ES2210646T3 - PROCEDURE FOR OBTAINING WASHING AND CLEANING AGENTS WITH ELEVATED BULK WEIGHT. - Google Patents

Abstract

A process for producing detergent particles with a high bulk density comprises mixing powdered ingredients with liquid ingredients and simultaneously compressing the mixture and converting into rounded particles. Production of detergent particles comprises mixing powdered ingredients with any liquid ingredients and simultaneously compressing the mixture and converting into rounded particles at a Froude's number of 20-80; where Froude's number = w<2>.R/g; (w = the angular velocity; r = tool radius; and g = acceleration due to gravity).

Description

Procedure for obtaining agents from washing and cleaning with high bulk weight.

The present invention relates to a procedure for obtaining washing and cleaning agents with high bulk weight, in which the products of starting, powdery, in a first stage of the procedure and mix the liquid components and the mixture obtained if necessary it is compacted and at the same time spheronized at another stage of procedure with a defined Froude number.

In recent years a plurality of procedures in the field of washing agents powdery to increase the bulk weight of these agents. Through these developments the form has also been modified external powder since the spherical shape or the shape of pearls allows, in the form of grain morphology, a bulk weight especially high. Washing agents in the form of spheres or either pearls can be obtained by extrusion or by spheronized granulation. The sphere shape or pearl in this case it presents not only aesthetic advantages over traditional mixed products but, on the contrary, by this form of grain morphology, especially in combination with the process of obtaining the extrusion, a high bulk weight in a relatively grain spectrum homogeneous and an almost complete absence of dust is achieved.

European Patent 486,592 discloses a procedure for obtaining compacted granules, which they can be used as washing or cleaning agents, in the that a homogeneous premix consisting of the components solid, usual, washing and cleaning agents, with addition of a plasticizing and / or lubricating agent, under pressure at through the perforated molds with hole openings of the previously determined dimension for the granulate, at pressures high between 20 and 200 bars, in the form of a bar, and the bar is chopped after its exit from the perforated mold, by means of a cutting device up to the previously determined dimension for the granulate. According to this procedure you get bodies extruded

Obtaining compacted washing agents by granulation described in the patent application International WO 94/13779. According to this publication it can be obtained granular cleaning and cleaning agents or components for same, that have a specific morphology with a surface practically sphere-shaped (macroscopically) and smooth (microscopically) as well as an internal structure almost monodispersed and an arbitrary diameter, which can be determined from beforehand. In a first stage of the described procedure, mix powdered starting products, ready to beforehand, with the liquid components, the mixture is compacted in a second stage of the procedure through the contribution of energy and, then the granules formed spheronize each other from compacting manner whereby a smooth surface and a internal structure almost monodispersed. By adding a finely divided powder stops this granulation by surface spheronized as soon as the granules have reached the expected size for the particles.

It is known by the patent application International WO 95/26394 a procedure for obtaining powder washing agents with high bulk weight, in the which powdered washing particles are mixed with a weight at bulk from 500 to 1,000 g / l in a mixer with input of shear forces by contacting the particles with each other. The Used mixer presents a rotating bowl. The particles Washing powders are mixed under the effect of forces of shear, dependent on the mutual contact of the particles, during 5 to 120 minutes in the mixing bowl with a number of Froude from 0.2 to 0.7, and with a loading speed, referred to volume, from 15 to 50%. Froude number is calculated according to the formula: Fr = V2 / (Rxg), where Fr means the number of Froude, V means the peripheral velocity (m / s) of the maximum external periphery of the mixer with rotating vessel, R means the radius (m) of the maximum external periphery of the mixer with rotating bowl, from the center of rotation, and g means the acceleration of gravity (m / s2).

The patent application 0 469 016 discloses a procedure for the manufacture of mixed products powder with a mixer with a mixing and wall tool cylindrical side, in which at least one of the starting products, powdery, with at least one liquid, spraying superficially, tangentially, in the sense rotating the liquid on the starting product, powdery Rotating in the mixer. The mixer is made to work with a Froude number between 1 and 10, so that the dusty starting product is in the form of a cloud in the whole of the internal enclosure of the mixer and the liquid is spray in the enclosure loaded with the mixed product pulverulent.

The published German patent application, no examined DE 42 11 699 A1 describes a procedure for augmentation of the bulk weight of the washing agents dried by spray, in which the spray dried material is spray, in the mixing device, simultaneously or successively, with a liquid, non-ionic surfactant and with a solution aqueous of an alkali silicate. The optimal range of the number of Froude is in this case between 250 and 500. The resulting material is freely dispersible at the time of leave the mixing device and has a high weight bulk.

European patent application EP 0 327 963 A2 describes a procedure to increase the density of the agents spray-dried wash without the use of liquid agents granulation aids, in which the powder of continuous way in a cylindrical mixer drum, slightly inclined, in which axially rotates a tree with a useful whisk arranged radially. In this chaos the optimal Froude number must be from 150 to 800.

Spherical washing agents, known by the state of the art, with high bulk weights, especially extruded bodies and granules have, however, the inconvenient that they do not always have a behavior satisfactory to dissolution due to its high compaction, often have a tendency to gel formation with small amounts of water

On the other hand the washing agents powder, obtained according to manufacturing procedures usual, which are obtained by spray drying traditional and, if necessary, subsequent granulation, have a noticeably lower bulk weight and a higher proportion of dust. The high proportion of dust can only be avoided by expensive screening of the final product. A combination of obtaining procedures such as spray drying and the subsequent compaction, which is also known, it certainly provides products with a relatively soluble good, they have no direct tendency to gel formation during the redisolution of the aqueous bath, however they have a spectrum relatively broad grain with significant proportions of Rude size and fine size.

The present invention had the task of putting provision of a procedure for obtaining washing agents and cleaning, powder, or mixtures thereof, similar to the powders obtained by extrusion in terms of grain morphology, the width of the grain spectrum and the weight at in bulk, but should present improved behavior to the dissolution and bulk weight greater than that of the products traditionally obtained, but with a behavior comparable or improved solution.

The object of the present invention is therefore both, a procedure for obtaining a washing agent and of cleaning with high bulk weight, in which, in a first stage of the procedure, the starting products are arranged powdery and, if necessary, mix with the components liquids and the mixture obtained is compacted in a second stage of the procedure with a Froude number from 20 to 80 and at the same time is spheronized, given the Froude number by the equation

\ frac {W2} \ cdot r} {g}

(W = angular velocity, r = tool length a starting from the central axis, g = acceleration land).

The process according to the invention enables the manufacture of washing and cleaning agent particles granular or sphere-shaped, which have a weight of bulk greater than that of washing and cleaning agents traditional manufactured by spheronized granulation etc., which approximate the bulk weight of the granules but which they do not present solubility problems like bodies extruded The particles of washing and cleaning agents obtained are characterized by a specific morphology of the surface. From the macroscopic point of view the particles they reach practically a spherical shape, while from the microscopic point of view have a certain porosity, being conditioned by it the good solubility of the particles. Through the second stage of the procedure they are not obtained homogeneous particles, as in other procedures of manufacturing. On the contrary the particles originally employees keep their composition substantially constant. I know verify a homogeneous distribution of the components in the mixture, but you don't get a homogeneous mass.

The powdered starting products can be individual substances or mother mixtures. In a possible way of realization are mixed together, in a first stage of procedure, stock mixtures of variable composition, which may proceed, for example, from spray drying or even from Other manufacturing procedures. In the second stage of procedure are added, if necessary, in addition to other substances or well sensitive mother mixtures, containing sensitive substances and the mixture as a whole is compacted according to the invention to a fraud number from 20 to 80. From the point of view macroscopic particles with a particle size and with an external aspect unit that, however, may have a variable composition A conduction of the procedure of this type makes it possible to disassociate the recipes of the washing and cleaning and then its transformation into pearls in a joint stage of the procedure.

In the first stage of the procedure they are arranged powdery starting products and mixed together. The Preferred powder starting products are in this case anionic surfactants, zeolite, silicate, sodium carbonate and, especially peroxy bleaching agents, such as perborate. Previous granular products can also be used, for example stock mixtures of surfactants dried by spray or granules. They will preferably also mix foam inhibitors, which are bound on a substance granular support, with the other starting products powdery, in the first stage of the procedure.

In the second stage of the procedure they can components of washing and cleaning agents are also added temperature sensitive such as for example bleaching and enzymes in the form of a mother mixture. In the second stage of the procedure are compacted and at the same time the individual components, specifically the mixture from the first stage of the procedure as well as the other components added. Through this process the components sensitive to temperature acquire the same morphological structure as the temperature insensitive components. The general appearance of agent prepared according to the invention is unitary even when the Individual particles have different components.

In the process according to the invention they can use arbitrary mixers as mixers that reach a Froude number between 20 and 80. As Examples may be mentioned the Eirich®, Marumerizer® and Spheronizer®.

The bulk weight of the washing agents and of cleaning, prepared according to the invention, with high bulk weight It is generally comprised between approximately 600 and 1,200 g / l. Especially preferably the bulk weight is It is between 700 and 950 g / l. The diameter of the particles of washing and cleaning agents, manufactured according to the invention is arbitrary, and the maximum of the particle size distribution below 2 mm. With relation to the solubility of the particles and the optics of the final product an optimum will be obtained with a distribution of particle size between 0.8 and 1.4.

The ability to make particles prepared in the first stage of the procedure can be improved by adding an auxiliary agent for plasticizing to powdery starting products. As auxiliary agents for plasticized come into consideration especially those non-ionic surfactants, liquid where appropriate, high point boiling, polyfunctional alcohols, polyalkoxylates spreadable at room temperature or slightly elevated and similar. The auxiliary agents for plasticizing they can be used in amounts from 3 to 19% by weight.

In order to further improve the properties surface particles of washing agents and cleaning manufactured according to the invention, has been revealed as adequate to add in the second stage of the procedure agents for surface modification. As agents for superficial modification come into consideration, for example, finely divided zeolite powders, for example zeolite A and zeolite X, magnesium silicate, silicic acids, defoamers powdery silicone. The agents for the modification surface can be contained in an amount of up to 10% by weight, preferably from 0.5 to 3% by weight, referred to the manufactured agent.

Washing and cleaning agents, manufactured according to the invention, they contain in the whole of their composition preferably 10% by weight, especially from 10 to 10 45% by weight of anionic and / or non-ionic surfactants. From the industrial application point of view are especially preferred washing and cleaning agents containing from 15 to 35% by weight of anionic and / or non-surfactants ionic

As sulphonate surfactants enter consideration, preferably, alkylbenzenesulfonate with 9 to 13 carbon atoms, olefin sulphonates, i.e. mixtures constituted by alkene- and hydroxyalkanesulfonates as well as disulfonates, such as those obtained, for example, from monoolefins with 12 to 18 carbon atoms, with double bond located at the end or inside the chain, by sulfonation with gaseous sulfur trioxide and, subsequently, alkaline or acid hydrolysis of sulfonation products. Also suitable are alkanesulfonates, which are obtained at from alkanes with 12 to 18 carbon atoms, for example by sulfocloration or sulfoxidation with subsequent hydrolysis or Well neutralization.

Preferred anionic surfactants they are also the salts of the alkylsulfosuccinic acids, which They are also called sulfosuccinates or acid esters sulfosuccinic, and represent monoesters and / or diesters of acid sulfosuccinic with alcohols, preferably fatty alcohols, and in  special ethoxylated fatty alcohols. Sulphosuccinates Preferred contain alcoholic residues with 8 to 18 atoms of carbon, or mixtures thereof. Sulfosuccinates especially Preferred contain a fatty alcohol moiety, which is derived from ethoxylated fatty alcohols, which constitute, considered in themselves same, nonionic surfactants such as those to be described later. In this case, again they are especially appropriate sulfosuccinates, whose fatty alcoholic residues are derived from ethoxylated fatty alcohols with homolog distribution narrowed Similarly, it is also possible to use alkylsuccinates, preferably with 8 to 18 carbon atoms in the alkyl (en) yl chain, or their you go out.

In addition, esters of the α-sulfograses acids (estersulfonates), by example the α-sulphonated methyl esters of hydrogenated coconut, palm kernel or fatty acids tallow.

By way of other suitable anionic surfactants, those of the sulfate type such as sulfates of
alk (en) yl, alkali salts, and especially sodium salts, of sulfuric acid half esters of fatty alcohols having 12 to 18 carbon atoms being preferred, for example from coconut fatty alcohols, fatty alcohols of tallow, lauric, myristic, cetyl or stearic alcohol, or oxoalcohols with 10 to 20 carbon atoms, and those semi-esters of secondary alcohols of these chain lengths. In addition, alkyl (en) yl sulfates of the aforementioned chain lengths are preferred, which contain a synthetic, straight-chain alkyl moiety, obtained on a petrochemical basis, which possess a degradation behavior similar to that of suitable compounds based on raw materials of fat chemistry. Of interest for washing technology are alkyl (en) yl sulfates with 16 to 18 carbon atoms. In this case, it may also be especially advantageous, and especially advantageous for machine washing agents, to use alkyl (en) ilo sulfates with 16 to 18 carbon atoms in combination with low melting anionic surfactants, and in especially with those anionic surfactants that have a lower Krafft point, and that show a reduced tendency to crystallization at relatively reduced washing temperatures, by way of example at room temperature at 40 ° C. Therefore, in a preferred embodiment of the invention, the agents contain mixtures consisting of short-chain and long-chain fatty alkyl sulfates, preferably mixtures consisting of fatty alkyl sulfates with 12 to 14 carbon atoms or sulfates of fatty alkyl with 12 to 18 carbon atoms with fatty alkyl sulfates with 16 to 18 carbon atoms and, especially, for fatty alkyl sulfates with 12 to 16 carbon atoms with fatty alkyl sulfates with 16 to 18 carbon atoms. However, in another preferred embodiment of the invention, not only saturated alkyl sulfates, but also unsaturated alkenyl sulfates having an alkenyl chain length preferably of 16 to 22 carbon atoms are employed. In this case, mixtures of saturated fatty alcohols, predominantly consisting of 16 carbon atoms, sulfates, and unsaturated fatty alcohols, sulfated fatty alcohols predominantly consisting of 18 carbon atoms are especially preferred, by way of example those derived from solid mixtures or fatty alcohol liquids, of type HD-Ocenol® (commercial product of the applicant). In this case, weighted proportions of alkyl sulfates are preferred over alkenyl sulfates of 10: 1 to 1: 2, and especially about 5: 1 to 1: 1.

In addition, they come into consideration as others anionic surfactants, especially soaps, preferably in amounts up to 8% by weight. Are appropriate soaps of saturated fatty acids, such as acid salts lauric, myristic acid, palmitic acid, stearic acid, acid hydrogenated erucic acid, and behenic acid, as well as, in particular, mixtures of soaps derived from natural fatty acids, by example coconut fatty acids, palm seeds or tallow. In Especially preferred are those mixtures of soaps that are composed of soaps of fatty acids with 12 to 24 atoms of carbon by 50 to 100% by weight, and by oleic acid soap in 0 to 50% by weight.

Surfactants can be presented in form of its sodium, potassium or ammonium salts, as well as in of 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, in Special in the form of sodium salts.

The content of washing agents and cleaning, manufactured according to the invention, with high bulk weight, amounts preferably from 5 to 20% by weight, referred to the agent as a whole. However, its content may be also above 20% by weight and may be, by example, 25% by weight. Preferred anionic surfactants they are: fatty alkyl sulfate. alkylbenzenesulfonates, sulfosuccinates as well as mixtures thereof, such as mixtures constituted by sulfates of fatty alkyl (en) yl and sulfosuccinates or fatty alkyl sulfate and benzenesulfonates of alkyl (fatty), especially in combination with soaps

They are used as non-ionic surfactants, preferably, alkoxylated, advantageously ethoxylated alcohols, especially primary, preferably, with 8 to 18 atoms of carbon, and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the remaining alcohol can be linear, or preferably it can be branched with methyl in position 2, or it may well contain linear and branched residues with methyl in mixture, such as those usually present in the remains of oxoalcohols. However, they are especially preferred ethoxylates of alcohols with linear residues of alcohols of origin natural with 12 to 18 carbon atoms, for example fatty alcohol of coconut, palm kernel, tallow, or oleic alcohol, and a average of 2 to 8 EO per mole of alcohol. To ethoxylated alcohols Preferred belong, by way of example, alcohols with 12 to 14 carbon atoms with 3 EO or 4 EO, alcohol with 9 to 11 atoms of carbon with 7 EO, alcohols with 13 to 15 carbon atoms with 3 EO, 5 EO, 7 EO or 8 EO, alcohols with 12 to 18 carbon atoms with 3 EO, 5 EO or 7 EO, and mixtures thereof, as well as mixtures of alcohol with 12 to 14 carbon atoms with 3 EO, and alcohol with 12 to 18 carbon atoms with 7 EO. The degrees of ethoxylate indicated represent statistical mean values, which can be a number whole or fractional for a special product. The ethoxylates of Preferred alcohols have a limited distribution of homologs (narrow range ethoxylates, NRE).

The content of fatty alcohols, ethoxylated, with 12 to 18 carbon atoms, in the finished agents, supposes, preferably, at least 2% by weight, preferably from 5 up to 15% by weight, especially from 8 to 15% in weight. In a preferred embodiment, the nonionic surfactants, liquid, in admixture with lower polyalkylene glycols, which are derived from glycols of linear or branched chain with 2 to 6 atoms of carbon, and / or highly ethoxylated fatty alcohols with more than 12 EO, especially 20 to 80 EO. Examples in this regard are fatty alcohols (tallow) with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO, Preferred lower polyalkylene glycols are polyethylene glycols or polypropylene glycols, which have a weight relative molecular between 200 and 12,000, especially between 200 and 4,000, for example up to 2,000. The proportion in weight between the liquid nonionic surfactant and the lower polyalkylene glycol and / or highly ethoxylated fatty alcohol in these mixtures, preferably, from 10: 1 to 1: 2, especially from 5: 1 to 1: 1.5 and is in some cases advantageously from 1.5: 1 to 1: 1.5, for example is 1: 1.

In addition, they can also be used as agents additional non-ionic alkyl glycoside surfactants of the formula general RO (G) x, where R means a remainder primary aliphatic, straight chain or branched with methyl, in special branched with methyl in position 2, with 8 to 22, preferably 12 to 18 carbon atoms, and G is the symbol that represents a glycosy unit with 5 or 6 carbon atoms, preferably glucose. The degree of oligomerized x, which indicates the distribution of monoglycosides and oligoglycosides, is a number arbitrary between 1 and 10; x is preferably between 1.2 to 1.4.

Other class of non-ionic surfactants preferably employed, which are used as the sole agent nonionic surfactant, or in combination with other non-surfactants ionic, especially together with alkoxylated and / or fatty alcohols alkyl glycosides, are alkyl esters of fatty acids alkoxylated, preferably ethoxylated, or ethoxylated and propoxylated, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester, as described, by way of example, in the patent application Japanese JP 58/217598, or which are preferably obtained according to procedure described in the international patent application WO-A-90/13533. Are especially preferred are methyl esters of fatty acids with 12 to 18 carbon atoms with an average of 3 to 15 EO, especially with an average of 5 to 12 EO.

Agents may also be appropriate. non-ionic amine oxide type surfactants, by way of example oxide of N-coco-alkyl-N, N-dimethylamine and oxide of N-tallow-alkyl-N, N-dihydroxyethylamine, and fatty acid alkanolamides. Preferably, the amount of these nonionic surfactants is not greater than that of ethoxylated fatty alcohols, especially does not amount to more than Half of these.

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

\uelm{O}{\uelm{\para}{R ^{3} }}

---N---[Z](I), R2 --- C

 \ uelm {O} {\ uelm {\ para} {R3}} 

--- N --- [Z]

wherein R2 CO represents an acyl moiety aliphatic with 6 to 22 carbon atoms, R 3 represents hydrogen, an alkyl or hydroxyalkyl moiety with 1 to 4 atoms of carbon, and [Z] represents a linear polyhydroxyalkyl moiety or branched with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.  Preferably the amides of polyhydroxy fatty acids are derived of reducing sugars with 5 or 6 carbon atoms, especially of the glucose.

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

\uelm{O}{\uelm{\para}{R ^{4} ---O---R ^{5} }}

---N---[Z](II), R3 --- C

 \ uelm {O} {\ uelm {\ para} {R 4} --- O --- R 5}} 

--- N --- [Z]

wherein R 3 represents an alkyl moiety or linear or branched alkenyl with 7 to 12 carbon atoms, R 4 represents a linear, branched or cyclic alkyl moiety, or a aryl moiety with 2 to 8 carbon atoms, and R 5 represents a linear, branched or cyclic alkyl moiety, or an aryl moiety or a oxy-alkyl moiety with 1 to 8 carbon atoms, with alkyl radicals having 1 to 4 carbon atoms being preferred or phenyl, representing [Z] a linear polyhydroxyalkyl moiety, whose alkyl chain is substituted with at least two groups hydroxyl, or alkoxylated derivatives, preferably ethoxylated or propoxylated, of this rest. In this case [Z] is obtained, preferably, by amination by reduction of a sugar, such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy compounds N-aryloxy-substituted can be then transform into polyhydroxy fatty acid amides desired, for example according to the teachings of the application for International Patent WO-A-95/07331, by reaction with fatty acid methyl esters in presence of an alkoxide as catalyst.

The content of washing agents and cleaning, manufactured according to the invention, in free water, that is -water not linked - is within known margins for washing and cleaning agents with high bulk weight, For example, it can be 20% by weight. Granules preferred contains, however, no more than 10% by weight of water Free, not linked.

As inorganic adjuvants are suitable, for example, phosphates, preferably tripolyphosphates, as well as orthophosphates and pyrophosphates, as well as zeolite and stratified silicates crystalline

The zeolite used, finely crystalline, synthetic, and that contains bound water, is preferably zeolite A and / or P. Zeolite P zeolite MAP® is especially preferred (commercial product of Crosfield) as well as zeolite A. However, zeolite X is also appropriate, as well as mixtures of A, X and / or P. Zeolite can be used as a powder dried by spraying, or also as an unwanted, still wet suspension of its obtaining, stabilized. In the case where zeolite is used as a suspension, it may contain small additions of agents nonionic surfactants as stabilizers, for example from 1 to 3% by weight, based on zeolite, of alcohols ethoxylated fatty acids with 12 to 18 carbon atoms, with 2 to 5 groups ethylene oxide, fatty alcohols with 12 to 14 carbon atoms with 4 to 5 ethylene oxide groups, or ethoxylated isotridecanoles. Appropriate zeolites have an average particle size of less than 10 µm (volume distribution; measurement method: Coulter Counter), and preferably contain from 18 to one  22% by weight, especially from 20 to 22% by weight of water linked.

The substituents or the substituents Partial, suitable, phosphates and zeolites are crystalline sodium silicates, stratified, of the formula general NaMSi_ {x} O_ {2x} +1. and H2O, meaning M sodium or hydrogen, x a number from 1.9 to 4, e and a number from 0 to 20, 2, 3 or 4 being the preferred values for x. Such are described crystalline layered silicates, by way of example, in the European patent application PE-A 0 164 514. The preferred crystalline layered silicates of the formula indicated are those in which M represents sodium and x adopts values 2 or 3. In particular, both disilicates of sodium?, as well as?, Na2Si2O5. Y H2O.

Organic structuring substances employable are, for example, acids polycarboxylic employables in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, acid glutaric acid, tartaric acid, saccharic acids, acids aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such employment is not questionable for ecological reasons, as well as mixtures thereof. Preferred salts are the salts of polycarboxylic acids, such as citric acid, adipic acid, acid succinic, glutaric acid, tartaric acid, saccharic acids, and mixtures thereof.

Suitable polymeric polycarboxylates are, of Example way, the sodium salts of polyacrylic acid or polymetacrylic acid, for example those with a relative molecular weight from 800 to 150,000 (referred to acid). Suitable copolymer polycarboxylates are, especially those of acrylic acid with methacrylic acid, and of Acrylic acid or methacrylic acid with maleic acid. They have shown especially suitable copolymers of acrylic acid with maleic acid, containing from 50 to 90% by weight of Acrylic acid, and from 50 to 10% by weight of acid Maleic Its relative molecular weight, based on free acids, it is, in general, from 5,000 to 200,000, preferably from 10,000 to 120,000, and especially from 50,000 to 100,000. The content of the agents in polycarboxylates (co-) polymers supposes, preferably from 1 to 8% in weight, especially from 2 to 6% by weight.

Polymers are also especially preferred. biodegradable consisting of two or more monomer units different, by way of example those that, according to the DE-A-43 00 772, contain as monomers salts of acrylic acid and maleic acid, as well as vinyl alcohol, or derivatives of vinyl alcohol, or, according to the DE-C-42 21 381, contain as monomers salts of acrylic acid and acid 2-alkylsulfonic acid, as well as derivatives of sugars

Other suitable adjuvant substances are polyacetals, which can be obtained by dialdehyde reaction with polyolcarboxylic acids, which have 5 to 7 atoms of carbon and at least 3 hydroxyl groups, for example as those described in the European patent application EP-A-0 280 223. Polyacetals Preferred are obtained from dialdehydes, such as glyoxal, glutaraldehyde, terephthalaldehyde as well as their mixtures and a from polycarboxylic acids such as gluconic acid and / or glucoheptonic acid

Other suitable components of the agents are water soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these, especially use alkali carbonates and amorphous alkali silicates, write down all sodium silicate with a Na2O molar ratio: SiO 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5. The content of the agents in sodium carbonate assumes this case, preferably, up to 20% by weight, advantageously It is between 2 and 15% by weight. The content of agents in sodium silicate generally represent up to 10% in weight and preferably is between 2 and 8% in weight.

Among the compounds that serve as agents of bleaching, which provide H2O2 in water, have a special meaning sodium perborate tetrahydrate and the sodium perborate monohydrate. Other bleaching agents Employable are, for example, sodium percarbonate, peroxyphosphates, citrateperhydrate as well as peracid salts or H 2 O 2 providing peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, acid phthaloiminoperoic or diperdodecanedioic acid. The content of agents in bleaching agents, preferably from a up to 25% by weight and, especially, from 10 to 20% in weight, advantageously using perborate monohydrate or percarbonate

Grating inhibitors have the task keep suspended dirt in the bathroom fibers and thus prevent dirt from depositing again. Water-soluble colloids are most suitable for this purpose. times of an organic nature, for example soluble salts in water of polymeric carboxylic acids, glues, jellies, salts of ethercarboxylic acids or of ethersulfonic acids of the starches or cellulose or salts of acidic acid esters sulfuric acid from cellulose or starches. Are also suitable for this purpose polyamides containing acid groups. further soluble preparations of starch and other products can be used of starch different from those indicated above, for example degraded starches, aldehyde starches etc. It is also employable polyvinylpyrrolidone However, preferably, cellulose ethers such as carboxymethyl cellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methyl carboxymethyl cellulose and mixtures thereof, as well as polyvinylpyrrolidone for example in amounts of 0.1 to 5% in weight, referred to the agent.

When used in washing procedures mechanical may be convenient to add to the inhibitors of The usual foam. As foam inhibitors are suitable, for for example, soaps of natural or synthetic origin, presenting a high proportion of fatty acids with 18 to 24 atoms of carbon. Suitable non-surfactant foam inhibitors they are, for example, organopolysiloxanes and their mixtures with acid Silicon microfine, if appropriate silanized as well as with paraffins, waxes, microcrystalline waxes and mixtures with silicic acid silanized or bistenylethylenediamide. Advantageously they will be used also mixtures consisting of various foam inhibitors, for example those constituted by silicones, paraffins or waxes. Preferably foam inhibitors, especially those foam inhibitors containing silicone and / or paraffin, are bonded on a granular, soluble or soluble support substance water dispersible In this case they are especially preferred mixtures consisting of paraffins and bisestearylethylene diamides.

As salts of polyphosphonic acids, preferably use neutral reaction sodium salts For example, him 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylene phosphonate or ethylenediamine tetramethylene phosphonate in amounts from 0.1 to 1.5% by weight.

Agents may contain, by way of optical brighteners, acid derivatives diaminoestilbendisufónico or of its salts with alkali metals.  Exemplary acid salts are suitable. 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilben-2,2'-disulfonic acid or similarly constituted compounds that bear, instead of morpholino group, a diethanolamino group, a methylamino group, a aniline group or a 2-methoxyethylamino group. further brighteners of the type of substituted diphenylstyriles, for example the alkaline salts of 4,4'-bis (2-sulfoestyryl) -diphenyl, of the 4,4'-bis (4-chloro-3-sulfoestyryl) -diphenyl, or of 4- (4-Chlorostyryl) -4 '- (2-sulfoestiryl) -diphenyl. Mixtures of the brighteners can also be used previously indicated.

Examples of bleach activators are N-acylated compounds or O-acylates, organic peracids with H 2 O 2, preferably polycylated alkylenediamines such as N.N'-tetraacylated diamines, glycolurils acylates, especially tetraacetylglycoluryl, hydantoins N-acylated, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, in addition, esters of carboxylic acids such as p- (alkanoyloxy) benzenesulfonates, especially sodium isononanoyloxybenzenesulfonate and p- (alkenyloxy) -benzenesulfonates, in addition derivatives of caprolactam, carboxylic acid anhydrides such as phthalic acid anhydride and esters and polyols such as the glucose pentaacetate Other known bleach activators they are acetylated mixtures consisting of sorbitol and mannitol, such as those described, for example, in the patent application European EP-A-0 525 239, and acetylated pentaerythrite. The content of the agents they contain bleaching agents, in bleaching activators, is inside of the usual range, preferably between 1 and 10% by weight and, especially, between 3 and 8% by weight. The activators of especially preferred bleaching are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).

Enzymes, especially those of the classes of hydrolases, such as proteases, esterases, lipases, or enzymes of lipolytic action, amylases, cellulases, or other glycosylhydrolases, and mixtures of the aforementioned enzymes come into consideration. All these hydrolases contribute, in washing, to the removal of stains, such as stains containing protein, fat or starch, and grated. In addition, cellulases and other glycosylhydrolases can contribute, by removing pilling and microfibrils, to maintaining color and increasing the softness of the textile material. For bleaching, or for the inhibition of color flow, oxirreductases can also be used. Enzyme active products, obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens, are particularly suitable. Preferably, subtilisin type proteases are used, and especially proteases that are obtained from Bacillus lentus . In this case, enzymatic mixtures are of particular interest, for example from protease and amylase, or protease and lipase, or enzymes of lipolytic action, or protease and cellulase, or from cellulase and lipase, or enzymes of action lipolytic, or from protease, amylase and lipase, or enzymes of lipolytic action, or protease, lipase, or enzymes of lipolytic action and cellulase, but especially mixtures containing protease and / or lipase, or mixtures with enzymes of lipolytic action Examples of such enzymes of lipolytic action are known cutinases. Peroxidases or oxidases have also been shown adequate in some cases. Suitable amylases include, in particular, α-amylases, iso-amylases, pululanases and pectinases. Cellulases, preferably, cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof are used as cellulases. Since the various types of cellulases are distinguished by their CMCase and avicelase activities, the desired activities can be adjusted by specific cellulase mixtures.

Enzymes may be adsorbed on supporting substances, or embedded in enveloping substances, for Protect them against premature decomposition. The proportion of enzymes, enzymatic mixtures or granules enzymatic can amount, by way of example, approximately from  0.1 to 5% by weight, preferably from 0.1 to approximately 2% by weight.

Examples

A mixture consisting of the components indicated in table 1, in an arm mixer plow (Lödige) and then rounded in a Spheronizer with a Froude number of 50 to give spheres.

TABLE 1

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one

The mother mixtures used were prepared by usual spray drying procedures and they contained the components indicated in table 2.

TABLE 2

two

TABLE 2 (continued)

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3

Claims (8)

1. Procedure for obtaining an agent washing and cleaning with high bulk weight, in which, in The products of powdery heading and, if necessary, mix with liquid components and the obtained mixture is compacted and at the same time is spheronized if necessary by adding other substances or sensitive mother mixtures, at another stage of procedure, with a Froude number from 20 to 80 to give the final product, given the Froude number by the relationship \ frac {W2} \ cdot r} {g} (W = angular velocity, r = tool length a starting from the central axis, g = acceleration land). 2. Method according to claim 1, characterized in that the agent has a bulk weight between about 600 and 1,200 g / l, especially between 700 and 950 g / l. 3. Method according to claims 1 or 2, characterized in that the particles have a particle size such that the maximum of the particle size distribution is below 2 mm, especially between 0.8 and 1.4 . 4. Method according to one of claims 1 to 3, characterized in that the first stage of the process is added auxiliary agents for plasticizing. 5. Method according to claim 4, characterized in that non-ionic surfactants, liquids, polyfunctional alcohols, spreadable polyalkoxylates at room temperature or at moderately high temperature are used as auxiliary agents for plasticizing. Method according to one of claims 1 to 5, characterized in that agents for surface modification are added to the mixture obtained in the first stage of the process. Method according to claim 6, characterized in that finely divided zeolite powder, for example zeolite A and zeolite X, magnesium silicate, silicic acids and pulverulent silicone defoamers are used as agents for surface purification. Method according to one of claims 1 to 7, characterized in that the prepared agents contain in their total composition at least 10% by weight, preferably at least 10 to 45% by weight and, especially, from 15 to 15 35% by weight of anionic and / or non-ionic surfactants.