polyacrylic acid, which provides realistic molecular weight values on account of its structural relationship with the polymers investigated.
  • These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard.
  • the molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are selected from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from Polyolcarbon Textren such as gluconic acid and / or glucoheptonic acid.
  • 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, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • 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.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • a preferred dextrin is in the British patent application 94 19 091 described.
  • 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 methods of their preparation are known.
  • a product oxidized at C6 of the saccharide ring may be particularly advantageous.
  • oxydisuccinates and other derivatives of disuccinates are further suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred, as described, for example, in US Pat US 4,524,009 . US 4,639,325 to be discribed.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present 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 co-builders are known.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates For example, the 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the washing and / or cleaning agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned for producing the granules.
  • oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts are also suitable.
  • oxidized oligosaccharides are also suitable.
  • polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • 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 granules which can be prepared according to the invention can also have acid salts or slightly alkaline salts.
  • Preferred acidifying components here are bisulfates and / or bicarbonates or organic polycarboxylic acids which can also be used simultaneously as builders. Particularly preferred is the use of citric acid.
  • the laundry and / or cleaning agent granules which can be prepared according to the invention can also comprise bleaching agents.
  • bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, Citrate perhydrates and H 2 O 2 supplying peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, Phthaloiminoperticacic acid or Diperdodecandiklare.
  • bleaching agents from the group of organic bleaching agents for the preparation of the washing and / or cleaning agent granules.
  • Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkyleneoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimido peroxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-Decyldip
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in the detergent and / or detergent granules preparable according to the invention.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribrornisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium hydantoin compounds, such as 1 3-dichloro-5,5-dimethylhydantoin are also suitable.
  • DICA dichloroisocyanuric acid
  • the content of bleaching agents is preferably from 0 to 25% by weight and in particular from 1 to 20% by weight, based on the total composition of the detergent and / or detergent granules obtainable according to the invention.
  • bleach activators may be included.
  • bleach activators for the preparation of the detergent granules according to the invention it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are the O- and / or N-acyl groups of said C atom number and / or optionally substituted benzoyl groups wear.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (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, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diisocyanate acetoxy-2,5-dihydrofuran.
  • TAED
  • bleach catalysts can also be used for the preparation according to the invention of the detergent granules and / or detergent granules.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Suitable bleach activators for the preparation according to the invention of the detergent granules are also the enol esters and acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example, N-benzoyl caprolactam.
  • PAG pentaacetylglucose
  • PAG pentaacetyl fructose
  • tetraacetylxylose tetraacetylxylose
  • octaacetyllactose as well as acetylated,
  • hydrophilic substituted acylacetals and acyl lactams are likewise preferably used for the preparation of the detergent and / or detergent granules according to the invention.
  • Combinations of conventional bleach activators can also be used to prepare the detergent and / or detergent granules according to the invention.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C18-C24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide.
  • Suitable enzymes for the preparation according to the invention of the washing and / or cleaning agent granules are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of mentioned enzymes in question. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains.
  • oxidoreductases For bleaching and oxidoreductases can be used. Particularly suitable for the preparation of detergents and / or detergent granules are those obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus Cinereus and Humicola insolens and from their genetically modified variants enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are obtained.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases. Oxireductases are also suitable.
  • cellulases may additionally be considered.
  • Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils.
  • Cellulases used are preferably cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures of these. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the proportion of the enzymes or enzyme mixtures may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%, based on the detergent and / or makesstoffgranulatzusammen experience.
  • the washing and / or cleaning agent granules which can be prepared according to the invention can also contain further enzyme stabilizers.
  • the washing and / or cleaning agent granules may contain sodium formate. 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. In addition to 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 ), the metaboric acid (HBO 2 ) and the pyroboric acid (tetraboric H 2 B 4 O 7 ).
  • the washing and / or cleaning agent granules may also contain grayness inhibitors.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • 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 of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g.
  • polyvinylpyrrolidone is useful.
  • dirt-repellent substances which have a positive effect on the oil and grease washability of textiles (so-called soil repellents) can also be used for the production of the detergent granules and / or detergent granules. This effect is particularly evident when a textile is dirty, which has been previously washed several times 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, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof.
  • nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and
  • Optical brighteners are organic dyes that convert part of the invisible UV radiation of sunlight into longer-wavelength blue light. The emission of this blue light complements the "gap" in the light reflected from the textile so that a fabric treated with optical brightener appears whiter and brighter to the eye. As the mechanism of action of brighteners presupposes their application to the fibers, a distinction is made depending on the "to be dyed" fibers, for example, brighteners for cotton, polyamide or polyester fibers.
  • Suitable brighteners include essentially five structural groups, namely the stilbene, diphenylstilbene, coumarin-quinoline, diphenylpyrazoline and the group of the combination of benzoxazole or benzimidazole with conjugated systems.
  • An overview of common brighteners is, for example, in G. Jakobi, A. Lohr "Detergents and Textile Washing", VCH Verlag, Weinheim, 1987, pages 94 to 100 Find.
  • Suitable salts are, for example, salts of 4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] stilbene-2,2'-disulphonic acid or compounds of similar construction which are used in place of the morpholino Group a Diethanolaminooeuvre, a methylamino group, an anilino group or a 2-Methoxyethylaminoxx carry.
  • brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used.
  • Fragrances can be added to the detergent and / or detergent granules to be produced according to the invention in order to improve the aesthetic impression of the resulting granules and to provide the consumer with a sensory "typical and unmistakable" washing and / or cleaning agent in addition to the cleaning performance and the color impression.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g.
  • the linear alkanals having 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the ionones, ⁇ -isomethylionone and methylcedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • fragrances are preferably used for the preparation of the detergent and / or cleaning agent granules according to the invention, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • tablet disintegrants In order to facilitate the disintegration of the detergent and / or detergent granules preparable in accordance with the invention in solid form, for example in tablet form, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in them in order to shorten the disintegration times.
  • tablet disintegrants or disintegrants are meant auxiliaries which ensure the rapid disintegration of tablets into water or gastric juice and for the release of the drugs in resorbable form.
  • Swelling disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used.
  • Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • washing and / or cleaning agent granules advantageously contain 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% of one or more disintegration aids, each based on the washing and / or detergent granules.
  • disintegrating agents which are suitable for the preparation of the detergent and / or cleaning agent granules according to the invention
  • disintegrating agents based on cellulose are used in the context of the present invention.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
  • the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use pure cellulose as the cellulose-based disintegrating agent for the preparation of the washing and / or cleaning agent granules according to the invention, which is free of cellulose derivatives.
  • microcrystalline cellulose can be used as a further cellulose-based disintegrating agent for the preparation of the washing and / or cleaning agent granules according to the invention.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulosic mass) of the celluloses, leaving the crystalline regions (about 70%) intact ,
  • the washing and / or cleaning agent granules can be dyed with suitable dyes, with the brightener phase (s) preferably containing the total amount of dye (s). contains / contain.
  • suitable dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of detergents and / or detergents and to light and no pronounced substantivity to textile fibers so as not to stain them.
  • Preferred for the production of detergents and / or cleaning agents according to the invention are all colorants which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants for the preparation of the detergent and / or cleaning agent granules according to the invention, which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.
  • One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which as a commercial product ® for example as Basacid Green 970 from BASF, Ludwigshafen, is, as well as mixtures thereof with suitable.
  • Pigmosol ® come ® Blue 6900 (CI 74160), Pigmosol ® Green 8730 (CI 74260), Basonyl Red 545 FL (CI 45170), Sandolan® ® rhodamine EB400 (CI 45100), Basacid® ® Yellow 094 (CI 47005) Sicovit ® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), pigment Blue 15 (CI 74160), Supranol Blue ® GLW (CAS 12219-32-8, CI Acidblue 221 ), Nylosan Yellow ® N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan ® Blue (CI Acid Blue 182, CAS 12219-26-0) is used.
  • the colorant When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergent and / or detergent granules varies.
  • the above-mentioned Basacid ® Green or the above-mentioned Sandolan ® Blue are typically dye concentrations in the range of some 10 -2 to 10 -3 wt .-%, each based on the total detergent and / or detergent granules , chosen.
  • the appropriate concentration of the colorant in detergents and / or cleaning agents is typically present in some 10 -3 to 10 -4. -%, based on the total washing and / or cleaning agent.
  • Oversize and undersize grains have been milled together with sodium carbonate, sodium sulfate, TAED and foam inhibitor concentrate to an average particle size d 50 of 9 ⁇ m with an eddy current mill.
  • Core material and the milled mixture were placed in a batch Lödige mixer. Mixture was via the plowshare mixer elements at a Froude number of 6.5. With addition of the granulation liquid, the fine particles were adhered to the core material.
  • coated core-shell aggregate was then mixed with coated enzyme-containing particles (uniform particle size d 50 of about 0.9 mm) and coated percarbonate-containing particles (uniform particle size d 50 of about 1.0 mm) to form a detergent.
  • the coated core-shell aggregates can not segregate as nearly all constituents are in each grain.
  • the coated core-shell aggregates are dust-free in the area of the invention and resistant to abrasion.
  • the particles are nearly spherical with correspondingly high form factors.
  • the particle size distributions are relatively narrow.
  • the visual appearance of a single coated core-shell aggregate as well as aggregates in the collective are excellent.
  • the coated core-shell aggregates have excellent powder properties in terms of flowability and storage stability.
  • the separated fines and the oversize were each ground by grinding to about one-twelfth of the particle diameter d 50 of each particle to be submitted.
  • the material thus ground in each case is referred to below as "particles to be added”.
  • Sokalan® CP 45 acrylic acid-maleic acid copolymer sodium salt ex BASF
  • the amount of each granulation liquid added was 9 parts by weight with respect to an amount of 100 parts by weight of particles (sum of the particles to be charged and added).
  • the resulting built-up granules / agglomerates each had a form factor of 0.87 for A, 0.85 for B, and 0.83 for C.
  • the ratio d 50 / d 90 was 0.75 to 0.82.

Landscapes

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

Claims (14)

  1. Procédé pour la production de granulés dans un dispositif de mélange/granulation par présentation d'une matière particulaire, que l'on désigne ci-après par l'expression « particules à présenter », que l'on soumet à une granulation/agglomération par addition d'un adjuvant de granulation et d'une matière particulaire supplémentaire, que l'on désigne ci-après par l'expression « particules à ajouter », caractérisé en ce que
    a) les particules à présenter présentent une granulométrie la plus uniforme possible ;
    b) les particules à ajouter présentent un diamètre de particule d50 qui représente au maximum un dixième du diamètre de particule d50 des particules à présenter, le diamètre de particule d50 des particules à ajouter se situant de préférence dans la plage de 3 à 50 µm ;
    c) les particules à ajouter étant ajoutées de manière conjointe avec un adjuvant de granulation, de préférence pendant un laps de temps d'au moins une minute ;
    d) les particules à ajouter étant obtenues via un processus de broyage ;
    dans lequel les granulés à présenter, les granulés à ajouter et/ou les adjuvants de granulation comprennent des constituants appartenant au domaine des agents de lavage et de nettoyage, les granulés résultants contenant moins de 5 % en poids d'enzymes, rapportés au granulé total.
  2. Procédé selon la revendication 1, caractérisé en ce que le diamètre d50 des particules à présenter se situe dans la plage de 0,15 à 5 mm, de préférence dans la plage de 0,2 à 2 mm, en particulier dans la plage de 0,3 à 1 mm.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la distribution granulométrique des particules à présenter est telle que le rapport d50/d90 des particules à présenter s'élève essentiellement à au moins 0,5, de préférence à au moins 0,6, de manière avantageuse à au moins 0,75, et en particulier à au moins 0,8.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que, en ce qui concerne l'adjuvant de granulation, il s'agit d'une mousse de granulation.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les particules à ajouter présentent un diamètre de particule d50 qui représente au maximum 1/12, de préférence au maximum 1/14, de manière avantageuse au maximum 1/16, de manière plus avantageuse au maximum 1/18, de manière plus avantageuse au maximum 1/20, de manière encore plus avantageuse au maximum 1/22, de manière tout à fait avantageuse au maximum 1/24 et en particulier au maximum 1/26 du diamètre de particule d50 des particules à présenter.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que les particules à présenter représentent moins de 50 % en poids, de préférence moins de 45 % en poids, de manière avantageuse moins de 40 % en poids, de manière plus avantageuse de 15 à 35 % en poids, en particulier de 20 à 30 % en poids, et en ce que les particules à ajouter représentent plus de 50 % en poids, de préférence plus de 55 % en poids, de manière plus avantageuse plus de 60 % en poids, de manière encore plus avantageuse de 65 à 85 % en poids, en particulier de 70 à 80 % en poids des substances solides impliquées dans le processus de granulation.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que les particules à ajouter présentent une granulométrie la plus homogène possible, dans lequel, de manière avantageuse, la distribution granulométrique des particules à ajouter est telle que le rapport d50/d90 des particules à ajouter s'élève de préférence à au moins 0,5, de manière plus préférée à au moins 0,6, en particulier à au moins 0,75.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que les granulés obtenus sont soumis à un tamisage et/ou à un triage, de préférence après le séchage, dans le but de séparer la fraction granulométrique désirée de la fraction granulométrique rejetée et des fractions fines, la fraction rejetée et les fractions fines
    a) étant par la suite soumises à un processus de broyage, si bien que ces particules, après le broyage, présentent un diamètre de particule d50 qui représente au maximum un dixième du diamètre de particule d50 des particules à présenter, si bien que les particules résultantes présentent de préférence un diamètre de particule d50 de 3 à 50 µm ; et
    b) ces particules étant ensuite réacheminées, à titre de particules à ajouter, au dispositif de mélange/granulation.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé par les étapes suivantes :
    a) un processus de séparation par tamisage pour séparer une matière particulaire possédant une granulométrie la plus uniforme possible, que l'on désigne ci-après par l'expression « particules à présenter », par rapport à la fraction rejetée et aux fractions fines à partir d'une matière de départ ;
    b) le broyage de la fraction rejetée et des fractions fines séparées, de manière facultative par addition de composants supplémentaires, jusqu'à au moins un dixième du diamètre de particule d50 des particules à présenter ou moins, de façon à obtenir les « particules à ajouter », si bien que ces dernières présentent de préférence un diamètre de particule d50 de 3 à 50 µm ;
    c) la granulation/agglomération des particules à présenter avec addition des particules à ajouter et d'adjuvants de granulation dans un dispositif de mélange/granulation ;
    d) le séchage et/ou le refroidissement des granulés/agglomérats dans un lit fluidisé ;
    e) la séparation de la fraction désirée par rapport à la fraction rejetée et aux fractions fines, par tamisage et/ou par triage ;
    f) le transfert de la fraction rejetée et des fractions fines dans un broyeur et le broyage de ces particules jusqu'à un diamètre de particule d50 qui représente au maximum un dixième du diamètre de particule d50 des particules à présenter, si bien que l'on atteint de préférence des diamètres de particules d50 de 3 à 50 µm ; et ensuite
    g) le renvoi des particules broyées, à titre de particules à ajouter, dans le dispositif de mélange/granulation.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que les granulés à présenter et ou les granulés à ajouter sont des produits pulvérulents de tours de séchage et/ou des produits (bruts) qui ne proviennent pas de technologies faisant appel à des tours de séchage, de préférence qui résultent de la granulation dans des dispositifs de granulation du type à tambours, à plateaux, à mélangeurs et à lits fluidisés, ou bien sont issus desdits produits, de préférence émanent du même processus.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que les granulés obtenus sous la forme de produit final issu du procédé, présentent essentiellement un facteur de forme moyen d'au moins 0,77, de préférence d'au moins 0,79, de manière avantageuse d'au moins 0,81, de manière plus avantageuse d'au moins 0,83, de manière plus avantageuse d'au moins 0,85, en particulier d'au moins 0.87.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que les granulés obtenus sous la forme de produit final issu du procédé, sont présents essentiellement dans une distribution granulométrique la plus uniforme possible, dans lequel le rapport d50/d90 s'élève à au moins 0,50, de préférence à au moins 0,6, de manière avantageuse à au moins 0,75, de manière plus avantageuse à au moins 0,80.
  13. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que l'on met en oeuvre, dans l'étape de granulation, le premier produit final résultant du procédé, à nouveau sous la forme de particules à présenter, afin d'obtenir un granulé plus gros et/ou plus rond.
  14. Procédé selon l'une quelconque des revendications précédentes 1 à 13, caractérisé en ce que le procédé est mis en oeuvre, au moins en partie, de préférence dans toutes ses étapes, à des températures élevées qui se situent de préférence dans la plage de 15 à 75 °C, en particulier de 28 à 40 °C.
EP05800573.7A 2004-11-02 2005-10-22 Procede de preparation des granules / agglomerats pour compositions detergentes Not-in-force EP1807498B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL05800573T PL1807498T3 (pl) 2004-11-02 2005-10-22 Sposób wytwarzania granulatów bądź aglomeratów środków piorących lub czyszczących

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE200410053385 DE102004053385A1 (de) 2004-11-02 2004-11-02 Kugelförmige Agglomerate
DE200510036346 DE102005036346A1 (de) 2005-07-29 2005-07-29 Beschichtete Kern-Schale-Aggregate
PCT/EP2005/011370 WO2006048142A2 (fr) 2004-11-02 2005-10-22 Granulats / agglomerats pour detergents ou produits de nettoyage

Publications (3)

Publication Number Publication Date
EP1807498A2 EP1807498A2 (fr) 2007-07-18
EP1807498B1 true EP1807498B1 (fr) 2012-11-28
EP1807498B2 EP1807498B2 (fr) 2019-02-20

Family

ID=35520649

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05800573.7A Not-in-force EP1807498B2 (fr) 2004-11-02 2005-10-22 Procede de preparation des granules / agglomerats pour compositions detergentes

Country Status (5)

Country Link
EP (1) EP1807498B2 (fr)
JP (1) JP2008519115A (fr)
ES (1) ES2397226T3 (fr)
PL (1) PL1807498T3 (fr)
WO (1) WO2006048142A2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006017312A1 (de) * 2006-04-11 2007-10-18 Henkel Kgaa Wasch- oder Reinigungsmittelgranulate
MX2008013356A (es) * 2006-04-20 2008-10-31 Procter & Gamble Una composicion detergente particulada solida para lavanderia que comprende particula estetica.
CA2848388A1 (fr) * 2011-09-13 2013-03-21 The Procter & Gamble Company Agents encapsules
WO2017017176A1 (fr) * 2015-07-29 2017-02-02 Basf Se Particules nettoyantes et leur utilisation

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1590432A (en) † 1976-07-07 1981-06-03 Novo Industri As Process for the production of an enzyme granulate and the enzyme granuate thus produced
US4524009A (en) 1984-01-31 1985-06-18 A. E. Staley Manufacturing Company Detergent builder
DE3434854A1 (de) * 1984-09-22 1986-04-03 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung einer koernigen, freifliessenden waschmittelkomponente
US4639325A (en) 1984-10-24 1987-01-27 A. E. Staley Manufacturing Company Detergent builder
DK435587D0 (da) † 1987-08-21 1987-08-21 Novo Industri As Fremgangsmaade til fremstilling af et enzymholdigt granulat
DK157937C (da) † 1987-08-21 1990-08-06 Novo Industri As Enzymholdigt granulat og fremgangsmaade til fremstilling deraf
DE3818829A1 (de) * 1988-06-03 1989-12-14 Henkel Kgaa Koerniges adsorptionsmittel mit verbessertem einspuelverhalten
US5733763A (en) † 1988-08-19 1998-03-31 Novo Nordisk A/S Enzyme granulate formed of an enzyme-containing core and an enzyme-containing shell
DK78089D0 (da) † 1989-02-20 1989-02-20 Novo Industri As Detergentholdigt granulat og fremgangsmaade til fremstilling deraf
AU6267694A (en) † 1993-02-26 1994-09-14 Procter & Gamble Company, The High active enzyme granulates
AU2568797A (en) † 1996-04-12 1997-11-07 Novo Nordisk A/S Enzyme-containing granules and process for the production thereof
US6610519B1 (en) † 1998-10-02 2003-08-26 Novozymes A/S Solid phytase composition stabilized with lactic acid provided by corn steep liquor
US6818605B1 (en) * 1999-06-16 2004-11-16 Kao Corporation Granulated detergent composition
DE19953057A1 (de) † 1999-11-03 2001-05-10 Henkel Kgaa Enzymhaltige höherviskose Flüssigwaschmittel
DE10054516A1 (de) † 2000-11-03 2002-05-16 Henkel Kgaa Extrudiertes Proteinhydrolysat, Verfahren zu dessen Herstellung und dessen Verwendung
JPWO2002038721A1 (ja) * 2000-11-08 2004-03-18 味の素株式会社 粒状界面活性剤およびその製造方法
EP1372713A4 (fr) * 2001-04-02 2010-01-13 Genencor Int Granule a pulverulence reduite
DE10124430B4 (de) 2001-05-18 2011-04-28 Henkel Ag & Co. Kgaa Granulationsverfahren mit Schäumen
AU2002351749A1 (en) † 2001-12-21 2003-07-15 Novozymes A/S Salt coatings
DE10338428A1 (de) * 2002-12-18 2004-07-01 Henkel Kgaa Feinpartikuläres Mittel
DE102007029643A1 (de) † 2006-09-08 2009-01-15 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007011236A1 (de) † 2007-03-06 2008-09-11 Henkel Ag & Co. Kgaa Carboxylgruppen tragende Benzophenon-oderBenzoesäureanilid-Derivate als Enzymstabilisatoren
DE102007041754A1 (de) † 2007-09-04 2009-03-05 Henkel Ag & Co. Kgaa Polycyclische Verbindungen als Enzymstabilisatoren
DE102008010429A1 (de) † 2008-02-21 2009-08-27 Henkel Ag & Co. Kgaa Harnstoff-Derivate als Enzymstabilisatoren
DE102008014760A1 (de) † 2008-03-18 2009-09-24 Henkel Ag & Co. Kgaa Imidazolium-Salze als Enzymstabilisatoren

Also Published As

Publication number Publication date
EP1807498B2 (fr) 2019-02-20
ES2397226T3 (es) 2013-03-05
PL1807498T3 (pl) 2013-04-30
WO2006048142A2 (fr) 2006-05-11
JP2008519115A (ja) 2008-06-05
WO2006048142A3 (fr) 2006-10-26
EP1807498A2 (fr) 2007-07-18

Similar Documents

Publication Publication Date Title
WO1995022592A1 (fr) Produit de lavage a adjuvants au silicate amorphes
EP0859827A1 (fr) Procede de production d'un silicate alcalin amorphe avec impregnation
EP0931137B1 (fr) Procede de production d'un detergent ou nettoyant particulaire
EP0804529B1 (fr) Compose silicate alcalin amorphe
EP1117759B1 (fr) Procede de granulation
EP1842900A1 (fr) Procédé destiné à la fabrication de granulés et leur utilisation dans des agents de lavage et/ou de nettoyage
EP1807498B1 (fr) Procede de preparation des granules / agglomerats pour compositions detergentes
EP1106678B1 (fr) Granules de surfactant nonionique et procédé d'obtention
EP1358310B1 (fr) Produits detergents et nettoyants possedant des microparticules fines qui renferment des constituants de produits nettoyants
EP0986629B2 (fr) Detergent granule
EP0839178B1 (fr) Compose amorphe de silicate alcalin
WO2007118733A1 (fr) Granulés de lessive ou de détergent
EP0846758B1 (fr) Additif détergent
EP0845028B1 (fr) Procede de production d'un silicate alcalin amorphe soumis a une impregnation
DE19622443A1 (de) Granulare Waschmittel, enthaltend optischen Aufheller
EP0888428A1 (fr) Procede de production de silicates granulaires a masse volumique apparente elevee
DE102004053385A1 (de) Kugelförmige Agglomerate
WO2000037595A1 (fr) Compactat contenant des agents renforçateurs a base de silicates
EP0919614B1 (fr) Procédé de production des compositions détergentes à haute densité
EP0888450B2 (fr) Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe
WO2002102959A1 (fr) Produit de lavage et/ou produit de nettoyage pauvre en zeolithe et stable au stockage
DE10116021A1 (de) Wasch-oder Reinigungsmittel mit verbesserter Reinigungsleistung
DE10123622A1 (de) Verfahren zur Herstellung von Tensidgranulaten
WO2000022076A1 (fr) Granules renfermant du phosphonate
WO2016142209A1 (fr) Détergent ou produit de nettoyage granulaire à solubilité améliorée

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070216

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HENKEL AG & CO. KGAA

17Q First examination report despatched

Effective date: 20090810

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 586198

Country of ref document: AT

Kind code of ref document: T

Effective date: 20121215

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502005013302

Country of ref document: DE

Effective date: 20130124

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2397226

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20130305

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20121128

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121128

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121128

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121128

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

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

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121128

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121128

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130301

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130328

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121128

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

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121128

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121128

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121128

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130228

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

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121128

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121128

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: NOVOZYMES A/S

Effective date: 20130823

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 502005013302

Country of ref document: DE

Effective date: 20130823

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

BERE Be: lapsed

Owner name: HENKEL A.G. & CO. KGAA

Effective date: 20131031

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

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121128

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20131022

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131031

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131031

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131022

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

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131031

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

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131022

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 586198

Country of ref document: AT

Kind code of ref document: T

Effective date: 20131022

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

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131022

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

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121128

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

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131022

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20051022

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

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

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121128

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

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

Ref country code: PL

Payment date: 20170926

Year of fee payment: 13

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

Ref country code: CZ

Payment date: 20171019

Year of fee payment: 13

Ref country code: FR

Payment date: 20171024

Year of fee payment: 13

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

Ref country code: IT

Payment date: 20171023

Year of fee payment: 13

Ref country code: ES

Payment date: 20171121

Year of fee payment: 13

PLBP Opposition withdrawn

Free format text: ORIGINAL CODE: 0009264

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20190220

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: DE

Ref legal event code: R102

Ref document number: 502005013302

Country of ref document: DE

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

Ref country code: CZ

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181022

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

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181031

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

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181022

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190220

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

Ref country code: DE

Payment date: 20191021

Year of fee payment: 15

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

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181022

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502005013302

Country of ref document: DE

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

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210501