EP1012221B1 - Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel - Google Patents

Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel Download PDF

Info

Publication number: EP1012221B1
Authority: EP; European Patent Office
Prior art keywords: weight; premix; shaping; process according; acid
Prior art date: 1997-09-11
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.): Expired - Lifetime

Application number

EP97913181A

Other languages

German (de)

English (en)

French (fr)

Other versions

EP1012221A1 (de

Inventor

Kathleen Paatz

Wilfried Rähse

Peter Sandkühler

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.)

1997-09-11

Filing date

1997-10-28

Publication date

2004-06-16

1997-09-11 Priority claimed from PCT/EP1997/004975 external-priority patent/WO1998012299A1/de

1997-10-28 Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA

1997-10-28 Priority to EP97913181A priority Critical patent/EP1012221B1/de

2000-06-28 Publication of EP1012221A1 publication Critical patent/EP1012221A1/de

2004-06-16 Application granted granted Critical

2004-06-16 Publication of EP1012221B1 publication Critical patent/EP1012221B1/de

2017-10-28 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

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
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions

Definitions

the invention relates to a method for producing particulate detergents or cleaning agents or of multi-component components that are mixed with other Ingredients such agents result with the help of a specially adapted Granulation process and detergents or cleaning agents produced in this way.
Particulate detergents or cleaning agents with bulk weights above 600 g / l belong state of the art for quite some time.
Increasing the bulk density also increases the concentration of active washing and cleaning Ingredients go hand in hand, so that the consumer not only less volume, but also less Mass had to be dosed per washing or cleaning process.
the increase in Bulk density and in particular the higher concentration of the detergent or cleaning-active substances were generally bought through from the point of view of the Consumers subjectively worse solubility due to the generally slower Dissolving speed of the agent used was caused. This unwanted The release delay is triggered, among other things, by the fact that a number of common practice anionic and nonionic surfactants and, above all, appropriate surfactant mixtures tend to form gel phases when dissolved in water.
European patent EP 0 486 592 B1 describes granular or extruded Detergents or cleaning agents with bulk weights above 600 g / l, the anionic and / or nonionic surfactants in amounts of at least 15% by weight and up to about Contain 35 wt .-%. They are manufactured using a process in which a firm, free-flowing premix, which is preferably a plasticizer and / or lubricant contains aqueous surfactant pastes and / or aqueous polymer solutions at high pressures between 25 and 200 bar extruded and the strand after exiting the Hole shape by means of a cutting device to the predetermined granule dimension is cut and rounded.
a firm, free-flowing premix which is preferably a plasticizer and / or lubricant contains aqueous surfactant pastes and / or aqueous polymer solutions at high pressures between 25 and 200 bar extruded and the strand after exiting the Hole shape by
the premix consists at least in part solid ingredients, which may contain liquid ingredients such as at room temperature liquid nonionic surfactants are added.
liquid ingredients such as at room temperature liquid nonionic surfactants are added.
plasticizers and / or In preferred embodiments lubricants used aqueous preparations.
lubricants used aqueous preparations.
the patent does not disclose any process conditions to be observed in the case of an anhydrous extrusion.
the Extrudates produced can either already be used as washing or cleaning agents or afterwards with other granules or powder components to produce washing or Detergents are processed. Due to the high compactness of the grain and the relatively high surfactant levels, but also by the ball or Pearl shape, which is much smaller than conventional granules Depending on the surfactant combinations selected, it may have a surface the difficulties mentioned above.
the German patent application DE 195 19 139 A1 proposes to solve the conflict between high degree of compaction of the individual grain, especially the extrudate, on the on the one hand and the rapid and, in particular, non-reworking requirements that are required
the detergents or detergents can be redissolved in aqueous liquors, particulate detergents or cleaning agents with a bulk density above 600 g / l, which anionic and / or nonionic surfactants in amounts of at least 15% by weight included to design such that at least two different granular components are used, at least one extruded and at least one not extruded , the maximum surfactant content of the extruded component including the soaps 15% by weight, based on the respective extruded component, should be.
Surfactant components of the finished detergent or cleaning agent are by or several non-extruded component (s) introduced into the agent.
This procedure solves the problem of gelling highly compressed and high-surfactant detergents or cleaning agents when used in an aqueous liquor, but it also contains one Series of new problems. There can be segregation processes and corresponding fluctuations in the reproducibility of the desired washing or cleaning result occur.
the extruded portion of the media is not only of high density dried extrudates are also comparatively hard. Under the conditions the comparatively softer granulate content can be used for transport, storage and use the non-extruded component (s) are thus exposed to mechanical forces that partly to reduce it and thus to form dust and fine particles lead through abrasion.
a method for the production of heavy granules with the help of an aqueous Granulation aid is the two-stage granulation, initially in a conventional Mixer / granulator still plastic primary agglomerates are generated, which then in devices such as a rounder, rotocoater, marumerizer etc. with liquid Binder and / or dust subsequently treated and then usually dried become.
the granulation and simultaneous rounding can, for example, in fluidized bed granulators, which contain a rotating disc. Solid starting materials are first fluidized in the fluidized bed and then with liquid binder that is fed into the fluidized bed via tangentially aligned nozzles is agglomerated ("Size Enlargement by Agglomeration", W. Pietsch, John Wiley & Sons, 1990, pages 450 to 451). In principle, this method can also be used for non-aqueous Processes are used (melt coating process), but then the advantage the apparatus to be able to effect simultaneous drying is not used.
Preferred liquid nonionic surfactants are ethoxylated linear or methyl-branched alcohols in the 2-position which have 8 to 20 carbon atoms in the carbon chain and an average of 1 to 15 moles of ethylene oxide per mole of alcohol.
water is also described as a structure breaker which is suitable in principle, the use of which is less preferred, however, since the agents can become poor in water during storage due to the internal drying of the agents and therefore no longer have the desired effect of improved dissolution rate by using a structure breaker or would no longer be fully effective.
the mixtures of nonionic surfactants and structural breakers which are present either as a solution or as a dispersion, can be used in all known granulation processes in which separately produced compounds and / or raw materials are used.
Use in an extrusion process according to international patent application WO-A-91/02047 (or European patent EP 0 486 592 B1) is also possible and even preferred.
the use of aqueous solutions, pastes or aqueous dispersions is also suggested, the water, as stated above, not being used as a structure breaker and usually being dried off after the extrusion.
European patent application EP 0 337 330 describes a method for increasing the Bulk weight of a spray-dried detergent by granulation in a mixer with the addition of nonionic compounds.
nonionic compounds include ethoxylated and / or propoxylated nonionic surfactants such as primary or secondary alcohols with 8 to 20 Carbon atoms and 2 to 20 moles of alkylene oxide per mole of alcohol, in particular Non-ionic surfactants with 2 to 6 EO and HLB values of 11 or less added in the mixer become.
Ethylene glycols and propylene glycols can also be used as nonionic Connections are used.
European patent application EP 0 711 828 describes a process for the production of Tablets described, wherein a coated particulate product is pressed.
the Wrapping substance is a water-soluble binder or disintegrant with melting temperatures between 35 and 90 ° C. It is stated here as an essential feature that the compacting / tableting is to be carried out at temperatures which at at least 28 ° C, but below the melting temperature of the binder.
Primary C 12 -C 15 alcohols with 3 to 7 EO are specified as nonionic surfactants.
Surfactant mixtures which contain up to 20% by weight of water are particularly advantageous in the context of the stated process, since this increases the viscosity of the mixture and makes the process more controllable.
the surfactant mixture can also contain polyethylene glycols.
builder agglomerates The production of builder agglomerates is described in US Pat. No. 5,108,646, 50 to 75 parts by weight of aluminosilicates or crystalline phyllosilicates being agglomerated with 20 to 35 parts by weight of a binder.
Suitable binders there are primarily highly viscous anionic surfactant pastes, which can contain up to 90% by weight of water.
polymers such as polyethylene glycols with molecular weights between 1000 and 20,000 are also possible, as are mixtures of these and customary nonionic surfactants such as C 9 -C 16 alcohols with 4 to 8 EO, as long as their melting range is not below 35 ° C or below 45 ° C begins.
the agglomeration takes place in a so-called intensive mixer with a very specific, relatively high energy input. With energy inputs above the specified values, over-agglomeration up to a dough-like mass occurs; with lower energy inputs, only finely divided powders or very light agglomerates with an undesirably wide grain spectrum are obtained.
the object of the invention was particulate washing or Detergents or multi-component components that are mixed with other Ingredients such agents produce, which even when reduced Surface, especially with a spherical shape (pearl shape) an improved disintegration have in the dissolution in the aqueous liquor.
the procedure should also be economical and can do without costly drying steps.
the invention therefore relates to a process for the production of particulate Detergents or cleaning agents or multi-component components or treated Raw materials that result in such agents when mixed with other ingredients Bulk weights above 600 g / l by assembling washing or Detergent compounds and / or raw materials with simultaneous or subsequent Shaping, whereby one first produces a premix, which individual raw materials and / or compounds that are solid at room temperature and a pressure of 1 bar are present, and then this premix using compression forces converted into a grain and, if necessary, subsequently processed or processed, which is characterized in that the premix essentially is anhydrous and one under the shaping conditions, in particular with Room temperature and a pressure of 1 bar, liquid molding aid in the form of a polymer swollen in non-aqueous solution, the non-aqueous Liquid component of the shaping aid from the following liquid at room temperature, di- or trihydric alcohols with boiling points (at 1 bar) above 80 ° C selected: n-propanol, iso-propano
a condition is "substantially water-free" understand, in which the content of liquid, that is, not in the form of water of hydration and / or constitutional water less than 2% by weight, preferably less than 1% by weight and in particular even less than 0.5% by weight, in each case based on the premix, lies. Accordingly, water can essentially only be chemically and / or physically bound form or as part of the at temperatures below 45 ° C. a pressure of 1 bar as raw materials or compounds, but not as a liquid, solution or dispersion in the process of making the Premix are introduced.
the premix advantageously has one overall Water content of not more than 15 wt .-%, so this water is not in liquid free form, but is chemically and / or physically bound, and it in particular it is preferred that the content of water not bound to zeolite and / or silicates in the solid premix not more than 10% by weight, preferably less than 7% by weight and with particular preference is a maximum of 2 wt .-% to 5 wt .-%.
Particulate detergents or cleaning agents are used in the context of the invention preferably understood those that have no dust-like portions and in particular none Have particle sizes below 200 microns. Such particle size distributions are in particular preferred, which at least 90 wt .-% particles with a Have a diameter of at least 400 ⁇ m.
the laundry or cleaning agents and compounds produced consist of the invention or treated raw materials to at least 70 wt .-%, advantageously at least 80% by weight and, with particular preference, up to 100% by weight spherical (pearl-shaped) particles with a particle size distribution which at least Has 80 wt .-% particles between 0.8 and 2.0 mm.
particulate washing or Cleaning agents in the sense of the present invention can also be tablets with usual for washing or cleaning agent tablets for household applications Dimensions, for example with weights from 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of about 35 mm to 40 mm.
Anhydrously swollen polymers which, in the context of the present invention, are Shaping aids used are those that are found in non-aqueous liquids lead gel-like conditions.
Systems from non-aqueous systems are particularly suitable Liquid and polymer which is a at room temperature in the presence of the polymer have at least 20 times, in particular 300 to 5000 times higher viscosity than that non-aqueous liquid alone.
the viscosity of the molding aid, that is Combination of non-aqueous liquid and polymer is preferably at room temperature in the range from 200 mPas to 10,000 mPas, in particular from 400 mPas to 6,000 mPas, measured for example using a Brookfield rotary viscometer.
the viscosity is preferably only relatively little from the values at room temperature and is preferably in the range of 250 mPas up to 2500 mPas.
the liquids include the following liquid at room temperature, di- or trihydric alcohols with boiling points (at 1 bar) above 80 ° C, especially above 120 ° C; n-propanol, iso-propanol, n-butanol, s-butanol, iso-butanol, ethylene glycol, 1,2- or 1,3-propylene glycol, glycerin, di- or triethylene or propylene glycol or their mixtures, in particular glycerol and / or ethylene glycol.
polymers that swell into such anhydrous liquids are suitable polyvinylpyrrolidone, polyacrylic acid, copolymers of acrylic acid and Maleic acid, polyvinyl alcohol, xanthan, partially hydrolyzed starches, alginates, amylopectin, Methyl ether, hydroxyethyl ether, hydroxypropyl ether and / or hydroxybutyl ether group-bearing Starches or celluloses, but phosphated starches such as starch disphosphate also inorganic polymers such as layered silicates and their mixtures.
the Polyvinylpyrrolidones are those with a molecular weight of up to 30,000 prefers.
Relative molecular mass ranges between are particularly preferred 3000 and 30,000, for example around 10,000.
preferred polymers also include hydroxypropyl starch and starch diphosphate.
concentration of the polymers in the anhydrous liquids is preferably 5% to 20% by weight. in particular about 6% to 12% by weight.
the content of shaping aids is preferably at least 2% by weight, but less than 20% by weight, in particular less than 15% by weight, with particular preference for amounts in the range from 3% by weight to 10% by weight.
Detergents or cleaning agents are understood to mean such compositions which are used for Washing or cleaning can be used without usually other ingredients must be added.
a multi-substance mixture or compound consists of at least 2 commonly used in washing or cleaning agents components; Compounds are usually only mixed with others Ingredients, preferably used together with other compounds.
a treated one In the context of this invention, raw material is a relatively finely divided raw material which is characterized by the The inventive method was converted into a coarser particle. Is strictly a treated raw material in the context of the invention a compound if the Treatment agent a usually used in detergents or cleaning agents Ingredient is.
the ingredients used in the process according to the invention can be produced separately Compounds, but also raw materials, which are powdery or particulate (finely divided to coarse), but in any case at room temperature and a pressure of 1 bar - with the exception the possibly existing at temperatures below 45 ° C and a Pressure of 1 bar liquid non-ionic surfactants - in solid form.
Particles can be, for example, beads or agglomerates produced by spray drying a granulation process etc. are used.
the composition of the compounds in itself is not essential to the invention except for the water content, which is so must be such that the premix is essentially anhydrous as defined above and preferably not more than 10% by weight of water of hydration and / or constitutional water contains.
over-dried compounds are used the premix.
Such compounds can, for example, by Spray drying can be obtained, the temperature control being regulated so that the Tower outlet temperatures above 100 ° C, for example at 110 ° C or above lie.
solid compounds are used in the premix as a carrier of liquid components, for example liquid nonionic surfactants or Silicone oil and / or paraffins.
These compounds can contain water in the above Contain frames, the compounds are free-flowing and preferably also at higher temperatures of at least 45 ° C free-flowing or at least remain eligible.
Free water i.e. water that is not in is bound to a solid in some form and is therefore "in liquid form" preferably not at all in the premix, since very small amounts are already present, for example by 0.2 or 0.5% by weight, based on the premix, is sufficient to achieve this to dissolve water-soluble shaping agents. This would have the consequence that the The melting point or softening point of the end product is reduced and it would lose both flow and bulk weight.
the content of bound Water in the premix is not more than 10% by weight and / or the content of water not bound to zeolite and / or silicates less than 7% by weight and is in particular a maximum of 2 to 5% by weight. It is particularly advantageous if that Premix contains no water at all, which is not bound to the builder substances. This is technically difficult to realize, however, because of the raw materials and Compounds at least always traces of water are brought in.
the content of the solid compounds used in the premix at at temperatures below 45 ° C non-aqueous liquid components, excluding those at room temperature liquid shaping aid, is preferably up to 10% by weight, advantageously up to 6% by weight, based in each case on the premix.
solid compounds are used in the premix, which are customary at temperatures contain liquid nonionic surfactants below 45 ° C and a pressure of 1 bar and according to all known types of production - for example by spray drying, Granulation or spraying of carrier beads - were produced separately.
premixes can be produced, for example up to about 10% by weight, preferably below, in particular up to a maximum of 8% by weight and for example between 1 and 5% by weight of nonionic surfactants, based on the finished agent.
Compounds that contain water in the form specified above and / or as a carrier for Liquids, in particular for nonionic surfactants which are liquid at room temperature, thus contain these ingredients which are liquid at room temperature and according to the invention can preferably be used have no softening point below 45 ° C.
the separately used raw materials also have a melting point of preferably at least 45 ° C.
the melting point is respectively the softening point of all individual raw materials and compounds used in the premix above 45 ° C and advantageously at least 50 ° C.
the molding temperatures for economic reasons alone not above 150 ° C, preferably not above 120 ° C.
at least 80% by weight of the used compounds and individual raw materials a softening point respectively Have a melting point above 150 ° C at normal pressure (1 bar).
the premix can be in addition to the solid components and at room temperature liquid shaping aid up to 10 wt .-% at temperatures below 45 ° C. and a pressure of 1 bar liquid non-ionic surfactants, especially those usually in Detergents or cleaning agents used alkoxylated alcohols, such as fatty alcohols or Oxo alcohols with a C chain length between 8 and 20 and especially an average of 3 up to 7 ethylene oxide units per mole of alcohol.
the addition of the liquid nonionic Surfactants can be used in amounts that still ensure that the premix in pourable form is present. If such liquid nonionic surfactants in the premix are introduced, it is preferred that liquid nonionic surfactants and disintegrating acting molding aids are introduced separately from one another in the process.
the liquid surfactants are in one continuous production process, in particular by means of nozzles on the powder stream applied and absorbed by the latter.
the premix also contains at least one raw material or at least one compound, which, as stated above, serves as a shaping aid.
the Shaping aid in the form of the water-free swollen polymer can before Shaping step are mixed with the other components of the premix. This is particularly preferred if the shaping by an extrusion step or with the help of a tableting or other pressing process. It can also be used during the Shaping are sprayed onto the premix or added dropwise to the premix, which is particularly preferred for shaping by means of build-up granulation.
the temperature during the shaping step is preferably at room temperature respectively the temperature resulting from the energy input of the shaping device, es
the shaping aid in the Process step of the compression molding as homogeneous as possible in the one to be compressed Is well distributed.
the applicant is believes that through a homogeneous distribution of the shaping aid in the sense of a binder within the premix under the process conditions of Compression of the solid compounds and any existing raw materials so enclosed by the binder and then glued together that the finished products are made almost exactly from these many small individual particles are built up by the binder, which is preferably thin Partition between these individual particles takes over, are held together.
the idealized form can be assumed to have a honeycomb-like structure, these honeycombs are filled with solids (compounds or individual raw materials).
the molding aid must be of the type that the adhesive properties the temperatures of the shape come into play. On the other hand, it is also essential for the choice of the type and the amount of shaping aid used, that the binding properties after the shaping step within the end product lost, the cohesion of the end product is thus ensured, however, that The end product itself is not glued under normal storage and transport conditions. It must be surprising that when using the liquid at room temperature Shaping aid is still obtained an end product that is neither at room temperature still at slightly elevated temperatures around 30 ° C, i.e. at summer temperatures and under storage or transport conditions, tends to stick.
the assembly of the detergent or cleaning agent compounds and / or raw materials under Simultaneous or subsequent shaping can be carried out by conventional methods in which Compaction forces such as granulating, compacting, for example Roll compacting or extruding, or tableting, optionally with addition usual explosives, and pelleting. It can be used as a prefabricated compound spray-dried granules can also be used in the premix, the invention is based on this however, in no way limited. Rather, the method according to the invention offers do not use spray-dried granules, since very fine-particle raw materials are also included Dust-like parts can be processed without problems according to the invention without first pre-compounded, for example to be spray dried.
the Granulation processes can be carried out continuously or batchwise. there one preferably proceeds in such a way that the solid components of the to be compressed Premixed in a granulator, which can also be used as a mixer, submitted, if necessary by adding a liquid nonionic surfactant existing dust binds and introduces the shaping aid into the granulator.
the Desired average particle size of the granulate can be determined by the type and amount of shaping aid and about the machine and operating parameters, such as Speed and dwell time as well as temperature can be set.
suitable granulators can for example pelletizing plates, rotary drums, ploughshare mixers with chopper Lödige® company, high-performance mixer with rotating mixing tank and swirler for Example from the companies Laeis Bucher® or Eirich®, intensive mixer with shaving heads for Example of the company LIPP Mischtechnik® or Imcatec®, Drais®, Fukae® or Forberg® mixer as well as the so-called Rotorcoater® from Glatt® with horizontal and with inclined turntable up to 50 °.
Lödige® CB mixers, zig-zag mixers are less suitable from PK-Niro®, a Ballestra® chain mix and Hosokawa® or Schugi® mixers.
a fluid bed or a horizontal mixer, for example a Nautamixer® also less suitable.
An advantage of the method according to the invention is that one does not rely on one for example, the two-stage described in European patent application EP 0 367 339 Pelletizing process, in which pellets first in a high speed mixer and then compressed in a slow-running mixer and granulator, is instructed, but using the water-swollen polymer, the compressing Can perform granulation in just one step.
Agents in tablet form according to the invention can be produced by means of conventional tablet presses, for example eccentric presses or rotary presses, with compression pressures in the range from, for example, 200 ⁇ 10 5 Pa to 1 500 ⁇ 10 5 Pa.
the solids for the preparation of the solid and free-flowing premix initially at room temperature to slightly elevated temperatures are up to 35 ° C in a conventional mixing and / or granulating with each other mixed.
the compression step of the method according to the invention is then carried out using an extrusion of the premix obtained in this way, for example in the European patent EP 0 486 592 B1 or international patent applications WO-A-93/02176 and WO-A-94/09111.
the premix is under pressure extruded and the strand after exiting from the hole shape by means of a Cutting device tailored to the predeterminable granule dimension.
the homogeneous and solid premix usually contains a plasticizer and / or lubricant, which causes the premix under the pressure or under the entry specific work is plastically softened and becomes extrudable.
a plasticizer and / or lubricant which causes the premix under the pressure or under the entry specific work is plastically softened and becomes extrudable.
EP 0 486 592 B1 particularly includes anionic surfactants such as alkylbenzenesulfonates and / or (fatty) alkyl sulfates, but also polymers such as polymeric polycarboxylates.
the shaping aid prevents or at least reduces sticking Apparatus walls and compaction tools. This does not only apply to processing in the Extruder, but equally for processing, for example, in continuous working mixers / granulators or rollers ..
the premix is preferably continuously one Planetary roller extruder or a 2-shaft extruder or 2-screw extruder fed with co-rotating or counter-rotating screw guide, its housing and whose extruder pelletizing head must be heated to the predetermined extrusion temperature can.
the premix is mixed in under the shear of the extruder screws Pressure, which is preferably at least 25 bar, at extremely high throughputs in Depending on the apparatus used, however, it can also be below that, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally the extrudate, preferably by means of a rotating knife, approximately reduced spherical to cylindrical granules.
the hole diameter of the Perforated nozzle plate and the strand cut length are set to the selected one Granule dimension matched.
particle diameters up to at most 0.8 cm are preferred.
Important Embodiments see the production of uniform granules in the Millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from about 0.8 to 3 mm.
the length / diameter ratio of the chipped primary In an important embodiment, granules are in the range from about 1: 1 to about 3: 1.
extrusions / pressings can also be carried out in low-pressure extruders Kahl press or in the Bextruder®.
the still plastic primary granules give a further shape
the primary granulate after the compression step any edges present are rounded, so that ultimately spherical to approximately spherical grains can be obtained if they are not already compacting in the first Shaping step arise.
small amounts of can be added at this stage
Dry powder for example zeolite powder such as zeolite NaA powder, can also be used.
the particle size distribution of the premix is much broader than that of the invention manufactured and end product according to the invention.
the premix can be essential Larger fractions of fine grain, even dust, possibly also coarser-grained fractions included, but it is preferred that a premix with a relatively broad particle size distribution and relatively high levels of fine grain in an end product with relative narrow particle size distribution and relatively small proportions of fine grain is transferred.
the process of the invention is essentially anhydrous - i.e. with the exception water-free ("impurities") of the solid raw materials used - is carried out is not only the risk of gelling the surfactant raw materials already minimized to excluded in the manufacturing process, in addition a ecologically valuable process provided, because by omitting a subsequent one Drying step not only saves energy but also emissions like they do mainly occur with conventional types of drying, can be avoided.
agents, compounds and treated raw materials thus show an improved dissolving speed such agents, compounds and treated raw materials, which have the same final composition have, but not produced by the inventive method were not swollen under anhydrous conditions using an anhydrous one Polymers were used as shaping aids.
the dissolving behavior of the particulate washing or Cleaning agent which was produced by the method according to the invention is only of the dissolving behavior of the individual raw materials and Compounds dependent. Without wanting to limit myself to this theory, it works The applicant assumes that this particular release behavior is due to a honeycomb-like Structure of the particles is effected, these honeycombs are filled with solid.
the invention further relates to the method according to the invention Compounds and treated raw materials, such as builder granules, Bleach activator granules or enzyme granules. Especially show treated raw materials an astonishingly high dissolution rate in water, especially when the raw material is on was used in a very finely divided, optionally ground form.
Compounds and treated raw materials such as builder granules, Bleach activator granules or enzyme granules.
Base granules, compounds and treated raw materials are particularly preferred provided which have spherical or pearl shape.
the bulk density of process end products produced according to the invention is preferably meadow above 700 g / l, in particular between 750 and 1000 g / l. Even if the granules with other ingredients, which have lower bulk weights, are reduced the bulk density of the final product is not as normal as expected would have been. It is believed that approximately spherical agents, and particularly extrudates, which were produced by the method according to the invention, rather the ideal shape a ball with a smooth, "smeared" surface resemble that of conventional and agents and extrudates produced in particular by aqueous processes. This will make one achieved better space filling, which leads to a higher bulk density, even if Components are added that have neither a spherical structure nor such a high bulk density exhibit.
the particulate process end products obtained can be used either directly as washing or Detergents used or previously treated by conventional methods and / or be processed.
the usual aftertreatments include, for example, powdering with finely divided ingredients of washing or cleaning agents, for example zeolites, whereby the bulk density may be increased further.
a preferred one Post-treatment also represents the procedure according to the German one Patent applications DE 195 24 287 and DE 195 47 457 are dusty or at least finely divided ingredients (the so-called fines) to the invention manufactured particulate process end products, which serve as a core, glued are and thus arise means that these so-called fines as an outer shell exhibit.
Bleach activators and foam inhibitors are mainly salts such as silicates (crystalline or amorphous) including metasilicate, carbonate, bicarbonate, sulfate, bisulfate, citrate or others Polycarboxylates, but also organic acids such as citric acid in the processing admixed. It is particularly preferred that the admixing components in granular Shape and are used with a particle size distribution that on the Particle size distribution of the agents and compounds produced according to the invention is coordinated.
a particulate detergent provided that at least 80 wt .-% of compounds produced according to the invention and / or treated raw materials. In particular, there is at least 80% by weight from a base granulate produced according to the invention.
the remaining ingredients can be prepared and mixed by any known method. However, it is preferred that also these remaining constituents, which compounds and / or treated Raw materials can be produced by the method according to the invention. In particular, this enables basic granules and remaining components to be approximated to produce the same pourability, bulk density, size and particle size distribution. It is also possible to mix the mixtures prepared according to the invention Compounds and / or treated raw materials with the remaining ingredients mentioned to produce larger moldings, for example tablets. As a special advantage, however to evaluate that it is actually possible using the method according to the invention all components of a complete washing or cleaning agent as a premix insert and granulate water-free into beads.
surfactants especially anionic surfactants preferably at least in amounts of 0.5% by weight in the agents according to the invention or the agents produced according to the invention are included.
anionic surfactants preferably at least in amounts of 0.5% by weight in the agents according to the invention or the agents produced according to the invention are included.
Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates of the kind obtained, for example, from C 12 -C 18 monoolefins having an end or internal double bond by sulfonating Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
alkanesulfonates obtained from C 12 -C 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, which by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C- Atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts are considered.
esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight.
⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
MES ⁇ -sulfofatty acids
saponified disalts are used with particular advantage.
Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 mol fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol glycerol be preserved.
alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are particularly preferred from the point of view of washing technology.
2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 -C 18 -Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are normally used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves.
sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Fatty acid derivatives of amino acids, for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants.
the sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred.
Other suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.2 to 5% by weight.
Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
the known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.
the anionic surfactants can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available.
the anionic surfactants are preferably in the form of their sodium or Potassium salts, especially in the form of the sodium salts.
the anionic surfactants are in the agents according to the invention or are in the inventive Process preferably in amounts of 1 to 30% by weight and in particular in amounts of 5 contain up to 25 wt .-% or used.
nonionic surfactants are preferred.
the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
EO ethylene oxide
alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO.
the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol is a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
polyhydroxy fatty acid amides of the formula (I) in which R 2 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R 4 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 5 represents a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 6 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
[Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
C 12 -C 18 fatty acids are nonionic surfactants.
Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amides can also be suitable.
the amount of such nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
gemini surfactants can be considered as further surfactants.
the two hydrophilic groups and two hydrophobic Have groups per molecule are usually characterized by a so-called "Spacer" separated from each other. This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient Distance so that they can act independently of each other.
Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. out. In exceptional cases However, under the term Gemini surfactants, not only dimeric but also also understood trimeric surfactants.
Suitable gemini surfactants are, for example, sulfated Hydroxy mixed ethers according to German patent application DE 43 21 022 A1 or Dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates according to the German Patent application DE 195 03 061 A1. End-capped dimers and trimers Mixed ethers according to German patent application DE 195 13 391 stand out especially by their bi- and multifunctionality. So have the named endgroup-sealed surfactants have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes suitable. Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides can also be used. as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955 can be described.
the inorganic and organic builder substances belong above all on the most important ingredients of washing or cleaning agents.
the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
zeolite P for example, zeolite MAP® (commercial product from Crosfield) is used.
zeolite X and mixtures of A, X and / or P are also suitable.
the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
the zeolite in the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 2, 3 or 4.
Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties.
the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
the term “amorphous” is also understood to mean “X-ray amorphous”.
silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 44 00 024 A1. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
phosphates are also used as builder substances possible, provided that such use is not avoided for ecological reasons should be.
the sodium salts of orthophosphates, pyrophosphates are particularly suitable and especially the tripolyphosphates.
Your salary in general no longer than 25% by weight, preferably not more than 20% by weight, in each case based on the finished product Medium.
tripolyphosphates in particular are already in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances to a synergistic improvement of the secondary washing ability to lead.
Suitable substitutes or partial substitutes for the zeolite are also layer silicates of natural and synthetic origin.
Layered silicates of this type are known, for example, from patent applications DE 23 34 899, EP 0 026 529 and DE 35 26 405. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here.
Suitable sheet silicates, which belong to the group of water-swellable smectites, are, for example, montmorrilonite, hectorite or saponite.
small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas.
the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca ++ .
the amount of water of hydration is usually in the range from 8 to 20% by weight and depends on the swelling state or the type of processing.
Layer silicates which can be used are known, for example, from US Pat. No. 3,966,629, EP 0 026 529 and EP 0 028 432. Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these.
Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used.
the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular. These acids are preferably used in anhydrous form if they are used in the premix according to the invention and are not subsequently added.
Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes.
DE dextrose equivalent
Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used.
a preferred dextrin is in European patent application EP 0 703 292 A1 described.
the oxidized derivatives of oligosaccharides are their reaction products with oxidizing agents which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function.
oxidizing agents which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function.
Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0 232 202, EP 0 427 349, EP 0 472 042 and EP 0 542 496 and international patent applications WO 92/18542, WO 93/08251, WO 94/28030 , WO 95/07303, WO 95/12619 and WO 95/20608.
a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
Oxidized oligosaccharides according to German patent application DE 196 00 018 are also suitable.
Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
glycerol disuccinates and glycerol trisuccinates are also particularly preferred in this context.
Suitable amounts used in formulations containing zeolite and / or silicate are from 3 to 15% by weight.
organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
Such cobuilders are described, for example, in international patent application WO 95/20029.
Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
the content of (co) polymeric polycarboxylates in the compositions is within the usual range and is preferably 1 to 10% by weight. %.
biodegradable polymers composed of more than two different monomer units, for example those which, according to German patent application DE 43 00 772, are salts of acrylic acid and maleic acid, as well as vinyl alcohol or vinyl alcohol derivatives, or according to German patent DE 42 21 381 Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
Other preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
polymeric aminodicarboxylic acids are also salts or their precursor substances.
polyaspartic acids or their salts and derivatives are particularly preferred, of which it is disclosed in German patent application DE 195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0 280 223.
Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
the agents can also contain components that make the oil and fat washable made of textiles. This effect is particularly evident when a textile is soiled that has previously been used several times with an inventive Detergent containing this oil and fat-dissolving component has been washed.
non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and from 1 to 15% by weight of hydroxypropoxyl groups, in each case based on the nonionic cellulose ether
those from the prior art Polymeric esters of phthalic acid and / or terephthalic acid known in the art monomeric and / or polymeric diols or their derivatives in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these.
Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates such as the above-mentioned dissolving-delayed silicates or mixtures thereof;
alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
the content of sodium silicate in the agents is, if it is not to be used as a builder, in general up to 10% by weight and preferably between 2 and 8% by weight, otherwise it can be higher.
alkali metal carbonates can also be replaced by sulfur-free amino acids and / or salts thereof having 2 to 11 carbon atoms and optionally a further carboxyl and / or amino group.
the alkali metal carbonates it is possible for the alkali metal carbonates to be partially or completely replaced by glycine or glycinate.
detergent ingredients include graying inhibitors, foam inhibitors, Bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents Substances, colors and fragrances as well as neutral salts such as sulfates and chlorides in the form of their Sodium or potassium salts.
Acid can also be used to reduce the pH of detergents or cleaning agents
Salts or slightly alkaline salts can be used.
Acidifying components Bisulfates and / or bicarbonates or the above-mentioned organic polycarboxylic acids, which can also be used as builder substances at the same time.
Particularly preferred is the use of citric acid, which is either subsequently admixed (usual procedure) or - in anhydrous form - in a solid premix is used.
bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.
Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used.
Suitable are substances which contain O- and / or N-acyl groups of the number of carbon atoms mentioned and / or where appropriate carry substituted benzoyl groups.
Multi-acylated alkylenediamines are preferred, especially 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, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from German patent applications DE-A-196 16 693
Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
the salts of polyphosphonic acids are preferably the neutral sodium salts for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5 % By weight used.
enzymes from the hydrolase class such as proteases, Lipases, cutinases, amylases, cellulases or their mixtures in question.
Oxireductases are suitable.
From bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic active ingredients.
Proteases of the subtilisin type are preferred and in particular proteases derived from Bacillus lentus are used.
Enzyme mixtures for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase of particular interest.
Peroxidases or oxidases have proven to be suitable in some cases.
Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and Pectinases.
Cellobiohydrolases, endoglucanases and ⁇ -glucosidases are preferably used as cellulases, which are also called cellobiases, or mixtures of these used. Because the different cellulase types are characterized by their CMCase and Avicelase activities can distinguish them by targeted mixtures of the cellulases desired activities.
the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
the proportion of enzymes, enzyme mixtures or enzyme granules can, for example, be approximately 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
the agents can also contain further enzyme stabilizers.
enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
calcium salts magnesium salts also serve as stabilizers.
boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening.
Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Soluble starch preparations and use starch products other than the above, e.g. degraded starch, Aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methyl carboxymethyl cellulose and mixtures thereof, and also polyvinyl pyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.
the agents can be derivatives of diaminostilbenedisulfonic acid or their Contain alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar connections, which instead of the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Can continue Present brighteners of the substituted diphenylstyryl type, e.g.
alkali salts 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls.
Mixtures of the aforementioned brighteners can also be used.
Agents E1 to E5, as well as agents V1 and V2 not according to the invention were prepared as follows:
Beaker would be rinsed over the sieve with very little cold water.
the sieves were dried in a drying cabinet at 40 ° C ⁇ 2 ° C to constant weight and the Balanced detergent residue. There was a double determination; the backlog will expressed as a percentage as the mean of the two individual determinations. In the event of deviations of the individual results by more than 20% of one another are usually further attempts carried out; however, this was not necessary in the present investigations.
a further agent V3 was prepared which contained the same ingredients in the end product as E2 , but in which the copolymer had not been introduced into the process in an anhydrous, swollen form, but rather as an approximately 30% by weight aqueous solution. The excess water was then dried off in a fluidized bed. The bulk weight of extrudate V3 was 770 g / l, the L test gave a value of 28%.
compositions of the spray-dried powders SP1 and SP2 are Compositions of the spray-dried powders SP1 and SP2:

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EP97913181A 1997-09-11 1997-10-28 Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel Expired - Lifetime EP1012221B1 (de)

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Application Number	Priority Date	Filing Date	Title
EP97913181A EP1012221B1 (de)	1997-09-11	1997-10-28	Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel

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Application Number	Priority Date	Filing Date	Title
WOPCT/EP97/04975		1997-09-11
PCT/EP1997/004975 WO1998012299A1 (de)	1996-09-20	1997-09-11	Verfahren zur herstellung eines teilchenförmigen wasch- oder reinigungsmittels
PCT/EP1997/005945 WO1999013045A1 (de)	1997-09-11	1997-10-28	Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel
EP97913181A EP1012221B1 (de)	1997-09-11	1997-10-28	Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel

Publications (2)

Publication Number	Publication Date
EP1012221A1 EP1012221A1 (de)	2000-06-28
EP1012221B1 true EP1012221B1 (de)	2004-06-16

Family

ID=8166743

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP97913181A Expired - Lifetime EP1012221B1 (de)	1997-09-11	1997-10-28	Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel

Country Status (7)

Country	Link
EP (1)	EP1012221B1 (zh)
JP (1)	JP2001515955A (zh)
CN (2)	CN1276006A (zh)
AT (2)	ATE269399T1 (zh)
DE (1)	DE59711728D1 (zh)
ES (1)	ES2224224T3 (zh)
WO (2)	WO1999013045A1 (zh)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE19848024A1 (de) *	1998-10-17	2000-04-20	Henkel Kgaa	Verfahren zur Herstellung extrudierter Formkörper
TWI409328B (zh) *	2006-01-25	2013-09-21	Kao Corp	Bleach activator granules
DE102006036895A1 (de) *	2006-08-04	2008-02-07	Henkel Kgaa	Teilchenförmiges Wasch- oder Reinigunsmittel
WO2010008712A1 (en)	2008-07-14	2010-01-21	3M Innovative Properties Company	Method of making a cleaning solution from hydrogel cleaning concentrate and packaged cleaning concentrate
DE102015206547A1 (de)	2015-04-13	2016-10-13	Henkel Ag & Co. Kgaa	Flüssiges Wasch- oder Reinigungsmittel mit suspendierten Partikeln
EP3241889B1 (en) *	2016-05-03	2019-03-20	The Procter and Gamble Company	Cleaning composition

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DD251044A3 (de) *	1984-07-20	1987-11-04	Fettchemie	Verfahren zur herstellung von granulierten wasch- und reinigungsmitteln
DE4024759A1 (de) *	1990-08-03	1992-02-06	Henkel Kgaa	Bleichaktivatoren in granulatform
DE4124701A1 (de) *	1991-07-25	1993-01-28	Henkel Kgaa	Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
EP0622454A1 (en) *	1993-04-30	1994-11-02	The Procter & Gamble Company	Structuring liquid nonionic surfactants prior to granulation process
DE4319666A1 (de) *	1993-06-14	1994-12-15	Henkel Kgaa	Verfahren zur Herstellung fester Wasch- oder Reinigungsmittel mit hohem Schüttgewicht und verbesserter Rheologie
EA000899B1 (ru) *	1995-09-04	2000-06-26	Унилевер Н.В.	Моющие составы и способ их получения

1997
- 1997-10-28 JP JP2000510835A patent/JP2001515955A/ja active Pending
- 1997-10-28 CN CN97182399.5A patent/CN1276006A/zh active Pending
- 1997-10-28 DE DE59711728T patent/DE59711728D1/de not_active Expired - Lifetime
- 1997-10-28 EP EP97913181A patent/EP1012221B1/de not_active Expired - Lifetime
- 1997-10-28 ES ES97913181T patent/ES2224224T3/es not_active Expired - Lifetime
- 1997-10-28 AT AT97913181T patent/ATE269399T1/de not_active IP Right Cessation
- 1997-10-28 WO PCT/EP1997/005945 patent/WO1999013045A1/de active IP Right Grant
1998
- 1998-09-02 WO PCT/EP1998/005548 patent/WO1999013046A1/de active IP Right Grant
- 1998-09-02 CN CN98810071.1A patent/CN1275160A/zh active Pending
- 1998-09-02 AT AT98947499T patent/ATE317003T1/de not_active IP Right Cessation

Also Published As

Publication number	Publication date
CN1275160A (zh)	2000-11-29
CN1276006A (zh)	2000-12-06
JP2001515955A (ja)	2001-09-25
WO1999013046A1 (de)	1999-03-18
DE59711728D1 (de)	2004-07-22
EP1012221A1 (de)	2000-06-28
ATE317003T1 (de)	2006-02-15
ES2224224T3 (es)	2005-03-01
WO1999013045A1 (de)	1999-03-18
ATE269399T1 (de)	2004-07-15

Publication	Publication Date	Title
EP1015550B1 (de)	2006-02-01	Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel
EP1235897B1 (de)	2004-10-13	Waschmitteltabletten
EP0859827B1 (de)	2001-06-27	Verfahren zur herstellung eines amorphen alkalisilikats mit imprägnierung
DE19956803A1 (de)	2001-06-13	Tensidgranulate mit verbesserter Auflösegeschwindigkeit
DE10120263A1 (de)	2002-10-31	Feste Tensidzusammensetzungen, deren Herstellung und Verwendung
DE19953793A1 (de)	2001-05-17	Tensidgranulate mit verbesserter Auflösegeschwindigkeit
EP0804529B1 (de)	2000-03-15	Amorphes alkalisilikat-compound
DE19941934A1 (de)	2001-03-15	Detergentien in fester Form
EP1012221B1 (de)	2004-06-16	Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel
EP0814152A2 (de)	1997-12-29	Verfahren zur Herstellung von festen Wasch- oder Reinigungsmitteln
EP0839178B1 (de)	1999-12-08	Amorphes alkalisilicat-compound
WO2005105973A1 (de)	2005-11-10	Verfahren zur herstellung von granulaten und deren einsatz in wasch- und/oder reinigugsmitteln
EP0845028B1 (de)	2000-01-05	Verfahren zur herstellung eines amorphen alkalisilikats mit imprägnierung
EP0724620B1 (de)	1999-02-03	Verfahren zur herstellung wasch- oder reinigungsaktiver extrudate mit verbessertem redispergiervermögen
EP0888428A1 (de)	1999-01-07	Verfahren zur herstellung von granularen silikaten mit hohem schüttgewicht
DE102015002877B4 (de)	2024-09-12	Wasch- oder reinigungsaktive Extrudate, deren Herstellung und Verwendung in granularen Wasch- oder Reinigungsmitteln
EP0888450B2 (de)	2003-01-15	Wasch- oder reinigungsmitteladditiv sowie ein verfahren zu seiner herstellung
WO2000039261A1 (de)	2000-07-06	Niederdosierter, löslicher builder
DE19936612A1 (de)	2001-02-08	Niederdosierter, löslicher Builder
DE19939806A1 (de)	2001-02-22	Schaumkontrollierte feste Waschmittel
WO2000022076A1 (de)	2000-04-20	Posphonathaltige granulate
DE19911570A1 (de)	2000-09-28	Aniontensid-Granulate
WO1997018290A1 (de)	1997-05-22	Verfahren zur herstellung von granularen wasch- oder reinigungsmitteln oder komponenten hierfür
DE19939805A1 (de)	2001-02-22	Schaumkontrollierte feste Waschmittel
WO1998001532A2 (de)	1998-01-15	Wasch- oder reinigungsmitteladditiv sowie ein verfahren zu seiner herstellung

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