ES2249255T3 - PROCEDURE FOR THE DEVELOPMENT OF MOLDED BODIES OF DETERGENT AGENTS AND QUICKLY DISGREGABLE CLEANING AGENTS. - Google Patents

Abstract

The invention relates to washing and cleaning agent shaped bodies which are characterized by having both a high degree of hardness and thus stability during transport and handling as well as excellent disintegration properties. The inventive shaped bodies can be produced using a known tabletting process in which the premix to be compacted has a temperature of less than 20 DEG C immediately before compaction.

Description

Procedure for body building molded detergent and cleaning agents quickly disaggregated.

The present invention relates to a procedure for the elaboration of molded bodies that have detergent and cleaning properties. The invention relates to particular to a procedure for body building molded detergent and cleaning agents for washing textiles in a household washing machine, so-called abbreviated as detergent tablets.

Today detergents and cleaning agents usual in the market are offered in the form of liquid products or solid. Within the last type of offer, a distinction is made between powders or traditional concentrates, which can be obtained for example by granulation or extrusion. Detergent and cleaning agents Concentrates present, compared to traditional powders, the advantage of requiring a lower packaging cost and a lower amount in the dosage per wash. In addition the costs are reduced of transport and conservation by the small size of the containers. The most concentrated way in which currently offered detergents and cleaning agents on the market in some countries are the molded bodies of detergent and cleaning agents tablets While water softeners and Mechanical dishwashers are widespread in this type of offer, appear in the case of detergents for textiles multiple inconveniences, which until now face a great dissemination and acceptance by the consumer. The problems that appear in the type of molded body offer are further aggravated due to the clearly higher contents in surfactants. Especially problematic are detergent tablets that contain alkoxylated nonionic surfactants, since this type of surfactants have a negative impact on the solubility of pills on the other hand, precisely these surfactants are especially desirable for its high detergent power.

The dichotomy between a molded body strong enough and a disintegration time what short enough is especially inconvenient important. Since only molded bodies can be manufactured sufficiently stable, that is, resistant to form and breakage, with proportionally high compaction pressures, is produces strong compaction of body components molded and, as a result, delayed disintegration of the body molded in the aqueous bath and thereby a release delayed active substances in the washing process or cleaning. The delayed disintegration of the molded bodies has also the disadvantage that the molded bodies of agents usual detergents and cleaning agents cannot be introduced to through the detergent drawer of the washing machines domestic, because the pills do not disintegrate sufficiently fast in secondary particles, small enough to reach to the drum of the washing machine through the bucket.

To solve this problem, they exist in the State of the art multiple approaches. Together with introduction of special constituents, which facilitate the disintegration, it is also proposed to cover each constituent separately or from the entire tablet. These approaches to solve the problem are somehow based "from the point of view of the formulation", that is, it introduce certain constituents or the tablet is optimized or its parts with additives. Along with these approaches "chemical" there are also proposals to solve the mentioned problem, which can be carried out independently of the formulation. These "physical" approaches affect generally to certain ways of operating the machines to form pills or other process parameters, in the that the compression pressure is at the point of interest. I also know proposes the refinement of the previous mixtures to be compressed up to certain granular fractions, thus obtaining properties advantageous of molded bodies regardless of the composition of the previous mixture.

The document EP-A-0 466 484 (Unilever) gives know in this sense detergent tablets in which the mixture to be compressed has a particle size of between 200 and 1200 µm, the difference between the upper limits and smaller than the particle size not exceeding 700 µm. This document does not explain anything about the surface treatment of Each constituent

The document EP-A-0 522 766 (Unilever) refers also to molded bodies of a compact detergent composition and in particulate form, which contains surfactants, adjuvants and disintegrating auxiliaries (based on cellulose, for example), in that at least a part of the particles is coated with the disintegrating substance and shows both binding and binding effects disintegrants during dissolution of molded bodies in water. This document also refers to the generalized difficulty to manufacture molded bodies with adequate stability and, simultaneously, with good solubility. Particle size of the previous mixture to be compressed must be greater than 200 \ mum, the difference between the upper and lower limits being of the particle size not exceeding 700 µm.

Document DE 40 10 533 (Henkel KGaA) gives know a procedure for the manufacture of tablets from of granules already compressed previously. In this case, they mix the granules made in a first operation by pressing by extrusion and fractionation, if necessary, with other substances constituents and auxiliaries and pills are formed. The percentage of the pellet previously compressed in the tablets is in this document up to 100%. Nothing is explained about a pretreatment of optionally added components used

EP 711 828 (Unilever) claims a procedure for making detergent tablets by compressing a composition in the form of particles that It contains a binding agent. The melting point of the agent binder must be between 35 and 90 ° C and compression must be carried out at temperatures below the melting point but above 28 ° C. This document therefore combines a form of "chemical" procedure with a procedure form "physical".

The "physical" proposals described until moment, they have the advantage that they can be done independently of both the composition of the previous mixture and of the type of machine used to form pills. In this way, the manufacturer may consider other requirements both during the composition of their molded bodies of detergent agents and of cleaning as during the acquisition and use of your machinery, without being subject to additional limitations. However, the detergent tablets, prepared according to the documents mentioned, they still have disadvantages. Specifically, they have a sufficient resistance, but often have speeds of disintegration such that they do not allow a dosage through the detergent drawer of a household washing machine. In the texts of the state of the art cited, the dissolution times below 10 minutes and values residuals below 50%, these values being totally insufficient for the use of detergent tablets through the washer tray

The present invention has been based solely on the objective of making available a procedure for production of molded bodies of detergent agents and cleaning, which allowed to make molded bodies without the mentioned disadvantages. Thus, they must be able to be elaborated, in a way simple and very reproducible, agent molded bodies detergents and cleaning agents that have a high resistance but distinguished by having a high rate of disintegration and can be used through the bucket of washing machines domestic. In addition, the manufacturer should be offered the greatest freedom of choice regarding the composition and choice of the machine pressing.

It has now been discovered that the production of molded bodies of detergent agents and cleaning with the mentioned advantageous properties if they cool the previous mixtures to be compressed and the pills are formed at low temperatures

The object of the invention is a process for the production of molded bodies of detergent agents and compression molding cleaning in a manner known per se same, in which the previous mixture to be compressed presents, just before compression, a temperature below 15 ° C

In the context of the present invention, it is preferred that the mixture to be compressed present, just before the formation of the tablets, a temperature clearly below 15 ° C Variants of the method according to the invention are carried out. therefore in such a way that the previous mixture to be compressed present, before compression, a temperature below 13ºC and especially below 10 ° C.

It is assumed that it is also possible according to the invention, a compression of previous mixtures presenting temperatures of 14ºC or 12ºC or 11ºC or 9ºC or 8ºC or 7ºC or 6ºC or 5ºC or 4ºC or 3ºC or 2ºC or 1ºC or 0ºC. It is also possible according to the invention a compression of previous mixtures with temperatures below freezing point, such as with temperatures of -1ºC, -2ºC, -3ºC, -4ºC, -5ºC, -6ºC, -7ºC, -8ºC, -9ºC, -10ºC, -11ºC, -12ºC, -13ºC, -14ºC, -15ºC, -16ºC, -17ºC, -18ºC, -19ºC or -20ºC, being able present the previous mixture even lower temperatures.

In the preferred embodiments according to the method of the invention, the previous mixture to be compressed contains one or more granules with surfactants as well as others preparation components The preparation of the granules with Surfactants can be performed with technical procedures usual granulation, such as compaction, extrusion, mixed granulation, pelletization or bed granulation fluidized It is advantageous for subsequent bodies molded detergent and cleaning agents, than the pre-mix to be compressed present an apparent specific gravity close to the usual compact detergent agent. It is especially preferred that the previous mixture to be compressed has a specific weight apparent of at least 500 g / l, preferably at least 600 g / l and especially at least 700 g / l.

For granules with surfactants, they are sufficient the particle size criteria determined in the Preferred variants of the procedure. Thus, they are preferred methods according to the invention in which the granulate with Surfactants have a particle size of between 100 and 2000 µm, preferably between 200 and 1800 µm, especially preferable between 400 and 1600 µm and especially between 600 and 1400 µm.

Surfactant granules also contain, together with the active substances (anionic surfactants and / or not ionic and / or cationic and / or amphoteric) preferably excipients which come especially from the group of support substances. Especially advantageous procedures are characterized because the previous mixture to be compressed contains a granulate with surfactants containing anionic and / or non-ionic surfactants as well as support substances and whose total content in Surfactants is 5 to 60% by weight, preferably 10 to 50% by weight and especially 15 to 40% by weight, in relation to respectively to the surfactant granulate.

To develop the washing performance, the surfactant granules contain surfactants of the group of anionic, nonionic, zwitterionic or surfactants cationic, surfactants being clearly preferable anionic for economic reasons and for its spectrum of performance.

As anionic surfactants are used, for example, those of the type of sulphonates and sulfates. How Surfactants of the sulphonate type are considered preferably alkylbenzenesulfonates C 9-13 and olefin sulphonates, that is, mixtures of alkenesulfonates and hydroxyalkanesulfonates as well as disulfonates, which are obtained for example from mono-olefins C 12-18 with double terminal or internal bond by sulfonation with sulfur trioxide gaseous and subsequent alkaline or acid hydrolysis of the products of sulfonation Also suitable are alkanesulfonates that are obtained from C 12-18 alkanes, for example by sulfocloration or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are fatty acid esters. α-sulfuric acids (ester sulfonates), such as α-sulfonated methyl esters of acids Coconut, palm kernel or tallow hydrogenated fatty.

Other suitable anionic surfactants are those glycerin esters of fatty acids. By glycerin esters of fatty acids are understood as mono, di and tri-esters as well as their compounds, which are obtained in the preparation by esterification of a monoglyceride with 1 to 3 mol of fatty acids or in the transesterification of triglycerides with 0.3 to 2 mol of glycerin. Glycerin esters of sulfonated fatty acids preferred are also sulfonated fatty acid products saturated with 6 to 22 carbon atoms, such as capronic acid, caprylic acid, capric acid, myristic acid, acid lauric, palmitic acid, stearic acid or acid Behenic

As alkylsulfates, they prefer alkaline salts and especially sodium salts of sulfuric acid half ester of C 12- C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauric, myristic, cetyl or stearic alcohol or oxoalcohols C_ {10} -C_ {20} and those half esters of secondary alcohols with these chain lengths. I also know they prefer alkylsulfates with the length of mentioned chain, which contain a straight chain alkyl moiety synthetic, obtained on a petrochemical basis with a behavior of decomposition analogous to suitable compounds based on Oleochemical raw materials. From the point of view of the technique washing, alkyl sulfates are preferred C 12 -C 16 and alkyl sulfates C 12 -C 15 as well as alkyl sulfates C_ {14} -C_ {15}. They are also surfactants suitable anionic 2,3-alkyl sulfates that are elaborate for example according to US Pat. numbers 3 234 258 or 5,075,041 and which can be obtained as a marketed product from the company "Shell Oil Company" with the DAN® brand.

Acid monoesters are also suitable sulfuric acid of straight chain C7-21 alcohols or branched ethoxylated with 1 to 6 mol of ethylene oxide, such as C 9-11 2-methyl alcohols branched with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 fatty alcohols with from 1 to 4 EO. Be used in detergents only in small quantities due to its high foaming power, for example in quantities from 1 to 5% by weight.

Other suitable anionic surfactants are also the alkylsulfonated succinic acid salts, called also sulfosuccinates or esters of sulfosuccinic acid, as well as the monoesters and / or diesters of the sulfonated succinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred Sulfosuccinates contain traces of C8-18 fatty alcohols or mixtures of these. Especially preferred sulphosuccinates they contain a fatty alcohol residue that is derived from alcohols ethoxylated fatty acids, which represent nonionic surfactants (see the description below). On the other hand, they are also especially preferred are sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with homolog distribution reduced It is also possible to use succinic acid from alkyla with preferably from 8 to 18 atoms of carbon in the alkyl (en) yl chain or its salts.

Other type of anionic surfactants considered They are especially soaps. Acid soaps are suitable saturated fatty acids, such as lauric acid salts, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and acid behenic as well as mixtures of soaps derived especially from natural fatty acids, for example coconut fatty acids, seed of palm or tallow.

Anionic surfactants, including Soaps, can be presented in the form of their sodium, potassium salts or ammonium and also as soluble salts of organic bases, such as mono, di or triethanolamine. Anionic surfactants are presented preferably in the form of its sodium or potassium salts, especially in the form of sodium salts.

Within the framework of the present invention, prefer molded bodies of detergents and cleaning agents containing 5 to 50% by weight, preferably 7.5 to 40% by weight and especially 10 to 20% by weight of anionic surfactant (s), in relation in each case to the weight of the molded body.

In the choice of anionic surfactants that come into action in the molded bodies of detergent agents and of cleaning according to the invention, there is complete freedom with respect to the formulation The molded bodies of detergents and cleaning however have a soap content that exceeds 0.2% by weight in relation to the total weight of the molded body. The Preferred anionic surfactants to be employed are those alkylbenzenesulfonates and sulfates of fatty alcohols, containing the molded bodies of detergent agents and preferred cleaning of 2 to 20% by weight, preferably 2.5 to 15% by weight and especially 5 to 10% by weight of sulfate (s) of fatty alcohols, in relation respectively to the weight of the molded body.

As nonionic surfactants, preferably alkoxylated, more advantageously ethoxylated and especially primary alcohols are used, preferably with 8 to 18 carbon atoms and an average of 1 to 12 mol of ethylene oxide (EO) per mol of alcohol, in which the The alcohol moiety may be linear or preferably branched with methyl in position 2 or it may contain linear and branched methyl moieties combined, as they usually appear for example in the oxoalcoholic moieties. Especially preferable are, however, alcohol ethoxylates with linear residues of naturally occurring alcohols with 12 to 18 carbon atoms, such as coconut, palm, tallow or oleic alcohol, and an average of 2 to 8 EO per mole of alcohol. Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO. The degrees of ethoxylation mentioned represent statistical average values, which can be, for a particular product, an integer or a fraction. Preferred alcohol ethoxylates have a reduced homolog distribution ( narrow range ethoxylates , NRE). In addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Other class of preferred non-ionic surfactants used, which are used as the sole non-ionic surfactant or in Combination with other nonionic surfactants, are the esters alkyl alkoxylated fatty acids, preferably ethoxylated or ethoxylated and propoxylated, preferably with 1 to 4 atoms of carbon in the alkyl chain, especially methyl esters of fatty acids, as described for example in the application for Japanese patent JP 58/217598 or which are preferably made according to the procedure described in the patent application International WO-A-90/13533.

Another class of non-ionic surfactants that You can use advantageously are alkyl polyglucosides (APG). For the usable alkyl polyglycosides the formula is sufficient general RO (G) z, in which R means a remainder linear or branched aliphatic, especially branched with methyl in position 2, saturated or unsaturated, with 8 to 22, preferably from 12 to 18 carbon atoms and G is the symbol that represents a glucose unit with 5 or 6 carbon atoms, preferably glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and especially between 1.1 and 1.4.

The use of linear alkyl polyglycosides, that is, alkyl polyglycosides, in which the polyglucosidic moiety is a glucose moiety and the rest alkyl is an n-alkyl moiety.

The molded bodies of detergents and cleaning according to the invention may preferably contain alkyl polyglycosides, in which contents are preferred in the APG molded bodies exceeding 0.2% by weight, relative to the entire molded body. The molded bodies of agents especially preferred detergents and cleaning agents contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% in weight and especially 0.5 to 3% by weight.

Non-surfactants may also be suitable. ions of the type of amine oxides, for example oxide of N-cocoalkyl-N, N-dimethylamine and oxide of N-tallowalkyl-N, N-dihydroxyethylamine and fatty acid alkanolamides. The amount of these nonionic surfactants preferably does not exceed that of alcohols ethoxylated fatty acids, especially does not exceed half of these.

Other suitable surfactants are the amides of polyhydroxy fatty acids of the formula (I),

\uelm{N}{\uelm{\para}{R ^{1} }}

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

 \ uelm {N} {\ uelm {\ para} {R1}} 

--- [Z]

in which RCO is an alkyl moiety aliphatic with from 6 to 22 carbon atoms, R1 is hydrogen, a alkyl or hydroxyalkyl moiety with 1 to 4 carbon atoms and [Z] it is a linear or branched polyhydroxyalkyl moiety with from 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. As for the polyhydroxy fatty acid amides, these are substances known that can usually be obtained by amination reductive of a reducing sugar with ammonia, an alkylamine or a alkanolamine and subsequent acylation with a fatty acid, an ester fatty acid alkyl or an acid chloride fatty.

To the group of fatty acid amides polyhydroxylated compounds also belong to the formula (II),

\uelm{N}{\uelm{\para}{R ^{1}  --- O --- R ^{2} }}

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

 \ uelm {N} {\ uelm {\ para} {R 1} --- O --- R 2}} 

--- [Z]

in which R is an alkyl moiety or linear or branched alkenyl with 7 to 12 carbon atoms, R1 is a linear, branched or cyclic alkyl moiety or a moiety aryl with from 2 to 8 carbon atoms and R2 is an alkyl moiety linear, branched or cyclic or an aryl moiety or an oxyalkyl moiety with 1 to 8 carbon atoms, in which residues are preferred C 1-4 alkyl or phenyl and [Z] is an alkyl moiety linear polyhydroxylated, whose alkyl chain is substituted with the minus 2 hydroxyl groups, or alkoxylated derivatives, preferably ethoxylated or propoxylated of this rest.

[Z] is preferably obtained by amination reductive of a reduced sugar, such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. Later the compounds N-alkoxy- or N-aryloxy substituted they can be converted, for example, according to the theory of the request International WO-A-95/07331, in the desired polyhydroxy fatty acid amide by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst

As already mentioned above, the Nonionic and anionic surfactants can be incorporated into the molded bodies of detergent and cleaning agents according to the invention in very different ways. They can be added for example to the pre-mix that will be compressed in solid form, or can be spray in liquid form in the previous mixture. Has been shown as advantageous the preparation of surfactant granules, which mix together with other powdered components in the pre-mix It will form the pill and compress. In this sense it preferred according to the invention molded bodies of agents detergents and cleaning agents containing surfactants in the form of a granulate containing the surfactants, which is contained in molded bodies in proportions of 40 to 95% by weight, preferably from 45 to 85% by weight and especially from 55 to 75% in weight, relative to the weight of the bodies respectively molded

To incorporate the desired amount of substance detergent in the molded bodies of detergent agents and cleaning, process variants are preferred in which the pre-mix contains a granulate with surfactants that presents a surfactant content of 5 to 60% by weight, preferably 10 to 50% by weight and especially 15 to 40% by weight, in ratio respectively to the weight of the surfactant granulate (see above). According to the invention, bodies are especially preferred molded detergent and cleaning agents in which the Anionic surfactant content of the surfactant granulate be 5 to 45% by weight, preferably 10 to 40% by weight and especially from 15 to 35% by weight, relative to weight of the surfactant granulate, as well as molded bodies of detergents and cleaning agents, in which the content in non-ionic surfactants of the surfactant granulate be from 1 to 30% by weight, preferably 5 to 25% by weight and especially of the 7.5 to 20% by weight, relative to the weight of the surfactant granulate.

To obtain stable surfactant granules in as for its conservation and capable of flowing, it is preferred that during the preparation of the surfactant granules substances are added excipients containing surfactant granules as substances of support. Other component substances of detergent agents and cleaning can be part of the surfactant granulate, especially small components, such as optical brighteners, polymers, defoamers, phosphonates, dyes and perfumes. These Substances are described below.

In the second stage of the procedure according to the invention, the surfactant granulate is mixed with other substances components of detergents and cleaning agents, resulting in a previous mixture capable of being compressed, and subsequently They form the pills. In this case, according to the invention, it is preferred the preparation of detergent tablets, so that the variants Preferred methods according to the invention are characterized because the proportion of the surfactant granulate in the previous mixture that will be compressed and therefore in the molded bodies of detergents and cleaning agents, is 40 to 95% by weight, preferably from 45 to 85% by weight and especially from 55 to 75% in weight, relative to the weight of the bodies respectively molded detergent and cleaning agents.

Support substances are substances important components of detergents and cleaning agents, as components of the surfactant granulate and as components of Optional preparation added additionally to the pre-mix. The supporting substances are, together with the detergent substances, the most important component substances of the agents detergents and cleaning. In the molded bodies of agents detergents and cleaning agents according to the invention can also be included all substances commonly used in detergents and cleaning agents, especially zeolites, silicates, carbonates, organic adjuvants and also phosphates, if they do not exist ecological prejudices against its use.

The microcrystalline and synthetic zeolite used, which contains bound water, is preferably zeolite A and / or P. As zeolite P is especially preferred zeolite MAP® (product of the Crosfield company). However, they are also suitable zeolites X as well as mixtures of A, X and / or P. Also commercially obtainable and preferably used within the framework of the present invention is for example a co-crystallized from zeolite X and zeolite A (approximately 80% by weight of zeolite X), prepared by the CONDEA Augusta S.p.A. with the VEGOBOND AX® brand and you can describe by the formula

nNa_ {2} O \ cdot (1-n) K_ {2} O \ cdot Al_ {2} O_ {3} \ cdot (2-2.5) SiO_ {2} \ cdot (3.5-5.5) H2O

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

Crystalline and shaped sodium silicates stratified suitable as support substances possess the formula general NaMSi_ {x} O_ {2x + 1} \ cdotH_ {O}, in which M means sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and 2, 3 or 4 are the preferred values for x. Silicates Stratified crystals of this type are described for example in European patent application EP-A-0 164 514. Silicates Preferred stratified crystals of the aforementioned formula are those in which M is sodium and x adopts the values 2 or 3. Especially preferred are sodium silicates? And δ Na_ {2} Si_ {2} O_ {5} \ cdot and H2O, being able obtain, for example, the sodium silicate? according to the procedure described in the international patent application WO-A-91/08171.

You can also use sodium silicates amorphous with a Na 2 O: SiO 2 module from 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and especially 1: 2 to 1: 2.6, which they dissolve in a delayed manner and have detergent properties high schools. The delay in dissolution against silicates usual amorphous sodium can be produced differently, by example by surface treatment, composition, compaction / concentration or by intense drying. Within the framework of this invention is understood by the concept of "amorphous" also "radiologically amorphous". This means that, in the X-ray diffraction experiments, silicates do not produce sharp radiological reflexes, as is typical of substances crystalline, but, in any case, produce one or several peaks of scattered radiation, which have a width of several degrees from diffraction angle However, they can also be obtained especially good properties of adjuvants, when silicate particles produce blurred diffraction peaks or even crisp, in electronic diffraction experiments. This it must be interpreted because the products have zones microcrystallines with a size of 10 nm to several hundred nm, values of up to 50 nm being preferred and especially up to a maximum of 20 nm. Silicates of this type called radiologically amorphous, which also has a delay in dissolution against current soluble silicates, are described in the German patent application DE-A-44 00 024. Especially Preferred are concentrated / compacted amorphous silicates, compound amorphous silicates and radiologically silicates intensely dried amorphous.

If desired, it can be incorporated into the mixture previous plus zeolite in addition to the amount of type P and / or X zeolite usually included in the surfactant granulate, adding Zeolite as preparation component. The crystalline zeolite and Synthetic used containing bound water is preferably a type A, P, X or Y zeolite. However, the X zeolites as well as mixtures of A, X and / or P. Suitable zeolites have an average particle size of less than 10 µm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, especially 20 22% by weight of bound water.

Of course, it is also possible to use as generally known phosphate adjuvants, provided that such use should not be avoided by ecological motives Sodium salts of orthophosphates, pyrophosphates and especially tripolyphosphates.

As organic adjuvants can be used in molded bodies of detergent and cleaning agents according to the invention especially polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic adjuvants (see below) as well as phosphonates. These classes of substances are described as follow.

As organic support substances you can use, for example, polycarboxylic acids in the form of their sodium salts, understood as polycarboxylic acids those carboxylic acids with more than one acidic function. Examples are the citric acid, adipic acid, succinic acid, acid glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that a use of this type should not be avoided for ecological reasons, as well as mixtures of these. Preferred salts are salts of acids polycarboxylic acids such as citric acid, adipic acid, acid succinic, glutaric acid, tartaric acid, acids sugars as well as mixtures of these.

You can also use the acids themselves. Acids, in addition to their adjuvant action, usually have also the property of an acidification component and serve well also to establish a lower and more attenuated pH value of detergents and cleaning agents. They are mentioned in this case especially citric acid, succinic acid, acid glutaric acid, adipic acid, gluconic acid and any mixture of these.

Other adjuvants are suitable polycarboxylates, for example alkali metal salts of poly (acrylic acid) or poly (methacrylic acid), for example those with a relative molecular mass of 500 to 70,000 g / mol.

The molecular masses given for Polymeric polycarboxylates are in the sense of this writing masses Average molecular weight M w in its acid form, determined basically by gel permeation chromatography (GPC), using a UV detector The measurement was performed with respect to a external sample of polyacrylic acid which, due to its ratio structural with the polymer examined, provides weight values real molecular. This data clearly differs from the data in molecular weight, in which polystyrene sulfonic acids are used Like it shows. The molecular masses measured with respect to polystyrene sulfonic acids are as a rule clearly higher than the molecular masses given in this document.

Suitable polymers are especially those polyacrylates that especially have a molecular mass of 2000 at 20,000 g / mol. Due to their superior dissolubility they are preferred, to their instead, within this group, the short chain polyacrylates that they have molecular masses of 2000 to 10,000 g / mol, especially of 3000 to 5000 g / mol.

Polycarboxylates are also suitable copolymers, especially those of acrylic acid with acid methacrylic and acrylic or methacrylic acid with maleic acid. Be acid copolymers have been found to be especially suitable acrylic with maleic acid, containing 50 to 90% by weight of Acrylic acid and 50 to 10% by weight maleic acid. Its mass molecular relative, in relation to free acids, is generally of 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and especially from 30,000 to 40,000 g / mol.

Polymeric (co-) polycarboxylates can be use as powders or as an aqueous solution. The proportion of polymeric (co-) polycarboxylate media is preferably 0.5 to 20% by weight, especially 3 to 10% in weigh.

To improve water solubility, the polymers may also contain acidic monomer allylsulfonic acids, such as allyloxybenzenesulfonic acid or acid metalyl sulfonic.

Especially preferred are also those biologically degradable polymers with more than two units different monomers, for example those that contain as monomers salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives, or those that contain as monomers salts of acrylic acid and acid 2-alkylsulfonic acid as well as derivatives of sugar.

Other preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and presenting preferably acrolein and acrylic acid / salts of acrylic acid or acrolein and vinyl acetate as monomers.

They also constitute adjuvant substances additional preferred polymeric aminodicarboxylic acids, its salts or its precursor substances. Especially preferred are polyaspartic acids or their salts and derivatives, of which It is set out in the German patent application DE-A-195 40 086 which, in addition to the adjuvant properties, they also have a stabilizing action bleaching

Other suitable adjuvant substances are the polyacetals, which can be obtained by the reaction of dialdehydes with polycarboxylic acids having 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde as well as its mixtures and from acids polycarboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic adjuvants are dextrins, such as oligomers or polymers of carbohydrates, obtainable by partial hydrolysis of starches Hydrolysis can be performed according to the procedures. common, such as acid or enzymatic catalysis. Preferably it is hydrolysis products with a mass Average molecular weight between 400 and 500000 g / mol. In this case it prefers a polysaccharide with a dextrose equivalent (SD) of 0.5 to 40, especially 2 to 30, DE being a common measure for reducing action of a polysaccharide compared to dextrose which has a DE of 100. Maltodextrin with a DE is useful between 3 and 20 and anhydrous glucose syrup with a DE between 20 to 37 as well as the so-called yellow dextrin and white dextrin with higher molecular masses in the range between 2000 and 30000 g / mol

As for oxidized derivatives of this type of dextrins, it is their reaction products with agents of oxidation, capable of oxidizing at least one alcoholic function of the saccharide ring in the carboxylic function. Oxidized dextrins of this type and the procedures for its elaboration are known by example in European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as in International Patent Applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. An oxidized oligosaccharide is also suitable according to the request of German patent DE-A-196 00 018. An oxidized product in the C6 can be especially advantageous. of saccharide ring.

Other suitable adjuvants are also those oxidisuccinates and other disuccinate derivatives, preferably ethylenediamine disuccinate. In this case it is used N, ethylenediamine N'-disuccinate (EDDS), preferably in the form of its sodium or magnesium salts. Likewise glycerin disuccinates are preferred in this context and glycerin trisuccinates. The preferred proportions of application found in formulations containing zeolites and / or silicates in 3 to 15% by weight.

Other usable organic adjuvants are, by example, hydroxycarboxylic acids as well as their salts, which given the case can also be presented in the form of lactone and that they contain at least 4 carbon atoms and at least one hydroxyl group as well as a maximum of 2 acid groups. This type of adjuvants is described for example in the international patent application WO 95/20029.

Another class of substance with adjuvant properties is phosphonates. In this case, it is especially hydroxyalkane or aminoalkane phosphonates. Among the hydroaxialcanophosphonates, 1-hydroxyethane-1,1-disphosphonate (HEDP) is an especially important adjuvant. It is preferably used as a sodium salt by reacting the disodium salt in neutral form and the tetrasodium salt in alkaline form (pH 9). As aminoalkanephosphonates, ethylenediaminetetramethylene phosphonate (EDTMP), diethylenetriaminepentamethylene phosphonate (DTPMP) as well as their higher homologs are preferably considered. They are preferably used in the form of neutral reactive sodium salts, for example as the hexasodium salt of EDTMP or as a hepta and octasodium salt of DTPMP. From the class of phosphonates, HEDP is preferably used as an adjuvant. The aminoalcanophosphonates also have a clear binding capacity with heavy metals. Accordingly, it may be preferable to use aminoalkane phosphonates, especially DTPMP or mixtures of the aforementioned phosphonates, especially when the agents also contain blanks.
Cheers.

They can also be used as adjuvants all compounds capable of forming complexes with ions alkaline earth.

The preparation of granules containing Surfactants are widely described in the state of the art, being able to resort, in addition to the extensive patent literature, to numerous general articles and monographs. So, W. Hermann of Groot, I. Adami, G.F. Moretti "The Manufacture of Modern Detergent Powders ", Hermann de Groot Academic Publisher, Wassenaar, 1995 describes different spray drying procedures, mixing and granulation for the preparation of detergents and cleaning.

In the context of the present invention it is preferred, for energy reasons, that the granulate containing surfactants is made through a granulation procedure instead of by spray drying. In addition to the usual procedures of granulation and agglomeration, which can be carried out in different granulators for mixtures and agglomerators for mixtures, can be also use, for example, agglomeration procedures by compression. Therefore, procedures in which the granulate containing surfactants is made by granulation, agglomeration, compression agglomeration or a combination of these procedures

Granulation can be performed in numerous appliances commonly used in the agent industry detergents and cleaning. Thus, for example, the usual rounding machines in the pharmaceutical sector. In these appliances with rotating discs, the treatment time of granules is usually less than 20 seconds. Mixers and granulators for common mixtures are also suitable for granulation As mixers you can use both high intensity mixers ("high-shear mixer ") as normal mixers with rotation speeds lower. Suitable mixers are for example the mixers Eirich® from the R or RV series (brands of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi® Flexomix, the mixers Fukae®FS-G (brands of Fukae Powtech, Kogyo Co., Japan), the Lödige®FM, KM and CB mixers (Lödige brands Maschinenbau GmbH, Paderborn) or Drais® mixers, T series or K-T (brands of DRais-Werke GmbH, Mannheim) The treatment times of the granules in the Mixers are less than 60 seconds, also depending on the treatment time of mixer rotation speed. In In this sense, treatment times are shortened correspondingly the faster the mixer rotates. The treatment times of the granules in the mixer / rounder they are preferably below one minute, preferably below 15 seconds. In the mixers more slow, for example in a Lödige KM, set times of treatment of up to 20 minutes, preferring times of treatment less than 10 minutes for reasons of economy of process.

In the agglomeration procedure by compression is compressed the granulate containing low surfactants pressure and under the effect of shear forces, it is homogenized and subsequently removed from the devices in a molded form. The compression agglomeration procedures technically more significant are extrusion, roller compaction, pelletization and pellet formation. The procedures of compression agglomeration for the preparation of the granulate that it contains surfactants preferably used within the framework of the present invention are extrusion, roller compaction and Pelletization

To facilitate the disintegration of bodies very compact molding it is possible to incorporate auxiliary agents of disintegration, the so-called dispersing agents of pills, to reduce disintegration times. By agents tablet dispersants or disintegration accelerators are understand, according to Römpp (9th edition, volume 6, page 4440) and Voigt "Lehrbuch der pharmazeutischen Technologie" (6th edition, 1987, pages 182-184), those auxiliary substances responsible for the rapid disintegration of pills in water or juice gastric and drug release in resorbable form.

These substances, which by their action also called "dispersant" substances, increase their volume with the presence of water, being able to increase the volume itself (swelling), which can also occur, on the other hand, a pressure through the release of gases, which disintegrates the small particle pills. Auxiliary Disintegration Agents known for a long time are, for example, acid systems carbonic / citric, other acids can also be used organic As inflatable disintegrating auxiliary agents, consider, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or substances natural modified as cellulose and starch and its derivatives, alginates or casein derivatives.

The molded bodies of detergents and Preferred cleansers contain 0.5 to 10% by weight, preferably from 3 to 7% by weight and especially from 4 to 6% in weight of one or more disintegration auxiliary agents, in relation to respectively to the weight of the molded bodies.

As preferred disintegrating agents are agents used in the context of the present invention disintegration based on cellulose, so that the bodies molded preferred detergent and cleaning agents contain a cellulose based disintegration agent of this type in proportions of 0.5 to 10% by weight, preferably 3 to 7% in weight and especially 4 to 6% by weight. Pure cellulose presents formal molecular composition (C 6 H 10 O 5) n and represents from a point of formal view a β-1,4-polyacetal cellobiose, constituted in turn by two glucose molecules. The celluloses suitable consist of approximately 500 to 5000 units of glucose and therefore have average molecular masses of 50,000 to 500,000. Cellulose derivatives, obtainable by analogous polymeric cellulose reactions, can also be use as cellulose-based disintegration agents in the framework of the present invention. Said modified celluloses chemically they comprise for example esterification products and etherifications, in which atoms of hydrogen hydroxyl. However, you can also use as cellulose derivatives, those cellulose, in which hydroxide groups have been replaced by functional groups, not bound through oxygen atoms. Within the group of cellulose derivatives are for example alkaline celluloses, the carboxymethyl cellulose (CMC), cellulose esters and ethers as well like aminocelluloses. The cellulose derivatives mentioned are not preferably use alone as disintegration agents based in cellulose, but mixed with cellulose. The proportion of derivatives of cellulose in said mixtures is preferably less than 50% in weight, especially less than 20% by weight, in relation to the agent of cellulose based disintegration. As a disintegration agent Especially preferred cellulose-based cellulose is used pure, free of cellulose derivatives.

The cellulose used as an auxiliary agent of the disintegration is preferably not used in the form of microparticles, but it transforms into a thicker form before being mixed with the previous mixture to be compressed, by example in a granulated or compacted form. Molded bodies of detergent and cleaning agents containing agents dispersants in granulated form or, if necessary, cogranulated, described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel), as well as in the application International Patent WO 98/40463 (Henkel). Of these writings they can also obtain more accurate data for the elaboration of granulated cellulose dispersing agents, compacted or cogranulates The particle size of said agents of disintegration is generally greater than 200 µm, preferably at least 90% by weight between 300 and 1600 µm and especially at least 90% by weight between 400 and 1200 \ mum. In the context of the present invention, the use of coarse disintegration aids based on cellulose mentioned above and described more exactly in the cited documents, as auxiliary agents of the disintegration These can be obtained in the market for example with the Arbocel® TF-30-HG brand of the Rettenmaier company.

As another disintegration agent based on cellulose or as part of this component you can use the microcrystalline cellulose. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under such conditions that only affects amorphous areas (approximately 30% of the mass total cellulose) of the cellulose and dissolves them completely, remaining, however, the crystalline zones (approximately the 70%) intact. Subsequent disintegration of cellulose microfines obtained by hydrolysis gives rise to microcrystalline celluloses that have primary particle sizes of approximately 5 um and that for example can be compacted in granules with a average particle size of 200 µm.

Therefore, they are preferred within the framework of the present invention those procedures, in which the mixture prior to being compressed additionally contains an agent disintegration aid, preferably an auxiliary agent of cellulose based disintegration, preferably in form granulated, cogranulated or compact, in proportions of 0.5 to 10% in weight, preferably 3 to 7% by weight and especially 4 to 4 6% by weight, relative to the weight of the mixture respectively previous.

In other preferred procedures, the mixture prior contains additionally one or more substances from the group of bleaching agents, bleaching activators, enzymes, fixatives pH, aromatic substances, aromatic carriers, agents fluorescent, dyes, defoamers, silicone oils, anti-redeposition agents, optical brighteners, dimming inhibitors, fading inhibitors and anticorrosive These substances are described below.

Among the compounds that give rise in water to H2O2 and serving as bleaching agents are especially important are sodium perborate tetrahydrate and sodium perborate monohydrate. Other useful bleaching agents they are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates as well as peracid or peracid salts that give rise to H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminic or diacid peracid diperdodecanoic With the use of bleaching agents it is It is also possible to renounce the use of surfactants and / or supporting substances, agent pads being elaborable pure bleaching. In case you should use the tablets Bleaching agent of this type for textile washing, is prefer a combination of sodium percarbonate with sesquicarbonate sodium, regardless of the other substances contained in the molded bodies In the event that tablets are made of detergent or bleaching agents for mechanical washing of the dishes can also be used bleaching agents from the group of organic bleaching agents. Organic bleaching agents Typical are diacyl peroxides, such as peroxide dibenzoyl Other typical examples of organic bleaching agents are peroxyacids, among which acids are mentioned peroxyalkyl and peroxyaryl acids. As representatives Preferred are (a) peroxybenzoic acid and its derivatives substituted ring, such as alkylperoxybenzoic acids, but also the acid peroxy-? -naphthoic and the magnesium monoperphthalate, (b) aliphatic peroxyacids or substituted aliphatics, such as peroxylauric acid, acid peroxystearic acid ε-phthalimidoperoxicapronic [acid phthaloiminoperoxyhexanoic acid (PAP)], acid o-carboxybenzamidoperoxicapronic acid N-nonenylamidoperadipic and N-nonenylamidopersuccinate, and (c) acids aliphatic and araliphatic peroxy dicarboxylic acids, such as acid 1,12-diperoxycarboxylic acid 1,9-diperoxyazelaic, diperoxisebacic acid, acid diperoxibrasilic, diperoxiftálic acids, diacid 2-decyl-1,4-diperoxybutyric acid, N, N-terephthaloyl-di (acid 6-aminopercapronic).

As bleaching agents in the bodies molded for mechanical dishwashing can be used also chlorine or bromine releasing substances. Between the Suitable chlorine or bromine releasing materials are considered by example N-bromamides and N-chloramides heterocyclics, such as trichloroisocyanuric acid, acid tribromoisocyanuric acid, dibromoisocyanuric acid and / or acid dichloroisocyanuric (DICA) and / or its salts with cations such as potassium and sodium Also suitable are the compounds of hydantoin, like 1,3-dichloro-5,5-dimethylhydantoin.

To achieve an optimized bleaching effect during washing or cleaning at temperatures of 60 ° C and below, bleach activators can be incorporated in the pre-mix. As bleaching activators, compounds that give place under conditions of perhydrolysis to peroxocarboxylic acids aliphatic with preferably 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms and / or, if necessary, acids substituted perbenzoic. Substances that have O- and / or N-acyl groups with the aforementioned amount of carbon atoms and / or, if necessary, substituted benzoic groups. Acylated alkylenediamines multiple times are preferred, especially tetraacetylethylenediamines (TAED), derivatives triazine acylates, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triacin (DADHT), acylated glycolurils, especially tetraacetylglycolurils (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially acid anhydride phthalic, acylated polyvalent alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to bleach activators traditional or instead, can be incorporated into the bodies also molded so-called bleaching catalysts. If of these substances, these are transition metal salts bleaching intensifiers or transition metal complexes such as, for example, saline complexes or carboxylic complexes of Mn, Fe, Co, Ru or Mo. They can also be used as catalysts for bleaching complexes of Mn, Fe, Co, Ru, Mo, Ti, V and Cu with ligands tripods containing N as well as amino complexes of Co, Fe, Cu and Ru.

Enzymes are those of the class of proteases, lipases, amylases, cellulases or mixtures thereof. Especially suitable are enzymatic active substances obtained from strains of bacteria or fungi, such as Bacillus subtilis , Bacillus licheniformis and Streptomyces griseus . Preferably, subtilisin type proteases and especially proteases, obtained from Bacillus lentus, are used . In addition, enzymatic mixtures, for example protease and amylase or protease and lipase or protease and cellulase or cellulase and lipase or protease, amylase and lipase or protease, lipase and cellulase, are especially interesting, however, especially mixtures containing cellulase. In some cases, peroxidases or oxidases have also been shown to be suitable. Enzymes may be adsorbed in the excipients and / or introduced into the coating substances, to protect them from premature decomposition. The proportion of enzymes, mixtures of enzymes or enzymatic granules in the molded bodies according to the invention can be for example from about 0.1 to 5% by weight, preferably from 0.1 to about 2% by weight.

Additionally, agent molded bodies detergents and cleaning agents may also contain components that positively affect the washing of oil and grease stains of textiles (called dirt repellents, "soil repellents "). This effect is especially evident, when stain a textile that has previously been washed in multiple occasions with a detergent that, according to the invention, contains these solvent components of oil and grease. Between the components Preferred oil and grease solvents are found, by example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion in methoxyl groups of 15 to 30% by weight and hydroxypropoxyl groups of 1 to 15% by weight, in relation to non-ionic cellulose ether, as well as polymers known in the state of the art of phthalic acid and / or terephthalic acid as well as its derivatives, especially polymers of ethylene terephthalate and / or terephthalate of polyethylene glycol or modified anionic and / or non-ionic derivatives of the same. Especially preferred among these are derivatives sulfonates of phthalic acid and acid polymers terephthalic

The molded bodies may contain as optical brighteners derived from diaminoestylbendisulfonic acid as well as its alkali metal salts. They are suitable, for example, acid salts 4,4-bis (2-anilino-4-morpholino-1,3,5-triacinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds constituted in a similar way that, instead of the group morpholino, have a diethanolamino group, a methylamino group, a aniline group or a 2-methoxyethylamino group. further bleaching agents of the diphenylstyryl type may be present substituted, for example alkaline salts of 4,4'-bis (2-sulfoestyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfoestiryl) -diphenyl or 4- (4-Chlorostyril) -4 '- (2-sulfoestyryl) -diphenyl. Bleach compounds can also be used mentioned above.

To the molded bodies of detergent agents and cleaning agents according to the invention are added coloring substances and aromatic, to improve the aesthetic appearance of the products and to make available to the consumer a product that, in addition to the power detergent and cleaning, either from a visual point of view and "typical and unmistakable" sensory. As essential oils aromatic or aromatic substances can be used differently aromatic compounds, for example synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrogens carbon Aromatic compounds of the type of esters are, by example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate linalyl, dimethylbenzyl carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, stiralyl propionate and benzyl salicylate Among the ethers are include, for example, benzylethyl ether, among the aldehydes by example linear alkanes with 8 to 18 carbon atoms, citral, citronelal, citronelliloxyacetaldehyde, aldehyde cyclamen, hydroxycitronal, lilial and bourgeonal, between ketones by example the ionone, α-isomethylionone and methylcedrylacetone, among alcohols, anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, at carbon hydrogens belong mainly terpenes as Limonos and Pinenos. However, mixtures of different types are preferred. aromatic substances, which together generate an aromatic note attractive Aromatic essential oils of this type can also contain mixtures of natural aromatic substances, which they can obtain for example from vegetable sources, for example oil essential pine, lemon, jasmine, patchouli, roses or ylang-ylang. The essences of Muscat, sage, chamomile, clove, lemon balm, mint, cinnamon leaf, Tila flower, juniper beech essence, vetiver essence, from olíbano, gálbano and laudano as well as essence of orange blossom, neroli, orange peel and sandalwood logs.

Usually the proportion in the bodies molded detergent and substance cleaning agents dyes are below 0.01% by weight, while aromatic substances can mean up to 2% by weight of The total formulation.

Aromatic substances can be introduced directly in the agents according to the invention, although it can also it is advantageous to apply the aromatic substances on the excipients, which intensify the fixation of the perfume on the clothes and allow to maintain a prolonged aroma in the tissues by means of a delayed release of aroma. As excipients of this type are consider, for example, cyclodextrins, being able to cover cyclodextrin-aromatic complexes together with others auxiliary substances

To improve the aesthetic appearance of the bodies molded detergent and cleaning agents according to the invention, They can be dyed with suitable coloring substances. The substances preferred dyes whose choice does not pose any difficulty for the technician, have a high conservation stability and are insensitive to the remaining substances contained in the agents and in the light, and they do not possess any important substantivity against textile fibers not to dye them.

Before compressing the pre-mix in the form of particles in the molded bodies of detergent and cleaning, you can "powder" the pre-mix with microparticles of surface treatment agents. This can be advantageous for the quality and for the physical properties of the pre-mixing (preservation, compression) as well as the bodies finished detergent and cleaning agent moldings. The agents of fine "dust" are long known in the state of the art, generally using zeolites, silicates or other organic salts. However, pre-mixing is preferred. "powdered" with fine zeolite, with zeolites preferred faujasita type. The concept "faolite zeolite" characterizes within the framework of the present invention the three zeolites formed by the faujasite subgroup of structural group 4 of the zeolites (compare with Donald. Breck: "Molecular Zeolite Sieves ", John Wiley & Sons, New York, London Sydney, Toronto, 1974, page 92). In addition to zeolite X they can be used by both zeolite Y and faujasite as well as mixtures of these compounds, with pure zeolite X being preferred.

In the context of the present invention, preferred the processes of elaboration of molded bodies of agents detergents and cleaning agents in which the or one of the components of preparation added is a zeolite of the faujasite type with sizes of particle below 100 µm, preferably below 10 µm and especially below 5 µm and constitutes the minus 0.2% by weight, preferably at least 0.5% by weight and especially more than 1% by weight of the previous mixture that is going to compress

The elaboration of the molded bodies according to the invention is first carried out by dry mixing the components, which may be totally or partially granulated previously, and subsequently by molding, especially by tablet compression, and procedures can be used usual. For the elaboration of the molded bodies according to the invention the pre mix is compressed in a matrix between two molds up to a solid tablet. This procedure, which in the following paragraphs are called abbreviated formation of pills, divided into four stages: dosage, compression (elastic deformation), plastic deformation and expulsion.

First, the pre-mix is introduced in the matrix, determining the amount of padding and, therefore, the weight and shape of the molded body that will be produced by the placement of the lower mold and by the shape of the machine compression. The dosage, which is the same also with superior performances of molded bodies, you get preferably through a volumetric dosage of the pre-mix In the course of the formation of pills the upper mold comes into contact with the pre-mix and descends into direction to the lower mold. In this compression, the particles of the previous mixture, continuously decreasing the volume of empty space inside the filling between the molds. TO from a certain position of the upper mold (and therefore from a certain pressure on the previous mixture) begins plastic deformation, in which particles flow jointly leading to the formation of the molded body. Depending on the physical properties of the previous mixture, it it also crushes a part of the particles of the previous mixture leading, in the case of higher pressures, to a subfusion of the pre-mix When the compression rate increases, it is that is, when the yield amounts are high, it is shortened increasingly the elastic deformation phase, so that the produced molded bodies may present in greater or lesser Measure large empty spaces. In the last stage of the training of pellets the finished molded body is ejected out of the matrix by the lower mold and moves through later transportation systems. At this time the final weight of the molded body, as the tablets can still change its shape and size due to physical processes (elastic recovery, crystallographic effects, cooling, etc.).

Pill formation occurs in presses for regular pads, which may be constituted mainly by single or double molds. In the latter case I don't know use only the upper mold to produce the pressure, but the lower mold also travels during the compression process in the direction of the upper mold, while the upper mold push down. For small production quantities, it preferably use presses for eccentric pads, in the that the mold (s) are fixed to an eccentric disk which in turn It is mounted on a shaft with a specific rotation speed. The movement of this mold of understanding is comparable to operation of a usual four-stroke engine. The understanding can be done with a top mold and a mold lower, however there may be more than one mold attached to the disc eccentric, in this case the amount of matrix holes is correspondingly increased. Press yields Eccentric vary depending on the type, from a few hundred Up to a maximum of 3000 pills per hour.

For higher yields presses are used for rotary pads, in which a greater number of matrices are is arranged on a so-called matrix table so circular. The number of matrices varies depending on the model between 6 and 55, it being possible to obtain even larger matrices in the market. Each matrix on the matrix table is assigned a mold upper and a lower mold, being able to exert the pressure of actively understanding only through the upper or lower mold but also through both molds. The matrix table and the molds move around a perpendicular common axis and the molds are brought with the help of curved tracks like rails during rotation to fill positions, compaction, plastic deformation and expulsion. In the places where requires a particularly important ascent or descent of the molds (filling, ejection compaction), these curved tracks are supported by low pressure parts, low traction rails and additional demould paths. The matrix filling takes to out through a rigidly placed supply system, called filling duct, attached to a reserve tank of the pre-mix The pressure of understanding on the previous mix is individually determined for the upper and lower molds to through the paths of understanding, producing the generation of the pressure through the bearing of the mold heads ahead of the movable pressure rollers.

The bearing presses can be provided also of two filling ducts to increase performance, having to go through the preparation of a tablet only one half cycle For the elaboration of modeled bodies of two or more layers are arranged several filling ducts in series, without the lightly pressed first layer is ejected before the next filling. By developing the appropriate procedure you can also prepare coated tablets and point, in which in the case of point pads it is not coated the upper face of the nucleus or the layers of the nucleus, thus remaining visible. Rotary tablet forming presses can be also equip with single or multiple instruments, so that for example an outer circle with 50 holes and a Inner circle with 35 holes simultaneously for understanding. The yields of rotary presses of pellet formation Modern are more than one million molded bodies per hour.

In the case of forming pills with presses It has been shown that it is advantageous to carry out the tablet formation with variations in the weight of the tablet as small as possible. In this way, the hardness variations of the tablet. You can get small Weight variations as follows:

- use of plastic plates with tolerances of small thickness

- reduced number of rotations of the rotor

- large filling ducts

- determination of the number of revolutions of the flap of the filling duct according to the number of revolutions of the rotor

- filling duct with dust height constant

- decoupling of the filling duct and the dust container

To reduce the adhesion of the molds there are Various nonstick coating techniques. Especially Advantageous are the plastic coatings, the plates plastic or plastic molds. They have also been shown as advantageous rotary molds in which, if possible, the Upper and lower molds should be rotating. Generally You can do without a plastic plate in the rotary molds. Here should be the surfaces of the molds electropolished

It has also been observed that the times of Long compression are advantageous. These can be adjusted with the pressure rails, several pressure rollers or a lower number of rotor revolutions. Since resistance variations of the tablet originate from variations in the forces of understanding, systems that limit the force of understanding. So you can use elastic molds, compensators tires or spring elements in the path of the forces. He Pressure roller can also be performed in the form of spring.

Within the framework of the present invention, obtain suitable pad machines for example in Apparatebau Holzwarth GbR companies, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILLIAN, Köln, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) as well as Courtoy N.V., Halle (BE / LU). It is especially suitable for example the double hydraulic press HPF 630 of the company LAEIS, D.

The molded bodies can be finished like this in a predetermined conformation and size. As conformation it consider virtually all configurations reasonably manageable, for example molding in the form of a tablet, stick or bar, cube, rectangle and their corresponding elements of conformation with smooth lateral surfaces, as well as especially cylindrical configurations with circular and oval sections. This last configuration acquires the form of presentation from the tablet up to compact cylindrical parts with a ratio of height to diameter greater than 1.

The portioned tablets may be formed as individual elements separated from each other, corresponding to the predetermined dose of the agents detergents and cleaning. It is also possible to make tablets with a multiple of said mass units in a tablet, being equipped, especially with pre-established breakpoints, of an easy division into small units into portions. For the use of textile detergents in machines of the usual type in Europe with horizontal mechanics, it can be practical preparation of tablets in portions in the form of pills, cylindrical or rectangular, preferring a relationship diameter / height in the range of about 0.5: 2 up 2: 0.5. The usual hydraulic presses, eccentric presses or rotary presses are suitable systems especially for the development of tablets of this type.

The conformation of another embodiment of the molded bodies are adapted in their dimensions to the bucket of washing the usual washing machines for domestic use, in such a way that molded bodies can be dosed without help for their Dosing directly into the wash basin, where they dissolve during the water injection process. Of course the use of detergent agent bodies with an aid to Dosing is also possible and preferred within the framework of the present invention

Another elaborately preferred molded body has a disk or tablet shaped structure with segments alternatively thick and long and thin and short, so that individual segments of this bar can be separated into breakpoints, represented by thin segments and short, and introduce them into the machine. This agent principle Bar-shaped molded body detergent can be performed also in other geometric shapes, for example in the form of triangles placed perpendicularly linked to each other by one of its sides

However, it is also possible that different components do not press on a single tablet, but molded bodies are obtained having several layers, that is, At least two layers. Therefore, it is also possible that the different layers have different dissolution rates. From this they can result advantageous technical application properties of the bodies molded In the case that, for example, molded bodies contain components that influence each other in a way negative, it is possible to integrate a component into the layer more rapidly soluble and the other component in a solubility layer slower, so that the first component has already reacted when the second starts the dissolution. The layered conformation of the molded bodies can be made in the form of a stack, in which the dissolution process of the layer (s) internal (s) starts at the edges when the outer layers they have not yet completely dissolved, however you can also get a complete coating of the (s) inner layer (s) through layers corresponding that are more externally, which prevents premature dissolution of the components of the (s) inner layer (s).

In another preferred embodiment of the invention, a molded body is composed of at least three layers, it is that is, two external and at least one internal layer, containing the minus one of the inner layers a peroxide bleaching agent while, however, in the case of the shaped body stack the two layers of coating are agent free peroxide bleach, just as it happens in the body molded into Capsule shape in the outermost layers. In a molded body agents can also be spatially separated from each other peroxide bleaches and, where appropriate, bleach activators and / or enzymes present. The multilayer molded bodies of This type has the advantage that not only can be used to through a wash basin or a dosing system that reaches the washing liquid, but in these cases it is also possible to insert the molded bodies into the machine directly on the textile, without fear of producing stains by the agents bleaches or the like.

Similar effects are achieved by coating of the components of the composition of detergent and cleaning agent to be compressed or of the molded body in its entirety. To do this, the bodies that are going to they can be coated, for example, with aqueous solutions or emulsions, or a coating can be obtained through the fusion coating procedure.

After understanding, the molded bodies of detergent and cleaning agent have great stability. The Breaking strength of cylindrical molded bodies is can record through the breaking resistance parameter diametral. This can be determined by:

\ sigma = \ frac {2P} {\ pi Dt}

Here \ sigma is the breaking strength diametral ("diametral fracture stress", DFS) in Pa, P is the force in N, which gives rise to the pressure exerted on the body molded causing the breakage of the molded body, D is the diameter of the body molded in meters and t is the height of the body molded

Another object of the present invention is the use of refrigerated pre-mixes with temperatures below 15ºC for the production of molded bodies of detergent agent and cleaning. This use according to the invention of previous mixtures chilled gives rise to molded bodies with properties advantageous, as shown in the following examples. With with respect to the preferred embodiments of the use according to the invention (low temperatures, pre-mix composition, etc.) the above is applied analogously to the procedure according to the invention.

Examples

By wet granulation in a mixer grilles of 130 liters of the company Lödige a granulate was elaborated surfactant, whose composition is given in table 1. At the end of the granulation the granulate was dried in a fluidized bed apparatus Aeromatic with an air temperature of 60ºC for 30 minutes. After drying the granulate was filtered to remove the elements thin <0.4 mm and thick elements> 1.6 mm.

The surfactant granulate was then prepared with other components in a previous mixture that can be pressed, whose composition is given in table 2. The previous mixture that can be Press was divided in two and wrapped each half tightly. The two quantities of the previous mixture were preserved for 18 hours at different temperatures (according to the invention: 9 ° C, example comparative: room temperature, 22 ° C) and then extracted from the wrap and pressed in an eccentric Korsch tablet press (diameter: 44 mm, height: 22 cm, weight: 37.5 g) .The measurements of the resistance and disintegration times of the pills are, respectively, the average values of a double determination, varying each value according to the type of molded body up to a maximum of 2 N or 2 s. Table 2, which shows the composition of the mixtures previous, also shows the temperature of the previous mixture corresponding directly before the pressing process.

TABLE 1 Composition of the surfactant granulate [% in weight]

Alkylbenzenesulfonate C_ {9-12} 19.4 Fatty alcohol sulphonate C_ {12-18} 5.2 C 12-18 fatty alcohol with 7 EO 4.8 Soap 1.6 Alcohol C 12-16 fatty -1,4-glycoside 1.0 Sodium carbonate 17.0 Zeolite A 28.5 Sodium Silicaro 5.6 Na-hydroxyethane-1,1-diphosphonate 0.8 Acrylic Acid Acid Copolymer maleic 5.6 Bleaching optical 0.3 Water, you go out rest

TABLE 2 Composition of the previous mixtures [% in weight]

AND V Granulated surfactant (table 1) 62.9 62.9 Percarbonate sodium 17.0 17.0 TAED 7.3 7.3

TABLE 2 (continuation)

AND V Defoamer 3.5 3.5 Enzymes 1.7 1.7 Repel-O-Tex®SRP 4* 1.1 1.1 Fragrance 0.5 0.5 Wessalith®P (zeolite A) 1.0 1.0 Auxiliary Disintegration Agent (cellulose) 5 5 Temperature of the pre-mix before compression [ºC] 9.8 21.4 * ester of ethylene glycol terephthalic acid polyethylene glycol (Rhodia, Rhône-Poulenc)

The strength of the tablets was measured after processing by deformation of the tablet until broken, acting the force on the lateral surfaces of the tablet and generating the maximum force that the pill endured.

To determine the disintegration of the tablet, placed the tablet in a glass of water (600 ml of water, temperature 30 ° C) and the time was measured until complete disintegration of the tablet.

Table 3 shows the experimental data:

TABLE 3 Detergent agent tablet [data physicists]

Tablet AND V Pill Resistance [N] 40 39 Time of disintegration [s] 9 eleven Resistance of the pill [N] 49 52 Disintegration time [s] 13 24 Pill Resistance [N] 58 61 Time of disintegration [s] 28 48

Table 3 shows that the times of disintegration of the molded bodies of detergent agent and of Cleaning are clearly reduced with the procedure according to the invention, which generates clear improvements especially in terms of superior resistances

Claims (11)

1. Procedure for the production of molded bodies of detergent and compression molding cleaning agents in a manner known per se, characterized in that the pre-compressed mixture has a temperature below 15 ° C just before compression. 2. Method according to claim 1, characterized in that the pre-compressed mixture has a temperature below 13 ° C and especially below 10 ° C just before compression. 3. Method according to one of claims 1 or 2, characterized in that the pre-compressed mixture contains one or more granules with surfactants as well as other preparation components. 4. Method according to claim 3, characterized in that the pre-compressed mixture contains a granulate with surfactants, containing anionic and / or non-ionic surfactants as well as support substances and whose total surfactant content is 5 to 60% in weight, preferably from 10 to 50% by weight and especially from 15 to 40% by weight, respectively relative to the granulate with surfactants. Method according to one of claims 3 or 4, characterized in that the granulate with surfactants has a particle size of between 100 and 2000 µm, preferably between 200 and 1800 µm, especially preferable between 400 and 1600 µm and especially between 600 and 1400 µm. Method according to one of claims 3 to 5, characterized in that the proportion of the granulate with surfactants in the molded bodies of detergent and cleaning agents is 40 to 95% by weight, preferably 45 to 85% by weight and especially of the 55 to 75% by weight relative to the weight of the molded bodies of detergent and cleaning agent respectively. Method according to one of claims 1 to 6, characterized in that the previous mixture to be compressed has an apparent weight of at least 500 g / l, preferably at least 600 g / l and especially 700 g / l. Method according to one of claims 1 to 7, characterized in that the pre-compressed mixture additionally contains an auxiliary agent for disintegration, preferably an auxiliary agent for disintegration based on cellulose, preferably in granulated, cogranulated or compact form. , in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and especially 4 to 6% by weight, respectively, relative to the weight of the previous mixture. Method according to one of claims 3 to 8, characterized in that the component or one of the components of preparation added (s) is (are) a faujasite type zeolite with particle sizes below 100 µm, preferably below 10 µm and especially below 5 µm and constitutes (n) at least 0.2% by weight, preferably at least 0.5% by weight and especially more than 1% by weight of the previous mixture which It will compress. 10. Method according to one of claims 1 to 9, characterized in that the pre-compressed mixture also contains one or more substances from the bleach group, bleach activators, enzymes, pH fixers, aromatic substances, carrier substances perfume, fluorescent substances, dyes, defoamers, silicone essential oils, anti-redeposition substances, optical brighteners, dimming inhibitors, dye inhibitors and anticorrosives. 11. Use of pre-refrigerated mixtures with temperatures below 15ºC for body building molded detergent and cleaning agent.