WO1998055575A1

WO1998055575A1 - Additive granules for moulded bodies having a detergent and cleaning action

Info

Publication number: WO1998055575A1
Application number: PCT/EP1998/003042
Authority: WO
Inventors: Hans-Friedrich Kruse; Andreas Lietzmann
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1997-06-03
Filing date: 1998-05-22
Publication date: 1998-12-10
Also published as: CN1259163A; JP2002502456A; SK164499A3; DE29724283U1; ES2226143T3; PL337040A1; HUP0003067A2; CA2290014A1; ATE271596T1; EP1007616B1; EP1007616A1; DE59811697D1; DE19723028A1

Abstract

The invention relates to moulded bodies having a detergent and cleaning action, especially tablets such as those consisting of detergent, dishwashing product, stain remover or water-softener. Thanks to the use of the additive granules provided for by the invention, the disintegration rate of said tablets conforms to the requirements for use in domestic washing machines. Said additive granules contain 10 to 95 weight percent cellulose having a particle size of less than 100 νm as well as 5 to 90 weight percent microcrystalline cellulose and/or one or several ingredients of detergents and cleaning agents. They are superior to known cellulose-based disintegrating additives in terms of their physical and washing properties.

Description

"Aid granules for washing and cleaning-active molded articles"

The present invention is in the field of disintegration aids for compact moldings which have washing and cleaning properties. In particular, the invention relates to so-called disintegrant granules for use in washing and cleaning-active moldings, such as, for example, detergent tablets, dishwasher tablets, stain remover tablets or water softening tablets for use in the home, in particular for mechanical use.

Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of advantages over powdered ones: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. Detergent tablets are therefore also comprehensively described in the patent literature. A problem that occurs again and again when using shaped articles which are active in washing and cleaning is the insufficient rate of disintegration and dissolution of the shaped articles under conditions of use. Since sufficiently stable, that is to say shape and break-resistant molded articles can only be produced by relatively high compression pressures, there is a strong compression of the molded article components and consequent delayed disintegration of the molded article in the aqueous liquor and thus to a slow release of the active substances in the Washing or cleaning process. The problem of the too long disintegration times of highly compressed moldings is known in particular from the pharmaceutical industry, where certain disintegration aids, so-called tablet disintegrants, have been used for a long time in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt, Xehrbuch der pharmaceuticalische Technologie "(6th edition, 1987, pp. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are suitable for the rapid disintegration of tablets in water or gastric juice and release of the pharmaceuticals in an absorbable form.

"Hager's Handbook of Pharmaceutical Practice" (5th edition, 1991, p. 942) divides the disintegration accelerators or disintegrants into different classes of substances according to their mechanism of action, the most important disintegration mechanisms being the swelling mechanism and the deformation mechanism "), the wicking mechanism (" wicking "), the rejection mechanism (" repulsion ") and the development of gas bubbles when in contact with water (effervescent tablets). In the swelling mechanism, the particles swell through the water and increase their volume local stresses that extend across the entire tablet and thus lead to the disintegration of the compacted structure. The deformation mechanism differs from the swelling mechanism in that the swelling particles were previously compressed by the compression during the tableting and now return to their original size when water enters reach SSE. When wicking mechanism, water is sucked through the disintegrant in the tablet interior and loosens it, the binding forces between the particles which also leads to the disintegration of the shaped body. The repulsion mechanism also differs from this in that the particles released by the water sucked into the pores repel each other by the resulting electrical forces. A fundamentally different mechanism is the basis of the "effervescent tablets", which contain active substances or active substance systems which release gaseous substances when they come into contact with water, which cause the shaped body to burst. In addition, there is the use of hydrophilizing agents which ensure the better wetting of the compressed particles Water and thus ensure faster decay, known. While substances that act according to the latter two mechanisms can easily be differentiated from other disintegration mechanisms, the effects on which the swelling and deformation mechanism as well as the wicking and rejection mechanism are based cannot always be clearly separated, which is why for practical reasons, a division into hydrophilizing agents, gas-releasing systems and swelling disintegrants makes more sense.

The first group includes, for example, polyethylene glycol sorbitan fatty acid esters, the second group systems composed of weak acids and carbonate-containing agents, in particular citric and / or tartaric acid in combination with bicarbonate or carbonate. Magnesium peroxide, which releases oxygen with water, is also used as a disintegrant.

By far the largest group of disintegrants works through swelling and / or wicking effects. These include, in particular starches, cellulose and cellulose derivatives, alginates, dextrans, crosslinked polyvinylpyrrolidones, gelatin, Formaldehydkasein, but also typical inorganic substances such as the wide variety of clay minerals (eg bentonite) and Aerosil ^® (silica) and certain ion exchange resins (amber lit ^® ).

In the field of detergents or cleaning agents, according to the teaching of the European patent EP-B-0 523 099, it is also possible to use the disintegrants which are known from the manufacture of pharmaceuticals. Swelling layer silicates such as bentonites, natural substances and natural substance derivatives based on starch and cellulose, alginates and the like, potato starch, methyl cellulose and / or hydroxypropyl cellulose are mentioned as disintegrants. These disintegrants can be mixed with the granules to be compressed, but can also be incorporated into the granules to be compressed.

International patent application WO-A-96/06156 also states that the incorporation of disintegrants in detergent or cleaning agent tablets can be advantageous. In turn microcrystalline cellulose, sugars such as sorbitol, but also sheet silicates, in particular finely divided and swellable sheet silicates of the bentonite and smectite type, are mentioned here as typical disintegrants. Substances that contribute to gas formation, such as citric acid, bisulfate, bicarbonate, carbonate and percarbonate, are also listed as possible disintegrants.

In the two last-mentioned documents of the prior art, no explicit information is given as to what exact particle size distribution the disintegrants that are to be used should have; Information regarding the microcrystallinity of the cellulose and the fineness of the layered silicates, however, indicate to the person skilled in the art, especially in connection with the literature known from the manufacture of pharmaceutical tablets, that conventional disintegrants should be used in finely divided form. This is in agreement with the fact that to date no coarser products, for example those obtained by granulating finely divided powders, which are expressly offered as disintegrants for tablets, are commercially available.

European patent applications EP-A-0 466 485, EP-A-0 522 766, EP-A-0 711 827, EP-A-0 711 828 and EP-A-0 716 144 describe the production of cleaning-active tablets , where compact, particulate material with a particle size between 180 and 2000 microns is used. The resulting tablets can have both a homogeneous and a heterogeneous structure. According to EP-A-0 522 766, at least the particles which contain surfactants and builders are coated with a solution or dispersion of a binder / disintegrant, in particular polyethylene glycol. Other binders / disintegrants are, in turn, the disintegrants which have already been described several times, for example starches and starch derivatives, commercially available cellulose derivatives such as crosslinked and modified cellulose, microcrystalline cellulose fibers, crosslinked polyvinylpyrrolidones, layered silicates etc. Also weak acids such as citric acid or tartaric acid, which, in connection with carbonate-containing sources, lead to bubbling effects when they come into contact with water and which, according to Römpp's definition, belong to the second class of disintegrants, can be used as coating material. In these cases, too, no explicit information is given on the particle size distribution of the disintegrants. However, the disintegrant is applied to the surface of granular particles. This is done either as stated in liquid to disperse form or in solid form. The person skilled in the art knows that to coat particles with solid particles, the so-called “powdering”, as fine as possible, namely powder-like solids, which usually also have relatively high amounts of dust, are to be used.

According to EP-A-0 711 827, the use of particles, which predominantly consist of citrate, which has a certain solubility in water, also leads to an accelerated disintegration of the tablets. It is believed that the dissolution of the citrate locally increases the ionic strength during a transition period, which suppresses the gelling of surfactants and, as a result, does not hinder the disintegration of the tablet. According to this patent application, citrate is therefore not a classic explosive, but serves as an anti-gelling agent.

The proposed solutions lead to the desired success in the manufacture of pharmaceutical tablets. In the area of detergents and cleaning agents, they do contribute to an improvement in the disintegration properties of tablets that are active in washing or cleaning; however, the improvement achieved is not sufficient in many cases. This applies in particular if the proportion of sticky organic substances in the tablets, for example anionic and / or nonionic surfactants, increases. In addition, the use of disintegrants in washing and cleaning-active moldings can lead to specific problems that are completely unknown to medicinal products.

A particular problem results from the use of cellulose as a disintegration aid in shaped articles which are active in washing and cleaning. If the primary particle size of the cellulose is too large, the problem of residue formation on the treated textiles arises. In the case of dark textiles in particular, the deposits of the comparatively large ß Cellulose primary particles, which are released in the wash liquor after the disintegration of the molded body from the disintegrant, can be clearly recognized after drying.

As is known from pharmaceutical applications, there is only a slight disintegrant effect if cellulose is only incorporated into the moldings in finely powdered form, which is why disintegrants and in particular cellulose are mostly introduced into the moldings both in granular and powdery form (cf. “Applied biopharmaceuticals ", Wissenschaftliche Verlagsgesellschaft mbH Stuttgart, 1973, page 382). In the production of detergent tablets, however, the additional addition of cellulose powder has proven to be unnecessary and in some cases even a hindrance to the disintegration of the tablets. For the production of granular disintegrants based on cellulose Usually compacted cellulose powder with particle sizes above 150 microns to granules with a grain size between 0.4 and 2.0 mm and pressed in this form with the other ingredients to wash and cleaning active moldings.

To avoid the formation of residues on textiles, it is advisable to use a more finely divided cellulose, which does not have this problem. Unfortunately, such a cellulose powder with primary particle sizes below 100 μm cannot be compacted, since the granules obtained are so unstable that they disintegrate when mixed with the other constituents of the detergent tablets, so that cellulose powder is ultimately pressed into the tablets, which alone has no significant explosive effects.

Accordingly, the object of the invention was to provide an auxiliary granulate for washing and cleaning-active moldings which, on the one hand, does not have the residue problem but, on the other hand, can be incorporated into the mixtures to be pressed in granular form without losing its effective shape. The object of the invention was also to develop a method for producing such disintegrant granules for incorporation into detergent tablets. It has now been found that the stability problems of a disintegrant granulate based on cellulose with particle sizes below 100 μm can be circumvented by granulating the cellulose together with microcrystalline cellulose or other detergent ingredients.

The invention therefore relates in a first embodiment to an auxiliary granulate for washing and cleaning-active molded articles, the

a) 10 to 95 wt .-% cellulose with particle sizes below 100 microns

b) 5 to 90 wt .-% microcrystalline cellulose and / or one or more ingredients of detergents and cleaning agents

contains. Substances from the group of builders, bleaching agents and bleach activators, foam inhibitors and soil-release polymers are preferably used as ingredients of washing and cleaning agents.

In the context of the present invention, auxiliary granules are understood to mean all those auxiliaries and, in particular, disintegrants which are per se in finely divided powder form and have been converted into a coarser granular form by a spray drying, granulating, agglomerating, compacting, pelletizing or extrusion process. This includes not only disintegrants in granular form, but also, for example, those in co-granulated form.

The terms “particle size” and “primary particle size” are used as synonyms in the context of the present invention if they are used to describe the cellulose in powder form. The granules obtained by granulating the cellulose powder naturally have particle sizes which are larger than the primary particle size of the cellulose powder used. The term “particle size” or “primary particle size” means that the corresponding powders pass completely through a sieve of the specified mesh size and leave less than 1% by weight residue, based on the sieved powder, on the sieve.

The auxiliary granules of the present invention have a number of advantages which make them stand out over conventional disintegrants. So there are no problems with residues on laundry that has been washed with detergent tablets containing the auxiliary granules according to the invention. Also quantitatively, compared to detergent tablets of otherwise analog composition, which contained cellulose granules from cellulose of primary particle sizes above 150 μm as disintegrants, better reflectance values, higher degrees of whiteness and an improved “soft touch of the laundry.

The cellulose, which is contained as component a) in the auxiliary granules according to the invention, has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, viewed formally, is a β-1,4-polyacetal of cellobiose, which in turn consists of two molecules Glucose is built up. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. A particle size of the cellulose prior to granulation of less than 100 μm is essential to the invention, primary particle sizes below 70 μm or below 50 μm being preferred. Cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used as component a) in the context of the present invention. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

The cellulose derivatives mentioned are preferably not used alone as component a), but are used in a mixture with cellulose. The content of these mixtures in Cel Lulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on component a). Pure cellulose which is free from cellulose derivatives is particularly preferably used as component a). In a particularly preferred embodiment, the granules contain as component a) 15 to 80% by weight, preferably 20 to 70% by weight and in particular 25 to 60% by weight of cellulose with a particle size below 70 μm, preferably below 50 μm.

The auxiliary granules according to the invention contain microcrystalline cellulose and / or the ingredients of detergents and cleaning agents in amounts between 5 and 90% by weight, based on the auxiliary granules. Amounts of these ingredients which are preferably used are in the range from 10 to 70% by weight, with amounts between 20 and 60% by weight and in particular between 30 and 50% by weight again being preferred.

Microcrystalline cellulose can be used as the sole component b) or as a component of this component. This cellulose has primary particle sizes of approx. 5 μm and was compacted into granules with an average particle size of 200 μm. These compacts are stable, can be mixed with other substances without disintegrating into the primary particles and are suitable, in turn, with the finely divided cellulose {component a)} to form stable auxiliary granules which are stable when mixed with other substances. In this way it is possible within the scope of the present invention to produce a completely cellulose-based auxiliary granulate which does not have the inherent problem of residues of conventional cellulose disintegrants. In the wash liquor, these auxiliary granules disintegrate into the primary particles, as a result of which no cellulose particles with particle sizes above 100 μm remain in the wash liquor.

In the context of the present invention, preference is given to auxiliary granules in which component b) contains 5 to 70% by weight, preferably 10 to 60% by weight and in particular 20 to 50% by weight, of microcrystalline cellulose, based on the auxiliary granules . The auxiliary granules according to the invention may contain all the usual ingredients of these detergents and cleaning agents as ingredients of detergents and cleaning agents (component b) alone or a component thereof, the use of auxiliaries which, in addition to their function, stabilizing the granules with the cellulose, still perform other tasks in the washing and cleaning process, is preferred. The ingredients of detergents and cleaning agents which are contained in the auxiliary granules according to the invention are preferably selected from the group of builders, bleaching agents and bleach activators, foam inhibitors and soil-release polymers.

Preferred components b) from this group are the bleaching agents and bleach activators, with auxiliary granules being preferred which contain 10 to 70, preferably 20 to 60 and in particular 30 to 50% by weight of a bleaching agent or bleach activator as component b). A preferred auxiliary granulate contains the bleach activator tetraacetylethylene diamine (TAED) as a component or sole ingredient of component b).

The auxiliary granules according to the invention preferably have no fines below 0.1 mm and preferably contain a total of only 0 to 5% by weight of particles with particle sizes below 0.2 mm. Preferred granules consist of at least 90% by weight of particles with a size of at least 0.3 mm and at most 2.0 mm.

In a further embodiment, the invention relates to a method for producing the auxiliary granules according to the invention, in which

a) 10 to 95 wt .-% cellulose with particle sizes below 100 microns and

be granulated under compacting conditions. To this end, components a) and b) are mixed, the cellulose having to meet the particle size criteria mentioned because of the residue problem, while component b) is not subject to any restrictions with regard to the particle size. In the interest of an intensive and homogeneous mixing of the two components, it may be advantageous, before the compacting process, to also grind component b) to particle size ranges below 1 mm, in particular below 500 μm and particularly preferably below 200 μm.

The granulation under compacting conditions can be carried out by all processes familiar to the person skilled in the art, with a wide variety of apparatuses being suitable for carrying out the process according to the invention. In the context of this application, the granulation under compacting conditions can be equated with terms such as granulation, agglomeration, compacting, extrusion and pelletizing.

As apparatuses in which the inventive method can be carried out, for example, a wide variety of types of mixers are suitable, such as Eirich ^® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), Kae the fu ^® FS-G mixer ( Trademarks of Fukae Powtech, Kogyo Co., Japan), the Lödige ^® FM, KM and CB mixers (trademarks of Lödige Maschinenbau GmbH, Paderborn) or the Drais ^® series T or KT (trademarks of Drais- Werke GmbH, Mannheim). Other suitable granulators are pellet presses, which are used as ring die presses in preferred embodiments. Roller compacting has proven to be particularly advantageous and particularly preferred in the context of the present invention, in which the dry premix of components a) and b) is compacted by two rollers rotating in opposite directions to form a sheet-like slug, which is then broken down by grinding and sieving Granules with particle sizes below 2 mm is brought. The following is a brief description of the ingredients of detergents and cleaning agents which are preferably to be used as component b), the substances from the group of builders, bleaching agents and bleach activator, foam inhibitors and soil-release polymers being described in succession.

In particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances are suitable as builders, which can be contained in the auxiliary granules according to the invention and in the process for the preparation of these auxiliary granules as the sole constituent or ingredient of component b) to call.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} Η 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. 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 β- and δ-sodium disilicate Na ₂ Si ₂ 0 ₅ -yH ₂ 0 are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171.

Amorphous sodium silicates with a module Na ₂ 0: Si0 ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates do not give sharp X-ray reflections in X-ray diffraction experiments as they do for crystalline substances. zen are typical, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, 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. In the event that the zeolite is used as a suspension, it may contain minor 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 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated as the sole constituent or as an ingredient of component b). Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated 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, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate and 2,5-glycol glycol Diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the moldings. These substances it is bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Lack of disclosure, Ti, V and Cu complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru-amine complexes can also be used as bleaching catalysts.

Suitable foam inhibitors, which can be part of component b), or used alone as component b), are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ . ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silicic acid or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

In addition, the agents as component b) or their constituent can also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight. , each based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred. Preferably used In the context of the present invention, bar is also carboxymethyl starch (CMS) as component b) or as a component of this component.

In a further embodiment, the invention provides for the use of the auxiliary granules according to the invention for washing and cleaning-active shaped articles as disintegration accelerators in such washing and cleaning agent shaped articles, in particular detergent tablets.

The invention thus also relates to shaped articles which are active in washing and cleaning, in particular detergent tablets, which contain 1 to 40, preferably 2.5 to 30 and in particular 5 to 20% by weight of an auxiliary granulate according to the invention.

These moldings are obtained by mixing the auxiliary granules with the other constituents of the detergent and cleaning agent and subsequent molding.

The moldings can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial form, for example, the design as a board, the rod or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points. For the use of laundry detergents in machines of the type common in Europe with horizontal arranged mechanics, the formation of the portioned compacts as tablets, in cylindrical or cuboid form may be expedient, a diameter / height ratio in the range from approximately 0.5: 2 to 2: 0.5 being preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such compacts.

The spatial shape of another embodiment of the shaped body is adapted in its dimensions to the induction chamber of commercially available household washing machines, so that the shaped bodies can be dosed directly into the induction chamber without metering aid, where they dissolve during the induction process. Of course, however, the detergent tablets can also be used without problems via a metering aid and are preferred in the context of the present invention.

Another preferred molded body that can be produced has a plate-like or plate-like structure with alternately thick long and thin short segments, so that individual segments are broken off from this “bar” at the predetermined breaking points, which represent the short thin segments, and into the This principle of the “bar-shaped” shaped body detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.

However, it is also possible that the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous performance properties of the molded articles. If, for example, components are contained in the moldings which have a mutually negative effect, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution. The layer structure of the Shaped bodies can be made in a stack-like manner, with the inner layer (s) already loosening at the edges of the shaped body when the outer layers have not yet been completely detached, but it is also possible for the inner layer (s) to be completely enveloped by the each layer (s) lying further outside can be reached, which prevents the premature dissolving of components of the inner layer (s).

In a further preferred embodiment of the invention, a shaped body consists of at least three layers, i.e. two outer and at least one inner layer, at least one peroxy bleaching agent being contained in at least one of the inner layers, while the two cover layers are used in the case of the stacked shaped body and the is in the case of the shell-shaped shaped body outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in one molded body. Such multilayered moldings have the advantage that they can not only be used via a dispensing chamber or via a metering device which is added to the wash liquor; rather, it is also possible in such cases to put the molded body in direct contact with the textiles in the machine without fear of bleaching and the like.

Similar effects can also be achieved by coating individual constituents of the detergent and cleaning agent composition to be pressed or the entire molded body. For this purpose, the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or via the process of melting. get a coating.

In addition to the auxiliary granulate according to the invention, which facilitates and accelerates the disintegration of the washing and cleaning-active moldings, the moldings according to the invention can contain all the usual constituents of washing and cleaning agents. If auxiliary granules according to the invention are used which contain certain ingredients of detergents and cleaning agents as component b), further addition can be made these substances can be dispensed with in the production of the shaped body. However, it can also be preferred to incorporate such constituents of detergents and cleaning agents both as component b) into the auxiliary granules and additionally into the shaped body. In addition to the constituents already mentioned above as a constituent of the auxiliary granulate, the shaped bodies according to the invention can contain further constituents which are not introduced into the shaped body via the auxiliary granulate. Surfactants and enzymes are to be mentioned here in particular as substances which are active in washing and cleaning and which are incorporated into the molded body.

Anionic, nonionic, cationic and / or amphoteric surfactants can be used in the detergent tablets according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants. The total surfactant content of the molded article is from 5 to 60% by weight, based on the weight of the molded article, with surfactant contents above 15% by weight being preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C ₉ _ ₁₃ -Alkylbenzolsul- sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfide, obtained, for example, from C _12th ₁₈ -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Alkanesulfonates which are derived from C ₁₂ are also suitable. _{] 8-} alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, such as those used in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained. Preferred sulfated fatty acid glycerol esters are the sulfie 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.

The alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C _{] 2} -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ - Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. From the washing are the C ₁₂ -C _I6 alkyl sulfates and C _I2 -C ₁₅ alkyl sulfates and C ₁₄ - C ₁₅ alkyl sulfates. In addition, 2,3-alkyl sulfates, which are produced for example according to U.S. Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^® are surfactants suitable anion.

The sulfuric acid monoesters of the straight-chain or branched C _7.21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ . _π alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ . _{] 8} fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable 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 especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _g . ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which by themselves considered non-ionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues 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.

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical 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. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow 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 _12.14 alcohols with 3 EO or 4 EO, C ₉ . _π alcohol with 7 EO, C _13.15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ _,. alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ . ₁₄ alcohol with 3 EO and C ₁₂ . ₁₈ - alcohol with 5 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 ranks ethoxyla- tes, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes 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 which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, 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 ester, as described for example in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.

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 alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I), R ^J

R-CO-N- [Z] (I)

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

R! -OR ²

R-CO-N- [Z] (II)

in which R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^! is a linear, branched or cyclic alkyl group or an aryl group containing 2 to 8 carbon atoms and R ² is a linear, branched or cyclic alkyl group or an aryl group or an oxyalkyl group having 1 to 8 carbon atoms, where C, _ ₄ - alkyl or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives of this radical.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example 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 the international application WO-A-95/07331 can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active substances obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. 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 in the shaped bodies according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

The shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the Moφholino group, have a diethanolamino group , a methyl amino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.

The invention can also take advantage of the fact that acidifying agents such as citric acid, tartaric acid or succinic acid, but also acidic salts of inorganic acids (“hy- drug salts "), for example bisulfates, especially in combination with carbonate-containing systems, can contribute to the improvement of the disintegration properties of the molded articles. Within the scope of this invention, however, it is provided that these acidifying agents also have a coarse-grained, in particular granular form, which have as little dust as possible and the granular acidifying agents can be present, for example, in quantities of 1 to 10% by weight in the shaped bodies.

The moldings according to the invention, in particular the detergent moldings and bleaching moldings which have hitherto been poorly disintegrating and poorly soluble, have excellent disintegration properties due to the use of the auxiliary granules according to the invention. By compacting the disintegration aid with a detergent ingredient, a broader distribution of the aid granules is achieved in the entire molded body. The improved disintegration can be tested, for example, under critical conditions in a conventional household washing machine (use directly in the washing liquor using a conventional dosing device, delicates program or colored laundry, washing temperature maximum 40 ° C) or in a beaker at a water temperature of 25 ° C. The execution of the corresponding tests is described in the example section. Under these conditions, the shaped bodies according to the invention not only completely disintegrate within 10 minutes; the preferred embodiments have disintegration times in the beaker test of less than 3 minutes, in particular less than 2 minutes. Particularly advantageous embodiments even have disintegration times of less than 1 minute. Disintegration times of less than 3 minutes in the beaker test are sufficient to allow the detergent tablets or the washing additive tablets to be rinsed into the washing liquor via the detergent dispenser of conventional household washing machines. In a further embodiment of the invention, a washing method is therefore claimed, the shaped body being introduced into the washing liquor via the induction device of the household washing machine. The dissolving times of the molded articles in the washing machine are preferably less than 8 minutes and in particular less than 5 minutes. The molded articles according to the invention are actually produced first by dry mixing the auxiliary granules with the remaining constituents and then providing information, in particular feeding to tablets, using conventional methods (for example as in the conventional patent literature for tablets, especially in the field of detergents or cleaning agents). in particular as can be used in the abovementioned patent applications and the article "Tablettierung: Stand der Technik", SÖFW-Journal, 122nd year, pp. 1016-1021 (1996).

B e i s p i e l e

The auxiliary granules 1, 2 and 3 as well as the comparative examples 4, 5 and 6, which had a composition according to Table 1, were produced by roller compaction and a subsequent grinding and sieving process.

The comparative examples contained either an unsuitable component a) (oversized primary particle size, example 4), unsuitable components b) (example 6: additional bubbling system which is not a common ingredient in detergents and cleaning agents) or no component b) (example 5)

In the case of Comparative Example 5, no stable granules could be obtained. The "granules" obtained disintegrate again into the primary particles before they are mixed with the other ingredients. In a further comparison, non-granulated, fine-powdered cellulose (50 μm) was used from the outset, the completely analog values for tablet hardness and disintegration times (Table 3) as comparative example 5 provided.

Table 1: Aid granules [% by weight]

The auxiliary granules produced in this way were mixed with further components to form a finished washing and cleaning agent, the base granules being a powder of the following composition:

Table 2: Basic granules [% by weight]

Cobuilder H 40 is an acrylic acid-maleic acid copolymer from Stockhausen HEDP is the sodium salt of hydroxyethane-l, l-diphosphonic acid

The mixed washing and cleaning agents were then pressed into tablets in a tablet press. The hardness of the tablets was measured by deforming the tablet to fracture, the force acting on the side surfaces of the tablet and the maximum force that the tablet was able to withstand. To determine the tablet disintegration, the tablet was placed in a beaker with water (600 ml water, temperature 25 ° C.) and the time until the tablet disintegrated completely.

The composition of the tablets and the experimental data are shown in Table 3:

Table 3: Detergent tablets [composition in% by weight]

Comparative Example 4 shows comparable values for the tablet hardness and in the disintegration test with Examples 1, 2 and 3 according to the invention. In order to demonstrate the superiority of the auxiliary granules according to the invention in detergent tablets, the following washing tests were carried out: 2 tablets (40 g each) were placed in the washing-up chamber of a washing machine. The machine was loaded with 3.5 kg of dark blue terry towels and operated under the following conditions: tap water of 23 ° d (equivalent to 230 mg CaO / 1), washing temperature 60 ° C, liquor ratio (kg of washing: liters of washing solution in the main wash) 1: 5, 7, rinse three times with tap water, spin off and dry. The dried towels were assessed after 10 washes according to the following criteria:

Grade 1 flawless, no recognizable residues Grade 2 tolerable, isolated, non-disturbing residues Grade 3 recognizable residues from grade 4 which are already annoying in the event of a critical assessment: clearly recognizable and disturbing residues in increasing number and quantity

In addition, the wash-in chamber was opened after the washing process and assessed visually. Here mean:

Grade 1 flawless, no recognizable residues, completely washed in Grade 2: tolerable, isolated, non-disturbing residues, very finely divided Grade 3 recognizable residues, which are already disturbing in the case of critical assessment, grade 4 clearly recognizable and disturbing residues in increasing number and quantity, agglomerate and Lump formation,

The individual detergent tablets were assessed as follows:

The shaped bodies 1, 2 and 3 according to the invention show the best residue values due to the use of the finely divided cellulose in conjunction with very good tablet disintegration (see Table 3). Example 4, which is not in accordance with the invention and also has a good disintegration rate (see Table 3), performs much worse due to the use of cellulose with a primary particle size of 150 μm: the cellulose residues on the laundry are visually recognizable as disruptive residues.

*) Due to the extremely long disintegration times of tablets 5 and 6, these do not show disintegration in the dispenser and cannot be dispensed via the dispenser of the washing machine. The tablets are almost unchanged in the dispenser after the wash cycle, which is why no residues can be observed on the treated textiles.

Claims

Patent claims

1. Aid granules for washing and cleaning-active molded articles, characterized by a content of

a) 10 to 95 wt .-% cellulose with particle sizes below 100 microns

b) 5 to 90 wt .-% microcrystalline cellulose and / or one or more ingredients of detergents and cleaning agents.

2. Auxiliary granules according to claim 1, characterized in that substances from the group of builders, bleaching agents and bleach activators, foam inhibitors and soil-release polymers are contained in the granules as ingredients of washing and cleaning agents.

3. Aid granules according to claim 1 or 2, characterized in that the microcrystalline cellulose and / or the ingredients of detergents and cleaning agents in amounts between 10 and 70 wt .-%, preferably between 20 and 60 wt .-% and in particular between 30 and 50% by weight, based on the auxiliary granulate, are contained in the granulate.

4. Auxiliary granules according to one of claims 1 to 3, characterized in that as component b) 5 to 70 wt .-%, preferably 10 to 60 wt .-% and in particular 20 to 50 wt .-% microcrystalline cellulose, based on the Auxiliary granules are contained in the granules.

5. Aid granules according to one of claims 1 to 3, characterized in that 10 to 70 wt .-%, preferably 20 to 60 wt .-% and in particular 30 to 50 wt .-% of a bleaching agent or bleach activator are used as component b) .

6. Auxiliary granules according to claim 5, characterized in that tetraacetylethylene diamine (TAED) is used as the bleach activator.

7. Auxiliary granules according to one of claims 1 to 6, characterized in that as component a) 15 to 80 wt .-%, preferably 20 to 70 wt .-% and in particular 25 to 60 wt .-% cellulose with a particle size below 70 μm, preferably less than 50 μm, is used.

8. A process for the preparation of auxiliary granules for washing and cleaning-active molded articles according to one of claims 1 to 7, characterized in that

a) 10 to 95 wt .-% cellulose with particle sizes below 100 microns

granulated under compacting conditions.

9. The method according to claim 8, characterized in that one

a) 10 to 95 wt .-% cellulose with particle sizes below 100 microns

compacted by roller compaction to form a leaf-shaped slug, which is then ground and sieved to granules with particle sizes below 2 mm.

10. Use of auxiliary granules for washing and cleaning-active molded articles according to one of claims 1 to 7, as disintegration accelerators in detergent and molded article bodies, in particular detergent tablets.

11. washing and cleaning-active molded articles, in particular detergent tablets, containing 1 to 40% by weight, preferably 2.5 to 30% by weight and in particular 5 to 20% by weight of an auxiliary granulate according to one of claims 1 to 6.

12. Washing method using a molded body according to claim 11, characterized in that the molded body is introduced into the washing liquor via the induction device of a household washing machine.