ES2253253T3 - COMPONENTS FOR CLEANING AGENTS WITH SOLID PRODUCTS FINALLY DIVIDED. - Google Patents

Abstract

The invention relates to long-time stable mixtures (dispersions/emulsions) with only a slight tendency to separate, which provide effective and stable detergent components. Said mixtures contain 10 to 89.9 wt. % tenside(s), 10 to 89.9 wt. % meltable substance(s) with a melting point above 30 DEG C and a water solubility of less than 20 g/l at 20 DEG C, 0.1 to 15 wt. % of one or more solids, at least 90 wt. % of whose particles have a particle size of less than 300 mu m and optionally, 0 to 15 wt. % other active agents and/or auxiliary agents.

Description

Components for cleaning agents with finely divided solid products.

The present invention is in the field of agents for machine scrubbing of machine ware Household for dishwashing. The invention relates to components for washing agents for use in agents for machine dishwashing (MGSM) as well as compositions of cleaning agents and tablets cleaning agents, which They contain such components.

Machine washing of dishes in household dishwashers usually includes a pre-scrub program, a main scrub program and a rinse rinse program, which are interrupted by intermediate rinse programs. In most machines the prewash program can be connected for dishes that are heavily soiled, however it is selected only in exceptional cases by the user so that, in most of the machines a scrubbing program is carried out main, an intermediate rinse program with pure water and a rinse rinse program. The temperature of the main scrubbing program varies in this case depending on the type of machine and the choice of the level of the program between 40 and 65ºC. In the rinse rinse program, rinse rinse agent is fed into the machine from a dosing tank, which usually contains non-ionic surfactants as the main component. Such rinse rinse agents are presented in liquid form and are widely described in the state of the art. Its task is essentially to prevent lime stains and coatings on clean dishes. In addition to water and low-foaming non-ionic surfactants, these rinse rinse agents often also contain hydrotropes, pH adjusting agents such as citric acid or depot inhibitor polymers.
cough.

The reserve tank in the machine for the dishwashing has to be refilled at regular intervals with rinse rinse agent, one being sufficient recharge, depending on the type of machine, every 10 to every 50 processes scrubbing If the filling of the tank is forgotten, especially the Glassware will become unattractive due to lime stains. In the state of the art therefore there are some proposals for solution to integrate a rinse aid into the agent cleaning for machine washing of dishes. These proposals of solution are related to the forms of commercialization of the compact molded body.

Thus the European patent application EP-A-0 851 024 (Unilever) describes cleaning agent tablets, with two layers, whose first layer contains peroxy bleaching agents, adjuvants and enzymes, while the second layer contains acidification agents and a continuous medium with a melting point between 55 and 70 ° C as well as coating inhibitors. Through the middle continuous, which has a high melting point, should be released in a delayed way the acid (s) and the inhibitor (s) coatings and would cause a rinse effect. In This publication has not cited agents for machine scrubbing of dishware in powder form or rinse rinse systems containing surfactants.

The German patent application, earlier DE 198 51 426 (Henkel KGaA) describes a procedure for obtaining molded bodies of multi-phase washing and cleaning agents, in that a previous mixture, in the form of particles, is pressed to give molded bodies, which have a cavity, which is filled subsequently with a fusion, prepared individually, consisting of a fusible substance and one or more products assets dispersed or suspended therein. Also the teachings of this publication are related to the form of marketing constituted by "tablets".

Suspensions or fusible emulsions, disclosed in the publication cited last, present, of course, especially during the incorporation of surfactants as active substance a storage stability that Requires be improved. Fusible substances must occlude the active substance after cooling the emulsion and protect it Against premature release. When the emulsion is insufficiently stable, it separates in molten state in part before dosing, which leads to inaccuracies in the dosage Slightly more stable emulsions can certainly dosed but separated in part before the solidification, so that the active substance is released prematurely during the cleaning process. This post disseminates the use of various agents as a solution proposal auxiliary or stabilizers. Even when they have been cited solid products, no indication is given about their properties  physical

In the Japanese application JP-A-60 250 100 (Lion Corporation) solid cleaning agents containing silicate particles, which have been impregnated with one or more oils or waxes The size of silicate particles is 0.1 up to 50 µm.

In the German patent application DE-A197 58 178 (Henkel KGaA) agents are disclosed chlorine bleaching, solids, containing, in addition to others substances with washing or cleaning activity, also fuse substances of the paraffin group.

The international patent application, not previously published WO 00/31223 A1 (Hindustan Lever Limited) discloses cleaning agent granules, which contain as support material at least 15% by weight of a silicate insoluble in water.

The present invention was intended continue the development of the teachings of the patent application  previous German DE 198 51 426.3 and make mixtures available stable to storage, which had no tendency to disintegration at the time of dosing and refrigeration and that, thus, provide components for the agents of effective and stable cleaning. These mixtures, stable in the long term, and components for cleaning agents, manufactured from of these, should allow the use of all known advantages of controlled release of components, especially a rinse rinse effect, both in the case of powdery cleaning agents as well as in the case of cleaning agent tablets.

It has now been found that they can be manufactured stable fusions to disintegration from substances hydrophobic, fuses, with melting point above 30 ° C one (or various) surfactants and, optionally, other components such as colorants and odorizing products, etc. if the mixtures contain at least 0.1% by weight of one or more products finely divided solids.

The melting point of such mixtures can specifically adjust in this case by type and quantity of the components used, especially through the melting point and the amount of the fuse substance (s) and of the surfactant (s), up to the desired value. Above the melting point there are stable mixtures at separation, by below the melting point the mixtures solidify at any geometry to be referred to in the scope of the present invention as components of the washing agents.

The object of the present invention is constituted by a component of washing agents in the form of a solidifiable fusion, containing

to)

since 10 to 89.9% by weight of one or more surfactants,

b)

since 20 to 80% by weight of one or more fusible substances with a melting point above 30 ° C and a solubility in water less than 20 g / l at 20 ° C,

C)

since 0.15 to 12.5% by weight of one or more products solids,

d)

since 0 to 15% by weight of other active products and / or auxiliary

with the proviso that at least 90% by weight of the particles c) present a particle size below 300 \ mum.

The expression "components of the agents of cleaning "characterizes in this case, in the scope of the present application, solidified mergers constituted by the components a) to d), regardless of its form. In the sense of present request the "components of cleaning agents" they are, for example, scales, pearls, pills, segments of molded bodies, molded bodies themselves, etc. For achieve as fine a distribution of the component as possible a) in a matrix of component b), both components will melt separately or mixed together, if necessary they will be combined and Shake by adding c) as well as, optionally, by d) addition. The suspension or the fusion emulsion obtained in this way, which will be briefly referred to as "mixture" can be transformed as desired.

The components of cleaning agents Preferred contain as component a) from 15 to 80, preferably from 20 to 70, especially preferably from 25 to 60 and, in particular, from 30 up to 50% by weight of one or more non-ionic surfactants, cationic or amphoteric. In this case, all the surfactants of the groups of anionic surfactants, not ionic, cationic or amphoteric, preferably characterized the components of cleaning agents because they contain as component a) one or more anionic and / or non-ionic surfactants, preferably one or more nonionic surfactants.

As nonionic surfactants are used preferably nonionic surfactants of the alcohol group alkoxylated Non-ionic surfactants will be used preferably especially primary alcohols, alkoxylated, advantageously ethoxylated, preferably with 8 to 18 atoms of carbon and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcoholic residue can be linear or, preferably, it may be branched with methyl in the position 2 or it may contain mixed remains and branched with methyl, as they usually occur in the remains of oxoalcohol. However, they are especially preferred ethoxylates of alcohols with linear residues of alcohols of origin natural with 12 to 18 carbon atoms, for example alcohols fatty from coconut, palm, tallow or oleyl alcohol, and in average with 2 to 8 EO per mole of alcohol. To the alcohols Preferred ethoxylates belong, for example, alcohols with 12 to 14 carbon atoms with 3 EO or 4 EO, alcohols with 9 to 11 carbon atoms with 7 EO, alcohols with 13 to 15 atoms of carbon with 3 EO, 5 EO, 7 EO or 8 EO, alcohols with 12 to 18 carbon atoms with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures formed by alcohols with 12 to 14 atoms of carbon with 3 EO and for alcohols with 12 to 18 carbon atoms with 5 EO. The degrees of ethoxylation indicated represent values statistical means that can be an integer or a number Fractional for a special product. The ethoxylates of alcohols Preferred have a narrow distribution of counterparts (narrow range ethoxylates, NRE). In addition to these surfactants, no Ionic can also be used fatty with more than 12 EO. Examples in this respect are tallow fatty alcohols with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, they can be used as others nonionic surfactants also alkyl glycosides of the formula general RO (G) x, where R represents a remainder primary aliphatic, linear or branched, especially branched with methyl in position 2, with 8 to 22, preferably 12 to 18 atoms of carbon, and G is the symbol that represents a glycosy unit with 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and of the oligoglycosides, it is an arbitrary number between 1 and 10; being comprised, preferably x between 1.2 and Four.

Other class of non-ionic surfactants, preferably employed, which are used as the sole agent nonionic surfactant, or in combination with other agents nonionic surfactants, are alkyl esters of fatty acids alkoxylated, preferably ethoxylated, or ethoxylated and propoxylated, preferably with 1 to 4 carbon atoms in the alkyl chain, especially methyl esters of acids fatty

Non-surfactants may also be suitable. ions of the type of amine oxides, for example the oxide of N-cocoalkyl-N, N-dimethylamine and the oxide of N-tallowalkyl-N, N-dihydroxyethylamine, and of the alkanolamines of fatty acids. Preferably the amount of these nonionic surfactants is not greater than that of ethoxylated fatty alcohols, especially not greater than Half of them.

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

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

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

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

- [Z]

in which RCO is an acyl moiety aliphatic with 6 to 22 carbon atoms, R1 is hydrogen, a alkyl or hydroxyalkyl moiety with 1 to 4 carbon atoms and [Z] a linear or branched polyhydroxyalkyl moiety with 3 to 10 atoms of carbon and with 3 to 10 hydroxyl groups. Acid amides Polyhydroxygreases consist of known substances, which they can usually be obtained through the reductive amination of a reducing sugar with ammonia, with an alkylamine or with a alkanolamine and subsequent acylation with a fatty acid, with a alkyl ester of fatty acids or with an acid chloride fatty

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

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

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

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

- [Z]

in which R is an alkyl moiety or alkenyl, linear or branched, with 7 to 12 carbon atoms, R1 is a linear, branched or cyclic alkyl moiety, or a aryl moiety, with 2 to 8 carbon atoms, and R2 is a moiety linear, branched or cyclic alkyl, or an aryl moiety or a moiety oxy-alkyl, with 1 to 8 carbon atoms, being Preferred are alkyl radicals with 1 to 4 carbon atoms or phenyl radicals, and [Z] is a linear polyhydroxyalkyl radical, 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 means of the reductive amination of a reducing sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy substituted compounds or N-aryloxy can be transformed, by means of reaction with fatty acid methyl esters, in the presence of a Alkoxide as a catalyst in the acid amides polyhydroxygreases, desired.

As preferred surfactants, the nonionic surfactants that form little foam. The components for cleaning agents for machine scrubbing of the tableware, according to the invention, especially contain preferred non-ionic surfactants, especially non-surfactants ionic alkoxylated alcohol group. As surfactants anionic, non-ionic surfactants of the group of alkoxylated alcohols. As non-ionic surfactants, they will preferably use especially primary alcohols, alkoxylated, advantageously ethoxylated, preferably with 8 to 18 carbon atoms and an average of 1 to 12 moles of oxide ethylene (EO) per mole of alcohol, in which the alcoholic residue it can be linear or, preferably, it can be branched with methyl in position 2 or it may contain residues in mixture linear and branched with methyl, as usually presented in the remains of oxoalcohol. However, they are especially preferred ethoxylates of alcohols with linear residues of alcohols  naturally occurring with 12 to 18 carbon atoms, for example of fatty alcohols of coconut, palm, tallow or oleyl alcohol, and on average with 2 to 8 EO per mole of alcohol. To the alcohols Preferred ethoxylates belong, for example, alcohols with 12 to 14 carbon atoms with 3 EO or 4 EO, alcohols with 9 to 11 carbon atoms with 7 EO, alcohols with 13 to 15 atoms of carbon with 3 EO, 5 EO, 7 EO or 8 EO, alcohols with 12 to 18 carbon atoms with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures formed by alcohols with 12 to 14 atoms of carbon with 3 EO and for alcohols with 12 to 18 carbon atoms with 5 EO. The degrees of ethoxylation indicated represent values statistical means that can be an integer or a number Fractional for a special product. The ethoxylates of alcohols Preferred have a narrow distribution of counterparts (narrow range ethoxylates, NRE). In addition to these surfactants, no Ionic can also be used fatty with more than 12 EO. Examples a in this respect are tallow fatty alcohols with 14 EO, 25 EO, 30 EO or 40 EO.

Especially preferred are the components of cleaning agents, according to the invention, containing a nonionic surfactant, having a melting point above of room temperature. Therefore, the components of the cleaning agents are preferably characterized in that contain, as component a), one or more non-ionic surfactants with a melting point above 20 ° C, preferably by above 25 ° C, especially preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C.

Suitable nonionic surfactants, which have melting or softening points in the cited range of temperatures, are, for example, non-surfactants Ionic foaming, which can be solid or highly viscous at room temperature. When surfactants are not used ionic, highly viscous at room temperature, will be preferred that these have a viscosity above 20 Pas, preferably above 35 Pas and, especially, above 40 Pas. Also preferred are non-ionic surfactants which have a consistency of waxy type at room temperature.

Non-ionic surfactants, to be used by preferably, solids at room temperature, come from group of alkoxylated nonionic surfactants, especially of the ethoxylated primary alcohols and mixtures thereof surfactants with structurally configured surfactants of a more complicated way such as surfactants of polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO). Such nonionic surfactants (PO / EO / PO) are characterized, In addition, for good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant with a point of fusion located above room temperature, is a ethoxylated nonionic surfactant, which has been obtained by reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with, preferably, at least 12 moles, so especially preferred, with at least 15 moles, especially with at least 20 moles of ethylene oxide per mole of alcohol or of alkylphenol

A non-ionic surfactant to be used in a manner Especially preferred, solid at room temperature, is obtained from a straight chain fatty alcohol with 16 to 20 atoms carbon (alcohol with 16-20 carbon atoms), preferably from an alcohol with 18 carbon atoms and at at least 12 moles, preferably at least 15 moles and, especially, at least 20 moles of ethylene oxide. Among these are preferred especially the so-called "narrow range ethoxylates (narrow, range ethoxylates) "(see above).

Therefore, the components of the agents of cleaning, according to the invention, contain as component a), of especially preferred, one or more surfactants not ethoxylated ionic, which has / have been obtained from monohydroxyalkanoles with 6-20 carbon atoms or alkylphenols with 6-20 carbon atoms or of fatty alcohols with 16-20 carbon atoms and more than 12 moles, preferably more than 15 moles and, especially, more than 20 moles of ethylene oxide per mole of alcohol.

The nonionic surfactant, solid at temperature ambient, preferably has additional oxide units of Propylene in the molecule. Preferably such PO units they constitute up to 25% by weight, especially preferably up to 20% by weight and, especially, up to 15% by weight of set of the molecular weight of the nonionic surfactant. The Especially preferred nonionic surfactants are monohydroxyalkanoles or ethoxylated alkylphenols, which have, In addition, units of polyethylene oxide-polypropylene oxide. The proportion of alcohol or alkylphenol of such molecules of nonionic surfactants in this case preferably supposes more than 30% by weight, more preferably more than one 50% by weight and, especially, more than 70% by weight of the set of the molecular weight of such non-ionic surfactants. The components of the preferred cleaning agents are characterized because they contain, as component a), non-ionic surfactants ethoxylated and propoxylated, in which the oxide units of Propylene in the molecule accounts for up to 25% by weight, preferably up to 20% by weight and, especially, up to 15% by weight of the total molecular weight of the surfactant no ionic.

Other non-ionic surfactants, to be used especially preferably, with melting points located above room temperature, contain from 40 to 70% by weight of a mixture of block copolymers of polyoxypropylene / polyoxyethylene / polyoxypropylene, containing 75% by weight of a polyoxyethylene reverse block copolymer and of polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, started with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants, which can used in a particularly preferred manner, are, for example, which can be obtained under the name Poly Tergen® SLF-18 of the firm Olin Chemicals.

Another component of cleaning agents, preferred according to the invention, it contains, as component a), nonionic surfactants of the formula

R 1 O [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] y} [CH 2 CH (OH) R ^ {2}]

in which R1 means a linear or branched aliphatic hydrocarbon moiety with 4 to 18 carbon atoms or mixtures thereof, R2 means a linear or branched hydrocarbon moiety with 2 to 26 atoms of carbon or mixtures thereof and x means values included between 0.5 and 1.5 e and means a value of 15, as minimum.

Other non-ionic surfactants, employable by preferably, they are nonionic surfactants poly (oxyalkylated) closed at the end groups, of the formula

R 1 O [CH 2 CH (R 3) O] x [CH 2] k CH (OH) [CH 2] j OR 2

in which R 1 and R 2 mean linear or branched, saturated hydrocarbon moieties or unsaturated, aliphatic or aromatic, with 1 to 30 atoms of carbon, R 3 means H or a methyl, ethyl moiety, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl, x means values between 1 and 30, k and j mean values between 1 and 12, preferably included between 1 and 5. When it is the value of x ≥ 2, each R 3 in the formula indicated above may be different. Preferably R 1 and R 2 are linear or branched hydrocarbon moieties, saturated or unsaturated, aliphatic or aromatic, with 6 to 22 carbon atoms, residues with 8 being especially preferred Up to 18 carbon atoms. The remainder R3 means Especially preferred H, -CH 3 or -CH 2 CH 3. The Especially preferred values for x are found in the range from 1 to 20, especially from 6 to fifteen.

As described above, each R3 may be different in the formula indicated above, when
x ≥ 2. In this case, the alkylene oxide unit between the square brackets can be varied. If, for example, x means 3, the R 3 moiety can be chosen to form ethylene oxide (R 3 = H) or propylene oxide (R 3 = CH 3), which they can be sequentially arranged in any order, for example (EO) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO), and (PO) (PO) (PO). The value 3 for x has been chosen here as an example and can be perfectly greater, increasing the spectrum of variations as the values for x increase, for example, it includes a larger number of groups (EO), combined with a number smaller groups (PO) or vice versa.

Closed poly (oxyalkylated) alcohols in the especially preferred end groups of the formula previously indicated have values of k = 1 and j = 1, so that the above formula is simplified in

R 1 O [CH 2 CH (R 3) O] x CH 2 CH (OH) CH 2 OR 2.

In the formula, last cited, R1, R 2 and R 3 are defined as above and x means numbers from 1 to 30, preferably from 1 to 20 and, especially from 6 to 18. Especially preferred are surfactants in which the R 1 and R 2 moieties have 9 up to 14 carbon atoms, R 3 means H and x take values from 6 to 15.

If the explanations cited in Lastly, agents according to the invention will be preferred, which contain poly (oxyalkylated) nonionic surfactants closed in the extreme groups, of the formula

R 1 O [CH 2 CH (R 3) O] x [CH 2] k CH (OH) [CH 2] j OR 2

in which R 1 and R 2 mean linear or branched, saturated hydrocarbon moieties or unsaturated, aliphatic or aromatic, with 1 to 30 atoms of carbon, R 3 means H or a methyl, ethyl moiety, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl, x means values between 1 and 30, k and j mean values between 1 and 12, preferably included between 1 and 5, the surfactants of the kind

R 1 O [CH 2 CH (R 3) O] x CH 2 CH (OH) CH 2 OR 2

in which x means numbers from 1 to 30, preferably from 1 to 20 and, especially, from 6 to 18.

As component b) the components of the agents cleaning according to the invention contain one or more substances fuses, having a melting point above 30 ° C and which they are little or nothing soluble in water. These substances form the "matrix", in which the component a) of the components of the cleaning agents according to the invention, this distribution being stabilized especially through component c). In the scope of the present invention, the components of the preferred cleaning agents contain as component b) from 15 to 85, preferably from a 20 to 80, especially preferably from 25 to 75 and, in particular, from 30 to 70% by weight of one or various fusible substances.

By choosing the melting point of the component b) can be varied within wide limits the temperature at which the components of the agents will release cleaning according to the invention to component a) and, optionally, d). Below this temperature the remaining components are protected against environmental influences.

Fusible substances, which are used in components of the cleaning agents according to the invention, they are they require different requirements, which, on the one hand, refer to the melting behavior or solidification, on the other side however they also refer to the properties of the material of coating in solidified state, that is to say in the components of the cleaning agents according to the invention. Market Stall that the components of the cleaning agents must remain durable protected against environmental influences during transport or storage, the fuse substance it presents a high stability against the requests for shock that occur, for example, during storage or transport. The fusible substance must therefore present at least partially elastic properties or partially plastics to react by elastic or plastic deformation in the in case a shock request is filed and it is not break down for this reason. The fusible substance should present a melting range (solidification interval) in a temperature range such that the other components of the components of the cleaning agents according to the invention are not left subjected to a too high thermal solicitation. For another side the melting range must be, however, sufficiently elevated so that effective protection is still offered when there is at least a slight increase in temperature, for occluded active products. According to the invention the fusible substances have a melting point above 30 ° C, the components of the cleaning agents being preferred Only presenting fusible substances with melting points above 40 ° C, preferably above 45 ° C and, of especially, above 50 ° C. The components of the agents Especially preferred cleaning agents contain component b) one or more products with a melting range between 30 and 100 ° C, preferably between 40 and 80 ° C and, especially, between 50 and 75 ° C.

It has been found advantageous that the substance envelope not present sharply defined melting point, such as It usually occurs in the case of crystalline substances, pure, but present a fusion interval that includes, under certain circumstances, several degrees Celsius.

The fusible substance preferably has a melting range, which is between about 52.5 ° C and approximately 80 ° C. This means, in the present case, that the melting range occurs within the temperature range indicated, and does not designate the amplitude of the melting range. The amplitude of the melting range preferably means at least at 1 ° C, preferably, from about 2 to approximately 3 ° C.

The aforementioned properties are met, as a rule, by the so-called waxes. It is understood by "waxes" a series of natural or obtained substances synthetically, they melt generally above 50 ° C without decomposition, and are of relatively low viscosity and not filamentous and a little above the melting point. These present a consistency and solubility strongly dependent on the temperature.

According to their origin, the waxes are divided into three groups, natural waxes, chemically modified waxes, and synthetic waxes

To natural waxes belong, for example, vegetable waxes, such as candelilla wax, carnauba wax, Japan, esparto wax, cork wax, guaruma wax, wax rice germ oil, sugar cane wax, ouricuri wax or Montana wax, animal waxes, such as beeswax, rubber wax lacquer, sperm whale, lanolin (wool wax), or fat uropigal, mineral waxes, such as ceresin or ozoquerite (wax mineral), or petrochemical waxes, such as petrolatum, waxes from paraffin or microceres.

To chemically modified waxes belong, for example, hard waxes, such as Montana ester waxes, sasol wax or hydrogenated jojoba wax.

As a general rule it is understood by waxes Synthetic polyalkylene waxes or polyalkylene glycol waxes. As wrapping materials are also used compounds of other classes of substances, which meet the requirements cited with with respect to softening point and water solubility. As appropriate synthetic compounds, they have been accredited, by example, the higher esters of phthalic acid, especially the dicyclohexyl phthalate, which can be purchased commercially under the name Unimoll® 66 (Bayer AG). Also suitable are waxes synthetically obtained from carboxylic acids lower and fatty alcohols, for example tartrate dimiristil, which can be acquired under the name of Cosmacol ETLP (Count).

Preferably, the enveloping substance, contained in the components of the cleaning agents, according to the invention, a proportion of paraffin wax. That is, at minus a proportion of 10% by weight of the fusible substances, contained in total, preferably a larger proportion, is constituted by paraffin waxes. They are especially appropriate contained in paraffin waxes (referred to the total amount of fusible substance) of approximately 12.5% by weight, for example of 15% by weight, or for example of 20% by weight, being able to be especially preferred proportions even higher, for example, above 30% by weight. In a special way of embodiment of the invention, the total amount of the substance fuse, used, consists exclusively of wax paraffin.

Paraffin waxes have, in comparison with the other natural waxes, cited, within the scope of the present invention, the advantage that hydrolysis of the waxes does not take place in the alkaline environment of the cleaning agent (as expected , for example, in the case of wax esters), since paraffin wax does not contain hydrolyzate groups.
bles.

Paraffin waxes are constituted, mainly, by alkanes, as well as by small proportions of isoalkanes and cycloalkanes. Preferably, the paraffin, to be used according to the invention, it does not essentially present components with a melting point above 70 ° C, of especially preferred mode located above 60 ° C. The proportions of high melting alkanes in paraffin may leave unwanted wax residue on surfaces to be cleaned, or on the material to be cleaned, when drop below this melting temperature in the bath of cleaning agent. Such wax residues lead, as a rule overall, to an ugly appearance of the cleaned surfaces and, so Therefore, they should be avoided.

The components of cleaning agents, preferred, contain, as component b), at least one wax of paraffin with a melting point from 30 ° C to 65 ° C.

Preferably, the paraffin wax, used, It has a content in alkanes, isoalkanes and cycloalkanes, solids at room temperature (as a rule from about 10 to about 30 ° C), as high as may be possible. The higher the present proportion of the waxy, solid components in a wax at temperature environment, the more useful it is the use of it in the field of The present invention. As the proportion of solid waxy type components increase the chances of load of cleaning agent components to shocks or friction on other surfaces, which leads to protection more durable of coated active substances. The proportions elevated oils or waxy type components, liquids, they can lead to a weakening of the particles, which pores open, and the active substances are exposed to the influences environmental cited at the beginning.

The fusible substance may contain, in addition to paraffin, also one or several waxes or substances of waxy type, cited above. Preferably, the mixture, which form the fusible substance, should be structured in such a way, that the components of the cleaning agents are at least widely insoluble in water. Water solubility should not exceed approximately 10 mg / l at a temperature of about 30 ° C and should be found, preferably by below 5 mg / l.

However, in any coating it should have a water solubility as low as it was possible at elevated temperature, to avoid, in the broadest way possible, a temperature dependent release of the active substances The components of cleaning agents preferred are characterized, therefore, because the solubility in water of component b), at 20 ° C, is less than 15 g / l, preferably  less than 10 g / l, especially preferably less than 5 g / l and, especially, less than 2 g / l. In this case it is especially it is preferred that the water solubility of component b), at 20 ° C, be is below the measurement limit, therefore the product b) is "insoluble in water" in the usual sense.

As component c), the components of the cleaning agents, according to the invention, contain from 0.1 up to 15% by weight of one or more solid products, presenting at least 90% by weight of the particles of c) a size d particle less than 300 µm. In the preferred components of the cleaning agents the amount of c) is within a narrow margin, and also particle sizes are preferably thinner. In this way they are preferred, by a side, the components of the cleaning agents, which contain the component c) in quantities from 0.2 to 10, so especially preferred from 0.25 to 7.5 and, especially, from 0.3 to 5% by weight, on the other hand minus 90% by weight of c) particles present in others preferred components of cleaning agents, sizes of particles below 200 µm, preferably below 190 µm, especially preferably below 175 µm, in particular below 150 µm and very especially preferred below 100 µm.

It is especially preferred that component c) not at all have particles that have a size above 200 µm, lowering the particle size limit preferably even lower values. In the components of especially preferred cleaning agents, component c) is consisting entirely of particles with sizes of particles below 200 µm, preferably below 175 µm, especially preferably below 150 um and, especially, below 100.

As component c) all products that are solid and that meet the criteria cited with Relation to particle size. The expression "product solid "means in this case that component c) remains solid even at the transformation temperatures of the components a) to d) and that does not melt for example during obtaining the fusion or dissolving in another component. Preferably those products c) are used as products whose melting point is clearly above the point of melting of the components of cleaning agents, for example at least 10 ° C above, preferably at least 25 ° C above and, especially, at least 50 ° C above. Can also be preferably use as component c) substances infusible to usual temperatures

In addition to inorganic salts, products minerals such as silicates, silicic acids, aluminosilicates, organic solid products, etc. have been specially credited alkali metal salts of organic acids such as component c), sodium and potassium salts being preferred. As organic acids, whose salts preferably constitute the component c), for example, formic acid, the acetic acid, propionic acid, succinic acid, acid citric, fumaric acid, oxalic acid, malonic acid, tartaric acid, etc. The components of cleaning agents Especially preferred are characterized as component c) contain alkali metal salts of organic acids, preferably alkali metal acetates and, especially, potassium acetate

Another preferred group of products, which may be used as component c), they are clay minerals. In this in case natural clay minerals can be used or Chemically modified Clay minerals especially Preferred in this case are bentonites, which are suitable for in a very good way as component c) in the scope of this invention.

Bentonites are impurified clays, which are they have formed through the action of the weather on tuffs volcanic In this case it is possible to modify the properties of the Bentonites according to the purposes of application. The Bentonites are frequent in tropical soils as an integral part of the clays and are exploited in the form of sodium bentonite by example in Wyoming / USA. Sodium Bentonite has the properties  more favorable from the point of view of industrial application so that your employment is preferred within the scope of this invention. Calcium bentonites of natural origin come from example, from Mississippi / USA or from Texas / USA or from Landshut / Germany. Calcium bentonites of natural origin are artificially transformed by exchanging Ca against Na in Inflatable sodium bentonites.

The main components of bentonites they form the so-called Montmorillonites, which in the field of The present invention can be used even in pure form. The Montmorillonites are clay minerals that belong to the phyllosilicates and in this case to dioctahedral smectites, which crystallize in a monocrine-pseudohexagonal manner. Montmorillonites form predominantly white, white masses grayish to yellowish, completely amorphous, easily crumbly, inflatable in water but not turning plastics, which can be described by means of the formulas

Al 2 [(OH) 2 / Si 4 O 10] \ O 2 O

or good

Al_ {2} O_ {3} \ cdot4SiO_ {2} \ cdotH_ {2} O \ cdotnH_ {2} O

or good

Al 2 [(OH) 2 / Si 4 O 10]

(dried to 150 ° C).

Montmorillonites have a structure with three layers, which is constituted by two tetrahedral layers, which are electrostatically crosslinked through the cations of an octahedral intermediate layer. The layers are not rigidly bonded, but can swell by reversible occlusion of water (in amounts from 2 to 7 times) and other substances such as for example alcohols, glycols, pyridine, α-picoline, ammonium compounds, hydroxy ions -aluminosilicate, etc. The formulas indicated above represent only approximate formulas since montmorillonite has a great capacity for ion exchange. In this way they can exchange the Al ions for Mg, Fe 2+, Fe 3+, Zn, Cr, Cu and other ions. As a result of a substitution of this
type results in a negative charge of the layers, which is compensated by other cations, for example Na + and Ca 2+.

The structure of the phyllosilicates, in which a central layer consisting of cations coordinated in a manner octahedral is surrounded by a sandwich formed by two layers formed by tetrahedra of [(Si, Al) O4], it can be varied widely by a large number of substitutions in the layer octahedral. In this way the octahedral layer can contain next to the At 3+, which is preponderant in most cases (montmorillonite-stratified silicate dioctahedral) for example also Mg2 + (trioctahedral stratified saponite-silicate) or Fe 3+ (stratified nontronite-silicate dioctahedral). In addition, content is also contained in cations such as Zn 2+ (in the case of sauconite-trioctahedral stratified silicate), Ni 2+ (nickel silicate sauconite stratified trioctahedral) and Li + (trioctahedral stratified hectorite-silicate). Also in the tetrahedral layer substitutions of this mode Si 4+ may be replaced in part by Al 3+ (in the case of stratified baidelite-silicate dioctahedral) and also by Fe 3+ (in the case of nontronite-dioctahedral stratified silicate). TO from these substitutions results an imbalance in the load balance that is compensated between the layer packages through interchangeable cations, usually sodium, calcium and Potassium, also magnesium.

As general formulas they can be indicated for dioctahedral phyllosilicates, therefore

(K, Ca, Na, Mg) i + [Si_4-x (Al, Fe3 +) xO10] [(Al, Fe3 +) 2- y (Mg, Fe 2+) and + 2 (OH) 2]

with i = approximately 0.6 until 0.2 for each O 10 (OH) 2 and also i = x + y - 2z and for phyllosilicates trioctahedral

(K, Ca, Na, Mg) i + [Si_ 4-x Al_ O x 10] [(Mg, Fe 2+) 3-y (Al, Fe 3 +) yz (OH) 2]

with i = x - y + 3z and 0.6 <i < 0.2.

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They will preferably be used in the field of present invention bentonites in the classical sense, that is Clays with a high content of Montmorillonite. The components preferred c) are phyllosilicates with a content of Montmorillonite above 60% by weight, preferably by above 75% by weight and, especially, above 90% in weight, referred respectively to the weight of the phyllosilicate.

As long as this is not desirable, For reasons of cost, the Pure Montmorillonite They are equally preferred according to the invention. the components of cleaning agents that contain Montmorillonite pure as bentonite.

The distance between the layers of the phyllosilicates can be modified by incorporating certain compounds, since they can swell - depending on the loading of the elementary layers and the cations of the layer intermediate - that is, the basic distance of your package with three layers can also be increased by occlusion of water molecule or long chain organic molecules up to a value greater than 15 \ ring {A}. In this way they can be used also, according to the invention, chemically modified bentonites to component mode c), the components of the components being preferred cleaning agents containing bentonites modified by quaternary ammonium compounds.

The components for cleaning agents Preferred, within the scope of the present invention, contain as component c) products of the clay minerals group, preferably from chemically modified clay minerals and, especially, of hydrophobic bentonites.

Other solid products, to be used in the scope of the present invention preferably as a component  c), are the ionic surfactants, as long as they present a melting point high enough and can be brought to the quoted range of particle sizes. These Surfactants have been described in detail above. In this case are especially preferred as component c) the sulfates of fatty alcohols, so that they will be preferred those components of cleaning agents that contain component mode c), one or more anionic surfactants, preferably sulfates of fatty alcohols and, especially, sulfates of fatty alcohols with 12 to 18 carbon atoms.

The components of cleaning agents according to the invention may preferably contain, as component d) other active products and / or auxiliary products of the group of colorants, odorizing products, polymers releasing the dirt, corrosion inhibitors, enzymes, bleaching agents, bleach activators or complexing agents in quantities from 0 to 10% by weight, preferably from 0.25 to 7.5% in weight, especially preferably from 0.5 to 5% by weight and especially from 0.75 to 2.5% by weight. The dyes and the odorizing products as well as the other substances mentioned are usual components of the washing or cleaning agents and described below in detail.

As already indicated above, they can be specifically modified, by choosing components a) to d), the physical and chemical properties of components of the cleaning agents according to the invention. When Only components that are liquid are used for example. the melting temperature of the emulsion, can be prepared easily single-phase mixtures that will be characterized by a special storage stability even in molten state. The addition of solid products, such as pigments for example dyes or products with high melting points, leads automatically to biphasic mixtures that, however, present also excellent storage stability and a extraordinarily reduced tendency to disintegration.

Regardless of the composition of the components of the cleaning agents according to the invention are preferred those components of the cleaning agents that are characterized by a melting point between 50 and 80 ° C, preferably between 52.5 and 75 ° C and, especially, between 55 and 65 ° C.

At room temperature the components of the cleaning agents according to the invention represent mixtures solidified constituted by the aforementioned components, which may Take any external form. It is also possible to apply the blends in a state of fusion on support materials and manufacture thus components of cleaning agents based on support material consisting of one or more solid support materials at room temperature and by a solidified fusion on these support materials. How supporting materials are suitable all solid products that do not soften at the melting temperature and that, in addition, have a sufficiently high absorption capacity for fusion. Especially preferred support materials are structuring products, which have been described in more detail ahead.

Another object of the present invention is constituted by a procedure for obtaining components of cleaning agents in the form of particles, in which a merger constituted by

to)

since 10 to 89.9% by weight of one or more surfactants,

b)

since 10 to 89.9% by weight of one or more fusible substances with a melting point above 30 ° C and a solubility in water less than 20 g / l at 20 ° C,

C)

since 0.1 to 15% by weight of one or more products solids,

d)

since 0 to 15% by weight of other active products and / or auxiliary

on one or several materials of stand and mix transform by molding

In this variant of the procedure it is prepared, in first, a suspension or a fusion emulsion, which May contain other active and auxiliary products. This is added to a support material and is transformed by molding in mixture with this support material.

In the case of the aforementioned procedure for obtaining for the components of the cleaning agents according to the invention variants of the process are preferred in which the fusible substance constitutes from 25 to 85% by weight, preferably from 30 to 70% by weight and, especially, from 40 to 50% by weight of the fusion.

The application of the merger on the material of support can be carried out completely by means of mixing devices The molding transformation stage of the mixture constituted by the fusion and the support material not is subject to any limitations related to the technology of procedure so that the technician can choose also in this case the most familiar procedure. During trials conducted by the applicant they have been presented as preferred those procedures in which the transformation by molding is carried out by granulation, compaction, pelletization, extrusion or entablatting.

The method according to the invention encompasses the application of the merger, consisting of components a) up to d), on the support materials. In principle they can be contents of the fusion and the support material (s) in quantities variables in the particles for rinse rinse resulting. Preferred procedures are characterized because a mixture consisting of a 5 is transformed by molding up to 50% by weight, preferably 10 to 45% in weight, especially preferably by 15 to 40% in weight and, especially, by 20 to 35% by weight of a fusion formed by components a) to d) and 50 to 95% in weight, preferably from 55 to 90% by weight, so especially preferred by 60 to 85% by weight and, especially, for 65 to 80% by weight of the or support materials As regards the components that they are used in the process according to the invention and that transform to give the components of cleaning agents based on support material, according to the invention, is valid, of analogously what was said above.

The components of the cleaning agents according to the invention can also be formulated in the absence of support materials so that they are only constituted by components a) to d). For the manufacture of cleaning agent components according to the invention, in the form of particles, in this case, the transformation into beads, the filling and the scaling by means of refrigeration cylinders has been especially proven
tion.

Another object of the present invention is constituted, therefore, in a first embodiment, by a procedure for obtaining components of agents from cleaning in the form of pearls, in which it is introduced, through a nozzles, a merger consisting of

to)

since 10 to 89.9% by weight of one or more surfactants,

b)

since 10 to 89.9% by weight of one or more fusible substances with a melting point above 30 ° C and a solubility in water less than 20 g / l at 20 ° C,

C)

since 0.1 to 15% by weight of one or more products solids,

d)

since 0 to 15% by weight of other active products and / or auxiliary

in a gas stream cold.

The process according to the invention, which is abbreviated as pearl formation encompasses obtaining  of granular bodies from fusible products, pulverizing the fusions constituted by the components a) to d) at the apex of a tower, in droplet sizes defined, which solidify in free fall and the pearls are they get as granules at the bottom of the tower.

As cold gas stream they can be used, of in a very general way, all those gases whose temperature of the gas is below the melting temperature of the fusion. To avoid large solidification paths, it work frequently with refrigerated gases, for example with very cold air or even with liquid nitrogen, which is introduced to through nozzles in the spray tower.

The grain size of the pearls formed can be modified by choosing the size of the droplets, finding the particle sizes that can be made easily from an industrial point of view, in the interval from 0.5 to 2 mm, preferably about 1 mm.

An alternative procedure to training of pearls, consists of the formation of pills. Another way to embodiment of the present invention therefore provides a procedure for obtaining components of agents of pill-shaped cleaning, in which a fusion is dosed constituted by

to)

since 10 to 89.9% by weight of one or more surfactants,

b)

since 10 to 89.9% by weight of one or more fusible substances with a melting point above 30 ° C and a solubility in water less than 20 g / l at 20 ° C,

C)

since 0.1 to 15% by weight of one or more products solids,

d)

since 0 to 15% by weight of other active products and / or auxiliary

on forming plates of pills, refrigerated

The formation of pills, which occasionally also called pelletized, covers the dosage of the fusion consisting of components a) to d) on turntables suitable that have a temperature below the melting temperature of the melting and cooling, preferably, below room temperature. Also in in this case variants of the procedure can be carried out in the which plates for patching are refrigerated to very low temperatures In this case, of course, they should be taken measures against condensation of air humidity.

The patterning provides larger particles that, in the case of the usual industrial procedures, they have sizes between 2 and 10 mm, preferably between 3 and 6 mm.

As an even cheaper variant for obtaining of the components of cleaning agents in the form of particles with the composition indicated from fusions, are offers the use of refrigeration cylinders. Another object of the The present invention is therefore constituted by a procedure for obtaining components of agents of cleaning in the form of particles, in which it is applied or sprayed a merger consisting of

to)

since 10 to 89.9% by weight of one or more surfactants,

b)

since 10 to 89.9% by weight of one or more fusible substances with a melting point above 30 ° C and a solubility in water less than 20 g / l at 20 ° C,

C)

since 0.1 to 15% by weight of one or more products solids,

d)

since 0 to 15% by weight of other active products and / or auxiliary

on a cooling cylinder, the solidified fusion is chipped and, if necessary, crumble

The use of refrigeration cylinders enables a smooth adjustment of the desired interval for the particle size that in this procedure according to the invention can be below 1 mm, for example from 200 to 700 µm.

It is obviously possible also, according to the invention, press the compositions in the form of particles to give a molded body or a segment thereof. This molded body it can then be dosed by the user but nevertheless it can also be mixed with powdery compositions. It is also possible to use the compositions in the form of particles, especially pearls, pads or cylinder products  refrigeration, in the form of a pre-mix capable of being transformed into tablets and used in the manufacture of bodies multi-phase molding. In this case the pressing provides so, for example, tablets with several layers, one of whose layers presents the composition of cleaning agents tablets traditional, presenting the other layers the composition of the components of the cleaning agents according to the invention, which also develop in this form of marketing their advantages.

Polyphase molded bodies can be also manufactured by manufacturing molded bodies with cavities, for example cavities or through holes and filling of These cavities then with other molded bodies. At Present case has been proven that the "base body" is say the tablet, which has a cavity, has the composition of a tablet of washing agent while the molded body cavity content is a molded body that has been pressed to from pearls, pills or scales. The adhesion of both bodies molded together can be achieved by gluing both molded bodies, however it is also possible to press superficially or crimping molded bodies. Mutual insertion is also possible, at the time of adhesion due to the geometric configuration of the cavity and of load.

As manufacturing process is preferred, for example, the manufacturing of the molded body by separate manufacturing (pressing) of a base molded body a) and of a molded core body b), which is preferably pressed to starting from beads of components for cleaning agents according to the invention, the meeting and the final pressing of both pieces.

The manufacture of molded bodies from components of the cleaning agents according to the invention in the form of particles can be carried out according to the usual procedures for the entabletado. These have been described in more detail more ahead.

The molded bodies can be manufactured in this case with a predetermined spatial shape and with a size predetermined. As a spatial form they come into consideration virtually all configurations that can be manipulated suitably, for example the formation in the form of a table, of barreta or of bars, of dice, of parallelepiped and elements corresponding spatial with flat side surfaces as well as especially cylinder-shaped configurations with section circular or oval cross. This last configuration covers in this case the way of marketing tablets up to pieces compact cylindrical with a relationship between height and diameter above 1.

The molded body, manufactured, can take any geometric shape, especially preferred concave, convex, biconcave, biconvex, cubic forms, tetragonal, orthorhombic, cylindrical, spherical, shaped cylinder segment, disk-shaped, tetrahedron-shaped, in dodecahedron shape, octahedron shaped, conical shaped, pyramidal, ellipsoid, prismatic pentagonal, heptagonal and octagonal as well as in rhombohedral form. Can also be done completely irregular base surfaces such as shaped arrow or animal-shaped, tree, cloud, etc. When he molded body, manufactured, present corners and edges, these They will be preferably rounded. As optical differentiation additionally an embodiment with corners is preferred rounded and with beveled edges ("chamfered").

The components of cleaning agents according to The invention can be delivered to the user directly in the hand so that you can dose them further according to the Cleaning agent needs. Because of this additional stage dosing would minimize, however, the advantages over Rinse agents for rinsing, liquids, except as which refers to the solid form of marketing and the addition in the same drawer. Therefore it is preferred to mix the components of the cleaning agents according to the invention with Agents for machine scrubbing of tableware in the form of particles or incorporate these into the molded body.

Another object of the present invention is constituted, therefore, by the use of agent components of cleaning in the form of particles constituted by

to)

since 10 to 89.9% by weight of one or more surfactants,

b)

since 10 to 89.9% by weight of one or more fusible substances with a melting point above 30 ° C and a solubility in water less than 20 g / l at 20 ° C,

C)

since 0.15 to 12.5% by weight of one or more products solids,

d)

since 0 to 15% by weight of other active products and / or auxiliary

in cleaning agents for the machine scrubbing crockery.

Another object of the present invention is also constituted by an agent for machine scrubbing of the particle-shaped tableware, which contains products structuring as well as other components, optional, of the cleaning agents, containing components of cleaning agents in the form of particles, which contain, based on weight

to)

since 10 to 89.9% by weight of one or more surfactants,

b)

since 10 to 89.9% by weight of one or more fusible substances with a melting point above 30 ° C and a solubility in water less than 20 g / l at 20 ° C,

C)

since 0.15 to 12.5% by weight of one or more products solids,

d)

since 0 to 15% by weight of other active products and / or auxiliary

The components of the agents for scrubbing to tableware machine, described below. Partly these they can also be contained as component d) or as materials of support in the components of the cleaning agents according to the invention.

The most important components of the agents For machine scrubbing of the dishes are the products structuring In cleaning agents, according to the invention, for machine washing of dishes, they can be used, so therefore, all the structuring products usually used in the washing and cleaning agents employed, especially by therefore, zeolites, silicates, carbonates, organic adjuvants and -when there is no ecological objection against their employment- even those phosphates The structuring products mentioned below are fully suitable as support materials for components of the cleaning agents according to the invention, such as It has already been indicated above.

Crystalline sodium silicates, in the form of adequate layers have the general formula NaMSi_ {O} {2x + 1} • H 2 O, where M means sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, and the preferred values for x are 2, 3 or 4. This type of silicates Layered crystals are described, for example, in the application for European patent EP-A-0 164 514. The layered crystalline silicates, preferred, of the indicated formula, are those in which M is sodium and x takes the values 2 or 3. Especially preferred are both the β and the δ sodium silicates Na_ {2} Si_ {2} O_ {5} \ cdotyH_ {2}, being able to obtain the sodium?-silicate, for example, according to procedure described in the patent application International WO-A-91/08171.

Amorphous silicates can also be used of sodium with a Na 2 O: SiO 2 module from 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and especially 1: 2 to 1: 2.6, which they are of delayed dissolution and have secondary properties of washed. In this case, the delay in dissolution, compared to traditional amorphous sodium silicates, may have been produced in different ways, for example through surface treatment, composition, compaction / compression or through the overestimate. In the scope of the present invention, by the concept "amorphous" is also understood as "amorphous for X-rays. "This means that silicates, in the case of X-ray diffraction experiments, do not provide reflections defined x-rays, such as those typical for crystalline substances, but at most one or several maxima of the scattered x-ray radiation, which have an angle width diffraction of several units of degrees. However, they can get, even very well, good adjuvant properties, if silicate particles provide little diffraction maximums clear or even defined. This should be interpreted such that microcrystalline products have areas with a size of 10 to a few hundred nm, with values up to a maximum of 50 being preferred nm and especially up to a maximum of 20 nm. This type of silicates called amorphous x-rays, which also have a Delay in dissolution against soluble glasses traditional, are described, for example, in the request for German patent DE-A-44 00 024. It they especially prefer amorphous silicates compacted / compressed, compound amorphous silicates and amorphous silicates for x-rays overlapped.

The zeolite used, finely crystalline, synthetic, which contains bound water, is preferably zeolite A and / or P. Zeolite P is preferred as zeolite MAP® (commercial product from Crosfield). However, zeolite is also suitable X, as well as mixtures of A, X and / or P. A product that can Obtained commercially and preferably used in the field of the present invention, it is also a co-crystallized product of zeolite X and zeolite A (approximately 80% by weight of zeolite X), marketed by CONDEA Augusta S.p.A. under the name commercial VEGOBOND AX®, and that can be described by means of the formula

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

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

Obviously, it is also possible to use phosphates generally known as adjuvant substances. Between large amount of phosphates that can be purchased commercially, in the washing agents and cleaning agents industry alkaline metal phosphates are most important, especially preferred pentasodium triphosphate or pentapotassium triphosphate (sodium or potassium tripolyphosphate).

Phosphates of alkali metals represent in this case a general designation for metal salts alkaline (especially sodium and potassium) of the various phosphoric acids, in which one can distinguish between acids metaphosphoric (HPO3) n and orthophosphoric acid H 3 PO 4 in addition to representatives of greater molecular weight. Phosphates in this case have several advantages: they act as alkali carriers, prevent lime coatings and They also contribute to the cleaning power.

Sodium Dihydrogen Phosphate, NaH 2 PO 4, exists as dihydrate (density 1.91 gcm-3, melting point 60 °) and as a monohydrate (density 2.04 gcm <3>). Both salts are white powders that dissolve very easily in water, they lose in water of crystallization by heating and that transform to 200º in the diphosphate weakly acidic (disodium hydrogenodiphosphate, Na 2 H 2 P 2 O 7), at higher temperatures it converted to sodium trimetaphosphate (Na 3 P 3 O 9) and in Maddrell salt (see below). The NaH_ {PO} {4} has acid reaction; is formed when phosphoric acid is adjusted to a pH value of 4.5 with sodium hydroxide bleach and spray the broth. Potassium Dihydrogen Phosphate (Potassium Phosphate primary or monobasic, potassium bisphosphate, KDP), KH2PO4 it is a white salt with a density of 2.33 gcm -3, it has a melting point of 253º [decomposition with polyphosphate formation of potassium (KPO3) x] and dissolves easily in Water.

Disodium hydrogen phosphate (sodium phosphate secondary), Na 2 HPO 4, is a colorless, crystalline salt that It dissolves very easily in water. It exists in anidia state and with 2 moles (density 2,066 gcm -3, water loss at 95 °), with 7 moles (density 1.68 gcm-3, melting point 48 ° with loss of 5 H 2 O) and with 12 moles of water (density 1.52 gcm-3, point melting 35 °) with loss of 5 H 2 O), at 100 ° it becomes anhydrous and it is transformed by strong heating in diphosphate Na 4 P 2 O 7. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with carbonate solution of sodium using phenolphthalein as an indicator. He dipotassium hydrogen phosphate (secondary potassium phosphate or dibasic), K 2 HPO 4, is a white, amorphous salt, which is dissolves easily in water.

Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 is formed by colorless crystals, which they have a density of 1.62 gcm -3 as a dodecahydrate and a melting point of 73-76º (decomposition), in form of decahydrate (which corresponds to 19-20% of P 2 O 5) have a melting point of 100 ° and in shape anhydrous (which corresponds to 39-40% of P 2 O 5) have a density of 2,536 gcm-3. He Trisodium phosphate is easily soluble in water with reaction alkaline and is prepared by concentration by evaporation of a solution consisting exactly of 1 mol of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary potassium phosphate or tribasic), K 3 PO 4, is a white granular powder, spreadable with a density of 2.56 gcm -3, has a point of fusion of 1,340º and is easily soluble in water with reaction alkaline It is formed, for example, by heating the slags of the Thomas procedure with coal and potassium sulfate. TO despite its higher price they are preferred many times in the industry of cleaning agents potassium phosphates that dissolve more easily and therefore have more activity, against the corresponding sodium compounds.

Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7, exists in anhydrous form (density 2,534 gcm <3>, melting point 988º, the value of 880º) and as decahydrate (density 1,815-1,836 gcm -3, melting point 94 ° with water loss). Both substances are colorless, water soluble crystals with reaction alkaline The Na 4 P 2 O 7 is formed by heating the disodium phosphate at> 200 ° or by reaction of phosphoric acid with sodium carbonate in stoichiometric proportions and dehydration  of the solution by spraying. Decahydrate forms complexes with heavy metal salts and with formators of the hardness and therefore reduces the hardness of water. The diphosphate of potassium (potassium pyrophosphate), K4 P2O7, exists in Trihydrate form and represents a colorless, hygroscopic powder with a density of 2.33 gcm -3, which is soluble in water, being the pH value of the solution at 1%, at 25 °, of 10.4.

By condensation of NaH_2PO4 or Sodium and potassium phosphates form well from KH2PO4 of high molecularity, in which they can be distinguished cyclic representatives, sodium metaphosphates or potassium or chain-shaped types, sodium polyphosphates or Potassium Especially for the latter, a large number of denominations: fusion or calcination phosphate, salt of Graham, leave Kurrol and Maddrell. All sodium phosphates and Potassium levels are referred to jointly as phosphates condensed

The important pentasodium triphosphate industrially, Na 5 P 3 O 10 (sodium tripolyphosphate), is  an anhydrous or crystallized salt with 6 H 2 O, non-hygroscopic, white, water soluble, of the general formula NaO- [P (O) (ONa) -O] n -Na with n = 3. At room temperature they dissolve in 100 g of water approximately 17 g, at 60º approximately 20 g, at 100º approximately 32 g of the salt free of crystallization water; to the After a 2-hour heating of the solution at 100 °, by hydrolysis, approximately 8% orthophosphate and 15% of diphosphate. In obtaining pentasodium triphosphate, it is done react the phosphoric acid with sodium carbonate solution or with bleach of sodium hydroxide in stoichiometric proportions and The solution is dehydrated by spraying. By way of similar to that of Graham salt and as sodium diphosphate, the pentasodium triphosphate dissolves many metal compounds insoluble (also lime soaps, etc.). Triphosphate Pentapotassium, K 5 P 3 O 10 (potassium polyphosphate), is found in commerce for example in the form of a solution to 50% by weight (> 23% of P2O5, 25% of K2O). He potassium polyphosphate finds wide application in the washing and cleaning agents industry. Also there are sodium and potassium tripolyphosphates, which can also be used within the framework of the present invention. These occur, for example, when sodium trimetaphosphate is hydrolyzed with KOH:

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

These can be used, just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; can also be used according to the invention the mixtures of sodium tripolyphosphate and sodium tripolyphosphate and potassium or mixtures of potassium tripolyphosphate and tripolyphosphate of sodium and potassium or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium and potassium tripolyphosphate.

As organic adjuvants they can be used in accommodation cavities, within the scope of the present invention, especially polycarboxylates / polycarboxylic acids, Polycarboxylates polymers, asparagine acid, polyacetals, dextrins, other organic adjuvants (see above for more forward), as well as phosphonates. These kinds of substances are described below.

The employable organic adjuvants are, by example, polycarboxylic acids that can be used in the form of its sodium salts, understood as polycarboxylic acids those carboxylic acids that carry more than one acidic function. These are, for example, citric acid, adipic acid, acid succinic, glutaric acid, malic acid, tartaric acid, acid maleic, fumaric acid, saccharic acids, aminocarboxylic acids,  nitrilotriacetic acid (NTA), provided that this type of use does not can be rejected for ecological reasons, as well as mixtures of same. Preferred salts are salts of acids 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 its adjuvant effect, acids also have typically the property of an acidification component and, with this also serves to adjust a low and soft pH value of washing agents and cleaning agents. Here they must especially named citric acid, succinic acid, acid glutaric acid, adipic acid, gluconic acid and any mixture of these.

In addition, adjuvants are suitable polymeric polycarboxylates, these are, for example, the salts of alkali metals of polyacrylic acid or acid polymethacrylic, for example those with a relative molecular weight from 500 to 70,000 g / mol.

As for the molecular weights indicated for Polycarboxylate polymers are treated, in the sense of this document, of molecular weights M_ {w} average in weight of the form of the acid, which were basically determined by gel permeation chromatography (GPC), for which a UV detector. In this regard, the measurement was performed against to an external standard of polyacrylic acid, which provides values of molecular weight similar to the real ones due to their affinity structural with the polymers analyzed. These data differ. markedly of the molecular weight data for which uses a pattern of polystyrene sulfonic acids. The pesos Molecules measured against polystyrene sulfonic acids are in general markedly higher than molecular weights indicated in this document.

Suitable polymers are, especially, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Due to their greater solubility, they can be preferred, within this group, in turn polyacrylates of short chain, which have molecular weights from 2,000 to 10,000 g / mol, and especially preferably from 3,000 to 5,000 g / mol

In addition, polycarboxylates are suitable copolymers, especially those of acrylic acid with acid methacrylic and acrylic acid or methacrylic acid with acid Maleic The copolymers have proved especially suitable of acrylic acid with maleic acid, containing 50 to 90% of Acrylic acid and 50 to 10% maleic acid. Its molecular weight relative, referred to free acid, is from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and especially from 30,000 to 40,000 g / mol.

Polycarboxylates (co) polymers can be used as a powder or as an aqueous solution. He agent content in polycarboxylates (co) polymers it is preferably from 0.5 to 20% by weight, especially from 3 to 10% by weight.

To improve solubility, polymers can also contain allylsulfonic acids as monomers, as per example allyloxybenzenesulfonic acid and metalylsulfonic acid.

Also especially preferred are biodegradable polymers consisting of more than two units of different monomers, for example those containing as monomers, salts of acrylic acid and maleic acid, as well as vinyl alcohol or derivatives of vinyl alcohol, or contain as monomers, salts of acrylic acid and acid 2-alkylsulfonic acid, as well as derivatives of sugar.

Other preferred copolymers are those that preferably acrolein and acrylic acid monomers / Acrylic acid salts or acrolein and vinyl acetate.

They should also be mentioned, like other substances preferred adjuvants, polymeric aminodicarboxylic acids, its salts or its precursor substances. Being especially polyasparaginic acids or their salts and derivatives are preferred, which also have a bleaching stabilizing effect, in addition of its properties as an adjuvant.

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

Other suitable organic adjuvant substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by hydrolysis partial starch. Hydrolysis can be performed according to usual procedures, for example catalyzed with acids or with enzymes Preferably it is hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol In this case, a polysaccharide with a Dextrose equivalent (SD) in the range from 0.5 to 40, especially from 2 to 30, the DE value being a usual measurement of the reducing effect of a polysaccharide compared to the dextrose, which has a DE value of 100. Both the maltodextrins, with a DE value between 3 and 20 and the dried glucose syrups with a DE value between 20 and 37, as well as the so-called yellow dextrins and dextrins white with higher molecular weights, in the range from 2,000 to 30,000 g / mol.

As for oxidized derivatives of this type of dextrins, it is their reaction products with agents oxidizers, which are capable of oxidizing at least one function alcoholic saccharide ring to give an acid function carboxylic. An oxidized product can be especially advantageous. in the C6 of the saccharide ring.

In addition, oxydisuccinates and other derivatives of Disuccinates, preferably ethylenediamine disuccinate are other suitable adjuvants. In this case the acid will be used N, N’-ethylenediamine-N, N-disuccinic (EDDS), preferably in the form of its sodium or magnesium salts. In this context, disuccinates of glycerin and glycerin trisuccinates. The amounts of Application, suitable, are from 3 to 15% by weight, in formulations, which contain zeolite and / or that contain silicate.

Other employable organic adjuvants are, by for example, acetylated hydroxycarboxylic acids or their salts, which, if appropriate, may also be present in the form of lactone and containing at least 4 carbon atoms and at least a hydroxyl group, as well as, at most, two acidic groups.

Another class of substances with properties adjuvants are phosphonates. In this case it is, especially, of hydroxyalkane phosphonates or aminoalkane. Among hydroxyalkane phosphonates, it has a special meaning 1,1-hydroxyethane 1,1-diphosphonate (HEDP) as an adjuvant. It will preferably be used as salt of sodium, with the disodium salt having a neutral reactivity and the salt Tetrasodium alkaline reactivity (pH 9). As phosphonates of aminoalkane preferably include phosphonate of ethylenediaminetetramethylene (EDTMP), the phosphonate of diethylenetriaminepentamethylene (DTPMP), as well as their counterparts superior. They will preferably be used in the form of the salts of neutral reactivity sodium, for example as the hexasodium salt of EDTMP or as a heptasodium and octasodium salt of DTPMP. In this case, preferably, the HEDP will be used among the class of phosphonates In addition, aminoalkane phosphonates have a marked binding capacity with heavy metals. Therefore it can be preferably using aminoalkane phosphonates, especially the DTPMP, or mixtures of the aforementioned phosphonates, especially when The agents also contain bleaching agents.

In addition, all can be used as adjuvants compounds capable of forming complexes with ions alkaline earth.

Agents for machine scrubbing of the dishes, preferred according to the invention, contain products Structuring in amounts from 20 to 80% by weight, preferably from 25 to 75% by weight and, especially, from 30 to 70% by weight, referred, respectively, to the weight from the people.

In addition to structuring products, they are important component of cleaning agents, especially the products of the groups of the surfactants, of the agents of bleaching, bleaching activators, enzymes, polymers as well as dyes and odorizing products. The following are important representatives of the classes of substances cited, referring to the description of the surfactants to the explanations given more above.

Agents for machine scrubbing of the tableware, in the form of particles, also contain one or more products from the group of bleaching agents, activators bleaching, bleaching catalysts, surfactants, of corrosion inhibitors, of polymers, of colorants and odorizing products, agents for adjust the pH of the complexers and enzymes.

Among the compounds, which serve as an agent of bleaching, which provide H2O2 in water, has especially meaning sodium percarbonate. Other agents of employable bleaching are, for example, perborate tetrahydrate sodium sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates, as well as salts peracids that provide H 2 O 2 or peracids, such such as perbenzoates, peroxophthalates, diperacelaic acid, phthaloiminoperácido, or diperdodecanoic diacid.

In this case "sodium percarbonate" is a name used in a non-specific manner for sodium carbonate peroxohydrates, which, from a point of view Strictly, they are not "percarbonates" (ie acid salts percarbonic) but hydrogen peroxide adducts on carbonate of sodium. The commercial article has the average composition 2 Na_ {2} CO_ {3} \ cdot3 H2 {O2} and, therefore, is not a peroxycarbonate Sodium percarbonate forms a white powder, soluble in water, with a density of 2.14 gcm -3, which is decomposes to give sodium carbonate and oxygen action bleaching or oxidizing.

The sodium carbonate peroxohydrate was obtained for the first time in 1899 by precipitation with ethanol from of a solution of sodium carbonate in hydrogen peroxide, but It was mistakenly considered as peroxycarbonate. In 1909 it recognized the compound as peroxide addition compound of hydrogen, however it has been established in practice the historical name of "sodium percarbonate".

The industrial manufacture of sodium percarbonate is usually carried out by precipitation from aqueous solution (the wet process). In this case, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and sodium percarbonate is precipitated by salification agents (predominantly sodium chloride), auxiliary agents for crystallization (for example polyphosphates, polyacrylates) and stabilizers ( for example Mg2 + ions). The precipitated salt, which still contains from 5 to 12% by weight of the mother liquors, is then separated by centrifugation and dried at 90 ° C in the fluidized bed dryer. The bulk weight of the finished product can range between 800 and 1200 g / l according to the manufacturing procedure. As a general rule, the percarbonate will be stabilized by an additional coating. The procedures for coating and products, which are used for coating, are widely described in the patent literature. Basically, all the usual types of percarbonate can be used according to the invention, such as those offered, for example, by the firms Solvay Interox, Degussa, Kemira or
Akzo

The cleaning agents, according to the invention, may also contain bleaching agents from the group of organic bleaching agents. Typical examples of the agents of Organic bleaching are diacyl peroxides, such as by example dibenzoyl peroxide. Other bleaching agents typical organic are peroxyacids, and should be cited in a manner especially exemplary alkylperoxyacids and arylperoxy acids. Preferred representatives are (a) the acid peroxybenzoic and its substituted ring derivatives, such such as alkylperoxybenzoic acids as well as acid peroxy-? -naphthoic and the magnesium monoperphthalate, (b) aliphatic peroxyacids or substituted aliphatics, such as peroxylauric acid, acid peroxystearic acid ε-phthalimidoperoxicapronic [acid phthaloiminoperoxyhexanoic acid (PAP)], the acid o-carboxybenzamidoperoxicapronic acid, the acid N-nonenylamidoperadipic and N-nonenylamidopersuccinate, and (c) acids aliphatic and araliphatic peroxy dicarboxylic acids, such as acid 1,12-di-peroxycarboxylic acid 1,9-diperoxyazelaic acid, diperoxisebacic acid, diperoxybrasilic acid, diperoxyxtalic acids, acid 2-decyldiperoxybutane-1,4-dicarboxylic acid, the acid N, N-terephthaloyl-di (6-aminopercapronic).

According to the present invention, they can be used, also, as bleaching agents substances that release chlorine or bromine. Among the suitable materials, which release chlorine or bromine, come into consideration, for example, N-bromoamides and heterocyclic N-chloroamides, for example acid trichloroisocyanuric acid, tribromoisocyanuric acid, acid dibromoisocyanuric and / or dichloroisocyanuric acid (DICA) and / or its salts with cations, such as potassium and sodium. They are also suitable hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin.

Similarly, the bleaching agents mentioned can be incorporated into the agents for machine scrubbing of the tableware, in part, through the components of the agents of cleaning, in which they represent the component d) according to the invention to achieve a "final bleaching",

Bleach activators, which reinforce the effect of bleaching agents are, for example compounds that they contain one or more N- or O-acyl groups, such as substances of a class of anhydrides, esters, of imides and acylated imidazoles or oximes. Examples they are tetraacetylstylenediamine (TAED), tetraacetylmethylenediamine (TAMD) and tetraacetylhexylenediamine (TAHD), as well as the pentaacetylglucose (PAG), the 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine (DADHT) and isatosauric acid anhydride (ISA).

Whitening activators can be used compounds that provide, under perhydrolysis conditions, aliphatic peroxocarboxylic acids, preferably with 1 to 10 carbon atoms, especially with 2 to 4 carbon atoms, and / or Perbenzoic acid, if substituted. Substances suitable are those that carry O- and / or groups N-acyl with the aforementioned number of carbon atoms and / or benzoyl groups, 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 glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), phenolsulfonates acylates, especially n-nonanoyl- or isononanoyloxybenzene (n-, or iso-NOBS), carboxylic acid anhydrides, especially acid anhydride phthalic, polyvalent acylated alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, methylsulfate n-methyl-morpholinium-acetonitrile  (MMA), and the enol esters known for the applications of German patents DE 196 16 693 and DE 196 16 767, as well as sorbitol and acetylated mannitol and mannitol or mixtures thereof (SORMAN), derivatives of acylated saccharics, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetylactose, as well as glucamine and acetylated glucolactone, if necessary N-rented, and / or lactams N-acylated, by way of example N-benzoylcaprolactam. The substituted acylacetals by hydrophilic route and acillactams, they are used equally preferential. Activator combinations can also be used of conventional bleaching.

In addition to bleach activators conventional, or instead, you can also incorporate called bleaching catalysts. In the case of these substances are transition metal salts, or transition metal complexes, which reinforce bleaching, such as for example salt complexes or carbonyl complexes of Mn, Fe, Co, Ru or Mo. They are also used as bleaching catalysts Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes, with tripod ligands, nitrogen, as well as amino complexes of Co, Fe, Cu and Ru.

Preferably activators of bleaching of the group of polycylated alkylenediamines, especially tetraacetylethylenediamine (TAED), the N-acylamides, especially the N-nonanoylsuccinimide (NOSI), phenolsulfonates acylates, especially n-nonanoyl- or sulphonate of isononanoyloxybenzene (n- or iso-NOBS), methylsulfate n-methyl-morpholinium-acetonitrile (MMA), preferably in amounts of up to 10% by weight, especially from 0.1 to 8% by weight, so especially preferred from 2 to 8% by weight and, in a way especially preferred from 2 to 6% by weight, based on agent set.

The transition metal complexes bleaching boosters, especially with the central atoms Mn, Fe, Co, Cu, Mo, V Ti and / or Ru, preferably chosen from the group formed by salts and / or manganese and / or cobalt complexes, of the cobalt complex (amine), the complete cobalt (acetate), the cobalt complex (carbonyl), Cobalt or manganese chlorides, manganese sulfate, are used in usual amounts, preferably in an amount of up to 5% by weight, especially from 0.0025% by weight up to 1% by weight and, especially preferably from 0.01% in weight up to 0.25% by weight, referred respectively to the set from the people. However, in special cases they can also be used various bleach activators.

Enzymes, especially those of the classes of hydrolases, such as proteases, esterases, lipases, or enzymes of lipolytic action, amylases, cellulases, or other glycosylhydrolases, and mixtures of the aforementioned enzymes come into consideration. All these hydrolases contribute, in washing, to the removal of stains, such as stains containing protein, fat or starch, and grated. In addition, cellulases and other glycosylhydrolases can contribute, by eliminating pilling and microfibrils, to maintaining color and increasing the softness of the textile material. For bleaching, or for the inhibition of color flow, oxirreductases can also be used. Enzyme active products, obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens , as well as enzymatic active products obtained from their genetically modified variants are very particularly suitable. Preferably subtilisin type proteases are used, and especially proteases, which are obtained from Bacillus lentus. In this case, enzymatic mixtures are of particular interest, for example from protease and amylase, or protease and lipase, or enzymes of lipolytic action, or protease and cellulase, or from cellulase and lipase, or enzymes of action lipolytic, or from protease, amylase and lipase, or enzymes of lipolytic action or protease, lipase, or enzymes of lipolytic action and cellulase, however, especially mixtures containing protease and / or lipase, or mixtures with enzymes of lipolytic action Examples of such enzymes of lipolytic action are known cutinases. Peroxidases or oxidases have also been shown adequate in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pululanases and pectinases.

Enzymes may be absorbed on support materials or may be embedded in substances of coating, for protection against decomposition early. The proportion of enzymes, of enzyme mixtures or of the enzymatic granules can suppose, for example, from about 0.1 to 5% by weight, preferably from 0.5 to 4.5% by weight.

To the agents for machine scrubbing of the dishes according to the invention can be added dyes and odorizing product to improve the aesthetic impression of trained products and provide the consumer in addition to performance, a "typical and unmistakable" product from the aesthetic and sensory point of view. As perfume scents or good odorizing product odorizing compounds can be used individual, for example synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. The odorizing compounds of type of esters are, for example, benzyl acetate, the phenoxyethyl isobutyrate acetate p-tert-butylcyclohexyl, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, glycinate ethylmethylphenyl, allylcyclohexyl propionate, propionate stiralyl and benzyl salicylate. To the ethers belongs, by For example, benzylethyl ether, aldehydes belong, for example linear alkalines with 8 to 18 carbon atoms, citral, citronelal, citronelliloxyacetaldehyde, cyclamenaldehyde, hydroxycitronal, lilial and bourgeonal, to ketones belong, for example the ionone, the α-isomethylionone and methyl ketyl ketone, to the alcohols belong anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, at hydrocarbons belong mainly terpenes, such as Limonene and Pinene. However, mixtures of different are preferred.  odorizing products, which together produce a smell note nice. Such scented essences may also contain mixtures of natural odorizing products, such as those that may Obtained from plant sources, for example the essence of pine, citrus, jasmine, patchouli, roses or Ylang-Ylang Essences of muscat, sage, chamomile, carnation, lemon balm, mint, cinnamon leaves, linden petals, juniper berries, vetiver, olibano, galbano and jara, as well as essence of orange blossom, neroli, orange peel and sandalwood.

Odorizing products can be incorporated directly in the cleaning agents, according to the invention, but it may also be advantageous to arrange the odorizing products on supports, which reinforce the adherence of the perfume on the clothes and to ensure that the smell of textile materials is Hold for a long time by slowly releasing the smell. They have been credited, for example, as support materials for this type cyclodextrins, being able to coat the complexes of cyclodextrin-perfume additionally with others auxiliary agents It is also possible to incorporate odorizing products as component d) in the components of cleaning agents, according to the invention, and leads to an impression of smell at the moment the machine is opened.

To improve the aesthetic impression of the agents according to the invention, these (or a part thereof) can color with suitable dyes. Suitable dyes, whose selection does not cause any difficulty to the expert, they have a high storage stability and insensitivity to other components of the agents and against the light, as well as neither do they have a marked substantivity against the substrates  to be treated with agents, such as glass, ceramic or tableware made of synthetic material, not to color them.

The cleaning agents, according to the invention, may contain corrosion inhibitors for the protection of scrubbed or machine objects, having a meaning special special agents for the protection of silver in the dishwashing machine sector. You can use the substances known from the state of the art. In general, they can used, above all, silver protective agents chosen from  the triazoles group, the benzotriazoles, the bisbenzotriazoles, of the aminotriazoles, of the alkylaminotriazoles and salts or complexes of metals transition. Especially preferred will be the benzotriazole and / or alkylaminotriazoles. In the formulations of cleaning agents also find chlorinated agents active, which can clearly reduce the corrosion of silver surfaces In chlorine-free cleaners frequently find application, in particular, compounds organic, with redox activity, containing oxygen and nitrogen, such as divalent and trivalent phenols, for example the hydroquinone, pyrocatechin, hydroxyhydroquinone, acid Gallic, floroglucin, pyrogallol or derivatives thereof classes of compounds. They also find frequent application inorganic saline and complex type compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce. In this case they are Preferred are the salts of the transition metals, which are chosen from the group of salts and / or manganese complexes and / or cobalt, especially preferably of the complexes of cobalt (amine), of cobalt (acetate) complexes, of complexes of cobalt- (carbonyl), cobalt chlorides or manganese and manganese sulfate. In the same way they can Zinc compounds are used to prevent corrosion of scrubbed items.

Agents for machine scrubbing of the tableware in the form of particles, according to the invention, may contain to the components of the washing agents according to the invention in variable amounts, the content being more or less agree with the composition of the components of the cleaning agents and according to the desired success through its application. The agents for machine washing of particle-shaped dishes Preferred contain components of cleaning agents in the form of particles in amounts from 0.5 to 30% in weight, preferably from 1 to 25% by weight and, especially, from 3 to 15% by weight, referred respectively to the agent as a whole.

The components of the cleaning agents according to the invention can be configured as a prior step to their composition such that they do not dissolve in the main scrubbing program or that they only dissolve in a small proportion (and also in the optional pre-scrubbing programs) . In this way it is achieved that the surfactants are released only in the rinse rinse process and that they develop their effect during it. In addition to this chemical preparation, a physical preparation is required, depending on the type of dishwashing machine, so that the particles of the rinse rinse agent are not removed by pumping at the time of water replacement in the machine and, thus, are no longer available for rinse rinse. Domestic dishwashing machines contain in front of the bleach pump, which pumps water or cleaning solution out of the machine according to individual cleaning programs, a filter that should prevent the pump from clogging due to debris of dirt If the user scrubs very dirty dishes, this filter has to be cleaned regularly which is possible without problems due to its easy accessibility and the possibilities of its extraction. The components for the cleaning agents according to the invention are now configured according to their size and shape preferably in such a way that they do not pass through the dishwashing machine filter even after the cleaning program, that is after the cleaning program. request due to movement in the machine and cleaning solution. This ensures that the components of the cleaning agents in the rinse rinse process are in the dishwashing machine, which releases the active substance (s) under the effect of hot water and causes the desired effect. of rinse by rinsing. Within the scope of the present invention, agents for machine washing of tableware in the form of particles are preferred, characterized in that the components of the particulate cleaning agents have particle sizes between 1 and 40 mm, preferably between 1.5 and 30 mm and, especially, between 2 and
20 mm

In dishwashing agents according to the invention, the components of the cleaning agents with the sizes indicated above can stand out from the matrix of the other particulate components, however the other particles may also have sizes that are are in the range cited in such a way that together formulate a cleaning agent that will consist of coarse particles of cleaning agents and components of cleaning agents Especially when the components of cleaning agents according to the invention are colored in the dough, for example they have a red, blue, green or yellow color, it is advantageous for the appearance of the product, that is to say of the whole of the cleaning agent than the components of the agents cleaning are visibly greater than the matrix constituted by particles of the remaining components of the cleaning agents. In this case, agents for machine scrubbing are preferred. the tableware in the form of particles, according to the invention, which submit (regardless of agent components particle-shaped cleaning) particle sizes between 100 and 6,000 µm, preferably up to 4,500 µm and, especially between 100 and 3,000 µm, being before all especially preferred particle sizes between 300 and 2,500 µm and, especially between 400 and 2,000 µm.

When cleaning agents according to the invention They are formulated in the form of a powdery mixture, may be presented -especially in the case of very different sizes between components of cleaning agents and matrix for agents cleaning - on the one hand a request for friction of the package, on the other hand the dosage may be different in two successive cleaning processes since the user does not have to always dose, necessarily, the same amount of agent cleaning and cleaning agent components. Whenever industrially desirable to always use an amount equal to cleaning process, this can be done by packaging, known by the person skilled in the art, of the agents according to the invention in bags consisting of water soluble sheets. An agent of the present invention also constitutes an agent. for machine washing of dishes, in the form of particles, characterized in that a dosage dose is presented in a bag consisting of water soluble foil.

In this way the user only has to arrange a bag in the drawer of your machine for the dishwashing, which contains, for example, an agent powder cleaner and various particles of components of agents cleaning, which stand out optically. This embodiment of the The present invention is therefore an optically alternative attractant regarding cleaning agent tablets Traditional

Since the user does not only use particulate cleaning agents for machine scrubbing  of the dishes, but you also want to use molded bodies, these constitute another object of the present invention. In this In case the merger consisting of components a) can be formulated up to d) in the form of a molded body phase, which, for example, It has the shape of a layer, of a core-shaped hairpiece, etc.

Another object of the present invention is constituted, therefore, by a molded body of the agents of Polyphasic cleaning for machine washing of dishes, which contains structuring products as well as, optionally, others components of cleaning agents, one of whose phases, when less, it is constituted by

to)

since 10 to 89.9% by weight of one or more surfactants,

b)

since 10 to 89.9% by weight of one or more fusible substances with a melting point above 30 ° C and a solubility in water less than 20 g / l at 20 ° C,

C)

since 0.1 to 15% by weight of one or more products solids,

d)

since 0 to 15% by weight of other active products and / or auxiliary

The individual phases of the molded body can present, within the scope of the present invention, geometric shapes different. The simplest possibility of realization lies in the tablets with two layers or with several layers, representing each of The body layers molded a phase. However it is possible also, according to the invention, manufacture molded bodies with several phases, in which individual phases present the form of occlusions in one or several different phases. In addition to the called "ring-core type tablets" are possible in this case, for example, coated tablets or combinations of the cited embodiments. Examples of molded, multi-phase bodies have been described in the figures of EP-A-0 055 100 publication (Jeyes), which describe cleaning blocks for toilets. The shape geometrical most industrially extended today molded bodies with several phases consists of tablets with two layers or with several layers. In the scope of the present invention it is preferred, therefore, that the phases of the molded body have the shape of layers and the molded body has 2, 3 or 4 phases

The molded bodies according to the invention can take any geometric shape, being especially preferred concave, convex, biconcave, biconvex, cubic forms, tetragonal, orthorhombic, cylindrical, spherical, shaped cylinder segment, disk-shaped, tetrahedron-shaped, in dodecahedron shape, octahedron shaped, conical shaped, pyramidal, ellipsoid, prismatic, pentagonal, heptagonal and octagonal as well as in rhombohedral form. Can also be done completely irregular base surfaces such as arrow or animal, tree, cloud, etc. When the molded bodies according to the invention have corners or edges, these will preferably be rounded. As differentiation additional optics an embodiment with corners is preferred rounded and with beveled edges ("chamfered").

Instead of stratified construction they can be also molded bodies, which contain the components of the cleaning agents, according to the invention, in form of other phases. In this case, the manufacturing of base bodies, which have one or several cavities and load or let the mergers constituted by the components a) to d) of the components of the agents of cleaning, according to the invention, in the cavities. Through this manufacturing process preferably bodies are produced molded cleaning agents with several phases, which are constituted by a base body, which has a cavity, and on the one hand, which is contained, at least in part, in the cavity.

The cavity, in the pressed part of such bodies molded, according to the invention, can present in this case any way. This can pass through the molded body, that is which can have a hole in different sides, for example in the upper side and the lower side of the molded body, without however, it may only be a cavity that does not pass through the entire molded body, whose hole is visible only on one side of the molded body. Also the shape of the cavity can Choose freely within wide limits. For reasons of Engineering economics have passed through holes, whose openings are on opposing surfaces of the molded body, and pressures with an opening on one side of the molded body In the preferred molded bodies of the agents washing and cleaning, the cavity has the shape of a through hole, whose openings are located on two surfaces Contrasts of the molded body. The shape of a through hole of this type can be freely chosen, with preference being given to molded bodies in which the through hole has a circular horizontal section, ellipse shaped, triangular, rectangular, square, pentagonal, hexagonal, heptagonal or octagonal Irregular shapes can also be made for holes such as arrow or animal shapes, of trees, of clouds, etc. In the same way as in molded bodies, in the case of the polygonal holes are preferred those with corners and  rounded edges or with rounded corners and with edges chamfering

The geometric forms of realization, previously cited, can be arbitrarily combined with each other. In this way molded bodies can be manufactured with the surface rectangular or square base and with circular holes as well as round molded bodies with octagonal holes, without being subject to no limit the multiplicity of possibilities combinatorics For reasons of engineering economics and due to the aesthetic impression that the consumer receives are especially preferred molded bodies with holes, in which the base surface of the molded body and the cross section of the hole have the same geometric shape, for example bodies molded with square base surface and square hole occluded in the center. In this case they are especially preferred annular molded bodies, i.e. shaped molded bodies of circle with circular hole.

When the principle is reduced to a hole cited above of the open hole on two opposite sides of the molded body, you reach molded bodies with a depression. The molded bodies of washing and cleaning agents according to the invention, in which the cavity has the form of a Depression are equally preferred. As in the case of "perforated molded bodies", the molded bodies according to the invention can also take in this embodiment any geometric shape, especially preferred concave, convex, biconcave, biconvex, cubic forms, tetragonal, orthorhombic, cylindrical, spherical, shaped cylinder segment, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal, heptagonal and octagonal binoculars as well as rhombohedral Base surfaces can also be made completely irregular such as arrow shapes or animals, trees, clouds, etc. When the molded body present corners and edges, these will preferably be rounded. As an additional optical differentiation, a embodiment with rounded corners and edges beveled ("chamfered").

Likewise, the form of depression, with molded bodies being preferred in which at less a depression can take concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, shaped cylinder segment, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal prismatic, heptagonal and octagonal as well as rhombohedral. They can also perform irregular forms of depression such as forms of arrow or animals, trees, clouds, etc. As in the In the case of molded bodies, depressions are preferred with rounded corners and edges or with rounded corners and with chamfered edges.

In the case considered above, the party contained, at least partially, in the cavity is constituted only for components a) to d) of the components of the cleaning agents However, it is also possible to introduce in the, or in the cavities, components of the cleaning agents based on support materials.

For reasons of the economics of the procedure are preferred, of course, molded bodies of the washing agents and cleaning with several phases, in which the part contained in the cavity is formed by

to)

since 10 to 89.9% by weight of one or more surfactants,

b)

since 10 to 89.9% by weight of one or more fusible substances with a melting point above 30 ° C and a solubility in water less than 20 g / l at 20 ° C,

C)

since 0.1 to 15% by weight of one or more products solids,

d)

since 0 to 15% by weight of other active products and / or auxiliary

The size of the depression or through hole compared to the total molded body depends on the desired application purposes of the molded body. Function of the amount of additional active substance to be charged in the remaining hollow volume and depending on what should be contained a lesser or greater amount of the components of the agents of cleaning, the size of the cavity may be varied. Independently For the purpose of application, molded bodies of washing and cleaning agents in which the volume ratio between the pressed part ("base molded body") and the components of cleaning agents be from 2: 1 to 100: 1, preferably from 3: 1 to 80: 1, especially preferably from 4: 1 to 50: 1 and, especially, from 5: 1 to 30: 1

In addition to the proportions in volume cited there may also be a proportion by weight of both parties, correlating each other both values through densities of the base molded body and respectively of the "core". Regardless of the density of the individual parts are preferred according to the invention those molded bodies of cleaning agents in which the weight ratio between the body base molding and the "core" is between 1: 1 until 100: 1, preferably from 2: 1 to 80: 1, especially preferably from 3: 1 to 50: 1 and, especially, from 4: 1 to 30: 1

Similar indications can also be made to the surfaces, which are visible respectively of the body base molding or components of the agents cleaning. In this case, molded bodies of the washing and cleaning agents on which visible surfaces outwards of the components of the cleaning agents represent from 1 to 25%, preferably from 2 up to 20%, especially preferably from 3 to a 15% and, especially, from 4 to 10% of the surface Total molded body.

The components of the cleaning agents and the molded base body will preferably be colored optically differentiable way. In addition to optical differentiation advantages in the industrial application can be achieved through the Different solubility of the various areas of the molded body. The molded bodies of washing and cleaning agents, in the that the components of cleaning agents dissolve more quickly that the base molded body are preferred according to the invention. By incorporating certain components the solubility of the components of cleaning agents, and on the other hand can lead the release of certain components from the components of the washing and cleaning agents to advantages in the cleaning procedure

Obviously those are also preferred molded bodies of washing and cleaning agents according to the invention in which the components of the cleaning agents are dissolve later than the base body. The advantages, as far as to benefits, which follow from this delayed release they can be achieved for example because, with the help of a component of the cleaning agent, which dissolves more slowly, one or more active substances will be released only in processes subsequent scrubbing. In this way it can be achieved, for example, in agents for machine washing of dishes, by components of the washing agents, which dissolve from a more slowly, in the case of rinse rinse, be / other active substances are available. Through products additional such as nonionic surfactants, acidification, soil release polymers, etc. they can improve the results of rinse rinse. It is also possible, without problems, an incorporation of perfume; by means of the delayed release can eliminate the "smell of bleach" that appreciate when the machine is opened, in the case of dishwashing machines.

In the preferred embodiments of the present invention the base body has a high weight specific. The bodies according to the invention are preferred molding of the washing and cleaning agents that characterize because the base molded body has a density greater than 1,000 gdm -3, preferably above 1,025 gdm -3, especially preferably, above 1050 gdm-3 and, in particular, above 1,100 gdm-3.

To facilitate the decomposition of the highly compacted molded bodies, according to the invention, it is possible to incorporate in the same auxiliary agents for disintegration, the so-called disintegrating agents of the tablets to reduce the decomposition times. Disintegrating agents of the tablets or decomposition accelerators will be understood, according to the publications Römpp (9th edition, volume 6, page 4440) and Voigt " Lehrbuch der pharmazeutischen Technologie " (6th edition, 1987, pages 182-184) products auxiliaries, which are responsible for rapid decomposition of tablets in water or gastric juice and the release of pharmaceutical products in resorbable form.

These products, which are also referred to as "disintegrating" agents increase their volume in the presence of water, which, on the one hand, increase their own volume (swelling), however, on the other hand, a pressure, due to the release of gases, which allows the decomposition of tablets into smaller particles. The auxiliary disintegration agents known since ancient times are, for example, carbonate / citric acid systems, being able to also use other organic acids. The auxiliary agents for disintegration, inflatables, are, for example, polymers synthetics such as polyvinylpyrrolidone (PVP) or polymers natural or modified natural products such as celluloses and starches and their derivatives, alginates or casein derivatives.

Preferred molded bodies for cleaning agents contain from 0.5 to 10% by weight, preferably from 3 to 7% by weight and, especially, from 4 to 6% by weight of one or more auxiliary agents of disintegration, referred, respectively, to body weight molded When the base bodies contain only agents auxiliary to disintegration, the indications given are refer only to the weight of the base body. In the case of incorporation of auxiliary agents of disintegration in components of the cleaning agents, according to the invention, are they will consider those as component d).

As preferred disintegrating agents, cellulose-based disintegrating agents will be employed within the scope of the present invention, so that the preferred molded bodies of the cleaning agents contain such a cellulose-based disintegrating agent in amounts from 0.5 to 10% by weight, preferably from 3 to 7% by weight and, especially, from 4 to 6% by weight. Pure cellulose has a crude composition in formula (C 6 H 10 O 5) n and represents, seen from the point of view of its formula, a β-1,4-polyacetal of cellobiose, which, in turn, is made up of two glucose molecules. Suitable celluloses are constituted in this case by approximately 500 to 5,000 glucose units and therefore have average molecular weights from 50,000 to 500,000. As cellulose-based disintegrating agents that can be used within the scope of the present invention are also cellulose derivatives, which can be obtained by reactions analogous to polymerization from cellulose. Such celluloses, chemically modified, include in this case, for example, products from esterifications or etherifications, in which the hydrogen atoms of the hydroxy have been substituted. Similarly, celluloses in which hydroxy groups have been replaced by functional groups that are not linked through an oxygen atom can be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkaline celluloses, carboxymethyl celluloses (CMC), esters and cellulose ethers as well as amino cells. The abovementioned cellulose derivatives are preferably not used alone as cellulose based disintegrating agents, but will be used in admixture with cellulose. The content of these mixtures in cellulose derivatives is preferably a proportion below 50% by weight, especially preferably below 20% by weight, based on the cellulose-based disintegrating agent. Especially preferred, pure cellulose, which is free of derivatives of
cellulose.

Preferably, cellulose, used as auxiliary agent of disintegration, is not used finely divided, but it transforms into a more rude way, by example is granulated or compacted, before mixing with premixes to be pressed. The molded bodies of the agents of washing and cleaning, which contain disintegrating agents in granulated form or, if appropriate, cogranulated, have been described in German patent applications DE 197 09 991 (Stefan Herzog) and in DE 197 10 254 (Henkel) as well as in the International Patent Application WO 98/40463 (Henkel). These publications should also be considered as further indications precise for the manufacture of the disintegrating agents of granulated, compacted or cogranulated cellulose. The sizes of the particles of such disintegrating agents are found, the most of the time, above 200 µm, preferably at minus 90% by weight between 300 and 1,600 µm and, especially, at minus 90% by weight between 400 and 1,200 µm. The agents coarser decay coarser, cited previously and described in greater detail in the publications cited, based on cellulose, should be used in the field of present invention, preferably, by way of auxiliary agents of disintegration and can be acquired in commerce under the Arbocel® TF-30-HG designation of the Rettenmaier firm.

As another disintegrating agent, based on Cellulose or as a constituent of this component, can be used microcrystalline cellulose. This microcrystalline cellulose is obtained through partial hydrolysis of celluloses, low conditions such that they only affect and completely dissolve the amorphous areas of cellulose (approximately 30% of the mass total cellulose), leaving the crystalline zones intact (approximately 70%). A subsequent breakdown of microfine cellulose, produced by hydrolysis, provides microcrystalline celluloses, which have sizes of primary particles of approximately 5 µm and which can compacted, for example, to give granules with an average size of 200 µm particles.

The molded bodies of cleaning agents, preferred within the scope of the present invention, they contain, in addition, a disintegration aid agent, preferably a auxiliary agent for cellulose-based disintegration, preferably in granulated, cogranulated or compacted form, in amounts from 0.5 to 10% by weight, preferably from 3 to 7% by weight and, especially, from 4 to 6% in weight, referred respectively to the weight of the molded body.

The molded bodies of cleaning agents, according to the invention, they can also contain both the body base molding as well as the components of the agents cleaning, an effervescent gas release system. The system effervescent, gas detacher, may be constituted by a single substance, which releases a gas in contact with water. Between these compounds should be mentioned especially the peroxide of magnesium, which releases oxygen in contact with water. Usually the effervescent system, gas releasing, is constituted, without However, on the other hand for at least two components, which react each other with gas formation. While in this case you can imagine and carry out a plurality of systems, which release, for example, nitrogen, oxygen or hydrogen, the system effervescent, used in the molded bodies of the agents of washing and cleaning, according to the invention, can be chosen both from an economic point of view as well as from a point of view ecological. Preferred effervescent systems are constituted by carbonates and / or by alkali metal bicarbonates as well as by an acidifying agent, which is suitable for releasing dioxide from carbon in aqueous solution from metal salts alkaline

In the case of carbonates or of alkali metal bicarbonates are clearly preferred sodium and potassium salts for cost reasons, compared to others you go out. Obviously the corresponding ones do not have to be used carbonates or bicarbonates of pure alkali metals; for him on the contrary, mixtures of various carbonates and bicarbonates due to their interest in washing technology.

In the preferred molded bodies of the cleaning agents will be used as effervescent systems from 2 to 20% by weight, preferably 3 to 15% by weight and, especially, from 5 to 10% by weight of a alkali metal carbonate or bicarbonate as well as from 1 to a 15, preferably from 2 to 12 and, especially, from 3 to 10% by weight of an acidifying agent, referred to respectively to the molded body assembly.

As acidifying agents, which release dioxide carbon in aqueous solution from alkaline salts, boric acid can be used, for example, as well as alkali metal bicarbonates, dihydrogen phosphates alkali metals and other inorganic salts. Of course it they will preferably use organic acidifying agents, being citric acid an especially preferred acidifying agent. However, the others can also be used especially solid mono-, oligo- and polycarboxylic acids. Among this group Tartaric acid, succinic acid, in turn, are preferred. Malonic acid, adipic acid, maleic acid, acid fumaric, oxalic acid as well as polyacrylic acids. Likewise, organic sulfonic acids such as amidosulfonic acids In the same way it can be used, preferably, the product obtainable commercially and employable as an acidifying agent in the scope of the present invention constituted by the Sokalan \ registered DCS (registered trademark of the signature BASF), a mixture consisting of succinic acid (maximum 31% by weight), glutaric acid (maximum 50% by weight) and acid adipic (at most 33% by weight).

In the scope of the present invention are preferred the molded bodies of cleaning agents in which an acidifying agent is used in the effervescent system a product of the group of di-, tri- and oligocarboxylic acids organic or mixtures of these.

The particulate cleaning agents according to the invention and / or the molded bodies of the washing and cleaning agents - as well as the components of the cleaning agents themselves, according to the invention -
they can be packaged after their manufacture, having been accredited, especially, the use of certain packaging systems. Another aspect of the present invention is a combination of one or more particulate cleaning agents, according to the invention or of one or more molded bodies of washing and cleaning agents, according to the invention and of a packaging system, which Contains the cleaning agent or molded body of the washing and cleaning agents, the packaging system having a degree of water vapor permeability of 0.1 g / m2 / day to less than 20 g / m2 / day, when the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.

The packaging system of the combination formed by the components of the cleaning agents and / or the agents of cleaning and / or the molded body or bodies of the washing agents and cleaning and packaging system presents, according to the invention, a degree of water vapor permeability of 0.1 g / m2 / day at less than 20 g / m2 / day, when the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%. The mentioned temperature and humidity conditions are the conditions test mentioned in DIN 53122, being accepted, according to DIN 53122, minimum deviations (23 ± 1ºC, 85 ± 2% relative humidity). The degree of vapor permeability of water from a packaging system or a material can determined according to other standardized methods and described also, for example, in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form " measure water vapor transmission of materials in the form of sheet)) and in the TAPPI T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature and Humidity "(Water vapor permeability of materials in form of sheets at high temperatures and with high humidity)). He Measurement principle of the usual procedures is based on the Water absorption of anhydrous calcium chloride, which is stored in a container in the corresponding atmosphere, the container on top with the material to be tested. TO from the surface of the container, which is closed with the material to be tested (permeation surface), increasing Calcium chloride weight and exposure time, can Calculate the degree of water vapor permeability according to

FDDR = \ frac {24 \ cdot10000} {A} \ cdot \ frac {x} {y} [g / m2 / 24h]

where A means the surface of material to be tested, in cm2, x is the weight gain of the calcium chloride in g and y is the exposure time in h.

The relative equilibrium humidity, called frequently as "relative humidity of the air", ascends, by measuring the degree of water vapor permeability, in the scope of the present invention, at 85% at 23 ° C. The capacity of Air absorption for water vapor increases with temperature up to a respective maximum content, the so-called content of saturation, and is indicated in g / m 3. In this way, for example 1 m3 of air at 17 ° C, is saturated with 14.4 g of water vapor, at a temperature of 11ºC already has a saturation with 10 g of water vapor. The relative humidity of the air is the ratio, expressed as a percentage, between the actual water vapor content present and the saturation content corresponding to the prevailing temperature For example, if the air at 17 ° C contains 12 g / m3 of water vapor, then the relative humidity of the air is = (12 / 14.4) \ cdot100 = 83%. If this air cools, then saturation (100% of h.r.) is reached at the so-called point of dew (in the example: 14ºC), that is, if it continues to cool it it forms a precipitation in the form of fog (dew). For the quantitative determination of moisture hydrometers are used and psychrometers

The relative equilibrium humidity of 85% at 23 ° C can be adjusted exactly, for example in laboratory chambers with humidity control, depending on the type of device in +/- 2%. TO through saturated solutions of certain salts they can also form well defined and constant relative humidity of air, to a temperature indicated, in closed systems, which are based on the phase balance between the partial pressure of the water, the solution saturated and the background body.

Naturally, the combinations according to the invention can, in turn, be packaged in secondary packages, by example in cartons or trays, without having to consider additional requirements to the secondary container. Therefore, the container Secondary is possible but not necessary.

Preferred packaging systems in the framework of the present invention have a degree of permeability to water vapor of 0.5 g / m2 / day to less than 15 g / m2 / day.

The combination packaging system according to the invention comprises, depending on the embodiment of the invention, a certain amount of the components of the cleaning agents according to the invention, a certain amount of a cleaning agent composition according to the invention or of one or several molded bodies of washing and cleaning agents. In This case is preferred, according to the invention, either to form a body molded in such a way that it comprises a unit of Application of washing and cleaning agent and packaging this body individually molded, or packaged in a packaging unit the number of molded bodies, whose sum covers a unit of application. That is, in the case of a theoretical dosage of 80 g of washing and cleaning agent, it is possible, according to the invention, manufacture a molded body of washing and cleaning agents with 80 g of weight and package it individually, being possible also, according to the invention, package two molded bodies of agents washing and cleaning of molded bodies for washing and cleaning of 40 g each in a container, to achieve a combination according the invention. Naturally, this principle can be extended, of so that the combinations according to the invention may contain also three, four, five or more molded bodies of agents washing and cleaning of detergent in a packaging unit. Naturally, two or more molded bodies may present Different compositions in a container. In this way it is possible spatially separate certain components from each other, to avoid, for example, stability problems.

The combination packaging system according to the invention may be composed of the most diverse materials and It can take any external form. However, for reasons economic and for reasons of an easier transformation, it they prefer, of course, the packaging systems in which the container material has a low weight, is easily transformable And be economical. In the preferred combinations, according to the invention, the packaging system is composed of a sack or a laminated paper bag or monolayer and / or a sheet of material synthetic.

In this case the bodies can be loaded molding of washing and cleaning agents without classification, that is, as bulk cargo, in a bag of materials mentioned. However, for aesthetic reasons and for classification of combinations in secondary packages, is it is preferable to package the molded bodies of the washing agents and cleaning individually or multiplely, classified, in bags or bags For the individual application units of the molded bodies of washing and cleaning agents, which are found in a sack or bag, the technique has been adopted expression "flow pack". Optionally, said "flow packs" they can then be packaged again preferably classified in a secondary container, which highlights the presentation Compact molded body.

Sacks or paper bags or of monolayer or laminated synthetic material sheet, to be used preferably as a packaging system, can be configured in the most diverse way and manner, for example as blown bags without a midline of connection or as bags with a medium joint line, which are closed by heat (heat fusion), glues or adhesive tapes. The materials for the bags or for the monolayer bags are the known papers, which, if necessary, can be impregnated, as well as the sheets of synthetic material, which, if necessary, can be coextruded. Synthetic material sheets, which can be used in the scope of the present invention as a packaging system, have been indicated, for example, in Hans Domininghaus's publication "Die Kunststoffe und ihre Eigenschaften" (Synthetic materials and their properties) , 3rd edition, VDI editorial, Düsseldorf, 1988, page 193. Figure 111, shown there, simultaneously offers benchmarks on the water vapor permeability of the aforementioned materials.

Especially preferred combinations in the scope of the present invention contain, as a packaging system, a sack or a foil bag of monolayer synthetic material or laminated, with a thickness from 10 to 200 µm, preferably from 20 to 100 µm and especially from 25 to 50 \ mum.

Even when it is possible to use, in addition to the sheets and papers mentioned, wax-coated papers in the form of cartons as a packaging system for the body molding of washing and cleaning agents, in the field of present invention it is preferred that the packaging system not Understand paper cartons coated with wax. In this sense, the expression "packaging system", within the scope of this invention, always characterizes the primary packaging of the components of the cleaning agents, of the combination of the cleaning or molded bodies, that is, the container that is directly in contact, through his inner face, with the surface of the components of the cleaning agents, of the combination of cleaning agents or molded bodies. No requirement of a secondary package is required, optional, so that, in this case, all the usual materials and systems.

As mentioned above, the components of cleaning agents, compositions of cleaning agents and molded bodies of washing agents and cleaning the combination according to the invention contain, depending on the intended use, other components of the agents washing and cleaning in varying amounts. Independently of the intended use of agents or molded bodies, is preferred, according to the invention that the agent (s) or the agent (s) molded bodies of washing and cleaning agents present a relative equilibrium humidity less than 30% at 35 ° C.

In this case, the equilibrium relative humidity of the agents or of the molded bodies of the agents of cleaning can be determined according to usual methods, having chosen in the scope of the present invention the following procedure: a 1 liter container, impermeable to water, with a lid that has a sealed opening for sample introduction, with 300 g of molded bodies of the washing and cleaning agents in total and held for 24 constant hours at 23 ° C, to ensure a uniform temperature of the container and the substance. Water vapor pressure in the space on the molded bodies can then be determined with a hygrometer (Hygrotest 6100, Testoterm Ltd., England). The Water vapor pressure is now measured every 10 minutes, until two consecutive values do not show any deviation (humidity relative balance). The hygrometer mentioned above allows a direct reading of the measured values in% humidity relative.

Similarly, forms of embodiment of the combination according to the invention, in which the packaging system is made in a rebogable way. Too combinations according to the invention can preferably be made in which the packaging system has a microperforation

As indicated above, they can manufactured components for cleaning agents, compositions for cleaning agents or cleaning agent tablets for machine washing of dishes according to the procedure according to invention. Therefore a cleaning procedure for cleaning the dishes in a dishwashing machine It is characterized by one or more cleaning agents. in the form of particles, according to the invention and / or one or more bodies molding of washing or cleaning agents according to the invention in the dosing chamber of the dishwasher and starts a scrubbing program, in whose development the chamber opens dosing and the cleaning agents and / or the  or molded bodies, constitutes another object of the present invention.

Also in the cleaning procedure according to the invention can be withdrawn from the dosing chamber and the components of the cleaning agents according to the invention or the compositions of the cleaning agents or the body molded according to the invention can be arranged for example in the cutlery basket. It is obviously possible without problems also in this case the use of auxiliary devices for dosage, for example a basket that is introduced into the enclosure for scrubbing Therefore another object of the present invention It consists of a cleaning procedure for cleaning the tableware in a dishwashing machine, characterized because one or more cleaning agents are arranged in the form of particles according to the invention and / or one or more molded bodies of washing or cleaning agents, according to the invention, with or without auxiliary dosing devices, in the enclosure for scrubbing the dishwasher and letting it develop scrubbing program, in whose development the or the cleaning agents and / or the molded bodies.

Examples

Dispersions or emulsions were prepared in fusion with the following composition [% by weight]:

V1 V2 E1 E2 E3 Paraffin 57-60ºC 50.0 45.0 50.0 45.0 45.0 Surfactant no ionic * 45.0 45.0 42.5 45.0 49.7 Acetate potassium ** - - 2.5 - - Bentonite modified *** - - - - 0.3 Powder FAS ^ {****} 5.0 5.0 Product auxiliary ^ {*****} fifty 5.0 5.0 5.0 5.0 * polyoxyalkylated alcohol closed with epoxy softening point 25-45 ° C ^ ** 100% <100 \ mum ^ {***} Thixogel® MP250, Südchemie ^ {****} E2: sulfate of fatty alcohols with 12 to 18 atoms of carbon, 90% <200 µm V2: sulfate alcohols fatty with 12 to 18 carbon atoms, 90%> 200 µm, average particle size 300 \ mum ^ {*****} poly-12-hydroxystearate of polyglycerin.

For this the non-ionic surfactant was heated to 85 ° C, paraffin was added under stirring and finally added The remaining components. The stability of the suspension / emulsion was evaluated at 85 ° C by disconnecting the agitator and evaluating simple sight

In this case the following scheme was applied:

\ text {++}

visible separation produced from> 60 s

\ text {+}

visible separation produced from> 30 s

\ text {-}

visible separation produced from <30 s

- -

visible separation after stirrer disconnection <10 s.

The following table shows the results.

V1 V2 E1 E2 E3 - - - - ++ ++ ++

Claims (35)

1. Components of cleaning agents, in form of a solidifiable fusion, which contain

to)

since 10 to 89.9% by weight of one or more surfactants,

b)

since 10 to 89.9% by weight of one or more fusible substances with a melting point above 30 ° C and a solubility in water less than 20 g / l at 20 ° C,

C)

since 0.15 to 12.5% by weight of one or more products solids,

d)

since 0 to 15% by weight of other active products and / or auxiliary

on the condition that at least 90% by weight of the particles c) present a particle size less than 300 \ mum. 2. Components of cleaning agents according to claim 1, characterized in that as component a) they contain from 15 to 80, preferably from 20 to 70, especially preferably from 25 to 60 and, especially, from a 30 to 50% by weight of one or more surfactants. 3. Components of cleaning agents according to one of claims 1 or 2, characterized in that they contain as component b) from 15 to 85, preferably from 20 to 80, especially preferably from 25 to 75 and, especially, from 30 to 70% by weight of one or more fusible substances. 4. Components of cleaning agents according to one of claims 1 to 3, characterized in that they contain component c) in amounts from 0.2 to 10, especially preferably from 0.25 to 7.5 and, especially, from 0 , 3 to 5% by weight. 5. Components of cleaning agents according to one of claims 1 to 4, characterized in that as component a) they contain one or more non-ionic surfactants with a melting point located above 20 ° C, preferably located above 25 ° C, especially preferably between 25 and 60 ° C and, especially, between 26.6 and 43.3 ° C. 6. Components of cleaning agents according to one of claims 1 to 5, characterized in that as component a) they contain one or more ethoxylated nonionic surfactants, which have been obtained from monohydroxyalkanoles with 6 to 20 carbon atoms or alkylphenols with 6 to 20 carbon atoms or fatty alcohols with 16 to 20 carbon atoms and more than 12 moles, preferably more than 15 moles and, especially, more than 20 moles of ethylene oxide per mole of alcohol. 7. Components of cleaning agents according to one of claims 1 to 6, characterized in that as component a) they contain ethoxylated and propoxylated surfactants, in which the propylene oxide units constitute in the molecule up to 25% by weight, preferably up to 20% by weight and, especially, up to 15% by weight of the total molecular weight of the non-ionic surfactant. 8. Components of cleaning agents according to one of claims 1 to 7, characterized in that as component a) they contain non-ionic surfactants of the formula R 1 O [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] y} [CH 2 CH (OH) R ^ {2}] in which R1 means a linear or branched hydrocarbon moiety, aliphatic, with 4 to 18 carbon atoms or mixtures thereof, R2 means a linear or branched hydrocarbon moiety with 2 to 26 atoms of carbon or mixtures thereof and x takes values between 0.5 and 1.5 e y means a value of 15, such as minimum. 9. Components of cleaning agents according to one of claims 1 to 8, characterized in that as component a) they contain poly (oxyalkylated) nonionic surfactants closed at the end groups of the formula R 1 O [CH 2 CH (R 3) O] x [CH 2] k CH (OH) [CH 2] j OR 2 in which R 1 and R 2 mean hydrocarbon moieties with 1 to 30 carbon atoms, linear or branched, saturated or unsaturated, aliphatic or aromatic, R 3 means H or means a methyl, ethyl moiety, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl, x means values between 1 and 30, k and j mean values between 1 and 12, preferably between 1 and 5, the surfactants of the kind R 1 O [CH 2 CH (R 3) O] x CH 2 CH (OH) CH 2 OR 2 in which x means numbers from 1 to 30, preferably from 1 to 20 and, especially, from 6 to 18. 10. Components of cleaning agents according to one of claims 1 to 9, characterized in that as component b) they contain one or more products with a melting range between 30 and 100 ° C, preferably between 40 and 80 ° C and, especially, between 50 and 75 ° C. 11. Components of cleaning agents according to one of claims 1 to 10, characterized in that as component b) they contain at least one paraffin wax with a melting range from 30 ° C to 65 ° C. 12. Components of cleaning agents according to one of claims 1 to 11, characterized in that the solubility of component b) at 20 ° C is less than 15 g / l, preferably less than 10 g / l, especially preferably less than 5 g / l and especially less than 2 g / l. 13. Components of cleaning agents according to one of claims 1 to 12, characterized in that at least 90% by weight of the particles of c) have a particle size of less than 190 µm, preferably less than 175 µm and, especially, less than 150 µm. 14. Components of cleaning agents according to one of claims 1 to 13, characterized in that component c) consists entirely of particles with a particle size of less than 200 µm, preferably less than 175 µm, particularly preferably less than 150 µm and, especially, less than 100 µm. 15. Components of cleaning agents according to one of claims 1 to 14, characterized in that as component c) they contain alkali metal salts of organic acids, preferably alkali metal acetates and, especially, potassium acetate. 16. Components of cleaning agents according to one of claims 1 to 14, characterized in that as component c) they contain products from the group of clay minerals, preferably from chemically modified clay minerals and, especially, from hydrophobic bentonites. 17. Components of cleaning agents according to one of claims 1 to 14, characterized in that as component c) they contain one or more surfactants, preferably sulfates of fatty alcohols and, especially, sulfates of fatty alcohols having 12 to 18 carbon atoms. 18. Components of cleaning agents according to one of claims 1 to 17, characterized in that as component d) they contain other active and / or auxiliary products from the group of dyes, odorizing products, dirt-release polymers, corrosion inhibitors, enzymes, bleaching agents, bleaching activators and complexing agents in amounts from 0 to 10% by weight, preferably from 0.25 to 7.5% by weight, especially preferably from 0.5 to 5% by weight and, especially, from 0.75 to 2.5% by weight. 19. Components of cleaning agents according to one of claims 1 to 18, characterized in that they have a melting point between 50 and 80 ° C, preferably between 52.5 and 75 ° C and, especially, between 55 and 65 ° C. 20. Procedure for obtaining components of cleaning agents in the form of particles, characterized in that a fusion is applied, consisting of

to)

since 10 to 89.9% by weight of one or more surfactants,

b)

since 10 to 89.9% by weight of one or more fusible substances with a melting point above 30 ° C and a solubility in water less than 20 g / l at 20 ° C,

C)

since 0.1 to 15% by weight of one or more products solids,

d)

since 0 to 15% by weight of other active products and / or auxiliary

on one or several materials of stand and mix transform by molding 21. Method according to claim 20, characterized in that the transformation by molding is carried out by granulation, compaction, pelletizing, extrusion, entablatting, by forming beads by introduction through nozzles in a cold gas stream, by means of patterning by means for dosing on refrigerated tablet forming plates or by application or spraying on a refrigerated cylinder, freezing of solidified melting, chipping and shredding if necessary. 22. Use of cleaning agent components in the form of particles constituted by

to)

since 10 to 89.9% by weight of one or more surfactants,

b)

since 10 to 89.9% by weight of one or more fusible substances with a melting point above 30 ° C and a solubility in water less than 20 g / l at 20 ° C,

C)

since 0.15 to 12.5% by weight of one or more products solids,

d)

since 0 to 15% by weight of other active products and / or auxiliary

in cleaning agents for the machine scrubbing crockery. 23. Agent for machine washing of dishes, in the form of particles, containing structuring products as well as, optionally, other components of the cleaning agents, characterized in that it contains components of the cleaning agents, in the form of particles, which contain, in relation to weight,

to)

since 10 to 89.9% by weight of one or more surfactants,

b)

since 10 to 89.9% by weight of one or more fusible substances with a melting point above 30 ° C and a solubility in water less than 20 g / l at 20 ° C,

C)

since 0.15 to 12.5% by weight of one or more products solids,

d)

since 0 to 15% by weight of other active products and / or auxiliary

24. Agent for machine washing of the dishes, in the form of particles, according to claim 23, characterized in that it contains structuring products in amounts from 20 to 80% by weight, preferably from 25 to 75% by weight and , especially, from 30 to 70% by weight, referred respectively to the weight of the agent. 25. An agent for machine washing of dishes, in the form of particles, according to one of claims 23 or 24, characterized in that it also contains one or more products from the groups of bleaching agents, bleaching activators , bleaching catalysts, surfactants, corrosion inhibitors, polymers, dyes and odorizing products, pH adjusting agents, complexing agents and enzymes. 26. Agent for machine washing of dishes, in the form of particles, according to one of claims 23 to 25, characterized in that it contains the components of cleaning agents, in the form of particles, in amounts from 0.5 to 30% by weight, preferably from 1 to 25% by weight and, especially, from 3 to 15% by weight, respectively referred to the agent as a whole. 27. Agent for machine washing of dishes, in the form of particles, according to one of claims 23 to 26, characterized in that the component of the cleaning agents, in the form of particles, has particle sizes between 1 and 40 mm, preferably between 1.5 and 30 mm and, especially, between 2 and 20 mm. 28. Agent for machine washing of dishes, in the form of particles, according to one of claims 23 to 27, characterized in that (regardless of the component of the cleaning agent, in the form of particles) it has particle sizes comprised between 100 and 3,000 µm, preferably between 300 and 2,500 µm and, especially, between 400 and 2,000 µm. 29. Agent for machine washing of dishes, in the form of particles, according to one of claims 23 to 28, characterized in that a dosing unit is presented in a sealed bag by welding a water-soluble sheet. 30. Molded body of polyphasic cleaning agents, for machine scrubbing of dishes, containing structuring products as well as, optionally, other components of cleaning agents, characterized in that it is constituted at least by a phase formed by

to)

     from 10 to 89.9% by weight of one or more surfactants,

b)

     from 10 to 89.9% by weight of one or more substances fuses with a melting point above 30 ° C and a water solubility less than 20 g / l at 20 ° C,

C)

     from 0.1 to 15% by weight of one or more products solids,

d)

     from 0 to 15% by weight of other active products and / or auxiliary

31. Molded body of polyphasic cleaning agents according to claim 30, characterized in that the phases have the shape of layers and the molded body has 2, 3 or 4 phases. 32. Molded body of polyphasic cleaning agents according to claim 30, characterized in that it is constituted by a base body, which has a cavity, and a part that is at least partially contained in the cavity. 33. Molded body of polyphase cleaning agents according to claim 32, characterized in that the part contained in the cavity is constituted by

to)

     from 10 to 89.9% by weight of one or more surfactants,

b)

     from 10 to 89.9% by weight of one or more substances fuses with a melting point above 30 ° C and a water solubility less than 20 g / l at 20 ° C,

C)

     from 0.1 to 15% by weight of one or more products solids,

d)

     from 0 to 15% by weight of other active products and / or auxiliary

34. Combination formed by one or more particulate cleaning agents according to one of claims 23 to 29 or one or more molded bodies of washing or cleaning agents according to one of claims 30 to 33 and a packaging system containing the cleaning agent or molded bodies of the washing and cleaning agents, characterized in that the packaging system has a degree of water vapor permeability of 0.1 g / m2 / day up to less than 20 g / m2 / day, when the packaging system is stored at 23 ° C and with a relative equilibrium humidity of 85%. 35. Cleaning procedure for cleaning the dishes in a dishwashing machine, characterized in that it is arranged in the metering chamber of the dishwasher or in the cavity for scrubbing, with or without auxiliary devices for dosing, of the dishwashing machine one or more cleaning agents, in the form of particles according to one of claims 23 to 29 and / or one or several molded bodies of washing or cleaning agents according to one of claims 30 to 33 and allowing the scrubbing program is developed, during which the dosing chamber is opened and the cleaning agents and / or the molded bodies are dissolved.