SK13142000A3 - Fragrant beads in detergent forms - 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

Technical field

The present invention relates to a process for the production of 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 moldings have a number of advantages: they are easier to dispense and need less packaging as well as reduced transport and storage capacities due to their high density. Another important advantage of such products is consumer acceptability, which is based not only on the described daily convenience benefits but also on the aesthetic features of the shaped products. Thus, in the field of machine dishwashing, tablets have widely dispensed conventional powder products from the market.

However, there are disadvantages over the above-mentioned advantages, the essence of which is in molded articles. Thus, the molded article must be sufficiently stable after manufacture to be packaged, transported and stored without breaking or abrasion. These stability requirements condition a certain hardness of the molded article, which again contradicts the rapid dissolution of the molded article. This dichotomy between hardness and disintegration time is a central problem in the production of shaped articles, irrespective of the area in which the shaped articles are to be used.

There are other specific problems in the manufacture of detergent molded articles. While tablet detergents contain relatively small amounts of surfactants and are largely composed of well-soluble ingredients, for example, laundry detergents contain considerably higher amounts of surfactants, resulting in solubility problems as some surfactants tend to form gelatin or they are

- Only slowly soluble. Also, the demands placed on the fabric washing composition in the form of a molded shaped article are considerably higher than those of the dishwashing detergent tablets. In the dishwasher, the tablet lies in the basket and dissolves there throughout the washing process. In household washing machines, the molded product of the laundry detergent must be dispensable through the hopper, i.e. it must disintegrate into small particles within a few seconds to allow them to be rinsed, while on the other hand it must be guaranteed that the product disintegrates completely and quickly to prevent far-reaching contact of solid, damp detergent with laundry to prevent spotting problems.

Shaped detergent products contain additional active ingredients over dishwashing detergent tablets that further enhance the dichotomy between hardness and disintegration time. While dishwashing detergents generally do not contain fragrances, perfumes in textured detergent products are of great importance: on the one hand, perfume provides a distinctive, "unmistakable" product, and on the other hand, perfume in treated fabrics is particularly important performance perceived by the consumer. However, fragrances are considerably hydrophobic substances which further impair the dissolution of detergents, since they hydrophobize when sprayed onto the powder compositions.

There are only a small number of publications dealing with the incorporation of hydrophobic and hydrophobicized substances into these molded articles in the prior art.

The earlier German patent application 197 39 384.5 (Henkel KGaA) discloses molded detergent articles of compacted, particulate detergent and cleaning compositions comprising a surfactant (s), activating agents, a cellulose-based disintegrant and optionally other detergent active ingredients. cleaning agents, in which the disintegrant is spatially separated from the hydrophobized material in a defined area of the shaped article. By separating the disintegrant from the substances that may prevent moisture access to the disintegrant, the moldings described herein have excellent disintegration properties.

This document only describes how the disintegrating effect of the disintegrating aid used can be optimally utilized. Nothing is said about the optimal incorporation of hydrophobized substances.

The earlier German patent application 197 39 383.7 (Henkel KGaA) discloses molded detergent articles made from compacted, particulate detergents and cleaners which again contain one or more surfactants, activating agents, cellulose-based disintegrant and optionally other detergent active ingredients. and cleaning agents, in which all hydrophobized substances are applied to the carrier material. Hydrophobized substances within the meaning of this application are, for example, perfume oils, and nothing is mentioned about the application to the carrier materials.

Accordingly, it is an object of the present invention to provide a process for the production of molded articles of detergents and cleaning products, the final product of which are molded articles having high hardnesses and fast disintegration times. In particular, this process should allow the incorporation of the perfume into the molded article in a suitable manner without worrying about the disadvantages of conventional perfumed molded detergent articles. It is therefore to be found possible to manufacture perfumed moldings of detergents and cleaning compositions which attain or exceed in their properties the unscented moldings.

The solution to this problem is successful when moldings having a high perfume content, in particular scented pearls, are incorporated into the detergent articles, wherein the perfume article is produced by granulation or pressure agglomeration (e.g. pelletization, extrusion, etc.).

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The present invention relates to a process for the manufacture of detergent articles in which a highly concentrated fragrance composition is produced by granulation or pressure agglomeration, admixed with other detergent and / or granular detergent active ingredients, and then premixed to form products.

In the process according to the invention, highly concentrated mixtures of fragrances are suitable for use, which can be produced by granulation or pressure agglomeration. Preference is given to mixtures of fragrances, in particular fragrance pearls whose bulk density is greater than 700 g / l. The production of "scented beads" advantageously usable in the process of the invention is described, for example, in the earlier German patent application 197 46 780.6 (Henkel KGaA). This application discloses a process for the production of shaped fragrance products, in particular fragrance beads, having a bulk density of more than 700 g / l, in which a solid and substantially anhydrous masterbatch composed of

a) 65 to 95 wt. carrier substance (s)

b) 0 to 10 wt. adjuvants as well as

c) 5 to 25 wt. perfume.

Preferred carrier materials are selected from the group of surfactants, surfactant mixtures, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates and are used in amounts ranging from 65 to 95% by weight, more preferably from 70 to 90% by weight. in each case based on the weight of the scented product formed.

In addition to the "scented beads" produced by the above-described process, the incorporation of scented beads as described in the earlier German patent application 197 46 781.4 (Henkel KGaA) is preferred in the process according to the invention. This document discloses a process for the manufacture of fragrance detergents or detergents or components thereof having a bulk density of greater than 600 g / l, in which a solid and substantially anhydrous premix of detergents and / or detergent raw materials containing at least 0.1 wt. % of the perfume, based on the masterbatch, and the masterbatch is then subjected to pressure agglomeration. Such scented detergents and cleaners or the aforementioned scented products may be incorporated into the masterbatches by the method of the invention.

The production of highly concentrated perfumed shaped articles is accomplished by granulation or pressure agglomeration. In granulation, the premix of the fragrance-shaped product is compacted and homogenized by a rotating stirrer and granulated to form the fragrance-shaped products, in particular fragrance beads. granulation

In this case, it provides scented pearls with a wide range of grains (coarse and fine grains), which makes the pressure agglomeration variant more advantageous than granulation.

In the process of pressure agglomeration, the masterbatch of the shaped fragrance product is compacted and plasticized by pressure and shearing, while homogenizing and finally discharged from the apparatus by molding. Technically the most important processes of pressure agglomeration are extrusion, roller compacting and pelleting.

In a more preferred embodiment of the invention, the premix of the shaped fragrance product is fed continuously into a planetary cylindrical extruder or a twin-shaft extruder or a twin-screw extruder or a twin-screw press with parallel or oppositely guided worms. extrusion temperature. Shearing action of the screw extruder, the pressure which is preferably at least 25.10 ⁵ Pa (25 bar) at extremely high flow rates can be but depending on the apparatus and lower premix is compacted, plasticized, extruded through slats hole jets in the form of fine fibers and finally the extrudate is comminuted by means of a rotating knife, preferably into approximately spherical to cylindrical granulate grains. The diameter of the orifice plate openings and the fiber length are adjusted to the selected granulate dimensions. In this embodiment, the granulate is produced to a substantially uniformly determined particle size, and the absolute particle size can be adapted to the intended use. Generally, particle diameters up to a maximum of 0.8 cm are preferred. Important embodiments envisage the production of uniform granulates in the millimeter range, for example in the range of 0.5 to 5 mm, and more preferably in the range of about 0.8 to 3 mm. In this important embodiment, the length / diameter ratio of the cut off primary granulate ranges from about 1: 1 to about 3: 1. It is furthermore advantageous to introduce still a plastic primary granulate for further processing by molding; the edges of the raw extrudate will be rounded, so that finally spherical to almost spherical grains of the extrudate are obtained. If desired, small amounts of dry powder, for example zeolite powder such as NaA powder zeolite, can be used together at this stage. This shaping can be carried out in conventional disc machines. In doing so, care must be taken that it arises at this stage

- Only a small amount of fine grains. Alternatively, extrusion / compression can also be carried out in low pressure extruders, in a Kahl press or in a Bextruder.

As in the extrusion process, it is advantageous in other processes for producing shaped fragrances to subject the resulting primary granules / compacts to a further processing step, in particular rounding, so that finally spherical to almost spherical (pearl-shaped) grains are obtained.

In a further preferred embodiment of the present invention, the process for producing the scented shaped articles is carried out by roller compacting. In this process, a solid premix containing fragrance substances is disposed between two smooth rollers or two rollers with a well-defined shape and is rolled between the two rollers by pressing on the leaf compact. The rollers exert a high linear pressure on the masterbatch of the fragrance-shaped article and can be additionally heated or cooled as required. The use of smooth rolls yields smooth, unstructured strips, while using structured rollers it is possible to produce correspondingly structured strips in which, for example, certain shapes of later shaped fragrance products can be adjusted. The compacted web is then broken up into smaller pieces by means of a breaking and comminution process and can be processed into granular grains, which can be further treated by a further known surface treatment method, in particular an approximately spherical shape.

In a further preferred embodiment, the manufacture of shaped fragrance products is performed by pelleting. To this end, a solid masterbatch of the fragrance-shaped article containing the fragrances is applied to the perforated surface and is pressed through the openings by plasticizing with a presser. In conventional embodiments of pellet presses, the masterbatch of pressurized fragrance products is compacted, plasticized, pushed through a perforated surface by means of a rotating fine-strand roller, and finally crushed into granular granules by means of a breaking device. Here, various shapes of the pressure cylinders and the perforated die are possible. Thus, for example, shallow perforated plates are used as well as concave or convex annular matrices through which the material is extruded by means of one or more pressure cylinders. extrusion

- the rollers may also be conical in the case of plate-type devices, in the ring-shaped devices the dies and the extruding rollers may have the same or opposite direction of rotation. A suitable apparatus for carrying out the process according to the invention is described, for example, in German publication DE 38 16 842 (Schluter GmbH). The annular die presses disclosed herein consist of rotating, annular matrices permeated by the press channels and at least one discharge roller in effective communication with their inner surfaces, which ejects the material introduced into the matrix space through the press channels into the material outlet. Here, it is possible to drive the annular die and the embossing roller in the same sense, whereby a reduced shear load and thus a low temperature increase of the masterbatch is feasible. Of course, it is also possible to work with heated or cooled rollers to set the desired premix temperature during pelleting.

In the manufacture of shaped fragrance products, it is advantageous to perform granulation or pressure agglomeration substantially free of water. In this context, "substantially free of water" means a condition in which the content of liquid water, ie water existing in the form of a hydrate and / or structurally bound, is less than 2% by weight, more preferably less than 1% by weight. % and most preferably even less than 0.5 wt. based on the premix of the fragrance-shaped article. Correspondingly, the water can exist essentially only in chemically and / or physically bound form, optionally as a constituent, which exists at a temperature below 45 ° C at a pressure of 10 ⁵ Pa (1 bar) as a solid of the raw materials or mixtures, but a premix of the fragrance shaped article introduced as a liquid, solution or dispersion. By practicing essentially water-free production of the scented products, i.e. with the exception of the water content (" contamination ") of the solids used, an ecologically valuable process is prepared, since renouncing the subsequent drying step saves not only energy but can be avoided emissions which arise mainly from conventional drying processes. Moreover, it is only the abandonment of the subsequent drying steps that sensitive or volatile fragrances can be incorporated into the masterbatch and thereby the production of shaped fragrance products, in particular fragrance beads.

Shaped fragrance products that are processed with other tablet premixing ingredients in the method of the invention can vary widely with

-8with regard to the perfume content. Preferred are shaped fragrances, in particular fragrance beads, which contain from 3 to 40% by weight, more preferably from 5 to 30% by weight. % and most preferably from 8 to 20 wt. perfume, based on the weight of the scented article.

Individual perfume compounds can be used as perfume oils or fragrances in the process for producing fragrance products, for example synthetic products such as esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. Ester-type fragrance compounds are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalylacetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allylcyclohexylpropionane, styralylpropionallate, floryl, propanesyl, phenylacetate, cyclohexyl, methylsulfanyl. Ethers include, for example, benzylethyl ether and ambroxane, aldehydes for example linear C8-18 alkanals, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, lilial and bourgeonal, ketones for example jonones, α-isomethylionone and methyl-cetyl anethole ketone, , citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include, in particular, terpenes such as limonene and pinene. However, it is preferable to use mixtures of different fragrances which together produce a corresponding odor.

Such perfume oils may also contain natural fragrance mixtures such as are available from plant sources, for example pine, citrus, jasmine, patchouly, pink or Ylang-Ylang-oil. Also suitable are nutmeg, sage oil, camomile oil, clove oil, lemon balm oil, peppermint oil, cinnamon leaf oil, lime blossom oil, juniper oil, vetiver oil, oliban oil, galban oil and labdan oil as well as orange flower oil. , neroliol, orange peel oil and sandalwood silica.

In addition to perfume, the scented products used in the method of the invention contain carriers. It is preferred to use, based on the weight of the fragrance shaped article, from 65 to 95% by weight, more preferably from 70 to 90% by weight, of carrier substances from the group of surfactants, surfactant mixtures, di- and polysaccharides, silicates, zeolites, carbonates, sulphates and Citrate. These compounds or classes of compounds will be described below, since they may also be a component of a tablet premix.

In addition to perfume and carrier substances, it is preferred that the fragrance shaped articles contain additional excipients which facilitate their manufacture or improve their later properties. Here, it is preferred that the fragrance shaped articles, in particular the perfume beads, contain one or more of polyethylene glycols, fatty alcohol alkoxylates and fatty acid alkoxylates in an amount of from 1 to 10% by weight, more preferably from 2 to 9% by weight. % and most preferably from 5 to 7 wt. based on the weight of the scented shaped articles.

Optionally useful fatty acid alkoxylates may be described by Formula I

R ¹ -COO- (CH ₂ -CH-O) _to -H (I)

I

R ² wherein R ^{1 is} selected from C 7-17 -alkyl or C 7-17 -alkenyl, R ² = -H or -CH 3 if = 2 to 10.

Preferred fatty alcohol alkoxylates correspond to the general formula II

R ³ -O- (CH ₂ -CH-O) -H (II)

I

R ⁴ wherein R ^{3 is} selected from C 8-18 -alkyl or C 6-18 -alkenyl, R ⁴ = -H or -CH 3 and I = 2 to 10.

In both cases, the corresponding excipients can be readily prepared by the ethoxylation or propoxylation of fatty acids or fatty alcohols in a known manner, with technical mixtures of the various types being preferred for economic reasons.

Other preferred excipients are polyethylene glycols (briefly PEG) which can be described by formula III

H- _{(O-CH2 -CH2) n} -OH (III)

-10V which the degree of polymerization n can vary from about 5 to> 100 000, corresponding to a molar weight of 200 to 5,000,000 gmol ^first Products having a molar mass of less than 25,000 g / mol ¹ are referred to as the actual polyethylene glycols, while higher molecular products are often referred to in the literature as polyethylene oxides (briefly: PEOX). Preferred polyethylene glycols may have a linear or branched structure, with linear polyethylene glycols particularly preferred and end-capped.

Particularly preferred polyethylene glycols include those having a relative molecular weight of from 2000 to 12,000, preferably about 4000, wherein polyethylene glycols having a relative molecular weight of less than 3,500 and greater than 5,000 can be used particularly in combination with polyethylene glycols having a relative molecular weight of about 4000 and such combinations preferably contain more than 50% by weight, based on the total amount of polyethylene glycols, polyethylene glycols having a relative molecular weight of from 3500 to 5000. Polyethylene glycols which are at room temperature at 10 ⁵ Pa (1 bar) may also be used as binder. in a liquid state; here in particular, we are talking about polyethylene glycol with relative molecular weights of 200, 400 and 600.

The shaped fragrance products, in particular fragrance beads, are now processed by the process according to the invention together with other active ingredients and / or detergent compositions into a tablet premix which is compressed in a known manner into a tablet.

Important active ingredients which may be incorporated into the masterbatch of the tablet are surfactants, skeletal substances, bleaching agents, bleach activators and salts (such as sulfates, carbonates, citrates, etc., in particular sodium and potassium salts), as well as other conventional active ingredients and laundry detergent compositions. resources. These will be described in more detail below.

Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures thereof may be used in the shaped articles of the detergents and cleaning compositions produced by the process of the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view. The total surfactant content of the moldings produced by the process of the invention is from 5 to 60 wt% based on the weight of the molded article, with surfactant contents above 15 wt% being preferred.

As anionic surfactants, for example, surfactants of the sulphonate and sulphate type are used. Suitable sulfonate surfactants are, in particular, C 9-13 alkylbenzenesulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates as well as disulfonates, such as are obtained, for example, from C 6-18 -one monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and by acid hydrolysis of sulfonation products. Also suitable are alkanesulfonates, which are obtained from C ₂ -ie alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. Also suitable are esters of α-sulfofatty acids (estersulfonates), for example α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow.

Other suitable anionic surfactants are sulfated fatty acid glycerol esters. Glycerin esters of fatty acid are understood to be mono-, di- and triesters as well as mixtures thereof as obtained in the manufacture by esterification of one monoglycerin with 1 to 3 moles of fatty acid or the transesterification of triglycerides with 0.3 to 2 moles of glycerin. Preferred sulfated fatty acid glycerol esters are the sulfated 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.

Preferred as alk (en) ylsulfates are the alkali and especially sodium salts of sulfuric acid semi-esters of C 12 -C 18 fatty alcohols, for example, coconut fatty alcohol, tallow alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 6 -oxoalcohols and semi-secondary esters. alcohols with this chain length. Further preferred are alk (en) ylsulphates of the stated chain length which contain a synthetic unbranched alkyl moiety made on a petrochemical basis, which are degraded as well as the corresponding compounds based on fatty chemical raw materials. To wash the art are preferably C ₂ -C ₆ alkyl sulfates and C ₂ -C ₅ alkyl sulfates and C _4-alkyl -Ci5. Suitable anionic surfactants are also 2,3-alkyl sulfates, which may be prepared, for example, in accordance with U.S. Pat. No. 3,234,258 or 5,075,041 and obtained as a sales product of Shell Oil Company under the name DAN®.

Also suitable are monoesters of sulfuric acid and straight or branched C7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methylbranched C9.11-alcohols with an average of 3.5 moles of ethylene oxide (EO) or C12-18 fatty alcohols with 1 to 6 moles. up to 4 EO. They are used in cleaning compositions only in relatively small amounts, for example in an amount of from 1 to 5% by weight, because of their high foaming power.

Other suitable anionic surfactants are also alkylsulfosuccinic acid salts, also referred to as sulfosuccinates or sulfosuccinic acid esters and the monoester and / or diester of sulfosuccinic acid with alcohols, more preferably fatty alcohols, and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 6-6 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which themselves are nonionic surfactants (see description below). Again, particularly preferred are sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a restricted homologous distribution. It is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain and salts thereof.

Suitable further anionic surfactants are, in particular, soaps. Saturated fatty acid soaps such as salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid as well as mixtures of soaps derived from natural fatty acids such as coconut, palm kernel or tallow are suitable.

The anionic surfactants, including soaps, exist in the form of their sodium, potassium or ammonium salts as well as the soluble salts of organic bases such as mono-, di- or triethanolamine. Preferred are anionic surfactants in the form of their sodium or potassium salts, especially in the form of the sodium salts.

Preferred nonionic surfactants are alkoxylated, more preferably ethoxylated, in particular primary alcohols having more 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 moiety may be linear or more preferably methyl-branched in the 2-position. optionally, it may comprise a mixture of linear and methyl branched residues, so

As usual, they exist in oxoalcohol moieties. However, alcohol ethoxylates having linear residues of alcohols of natural origin having 12 to 18 carbon atoms, such as coconut, palm, tallow alcohol or oleyl alcohol, and having an average of 2 to 8 EO per mole of alcohol, are particularly preferred. Preferred ethoxylated alcohols include, for example, a C ₂ .i4 alcohols containing 3 EO or 4 EO, Cg.n alcohols with 7 EO, and _Ci3-5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C ₂ - s alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, as a mixture of Cl 2-i4-alcohols with 3 EO and C ₂ -i8 alcohol containing 5 EO. The degrees of ethoxylation indicated are a statistical mean, which may be an integer or a fraction for a special product. Preferred alcohol ethoxylates have a narrowed distribution of homologs (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO may also be used. An example for these is tallow alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of preferred nonionic surfactants to be used either as a single nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, more preferably ethoxylated or ethoxylated and propoxylated alkyl esters of fatty acids, more preferably of 1 to 4 carbon atoms in the alkyl chain, especially methyl esters. acids such as those disclosed in Japanese Patent Application JP 58/217598 or more preferably made by the method described in International Patent Application WO-A90 / 13533.

Nonionic surfactants of the amine oxide type, for example, N-alkyl-N, N-dimethylamino oxide and N-ω-alkyl- N, N -dihydroxyethylamine oxide, and the fatty acid alkanolamide type may also be suitable. The preferred amount of these nonionic surfactants is not more than the amount of ethoxylated fatty alcohols, especially not more than half.

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

R ⁵

I

R-CO-N- [Z] (IV) wherein RCO is an aliphatic acyl radical of 6 to 22 carbon atoms, R ⁵ is hydrogen, an alkyl or hydroxyalkyl radical of 1 to 4 carbon atoms, and [Z] is a linear or branched poly hydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can be obtained in a conventional manner by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent 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

I

R-CO-N- [Z] (V) wherein R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ⁶ is a linear, branched or cyclic alkyl group or an aryl group containing 2 to 8 carbon atoms, and R ⁷ is a linear, branched, or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-6 being preferred. _4- alkyl or phenyl radicals and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, in particular ethoxylated or propoxylated derivatives thereof.

[Z] is preferably obtained by reductive amination of a reducing sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. These N-alkoxy or N-aryloxy-substituted compounds can then be converted, for example, by teaching WO-A-95/07331 by reaction of fatty acid methyl esters.

-15 acids in the presence of an alkoxide catalyst for the desired polyhydroxy fatty acid amides.

Within the scope of the present invention, it is advantageous to incorporate anionic and nonionic surfactants by the process of the invention into shaped detergent articles, and application benefits may result from certain quantitative ratios in which the individual surfactants are used.

For example, detergent moldings in which the ratio of anionic surfactant to niotenside is from 10: 1 to 1:10, more preferably from 7.5: 1 to 1: 5 and most preferably from 5: 1 to 1: 2 are particularly preferred. wherein the surfactants can be incorporated into the shaped article by the method of the invention in the shaped articles of the fragrance or in the processed ingredients in the tablet premix.

Within the scope of the present invention, the processes according to the invention are advantageous in which the highly concentrated shaped perfume is mixed with at least one surfactant granulate.

From an application point of view, it may be advantageous for certain phases of the detergent articles to be formed or for the entire molded article, i. in all phases, certain classes of surfactants are not included. In the context of the present invention, a phase is understood to mean any spatial separation, that is to say multiphase in multilayer or ring-core or sheathed tablets. However, the individual phases are also produced by molding fragrance products, in particular fragrance beads, with the method according to the invention, wherein the fragrance product forms one phase, while the other phases are formed by further particles of tablet premixes. Thus, another important embodiment of the present invention contemplates that at least one phase of the molded article does not contain a nonionic surfactant. This variant can be realized particularly easily by the method according to the invention, when the non-ionic surfactant is completely omitted from the shaped perfume products or from other components of the tablet premix.

Conversely, however, it is possible to contain certain surfactants in individual phases or in the entire molded product, i.e. in all phases, to achieve a positive effect.

The incorporation of the alkyl polyglycosides described above has proven to be advantageous, so that shaped detergent products are preferred in which

At least one phase of the molded article contains alkyl polyglycosides, which is achieved by incorporating APG into the tablet premix.

As with nonionic surfactants, omitting anionic surfactants from individual or all phases of detergent molded articles may result in these being more suitable for certain application areas. Accordingly, detergent formulations are also possible within the scope of the present invention in which at least one phase of the molded product does not contain anionic surfactants, the implementation being particularly easy to accomplish analogously to the embodiment described above by the method according to the invention when the anionic surfactant is completely omitted either. of the scented product or other components of the tablet premix.

In more preferred embodiments of the present invention, the masterbatch comprises tablets for compressing one or more detergent active ingredients, in particular from the group of skeleton substances, bleaching agents, bleach activators, enzymes, dyes and disintegrating aids. These will be described below.

In addition to detergents, skeleton substances are the most important detergent and cleaning agent active ingredients. In the process according to the invention, it is possible to incorporate into the molded articles of detergents all the skeletal substances commonly used in detergents, in particular zeolites, silicates, carbonates, organic co-activating additives, and where there are no environmental prejudices against their use, phosphates .

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2 x} + 1 H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and values for x 2, 3 or 4. Such crystalline layer silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layer silicates of the formula are those in which M is sodium and x is 2 or 3. Particular preference is given to both β- and δ-di-silicates. sodium Na ₂ Si ₂ O ₅ yH ₂ O, wherein the sodium β-disilicate can be obtained, for example, by the method described in International Patent Application WO-A91 / 08171.

Amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, more preferably of from 1: 2 to 1: 2.8 and most preferably of from 1: 2 to 1: 2.6 are also applicable. which dissolve late and have secondary washing properties. The delayed dissolution compared to conventional amorphous sodium silicates can be carried out in various ways, for example by surface treatment, compounding, compacting / compacting or drying. Within the scope of the present invention, the term "amorphous" also means "X-ray amorphous". That is, silicates do not produce sharp X-ray reflections in X-ray diffraction experiments, as is typical of crystalline substances, but in all cases one or more maxima of diffuse X-ray radiation having a width of several degrees of bending angle. However, when silicate particles provide blurred or even sharp bending maxima in electron diffraction experiments, they may even have very good activating additive properties. It is to be understood that the products have microcrystalline regions of 10 to several hundred nm, with values up to a maximum of 50 nm and more preferably up to a maximum of 20 nm being preferred. Such so-called X-ray amorphous silicates, which dissolve equally delayed in comparison to conventional waterglasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and dried X-ray silicates.

It is preferred to use zeolite A and / or P as finely crystalline, synthetic zeolite containing bound water. As zeolite P, zeolite MAP® (sold by Crosfield) is particularly preferred. However, zeolite X as well as mixtures of A, X and / or P are also suitable. For example, a co-crystal of zeolite X and zeolite A (about 80% by weight of zeolite X) which is distributed commercially is advantageously usable in the present invention. by CONDEA Augusta SpA under the trade name VEGOBOND AX® and can be described by the formula nNa ₂ O. (1-n) to O _2. AI ₂ O ₃ . (2-2.5) SiO ₂ . (3.5-5.5) H ₂ O

The zeolite can be used as a skeleton substance in a granular mixture, but also for dusting the total mixture to be pressed, usually

Both pathways utilize the incorporation of zeolite into the masterbatch. Suitable zeolites have a mean particle size of less than 10 µm (Volume Distribution; Coulter Counter) and preferably contain from 18 to 22 wt%, more preferably from 20 to 22 wt%. bound water.

Of course, it is also possible to use phosphates as well-known as activating agents, if such use is not to be avoided for environmental reasons. Sodium salts of orophosphates, pyrophosphates, and especially tripolyphosphates are particularly suitable.

Useful organic constituents of the skeleton are, for example, polycarboxylic acids useful 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), for environmental reasons, as well as mixtures thereof. Preferred 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 articles, disintegrating aids, so-called tablet disintegrants, can be incorporated into these to reduce disintegration times. Tablet disintegrators and disintegrants are understood to mean, according to Römpp (9th edition, Volume 6, page 4440) and Voigt, "Lehrbuch der pharmazeutischen Technologie" (6th edition, 1987, pages 182-184) excipients which promote the rapid disintegration of tablets in water or gastric juice and release of the pharmaceutical in resorbable form.

These substances, known as "disintegrants" because of their action, increase their volume on contact with water, while on the one hand increasing their own volume (swelling), on the other, they can exert pressure by releasing gases to allow the tablet to break into small particles. Old known disintegrants are, for example, carbonate / citric acid systems, and other organic acids may also be used. The swellable disintegrating aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starches and their derivatives, alginates or casein derivatives.

Preferred detergent moldings comprise from 0.5 to 10% by weight, more preferably from 1 to 5% by weight. % and most preferably from 2 to 4 wt. a disintegrating aid, each based on the weight of the shaped article.

Preferred disintegrants in the context of the present invention are cellulose-based disintegrants such that preferred molded laundry detergent compositions contain such a cellulose-based disintegrant in an amount of from 0.5 to 10 wt%, more preferably from 1 to 5 wt% . % and most preferably from 2 to 4 wt. Pure cellulose has a formal gross composition (CeHioOsjn) and is a formally perceived β-1,4-polyacetal cellobiose, which is composed of two glucose molecules on its side. Suitable celluloses consist of approximately 500 to 5000 glucose units and have an average molar mass of approx. Cellulose derivatives which are obtainable from cellulose by reactions analogous to polymerization are useful in the context of the present invention, such chemically modified celluloses including, for example, esterification or etherification products in which hydroxy-hydrogen are substituted. However, it is also possible to use as cellulose derivatives celluloses in which the hydroxyl groups are replaced by a functional group which is not bonded via an oxygen atom, for example, the cellulose derivatives include alkali celluloses, carboxymethylcellulose (CMC), es. cellulose ethers and ethers as well as aminocellulose.

It is preferred not to use the cellulose derivatives alone as a cellulose-based disintegrant, but to use them in admixture with cellulose. The preferred content of cellulose derivatives in these compositions is less than 50 wt%, more preferably less than 20 wt%. based on a cellulose-based disintegrant. Particularly preferred is the use of pure cellulose as a cellulose-based disintegrant which contains no cellulose derivatives.

Microcrystalline cellulose may be used as an additional cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of cellulose under conditions that attack and completely break down only amorphous regions (approximately 30% of total cellulose).

Cellulose, the crystalline regions (approximately 70%) are left undamaged. Subsequent disaggregation of the microfine cellulose resulting from the hydrolysis yields microcrystalline cellulose having a primary particle size of about 5 µm and, for example, compactable to granules with an average particle size of 200 µm.

Within the scope of the present invention, detergent moldings are preferred which additionally comprise a cellulose-based disintegrant in the molded article.

In addition to the surfactant, activating ingredients and disintegrating adjuvants mentioned herein, the laundry detergent compositions of the present invention may comprise other laundry and detergent ingredients from the bleach, bleach activator, enzyme, fluorescent, colorant, suds, silicone, antiredeposition agents, optical brighteners, graying inhibitors, coloring inhibitors and corrosion inhibitors.

Among the bleaching compounds which provide H2O2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, perphosphate, citrate peroxohydrates as well as peroxyacid salts or peroxyacids providing H ₂ O ₂ , such as peroxobenzoates, peroxophthalanes, diperoxyazelaic acid, phthaliminoic acid peroxyacid or diperoxydodecanoic acid.

In order to achieve an improved bleaching effect at washing temperatures of 60 ° C and below, it is possible to incorporate bleach activators as a separate component or as an active ingredient in component b). Bleach activators which may be used are compounds which give, under conditions of perhydrolysis, aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acids. Compounds having O- and / or N-acyl groups with the indicated number of carbon atoms and / or optionally substituted benzoyl groups are suitable. Preferred are multiple 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-nonanoyl-21 succinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or z-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated especially polyhydric alcohols, 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 incorporated into the shaped articles. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Μη-, Fe-, Co-, Ru- or Mosalene complexes or -carbonyl complexes. Also useful as bleach catalysts are Μη-, Fe-, Co-, Ru-, Μο-, Τί-, V- and Cu-complexes with nitrogen-containing tripod ligands as well as Co-, Fe-, Cu- and Ru-ammonium complexes .

Suitable enzymes are those 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 grisus. Preference is given to the use of Subtilisin-type proteases and in particular to proteases derived from Bacillus lentus. Of particular importance here are mixtures of enzymes, for example proteases and amylases or proteases and lipases or proteases and cellulases or cellulases and cellulases or lipases or proteases, amylases and lipases or proteases, lipases and cellulases, in particular mixtures containing cellulase. In several cases, peroxidases or oxidases have also proven suitable. The enzymes may be adsorbed onto the support and / or stored in packaging materials to protect them against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules in the shaped articles according to the invention may be, for example, from 0.1 to 5% by weight, more preferably from 0.1 to about 2% by weight.

In addition, molded detergent products may also contain ingredients that positively affect the washability of oils and fats from textiles (so-called soil beet only). This effect is particularly pronounced when soiling a fabric which has been washed several times with a detergent according to the invention which contains these oil- and fat-dissolving components. Preferred oils and fat solubilizers include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of from 15 to 30% by weight. % and hydroxypropoxy groups of from 1 to 15 wt. always refer to non-ionic

Cellulose ether as well as polymers of phthalic acid and / or terephthalic acid or derivatives thereof known in the art, in particular polymers of ethylene terephthalanes and / or polyethylene glycol terephthalanes or their anionically and / or nonionically modified derivatives. Of these, sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

The shaped articles may contain as optical brighteners diaminostilbenedisulfonic acid derivatives or alkali metal salts thereof. Suitable salts are, for example, 4,4'-b / s (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid salts or compounds of the same structure having instead of a morpholine group, a diethanolamine group, a methylamine group, an aniline group or a 2-methoxyethylamine group. Substituted diphenylstyryl-type brighteners may also be present, for example the alkali salts of 4,4'-bis (2sulfostyryl) diphenyl, 4,4'-b / s (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) 4 '(2-sulfostyryl) biphenyl. It is also possible to use mixtures of the abovementioned brighteners.

In order to improve the aesthetic impression of the compositions according to the invention, they can be colored with suitable dyes. Preferred dyes, which are not difficult to select for the skilled person, have a high storage stability and are not sensitive to the other active ingredients of the composition and to light, as well as have no pronounced substantivity to the fibers of the fabrics to dye them.

For aesthetic reasons, it may be desirable to manufacture shaped articles in which only individual phases or layers are colored. This can be accomplished without difficulty by the method according to the invention in various variants. Thus, there are at least two stages in the shaped article already conditioned by the incorporation of the shaped articles of fragrance, of which only one or both can be colored differently to obtain a 'dotted' shaped article.

The coloring of the individual phases can be carried out in a conventional manner by adding colorants or dye solutions to the shaped products of the fragrances or to the granules or powders of the tablet premix. However, it is preferable to use colored powder compositions which cover the surface of the particles and thus optically impart the colored grain. This saves the dye on one side, on the other

Secondly, the problem of incorporating high amounts of dyes in the molded article and consequently in the water bath is avoided.

The production of the detergent moldings is carried out by the method according to the invention in a known manner by compressing the premix of a tablet containing the fragrance moldings. For production, the masterbatches are compacted to a solid compress in a so-called matrix between two punches. This process, shortly referred to as tabletting, is divided into four stages: dosing, compacting (elastic shaping), plastic shaping and extrusion.

Tableting is carried out on conventional tablet presses which can in principle be equipped with a single or double punch. In the latter case, not only the upper punch is used to generate pressure, but also the lower punch moves towards the upper punch during compression, while the upper punch presses downward. For small quantities produced, more preferably, eccentric tablet presses are used, in which the punches are mounted on an eccentric disk 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 be carried out with one upper and lower punches, but several punches can also be mounted on one eccentric disk, and the number of holes in the die must be increased accordingly. The flow rates of the eccentric presses can vary, depending on the type, from a few hundred to a maximum of 3000 tablets per hour. For larger flow rates a carousel tablet press is chosen, in which a plurality of matrices are arranged on a so-called die table in a circle. The number of dies varies from 6 to 55 depending on the model, with larger dies available. Each die on the die table includes an upper and a lower punch, and the pressing pressure can again be generated not only by the upper or lower punch but also by means of both punches. The die table and punches are moved around a common vertical axis, wherein the punches are placed in a position for filling, compaction, plastic shaping and extrusion by rail cam guides. In places where a particularly high punching or lowering of the punch (filling, compaction, extrusion) is required, these cam guides are supported by additional pressure pieces, pressure rails and lifting guides. The filling of the matrix is carried out by means of a stationary feeding device,

-24 the so-called "filling shoe", which is connected to the masterbatch container. The pressing pressure for a given premix is individually adjustable by the pressing paths of the upper and lower punches, the pressure being generated by rotating the punch heads on an adjustable pressure roller.

Rotary presses can also have two or more filling shoes to increase flow. For the production of two- and multi-layer molded articles, a plurality of filling shoes are arranged in series without the lightly compressed first layer being extruded before the next filling. Sheathed and pointed tablets having an onion-like structure can also be produced by suitable process control, in the case of a pointed tablet, the top side of the core or core layers is not covered and remains visible. The carousel tablet presses can also be equipped with single or multiple tools so that, for example, the outer circle with 50 and the inner circle with 35 holes can be used simultaneously for compression. The flow rates of modern carousel tablet presses are greater than a million shaped products per hour.

Suitable tableting machines within the scope of the present invention can be obtained, 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 (CH) and Courtoy NV, Halle (BE / LU). Particularly suitable is, for example, the HPF 630 double-pressure hydraulic press from LAEIS, D.

The shaped articles can be made in a predetermined spatial shape and in a predetermined size, and can consist of a plurality of phases, i. layers, inserts or cores and rings. As a spatial shape, practically all meaningfully manageable shapes are possible, for example shapes such as sheets, rods or bars, cubes, cuboids and corresponding spatial elements with flat sides, and in particular cylindrical shapes with a circular or oval cross-section. This last embodiment comprises embodiments from a tablet to a compact roller having a height to diameter ratio of greater than 1.

In this case, the metering moldings can be designed as individual pieces which are separated from one another, corresponding to a certain quantity of detergent and / or cleaning agent to be dispensed. However, it is also possible to produce moldings which connect them

A plurality of such quantitative units in a single compact, wherein the readily separable dosage of the smaller units is ensured by the given fracture points. For the use of fabric laundry detergents in machines of the type common in Europe with horizontally arranged mechanics, it may be useful to shape the dispensed moldings as a tablet in the form of a cylinder or block, with a diameter / height ratio of about 0.5: 2 to 2: 0.5 . Commercially available hydraulic presses, eccentric presses or carousel presses are particularly suitable for the production of such moldings.

The spatial shape of one further embodiment of the molded article is adapted by its parameters to the hopper of a commercially available household washing machine, so that the molded article can be dispensed without the aid of dosing directly into the hopper where it dissolves during the flushing process. Of course, it is also possible to use shaped detergent products by means of a dispensing aid without any problems.

Another preferred molded article that can be produced has a plate or plate structure with alternately thick long and thin short segments, so that it is possible to break off the individual segments from this "table" at designated fracture points that represent short thin segments and insert them into machine. This principle of "tabular" shaped detergent articles can also be carried out in other geometrical shapes, for example as vertical standing triangles, which are connected longitudinally to one another only on one of their sides. Here, for optical reasons, it is advisable to form the base of the triangles which interconnects the individual segments as one phase, while the vertices of the triangles form the second phase. The different coloring of the two phases is particularly impressive in this embodiment.

After molding, the detergent moldings have high stability. The breaking strength of cylindrical shaped articles can be registered by a measure of the diametrical fracture stress. This can be determined by σ = (2P) / (π D t)

-26σ means diametral fracture stress (DFS) in Pa, P is the force in N that exerts a pressure on the shaped article which causes the shaped article to break, D is the diameter of the shaped article in meters and t is the height of the shaped article.

In the premix to be pressed into the detergent moldings, the amount of highly concentrated fragrance moldings may vary. Within the scope of the present invention, the proportion of highly concentrated fragrant shaped products in the premix to be compressed is preferably from 1 to 15% by weight, more preferably from 2 to 12% by weight. % and most preferably from 5 to 10 wt. always based on premix.

A further object of the invention is the use of highly concentrated mixtures of fragrances, in particular fragrance beads, with a bulk density of more than 700 g / l produced by granulation or pressure agglomeration in shaped detergent products.

By incorporating perfume in this concentrated and extremely homogeneous form, the physical properties of the shaped article are positively influenced. The tendency of the perfume to migrate due to the compression pressure of the tablet over the entire molded product is avoided, and the hydrophobized perfume oil is concentrated in the narrow region of the tablet in this way. Thus, the detergent moldings produced by the process according to the invention have at least the same positive properties as the moldings containing no perfume at all.

Compared to perfume-containing shaped articles, not only the physical properties of the shaped articles, but also the olfactory features of the compositions and fabrics treated with the composition, are greatly improved. As seen with the "scented beads" in the earlier German patent application 197 46 781.4, the smell and shaped articles of the laundry and cleaning products according to the invention and the fabrics treated in a laundry bath prepared from these compositions are better impressed.

DETAILED DESCRIPTION OF THE INVENTION

According to the description in the earlier German patent application 197 46 780.6, fragrant pearls were produced by spray-drying the surfactant granulate (carrier)

It was blended with other excipients and perfume and was subsequently loaded into a Lihotzky twin-shaft extruder and plasticized and extruded under pressure.

The composition of the spray-dried surfactant granules is shown in Table 1, the composition of the premix of pearl beads in Table 2.

Table 1: Spray-dried surfactant granulate [wt%]

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: Premixed pearl premix [% by weight]

C 12-18 -alcohol 5.0 zeolite X 10,0 PEG 4000 4.0 surfactant granulate (Table 1) 68.0 perfume oil 10,0

The plasticized premix left the extruder at a pressure of 85 bar ( ⁵ bar) through an orifice plate with 0.5 or 0.7 or 0.85 or 1.2 mm diameter orifices.

The extruded strands were chopped with a rotating knife to a length / diameter ratio of approximately 1 and rounded with Marumizer®.

In parallel to the fragrance beads, another surfactant granulate having the composition given in Table 3 was produced:

-28Table 3: Surfactant granulate [wt%]

Cg.i3-alkyl benzene sulfonate 18.6 sulfate _C12-fatty alcohol -i8 5.4 C ₂ -i8 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 a copolymer of acrylic acid and maleic acid 5.4 water, salts 10.3

The premixes of tablets E1 as well as V1 and V2 have now been prepared by mixing the surfactant granulate described in Table 3 with the other detergent active ingredients. The masterbatch of the present invention E1 contained the scented pearls described in Table 2, while in Comparative Example V1, the perfume was sprayed in an appropriate amount onto the masterbatch. For comparison, a perfume without perfume V2 was also produced.

The masterbatches were compressed into detergent tablets on a Korsch tablet press. The pressing pressure was adjusted in such a way that three series of shaped articles (E1, E1, E1, analogously V1 and V2) were obtained which differed in their hardness. The composition of the premixes to be pressed (and the moldings made therefrom) is shown in Table 4.

-29Table 4: Premixtures / Molded Detergent Products [wt%]

E1 V1 V2 surfactant 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-silicone antifoam 15% on soda 3.5 3.5 3.5 enzymes 2.5 2.5 2.5 terephthalic acid-ethylene glycol-PEG ester 1.1 1.1 1.1 scented pearls (Table 2) 5.0 - - perfume oil - 0.5 - cellulose-based disintegrating aid 5.0 5.0 5.0 zeolite A (powder) 1.0 1.0 1.0

The hardness of the tablet was measured by deforming the tablet until breaking, with the force acting on the faces of the tablet and determining the maximum force the tablet could withstand.

To determine the disintegration of the tablet, the tablet was placed in a beaker of water (600 mL of water, 30 ° C) and the time after complete tablet disintegration was measured. The experimental data is in Table 5:

Table 5: Detergent tablets [physical data]

tablet E1 EI E1 V1 VI ' V1 V2 V2 ' V2 tablet hardness 40 N 53 N 63 N 41 N 50 N 62 N 41 N 51 N 60 N disintegration time tablets 10s 14 p 21 p 14 p 22 p 53 p 9 p 16s 21 p

The data in Table 5 shows that the incorporation of perfume as highly concentrated scented fragrance products brings significant advantages:

-30 first, the disintegration time of the tablet does not depend as much on the tablet hardness as on tablets in which the perfume has been sprayed onto the masterbatch (cf. E1: V1). or even better (cf. E1: V2).

Also, the olfactory impressions of the molded articles made according to the invention are better than conventional molded articles. For this purpose, the molded products E1 and V1 were compared.

The composition of the perfume oil contained in the shaped articles or the scented pearls is given in Table 6. The fragrance of the product as well as of the treated fabrics (cotton) was judged by the subjective sense of smell of the perfume. Here, the numerical values in the rating table (Table 7) indicate the number of perfumers who rated the product or fabric treated with it as "more fragrant". Out of the 7 perfumers, 6 shaped laundry and cleaning products manufactured according to the invention were therefore rated better. The olfactory test results are summarized in the table

Claims (10)

PATENT CLAIMS 1. A process for the production of molded detergent articles, comprising granulating or agglomerating a highly concentrated fragrance composition, mixing with other powder and / or granular detergent active ingredients, and then compressing. masterbatch in a known manner for shaped articles. Method according to claim 1, characterized in that the highly concentrated fragrance mixtures have a bulk density of more than 700 g / l. A method according to any one of claims 1 or 2, characterized in that highly concentrated perfume mixtures, in particular perfume beads, which have been produced by substantially anhydrous granulation or pressure agglomeration are used. Method according to any one of claims 1 to 3, characterized in that the shaped fragrance products, in particular fragrance beads, contain from 3 to 40% by weight, more preferably from 5 to 30% by weight. % and most preferably from 8 to 20 wt. perfume, based on the weight of the scented article. Method according to any one of claims 1 to 4, characterized in that the fragrance-shaped products, in particular fragrance beads, contain from 65 to 95% by weight, more preferably from 70 to 90% by weight, based on the weight of the fragrance shaped product. . carrier substances from the group of surfactants, surfactant mixtures, di- and polysaccharides, silicates, zeolites, carbonates, sulphates and citrates. Method according to any one of claims 1 to 5, characterized in that the fragrance-shaped products, in particular perfume beads, contain, based on the weight of the fragrance-shaped product, one or more of the polyethylene glycols, fatty alcohol alkoxylates and fatty alkoxylates % -33 acids in an amount of from 1 to 10 wt.%, More preferably from 2 to 9 wt. % and most preferably from 5 to 7 wt. Method according to any one of claims 1 to 6, characterized in that the highly concentrated perfumed shaped products are mixed with at least one surfactant granulate. Method according to any one of claims 1 to 7, characterized in that the premix to be compressed contains one or more active substances of detergents and cleaning agents, in particular from the group of skeleton substances, bleaching agents, bleach activators, enzymes, dyes and disintegrating agents. aids. The process according to any one of claims 1 to 8, characterized in that the proportion of highly concentrated perfumed shaped articles in the premix to be pressed is from 1 to 15% by weight, more preferably from 2 to 12% by weight. and most preferably from 5 to 10% by weight, based on each premix. 10. Use of highly concentrated mixtures of odoriferous substances, in particular odoriferous pearls, with a bulk density of more than 700 g / l, which have been produced by granulation or pressure agglomeration, in shaped articles of detergents and cleaning agents.