CZ20003203A3 - Process for preparing washing and cleansing compositions - Google Patents

Abstract

The invention relates to a method for producing detergent forms. According to said method, highly dosed fragrant compounds with apparent densities of more than 700 g/l are produced by granulation or pressure agglomeration and mixed with other powder-form and/or granular detergent constituents. These premixtures are then compacted into forms using a known method. The incorporation of the perfume according to the invention results in detergent forms which are characterised in that they are harder and in that they disintegrate more quickly than conventionally produced forms.

Description

Method for producing detergents or cleaning agents

Technical field

The present invention relates to a method for manufacturing detergent moldings, in particular detergent tablets for use in household washing machines.

BACKGROUND OF THE INVENTION

Compared to powder or liquid detergents and cleaning agents, detergent articles in the form of shaped bodies have a number of advantages that can be easily dispensed and, due to their high density, have lower packaging requirements and reduced space for transportation and storage. Another important advantage of such products is their acceptance by consumers, which is based not only on the above advantages but also on the aesthetic features of the shaped bodies. Thus, in the field of machine dishwashing, tablets have already largely displaced the previously conventional powder products.

Against these advantages, however, are disadvantages based on the shaped bodies themselves. Thus, the molded bodies must be sufficiently stable after manufacture to be packaged, transported and stored without breaking or rubbing. These stability requirements require a certain hardness of the shaped bodies, which in turn opposes the rapid dissolution of the shaped bodies. This analysis between hardness and disintegration time is a key problem in the production of shaped bodies, irrespective of the area in which the shaped bodies are to be used.

Other specific problems are encountered in the manufacture of detergent articles in the form of shaped bodies. While dishwashing detergents in tablet form contain relatively small amounts of surfactants and are predominantly composed of well soluble

The detergent compositions contain, for example, a significantly higher amount of surfactant, which causes dissolution problems, as some surfactants tend to gel or only dissolve slowly. The requirements which are placed on a textile washing composition in the form of molded molded bodies are also considerably higher than for dishwashing tablets in dishwashers. In the dishwasher, the tablet lies in a basket and dissolves there throughout the wash. In household washing machines, the textile detergent body must on the one hand be dispensable by means of a flushing chamber, so it must disintegrate into seconds so small particles that can be rinsed; on the other hand, it must also be ensured, when dosed by direct insertion into the drum, that the shaped bodies dissolve completely and quickly, so as to avoid as much as possible a solid moist detergent from contacting the laundry, thereby avoiding spotting problems in the laundry .

Detergent detergents in the form of corpuscles contain additional ingredients to dishwasher tablets that further increase the discrepancy between hardness and disintegration time. While dishwashing detergents generally do not contain fragrances, perfumes in detergents are of great importance: on the one hand, fragrance provides a clearly identifiable, "unmistakable" product; on the other, fragrance of washed textiles is an important feature in evaluating product properties recommended by the consumer.

However, fragrances are highly hydrophobic substances which further make it difficult to dissolve detergents containing these fragrances, since they cause their hydrophobization when sprayed onto the powder mixture.

There are only a small number of published publications in the prior art relating to detergent formulations.

which relate to the incorporation of hydrophobic and hydrophobic substances into these shaped bodies.

Thus, the earlier German patent application 197 39 384.5 (Henkel KGaA) discloses detergent formulations of compacted particulate detergent and detergent compositions containing a surfactant or surfactants, a builder, a cellulose-based disintegrant and any other laundry detergent ingredients and detergents. In separating the disintegrant from substances that may prevent moisture from accessing the disintegrant, the disks described herein have excellent dissolution properties.

This document exclusively describes how the disintegration effect of the disintegrant used can be optimally utilized.

There is no mention of optimized incorporation of hydrophobizing agents.

The earlier German patent application 197 39 383.7 (Henkel KGaA) discloses detergent formulations of compacted particulate detergent and detergent compositions containing a surfactant or surfactants, a builder, a cellulose-based disintegrant and optionally other laundry and cleaning ingredients. compositions in which all hydrophobizing substances are applied to the carrier material. Hydrophobic substances for the purposes of this application are, for example, also perfume oils, the application of which to carriers is not mentioned in this specification.

It is an object of the present invention to provide a process for manufacturing detergent compositions in the form of shaped bodies which, as the final product of the manufacturing process, provide shaped bodies that are characterized by high hardnesses and short disintegration times. In particular, the method should make it possible to appropriately incorporate perfume into the moldings without the product having the disadvantages of conventional detergent articles in the form of moldings. • ······ · · · · · · · · · · · · · · · · · · ·

- 4 containing perfume. Provision should also be made for perfume-containing laundry detergents and cleaners in the form of shaped bodies which achieve or exceed the perfume-free shaped articles in terms of properties.

SUMMARY OF THE INVENTION

The object has been achieved by incorporating molding bodies, in particular fragrance-containing pearls, in molding detergents and cleaning compositions, wherein the fragrance-containing moldings are produced by granulation or agglomeration in presses (e.g. pelletizing presses, extrusion, etc.). .).

The object of the invention is a process for the production of shaped articles in the form of detergent compositions in which high fragrance compositions (hochdosierte Duftstoff-Compounds) are produced by granulation or agglomeration in presses, mixed with other powder and / or granular detergent and cleaning ingredients. and the premix is compressed in a known manner into shaped bodies.

For use in the process of the present invention, high aromatic compositions are suitable, which can be produced by granulation or agglomeration in presses. Fragrant particles, in particular fragrant pearls having a bulk density of more than 700 g / l, are preferred. The manufacture of "fragrance-containing pearls" (Duftperlen) used advantageously in the process according to the invention is described, for example, in an earlier German patent application

197 46 780.6 (Henkel KGaA). This application discloses a process for the manufacture of fragrance-containing shaped bodies, in particular fragrance-containing pearls, having a bulk density of more than 700 g / l, in which a solid and substantially anhydrous masterbatch consisting of:

(a) 65 to 95% by weight of the carrier or carriers;

(b) 0 to 10% by weight of excipient (s); and

c) 5 to 25% by weight of perfume.

Preferred carriers are selected from the group of surfactants, mixtures of surfactants, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates and are used in amounts of between 65 and 95% by weight, preferably 70 to 90% by weight, based on each the weight of the fragrance-containing shaped body obtained.

In addition to the "fragrance-containing pearls" obtainable as described above, the process according to the present invention is advantageous in the treatment of the fragrance-containing pearls described in the earlier German patent application 197 46 781.4 (Henkel KGaA). This publication discloses a process for the manufacture of detergent or detergent compositions or enhancement fragrance components thereof having a bulk density of more than 600 g / l, wherein a solid and substantially anhydrous premix of detergent or detergent ingredients and / or raw materials is produced, which contains at least 0.1% by weight of perfume based on the masterbatch, and the masterbatch is treated by agglomeration in a press. These flavor enhancement detergents or cleaners or the aforementioned fragrance-containing moldings can be incorporated into the masterbatch in the process of the present invention.

The production of shaped bodies with a high content of fragrances is carried out by granulation or agglomeration in presses. In granulation, the masterbatch for fragrance-containing moldings is compacted and homogenized in a circulating mixer and granulated to form fragrance-containing moldings, especially fragrance-containing pearls. The granulation provides a fragrance-containing pearl with a wider grain size range (coarse and fine fractions), and for this reason the process variant with agglomeration in presses is preferable to granulation.

In the compression agglomeration process, the fragrance-containing masterbatch composition is compacted and plasticized using shear forces, homogenizing and then extruding from the device in the desired shape. Technically important methods of compression agglomeration are extrusion, roller compacting and pelletization.

In a preferred embodiment of the invention, the premix for the aqueous-containing shaped bodies is preferably fed continuously into a planetary cylindrical extruder or a twin-roll extruder or a twin-screw extruder or a twin-screw extruder with simultaneous or counter-rotating worms. determined extrusion temperature. Under the action of the shear forces of the extruder screws, the premix at a pressure of preferably at least 2.5 MPa, but at extremely high throughputs depending on the equipment used, may be even lower, densified, plasticized, extruded in the form of fine strands through a perforated die head and finally, the extrudate is preferably reduced to a approximately spherical to cylindrical granulate grain by a rotating cutting knife. The diameter of the nozzle head openings and the cross-section of the strands are adapted to the selected size of the granulate. In this embodiment, it is possible to produce granules having a substantially uniformly preset particle size, and the absolute particle sizes can be adapted to the intended use. Generally, particle diameters of at most 0.8 cm are preferred. Preferred embodiments herein contemplate the production of uniform granulates in the millimeter range, for example in the range of 0.5 to 5 mm, and particularly in the range of about 0.8 to 3 mm. In the most important embodiment, the length / diameter ratio in the primary granulate to be cut ranges from about 1: 1 to about 3: 1. Furthermore, it is advantageous to feed the plastic primary granulate for further forming processing;

the edges present on the raw extrudate are rounded, so that a spherical to almost spherical grain of the extrudate can finally be obtained. If desired, small amounts of dry powder, for example a zeolite powder such as NaA powder zeolite, may be added at this stage. This molding can take place in conventional rounding devices. It is important to ensure that only small amounts of fine-grained particles are produced at this stage. Alternatively, extrusion / compression can also be carried out in low-pressure extruders, in a Kahl-Presse or in a Bextruder.

As with the extrusion process, it is also advantageous in other processes for producing fragrance-containing shaped bodies to feed the resulting primary granulates / compactates into a further forming processing step, in particular a rounding step, so that spherical to almost spherical (pearly) particles can finally be obtained.

In a further preferred embodiment of the present invention, the production of fragrance-containing shaped bodies is performed by roller compacting. In this case, the solid fragrance-containing premix is fed in a targeted manner between two smooth rollers or rollers provided with depressions of a defined shape, and between the two rollers it is rolled under pressure into a sheet-like compact (Scholepe). The cylinders exert a high linear pressure on the premix of the fragrance-containing shaped bodies and can additionally be heated or cooled as required. The use of smooth rollers yields smooth, unstructured compacted strips, while using structured rollers it is possible to produce correspondingly structured compacts, which can be pre-treated, for example, with certain forms of later fragrance-containing shaped bodies. The compacted web is then broken up during crushing and shrinking into small pieces and then processed to granulate grains which are processed by known surface treatment methods, in particular to nearly spherical shapes.

In a preferred embodiment, the production of fragrance-containing shaped bodies is carried out by pelletizing. In this case, a solid premix of fragrant-containing shaped bodies is applied to the perforated surface and extruded by means of pressure-modified tools to plasticize

holes. In a conventional pelletizing press, the premix of perfume-containing shaped bodies is compacted under pressure, plasticized, extruded by a rotating roller into a fine strand form by a perforated surface, and finally reduced by a granulate cutter. A wide variety of press rolls and perforated dies can be used. Thus, for example, flat perforated plates can be used as well as concave or convex circular dies by which the material is extruded by means of one or more compression rollers. The press rolls can also be conical in the case of the disk devices, and in the case of the ring devices, the die and the press roll or press rolls can be rotated in parallel or counter-rotating. An apparatus suitable for carrying out the process according to the invention is described, for example, in DE 38 16 842 (Schlüter GmbH). The circular die press described herein consists of a rotating press die provided with a circular die and at least one press roller arranged in a working position relative to the internal surface of the die, which presses the material introduced into the matrix space through the press channels into the material exit space. In this case, the annular die and the press roller can be rotated in a consistent manner, which results in reduced shear and thus a lower temperature of the masterbatch. Of course, it is also possible to work with pelletization with heated or cooled rollers to set the desired premix temperature.

In the manufacture of fragrance-containing shaped bodies, it is advantageous to carry out the granulation or pressure agglomeration in a substantially anhydrous manner. In this context, the term "substantially anhydrous" means a condition in which the liquid water content, i.e. water which is not in the form of hydrate water 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 of perfumes. Thus, water can only be substantially fed into the premix of fragrant form bodies

- 9 9 9 999 9 9 999 in a chemically and / or physically bound form, or as a constituent which, at temperatures below 45 ° C and at a pressure of 0,1 MPa, as a solid but not in the form of a liquid, solution or dispersion . In that the process for producing fragrance-containing shaped bodies is carried out in a substantially anhydrous manner, i. with the exception of the water ("impurities") contained in the solid raw materials used, an ecologically valuable process is achieved, since bypassing the subsequent drying step not only saves energy but also reduces the emissions that are predominantly present in the previous drying processes. Moreover, the omission of the subsequent drying step allows the incorporation of sensitive or volatile fragrances into the masterbatch and thus the production of shaped bodies, in particular fragrance-containing beads.

Fragrance-containing moldings which are processed with the other ingredients into a tablet masterbatch in the process of the present invention can be very diverse in terms of perfume content. Preference is given to shaped bodies, in particular fragrance-containing pearls containing 30 to 40% by weight, preferably 5 to 30% by weight, and in particular 8 to 20% by weight of perfume, based on the weight of the fragrance-containing molding.

As perfume oils or fragrances, individual fragrance compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used in the process for producing fragrance-containing moldings. Aromatic esters of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalylacetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, cyclohexyl salicylate, floryl salicylate. Ethers include, for example, benzylethyl ether and ambroxane, aldehydes for example straight C8-18 alkanals, citral, citronelal, citronelyloxyacetaldehyde, cyclamenaldehyde, lilial and bourgeonal, ketones for example jonone, α-isomethyljonone and methylcedrylketone,

- 10 99 · ♦ β β β β 9 9 9 9

9 999 9 9 9 · 9 9 9 to alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together provide a corresponding scent.

These perfume oils may also contain natural fragrance mixtures which are obtainable, for example, from vegetable sources, for example pineol, citrus, jasmine, patchouli, rose oil or ylang-ylang oil. Also suitable are nutmeg oil, sage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon oil, lime blossom oil, juniper oil, vetiver oil, oliban oil, galban oil and laban oil as well as oil orange blossom, non - rosin oil, orange peel oil and sandalwood oil.

In addition to the perfume, the fragrance-containing shaped bodies of the present invention contain carriers. It is preferred to use from 65 to 95% by weight, preferably from 70 to 90% by weight, of a carrier or carriers of the group of surfactants, surfactant mixtures, di- and polysaccharides, silicates, zeolites, carbonates, sulphates and citrates, each based on the weight of the shaped bodies. containing fragrances. These compounds, optionally, classes of compounds will be described in more detail below, as they may also be components of a masterbatch for tablets.

In addition to the perfume and the carrier or carriers, the fragrance-containing moldings may advantageously contain other excipients which facilitate their manufacture or improve their later properties. In this case, it is preferred that the moldings, especially the fragrance-containing pearls, contain one or more of the polyethylene glycols, fatty alcohol alkoxylates and fatty acid alkoxylates in an amount of 1 to 10% by weight, preferably 2 to 9% by weight, and in particular 5 to 7% by weight, in each case based on the weight of the fragrance-containing shaped bodies.

The fatty acid alkoxylates which can be added can be described by the general formula I:

R ¹ -COO- (CH ₂ -CH-O) _to -H (I) wherein R ¹ is selected from C 7-17 alkyl- or -alkenyl, R ² = -H or -CH 3 when 2 to 10. Suitable fatty alcohol alkoxylates fall under formula II:

R ³ -O- (CH ₂ -CH-O) 1 H (II) wherein R ³ is selected from C 6-6 alkyl- or -alkenyl, R ⁴ = -H or -CH 3 and I = 2-10. If appropriate, the corresponding auxiliaries can be readily prepared by ethoxylation or propoxylation of fatty acids or fatty alcohols in a known manner, technical mixtures of the individual substances being preferred for economic reasons.

Other suitable excipients are polyethylene glycols (abbreviated

PEG), which can be described by the general formula III:

H- (O-CH ₂ -CH ₂ ) _n -OH (III) whose degree of polymerization n may be from about 5 to> 100,000 and may have a corresponding molecular weight of 200 to 5,000,000 gmol ¹ (200 to 5,000,000) . Products with molecular weights of less than 25,000 gmol- ¹ (25,000) are referred to as the actual polyethylene glycols, while higher molecular weight products are reported in the literature.

9,999,999 9 9 9 9 9 9 9 9 9 9 9 9

9 9 9 9 99 99 9 9 9 9

- 12 are often referred to as polyethylene oxides (PEOX). Preferred polyethylene glycols may have a straight or branched structure, with straight-chain polyethylene glycols particularly preferred, and may be capped.

Particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12,000, preferably about 4000, and preferably polyethylene glycols with relative molecular weights of less than 3500 and greater than 5000 may be used, particularly in combination with polyethylene glycols of both molecular weight and relative molecular weight. about 4000, and these combinations preferably contain more than 50% by weight of polyethylene glycols with a relative molecular weight between 3500 and 5000 based on the total amount of polyethylene glycols. However, polyethylene glycols which are liquid at room temperature and at a pressure of 1 bar may also be used as binders; in particular polyethylene glycol with relative molecular weights of 200, 400 and 600.

The moldings, in particular the fragrance-containing beads, are processed by the process according to the invention with further ingredients and / or mixtures of detergents and cleaning compositions into tablet premixes which are compressed in known manner into tablets.

Important ingredients that may be included in the masterbatch for tablets are surfactants, skeletal formers, bleaching agents, bleach activators and salts (such as sulfates, carbonates, citrates and the like, especially sodium and potassium salts) and other conventional ingredients and mixtures contained in tablets. cleaning agents. These will be described in more detail below.

Molding detergents and cleaning compositions prepared by the process of the present invention may contain anionic, nonionic, cationic and / or amphoteric surfactants, or mixtures thereof. Mixtures of anionic and nonionic surfactants are suitable for use. The total surfactant content of the moldings produced by the process of the present invention is 5 to 60%

13% by weight based on the weight of the shaped body, with surfactant contents of more than 15% by weight being preferred.

Particularly used as anionic surfactants are those of the sulfonate and sulphate type, while those of the sulphonate type are preferably C9-13 alkylbenzene sulphonates, olefin sulphonates, i.e. mixtures of alkene and hydroxyalkane sulphonates and disulphonates, which are obtained, for example, from C ₁₂ -is monoolefins. with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. Also suitable are alkane sulfonates which are obtained from C12-18 alkanes by, for example, sulfochlorination or sulfoxidation followed by hydrolysis or neutralization. Also suitable are esters of α-sulfofatty acids (estersulfonates), for example α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfated glycerol fatty acid esters. Glycerol fatty acid esters are to be understood as meaning mono-, di- and triesters and mixtures thereof, obtained by the esterification of monoglycerol with 1 to 3 moles of fatty acid or by esterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated glycerol fatty acid esters are the sulfation products of saturated fatty acids having 6 to 22 carbon atoms, such as, for example, caproic, caprylic, capric, myristic, lauric, palmitic, stearic or behenic acids.

Alk (en) yl sulfates are suitable alkali metal and especially sodium salts of monoesters of C ₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C10 -C20 oxoalcohols with sulfuric acid, and these semi-esters of secondary alcohols with the indicated chain lengths. Further preferred are alk (en) ylsulphates of the indicated chain lengths which contain a synthetic, petrochemical alkyl residue

with a straight chain having an analogous degradation method as the corresponding compounds based on the technology of fatty raw materials processing. In terms of wash technology are preferred C12-C16 alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates, as well as the C14 -C15 alkyl sulfates. Suitable anionic surfactants are also 2,3-alkyl sulfates, which are prepared, for example, in U.S. Patents 3,234,258 or 5,075,041 and are commercially available from Shell Oil Company under the name DAN®.

Also suitable are monoesters 1 and 6 moles of ethylene oxide of ethoxylated straight or branched C7-21 alcohols, such as the methyl group in the 2-position of branched C8.n alcohols containing on average 3.5 moles of ethylene oxide (EO) or C12-18 fatty alcohols with 1 up to 4 EO, with sulfuric acid. Due to their high foaming properties, these substances are used in cleaning compositions only in relatively low amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also alkylsulfosuccinic acid salts, also referred to as sulfosuccinates or sulfosuccinic acid esters, and sulfosuccinic acid monoesters and / or diesters with alcohols, preferably fatty alcohols, and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 6 -C 10 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue that is derived from ethoxylated fatty alcohols, which are themselves nonionic surfactants (see description below). Particular preference is given to sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrowed homolog distribution. It is also possible to use alk (en) ylsuccinic acid, preferably having 8 to 18 carbon atoms in the alk (en) yl chain or a salt thereof.

Suitable further anionic surfactants are, in particular, soaps.

Saturated fatty acid soaps such as salts are suitable

- 15 0 0 00 0 «0 00 000 0 0 000 0 00 0000 00 0 00

000000 0 0 00 0

00 00 000 0 · 0 lauric, myristic, palmitic, stearic, hydrated erucic and behenic acids, and in particular soap mixtures derived from naturally occurring fatty acids, for example coconut, palm kernel or tallow fatty acids. The anionic surfactants including soaps may be in the form of their sodium, potassium or ammonium salts as well as in the form of soluble salts with organic bases such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, especially in the form of their sodium salts.

Preferred nonionic surfactants are alkoxylated, more preferably ethoxylated, especially primary alcohols, preferably containing from 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 may be straight or in the 2-position preferably a branched methyl group, optionally straight and methyl-branched residues in the mixture, as usually found in oxoalcohol residues, may be present. Especially preferred are, however, ethoxylates of alcohols having straight-chain residues derived from alcohols of natural origin having from 12 to 18 carbon atoms, for example from the group of coconut, palm, tallow alcohol or

2o oleyl alcohol containing on average 2 to 8 EO per mole of alcohol. Preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 EO or 4 EO, C ₉ -n-alcohols with 7 EO, C ₁₃ -15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 alcohols with 7 EO 3 EO, 5 EO or 7 EO and mixtures thereof, as well as mixtures of C12-14 alcohols with 3 EO and C12-18 alcohols with 5 EO. The degrees of ethoxylation shown are statistical mean values, which may be an integer or a fraction for a particular product. Preferred alcohol ethoxylates have a narrowed homolog distribution (NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO may also be used.

Examples are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

- 16 · 9 9 9 9

9,999 9 9 9 9,999 · 9 9 9 9 9 9 9

99 99,999 9 · 9

In addition, alkyl glycosides of the formula RO (G) _X may also be used as further nonionic surfactants, wherein R is a primary aliphatic group having from 8 to 22, preferably 12 to 18, straight-chain or methyl-branched-chain carbon atoms, especially in position 2, and G represents a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the proportion of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is from 1.2 to 1.4.

Another class of preferred nonionic surfactants which may be used either as a single nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated alkyl esters of fatty acids, preferably having 1 to 4 carbon atoms in the alkyl chain esters, especially fatty acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598, or are preferably produced by the method 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) 2 O, 20-dihydroxyethylamine oxide, and the alkanolamide type may also be suitable. The amount of these nonionic surfactants is preferably not more than the amount of ethoxylated fatty alcohols, in particular not more than half.

Other suitable surfactants are the polyhydroxy fatty acid amides of formula (IV),

R ⁵

AND

R-CO-N- [Z] (IV) · 9 · 9 · 9 · ·· ··· 9 9 9

Where RCO is an aliphatic acyl radical of 6 to 22 carbon atoms, R ⁵ is a hydrogen atom, an alkyl or hydroxyalkyl radical of 1 to 4 carbon atoms and [Z] is a straight or branched polyhydroxyalkyl radical of 3 to 10 carbon atoms and 3 to 10 carbon atoms 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine followed by acylation with a fatty acid, an alkyl ester of a fatty acid or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of formula (V),

R ⁶ -OR ⁷

AND

R-CO-N- [Z] (V) wherein R is a straight or branched alkyl or alkenyl radical of 7 to 12 carbon atoms, R ⁶ is a straight, branched or cyclic alkyl radical or aryl radical of 2 to 8 carbon atoms, and

R ⁷ represents a straight, branched or cyclic alkyl or aryl radical, or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 -alkyl or phenyl groups being preferred and [Z] denoting a straight polyhydroxyalkyl radical whose alkyl chain is substituted by at least with two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

[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 be converted, for example, according to WO-A3095 / 07331 to the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide catalyst.

• · · · ·

- 18 ····························

Within the scope of the present invention, it is preferable to add anionic (anionic) and nonionic (nonionic) surfactants to the detergent moldings in such a way that advantages resulting from certain molar ratios in which the individual surfactant classes are used may be manifested.

For example, detergent formulations in which the ratio of anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1: 10, preferably between 7.5: 1 and 1: 5, are particularly preferred and in particular between 5: 10 and 1: 2, wherein the surfactants can be added to the shaped bodies in the process according to the invention by means of shaped bodies containing fragrances or as components of a masterbatch for tablets.

Within the scope of the present invention, those processes 15 according to the invention are advantageous in which moldings having a high perfume content are mixed with at least one surfactant granulate.

From a technical point of view, it may be advantageous if certain classes of surfactants are not present in some phases of the detergent / cleaning molding elements or in the molding body as a whole, i. in all phases. In the context of the present invention, the term phase refers to any spatial distribution, that is to say, a multiphase state in multilayer tablets, ring-core tablets or sheath tablets. However, the individual phases are also formed by compressing fragrance-containing moldings, in particular fragrance-containing pearls, in the process according to the invention, wherein the fragrance-containing moldings form one phase, while the other phase is formed from other masterbatch particles for tablets. Thus, another important embodiment of the present invention contemplates that at least one phase of the shaped bodies does not comprise nonionic surfactants.

This variant can be realized particularly easily if the nonionic surfactants are completely omitted

- 19 • 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9

9

9 to 9 fragrance-shaped bodies or other components of tablet premixes.

Conversely, however, it is also possible to achieve certain surfactant contents in some phases or in the moldings as a whole, i.

in all phases, positive effect. The addition of the alkylglycosides described above has proven to be advantageous, so that detergent formulations are preferred, in which at least one phase of the formulations comprises alkyl glycosides, which can be achieved by adding alkyl polyglycosides to the tablet premix.

As in the case of nonionic surfactants, the anionic surfactant may be formed from individual or all phases of detergent formulations that are better suited to certain areas of use. Therefore, detergent molds in which at least one phase of the molding does not contain anionic surfactants are contemplated within the scope of the present invention, and this possibility can be realized analogously to the above-mentioned possibilities particularly easily by the method according to the invention, in which the anionic surfactants either of fragrant shaped bodies or of other components of the tablet premix.

In preferred embodiments of the invention, the masterbatch for tablets to be compressed comprises one or more laundry and cleaning ingredients, in particular from the group of builders, bleaches, bleach activators, enzymes, dyes and disintegrants. These components are described below.

In addition to detergents, builders (Geruststoffe) are an important component of detergents. In the process according to the invention, all the customary builders which are added to the detergents and cleaning agents, in particular zeolites, silicates, carbonates, organic auxiliary builders, and - where there is no objection to environmental use - can be added to the detergent moldings also phosphates.

- 20 fc · fcfc * · c <<<<<<<<«« «« «« «« «« « Fc fc fc fc fc fc fc fc fc fc fc fc

Suitable crystalline layered sodium silicates have the general formula NaMSi _x C> 2x + 1. yFbO, where M is sodium or hydrogen, x is from 1.9 to 4 and y is from 0 to 20, with preferred values for x being 2, 3 or 4. These crystalline layered silicates are described, for example, in the European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the above formula are those wherein M is sodium and x is 2 or 3. Sodium β- and δ-sodium silicates of the formula Na ₂ Si ₂ O ₅ are particularly preferred. yhhO, wherein according to the present method, for example, sodium β-silicate, which is described in WO-A-91/08171, may also be included.

Amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8, and in particular 1: 2 to 1: 2.6, having a reduced solubility and secondary washability. The retardation of solubility against conventional amorphous sodium silicates can be induced in various ways, for example by surface treatment, mixing with other components, compacting / compacting or drying. In the context of the present invention, the term "amorphous" also means "X-ray amorphous".

That is, silicates do not give sharp X-ray reflections, which are typical of crystalline substances, in X-ray bending experiments, but in all cases provide one or more scattered X-ray maxima having a width of multiple units of bending angle degrees. However, even if silicate particles have washed or even sharp bending maxima in electron bending experiments, they can lead to particularly good builder properties. This should be interpreted as meaning that the products have a size in the microcrystalline range of 10 to several hundred nanometers, with values up to a maximum of

50 nm and in particular up to a maximum of 20 nm. These so-called x-ray amorphous silicates, which also have a reduced solubility compared to conventional waterglasses, are described, for example, in the German patent application. ··· ·····················

DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, amorphous silicates in admixture with other substances, and dried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water containing zeolite used is preferably zeolite A and / or P. Zeolith MAP® (manufactured by Crosfield) is particularly preferred as zeolite P. Also suitable are zeolite X and zeolite A (zeolite X approximately 80% by weight) supplied by CONDEA Augusta SpA under the trade name VEGOBOND AX®, which can be described by the formula nNa ₂ O. (1-n) K2O.Al2O3. 2.5) SiO2. (3.5-5.5) H ₂ O

The zeolite can be added as a builder both to the granular mixture and to the &quot; dusting &quot; of the total mixture to be compressed, both of which are generally used to add the zeolite to the masterbatch.

Suitable zeolites have a mean particle size of less than 10 µm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, especially 20 to 22% by weight of bound water.

Of course, it is also possible to use generally known phosphates as builder substances, provided that their use should not be omitted for environmental reasons. Sodium salts of orthophosphates, pyrophosphates and especially tripolyphosphates are particularly suitable.

Useful organic builder substances are, for example, polycarboxylic acids such as citric, adipic, succinic, glutaric, tartaric, sugar, aminocarboxylic acids, nitrilotriacetic acid (NTA), used, for example, in the form of their sodium salts if their use is suitable for environmental reasons , and mixtures thereof. Preferred salts are salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, and mixtures thereof.

In order to facilitate the disintegration of the highly compacted shaped bodies, it is possible to add disintegrating aids, so-called tablet disintegrants, to the bodies to reduce the disintegration time. Materials referred to as disintegrating or disintegrating accelerators are understood to be excipients according to Römpp (9th edition, volume 6, page 4440) and Voigt "Lehrbuch der pharmazeutischen Technologie" (6th edition, 1988, pages 182-184), which are intended to rapidly disintegrate tablets in water or gastric juice and release the drug in resorbable form.

Substances known as "disintegrants" by virtue of their action increase their volume in access to water, on the one hand increasing their own volume (swelling), but on the other hand, pressure may also be generated by releasing gases, so that the tablet disintegrates into smaller particles. Disintegrating aids known for a long time are, for example, carbonate / citric acid systems, and other organic acids can also be used. Swelling disintegrants are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers, or modified natural substances such as cellulose and starch or derivatives thereof, alginate or casein derivatives.

Preferred detergent moldings comprise from 0.5 to 10% by weight, preferably from 1 to 5% by weight and in particular from 2 to 4% by weight of disintegrating aids, each based on the weight of the molding bodies.

Cellulose-based disintegrants are used as suitable disintegrants in the present invention, such that preferred mold-shaped laundry detergents and cleaning agents contain such cellulose-disintegrants in an amount of 0.5 to 10% by weight, preferably 1 to 5% by weight and in particular 2 to

4% by weight. Pure cellulose has the formal composition (C6Hio0 _{5) n} and formal terms beta-1,4-polyacetal of cellobiose which is • · ·· ·· ·· · · • · · · · · · · · ··· ··· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

- 23 itself built from two glucose molecules. Suitable celluloses are composed of approximately 500 to 5000 glucose units and thus have an average molecular weight of 50,000 to 500,000. Also cellulose derivatives obtainable by polymer-analogous cellulose reactions are useful in the present invention as cellulose disintegrating agents. These chemically modified celluloses include, for example, esterification or etherification products in which the hydroxyl group hydrogen atoms have been substituted. However, cellulose derivatives in which hydroxyl groups have been replaced by functional groups not bonded via an oxygen atom can also be used as cellulose derivatives. Cellulose derivatives include, for example, alkaline celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers and aminocellulose.

Said cellulose derivatives are preferably used not as cellulose disintegrating agents alone but in admixture with cellulose. The content of cellulose derivatives in these mixtures is preferably less than 50% by weight, particularly preferably less than 20% by weight, based on the cellulose disintegrant.

It is particularly preferred to use pure cellulose free of cellulose derivatives as the cellulose disintegrant.

Microcrystalline cellulose may be used as another cellulosic disintegrant or as part of this component. This microcrystalline cellulose is obtained by partial hydrolysis of the celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose weight) of the celluloses but leave the crystalline regions (about 70%) intact. Subsequent disaggregation of microfine celluloses formed by hydrolysis yields microcrystalline celluloses having a primary particle size of approximately 5 μιτι and can be compacted, for example, into granules with an average particle size of 200 µm.

• * 9 · 9 · · 9 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Within the scope of the present invention, detergent compositions in the form of shaped articles are preferred which additionally comprise a cellulose disintegrant in the shaped articles.

In addition to the surfactant, builder and disintegrating aids, the customary detergent compositions of bleaches, bleach activators, enzymes, fluorescent agents, dyes, foam inhibitors can be incorporated into the molding compositions of the present invention. , silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

Among the bleaching compounds providing H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, and H ₂ O ₂ -performing peracids or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid, or diperdodecanedioic acid.

Bleach activators may be added as a separate component or as part of component (b) in order to achieve improved bleaching effects at 60 ° C and below. As bleach activators, compounds can be used which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids preferably having 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms and / or optionally substituted perbenzoic acid. Substances which carry O- and / or N-acyl groups with the indicated numbers of carbon atoms and / or optionally substituted benzoyl groups are suitable. Multiple acylated alkylenediamines, in particular tetraacetylethylenedi30-amine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, are preferred. • · • ·

For example tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (η- or isoNOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acyl especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to or instead of conventional bleach activators, so-called bleach catalysts can also be added to the shaped bodies. These are transition metal salts or bleach-enhancing transition metal complexes, such as salene complexes or carbonyl complexes of Mn, Fe, Co, Ru or Mo. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen containing trivalent ligands and amine complexes of Co, Fe, Cu and Ru are also useful as bleach catalysts.

Suitable enzymes are materials from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are enzymatic active compounds obtained from strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus. Proteases of the subtilisin type and in particular proteases obtainable from Bacillus lentus are preferably used. Of particular interest are mixtures of enzymes, for example proteases and amylases or proteases and lipases or proteases and cellulases or cellulases and cellulases and lipases or proteases, amylases and lipases or proteases, lipases and cellulases, in particular mixtures containing cellulase. Peroxidases or oxidases have also proven suitable in some cases. Enzymes may be adsorbed onto carriers and / or encapsulated in coatings to protect them from premature degradation. The proportion of enzymes, enzymatic mixtures or enzyme granules in the shaped bodies according to the present invention

For example, the invention may be from about 0.1 to about 5% by weight, preferably from about 0.1 to about 2% by weight.

• »♦ * * * * *

9 9 9 9 9 9 999 999 99

- 26 In addition, molded detergents and cleaners can also contain ingredients that have a positive effect on the washability of oils and fats from textiles (soil repellents). This effect will be particularly pronounced if the textile which has been washed several times with a detergent according to the invention containing this oil-and-grease-releasing component is soiled. Preferred fat and oil releasing components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with 15 to 30% by weight of methoxy groups and 1 to 15% by weight of hydroxypropoxy groups, each based on nonionic cellulose ethers, and polymers known in the art. phthalic and / or terephthalic acids or their derivatives, in particular polymers of ethylene terephthalate and / or polyethylene glycol terephthalate or anionically and / or nonionic modified derivatives of these compounds.

Of these, sulfonated derivatives of phthalic acid polymers and terephthalic acid polymers are particularly preferred.

The shaped bodies may contain as optically brighteners diaminostilbendisulfonic acid derivatives or alkali metal salts thereof. Suitable salts are, for example, 4,4'-bis (220-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid salts or compounds exposed in the same manner to the morpholine group they have a diethanolamine, methylamine, aniline or 2-methoxyethylamine group. In addition, optically brighteners of the substituted diphenylstyryl type can be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl or 4- (4 (chlorostryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of said optically brighteners can also be used.

In order to improve the aesthetic impression produced by the compositions of the present invention, these compositions may be colored with suitable dyes. Preferred dyes, the selection of which does not cause any difficulties for the skilled person, have a high storage stability. 9 9 9

9

99 99

and are not sensitive to the usual components of the compositions or to light; likewise, they do not bind to textile fibers so as not to cause them to become discolored.

For aesthetic reasons, it may be desirable to produce shaped bodies in which only certain phases or layers are colored. This can be achieved by the method of the present invention without problems in a variety of variations. Thus, at least two phases are available in the moldings, depending on the incorporation of the fragrance-containing moldings, of which only one phase can be colored or both phases can be colored differently to form colored particles.

The dyeing of the individual phases can be carried out in the customary manner by the addition of dyes or dye solutions to the fragrance-containing shaped bodies or the granules or powders of the tablet premix. However, it is preferred to use colored dusting agents which cover the surface of the particles and thus optically induce a grain colored throughout the volume. This saves on one hand the dye and on the other hand the problems caused by the incorporation of high amounts of dyes into the shaped bodies and thus into the washing bath are avoided.

The production of detergent compositions in the form of shaped bodies is carried out by the method of the present invention in a known manner by compressing a masterbatch for tablets containing shaped bodies containing fragrances. For production, the premixes are compacted in a so-called matrix between two punches to form a solid compress. This operation, shortly referred to as tabletting in the following, is divided into four steps: dosing, compaction (elastic shaping), plastic shaping and extrusion.

Tableting is carried out on conventional tablet presses which can be essentially equipped with single or double punches. In this case, not only the upper punch is used to exert pressure, but also the lower punch moves against the upper punch during compression, while the upper punch pushes downward. For the little ones

• • •

The quantities produced are preferably used with eccentric tablet presses in which the punch is mounted on an eccentric disc which is mounted on an axis with a certain speed of rotation. The movement of this punch is comparable to that of a conventional four-stroke engine.

Pressing can take place with either one upper and lower punches, but a plurality of punches can be mounted on the eccentric disk, and the number of die holes is correspondingly increased. The throughput of eccentric presses varies by type and can range from a few hundred to a maximum of 3000 tablets per hour.

io For greater throughput, rotary tablet presses are used, in which a plurality of dies are arranged on a so-called die table. The number of matrices varies by model and can range between 6 and 55, with larger matrices available in the shop. Each die on the die table is associated with an upper and a lower die, and the pressing pressure can be actively exerted only by the upper or lower die, but also by both dies. The die table and dies are moved around a common vertically arranged axis, the dies being brought into the position for filling, compaction, plastic deformation and extrusion by means of a track during the cycle. In places where particularly high lifting or lowering of the matrix is necessary (filling, compacting, extrusion), these tracks are supported by additional compression elements, rail recesses and removal paths.

The filling of the matrix takes place by a stationary feeding device, the so-called filling shoe, which is connected to the pre-mixer of the premix.

The compression pressure for each such masterbatch is individually adjustable by the pressing path of the upper and lower punches, the pressure being generated by rolling the head of the punch shaft over the adjustable thrust rollers.

Rotary presses can also be equipped with two or more filling shoes to increase throughput. To produce two- and multi-layer shaped bodies, a plurality of filling shoes are provided one behind the other, and the slightly compressed first layer is not extruded prior to further filling. In this way, coatings and point tablets are also produced by a suitable process arrangement and are constructed from layers such as onions, and in the case of point tablets the top core layer or core layers are covered and thus remain visible. Also, rotary tablet presses can be provided with single or multiple workstations so that, for example, the outer ring uses the holes 50 for the pressing and the inner ring 35 simultaneously. The throughputs of modern rotary tablet presses are over one million shaped bodies per hour.

Suitable tableting machines for carrying out the present invention are available, for example, from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Köln, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (Switzerland) and Courtoy NV, Halle (Belgium / Luxembourg). Particularly suitable is, for example, the HPF 630 hydraulic double-action press from LAEIS, Germany.

The shaped bodies can be made in a certain shape and a certain size and can consist of several phases, i. layers, within the present regions or cores and rings. Virtually all suitable manipulating embodiments can be used as shapes, for example, the shape of a table, rod, cube, cuboid and corresponding spatial elements with flat lateral surfaces, as well as particularly cylindrical designs with a circular or oval cross-section. The latter embodiments comprise tablet to compact cylindrical bodies having a height to diameter ratio of more than 1.

The portioned moldings may be in the form of separate individual elements which correspond to a specified dose of detergent and / or cleaning agent. However, it is also possible to form moldings which combine a plurality of such weight units in a single molding, * · · · · · · · · · · · · · · · · · · · · · · · »* ··

30, provided that the smaller units containing a certain dose are readily separable, in particular by means of pre-formed breaking points. For the use of textile detergents in dishwashers customary in Europe with horizontally arranged mechanics, it may be useful to produce portioned moldings such as tablets, cylindrical or cuboid, with a preferred diameter to height ratio ranging from 0.5: 2 to 2: 0 on average. 5. Commercially available hydraulic presses, eccentric presses or rotary presses are suitable for the production of these moldings.

The shape of other embodiments of the shaped bodies is adapted to the dimensions of the rinsing chambers of available household washing machines, so that the shaped bodies can be directly dispensed into the rinsing chamber without auxiliary dispensing devices where they dissolve during rinsing. Of course, it is also possible to use detergent in the form of shaped bodies by means of an auxiliary dosing device.

Another preferred shaped body that can be produced has a plate or tabular structure with alternating thick long and thin short segments, so that the individual segments break off at the indicated breakpoints, which are short thin sections, and can be added to the washing machines. This principle of bar-shaped detergent bodies can also be realized in other geometrical shapes, for example parallel-arranged triangles, which are connected longitudinally only on one side. Here, for optical reasons, it is also possible to form a base of triangles which connects the individual segments as one phase, while the tip of the triangles is formed by the second phase. In this embodiment of the invention, the different colors of the two phases look particularly nice.

After pressing, the detergent moldings have a high stability. Fracture strength of cylindrical shaped body · · · • t t t t t t t t t t t t t t t

31 can be detected by measuring the force required to break. This force can be determined from the equation

2P _{5 σ} = πϋί

In this equation, σ means the diametral fracture stress (DFS) in Pa, P is the force N that causes the pressure on the shaped body that leads to the breakage of the body, D is the diameter of the shaped body in meters and t is the height of the shaped body.

The preformed detergent compositions in the form of shaped bodies may contain shaped bodies with different fragrances in varying amounts. In the context of the present invention, it is preferred that the proportion of high-perfusion moldings in the compressed masterbatch be 1 to 15% by weight, preferably 2 to 12% by weight, and in particular 5 to 10% by weight, based on the masterbatch.

It is a further object of the present invention to use high perfume compositions, in particular perfume beads, having bulk densities of more than 700 g / l and which are produced by granulation or agglomeration in presses, in the form of detergent articles.

The incorporation of perfumes in this concentrated and, for their method of production, most homogeneous form positively influences the physical properties of the shaped bodies. The tendency of the perfumes to migrate under the compression pressure when compressing the tablets into the entire molding body is suppressed and the hydrophobizing perfume oil is concentrated in this way into the narrow region of the tablet. In this way, the molding bodies of the detergents and cleaning agents produced by the method according to FIG

4 4 4 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

4 4 »4« 444444 4 4 4 4 4 44 44 4 4 44 444

32 of the present invention have the same positive properties as shaped bodies in which perfumes are not present at all.

Against perfume-containing moldings, not only will the physical properties of the moldings be significantly improved, but also the other properties of the composition will be improved and the properties of the fabrics washed by these compositions will be improved. As with the &quot; fragrance-containing pearls &quot; in sterile German patent application 197 46 781.4, the detergent moldings of the present invention are also improved in the smell of the moldings and the smell of the fabrics treated with the wash liquor formed therefrom.

DETAILED DESCRIPTION OF THE INVENTION

According to the earlier German patent application 197 46 780.6, fragrance-containing pearls were produced, in which the spray-dried tenside granulate (carrier) was mixed with other excipients and perfume, and the mixture was then plasticized and extruded on a Lihotzky two-wave extruder.

The composition of the spray dried surfactant granules is shown in Table 1, the composition of the premix for the fragrance-containing pearls is shown in Table 2.

Table 1: Spray-dried granulate of surfactant (% by weight) This to this This to this This to this To ···························

Sodium C-13-alkylbenzenesulfonate 26.17 Sodium carbonate 4.00 Zeolite 4A 55.63 Salts from solution 0.70 Water 13.00 Sodium hydroxide 0.50

Table 2: Premix for pearls containing fragrances (% by weight)

C 12-18 fatty alcohol 5.0 Zeolite X 10.0 PEG 4000 4.0 Tenside granulate (Table 1) 68.0 Perfume oil 10.0

The plasticized masterbatch exited the extruder at a pressure of 8.5 MPa through a perforated plate with outlet orifices diameters of 0.5, 0.7 and 0.85 and 1.2 mm respectively.

The extruded strands were cut with a rotating body cutter with a length to diameter ratio of approximately 1, which was rounded on a Marumerizer®.

In parallel to the fragrance-containing pearls, an additional tenside granulate having the composition given in Table 3 was produced by granulation.

0

Table 3: Tenside granulate (% by weight)

00 • t · 0 ·

0 0 0 0 0 0 0 000 0 4 0

0 0 0 0

0 · * ·

C8-alkylbenzenesulfonate 18.6 C 12-18 fatty alcohol sulfate 5.4 C12-18 fatty alcohol with 7 EO 5.7 Soap 1.6 Sodium carbonate 16.6 Sodium silicate 5.4 Zeolite A (anhydrous active substance) 29.9 Optical brightener 0.3 Sodium hydroxyethane-1,1-diphosphonate 0.8 Copolymer of acrylic acid and maleic acid 5.4 Water, salts 10.3

In this case, premixes were prepared for tablets E1 and V1 5 and V2, with the surfactant granulate described in Table 3 being mixed with the other detergent and detergent ingredients. The E1 masterbatch of the present invention contained fragrance-containing pearls, while the perfume in Comparative Example V1 was sprayed in a corresponding amount directly onto the masterbatch. In addition, a perfume-free premix V2 was produced.

The masterbatches were compressed in a Korsch tablet press for detergent tablets. The pressing pressure was adjusted in such a way that three series of shaped bodies (E1, ET, E1 ”, analogously for V1 and V2) were obtained, which differed in their hardness. The composition of the molded masterbatches (and hence the molded bodies produced therefrom) is shown in Table 4.

- 35 Table 4: Masterbatches for detergent moldings (% by weight)

• • • · • · 9 • • 9 9 • • · • • · • • • · • • ··· • · 9 • • · • • • • · • 9 • • • • • · • · 99 • · · • · • »·

E1 V1 V2 Tenside granulate (Table 3) 56.8 61.3 61.8 Sodium perborate monohydrate 17.8 17.8 17.8 Tetraacetylethylenediamine 7.3 7.3 7.3 Paraffin and silicone defoamer, 15% on sodium 3.5 3.5 3.5 Enzymes 2.5 2.5 2.5 Ethylene glycol-PEG ester of an acid terephthalos 1.1 1.1 1.1 Fragrance Pearls (Table 2) 5.0 - - Perfume oil - 0.5 - Cellulose-based disintegrant 5.0 5.0 5.0 Zeolite A (dusting agent) 1.0 1.0 1.0

The hardness of the tablets was measured by molding the tablet until fracture, 5 to determine the force acting on the side surfaces of the tablet and the maximum force with which the tablet could withstand.

To determine the disintegration of the tablets, the tablet was placed in a beaker of water (600 ml of water, temperature 30 ° C) and the time to complete disintegration of the tablet was measured. Experimental data are shown in Table 5:

· *

- 36 Table 5: Detergent tablets (physical data)

Tablet E1 ΕΓ E1 ” V1 V1 ’ V1 ” V2 V2 ’ V2 ” Tablet hardness 40 N 53 N 63 N 41 N 50 N 62 N 41 N 51 N 60 N Disintegrating tablets 10 p 14 p 21 p 14 S 22 p 53 p 9 p 16 p 21 p

The data in Table 5 shows that the addition of perfume through high-perfume molding bodies brings substantial advantages: firstly, the disintegration time of the tablets does not depend as much on the hardness of the tablets as the tablets in which the perfume was sprayed onto the masterbatch (comparison Example E1: V1), secondly, the shaped bodies produced according to the present invention, despite the use of the perfume, achieve, or exceed the perfume tablets at the same hardness, the good disintegration times which are characterized by or without perfume (comparison E1: V2).

Also, the overall impression in terms of perfuming of the moldings produced according to the invention is better than the moldings produced in the conventional manner. For this purpose the shaped bodies E1 and V1 were compared.

The composition of perfume oils contained in shaped bodies or pearls containing fragrances is given in Table 4. Perfume of the product and treated fabrics (cotton) was assessed as a subjective olfactory sense of perfume. The figures in the evaluation table (Table 7) indicate the number of perfumers who have classified the products concerned or, where appropriate, with certain fabric-treated fabrics, in the 'strong-smelling' group. Thus, out of seven perfume makers, six persons judged the detergent articles made according to the present invention to be better. The results of this test are summarized in Table 7.

······················ 9 9

9 9 · 9,999 9 9 9

9 · · · ·

99 99 999

- 37 Table 6: Composition of perfume oils (% by weight)

Phenylethyl alcohol 52.0 Dimethylbenzylcarbinyl acetate 2.5 Iraldein gamme 5.0 Phenylacetic acid 0.5 Geranylacetate 2,0 Benzyl acetate 30.0 Rosenoxide L 10% in PEG 2.5 Romilat 20.0 Irotyl 0.5 Cyclohexyl salicylate 20.0 Floramát 10.0

Table 7: Smell intensification (intensity preference)

Number of perfumes (intensity preference) product damp linen dry linen E1 (5% perfume oil in pearls containing fragrances) 1 2 2 V1 (0.5% perfume oil) sprayed) 6 5 5

Represented by:

Claims (10)

1. A method for producing detergent shaped bodies, 5, characterized in that mixtures of high perfume content are produced by granulation or agglomeration by compression, which are mixed with the powdered and / or granular detergent and cleaning ingredients, and the masterbatch is compressed into moldings in a known manner. A process according to claim 1, characterized in that the high perfume compositions have a bulk density of more than 700 g / l. 15 Dec Method according to either of Claims 1 and 2, characterized in that mixtures with a high content of fragrances, in particular fragrances containing fragrances, which have been produced by essentially anhydrous granulation or agglomeration by compression, are used. Method according to one of Claims 1 to 3, characterized in that the fragrant-containing shaped bodies, in particular the fragrance-containing pearls, contain 3 to 40% by weight, preferably 5 to 30% by weight and in particular 8 25 to 20% by weight of perfume, based on the weight of the fragrance-containing shaped bodies. Method according to one of Claims 1 to 4, characterized in that the shaped bodies with a fragrance content. «Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z Z ♦ ♦ · ♦ · · · · · · Z Z Z Z Z Z Z Z · ·· ·· ··· ·· ··· - 39 in particular, fragrances containing a fragrance content of 65 to 95% by weight, preferably 70 to 90% by weight, of a carrier or carriers of the tenside group, mixtures of tensides, di- and polysaccharides, silicates, zeolites, carbonates, sulphates and citrates, 5 is always based on the weight of the fragrance-containing shaped bodies. Method according to one of Claims 1 to 5, characterized in that the fragrant-containing moldings, in particular fragrance-containing pearls, contain one or more substances of the group polyethylene glycols, fatty alcohol alkoxylates and fatty acid alkoxylates in an amount of 1 to 10% %, preferably 2 to 9% by weight and in particular 5 to 7% by weight, in each case based on the weight of the moldings 15 bodies containing fragrances. Method according to one of Claims 1 to 6, characterized in that the fragrant-containing shaped bodies are mixed with at least one surfactant granulate. Method according to one of Claims 1 to 7, characterized in that the molded masterbatch comprises one or more detergent and cleaning agent components selected in particular from the group of builders, bleaching agents, bleach activators, 25 enzymes, dyes and disintegrating aids. Method according to one of Claims 1 to 8, characterized in that the proportion of moldings having a high content of fragrances in the pressed masterbatch is 1 to 15%. · · * * * * * * * 40% by weight, preferably 2 to 12% by weight and in particular 5 to 10% by weight, in each case based on the premix. 10. Use of mixtures with a high odor content, especially pearls 5 with a odor content, with bulk densities higher than 700 g / l produced by granulation or agglomeration by pressing in shaped bodies of detergents and cleaning agents. Represented by: