ES2255995T3 - MOLDED BODIES OF MONO- OR POLYPHASIC WASHING AND CLEANING AGENTS WITH SPECIAL WHITENING ACTIVATORS. - Google Patents

Abstract

Molded bodies of single- or multi-phase washing and cleaning agents from compacted washing and cleaning agents in the form of particles, comprising bleaching agents, bleaching activator (s), as well as, where appropriate, other agent components for washing and cleaning, characterized in that the molded bodies, or at least one phase thereof, contain as a bleaching activator a cationic nitrile of the formula (I) in which R1 represents -H, -CH3, an alkyl moiety or alkenyl with 2 to 24 carbon atoms, an alkyl or alkenyl moiety substituted with 2 to 24 carbon atoms, with at least one substituent of the group -Cl,, -Br, -OH, -NH2, -CN, N, a moiety alkyl or alkenylaryl with an alkyl group with 1 to 24 carbon atoms, or an alkyl or alkenylaryl moiety substituted with an alkyl group with 1 to 24 carbon atoms, and at least one other substituent on the aromatic ring, R2 and R3, independently from yes, they are selected from -CH2 -CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH (CH3) -CH3, -CH2-OH, -CH2-CH2-OH, -CH (OH) -CH3, -CH2-CH2 -CH2-OH, -CH2-CH (OH) -CH3, -CH (OH) -CH2CH3, - (CH2CH2-O) nH with n = 1, 2, 3, 4, 5 or 6 and X is an anion, the pH value of the aqueous molded body solution being 1% by weight being less than 7, or of the phase containing the Nitrilquat.

Description

Molded bodies of washing and cleaning agents single- or multi-phase with special bleach activators.

The present invention relates to bodies molded washing and cleaning agents containing the called Nitrilquats as bleach activators. Especially, The invention relates to those molded bodies, such as washing agent tablets, agent tablets cleaning, especially tablets of cleaning agents for the machine dishwashing, bleaching tablets or water de-hardening tablets, with said activators of bleaching.

The compositions of washing and cleaning agents in the form of molded bodies, especially tablets, have long been known and are widely described in the state of the art, although this form of offer has no pronounced meaning in the market to date. . This has its cause in that the form of offer of the molded body, in addition to a series of advantages, also has disadvantages, negatively influences both the acquisition and use, as well as the consumer acceptance. The essential advantages of molded bodies, such as the suppression of the dosage of the amount of product required by the user, the higher density, and thus the reduced cost of packaging and storage, and an aesthetic aspect that should not be underestimated, are Relativize in this case due to inconveniences, such as the dichotomy between acceptable hardness and sufficiently rapid disintegration and dissolution of molded bodies, as well as numerous technological difficulties in obtaining and
packing.

Especially the dichotomy between a sufficiently hard molded body and a sufficiently rapid decomposition time is a central problem in this case. Since sufficiently stable molded bodies, that is dimensionally stable and at breakage, can be obtained, only by relatively high pressures, a strong compaction of the molded body components is achieved, and a subsequent delayed disintegration of the molded body in the aqueous bath, and with it a slow release of the active substances in the washing process, or cleaning. The delayed disintegration of molded bodies also has the disadvantage that molded bodies of washing and cleaning agents cannot be dragged through the sweeping chamber of domestic washing machines, since the tablets do not decompose in a sufficiently short time into particles. secondary ones that are small enough to be dragged into the washing drum from the chamber of
swept.

To overcome the dichotomy between hardness, that is to say stability to transport and handling, and simple decomposition of the molded bodies, many proposals for solution have been developed in the state of the art. A proposal known especially by the pharmacy, and extended in the field of molded bodies of washing and cleaning agents, is the incorporation of certain auxiliary agents of disintegration, which facilitate the access of water, or swell, or release gases in the case of water access, or exert a disintegrating effect in another way. Other proposals for the solution of the patent literature describe the pressing of previous mixtures of certain particle sizes, the separation of content substances isolated from other determined content substances, as well as the coating of isolated content substances or the total molded body with agents
binders

The bleaching agent compositions that contain bleach activators of type Nitrilquat described in The state of the art. Thus, the patent application European EP 303 520 (Kao Corp.) unveils agent compositions bleaching containing a peroxide and a peracid precursor, that contain at least one group N + - CH 2 -CN or N + (CH2CN) 2. In this document I don't know They mention molded bodies of washing and cleaning agents.

European patent application EP 458 396 (Unilever) also describes bleaching agent compositions containing a peroxide bleaching agent and a precursor of peracid with at least one group N + - CH 2 -CN or N + (CH2CN) 2. Nor in this document molded bodies of washing and cleaning agents are mentioned single-phase or multi-phase.

Cationic nitriles of the general formula R 1 R 11 R 111 N + CR 1 R 2 -CN and its use as a bleach activator is described in the application for European patent EP 464 880 (Unilever). Nor in this document is finds no data on molded bodies of washing agents and cleaning.

The washing agent tablets, in which isolated content substances are presented separately from others are described, by way of example, in the EP-A-0 481 793 (Unilever). The washing agent tablets disclosed in this document contain sodium percarbonate, which is presented separately especially of all other components, which could influence on its stability (as an example bleach activators). Nitrilquat type bleach activators are not mentioned in this document. Similarly, in this document you cannot find data regarding pH values of the layer solution isolated, or from the total molded body.

In none of the cited state documents of the technique, which deal with molded bodies of agents washing and cleaning, molded bodies of agents of washing and cleaning containing bleach activators based on "Nitrilquat." Nowhere is a pH range described well defined for molded bodies or sectors of bodies molded, containing bleach activators based on "Nitrilquat." None of the aforementioned documents deals with the improved stability of washing agent tablets and cleaning by selective use of these bleach activators special intervals with defined pH value.

Therefore, the present invention takes as base the task of making molded bodies of agents available washing and cleaning containing as bleaching activators the called Nitrilquats, and have a high hardness, and that have decomposition properties in the same way extraordinary. These molded bodies of washing agents and cleaning must also be dosed through the chamber of swept in this case, without causing inconvenience to the user of this mode due to residues in the scanning chamber, and an amount Too much washing agent in the bleach. further of these specific properties of molded bodies, also the washing and cleaning performance of molded bodies according to the Invention must be exemplary. In this case, they will be guaranteed also the storage stability of molded bodies and the maintenance of bleaching performance also in the case of longer storage

Now it was discovered that the stability of "Nitrilquat" based bleaching activators in bodies molded washing and cleaning agents can be increased using these bleach activators in molded bodies or molded body areas that have a pH value below of 7 after dissolution in water.

Molded bodies of single- or multi-phase washing and cleaning agents from agents of washing and cleaning compacted in the form of particles, which comprise bleaching agents, bleach activator (s), as well as, where appropriate, other components of washing agents and cleaning, which are characterized by molded bodies, or well at least one phase of them, contain as activator of bleaching a cationic nitrile of the formula (I)

\melm{\delm{\para}{R ^{3} }}{N ^{(+)} }{\uelm{\para}{R ^{1} }}

--- (CH_{2}) --- CN

\hskip3cm

X^{(-)}(I), R2 ---

 \ melm {\ delm {\ para} {R 3}} {N ^ {(+)}} {\ uelm {\ para} {R 1}}} 

--- (CH_ {2}) --- CN

 \ hskip3cm 

X <(-)}

wherein R 1 represents -H, -CH 3, an alkyl or alkenyl moiety with 2 to 24 carbon atoms, an alkyl or alkenyl moiety substituted with 2 to 24 carbon atoms, with at least one substituent of the group -Cl, -Br, -OH, -NH2, -CN, an alkyl or alkenyl group with an alkyl group having 1 to 24 carbon atoms, or an alkyl or alkenyl group substituted with an alkyl group with 1 at 24 carbon atoms, and at least one other substituent on the aromatic ring, R2 and R3, independently from each other, are selected from -CH2 -CN, -CH3 , -CH_ {2} -CH_ {3}, -CH_ {2} -CH_ {2} -CH_ {3},
-CH (CH 3) - CH 3, -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3, -CH 2 } -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3, -CH (OH) -CH 2 -CH 3, - (CH_ { 2 CH 2 -O) n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion, with the pH value of the aqueous molded body solution being less than 7 1% by weight, or of the phase containing the Nitrilquat.

The molded bodies according to the invention can be configured in one or several phases. The different phases of molded body may present different spatial forms in the scope of the present invention. In this case, the possibility of simplest embodiment consists of tablets of two or several layers, each molded body layer constituting a phase. Do not However, according to the invention it is also possible to obtain bodies polyphase molding, in which the isolated phases present the form of inclusions in another phase (s). Besides called "annular core tablets", in this case they are possible, by way of example, coated tablets or combinations of the aforementioned forms of execution. Examples of multiphase molded bodies in the figures of the EP-A-0 055 100 (Jeyes), which describes toilet cleaning blocks. The spatial form of bodies Polyphase molding more technically extended today is the tablet of two or several layers. Therefore, in the field of the present invention is preferred that the body phases molded present the shape of layers. In the scope of this invention two, three and four tablets are preferred layers.

The pH value of a 1% aqueous solution in weight can be determined within the scope of the present invention by preparing a molded body solution, or the phase containing the cationic nitrile of the formula (I), in water demineralized For this purpose it is dissolved, or the corresponding amount of molded body, or phase in water, and the pH value is determined by known methods, such as Indicator papers or metric chains of a wand. As certain methods of determining the pH value are dependent on temperature, within the scope of this invention the values mentioned for a temperature of solution, or suspension, of 20 ° C.

In molded bodies of washing agents and cleaning of one or several phases, the pH value of the solution 1% aqueous by weight of molded body, or phase containing Nitrilquat, amounts to less than 6.

Within the aforementioned pH range are preferred molded bodies of mono- or cleaning agents polyphasics, in which the pH value of the 1% aqueous solution by weight of molded body, or phase containing the Nitrilquat, amounts to less than 6.5, preferably less than 6.0, especially preferably less than 5.5, and especially less of 5.

The molded bodies according to the invention may contain the cationic nitriles of the general formula (I) in varying amounts, depending on the amount of use of the molded bodies. Thus, washing agent tablets and cleaning agent tablets for machine dishwashing usually contain less bleach activator than, for example, bleaching agent tablets that are largely constituted by agent. bleach and bleach activator. The molded bodies of preferred washing and cleaning agents within the scope of the present invention are characterized in that they contain the cationic nitrile of the formula (I) in amounts of 0.1 to 20% by weight, preferably 0.25 at 15% by weight, and especially from 0.5 to 10% by weight, referred respectively to body weight
molded

It is especially preferred that the bodies molding of washing and cleaning agents according to the invention contain the cationic nitrile of the formula (I) in more form rude In molded bodies of washing and cleaning agents preferred, at least 90% by weight of the nitrile particles The cationic formula (I) has a particle size per above 0.2 mm.

In the scope of the present invention it is preferred that cationic nitrile particles not only have more than 90% by weight of particles with sizes above 0.2 mm, but contain even coarser particles in a high fraction In this case, the molded bodies of agents preferred washing and cleaning are characterized by at least 40% by weight, preferably at least 50% by weight, and in at least 60% by weight of cationic nitrile particles of the formula (I) has a particle size above 0.4 mm

The fraction of particles with sizes above of 200 µm will preferably amount to more than 90% by weight, referred to all cationic nitrile particles. For have an advantageous homogeneous particle size distribution, the bleaching activators used must be specially free of fractions that are too thin, or powdery, is say, especially preferably they should not contain particles below 0.2 mm in diameter. In molded bodies of especially preferred washing and cleaning agents, nitriles cationic are substantially free of particles with sizes below 0.2 mm. Within the scope of the present invention, means "substantially exempt" contents below 2% by weight, preferably below 1% by weight, and in special below 0.5% by weight, referred respectively to The totality of particles.

In molded bodies of washing agents and especially preferred cleaning, the cationic nitrile of the formula (I) has a particle size above 400 µm, preferably above 500 µm, so especially preferred above 600 µm, and especially for above 700 µm.

They belong to the general formula (I) a plurality of cationic nitriles, which are employable in the field of the present invention. In this case, the molded bodies of washing and cleaning agents according to the invention so contain especially advantageous cationic nitriles, in which R1 represents methyl, ethyl, propyl, isopropyl, or a moiety n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. R2 and R 3 are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, which may be one or both advantageously also a cyanomethylene moiety. In the following table, the cationic nitriles of the formula (I) Preferred according to the invention are characterized by their moieties R 1, R 2 and R 3:

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

       \ vskip1.000000 \ baselineskip
    

(Table goes to page next)

one

2

       \ newpage
    

For reasons of simpler synthesis they are preferred compounds in which the R 1 to R 3 moieties are identical, by way of example (CH 3) 3 N (+) CH 2 -CN X -, (CH 3 CH 2) 3 N (+) CH 2 -CN X -, (CH 3 CH 2 CH 2) 3 N (+) CH 2 -CN X <->, (CH 3 CH (CH 3)) 3 N (+) CH 2 -CN X <->, or (HO-CH 2 -CH 2) 3 N (+)} CH 2 -CN X <->. The molded bodies of mono- washing and cleaning agents or polyphasic, containing as cationic nitrile of the formula (I) a cationic nitrile of the formula (Ia)

\melm{\delm{\para}{R ^{6} }}{N ^{(+)} }{\uelm{\para}{R ^{4} }}

--- (CH_{2}) --- CN

\hskip3cm

X^{(-)}(Ia), R5 ---

 \ melm {\ delm {\ para} {R 6}} {N ^ {(+)}} {\ uelm {\ para} {R 4}}} 

--- (CH_ {2}) --- CN

 \ hskip3cm 

X <(-)}

in which R 4, R 5 and R 6, independently of each other, are selected from -CH 3, -CH 2 -, CH 3, -CH_ {2} -CH_ {2} -CH_ {3}, -CH (CH 3) - CH 3, which may be R 4 additionally also -H, and X being an anion, being valid preferably R 5 = R 6 = -CH 3, and especially R 4 = R 5 = R 6 = -CH 3, are especially preferred according to the invention.

The molded bodies of washing agents and cleaning containing as cationic nitrile (CH 3) 3 N (+) CH 2 -CN X -, X - representing an anion, which is selected from the chloride, bromide, iodide, hydrogen sulfate, methosulfate group p-toluenesulfonate (tosylate) or xylene sulfonate, They are especially preferred according to the invention.

The molded bodies of washing agents and cleaning according to the invention contain a system for "activated bleaching", that is, both bleaching agents and also bleach activators, employed as the latter cationic nitriles according to the invention, to obtain properties of molded body advantageous. In addition to nitriles cationic, molded bodies of washing and cleaning agents according to the invention they may still contain other activators of bleaching, which are also described below. However, the molded bodies of washing and cleaning agents according to the invention preferably contain the cationic nitriles of the general formula (I) as the only bleach activator, or as main bleach activator, i.e. at least 50% by weight of bleach activators contained in molded bodies of washing and cleaning agents according to the invention are nitriles cationic of the formula (I). To get a bleaching action improved in washing at temperatures of 60 ° C and below bleach activators are added to the washing agents and cleaning containing bleaching agents. As activators of bleaching to be used in addition to cationic nitrile, in the scope of the present invention compounds that provide aliphatic peroxocarboxylic acids preferably with 1 to 10 carbon atoms, especially 2 to 4 carbon atoms, and / or perbenzoic acid, if substituted, under conditions of perhydrolysis Substances bearing O- and / or groups are appropriate N-acyl of the quoted C atom index, and / or groups benzoyl, if any substituted. Are preferred polycylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated columnaries, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), phenolsulfonates acylates, especially phthalic acid anhydride, polyvalent acylated alcohols, especially triacetin, diacetate of ethylene glycol and 2,5-diacetoxy-2,

In addition to bleach activators conventional, or instead, within the scope of this invention, in addition to the cationic nitriles of the formula (I) the so-called catalysts of bleaching to molded bodies. In the case of these substances, it is about transition metal salts, or metal complexes of transition, which intensify bleaching, such as complexes salines or carbonyl complexes of Mn, Fe, Co, Ru or Mo. They are also complexable Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with ligands nitrogen tripod, as well as amino complexes of Co, Fe, Cu and Ru, as bleaching catalysts. In the scope of this invention can also be used as bleaching catalysts bleaching intensifying active product combinations, which are obtainable by intimate mixing of a water-soluble salt of a divalent transition metal selected from cobalt, iron, copper and ruthenium, as well as their mixtures, a salt water-soluble ammonium, and if necessary an oxidizing agent based on peroxide, as well as inert support material. If in the field of present invention bleaching catalysts are used, for these the particle size restrictions are equally valid cited above.

A bleach activator additionally used to the cationic nitrile of the formula (I) especially Preferred is N, N, N ', N'-tetraacetylethylenediamine, which finds extensive employment in washing and cleaning agents. Correspondingly, the molded bodies of washing agents and cleaning are characterized because they contain as activators of bleaching a cationic nitrile of the formula (I) and tetraacetylethylenediamine (TAED).

In such combinations of "Nitrilquat" -TAED, the weight ratios of "Nitrilquat" TAED are located preferably in the range of 1: 2 to 10: 1. Especially preferably, in such combinations, 1/3 to 2/3 of the total amount The bleaching activator is cationic nitrile of the formula (I).

The molded bodies of washing agents and cleaning according to the invention contain the activator (s) of bleaching in amounts of 0.5 to 30% by weight, preferably from 1 to 20% by weight, and especially from 2 to 15% by weight, referred respectively to the molded bodies of agents of total washing and cleaning, referring to the previous data Quantitative for cationic nitrile.

       \ newpage
    

According to end of use of molded bodies obtained may vary the total amounts of activators of Whitening. Thus, in tablets of washing agents Typical universals are common contents in activator of bleaching between 0.5 and 10% by weight, preferably between 2 and 8% by weight, and especially between 4 and 7% by weight, while that bleaching agent tablets may have considerably higher contents, by way of example between a 5 and a 30% by weight, preferably between 7.5 and 25% by weight, and in Special between 10 and 20% by weight. In this case, the specialist it is not limited in its freedom of formulation, and in this way it can get bleaching action wash tablets more or less intense, cleaning agent tablets or tablets of bleaching agents, varying the activator contents of bleaching and bleaching agent.

The bleach activator (s) serves in the molded bodies of washing and cleaning agents according to the invention to activate the bleaching agent or the agents of bleaching at lower washing or cleaning temperatures, and thus ensuring a high bleaching performance also at reduced temperatures As bleaching agents they have special meaning sodium perborate tetrahydrate and sodium perborate monohydrate Other useful bleaching agents are, by way of example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates, as well as peracid or peracid salts that provide H2O2, such as perbenzoates, peroxophthalates, diperacelaic acid, phthaloiminoperacid, or diperdodecanoic diacid. Also in the case of use of bleaching agents it is possible to dispense with the use of surfactants and / or adjuvant substances, so that they are obtainable tablets of pure bleaching agents. If they are used such bleaching agent tablets for washing textile materials, a combination of percarbonate is preferred sodium with sodium sesquicarbonate, regardless of what additional content substances are included in the bodies molded If cleaning agent tablets are obtained or bleaching for machine dishwashing, can be used also bleaching agents from the bleaching agents group organic Typical organic bleaching agents are peroxides. of diacyl, such as dibenzoyl peroxide. Other agents Typical organic bleaching agents are peroxyacids, cited as examples especially alkylperoxy acids and arylperoxy acids. Preferred representatives are (a) the acid peroxybenzoic and its substituted derivatives in the ring, such as alkylperoxybenzoic acids, but acid can also be used peroxy-? -naphthoic and magnesium monoperphthalate, (b) aliphatic peroxyacids or substituted aliphatics, such as peroxylauric acid, acid peroxystearic acid ε-phthalimidoperoxicapronic [acid phthalimidoperoxyhexanoic acid (PAP)], acid o-carboxybenzamidoperoxicapronic acid N-nonenylamidoperadipic and N-nonenylamidopersuccinates, and (c) acids aliphatic and araliphatic peroxy dicarboxylic acids, such as acid 1,12-diperoxiftálicos, 1,4-diacid-2-decylpiperoxybutanic, N, N-terephthaloyl-di (acid 6-aminopercapronic).

Whitening agents can be used also substances that release chlorine or bromine. Between the materials appropriate that release chlorine or bromine come into consideration, by way of example, N-bromo- and N-chloroamides heterocyclics, by way of example trichloroisocyanuric acid, acid tribromo-isocyanuric, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or its salts with cations, such as potassium and sodium. Equally suitable are compounds of hydantoin, like 1,3-dichloro-5,5-dimethylhydantoin.

In molded bodies of washing agents and cleaning for washing textile materials, which are called tablets of washing agents in an abbreviated manner, but also for tablets of cleaning agents for dishwashing by machine, the bleaching agent to be used is preferably sodium percarbonate. In this case, "sodium percarbonate" is a name used unspecifically for sodium carbonate peroxohydrate, which are not strictly "percarbonates" (it is ie, salts of percarbonic acid), but peroxide adducts of hydrogen in sodium carbonate. The commercial product has the average composition 2 Na 2 CO 3 • 3 H 2 O 2, and no It is, therefore, a peroxycarbonate. Sodium percarbonate form a white, water-soluble powder, with a density of 2.14 gcm -3, which is easily decomposes into sodium carbonate, and oxygen action bleaching, or oxidizing.

Sodium carbonate peroxohydrate was obtained by first time in 1899 by precipitation with ethanol from a solution of sodium carbonate in hydrogen peroxide, but it considered the same peroxycarbonate in the wrong way. Only in 1909 the compound was identified as peroxide addition compound of hydrogen, although in practice the denomination has been imposed historical "sodium percarbonate".

The industrial production of sodium percarbonate is predominantly carried out by precipitation from aqueous solution (the so-called wet process). In this case, aqueous solutions of sodium carbonate and peroxide meet of hydrogen, and sodium percarbonate is precipitated by agents salinized (predominantly sodium chloride), auxiliary agents of crystallization (by way of example polyphosphates, polyacrylates) and stabilizers (by way of example Mg2 + ions). The salt precipitate, which still contains 5 to 12% of mother liquor, is centrifuge then, and dry in bed dryers fluidized at 90 ° C. The apparent weight of the finished product can oscillate between 800 and 1200 g / l according to the process of obtaining. As a rule general percarbonate is stabilized by a coating additional. The coating procedures and the substances that they are used for coating, they are widely described in the patent literature. In principle, all the commercial percarbonate types, as offered, by way of example, by the firms Solvay Interox, Degussa, Kemira or Akzo.

The molded bodies of washing agents and cleaning according to the invention can be monophasic, that is to say they may have pressed from a pre-mix to give a homogeneous molded body. However, according to the invention also it is possible and preferred to make molded bodies available polyphasic, being able to divide active products into limited areas spatially, where this seems reasonable. In the field of present invention molded bodies of agents of bi- or multi-phase washing and cleaning, in which one phase contains the cationic nitrile of the formula (I) in amounts of 2.5% in weight, preferably 5% by weight, and especially 7.5% in weight, referred respectively to the weight of the phase, while the other phase (s) is preferably free of cationic nitrile of the formula (I), and especially exempt of total bleach activators.

\hbox{contenidos elevados en activador de blanqueo.}

By dividing the total mass of a molded body into various phases, in an isolated phase a high content can be achieved in certain content substances, especially bleach activators, if the content of this substance is correspondingly reduced in the / other phase (s), without in this case varying the total content of the molded body in this active substance. As can be seen from the amounts of bleach activator (s) in the total molded body mentioned above, and the amounts of bleach activator (s) in an isolated phase mentioned above, according to the invention it is preferred to concentrate the activator (s). es) of bleaching in a molded body phase, so that the corresponding phase present

 \ hbox {high contents in bleach activator.} 

Facing the single-phase molded bodies, the Polyphase molded bodies have the advantage that the criterion pH according to the invention can be carried out more simply and universal than for the total molded body. Due to the pH value reduced, which must present the phase after dissolution in water, a use of more highly alkaline raw materials is not possible in unlimited quantity, or it should be avoided according to the invention. In if necessary, an addition of acidifying agents is necessary, for keep in mind the cationic nitriles of the formula (I) in the slightly alkaline to slightly acid medium, desired according to invention. However, if they must be incorporated into the agents alkaline raw materials, which cannot be dispensed with, in the In case of a single-phase tablet, a job of high amounts of acidifying agents. Through a cut of phases can be performed both the cationic nitrile stabilized, advantageous according to the invention, as well as the use of materials alkaline premiums, presenting alkaline raw materials, such as carbonates, phosphates, silicates, etc. in the phase (s), which is (n) exempt (s) from cationic nitrile of the formula (I).

According to the invention, it is also possible to release the bleaching system activated in a delayed or accelerated manner, to get other advantages in washing or cleaning performance. TO as an example, a delayed release can be achieved by coating of particles or of the total phase, while that an accelerated release can be achieved, by way of example, by adding auxiliary disintegration agents to give A phase. With such measures, by way of example it is possible to release the cationic nitrile of the formula (I) at the beginning of the washing step or cleaning, presenting the washing bath, or cleaning, a value slightly alkaline or neutral to slightly acidic pH, if dissolves only the phase that contains the nitrile. After dissolution of the other phase (s), the pH value can be Raise dramatically according to the composition of the phase (s). By on the contrary, the delayed release of cationic nitrile of the formula (I). If in this case the dissolution of the other phase (s), accelerated against the phase containing nitrile, will provide a high pH value, this can be compensated by acidifying agents in the phase containing nitrile, if you want to release the nitrile in medium Neutral to slightly acidic.

The separation of the molded body into two or more phases can also be used for the separation of substances from Incompatible content The molded bodies of washing agent and bi- or multi-phase cleaning, in which one phase contains nitrile cationic formula (I), while another phase contains the total amount of bleaching agents included in the bodies molded, are preferred according to the invention.

If in addition to bleaching agents and nitrile cationic of the formula (I) other substances of content, it is equally preferred to separate certain content substances. In the case of agent tablets washing for washing machine dishes and tablets washing agents for washing textile materials, are preferred molded bodies of washing and cleaning agents bi-or polyphasic, containing cationic nitrile of the formula (I), bleaching agents and enzymes, not being enzymes contained in one phase together with the bleaching agent and cationic nitrile

For the rest, in the case of tablets of washing agents for machine dishwashing are preferred molded bodies of bi- o cleaning and cleaning agents polyphasics, which contain the cationic nitrile of the formula (I), bleaching agents and silver protective agents, not being contained the silver protective agent in a phase together with the bleaching agent and cationic nitrile.

The cited content substances are described in detail below. In addition to the substances of content cited bleach activator and bleaching agent, the molded bodies of washing and cleaning agents according to the invention they may have other content substances, whose quantities are adjust the use of molded bodies. They are especially appropriate substances of the group of surfactants, of adjuvants and polymers for use in the molded bodies of washing and cleaning agents according to the invention. In this case, no it will cause difficulties for the specialist to select the components isolated and their quantitative contents. In this way, a Universal washing agent tablet will contain more amounts elevated in surfactant agent (s), while in one tablet of bleaching agents can be dispensed with even completely to your employment eventually. Also the amount of adjuvant (s), which are used, varies by end of employment wanted.

In the molded bodies of washing agents and cleaning according to the invention, all adjuvants used usually washing and cleaning agents may be contents, that is, especially zeolites, silicates, carbonates, organic adjuvants, and - where there are no ecological prejudices against its use - also phosphates.

Layered crystalline sodium silicates appropriate have the general formula NaMSi_ {x} O2_ {x + 1} \ cdot H2O, meaning M sodium or hydrogen, x a number from 1.9 to 4, e and a number from 0 to 20, and being preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, by way of for example, in the European patent application PE-A 0 164 514. The preferred crystalline layered silicates of the indicated formula are those in which M represents sodium and x adopts values 2 or 3. In particular, disilicates are preferred both of β-sodium, as well as of δ-sodium, Na 2 Si 2 O 5, and H2O, being able to obtain disilicate of β-sodium, by way of example, according to procedure described in the patent application International WO-A-91/08171.

Amorphous sodium silicates are also employable with a module Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8, and especially from 1: 2 to 1: 2.6, which are delayed in solution, and have properties of secondary wash The delay of dissolution against silicates conventional amorphous sodium may have been caused in this case in various ways, by way of example by treatment superficial, mixed, compacted / thickened, or by overdried Within the scope of this invention it is understood by the "amorphous" concept also "amorphous according to x-rays". This means that silicates do not provide x-ray reflections crisp in x-ray diffraction experiments, as are typical for crystalline substances, but, in any case, one or more maximum scattered X radiation, which have a width of Several units of degree of diffraction angle. However, this it can even lead, very conveniently, to properties especially good adjuvants, if silicate particles they provide blurred, or even sharp, diffraction maxima in electronic diffraction experiments. This should be interpreted as such that the products have microcrystalline zones of size 10 up to a few hundred nm, values being preferred up to a maximum of 50 nm, and especially up to a maximum of 20 nm. Be describe such silicates called amorphous X-rays, which they also have a dissolution delay against glasses conventional soluble, by way of example, in the application for German patent DE-A-44 00 024. In Especially preferred are thickened / compacted amorphous silicates, Composite amorphous silicates and over-dried amorphous silicates according to x-rays

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 the firm Crosfield). However, it is also appropriate zeolite X, as well as mixtures of A, X and / or P. It is also commercially available, and preferably used in the scope of the present invention, by way of example, a co-crystallized from zeolite X and zeolite A (approximately 80% in weight of zeolite X), which is distributed by CONDEA Augusta Spa. under the trademark VEGOBOND AX®, and can be described by the formula

       \ vskip1.000000 \ baselineskip
    

nNa_ {2} O \ cdot (1-n) K_2O \ Ald {2} O_ {3} \ cdot (2-2.5) SiO_ {2} \ cdot (3.5-5.5) H2O.

In this case, the zeolite can be used both as a skeleton substance in a granulated compound, as well as in a type of "powder" of the total mixture to be pressed, using both ways for the incorporation of the Zeolite in the previous mixture. The appropriate zeolites have a average particle size of less than 10 µm (distribution of volume; measurement method: Coulter Counter) contain preferably 18 to 22% by weight, especially 20 to 22% by weight of bound water.

Naturally, it is also possible to use the phosphates generally known as adjuvant substances, in so much such employment should not be avoided for ecological reasons. Between plurality of commercially available phosphates, have the maximum meaning alkali metal phosphates, special bass preference of pentasodium triphosphate, or pentapotassium (sodium tripolyphosphate, or potassium) in the agent industry of washing or cleaning. Currently, these are mostly used in machine dishwashing agents.

In this case, alkali metal phosphates is the general name for alkali metal salts (in special sodium and potassium) of various phosphoric acids, in the that can differentiate metaphosphoric acids (HPO 3) n and orthophosphoric acid H 3 PO 4, in addition to representatives of higher molecular weight. In this In this case, phosphates have several advantages: they act as support alkali, prevent deposits of lime in machine parts, or lime inlays in tissues, and also contribute to cleaning performance

Sodium Dihydrogen Phosphate, NaH2PO4, exists as dihydrate (1.91 gcm -3, melting point 60 °) and as monohydrate (density 2.04 gcm -3). Both salts are powders white, very easily soluble in water, which lose water from crystallization on heating, and they are transformed, at 200 ° C, into the slightly acid diphosphate (disodium hydrogen phosphate Na 2 H 2 P 2 O 7) at a higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9) and Maddrell salt (see below). NaH2PO4 has reactivity acidic occurs if phosphoric acid is adjusted to a pH value of 4.5 with sodium hydroxide, and the porridge is sprayed. He potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium diphosphate, KDP), is a white salt of density 2.33 gcm <3>, has a melting point 253º [low decomposition formation of potassium polyphosphate (KPO3) x] and is Easily soluble in water.

Disodium hydrogen phosphate (sodium phosphate secondary), Na 2 HPO 4, is a colorless crystalline salt, very easily water soluble. This exists in anhydrous form, and with 2 moles (density 2,066 gcm -3, loss of water at 95 ° C), 7 moles (density 1.68 gcm -3, melting point 48 °, low loss of 5 H 2 O) and 12 moles of water (density 1.52 gcm-3, point of melting 35 °, under loss of 5 H 2 O), becomes anhydrous at 100 ° C, and it is transformed into the diphosphate Na 4 P 2 O 7 in the case of more intense heating. Disodium hydrogen phosphate is obtained by neutralizing phosphoric acid with low soda solution  use of phenolphthalein as an indicator. Hydrogen phosphate dipotassium (secondary or dibasic potassium phosphate), K 2 HPO 4, is an amorphous white salt, which is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4, consists of colorless crystals, which they have, as dodecahydrate, a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (correspondingly 19-20% of P 2 O 5) a melting point of 100 ° C, and in anhydrous form (corresponding to 39-40% of P2O5) a density of 2,536 gcm -3. Trisodium phosphate is easily soluble in water under alkaline reaction, and is obtained by evaporation concentration of a solution consisting of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Phosphate tripotassium (tertiary or tribasic potassium phosphate), K_ {3} PO_ {4}, is a white, deliquescent, granulated powder of density 2.56 gcm -3, has a melting point of 1340 °, and is Easily soluble in water with alkaline reaction. This occurs, for example, in the case of Thomas slag heating with carbon and potassium sulfate. Despite the higher price, in the cleaning agents industry are frequently preferred easily soluble potassium phosphates, therefore highly effective, against corresponding sodium compounds.

Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7, exists in anhydrous form (density 2,534 gcm-3, melting point 988 °, also indicated 880 °) and as decahydrate (density 1,815-1,836 gcm-3, melting point 94 ° under water loss). In the case of substances, colorless, water soluble crystals with alkaline reaction are preferred. Na 4 P 2 O 7 is produced in the case of heating of disodium phosphate to> 200 °, or by reacting phosphoric acid with soda in stoichiometric proportion, and dehydrating the solution by spraying. The complex decahydrate salts of heavy metals and hardness formers, and consequently reduces the hardness of water. Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7, exists in the form of trihydrate, and constitutes a colorless, hygroscopic powder, with a density of 2.33 gcm-3, which is soluble in water, increasing the pH value of the solution to 1% to 10.4 a
25 ° C

By condensation of NaH2PO4, or either from KH 2 PO 4, sodium and potassium phosphates are produced high molecular weight, which can be differentiated cyclic representatives, sodium metaphosphates, or potassium, and types in the form of chains, sodium polyphosphates, or Potassium Especially for the latter, a plurality is used of denominations: fusion or calcined phosphates, Graham salt, Kurrol salt and Maddrell salt. All sodium phosphates and higher potassium are called phosphates together condensed

The pentasodium triphosphate, technically important, Na 5 P 3 O 10 (sodium tripolyphosphate), is an anhydrous salt or crystallizes with 6 H 2 O, non-hygroscopic, white, water-soluble , of the general formula NaO [P (O) (ONa) -O] n
-Na with n = 3. About 17 g are dissolved in 100 g of water at room temperature at about 20 g at 60 °, at about 100 g of salt free of crystallization water; After heating for two hours of the solution at 100 °, approximately 8% orthophosphate and 15% diphosphate are produced by hydrolysis. In the case of obtaining pentasodium triphosphate, phosphoric acid is reacted with sodium hydroxide solution or sodium hydroxide in stoichiometric proportion, and the solution is dehydrated by spraying. Similarly to Graham salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (also lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is marketed, by way of example, in the form of a 50% solution by weight (> 23% P 2 O_ { 5}, 25% of K2O). Potassium polyphosphates find extensive employment in the washing and cleaning agents industry. In addition, there are also sodium and potassium tripolyphosphates, which can also be used within the scope of the present invention. These are produced, by way of example, if sodium trimetaphosphate is hydrolyzed with KOH:

(NaPO 3) 3 + 2 KOH → Na_ {3} K_ {P} {3} O_ {10} + H2O

According to the invention, these are employable exactly as sodium tripolyphosphate, potassium tripolyphosphate, or mixtures of both; tripolyphosphate mixtures are also used sodium and sodium tripolyphosphate sodium, or mixtures of potassium tripolyphosphate and sodium and potassium tripolyphosphate, or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium and potassium tripolyphosphate.

As organic adjuvants, in the bodies molding of washing or cleaning agent according to the invention is they can especially use polycarboxylates / acids polycarboxylic, polycarboxylate polymers / aspartic acid, polyacetals, dextrins, other organic adjuvants (see a continued), as well as phosphonates. They are described below. these kinds of substances.

Useful organic skeleton substances they are, by way of example, the polycarboxylic acids that can be used in form of its sodium salts, understood as acids polycarboxylic acids those carboxylic acids that carry more than one acid function By way of example, these are citric acid, acid adipic acid, succinic acid, glutaric acid, malic acid, acid tartaric acid, maleic acid, fumaric acid, saccharic acids, acids aminocarboxylic acid, nitrilotriacetic acid (NTA), as long as it is not must make repairs to such employment for ecological reasons, as well as mixtures thereof. Preferred salts are acid salts. polycarboxylic acids, such as citric acid, adipic acid, acid succinic, glutaric acid, tartaric acid, saccharic acids, and mixtures thereof.

The acids themselves can also be used. In addition to their adjuvant action, acids typically possess also the property of an acidified component, and they serve, by consequently, also for the adjustment of a lower pH value and softer washing or cleaning agents. In this case they must Quote especially citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixture of same.

As adjuvants they are also suitable polymeric polycarboxylates, these are, by way of example, salts alkali metal polyacrylic acid or acid polymetacrylic, by way of example those with a molecular weight relative from 500 to 70,000 g / mol.

In the sense of this document, in the case of the indicated molecular weights for polymeric polycarboxylates, these are weight average molecular weights M w of the respective acid form, which were determined primarily by means of gel permeation chromatography (GPC ), using a UV detector. In this case, the measurement was made against an external polyacrylic acid pattern, which provides realistic molecular weight values due to its structural analogy with the polymers investigated. These data clearly diverge from the molecular weight data in which polystyrene sulfonic acids are used as the standard. As a general rule, the molecular weights measured against polystyrenesulfonic acids are clearly higher than the molecular weights indicated in this
document.

Appropriate polymers are especially polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g / mol. Due to its superior solubility, of this group short chain polyacrylates may be preferred again, which have molecular weights of 2000 to 10000 g / mol, and so Especially preferred from 3000 to 5000 g / mol.

In addition, polymeric polycarboxylates are suitable, 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 50 to 90% by weight of acid acrylic, and 50 to 10% by weight of maleic acid. His weight molecular relative, referred to free acid, generally amounts to 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and Special 30,000 to 40,000 g / mol.

Polycarboxylates (co-) polymers can be Use as a powder, or as an aqueous solution. Content the agents in polycarboxylates (co-) polymers amounts preferably 0.5 to 20% by weight, especially 3 to a 10% by weight.

To improve water solubility, the polymers may also contain allylsulfonic acids, as per example allyloxybenzenesulfonic acid and metalylsulfonic acid, such as monomer

Especially preferred are also polymers. biodegradable consisting of more than two monomer units different, by way of example those containing as monomers salts of acrylic acid and maleic acid, as well as alcohol vinyl, or derivatives of vinyl alcohol, or containing as monomers salts of acrylic acid and acid 2-alkylsulfonic acid, as well as derivatives of sugars

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

Similarly, like other adjuvant substances Preferred should be mentioned polymeric aminodicarboxylic acids, their salts or their precursor substances. They are especially preferred polyaspartic acids, or their salts and derivatives, of which, in the German patent application DE-A-195 40 086, it is disclosed that they also have a bleaching stabilizing action, in addition to its adjuvant properties.

Other appropriate adjuvant substances are polyacetals, which can be obtained by dialdehyde reaction with polyolcarboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes, such as glyoxal, glutaraldehyde, terephthalic aldehyde, as well as mixtures thereof, and from acids polyolcarboxylic acids, such as gluconic acid and / or acid glucoheptonic

Other appropriate organic adjuvants they are dextrins, for example oligomers, or polymers of carbohydrates, which can be obtained by hydrolysis partial starch. Hydrolysis can be carried out according to usual procedures, by way of example catalyzed by acids or enzymes Preferably it is hydrolysis products with a molecule weight in the range of 400 to 500000 g / mol. In this case a polysaccharide with a dextrose equivalent (DE) is preferred in the range of 0.5 to 40, especially 2 to 30, with DE being a common measure for the reducing action of a polysaccharide in comparison with dextrose, which has a DE of 100. They are employable both maltodextrins with a DE between 3 and 20, and glucose syrup dry with a DE between 20 and 37, as well as the so-called dextrins yellow, and white dextrins, with higher molecular weights, in the range of 2000 to 30000 g / mol.

In the case of oxidized derivatives of such Dextrins are reaction products with oxidizing agents, which are capable of oxidizing at least one alcohol function of the ring of saccharide to give the carboxylic acid function. Such are known oxidized dextrins, and procedures for obtaining them, by way of example by 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 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. Is equally suitable an oxidized oligosaccharide according to the request of German patent DE-A-196 00 018. A oxidized product in the C6 of the saccharide ring can be especially advantageous.

Also the oxidisuccinates, and other derivatives of Disuccinates, preferably ethylenediamine disuccinate, are other appropriate adjuvants. In this case it is used ethylenediamin-N, N'-disuccinate (EDDS), preferably in the form of its sodium or magnesium salts. In addition, succinates of glycerin and glycerin trisuccinates. The amounts of employment appropriate are placed at 3 to 15% by weight in formulations that contain zeolite and / or contain silicate.

Other useful organic adjuvants are, by way of for example, acetylated hydroxycarboxylic acids, or their salts, which may occur, if necessary, also in the form of lactone, and containing at least 4 carbon atoms, and at least one group hydroxy, as well as a maximum of two acid groups. Such are described adjuvants, by way of example, in the patent application International WO 95/20029.

Another class of substances with properties adjuvants constitute the phosphonates. In this case it is especially hydroxyalkane phosphonates, or aminoalkane. Among hydroxyalkane phosphonates, it is of special significance. as 1,1-diphosphonate adjuvant of 1-hydroxyethane (HEDP). This is used preferably as sodium salt, presenting the disodium salt neutral reactivity, and tetrasodium salt alkaline reactivity (pH 9). How aminoalkane phosphonates come into consideration preferably ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP), as well as its superior counterparts. These are preferably used in the form of sodium salts of neutral reactivity, for example as hexasodium salt of EDTMP, or as a hepta- and octasodium salt of DTPMP. In this case HEDP is preferably used as an adjuvant of the class of phosphonates The aminoalkane phosphonates also have a label binding power of heavy metals. Correspondingly, in especially if the agents also contain bleach, it can be it is preferred to use aminoalkane phosphonates, especially DTPMP, or mixtures of said phosphonates.

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

The amount of adjuvant is usually placed between 10 and 70% by weight, preferably between 15 and 60% in weight, and especially between 20 and 50% by weight. The amount of adjuvants employed is again dependent on the end of employment, of so that bleaching agent tablets can present amounts of adjuvant substances (by way of example between 20 and 70% by weight, preferably between 25 and 65% by weight, and in special between 39 and 55% by weight), higher than, by way of example, washing agent tablets (usually 10 to one 50% by weight, preferably 12.5 to 45% by weight, and especially between 17.5 and 37.5% by weight).

The molded bodies of washing agents and Preferred cleaning also contain one or more agents surfactants In the molded bodies of washing agents and cleaning according to the invention surfactants can be used anionic, nonionic, cationic and / or amphoteric, or mixtures of the same. In the technical point of view of application are preferred mixtures of anionic and non-ionic surfactants. The total surfactant content of molded bodies stands at 5 to 60% by weight, based on body weight molded, with surfactants being preferred by up to 15% by weight in the case of tablets of agents of washing, and containing the cleaning agent tablets for the machine wash usually less than 3% by weight of surfactant.

As an example, they are used as agents anionic surfactants those of the type of sulphonates and sulfates. In this case they come into consideration as surfactants of sulfonate type preferably alkylbenzene sulfonates with 9 to 13 carbon atoms, olefin sulfonates, i.e. mixtures constituted by alkene sulphonates and sulphonates of hydroxyalkane, as well as disulfonates, as obtained, by way of example, from monoolefins with 12 to 18 carbon atoms with double bond in terminal or internal position, by sulfonated with Sulfur trioxide gas and subsequent alkaline hydrolysis or Acid from sulfonated products. They are also appropriate alkane sulfonates, which are obtained from alkanes with 12 to 18 carbon atoms, by way of example by sulphochlorinated or sulfooxidation with subsequent hydrolysis, or neutralized. Of the likewise, acid esters are also suitable α-sulfograms (ester sulphonates), by example the α-sulphonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Other appropriate anionic surfactants they are glyceric esters of sulfated fatty acids. It is understood by glyceric esters of mono-, di- and tri-fatty acids, as well as their mixtures, as they are formed in obtaining by esterified with a monoglycerin with 1 to 3 moles of fatty acid, or in the case of transesterified triglycerides with 0.3 to 2 moles of glycerin. In this case, glyceric esters of fatty acids Preferred sulfates are the sulfated acid products saturated fats with 6 to 22 carbon atoms, as an example of capronic acid, caprylic acid, caprinic acid, myristic acid, lauric acid, palmitic acid, stearic acid or acid Behenic

They are preferred as sulfates of Alkyl (alkaline salts), and especially sodium, of semisulfates of fatty alcohols with 12 to 18 atoms of carbon, by way of example from coconut fatty alcohol, tallow fatty alcohol, lauric alcohol, myristic, cetyl or stearic, or oxoalcohols with 10 to 20 carbon atoms, and those semi-esters of secondary alcohols of these lengths of chain. In addition, alkyl (en) ilo sulfates are preferred of the aforementioned chain lengths, which contain an alkyl moiety synthesized, linear chain, obtained on a petrochemical basis, which they have a degradation behavior similar to that of the compounds suitable based on fatty chemical raw materials. Are of interest washing technician alkyl sulfates with 12 to 16 atoms of carbon, and alkyl sulfates with 12 to 15 carbon atoms, as well as alkyl sulfates with 14 to 15 carbon atoms. They are also appropriate anionic surfactants sulfates of 2,3-alkyl, which can be obtained according to Patent applications US 3,234,258 or 5,075,041, and as products trademarks of Shell Oil Company under the name DAN®.

Also suitable are the monosulfates of alcohols with 7 to 21 ethoxylated carbon atoms with 1 to 6 moles ethylene oxide, straight chain or branched, such as alcohols with 9 to 11 carbon atoms branched with 2 methyl, with a average of 3.5 moles of ethylene oxide (OE), or fatty alcohols with 12 to 18 carbon atoms with 1 to 4 OE. Because of its high power foaming, these are used in washing agents only in quantities relatively small, for example in quantities of 1 to 5% by weight.

Other preferred anionic surfactants they are also the salts of alkylsulfosuccinic acid, which are also they call sulfosuccinates or esters of sulfosuccinic acid, and represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols, and especially alcohols ethoxylated fatty. Preferred sulfosuccinates contain residues alcohol with 8 to 18 carbon atoms, or mixtures thereof. The Especially preferred sulfosuccinates contain an alcohol moiety fatty, which is derived from ethoxylated fatty alcohols, which constitute in themselves non-ionic surfactants (see description more down). In this case, the sulfosuccinates, whose fatty alcohol residues are derived from alcohols ethoxylated fatty acids with limited homolog distribution. Of the same so, it is also possible to use alkylsuccinates, preferably with 8 to 18 carbon atoms in the chain of alkyl (en) ilo, or its salts.

As additional anionic surfactants, especially soaps come into consideration. Soaps are appropriate of saturated fatty acids, such as lauric acid salts, acid myristic, palmitic acid, stearic acid, erucic acid hydrogenated, and behenic acid, as well as, in particular, mixtures of soaps derived from natural fatty acids, for example acids Coconut, palm kernel or tallow fatty.

Anionic surfactants, including Soaps can be presented in the form of their sodium salts, potassium or ammonium, as well as in the form of soluble base salts organic, such as mono-, di- or triethanolamine. The agents anionic surfactants are preferably presented in the form of their sodium or potassium salts, especially in the form of salts Sodium

They are preferably used as agents non-ionic alkoxylated alcohols surfactants, advantageously ethoxylates, especially primary, preferably with 8 to 18 atoms of carbon, and an average of 1 to 12 moles of ethylene oxide (OE) 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, as they usually occur in oxoalcohol residues. Do not However, ethoxylates of alcohols with linear residues of alcohols of native origin with 12 to 18 atoms of carbon, for example coconut fatty alcohol, palm kernel, tallow, or oleic alcohol, and an average of 2 to 8 OE per mole of alcohol. To the Preferred ethoxylated alcohols belong, by way of example, alcohols with 12 to 14 carbon atoms with 3 OE or 4 OE, alcohol with 9 to 11 carbon atoms with 7 OE, alcohols with 13 to 15 atoms of carbon with 3 OE, 5 OE, 7 OE or 8 OE, alcohols with 12 to 18 atoms of carbon with 3 OE, 5 OE or 7 OE, and mixtures thereof, as mixtures of alcohol with 12 to 14 carbon atoms with 3 OE, and alcohol with 12 at 18 carbon atoms with 5 OE. 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). Additionally to these nonionic surfactants can also be used alcohols fatty with more than 12 OE. Examples of them are tallow fatty alcohol with 14 OE, 25 OE, 30 OE or 40 OE.

As additional non-ionic surfactants alkyl glycosides of the formula can also be used 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 1.2 a 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, they are alkyl esters of alkoxylated fatty acids, 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 for example, in Japanese patent application JP 58/217598, or that are preferably obtained according to the procedure described in the international patent application WO-A-90/13533.

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-ihydroxyethylamine, and acid alkanolamides fatty. Preferably, the amount of these surfactants non-ionic is not greater than that of ethoxylated fatty alcohols, in Special does not amount to more than half of it.

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

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

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

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

--- [Z]

in which RCO represents a remainder aliphatic acyl with 6 to 22 carbon atoms, R 1 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. In the case of polyhydroxy fatty acid amides it is about known substances, which can be obtained by aminated by reduction of a reducing sugar with ammonia, an alkylamine, or a alkanolamine, and subsequent acylated with a fatty acid, an ester fatty acid alkyl, or an acid chloride fatty.

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

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

--- [Z](III), R --- CO ---

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

--- [Z]

in which R represents a remainder linear or branched alkyl or alkenyl with 7 to 12 atoms of carbon, R 1 represents a linear, branched or branched alkyl moiety cyclic, or an aryl moiety with 2 to 8 carbon atoms, and R2 represents a linear, branched or cyclic alkyl moiety, or a moiety aryl or an oxy-alkyl moiety with 1 to 8 atoms of carbon, with alkyl moieties having 1 to 4 atoms of preference being preferred carbon or phenyl, [Z] representing a polyhydroxyalkyl moiety linear, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated derivatives, preferably ethoxylated or propoxylated, of this rest.

Preferably [Z] is obtained by aminated by reduction of a sugar, by way of example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The compounds N-alkoxy N-aryloxy-substituted can be then transform into polyhydroxy fatty acid amides desired, by way of example according to the teaching of the application International WO-A-95/07331, by reaction with fatty acid methyl esters in presence of an alkoxide as catalyst.

In the scope of the present invention are preferred molded bodies of washing and cleaning agents that contain anionic surfactant (s) and / or non-ionic (s), and that present contents in agents total surfactants above 2.5% by weight, preferably above 5% by weight, and especially above 10% in weight, referred respectively to the weight of the molded body. In this case, technical advantages of application may result from certain quantitative proportions, in which the classes of isolated surfactants.

By way of example, they are especially preferred molded bodies of washing and cleaning agents in which the proportion of surfactant agent (s) anionic (s) with respect to agent (s) non-ionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and especially between 5: 1 and 1: 2

From the technical point of view of application it may be advantageous that certain kinds of surfactants in some phases of the molded body of washing or cleaning agent, or in the total molded body, is say, in all phases. Another important way of executing the The present invention provides that at least one phase of the molded body free of nonionic surfactants.

However, on the contrary also through the content of isolated phases or of the total molded body i.e. of all phases, in certain surfactants, you can Get a positive effect. The introduction of polyglycosides of alkyl described above has proved advantageous in this case, so that molded bodies of agents of washing and cleaning in which at least one of the phases of the body molded contains alkyl polyglycosides.

Similarly to the case of non-surfactants ionic, also the suppression of anionic surfactants from isolated phases or from all phases bodies may result molding washing and cleaning agents that are more appropriate for certain fields of application. Therefore, in the field molded bodies are also conceivable from the present invention of washing and cleaning agents, in which at least one phase of the molded body is free of anionic surfactants.

To facilitate the decomposition of highly compacted molded bodies it is possible to incorporate in these auxiliary agents of disintegration, the so-called explosive agents for tablets, to shorten the decomposition times. According to Römpp (9th edition, volume 6, page 4440) and Voigt " Lehrbuch der pharmazeutischen Tecnologie " (6th edition, 1987, pages in water or gastric juice, and the release of drugs in resorbable form.

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These substances, which are also called "explosive agents" due to its action, increase its volume in the case of water admission, being able to increase the own volume (swelling), being able to generate on the other hand, also through the release of gases, a pressure that allows break down the tablets into smaller particles. The agents disintegration auxiliaries formerly known are, by way of example, carbonate / citric acid systems, being able to use also other organic acids. The auxiliary agents of disintegration susceptible to swelling are, by way of example, synthetic polymers, such as polyvinylpyrrolidone (PVP), or polymers natural, or modified natural substances, such as cellulose and starch, and its derivatives, alginates or casein derivatives.

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

As preferred disintegrating agents, in the scope of the present invention agents of cellulose based disintegration, so that molded bodies Preferred basics contain such a disintegrating agent based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight, and especially 4 to 6% by weight. The Pure cellulose presents the formal gross composition (C 6 H 10 O 5) n, and constitutes, considered from the formal point of view, a β-1,4-polyacetal cellobiose, which is constituted by two glucose molecules. In In this case, the appropriate celluloses are constituted by approximately 500 to 5000 glucose units, and have, per consequently, average molecular weights of 50,000 to 500,000. At scope of the present invention, they are also employable as agents of cellulose-based cellulose-based disintegration, which are obtainable by cellulose reactions analogous to polymerization. Such chemically modified celluloses comprise in this case, by way of example, esterified products, or etherified, in which hydrogen atoms were replaced hydroxy But they can also be used as cellulose derivatives celluloses in which hydroxy groups were replaced by groups functional that are not linked through an oxygen atom. By way of example, they correspond to the group of cellulose derivatives alkaline celluloses, carboxymethyl cellulose (CMC), esters and ethers of cellulose, as well as aminocelluloses. The aforementioned cellulose derivatives they are not preferably used separately as agents of Disintegration based on cellulose, but used in mixture with cellulose. The content of these mixtures in cellulose derivatives preferably amounts to less than 50% by weight, so especially preferably less than 20% by weight, based on the agent of cellulose based disintegration. Especially preferably, it is used as a disintegrating agent based on cellulose, pure cellulose that is free of derivatives of cellulose.

Preferably, the cellulose used as auxiliary disintegration agent is not used finely divided, but it transforms into a more rude way, by way of example is granulated or compact, before addition with mixing to the mixtures before pressing. The molded bodies of agents washing and cleaning, containing explosive agents in the form granulated, or if appropriate cogranulated, are described in the German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 254 (Henkel), as well as in the international patent application WO98 / 40463 (Henkel). From these documents you can also extract more detailed data for obtaining explosive agents from granulated, compacted or cogranulated cellulose. The sizes of particle of such disintegrating agents are almost always located above 200 µm, preferably at least 90% by weight between 300 and 1600 µm, and especially at least 90% by weight between 400 and 1200 µm. The auxiliary agents of disintegration more coarse based on cellulose, cited above, and described in more detail in the aforementioned documents, they can be used preferably with auxiliary agents of disintegration in the scope of the present invention, and are commercially available, to by way of example, under the name Arbocel® Signature TF-30-HG Rettenmaier

As an additional disintegration agent based on Cellulose, or as a member of this component, can be used microcrystalline cellulose. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions such that attack and completely dissolve only amorphous areas (approximately 30% of the total cellulose mass) of the cellulose, but they leave the crystalline zones intact (approximately 70%). A subsequent breakdown of Microfin cellulose produced by hydrolysis provides microcrystalline celluloses, which have particle sizes primary of approximately 5 µm, and are compactable, by way of example, to give granulate with an average particle size of 200 \ mum.

In the scope of the present invention are preferred molded bodies of mono- washing and cleaning agents or polyphasic, which additionally contain an auxiliary agent of disintegration, preferably an auxiliary disintegration agent based on cellulose, preferably in granulated, cogranulated form or compacted, in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight, and especially from 4 to a 6% by weight, referred respectively to the molded body weight.

In addition to the aforementioned activator components of bleaching, bleaching agent, adjuvant, surfactant and auxiliary agent of disintegration, molded bodies of agents washing or cleaning according to the invention may contain one or more substances from the group of adjuvants, enzymes, adjusting agents pH, perfume substances, perfume supports, agents fluorescent, dyes, foam inhibitors, oils silicone, anti-redeposition agents, optical clarifiers, graying inhibitors, color transfer inhibitors and corrosion inhibitors These substances are described at continuation.

Enzymes, especially those of the class of hydrolases, such as proteases, esterases, lipases, or enzymes of lipolytic action, amylases, cellulases, or other glycosyl hydrolases, and mixtures of the enzymes mentioned are particularly important. All these hydrolases contribute, in washing, to the removal of stains, such as stains containing protein, fat or starch, and grated. Cellulases and other glycosylhydrolases can contribute to the conservation of color and to the increase of the softness of the textile material by eliminating pilling and microfibrils. For bleaching, or for the inhibition of color transmission, oxidoreductases can also be used. Enzymatic active ingredients obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus Cinereus and Humicola insolens , as well as enzymatic active products obtained from their genetically modified variants are very suitable. Preferably, subtilisin type proteases are used, and especially proteases that are obtained from Bacillus lentus . In this case, mixtures of enzymes, 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 particular interest, are of particular interest lipolytic action, 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 the known cutinases. In some cases, peroxidases or oxidases have also been shown to be advantageous. Appropriate amylases include, in particular, α-amylases, iso-amylases, pululanases and pectinases. Cellobiohydrolases, endoglucanases, and? -Glucosidases, which are also called cellobiases, or mixtures thereof are preferably used as cellulases. Since the various types of cellulases differ in their CMcasease and avicelase activities, the desired activities can be adjusted by selective mixtures of cellulases.

Enzymes may be adsorbed on carrier substances and / or housed in enveloping substances, to protect them against premature decomposition. The fraction of enzymes, mixtures of enzymes or enzyme granules, can rise, by way of example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.

The selection of the enzymes in question is also dependent on the purpose of use of the molded bodies of washing and cleaning agents according to the invention. Tablets of cleaning agents for machine dishwashing include enzymes especially those of the hydrolase class, such as proteases, esterases, lipases, or enzymes of lipolytic action, amylases, cellulases, or other hydrolases glycosylics, and mixtures of said enzymes. All these hydrolases contribute to the removal of dirt, such as stains that contain protein, fat or starch. Oxidoreductases can also be used for bleaching. Enzymatic active products obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus Cinereus and Humicola insolens , as well as enzymatic active products obtained from their genetically modified variants are very suitable. Preferably, subtilisin type proteases are used, and especially proteases that are obtained from Bacillus lentus . In this case, mixtures of enzymes, for example from protease and amylase, or protease and lipase, or enzymes of lipolytic action, or of protease amylase and lipase, or enzymes of lipolytic action, or protease, are of particular interest , lipase, or enzymes of lipolytic action, 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. In some cases, peroxidases or oxidases have also been shown to be advantageous. Appropriate amylases include, in particular, α-amylases, iso-amylases, pululanases and pectinases.

Also in the case of agent tablets cleaning, enzymes may be adsorbed on substances carriers and / or housed in enveloping substances, to protect them against premature decomposition. The enzyme fraction, mixtures of enzymes or enzyme granules, can be promoted, by way of example, about 0.1 to 5% by weight, preferably 0.5 up to about 4.5% by weight.

Molded bodies of cleaning agents according to the invention for machine dishwashing can contain corrosion inhibitors to protect the material from washing or machine, having a special meaning agents Silver protectors in the machine dishwashing sector. Substances known from the prior art are employable. In general, silver protective agents can be used selected from the group of triazoles, of benzotriazoles, of bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, and salts or complexes of transition metals. Especially Preferably, benzotriazole and / or alkylaminotriazole can be used. In addition, in formulations of cleaning agents is found frequently agents containing active chlorine, which can Clearly reduce the corrosion of the silver surface. In Chlorine-free cleaners are especially used compounds organic with redox activity that contain oxygen and nitrogen, as di- and trivalent phenols, for example hydroquinone, benzocatechin, hydroxyhydroquinone, gallic acid, floroglucin, pyrogallol, or derivatives of these classes of compounds. Too find inorganic compounds of salt type and complex, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce. In this case, transition metal salts are preferred, which are selected from the group of salts and / or manganese complexes and / or cobalt, especially preferably complexes (amino) of cobalt, of complexes (of acetate) of cobalt, of complexes (carbonyl) of cobalt, of cobalt chlorides or manganese, and manganese sulfate. In the same way you can employ zinc compounds for corrosion inhibition in the washing material

Additionally, agent molded bodies washing and cleaning can also contain components that positively influence the aptitude for oil washing and greases from textile materials (so-called repellents of dirt). This effect is especially evident if it gets dirty a textile material that was previously washed several times with a washing agent according to the invention, which contains these components oils and fats solvents. To the solvent components of preferred oils and fats belong, by way of example, ethers non-ionic cellulose, such as methylcellulose and methylhydroxypropylcellulose, with a fraction in methoxyl groups of 15 to 30% by weight, and in hydroxypropoxy groups of 1 to 1 15% by weight, referred respectively to non-cellulose ethers ionic as well as polymers of phthalic acid and / or acid Terephthalic known for the state of the art, or its derivatives, especially polymers of ethylene terephthalates and / or polyethylene glycol terephthalates, or derivatives thereof modified by anionic and / or non-ionic route. Of these are Especially preferred are sulfonated derivatives of polymers of phthalic acid and terephthalic acid.

The molded bodies may contain as optical brighteners derived from diamino stilbene disulfonic acid, or its alkali metal salts. They are appropriate, for example, acid salts 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid, or compounds of similar structure, which carry, instead of the group morpholino, a diethanolamino group, a methylamino group, a group anilino or a 2-methoxyethylamino group. They can also be present with diphenylstyrene type clarifiers substituted, for example alkaline salts of 4,4'-bis (2-sulfoestiren) -diphenyl, 4,4'-bis (4-chloro-3-sulfoestiren) -diphenyl,  or 4- (4-chlorostyrene) -4 '- (2-sulfoestiren) -diphenyl. Mixtures of the clarifiers mentioned may also be used. previously.

Dyes and substances can be added Perfumers to the molded bodies of washing and cleaning agents according to the invention to improve the aesthetic impression of the products, and make available to the consumer, in addition to the Product performance, a "typical and unmistakable" product from the organoleptic point of view. They can be used as scented oils, or scented substances, compounds isolated aromatics, for example synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. Aromatic compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, acetate p-tert-butyl-cyclohexyl, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl, linalyl benzoate, benzyl formate, glycinate ethylmethylphenyl, allylcyclohexyl propionate, stiralyl and benzyl salicylate. Among the ethers, by way of for example, benzylethyl ethers, among the aldehydes, by example, linear alkanes with 8 to 18 carbon atoms, citral, citronelal, citronelliloxyacetaldehyde, cyclamenaldehyde, hydroxycitronal, lilial and bourgeonal, between ketones, by example, the yonones, α-isomethylionone and methylcedrylacetone, among the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, at hydrocarbons belong mainly terpenes, such as limonene and pinene. However, preferably mixtures of various aromatic substances, which generate a smell note nice together. Such scented oils may contain also mixtures of natural aromatic substances, such as accessible from plant sources, for example essence of pine, lemon, jasmine, patchouli, rose or Ylang-Ylang. Also suitable are muscat essence, sage essence, chamomile essence, carnation essence, melissa essence, essence of mint, cinnamon leaf essence, linden flower essence, essence of juniper, essence of vetiver, essence of olíbano, essence of gálbano and essence of ladano, as well as essence of flowers of orange, neroli essence, orange peel essence and essence of sandalwood.

Usually, the dye content of the molded bodies of washing and cleaning agents according to the invention it is below 0.01% by weight, while the Perfume substances may constitute up to 2% by weight of the total formulation

Perfume substances can be incorporated directly on the agents, but it can also be advantageous apply perfume substances on intensifying supports the adhesion of the perfume on the clothes, and that provide a long-lasting perfume of textile materials through a release of slower perfume. As such support materials have given good result, by way of example, cyclodextrins, being able to be coated the cyclodextrin-perfume complexes additionally with other auxiliary substances.

To improve the aesthetic impression of the agents according to the invention, these can be dyed with appropriate dyes. Preferred dyes, whose selection does not cause any type of difficulty to the specialist, they have a high stability when insensitivity storage against content substances remaining agents and facing the light, and do not possess a pronounced substantivity against treated substrates, such as for example pieces of crockery, not to dye these.

Obtaining molded bodies with activity Washing and cleaning is done by applying pressure on a mixture to be pressed, which is in the cavity of a press. In the simplest case of obtaining molded bodies, than to Then it is called simplified tabletting, it is pressed the mixture to be tabletted directly, that is, without prior granulation. The advantages of this so-called direct tabletting are its application simple and economical, since no procedural steps are required additional, and therefore neither additional facilities. However, these advantages are also opposed. From this way, a powdery mixture, which should be tabletted directly, you must have sufficient plastic conformability and present good fluidity properties, in addition to not showing any type of tendency to disintegrate during storage, the transport and load of the matrices. These three conditions are extraordinarily difficult to master in many mixtures of substances, so that direct tabletting, especially in the obtaining tablets of washing and cleaning agents, it is not apply frequently. The usual way to obtain washing agent and cleaning agent tablets part of components powdery ("primary particles"), which agglomerate, or well granulate by appropriate procedures to give particles Secondary with higher particle diameter. These granules, or mixtures of various granules, then mixed with loads powdered insulated, and fed to the tablet.

Another object of the present invention is a procedure for obtaining molded bodies of agents mono- or multi-phase washing and cleaning by forming press of one or more prior mixtures in the form of particles so known itself, which is characterized in that the pre-mix for the total molded body, or for at least one of the phases, it contains a cationic nitrile of the formula (I).

\melm{\delm{\para}{R ^{3} }}{N ^{(+)} }{\uelm{\para}{R ^{1} }}

--- (CH_{2}) --- CN

\hskip3cm

X^{(-)}(I), R2 ---

 \ melm {\ delm {\ para} {R 3}} {N ^ {(+)}} {\ uelm {\ para} {R 1}}} 

--- (CH_ {2}) --- CN

 \ hskip3cm 

X <(-)}

in which R 1 represents -H, -CH 3, an alkyl or alkenyl moiety with 2 to 24 atoms of carbon, an alkyl or alkenyl moiety substituted with 2 to 24 atoms carbon, with at least one substituent of the group -Cl, -Br, -OH, -NH2, -CN, an alkyl or alkenylaryl moiety with a group alkyl with 1 to 24 carbon atoms, or an alkyl moiety or alkenylaryl substituted with an alkyl group with 1 to 24 atoms of carbon, and at least one other substituent in the aromatic ring, R 2 and R 3, independently of each other, are selected at from -CH 2 -CN, -CH 3, -CH_ {2} -CH_ {3}, -CH_ {2} -CH_ {2} -CH_ {3}, -CH (CH 3) - CH 3, -CH2 -OH, -CH2 -CH2 -OH, -CH (OH) -CH 3, -CH2 -CH2 -CH2 -OH, -CH 2 -CH (OH) -CH 3, -CH (OH) -CH 2 -CH 3, - (CH 2 CH 2 -O) n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion, the pH value being below 7 of a 1% aqueous pre-mix solution in question in weight.

If molded bodies of agents are obtained single-phase washing and cleaning, the total pre-mix must correspond to the aforementioned pH value criterion. In obtaining multi-phase molded bodies, which are obtained by stacking pressure or pressing of various previous mixtures, only the mixture prior to containing the cationic nitrile of the formula (I) must have a pH value below 7 in 1% aqueous solution in weigh.

Preferred forms of execution of procedure according to the invention should be considered analogous to molded bodies of washing and cleaning agents according to the invention. Thus, according to the invention, they are preferred. procedures in which the pH value of an aqueous solution at 1% by weight of pre-mix for the total molded body, or for the phase containing the cationic nitrile of the formula (I), places below 6.

Also in the process according to the invention, the pH value is more preferably within a narrower range, so that according to the invention are more preferred processes in which the pH value of a 1% aqueous solution by weight, pre-mix for the body total molding, or for the phase containing the nitrile cationic of the formula (I), is below 6.5, preferably below 6.0, especially preferably below 5.5, and especially below 5.0.

Regarding other preferred forms of execution of the method according to the invention refers to the above data regarding molded bodies of washing and cleaning agents according to the invention. In this way, contents of pre-mixing in cationic nitrile from 0.25 to 15, and especially from 0.5 to 10% by weight, referred respectively to the pre-mix

Also regarding particle sizes of Cationic nitrile is valid as stated above. In the same way, according to the invention, processes in which the minus 90% by weight of cationic nitrile particles of the formula (I) have a particle size above 0.2 mm, preferably at least 40% by weight, preferably at minus 50% by weight, and especially at least 60% by weight of cationic nitrile particles of the formula (I) present a size of particle above 0.4 mm. They are especially preferred process variants in which the cationic nitrile (I) has an average particle size above 400 µm, preferably above 500 µm, especially preferably above 600 µm, and especially above 700 \ mum.

Also regarding cationic nitriles a use preferably you can refer to the explanations previous. In especially preferred procedures, the mixture previous contains as cationic nitrile (CH 3) 3 N (+) CH 2 -CN X -, X - representing an anion that is selected from the chloride, bromide, iodide, hydrogen sulfate, methosulfate group, p-toluenesulfonate (tosylate) or sulfonate of xylene.

The molded bodies of preferred washing and cleaning agents within the scope of the present invention are obtained by pressing a pre-mix in the form of particles from at least one granulate containing surfactants and at least one pulverulent component added with subsequently mixed . In this case, the obtaining of granules containing surfactants can be carried out by usual granulation procedures, such as compacting, extrusion, granulator in mixer, pelletizing or granulating in fluidized bed. In this case, for the subsequent molded bodies of washing and cleaning agents it is advantageous that the pre-pressed mixture has an apparent weight that approximates that of the usual compact washing agent. In particular, it is preferred that the pre-mix in the form of particles additionally contain granulate (s) containing (n)
surfactants, and have an apparent weight of at least 500 g / l, preferably at least 600 g / l, and especially at least 700 g / l.

       \ newpage
    

The granulate containing surfactants also meets certain criteria for particle sizes in preferred process variants. Thus, processes according to the invention are preferred in which the granulate containing surfactants has particle sizes between 100 and 2,000 µm, preferably between 200 and 1,800 µm, especially preferably between 400 and 1,600 µm, and especially between 600 and
1,400 µm.

In addition to the active substances (agents anionic and / or non-ionic and / or cationic and / or surfactants amphoteric), surfactant granules contain preferably support substances, which proceed in a manner Especially preferred by the group of adjuvants. Therefore, the Especially advantageous procedures are characterized because the granulate containing surfactants comprises agents anionic and / or non-ionic surfactants, as well as adjuvants, and present contents in total surfactants of at least one 10% by weight, preferably at least 20% by weight, and especially at least 25% by weight.

Before pressing the pre-mix in form of particles to give molded bodies of washing agents and cleaning, the pre-mix can be "powdered" with agents Finely divided surface treatment. This could be advantageous for the nature and physical properties of both the pre-mixing (storage, pressing), as well as bodies molded washing and cleaning agents finishes. The agents of finely divided powdered are long known in the state of the art, almost always using zeolites, silicates, or other inorganic salts. However, preferably "dust" the pre-mixed with finely divided zeolite, Faujasite-type zeolites are preferred. In the field of present invention, the concept "zeolite of type faujasita" characterizes the three zeolites that form the subgroup of faujasita from the structural group of zeolite 4 (see Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). Therefore, in addition to zeolite X, zeolite Y and faujasite are also employable, as well as mixtures of these compounds, zeolite X being preferred pure.

They are also employable as dust agents mixtures or co-crystallized zeolites of the faujasite type with others zeolites, which must not necessarily belong to the structural group of zeolite 4, it being especially advantageous that at least 50% in powder agent weight is constituted by a type zeolite Faujasita

In the scope of the present invention are preferred molded bodies of washing and cleaning agents, which they consist of a pre-mix in the form of particles, which contains granulated components and additional substances mixed powders, being the component, or one of the powder components added with additional mixing, a Faujasite type zeolite with particle sizes below 100 µm, preferably below 10 µm, and especially by below 5 µm, and constituting at least 0.2% by weight, preferably at least 0.5% by weight, and especially more than 1% by weight of the mixture before pressing.

In addition to the aforementioned agent components surfactant, adjuvant and disintegrating auxiliary agent, the prepress mixtures may additionally contain one or various substances in the group of bleaching agents, activators of bleaching, disintegrating auxiliary agents, enzymes, pH adjustment, perfume substances, perfume supports, agents fluorescent, dyes, foam inhibitors, oils silicone, anti-redeposition agents, optical clarifiers, graying inhibitors, color transfer inhibitors and corrosion inhibitors These substances were described previously.

Obtaining the molded bodies according to the invention is first carried out by dry mixing of components, which may be completely or partially pregranulated and subsequent molding, especially pressing to give tablets, being able to resort to conventional procedures. For the obtaining of molded bodies the previous mixture is compacted in a called matrix between two pistons to give a solid tablet. This process, which is called tableted below abbreviated, it is divided into four sections: dosage, compacted (elastic forming), plastic forming and expulsion.

First, the pre-mix is introduced in the matrix, determining the amount of load, and with it the weight and the shape of the molded body produced, by the position of the Bottom plunger and the shape of the pressing tool. The constant dosage, also in the case of body yields higher molding, is preferably achieved through a volumetric dosing of the previous mixture. In the development subsequent tableting, the upper plunger is in contact with the previous mixture, and descends additionally in the sense of lower plunger In the case of this compaction, the pre-mixed particles by pressing down continuously the volume of cavity inside the load between the plungers From a certain position of the upper piston (and with it from a certain pressure on the previous mixture) plastic forming begins, in which particles flow, and the formation of the molded body is reached. According to the properties physical of the pre-mix is also compressed a part of pre-mix particles, and you get to a sinter of the pre-mixing at even higher pressures. At pressing speed increasing, that is, in the case of yield quantities high, the elastic forming phase is increasingly shortened, so that the molded bodies produced can have cavities more or less large. In the last tabletting step, the die molded body of the die through the lower plunger, and It is ejected through subsequent transport facilities. In this moment is definitely determined only the body weight molded, as the tablets, due to physical processes (elastic recovery, crystallographic effects, cooling, etc.), its shape and size may vary.

The tabletting is done in presses for commercial tablets, which may be equipped, in principle, with single or double plungers. In the latter case, only the upper plunger for pressure development, also the plunger lower moves over the upper plunger during the process of pressing, while the upper plunger presses up. For small production quantities, they are preferably used presses for eccentric tablets, in which the plunger or the pistons are fixed to an eccentric disc, which is mounted, by its part, in an axis with a certain speed of circulation. He movement of this pressing plunger is comparable to the mode of Work of a usual four-stroke engine. The pressing is can perform respectively with an upper and lower piston, but several plungers can also be attached to a disk eccentric, the number of matrix perforations Eccentric press yields they vary from a few hundred to a maximum of 3000 tablets per hour, according to type

For higher yields presses are selected for concentric tablets, in which a number is arranged higher of matrices in a so-called matrix table. The number of matrices vary between 6 and 55 depending on the model, being available in the trade also major matrices. To each matrix on the table of matrices are assigned an upper and lower plunger, being able to actively develop pressure only by means of the plunger upper, or lower, but also by both pistons. The Matrix tables and the plunger move in a common vertical axis, taking the pistons to the positions for loading, compacted, plastic forming and expulsion with the help of curved paths type rails during circulation. At the points where it is a lift, or a plunger descent, is necessary, especially aggravating (load, compacted, expulsion), they are supported these curved paths by means of low pressure parts, rails lower traction and lifting tracks. The load of the matrices is carried out through a power installation arranged rigid way, the so-called fill section, which is attached to a Reserve deposit for pre-mix. The pressure on the pre-mix is individually adjustable through the ways of pressure for upper and lower piston, development being carried out of pressure by means of the rolling of passage of the heads of pistons in adjustable pressing cylinders.

Concentric presses can also be equipped of two sections of load for the increase of the performance, being due still run only a semicircle to obtain a tablet. To obtain molded bodies of two and more layers, they have several sections of cargo in succession, without the expulsion of First layer, lightly pressed before subsequent loading. By appropriate process control, they are thus obtainable coated and punctual tablets, which have a type structure layers of onion, not coating and, consequently, the upper side of the core remaining visible, or of the core layers in the case of point tablets. Also the Concentric tablet presses are equipped with single or multiple tools, so that, for example, they use an outer circle with 50 and an inner circle with 35 perforations simultaneously for pressing. The yields of the modern presses for concentric tablets amount to more than one million molded bodies per hour.

In the case of tableting with concentric presses it has proved advantageous to carry out the tabletting with weight swings as small as possible. In this way, it they can also reduce the oscillations of hardness before tablets Reduced weight oscillations of as follows:

-

job of interspersed pieces of synthetic material with tolerances of reduced thickness,

-

number reduced rotor speed,

-

sections large cargo,

-

adjustment from the number of revolutions of pallet of load section to the number of rotor revolutions,

-

stretch loading with constant dust height,

-

decoupling cargo section and dust tank

For the reduction of agglomerates in plungers offer all non-stick coatings known to the technique. Material coatings are especially advantageous. synthetic, interspersed pieces of synthetic material or pistons synthetic material. Advantageous plungers have also been shown rotating, the piston must have a rotating configuration upper and lower if possible. In the case of rotating pistons a piece of material can usually be dispensed with synthetic. In this case, the plunger surfaces will be polished by electrolysis.

It was also shown that advantageous times are long press These can be adjusted with pressure rails, several pressing cylinders, or rotor speed numbers reduced Since the hardness oscillations of the tablets are caused by the oscillations of the pressing forces, must be apply systems that limit the pressing force. In this case it they can use elastic pistons, pneumatic compensators or elastic elements in the force path. Can also be done the pressing cylinders elastically.

The appropriate tableting machines in the scope of the present invention are available, by way of example, at Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackugssysteme GmbH Viersen, KILIAN, Köln, KOMAGE, Kell am See KORSCH Pressen AG, Berlin, as well as Romaco GmbH, Worms. Other providers are, for example, Dr. Hebert Pete, Wien (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU), as well as Mediopharm Kamnik (SI). As an example, it is especially Appropriate double pressure hydraulic press HPF 630 from the firm LAEIS, D. Tabletting tools are available, as a example, from Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharmatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm. Other providers are, for example, Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

In this case, the bodies can be made molded in predetermined spatial form and predetermined size. As a spatial form, virtually all reasonably manageable conditioning, that is, by way of as an example, the configuration as a plate, the rod shape, or bar, cube, parallelepiped, and corresponding spatial elements with flat side surfaces, as well as especially cylindrical fittings with circular cross section or oval In this case, the latter conditioning includes the tablet presentation form to cylindrical parts compact with a ratio of height to diameter by over 1.

In this case, portioned tablets may be configured respectively as separate isolated elements each other, which correspond to the dosage amount default washing and / or cleaning agents. However, of similarly it is possible to form tablets that bind a plurality of such mass units in a tablet, the easy being provided separability of smaller portioned units, especially by predetermined controlled breakpoints. For employment of textile washing agents in machines of the usual type in Europe, with mechanics arranged horizontally, can be convenient the formation of portioned pressed parts as tablets in the form of a cylinder or parallelepiped, being preferred a diameter / height ratio in the range of approximately 0.5: 2 to 2: 0.5. Hydraulic presses, eccentric presses or commercial concentric presses are appropriate devices, in Special for obtaining such pressed parts.

The spatial form of another form of execution of molded bodies is adapted in its dimensions to the chamber of sweeping of commercial washing machines, so that the bodies molded can be introduced, without dosing aid, directly in the scanning chamber, where they dissolve during the scanning process However, of course it is also possible without problem, and preferred within the scope of the present invention, a use of molded bodies of washing agents through a Dosing aid

Another preferred molded body, which can be get, it has a plate or table type structure with segments alternately thick long and thin short, so that it they can break, and introduce into the machine, isolated segments of this "pill" at the controlled breakage points, which they constitute thin short segments. This agent principle of "body-shaped" molded body wash can be also perform in other geometric shapes, by way of example vertical triangles, which are linked together only to what along one of its sides.

However, it is also possible not to press the different components to give a homogeneous tablet, but obtain molded bodies that have several layers, that is, when minus two layers. In this case, it is also possible that you are Different layers have different dissolution rates. From this may be advantageous technical application properties of molded bodies. As an example, if in the bodies molded are component contents that are negatively influenced reciprocally, it is possible to integrate a component into the layer more quickly soluble, and incorporate the other component in a layer more slowly soluble, so that the first component has reacted already when the second dissolves. The structure stratified of the molded bodies can be performed both at battery mode, and then a process of dissolution of the inner layer (s) in the edges of the molded body, if the outer layers have not yet dissolved completely, but you can also get a coating full of the inner layer (s) by the layer (s) located more externally in each case, which leads to a reduction of premature dissolution of components of the inner layer (s).

In another preferred form of execution of the invention, a molded body is constituted by at least three layers, that is, two outer layers and at least one inner layer, a peroxide bleaching agent being contained in at least one of the inner layers, while, in the case of molded body in the form of a pile, both covering layers, and in the case of the body Wrapped molded outer layers are exempt of peroxide bleaching agents. In addition, it is also possible spatially separate peroxide bleaching agents from each other, and bleach activators and / or enzymes present, where appropriate, in a molded body Such multilayer molded bodies feature the advantage of being able to use not only through a camera scanning or through a dosing device, which is added to the washroom; rather, in such cases it is also possible insert molded body into the machine in direct contact with textile materials, without fear of stains due to bleaching agents and the like.

Similar effects can be achieved too. by coating ("coating") of insulated components of the composition of washing and cleaning agents to be pressed, or of the total molded body. For this purpose, the molded bodies to they can be coated, for example, with solutions or aqueous emulsions, or a coating can be obtained at through the fusion coating process.

After pressing, the molded bodies of washing and cleaning agents have high stability. The Breaking strength of cylindrical molded bodies can be record through the extent of breakage stress measurement diametral. This is determinable according to

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

In this, \ sigma represents the effort of diametral rupture (diametral fracture stress, DFS) in Pa, P is the force in N, which leads to the pressure exerted on the body molded, which causes the molded body to break, D is the body diameter molded in meters and t is the height of the body molded

Claims (19)

1. Molded bodies of single- or multi-phase washing and cleaning agents from compacted washing and cleaning agents in particulate form, comprising bleaching agents, bleaching activator (s), as well as, where appropriate, other components of washing and cleaning agents, characterized in that the molded bodies, or at least one phase thereof, contain as a bleach activator a cationic nitrile of the formula (I) (I), R2 ---

 \ melm {\ delm {\ para} {R 3}} {N ^ {(+)}} {\ uelm {\ para} {R 1}}} 

--- (CH_ {2}) --- CN

 \ hskip3cm 

X <(-)} wherein R 1 represents -H, -CH 3, an alkyl or alkenyl moiety with 2 to 24 carbon atoms, an alkyl or alkenyl moiety substituted with 2 to 24 carbon atoms, with at least one substituent of the group -Cl, -Br, -OH, -NH2, -CN, an alkyl or alkenyl group with an alkyl group having 1 to 24 carbon atoms, or an alkyl or alkenyl group substituted with an alkyl group with 1 at 24 carbon atoms, and at least one other substituent on the aromatic ring, R2 and R3, independently from each other, are selected from -CH2 -CN, -CH3 , -CH_ {2} -CH_ {3}, -CH_ {2} -CH_ {2} -CH_ {3},
-CH (CH 3) - CH 3, -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3, -CH 2 } -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3, -CH (OH) -CH 2 -CH 3, - (CH_ { 2 CH 2 -O) n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion, with the pH value of the aqueous molded body solution being less than 7 1% by weight, or of the phase containing the Nitrilquat. 2. Molded bodies of single or multi-phase washing and cleaning agents according to claim 1, characterized in that the pH value of the 1% by weight aqueous solution of the molded body, or of the phase containing the Nitrilquat is less than 6. 3. Molded bodies of single- or multi-phase washing and cleaning agents according to one of claims 1 or 2, characterized in that they contain the cationic nitrile of the formula (I) in amounts of 0.1 to 20% by weight, preferably from 0.25 to 15% by weight, and especially from 0.5 to 10% by weight, referred respectively to the weight of the molded body. 4. Molded bodies of single- or multi-phase washing and cleaning agents according to one of claims 1 to 3, characterized in that they contain as cationic nitrile of the formula (I) a cationic nitrile of the formula (Ia) (Ia), R5 ---

 \ melm {\ delm {\ para} {R 6}} {N ^ {(+)}} {\ uelm {\ para} {R 4}}} 

--- (CH_ {2}) --- CN

 \ hskip3cm 

X <(-)} in which R 4, R 5 and R 6, independently of each other, are selected from -CH 3, -CH 2 -, CH 3, -CH_ {2} -CH_ {2} -CH_ {3}, -CH (CH 3) - CH 3, which may be R 4 additionally also -H, and X being an anion, being valid preferably R 5 = R 6 = -CH 3, and especially R 4 = R 5 = R 6 = -CH_ {3}. 5. Molded bodies of single- or multi-phase washing and cleaning agents according to one of claims 1 to 4, characterized in that they contain as cationic nitrile (CH 3) 3 N (+) CH 2 -CN X -, representing X - an anion that is selected from the group chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulphonate. 6. Molded bodies of single- or multi-phase washing and cleaning agents according to one of claims 1 to 5, characterized in that they contain as a bleaching activator a cationic nitrile of the formula (I) and tetraacetylethylenediamine (TAED). 7. Molded bodies of single- or multi-phase washing and cleaning agents according to one of claims 1 to 6, characterized in that they additionally contain a disintegrating auxiliary agent, preferably a cellulose-based auxiliary disintegrating agent, preferably in granulated, cogranulated form or compacted, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight, and especially 4 to 6% by weight, respectively based on the weight of the molded body. 8. Molded bodies of single- or multi-phase washing and cleaning agents according to one of claims 1 to 6, characterized in that they contain anionic (s) and / or non-ionic surfactant (s), and have contents in total surfactants above 2.5% by weight, preferably above 5% by weight, and especially above 10% by weight, respectively referred to molded body weight. 9. Molded bodies of single- or multi-phase washing and cleaning agents according to one of claims 1 to 7, characterized in that a phase contains the cationic nitrile of the formula (I) in amounts of 2.5% by weight, preferably of 5% by weight, and especially 7.5% by weight, referred respectively to the weight of the phase, while the other phase (s) is / are preferably free of nitrile cationic formula (I), and especially free of bleach activators in total. 10. Molded bodies of single or multi-phase washing and cleaning agents according to claim 6, characterized in that one phase contains the cationic nitrile of the formula (I), while another phase contains the total amount of bleaching agents contained in the bodies molded 11. Molded bodies of single- or multi-phase washing and cleaning agents according to one of claims 8 or 9, characterized in that they contain the cationic nitrile of the formula (I), bleaching agents and enzymes, the enzymes not being contained in one phase together with the bleaching agent and cationic nitrile. 12. Molded bodies of single- or multi-phase washing and cleaning agents according to one of claims 8 to 10, characterized in that they contain the cationic nitrile of the formula (I), bleaching agents and silver protective agents, the agent not being contained Silver protector in one phase together with the bleaching agent and cationic nitrile. 13. Procedure for obtaining molded bodies of single- or multi-phase washing and cleaning agents by means of forming press of one or more prior mixtures in the form of particles in a manner known per se, characterized in that the previous mixture for the total molded body, or either for at least one of the phases, it contains a cationic nitrile of the formula (I). (I), R2 ---

 \ melm {\ delm {\ para} {R 3}} {N ^ {(+)}} {\ uelm {\ para} {R 1}}} 

--- (CH_ {2}) --- CN

 \ hskip3cm 

X <(-)} wherein R 1 represents -H, -CH 3, an alkyl or alkenyl moiety with 2 to 24 carbon atoms, an alkyl or alkenyl moiety substituted with 2 to 24 carbon atoms, with at least one substituent of the group -Cl, -Br, -OH, -NH2, -CN, an alkyl or alkenyl group with an alkyl group having 1 to 24 carbon atoms, or an alkyl or alkenyl group substituted with an alkyl group with 1 at 24 carbon atoms, and at least one other substituent on the aromatic ring, R2 and R3, independently from each other, are selected from -CH2 -CN, -CH3 , -CH_ {2} -CH_ {3}, -CH_ {2} -CH_ {2} -CH_ {3},
-CH (CH 3) - CH 3, -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3, -CH 2 } -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3, -CH (OH) -CH 2 -CH 3, - (CH_ { 2 CH 2 -O) n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion, the pH value of the aqueous molded body solution being below 7 at 1% by weight. 14. Method according to claim 12, characterized in that the pH value of a 1% by weight aqueous solution of pre-mix for the total molded body, or for the phase containing the cationic nitrile of the formula (I), is places below 6. 15. Method according to one of claims 12 or 13, characterized in that the pre-mixture contains as cationic nitrile (CH 3) 3 N (+) CH 2 -CN X - , X - representing an anion that is selected from the group chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulphonate. 16. The method according to one of claims 12 to 14, characterized in that the pre-mix in the form of particles additionally contains granulate (s) containing (n) surfactants, and has an apparent weight of at least 500 g / l, preferably at at least 600 g / l, and especially at least 700 g / l. 17. Method according to claim 15, characterized in that the granulate containing surfactants has particle sizes between 100 and 2,000 µm, preferably between 200 and 1,800 µm, especially preferably between 400 and 1,600 µm, and especially between 600 and 1,400 µm. 18. Procedure according to one of claims 15 to 16, characterized in that the granulate containing surfactants comprises anionic and / or non-ionic surfactants, as well as adjuvants, and has contents in total surfactants of at least 10% by weight, preferably at least 20% by weight, and especially at least 25% by weight. 19. Method according to one of claims 12 to 17, characterized in that the pre-mixing in the form of particles additionally contains one or more substances from the group of bleaching agents, bleaching activators, disintegrating auxiliary agents, enzymes, pH adjusting agents , perfume substances, perfume holders, fluorescent agents, colorants, foam inhibitors, silicone oils, anti-redeposition agents, optical clarifiers, grating inhibitors, color transfer inhibitors and corrosion inhibitors.