ES2263065T3 - PROCEDURE FOR OBTAINING PORTIONS OF WASHING OR CLEANING AGENTS, COVERED. - Google Patents

Abstract

Disclosed is a simple and universally applicable method for producing detergent or cleansing agent portions that are tightly coated with water-soluble coatings. The inventive method comprises the following steps: a water-soluble bottom film is placed upon a conveyor chain or a molding tool; one or several detergent or cleansing agent portion/s is/are disposed on the bottom film; a water-soluble top film is placed upon the detergent or cleansing agent portion/s that lie/s on top of the bottom film; the top film is fixed onto the bottom film such that the detergent or cleansing agent portion/s is/are enclosed; the films are sealed and optionally cut.

Description

Procedure for obtaining portions of washing or cleaning agents, coated.

The present invention relates to a procedure for obtaining portions of washing agents or cleaning, which have a coating consisting of water soluble materials, surrounding narrowing to the compositions contained in the portion.

Washing and cleaning agents in portions They have been widely described in the state of the art and are increasingly appreciated by the consumer due to its easy dosage. Portioning can be achieved in this case, for example, by transforming into a compact form or by individual packaging. In the first of the cases cited the entablet has a preponderant role, in the last of the cases are used predominantly portions in the field of washing and cleaning agents that are surrounded by materials Water soluble from containers. In this way the publication EP-A-700 989 discloses washing agents packed in portions in a soluble sheet in Water. Of course these portions have the disadvantage of having the high degree of compaction like the one presented by the tablets. The filling of the flexible bags leads, on the one hand, to a low degree of compaction, on the other hand at an empty volume, conditioned by technology, so that an amount of a washing or cleaning agent, measured for a washing process or cleaning takes up more space than an amount corresponding in tablet form. In addition the empty volume makes that the stuffed bag is labile against mechanical effects and that may explode

The tablets of washing or cleaning agents, that are in the market, have the disadvantage that they must also be equipped with a wrap, which protects the components against the effects of the environment (especially humidity). These empty "flow packs" packages for water insoluble materials they have to be removed by of the user as a previous step to dosing, which can be annoying for the user and causes waste. They have proposed solutions to this problem by covering the body molded with water-soluble polymer or by using water soluble containers.

A coating provides tablets optically attractive with smooth, shiny surface and properties advantageous haptics. Of course the coating of the tablets is expensive from an industrial point of view. The use of packaging water soluble in the form of bags consisting of sheets Water soluble has been described in the state of the art. From Example way are known by the publications WO-A-0055 415 and by publication GB-A-2 361 685 procedures for Obtaining water soluble containers. Of course the tablets they have ascetic problems with tablets Traditional In the same way the acceptance by the consumers are less in this form of marketing since the wrap suggests to the user that it has to be removed - with what which is not recognized by users the real advantage of Water soluble flow packs.

The present invention had the task of putting provision a procedure for the manufacture of portions of aesthetically appealing washing or cleaning agents, in this case the procedure should be so variable, that they could be packaged both tablets and other compositions made of cleaning or cleaning agents such as, for example, cast bodies, powders, granules, bodies extrudates, scales, etc. in an aesthetically appealing way. For the alternatives of the procedure, in which they are not packed tablets should be able to make portions that combine the advantages of compacting tablets with those of rapid solubility of portion systems and, in addition, should not need to be equipped with a coating consisting of insoluble sheets in Water.

It has been found now that it is aesthetically attractant a coating consisting of soluble sheets in water, lying closely on a tablet or on a load in the form of particles, which does not represent molded bodies and which It is accepted by consumers. The degree of compaction of such systems is close to that of traditional tablets and is clearly above that of portion systems traditional, which clearly exceed the solubility of tablets and that of washing or cleaning agents traditional in the form of particles. In addition, it has been found that a special coating procedure can be used universally for both particulate compositions as well as for tablets and that provides portions with a Coating narrowing supported.

The object of the present invention consists, by therefore, in a process for manufacturing portions of washing or cleaning agents coated with coatings water soluble, characterized by the stages

to)

        application of a water soluble bottom sheet on a chain of transport or in a tool with one or several molds;

b)

        application of one or more portions of washing agents or cleaning on the bottom sheet;

C)

        application of a top sheet, soluble in water on the or portions of the washing or cleaning agents on the sheet lower;

d)

        fixing the upper sheet on the lower sheet with occlusion of the portion or portions of the washing agents or cleaning;

and)

        sealing and, optionally, cutting of the sheets.

A description of the process according to the invention is given below, by means of its steps. A detailed description of the sheets, to be used in the process, according to the invention, and of the components of the portions of the washing or cleaning agents is following these explanations.
nes.

In the first stage of the procedure, according to the invention, a water soluble bottom sheet is prepared which is it has on a transport chain or on a tool with one or several molds. Also, according to the invention, a combination of transport chains and tools with one or more molds As transport chains, in the sense of the present invention, conveyor belts, etc. will also be understood. The chains or transport belts are preferred over fixed molding tools for reasons of economy in the process. A combination of transport chains and tools with one or several molds constitute, for example, an assembly line that present recessed at regular intervals.

When using tools with one or more molds, molding tools may be configured as units  individual, however it is also possible, and is preferred Due to the economics of the process, use molding tools that present a plurality of molds. In stage a) of method, according to the invention, is applied on these molds a water soluble sheet, on which they are applied, in the following step of the procedure one or more portions of the agents of washing or cleaning.

According to the invention, it is possible, and preferred, pre-mold the sheet that is applied in step a) on the transport chain or on the tool with one or several molds. Especially in the case of the subsequent application of compositions in the form of particles it is advisable to use useful with one or several molds and mold the applied sheet. In this way the particles are fixed in the space, which facilitates the Next stage of the procedure.

Preferred procedures, according to the invention, are characterized in that the bottom sheet is molded by applying a vacuum and / or by heating. From this mode is provided to the sheet with a cavity for accommodation of the composition of the washing or cleaning agents in the form of particles The procedure stage, described above, It is not limited, however, to the dosage of compositions in the form of particles, but can also be used for tablet packaging according to the invention.

In this case, according to the invention, it is preferred that the sheet, soluble in water, be heated, as a previous step to the application on the tool with one or several molds, at temperatures located above 50 ° C, preferably above 70 ° C and, especially, above 90 ° C. This facilitates the further molding. Alternatively to heating as a previous step to the application on the tool with one or several molds or as complement of it, the sheet can continue to be heated during the molding process. In this case, those are preferred. variants of the process in which the molding of the sheet Water soluble is favored by heating the sheet to temperatures from 100 to 120 ° C. A combination of both variants of the procedure, ie the application of a sheet heated and additional heating, is possible and preferred.

The sheet can also be inserted into the mold. by means of the dosage of the tablets or of the composition in the form of particles. This is possible, for example, in the case of the compositions in the form of particles being applied a ring-shaped tool on the sheet applied above the mold and dosing in the mold the composition, in the form of particles, through this tube. In this case you can descend by the mold the sheet well due to the mass of the composition, but the Dosing process can also be favored by means of a compression of the composition into the mold, by example, by means of a punch in the tube-shaped dispenser. In the case of tablets you can find application also this dosage unit, but without plasticizing the tablets Due to the compact structure of the molded body.

When a particle-shaped composition is used, it can be pre-compacted slightly, to ensure the fullest possible filling of the mold. When polyphasic portions have to be prepared, the compression of the particulate composition, dosed first, guarantees a flat boundary surface between the two layers. Optically, such biphasic portions are closely supported on tablets with two known layers. In this case, the forces for compression of the composition in the form of particles will of course be chosen, such that the field of elastic deformation is not abandoned. The dosing pressure therefore does not lead to a sintered set of the particles (as would be the case in the case of a entablet), but only leads to a removal of the hollow cavities of the bulk cargo and to a flat surface. In this case, those methods according to the invention are preferred, in which a pre-mixed mixture, in the form of particles, with the aid of a punch is compacted slightly, the compression forces below
1 kN

The compositions in the form of particles, slightly precompacted, they can rise slightly from of the mold as a previous step to the sealing process without breaking immediately - this can be used advantageously for the joint position by subsequent sealing, see below.

Preferred procedures, according to the invention, for coating compositions in the form of particles are characterized in that the first agent is dosed washing or cleaning, particulate, precompacted, other washing or cleaning agent in the form of particles. In this way optically attractive portions can be manufactured.

When a tool with mold is used, its depth, in combination with the height of the inserted tablets  or of the composition in the form of particles, loaded in its inside, determines the height at which the composition excels out of the plane of the sheet. The subsequent application of the upper sheet in step c) of the process, according to the invention, then determines the position of the joint by sealing generated later.

When the composition of the washing agent or cleaning, dosed in the mold, make up with the upper side of the mold, the joint will be formed by sealing as "flange" on a front surface of the portion. In this case, a simple sealing plate, which has, of course, the drawback that it is also subjected to the sheet, which covers the upper side of the portion, to the thermal effect.

Alternatively, the seal joint can be configured however also in such a way that it runs at along the lateral surface of the portion. In this case it stands out the portion of the mold and the portion of the portion, which protrudes from the mold, covered with another sheet. Now the sealed with a plate-shaped sealing tool but it is carried out with a ring-shaped tool. This procedure has the advantage of lowering the sealing tool, in the form of a ring, straighten under tension additionally to the top sheet. Also the effect of heat on the portion is clearly less than in the case of a "heating plate".

For this reason, those are preferred methods, according to the invention, in which the portion (s)  of washing or cleaning agents do not make up / make up the same level with the upper side of the mold in stage b), after the application on the bottom sheet, but protrude / protrude from it, being preferred that it is in the inside the mold at most 50%, preferably at most 40% and especially at most 30% of the maximum height of the or of the portions of the washing or cleaning agents.

In the extreme case there is no mold in the that the portion can be dosed, that is to say that the composition of washing or cleaning agents or tablets of washing or cleaning agents are arranged on a sheet lower, which, meanwhile, is arranged on a chain flat transport or on an "assembly line". The methods, according to the invention, in which the bottom sheet  be completely flat during stages b) through e) are preferred, according to the invention, due to the more configuration simple installation and simplified form of process.

The portion of the washing agents or of cleaning to be arranged on or on the bottom sheet can be, as already indicated, in the form of particles or may be constituted by a plurality of molded bodies. further it is also possible, and preferred, to be constituted by a tablet of washing or cleaning agents or by a cast body with components with washing or cleaning activity. The tablets and molded bodies have the advantage that they can be arranged exactly on the sheet and also have the advantage of not they are drained during the transport of the sheet on a band of flat transport or on a transport chain. The particle accumulations can modify its configuration in This way of proceeding. Preferred procedures, according to the invention, therefore, are characterized in that the portion (s) of washing or cleaning agents, which are arranged on the bottom sheet in step b) is / are washing agent tablets or cleaning.

Obviously it is possible, according to the invention, also carry out a combination of the possibilities previously cited, applying on or on the sheet lower both a particulate composition and also One or more tablets. Instead of tablets or as a supplement to they can also be used other molded bodies alone or in combination with dust, for example, cast bodies or bodies gaps loaded with dust or loaded with liquids, which can be manufactured, for example, by injection casting, by bottle blowing, by drawing, etc. In the field of present invention are especially preferred capsules of gelatin with powder loading or (preferably) with liquid loading, that are arranged or inserted into the bottom sheet together with a composition in the form of particles and / or with a tablet.

The process, according to the invention, is will use especially preferably for the packaging of cast bodies with washing or cleaning activity, being especially preferred that the molded body is present combined in the package with one or more washing agents or cleaning in the form of particles, such as, for example, powders, extruded or granulated bodies. A more accurate description of the preferred castings, according to the invention, is carried out later in the text.

On the bottom sheet, covered with one or several portions of the washing or cleaning agents are available, in step c) of the process, according to the invention, a sheet upper, which is fixed in stage d) and sealed in stage e). Preferably the application of the top sheet is carried out with the help of a tool that has the dome shape, which carries itself same top sheet and that is covered by the portions of the washing or cleaning agents located on the sheet lower. In this case it is preferred that the topsheet is not flat, that is to say that it is not tensioned, but that it is configured also in the form of a dome. This can be achieved by applying the upper sheet in the tool on its side walls. The Preferred procedures are characterized in this case because the top sheet deforms into a dome, as a previous step to the application in step c), by applying a vacuum and / or by heating.

In this case it is advantageous to heat the sheet higher than temperatures between 100ºC and 200ºC, being preferred temperatures between 100 ° C and 120 ° C. He dome-shaped mold with the top sheet is then arranged on the or the portions of the washing or cleaning agents, which They are on the bottom sheet. In this case a portion of washing or cleaning agent already complete, surrounded by the water soluble sheet, which is separated from the sheet in part by means of an air cushion. In order to guarantee a packaging that present the most similar skin shape possible, the air through grooves on the surface of the foot of the tool higher. The application of a vacuum in these slots also causes that the top sheet detaches from the dome, as soon as it is ventilate the dome-shaped tool from above. In this In this case, the procedures according to the invention are preferred in which stage c) is initiated by prior ventilation from above.

Once the top sheet lies without tension on the or the portions of the washing or cleaning agents, located on the bottom sheet, the Useful in the form of a dome. Preferably a coating is achieved in the form of skin, also applying a vacuum on the surface of junction between the top sheet and the bottom sheet. Alternatively or as a complement the tool can be driven in dome shape with an overpressure, which presses the top sheet on the or the portions of the washing or cleaning agents, according to the invention, those processes are preferred characterized in that the work stages c) and / or d) are favored by evacuating the intermediate cavity between the top sheet and the bottom sheet and / or by applying pressure on the top sheet.

In stage d) the sheets are sealed, in all their surface, around the side of the agent portions of washing or cleaning. After sealing, the sheets by a different pressure in the mold to prevent a reverse molding. As a complement to the above, the mold can refrigerated to obtain the product sealed in unmodified its configuration and shorten residence times in the mold.

Another variant of the procedure provides for portion packaging first in soluble sheets in water, well according to what has been said above and then the sheet-shaped container is contracted on the portions. The contracted sheet is a sheet that has been stretched and that contracts again by heating. In this case it is possible to generate coatings located very closely on the surface of the portions

According to the invention, the procedures preferred are also characterized as as sheet or sheets water soluble in steps a) and c) sheets are used pre-stretched, which contract in stage e) or after it, on the or the portions of the washing or cleaning agents.

Instead of a sheet with a single layer they can according to the invention, also laminated laminates multilayer Such laminates have the advantage that the layers individual can be adapted to the corresponding conditions enviroment. This way you can take advantage, for example, an inner sheet, which is inert against the composition to be packaged and that does not intervene in undesirable reactions with the load.  An outer sheet, which better resists environmental effects it can protect, in a laminate of two layers of this type, the composition against external influences. According to the invention, obviously laminated with three sheets can also be used, laminated with four sheets, etc. being able to assign to the sheets individual different functions (mechanical stabilization, barrier Steamed, optical, functionality by incorporating components, etc.).

Below is a description of the sheets used in the process according to the invention:

The sheets, used in the procedure, according to the invention, they can be an individual material or a mixture of various materials. The water soluble coating encompasses the preferred methods, according to the invention, one or more materials of the group formed by polyvinyl alcohol (PVAL) (in given acetalized case) and / or PVAL copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, gelatins, cellulose and its derivatives, especially MC, HEC, HPC; HPMC and / or CMC, and / or copolymers as well as mixtures thereof. If necessary they can be mixed with plasticizing coatings known by the technician in the material to increase the flexibility of the material.

In the scope of the present invention are Especially preferred are polyvinyl alcohols as polymers.  water soluble In this case the expression "alcohols polyvinyl "(abbreviated designation PVAL, occasionally also PVOH) refers in this case to polymers with the structure general

\delm{C}{\delm{\para}{OH}}

H --- CH_{2} ---

\delm{C}{\delm{\para}{OH}}

H ------ CH_ {2} ---

 \ delm {C} {\ delm {\ para} {OH}} 

H --- CH_ {2} ---

 \ delm {C} {\ delm {\ para} {OH}} 

H ---

that contain, in small proportion (approximately 2%) also structural units of the kind

\delm{C}{\delm{\para}{OH}}

H ---

\delm{C}{\delm{\para}{OH}}

H --- CH_{2} ------ CH_ {2} ---

 \ delm {C} {\ delm {\ para} {OH}} 

H ---

 \ delm {C} {\ delm {\ para} {OH}} 

H --- CH_ {2} ---

The usual polyvinyl alcohols in the trade, offered as dust yellowish-white or as granules with degrees of polymerization in the range from about 100 to 2,500 (molecular weights from approximately 4,000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%, therefore still contain a residual content in acetyl groups. Polyvinyl alcohols are characterized, by the manufacturer, by grade data polymerization of the starting polymer, the degree of hydrolysis, of the saponification index or the viscosity in solution.

Polyvinyl alcohols are, depending on the degree of hydrolysis, soluble in water and in organic solvents less strong polar (formamide, dimethylformamide, dimethylsulfoxide); these are not attacked by hydrocarbons (chlorinated), by esters, by fats or by oils. The polyvinyl alcohols are considered toxicologically safe and are at least partially biodegradable. Water solubility can be reduced by further treatment with aldehydes (acetalization), by complex formation with salts of Ni or of Cu or by treatment with dichromates, with boric acid or with Borax. Polyvinyl alcohol is widely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, however, can be traversed by the water vapor.

Preferred procedures, in the field of The present invention is characterized in that the coatings Water soluble include polyvinyl alcohols and / or copolymers of PVAL, whose degree of hydrolysis is from 70 to a 100 mol%, preferably 80 to 90 mol%, of especially preferred from 81 to 89 mol% and, especially, from 82 to 88% in moles.

Preferably, alcohols will be used polyvinyl with a certain range of molecular weights, those procedures according to the invention being preferred in those that the water-soluble coating encompasses alcohols polyvinyl and / or copolymers of PVAL, whose molecular weight is found in the range from 3,500 to 100,000 gmol -1, preferably from 10,000 to 90,000 gmol -1, so especially preferred from 12,000 to 80,000 gmol -1 and, especially, from 13,000 to 70,000 gmol -1.

The degree of polymerization of such alcohols polyvinyl, preferred, is approximately between 200 and about 2,100, preferably between about 220 and about 1,890, especially preferably between about 240 and about 1,680 and, especially, between about 260 and about 1,500.

Preferred procedures, according to the invention, are characterized in that the water soluble coating covers polyvinyl alcohols and / or PVAL copolymers, the degree of which polymerization medium is between 80 and 700, preferably between 150 and 400, especially preferably between 180 and 300 and / or whose molecular weight ratio MG (50%) and MG (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and, especially, between 0.45 and 0.6.

Polyvinyl alcohols, previously described, are already commercially available, for example, under the registered trademark Mowiol® (Clariant). Polyvinyl alcohols Especially suitable in the scope of the present invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88 as well as Mowiol® 8-88.

Other polyvinyl alcohols especially suitable as a material for water soluble coating They can be seen in the following table:

Denomination Grade of Weight molecular Point of fusion hydrolysis [%] [kDa] [ºC] Airvol® 205 88 15 - 27 230 Vinex® 2019 88 15 - 27 170 Vinex® 2144 88 44 - 65 205 Vinex® 1025 99 15 - 27 170 Vinex® 2025 88 25 - 45 192 Gohsefimer® 5407 30 - 28 23,600 100 Gohsefimer® LL02 41 - 51 17,700 100

Other suitable polyvinyl alcohols such as Water soluble coating material are ELVANOL® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (registered trademarks of Du Pont), ALCOTEX® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademarks of the signature Harlow Chemical Co.), Gohsenol® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademarks of the Nippon firm Gohsei K.K.). ERKOL signature types are also suitable Wacker

Another preferred group of soluble polymers in water, which can serve as a coating, according to the invention, They are polyvinylpyrrolidones. These are marketed, for example, under the name Luviskol® (BASF). Polyvinylpyrrolidone [poly (1-vinyl-2-pyrrolidinone)], abbreviated PVP, they are polymers of the general formula (I)

one

that are prepared by radical polymerization of the 1-vinyl pyrrolidone according to the procedure of the polymerization in solution or in suspension with the use of trainers of radicals (peroxides, azo compounds) as initiators. The ionic polymerization of the monomers provides only products With low molecular weight. Polyvinylpyrrolidones, common in the trade, they have molecular weights in the range from approximately 2,500 to 750,000 g / mol, which are characterized by indicating the K values and which have -in function of the K value - glass transition temperatures from 130 to 175 ° C. These are marketed in the form of white powder, hygroscopic, or in aqueous solution. Polyvinylpyrrolidones are perfectly soluble in water and in a plurality of solvents organic (alcohols, ketones, glacial acetic acid, hydrocarbons chlorinated, phenols and Similar).

Also, copolymers of the vinyl pyrrolidone with other monomers, especially copolymers of vinyl pyrrolidone / vinyl esters, such as those marketed, for example, under the trademark Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73 products, respectively vinyl pyrrolidone / vinyl acetate copolymers they are especially preferred nonionic polymers.

Vinyl ester polymers are polymers. obtainable from vinyl esters, with grouping of the formula (II)

2

as a characteristic component of the macromolecule Among these, vinyl acetate polymers (R = CH 3) with polyvinyl acetates have, as representatives most important, at a distance, the industrial meaning maximum.

Polymerization of vinyl esters is carried out by radicals according to various procedures (solution polymerization, suspension polymerization, emulsion polymerization, substance polymerization). The Vinyl acetate copolymers with vinyl pyrrolidone contain monomer units of formulas (I) and (II).

Other suitable water soluble polymers are polyethylene glycols (polyethylene oxides), which are called abbreviated as PEG. PEGs are polymers of ethylene glycol, which satisfy the general formula (III)

(III) H- (O-CH2 -CH2) n -OH

in which n can take values between 5 and> 100,000.

PEGs are manufactured industrially by anionic polymerization by opening the oxide ring of ethylene (oxirane) most often in the presence of quantities Small water According to the conduct of the reaction they have molecular weights in the range from about 200 up to 5,000,000 g / mol, which corresponds to degrees of polymerization from about 5 to> 100,000.

Products with molecular weights approximately <25,000 g / mol are liquid at temperature environment and are referred to as authentic polyethylene glycols, in PEG abbreviation. These short chain PEGs can be added, especially to other water soluble polymers, for example, polyvinyl alcohols or cellulose ethers by way of plasticizers Solid polyethylene glycols at temperature environment, employable, according to the invention, are referred to as oxides of polyethylene, in abbreviation PEOX. Polyethylene oxides of high molecular weight have an extraordinary concentration low in reactive hydroxy groups located at the ends and so both have glycol properties still very weak.

According to the invention, the gelatin as another water soluble coating material, it is preferably used together with other polymers. The Gelatin is a polypeptide (molecular weight: approximately from 15,000 to> 250,000 g / mol), which is predominantly obtained by hydrolysis of the collagen contained in the skin and in the animal bones under acidic or alkaline conditions. The amino acid composition of gelatin corresponds broadly to that of collagen, from which it has been obtained and varies in function of its origin. The use of gelatin as a material for water soluble coating is extraordinarily extended especially in pharmacy, in the form of hard gelatin capsules or of soft gelatin capsules. The jelly finds only one reduced application in the form of sheets due to its high price compared to the price of polymers previously cited.

Other polymers are described below. water soluble, suitable as coating agents, according to the invention:

-

         cellulose ethers, such as hydroxypropyl cellulose, the hydroxyethylcellulose and methylhydroxypropylcellulose, such as those They are marketed under the Culminal® and Benecel® trademarks (AQUALON).

Ethers of Cellulose can be described by means of the general formula (IV),

3

in which R means H or an alkyl, alkenyl, alkynyl, aryl moiety or rented. In preferred products R means at least formula (III) -CH 2 CH 2 CH 2 -OH or -CH 2 CH 2 -OH. The cellulose ethers are industrially manufactured by etherification of celluloses alkaline (for example, with ethylene oxide). The ethers of the Cellulose are characterized by the average degree of substitution DS or either by the degree of molar substitution MS, which indicates the number of hydroxy groups of an anhydroglucose unit of the cellulose that has reacted with the etherification reagent or the number of moles of the etherification agent on average over the that an anhydroglucose unit has been added. The hydroxyethylcelluloses are soluble in water from a DS of about 0.6 or from an MS of about 1. The hydroxyethylcelluloses or hydroxypropylcelluloses, common in trade, have degrees of substitution in the range of 0.85 - 1.35 (DS) or 1.5 - 3 (MS). Hydroxyethylcelluloses and Hydroxypropylcelluloses are marketed in the form of white powder yellowish, odorless and tasteless in degrees of polymerization strongly variable. Hydroxyethylcelluloses and hydroxypropyl celluloses are soluble in cold water and hot water as well as in some organic solvents (hydrated), by the On the contrary, they are insoluble in most organic solvents (anhydrous); its aqueous solutions are relatively insensitive against the variations in the pH of the electrolytic additive.

Preferred procedures, according to the invention are characterized in that the coatings, soluble in water, include hydroxypropyl methylcellulose (HPMC), which has a degree of substitution (average number of methoxy groups per unit of cellulose anhydroglucose) from 1.0 to 2.0, preferably from 1.4 to 1.9, and by a molar substitution (average number of hydroxypropyl groups per anhydroglucose unit of the cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25.

Other suitable polymers, according to the invention, they are water soluble amphipolymers. In the general expression of ampho-polymers are gathered polymers amphoteric, that is polymers that contain in the molecule both free amino groups as well as -COOH- or SO 3 H- groups free and that are capable of forming internal salts, polymers Zwitterionics, which contain ammonium groups in the molecule quaternary and groups -COO - - or -SO 3 - - and those polymers containing -COOH- groups and SO3H groups and groups of quaternary ammonium. An example of an amphotopolymer, employable, according to the invention, it is the acrylic resin obtainable under the Amphomer® designation, which represents a copolymer consisting of tert-butyl aminoethyl methacrylate, by N- (1,1,3,3-tetramethylbutyl) acrylamide as well as by two or several monomers chosen from the group formed by the Acrylic acid, methacrylic acid or its simple esters. Of the similarly, the preferred amphipolymers are constituted by unsaturated carboxylic acids (for example, acrylic acid and methacrylic acid), cationically unsaturated carboxylic acids derivatives (for example, chloride acrylamidopropyl trimethyl ammonium) and, if necessary, other ionic or non-ionic monomers, such as which can be seen, for example, in the descriptive memory of the German patent application, published, unexamined 39 29 973 and in the state of the art, cited there. Acid terpolymers acrylic, methyl acrylate and chloride methylacrylamidopropyltrimony, such as those obtainable in the trade under the name Merquat® 2001 N, are especially preferred amphipolymers, according to the invention. Other suitable amphoteric polymers are, for example, octyl acrylamide / methyl methacrylate / methacrylate copolymers  of tert-butylaminoethyl / methacrylate 2-hydroxypropyl that can be purchased under the designations Amphomer® and Amphomer® LV-71 (DELFT NATIONAL).

Anionic, water soluble polymers, Suitable, according to the invention, are, among others:

-

vinyl acetate / acid copolymers crotonic, such as those found in the market, for example, under the names Resyn® (NATIONAL STARCH), Luviset® (BASF) and Gafset® (GAF).

quad

These polymers have, in addition to the units monomers of the formula (II), cited above, also monomer units of the general formula (V):

(V) [- CH (CH 3) - CH (COOH) -] n

-

vinylpyrrolidone / acrylate copolymers of vinyl, which can be obtained, for example, under the registered trademark Luviflex® (BASF). A preferred polymer is the terpolymer of vinyl pyrrolidone / acrylate obtainable under the name Luviflex® VBM-35 (BASF).

-

acrylic acid / acrylate terpolymers of ethyl / N-tert-butylacrylamide, which is marketed, for example, under the name Ultrahold® strong (BASF).

-

graft polymers consisting of esters of vinyl, esters of acrylic acid or methacrylic acid alone or in mixture, copolymerized with crotonic acid, acrylic acid or with methacrylic acid with polyalkylene oxides and / or with polyalkylene glycols

Such graft polymers of the esters of vinyl, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on Polyalkylene glycols are obtained by polymerization in warm in homogeneous phase by introduction under stirring of the polyalkylene glycols in the monomers of vinyl esters, the esters of acrylic acid or methacrylic acid, in the presence of radical formers

Suitable vinyl esters, for example, are vinyl acetate, vinyl propionate, vinyl butylate, vinyl benzoate and as esters of acrylic acid or methacrylic acid, those that can be obtained with alcohols have been accredited low molecular weight aliphatics, that is especially with ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol,
3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol.

Polypropylene glycols (abbreviated PPG) they are polymers of propylene glycol, which satisfy the general formula SAW

\delm{H}{\delm{\para}{CH _{3} }}

--- CH_{2})_{n} --- OH(VI) H --- (O --- C

 \ delm {H} {\ delm {\ para} {CH3}} 

--- CH 2) n --- OH

in which n can take values between 1 (propylene glycol) and several thousand. From an industrial point of view, di-, tri- and tetrapropylene glycol are significant in this case, that is, representatives with
n = 2, 3 and 4 in formula VI.

Especially copolymers can be used of vinyl acetate, grafted onto polyethylene glycols and grafted vinyl acetate and crotonic acid polymers about polyethylene glycols.

-

grafted and crosslinked copolymers from the copolymerization of

i)

         at least one non-ionic type monomer,

ii)

        at least one ionic monomer,

iii)

                of polyethylene glycol and

iv)

                a crosslinker.

The polyethylene glycol used has a weight molecular range between 200 and several million, preferably between 300 and 30,000.

Nonionic monomers can be of the very type variable and among these the following are preferred: acetate vinyl, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methacrylate methyl, cetyl vinyl ether, stearyl vinyl ether and 1-hexene

Non-ionic monomers can also be of very diverse types, being contained in graft polymers, particularly preferably, crotonic acid, acid allyloxyacetic, vinylacetic acid, maleic acid, acid Acrylic and methacrylic acid.

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As crosslinkers, preferably, ethylene glycol dimethacrylate, diallyl phthalate, ortho-, the meta- and para-divinylbenzene, the tetraalkyloxyethane and polyallyl sucrose with 2 to 5 groups allyl per saccharin molecule.

The copolymers described above, grafted and crosslinked, they are preferably formed from:

i)

         from 5 to 85% by weight at least one monomer of the type nonionic,

ii)

        from 3 to 80% by weight at least one monomer of the type ionic,

iii)

       from 2 to 50% by weight, preferably from 5 to 5 30% by weight of polyethylene glycol and

iv)

       from 0.1 to 8% by weight of a crosslinker, forming the percentage of the crosslinker by the proportion of the total weight of i), ii) and iii).

-

copolymers obtained by copolymerization of at least one monomer of each of the three groups following:

i)

         esters of unsaturated alcohols and carboxylic acids saturated, short chain and / or esters of saturated alcohols, of short chain and unsaturated carboxylic acids,

ii)

        unsaturated carboxylic acids,

iii)

                esters of long chain carboxylic acids and of unsaturated alcohols and / or esters consisting of acids carboxylic acids of group ii) with saturated or unsaturated alcohols, of linear or branched chain with 8 to 18 atoms of carbon.

They will be understood by carboxylic acids or by Short chain alcohols in this case those with 1 to 8 carbon atoms, the chains may be interrupted carbonates of these compounds if given by hetero groups divalents such as -O-, -NH-, -S-.

-

terpolymers consisting of crotonic acid, vinyl acetate and an allyl or metalyl ester.

These terpolymers contain monomer units of the general formulas (II) and (IV) (see above) as well as monomer units from one or more allyl esters or from metalyl of formula VII:

\melm{\delm{\para}{CH _{3} }}{C}{\uelm{\para}{R ^{1} }}

--- C(O) --- O --- CH_{2} ---

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

\longequal CH_{2}(VII) R2 ---

 \ melm {\ delm {\ para} {CH 3}} {C} {\ uelm {\ para} {R 1}}} 

--- C (O) --- O --- CH_ {2} ---

 \ uelm {C} {\ uelm {\ para} {R3}} 

\ longequal CH2

in which R3 means -H or -CH 3, R 2 means -CH 3 or -CH (CH 3) 2 and R 1 means -CH 3, or a saturated, straight chain or branched chain alkyl moiety, with 1 to 6 carbon atoms and the sum of carbon atoms in residues R1 and R2 preferably take the values 7, 6, 5, 4, 3 or 2.

The terpolymers, cited above, they result, preferably, from the copolymerization of a 7 to a 12% by weight of crotonic acid, from 65 to 86% by weight, preferably from 71 to 83% by weight of vinyl acetate and from 8 to 20% by weight, preferably from 10 to 10 17% by weight of allyl or metalyl esters of the formula VII.

-

constituted tetrapolymers and pentapolymers by

i)

         crotonic acid and allyloxyacetic acid,

ii)

        vinyl acetate or vinyl propionate,

iii)

                branched allyl or metalyl esters,

iv)

                vinyl ethers, vinyl esters or allyl esters or of linear chain metalyl.

-

copolymers of crotonic acid with one or more monomers of the group formed by ethylene, vinylbenzene, vinyl methyl ether, acrylamide and its soluble salts in Water.

-

terpolymers consisting of vinyl acetate, crotonic acid and vinyl esters of one monocarboxylic acid saturated, aliphatic, branched in the α position.

       \ newpage
    

Other polymers, preferably employable, according to the invention, as a coating are cationic polymers.  Among the cationic polymers in this case the permanently cationic polymers. They will be understood as polymers "permanently cationic", according to the invention, those who present a cationic group regardless of the pH value. These are, as a rule, polymers that contain an atom of quaternary nitrogen, for example, in the form of a group ammonium.

Preferred cationic polymers are, by example:

-

quaternized cellulose derivatives, such as those can be obtained under the names Celquat® and Polymer JR®. The Celquat® H 100, Celquat® L 200 and Polymer JR®400 compounds are preferred quaternized cellulose derivatives,

-

polymyloxanes with quaternary groups, such such as commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamidomethomna), Dow Corning® 929 Emulsion (containing a silicone hydroxy-amino-modified, which is also called amidomethicone), SM-2059 (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) as well as Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; quaternary polydimethylsiloxane, Quaternium-80),

-

cationic guar derivatives, such as marketed products, especially under the denominations from Cosmedia® Guar and Jaguar®,

-

polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and acid methacrylic Products that are obtained commercially under the Merquat®100 denominations (chloride poly (dimethyldiallylammonium) and Merquat®550 (copolymer of dimethyldiallylammonium acrylamide chloride) they constitute examples of this type of polymers cationic,

-

vinyl pyrrolidone copolymers with derivatives quaternized dialkylaminoacrylate and dialkylaminomethacrylate, such as, for example, copolymers vinyl pyrrolidone dimethylaminomethacrylate quaternized with diethyl sulfate. These types of compounds can be acquired commercially under the names Gafquat®734 and Gafquat®755,

-

copolymers of vinyl pyrrolidone-methimidazolinium chloride, such as those offered under the name Luviquat®,

-

quaternized polyvinyl alcohol,

as well as polymers with atoms of quaternary nitrogen in the main polymer chain, known under the denominations

-

Polyquaternium 2,

-

Polyquaternium 17,

-

Polyquaternium 18 and

-

Polyquaternium 27.

The polymers mentioned have been designated in this case according to the nomenclature called INCI, being detailed indications in the CTFA International publication Cosmetic Ingredient Dictionary and Handbook, 5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, a which will be referred to here expressly.

The cationic polymers, preferred according to invention, are quaternized cellulose derivatives as well as polymer salts of dimethyldiallylammonium and their copolymers. The cationic cellulose derivatives, especially the product Commercial Polymer® JR 400, they are very cationic polymers especially preferred.

In the process, according to the invention, the coating or the sheet material may contain, in addition to the water soluble polymer or soluble polymers in water, other components, which especially improve the ability to the transformation of the starting materials to form the coating. In this case, especially the plasticizers and mold release agents. They can also dyes and / or odorizing products are incorporated as well as optical brighteners in the water soluble coating, for get aesthetic effects in it.

As plasticizers they can be used, according to the invention, especially hydrophilic liquids, of high point boiling, being able to use products if necessary solids at room temperature in solution, dispersion form or fusion. Especially preferred plasticizers come from from the glycol group, from di-, from tri-, from tetra-, from penta-, Hexa-, hepta-, octa-, nona-, deca-, undeca-,  of dodecaethylene glycol, glycerin, neopentyl glycol, trimethylolpropane, pentaerythrite, mono-, di-, triglycerides, of surfactants, especially those nonionic surfactants, as well as mixtures thereof.

Ethylene glycol (1,2-ethanediol, "glycol") is a colorless, viscous, sweet-tasting liquid, strongly hygroscopic, which can be mixed with water, with alcohols and with acetone and having a density of 1,113. He solidification point of ethylene glycol is at -11.5 ° C, The liquid boils at 198 ° C. Industrially you get the ethylene glycol from ethylene oxide by heating With water under pressure. Promising procurement procedures they can also be based on ethylene acetoxylation and hydrolysis subsequent or in the synthesis gas reactions.

Diethylene glycol (2,2'-oxidietanol, digol), HO- (CH 2) 2 -O- (CH 2) 2 -OH, It is a colorless, viscous, hygroscopic, sweet-tasting liquid with a density of 1.12, which melts at -6 ° C and boils at 245 ° C. He diglycol can be mixed in any proportion with water, with alcohols, with glycol ethers, with ketones, with esters, with chloroform, however, is not miscible with hydrocarbons or with the oils Diethylene glycol, cited in practice in most briefly as diglycol, it is prepared from oxide of ethylene and ethylene glycol (ethoxylation) and therefore is practically the initial member of polyethylene glycols (see higher).

Glycerin is a colorless liquid, of course, movable with difficulty, odorless, sweet, hygroscopic with a density of 1,261, which solidifies at 18.2 ° C. The glycerin was initially only a secondary product of the saponification of fats, but currently it is synthesized industrially in large quantities. Most industrial procedures they start from propene, which is made from products intermediates consisting of allyl chloride, epichlorohydrin to give glycerin. Another industrial procedure consists in the hydroxylation of allyl alcohol with hydrogen peroxide over WO 3 contact going through the glycidol stage.

Trimethylolpropane [TMP, etriol, ettriol, 1,1,1-tris (hydroxymethyl) propane] is, according to its exact chemical name the 2-ethyl-2-hydroxymethyl-1,3-propanediol and is marketed as a colorless, hygroscopic mass with a melting point of 57-59 ° C and with a melting point 160 ° C (7 hPa). It is soluble in water, in alcohol, in acetone but insoluble in aliphatic and aromatic hydrocarbons. The making is carried out by reaction of formaldehyde with butyraldehyde in the presence of alkalis.

Pentaerythrite [2,2-bis (hydroxymethyl) -1,3-propanediol, penta, PE] is a white, crystalline powder with a sweet taste, which does not it is hygroscopic and it is combustible and it has a density of 1,399, a melting point of 262 ° C as well as a boiling point of 276 ° C (40 hPa). Pentaerythrite is perfectly soluble in water  boiling, slightly soluble in alcohol and insoluble in benzene, in tetrachloromethane, in ether, in petroleum ether. Industrially the Pentaerythrite is manufactured by reaction of formaldehyde with acetaldehyde in aqueous solution of Ca (OH) 2 or also NaOH at 15-45 ° C. In this case it takes place, in first, a mixed aldol reaction, in which the formaldehyde reacts as a carbonyl component, acetaldehyde It reacts as a methylene component. Due to the high activity of formaldehyde carbonyl practically no Acetaldehyde reaction with itself. Then you transforms the tris (hydroxymethyl) acetaldehyde, formed thus, with formaldehyde in a cross reaction of Cannizzaro in pentaerythrite and formate.

Mono-, di-, triglycerides are esters of fatty acids, preferably long chain fatty acids with glycerin, being esterified, according to each type of glycerin, one, two or three OH groups of glycerin. As an acid component, with which glycerin can be esterified in mono-, di- or triglycerides, which can be used as plasticizers, according to the invention, for example, hexanoic acid (acid capronic), heptanoic acid (enantoic acid), acid octanoic (caprylic acid), nonanoic acid (acid pelargonic acid), decanoic acid (caprinic acid), acid undecanoic etc. In the scope of the present invention it is preferably the use of fatty acids such as acid dodecanoic acid (lauric acid), tetradecanoic acid (acid myristic), hexadecanoic acid (palmitic acid), acid octadecanoic acid (stearic acid), eicoxanoic acid (acid arachidic), docosanoic acid (behenic acid), acid tetracosanic (lignocerinic acid), hexacosanic acid (acid cerotinoic), triacotanoic acid (melisinic acid) as well as unsaturated species constituted by acid 9c-hexadecenoic acid (palmitoleic acid), acid 6c-octadecenoic acid (petroselinic acid), acid 6t-octadecenoic acid (petroselaidinic acid), acid 9c-octadecenoic acid (oleic acid), acid 9t-octadecenoic acid (elaidinic acid), acid 9c, 12c-octadecadienoic acid (linoleic acid), acid 9t, 12t-octadecadienoic acid (linolaidinic acid) and the 9c, 12c, 15c-octadecatreinic acid (acid linolenic). For reasons of cost, you can also use natural fatty products (triglycerides) or fatty products natural modified (partially hydrolyzed fats and oils). Alternatively, fatty acid mixtures can also be prepared by dissociation of fats and natural oils and then separate, converting the purified fractions further, in turn, in mono-, di- or triglycerides. The acids, which are esterified in this case with glycerin, they are especially coconut oil fatty acids (approximately 6% by weight of C 8, 6% by weight of C 10, 48% by weight of C 12, 18% by weight of C 14, 10% by weight of C 16, 2% by weight of C 18, 8% by weight of C 18 ', 1% by weight of C 18' '), the acids fatty palm kernel oil (approximately 4% by weight of C 8, 5% by weight of C 10, 50% by weight of C 12, 15% by weight of C 14, 7% by weight of C 16, 2% by weight of C 18, 15% by weight of C 18 ', 1% by weight of C 18' '), the acids tallow fatty acids (approximately 3% by weight of C 14, 26% by weight of C 16, 2% by weight of C 16 ', 2% by weight of C 17, 17% in weight of C 18, 44% by weight of C 18 ', 3% by weight of C 18 ', 1% by weight of C 18'), tallow fatty acids hardened (approximately 2% by weight of C 14, 28% by weight of C 16, 2% by weight of C 17, 63% by weight of C 18, 1% in weight of C 18 '), industrial oleic acid (approximately 1% by weight of C 12, 3% by weight of C 14, 5% by weight of C 16, 6% by weight of C 16 ', 1% by weight of C 17, 2% by weight of C 18, 70% by weight of C 18 ', 10% by weight of C 18 ', 0.5% by weight of C 18'), the acid industrial palmitic / stearic (approximately 1% by weight of C 12, 2% by weight of C 14, 45% by weight of C 16, 2% by weight of C 17, 47% by weight of C 18, 1% by weight of C 18 ') as well as the fatty acids of soy bean oil (approximately 2% by weight of C 14, 15% by weight of C 16, 5% by weight of C18, 25% by weight of C18 ', 45% by weight of C_ {18``}, 7% by weight of C_ {18 '' '}).

They also come into consideration, as others plasticizers, especially non-ionic surfactants. How nonionic surfactants will preferably be used alcohols alkoxylated, advantageously ethoxylated, especially primary, preferably with 8 to 18 carbon atoms, and an average of 1 up to 12 moles of ethylene oxide (EO) per mole of alcohol, in that the alcoholic residue can be linear, or branched with methyl preferably in position 2, or it may contain residues linear and branched with mixed methyl, such as those They usually present in the remains of oxoalcohols. Do not However, especially the ethoxylates of the alcohols with linear residues, consisting of alcohols of origin natural with 12 to 18 carbon atoms, for example, from fatty alcohols of coconut, palm, tallow, or alcohol oleyl, and an average of 2 to 8 moles of EO per mole of alcohol. TO the preferred ethoxylated alcohols belong, by way of For example, alcohols with 12 to 14 carbon atoms with 3 OE or with 4 EO, alcohols with 9 to 11 carbon atoms with 7 OE, the alcohols with 13 to 15 carbon atoms with 3 OE, 5 OE, 7 EO or 8 OE, alcohols with 12 to 18 carbon atoms with 3 OE, 5 EO or 7 SO, and mixtures thereof, such as mixtures constituted by the alcohols with 12 to 14 carbon atoms with 3 OE, and alcohols with 12 to 18 carbon atoms with 5 OE. The degrees of ethoxylation indicated represent statistical mean values, which may be an integer or fractional number for a special product. The ethoxylates of preferred alcohols have a distribution narrow of the homologs (narrow range ethoxylates, NRE). further of these nonionic surfactants, can be used, also, fatty alcohols with more than 12 OE. Examples to this respect are tallow fatty alcohols with 14 OE, with 25 OE, with 30 EO or with 40 OE.

Especially preferably they will be used nonionic surfactants such as plasticizers, which have a melting point above room temperature. Thus preferred coatings are characterized because as plasticizers one or more non-ionic surfactants are used with a melting point above 20 ° C, preferably above of 25 ° C, especially preferably between 25 and 60 ° C and, especially, between 26.6 and 43.3 ° C.

Suitable non-ionic surfactants, which have melting or softening points throughout the temperature range, are, for example, non-surfactants low foam ionic generators, which can be solid or highly viscous at room temperature. When used highly viscous nonionic surfactants at room temperature, it will be preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and, especially, by over 40 Pas. Also preferred are non-surfactants. ionics that have a waxy type consistency at temperature ambient.

The surfactants to be used preferably, solids at room temperature, come from the group of alkoxylated nonionic surfactants, especially those ethoxylated primary alcohols and mixtures of these surfactants with surfactants constituted by a more complicated structure such as the propylene polyoxide / polyoxide surfactants of ethylene / propylene polyoxide (PO / EO / PO).

In a preferred embodiment of the present invention, the nonionic surfactant with a point of melting above room temperature, it is a non-surfactant ionic, ethoxylated, which has been produced from the reaction of a monohydroxyalkanol or an alkylphenol with 6 to 20 atoms of carbon with, preferably, at least 12 moles, so especially preferred with at least 15 moles, so especially preferred with 20 moles of ethylene oxide per mole of alcohol or alkylphenol.

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

Therefore, it will be used or used in especially preferred methods, according to the invention, the or ethoxylated nonionic surfactants that have been obtained at from monohydroxyalkanoles with 6 to 20 carbon atoms or from alkylphenols with 6 to 20 carbon atoms or fatty alcohols with 16 to 20 carbon atoms and with more than 12 moles, preferably with more than 15 moles and, especially, with more than 20 moles of oxide of ethylene per mole of alcohol.

In addition, the nonionic surfactant has, preferably, propylene oxide units in the molecule. Preferably such PO units constitute up to 25% in weight, especially preferably up to 20% by weight and, especially, up to 15% by weight of the total molecular weight of the nonionic surfactant. Nonionic surfactants especially Preferred are monohydroxyalkanoles or alkylphenols ethoxylates, which also have copolymerized units in polyoxyethylene-polyoxypropylene block. The part alcoholic or alkylphenolic of such molecules of nonionic surfactants in this case preferably represent more than  30% by weight, especially preferably more than 50% by weight and, especially, more than 70% by weight of the total molecular weight of such nonionic surfactants.

Other non-ionic surfactants, to be used especially preferably, with melting points above of the room temperature, they contain from 40 to 70% in weight of a mixture of block polymers of polyoxypropylene / polyoxyethylene / polyoxypropylene, which contains a 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.

Other preferred non-ionic surfactants correspond to 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 means values included between 0.5 and 1.5 e and means a value of 15 as minimum.

Other non-ionic surfactants, preferably employable, 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 the value of x is ≥ 2, each R3 may be different in the formula indicated above. Preferably R1 and R2 are linear hydrocarbon moieties or branched, saturated or unsaturated, aliphatic or aromatic with 6 up to 22 carbon atoms, with 8 residues being preferred Up to 18 carbon atoms. Preferred meanings for R 3 are H, -CH 3 or -CH 2 CH 3. The values especially preferred for x are in the range from 1 to 20, especially from 6 to fifteen.

As described above, each R 3 may be different in the formula indicated above, in the case where it is fulfilled that x \ geq 2. In this case they can vary the alkylene oxide units located inside of the square brackets. If, for example, x means 3, the remainder R3 may be chosen to form ethylene oxide units (R3 = H) or propylene oxide units (R 3 = CH 3), which can  be in any successive order, for example, (EO) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO). In this case it has been chosen, for example, the value 3 for x and can be perfectly higher, increasing the amplitude of the variations as the values of x increase including, for example, a high number of groups (EO) with a Small number of groups (PO), and vice versa.

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

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

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

Other substances to be used preferably as plasticizers may be the carbonate of glycerin, propylene glycol and propylene carbonate.

Glycerin carbonate can be obtained by reaction of ethylene carbonate or dimethyl carbonate  with glycerin, forming ethylene glycol or methanol as secondary products Another way of synthesis starts from glycidol (2,3-epoxy-1-propanol), which is reacted under pressure in the presence of catalysts, with CO2 to give glycerin carbonate. Carbonate Glycerin is a clear liquid, easily agitable, with a density of 1,398 gcm -3, which boils at 125-130 ° C (0.15 mbar).

There are two isomers of propylene glycol, the 1,3-propanediol and the 1,2-propanediol. 1,3-propanediol (trimethylene glycol) is a neutral, colorless and odorless liquid of sweet taste with a density of 1.0597, which solidifies at -32 ° C and boiling at 214 ° C. The manufacture of 1,3-propanediol is obtained from acrolein and of water under subsequent catalytic hydrogenation.

1,2-propanediol is very significant from an industrial point of view (propylene glycol), which represents an oily, colorless, almost odorless liquid, with a density of 1.0381, which solidifies at -60 ° C and boils at 188 ° C. He
1,2-propanediol is manufactured from propylene oxide by adding water.

Propylene Carbonate is a liquid crystalline, easily agitable, with a density of 1.21 gcm -3, whose melting point is at -49 ° C, and the point boiling at 242 ° C. Propylene carbonate can be obtained at large scale by the reaction of propylene oxide and CO2 at 200ºC and 80 bars.

As additional additives, which are presented, preferably, in solid form at room temperature, they are especially suitable highly dispersed silicic acids. In this case the pyrogenic silicic acids are marketed such as Aerosil® or precipitation silicic acids. The procedures, according to the invention, especially preferred are characterized in that, by way of other additives, one or various materials of the group formed by silicic acid (highly dispersed preferably), dispersion powder, high molecular weight polyglycols, stearic acid and / or salts of stearic acid, and / or of the group formed by salts inorganic such as sodium sulfate, calcium chloride and / or of the group formed by the inclusion trainers, such as the urea, cyclodextrin and / or the group formed by superabsorbents such as polyacrylic acid (preferably crosslinked) and / or its salts such as Cabloc 5066 / CTF as well as its mixtures

As indicated at the beginning, they will use the method according to the invention in a manner especially preferred cast bodies as a portion of washing or cleaning. As starting materials especially advantageous for the cast bodies mentioned above have been Accredited dispersions of washing or cleaning agents. The elaboration of these dispersions to give cast bodies and the subsequent packaging by means of the procedure, according to the Invention, it has a number of advantages. First of all they can be made geometric shapes by casting technology, that are not accessible through entablet. In addition, the cast bodies are characterized, as will be described more forward, compared to tablets, for improved solubility. Finally the cast bodies, contrary to what happens in the In the case of tablets, they are ductile as a rule, and can deform plastically in the course of the procedure of packaging, according to the invention, to a certain degree by means of the pressure, for example, when the top sheet is applied or in the time of subsequent fixation of the top sheet on the bottom sheet. Through this plastic deformation they can correct irregularities during casting body fabrication (for example, height, thickness, etc.) and / or can be applied proven optical characteristics in cast bodies.

Another object of this application is, therefore, in a process, according to the invention, in which a washing or cleaning agent is used in the form of portions of washing or cleaning agent, in the state of a dispersion of solid particles in a dispersing agent, comprising, with relation to its total weight,

i)

         from 10 to 65% by weight dispersing agent and

ii)

        from 30 to 90% by weight of dispersed product.

Especially preferred dispersions are characterize, in this case, because the dispersions have a density above 1,040 g / cm3, according to the invention, will be those dispersions with a density between 1,040 and 1,670 g / cm3, preferably between 1,120 and 1,610 g / cm3, especially preferably between 1,210 and 1,570 g / cm3, very especially preferred between 1,290 and 1,510 g / cm3 and, especially, between 1,340 and 1,480 g / cm3. The Density data refer respectively to densities of the dispersions at 20 ° C.

As dispersion it will be called in this application to a system with several phases, one of which is continuous (dispersing agent) and at least one other is finely divided (dispersed product).

Washing or cleaning agents especially preferred, according to the invention, are characterized because the dispersing agent is contained in quantities located above 11% by weight, preferably above 13% by weight, especially preferably above 15% by weight, very especially preferably above 17% by weight and, especially, above 19% by weight, referred respectively to the total weight of the dispersion. They can also be done and are, also, preferred agents according to the invention, which have a dispersion with a weight ratio of agent dispersant above 20% by weight, preferably above 21% by weight and, especially, above 22% by weight, respectively referred to the total weight of the dispersion. He maximum content of the preferred dispersions, according to the invention, in dispersing agent supposes, in relation to the total weight of the dispersion, preferably a proportion less than 63% by weight, preferably less than 57% by weight, so especially preferably less than 52% by weight, very especially preferred less than 47% by weight and, especially, less than 37% by weight. In the scope of the present invention those washing agents or of cleaning agents containing, in relation to the total weight, the agents dispersants in amounts from 12 to 62% by weight, preferably from 17 to 49% by weight and, especially, from 23 to 38% by weight.

The dispersing agents used are, preferably, water soluble or water dispersible. The solubility of these dispersing agents amounts, in this case to 25 ° C, preferably at more than 200 g / l, preferably at more than 300 g / l, especially at more than 400 g / l, very especially preferred between 430 and 620 g / l and, especially, between 470 and 580 g / l.

As dispersing agents are suitable, in the scope of the present invention, preferably polymers water soluble or water dispersible, especially polymers non-ionic water soluble or water dispersible. The agents dispersants can be constituted in this case by both a polymer only as well as mixtures of various polymers different water soluble or water dispersible. In another way preferred embodiment of the present invention, the agent dispersant is constituted, or as long as the agent dispersant comprises substances other than polymers water soluble or water dispersible, at least 50% by weight of the polymer mixture consisting of non-ionic polymers, water soluble or water dispersible from the group consisting of the polyvinylpyrrolidone, vinyl pyrrolidone / ester copolymers vinyl, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, especially polyethylene glycol and / or the polypropylene glycol

In the scope of the invention the agents Dispersants are preferably polyvinylpyrrolidones. The polyvinylpyrrolidone [poly (1-vinyl-2-pyrrolidinone)], abbreviated PVP, they are polymers of the general formula (I)

4

that are prepared by radical polymerization of the 1-vinyl pyrrolidone according to the procedure of the polymerization in solution or in suspension with the use of trainers of radicals (peroxides, azo compounds) as initiators. The ionic polymerization of the monomers provides only products With low molecular weight. Polyvinylpyrrolidones, common in the trade, they have molecular weights in the range from approximately 2,500 to 750,000 g / mol, which are characterized by indicating the K values and which have -in function of the K value - glass transition temperatures from 130 to 175 ° C. These are marketed in the form of white powder, hygroscopic, or in aqueous solution. Polyvinylpyrrolidones are perfectly soluble in water and in a plurality of solvents organic (alcohols, ketones, glacial acetic acid, hydrocarbons chlorinated, phenols and Similar).

The copolymers of vinyl pyrrolidone / esters of vinyl, such as those sold, for example, under the brand Registered Luviskol® (BASF). Luviskol® VA 64 products and Luviskol® VA 73, respectively copolymers of vinyl pyrrolidone / vinyl acetate are nonionic polymers especially preferred.

Vinyl ester polymers are polymers. obtainable from vinyl esters, with grouping of the formula (II)

5

as a characteristic component of the macromolecule Among these, vinyl acetate polymers (R = CH 3) with polyvinyl acetates have, as representatives most important, at a distance, the industrial meaning maximum.

Polymerization of vinyl esters is carried out by radicals according to various procedures (solution polymerization, suspension polymerization, emulsion polymerization, substance polymerization). The Vinyl acetate copolymers with vinyl pyrrolidone contain monomer units of formulas (I) and (II).

Cellulose ethers, such as the hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose, such as those sold under the trademarks Culminal® and Benecel® (AQUALON).

Cellulose ethers can be described by middle of the general formula,

6

in which R means H or a remainder alkyl, alkenyl, alkynyl, aryl or alkylaryl. In the products preferred R means at least in the formula -CH 2 CH 2 CH 2 -OH or -CH 2 CH 2 -OH. The cellulose ethers are industrially manufactured by etherification of celluloses alkaline (for example, with ethylene oxide). The ethers of the Cellulose are characterized by the average degree of substitution DS or either by the degree of molar substitution MS, which indicates the number of hydroxy groups of an anhydroglucose unit of the cellulose that has reacted with the etherification reagent or the number of moles of the etherification agent on average over the that an anhydroglucose unit has been added. The hydroxyethylcelluloses are soluble in water from a DS of about 0.6 or from an MS of about 1. The hydroxyethylcelluloses or hydroxypropylcelluloses, common in trade, have degrees of substitution in the range of 0.85 - 1.35 (DS) or 1.5 - 3 (MS). Hydroxyethylcelluloses and Hydroxypropylcelluloses are marketed in the form of white powder yellowish, odorless and tasteless in degrees of polymerization strongly variable. Hydroxyethylcelluloses and hydroxypropyl celluloses are soluble in cold water and hot water as well as in some organic solvents (hydrated), by the On the contrary, they are insoluble in most organic solvents (anhydrous); its aqueous solutions are relatively insensitive against variations in the pH of the additive electrolytic.

Polyvinyl alcohols, called abbreviated PVAL, they are polymers with the general structure

[-CH 2 -CH (OH) -] n

which also contain in small proportions, structural units of kind

[-CH 2 -CH (OH) -CH (OH) -CH 2]

Since the corresponding monomer, the Vinyl alcohol, is not stable in free form, the polyvinyl alcohols by reactions similar to polymerization by hydrolysis, however industrially by reaction, catalyzed by means of alkalis, of acetates of polyvinyl with alcohols (preferably methanol) in solution. Through this industrial procedure, PVALs are also accessible containing a predetermined residual proportion of groups acetate.

The usual commercial PVALs (for example, Mowiol® types from Hoechst) are marketed as white-yellowish powders or granules with grades of polymerization in the range of approximately 500-2,500 (corresponding molecular weights of approximately 20,000-100,000 g / mol) and have varying degrees of hydrolysis of 98-99 or 87-89 mol% Therefore, they are acetates of partially saponified polyvinyl with a residual content in acetyl groups of about 1-2 or 11-13% in moles.

How polyalkylene glycols enter consideration, especially, polyethylene glycols and polypropylene glycols The polymers of ethylene glycol, which satisfy the general formula III

(III) H- (O-CH2 -CH2) n -OH

in which n can take values between 1 (ethylene glycol) and several thousand. For the polyethylene glycols there are several nomenclatures, which can lead to mistakes. In industry the indication of the average relative molecular weight in connection with the indication "PEG", so that, "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to about 210. For cosmetic components uses a different nomenclature, in which the abbreviation PEG equipped with a hyphen and a number immediately behind the hyphen, which corresponds to the number n in the preceding formula VII. Agree with this nomenclature (called INCI nomenclature, CTFA International Kosmetik Ingredient Dictionary and Handbook, 5th Edition, The Kosmetik, Toiletry and Fragante Association, Washington, 1997) can be used, for example, PEG-4, PEG-6, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14 and PEG-16 Polyethylene glycols can be obtained at trade, for example, under the trade names Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HÜLS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rh \ hat {o} ne-Poulenc), Lutrol® E300 (BASF) as well as the corresponding trade names with major numbers The average relative molecular weight of at least one of the dispersing agents used in the washing agents and of cleaning, according to the invention, especially of at least one of the poly (alkylene) glycols used, it is found between 200 and 36,000, preferably between 200 and 6,000 and, especially preferably, between 300 and 5,000

Polypropylene glycols (abbreviated PPG) they are polymers of propylene glycol, which satisfy the general formula (IV)

\delm{H}{\delm{\para}{CH _{3} }}

--- CH_{2})_{n} --- OH(IV) H --- (O --- C

 \ delm {H} {\ delm {\ para} {CH3}} 

--- CH 2) n --- OH

in which n can take values between 1 (propylene glycol) and several thousand. From an industrial point of view, di-, tri- and tetrapropylene glycol are significant in this case, that is, representatives with
n = 2, 3 and 4 in formula IV.

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Washing or cleaning agents Especially preferred, according to the invention, contain by way of dispersing agent, a non-ionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, the proportion being found in weight of poly (ethylene) glycol over the total weight of all dispersing agents preferably between 10 and 90% by weight, especially preferably between 30 and 80% in weight and, especially, between 50 and 70% by weight. They are especially preferred, according to the invention, the agents of washing or cleaning in which the dispersing agent is constituted by more than 92% by weight, preferably by more than 94% by weight, especially preferably by more than 96% by weight, very particularly preferably by more than 98% in weight and especially 100% by weight for a poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, especially however it is constituted by poly (ethylene) glycol. The agents dispersants, which contain in addition to poly (ethylene) glycol too poly (propylene) glycol, preferably have a relationship between the weight ratio of poly (ethylene) glycol and the poly (propylene) glycol between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, especially preferably between 10: 1 and 1.5: 1 and, especially, between 7: 1 and 2: 1.

Other preferred dispersing agents are those nonionic surfactants, which are used both alone and, in a way especially preferred, in combination with a non-polymer ionic.

As nonionic surfactants they will be used, preferably, alkoxylated, advantageously ethoxylated alcohols, especially primary, preferably with 8 to 18 atoms of carbon, and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcoholic residue can be linear, or be branched with methyl preferably in position 2, or may contain linear and branched moieties with methyl in mixture, such as those usually presented in remnants of oxoalcohols. However, especially those are preferred. ethoxylates of alcohols with linear residues, consisting of naturally occurring alcohols with 12 to 18 carbon atoms, per example, from the fatty alcohols of coconut, palm, of tallow, or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol. To ethoxylated, preferred alcohols, belong, for example, alcohols with 12 to 14 atoms of carbon with 3 OE or with 4 EO, alcohols with 9 to 11 atoms of carbon with 7 OE, alcohols with 13 to 15 carbon atoms with 3 OE, 5 OE, 7 EO or 8 OE, alcohols with 12 to 18 atoms of carbon with 3 OE, 5 EO or 7 OE, and mixtures thereof, such as mixtures consisting of alcohols with 12 to 14 carbon atoms with 3 OE, and alcohols with 12 to 18 carbon atoms with 5 OE. The degrees of ethoxylation indicated mean mean values statistics, which can be an integer or fractional number for A special product The ethoxylates of the preferred alcohols have a narrow distribution of homologues (narrow range ethoxylates, NRE). In addition to these surfactants, no ionic, fatty alcohols with more than 12 can also be used OE Examples in this regard are tallow fatty alcohols with 14 OE, with 25 OE, with 30 EO or with 40 OE.

In addition, they can be used as others nonionic surfactants also the alkyl glycosides of the formula general RO (G) x, where R means a remainder linear or branched methyl chain primary aliphatic, in special branched with methyl in position 2, with 8 to 22, preferably 12 to 18 carbon atoms, and G is the symbol which means a glycosal unit with 5 or 6 carbon atoms, preferably means glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, in an arbitrary number between 1 and 10; preferably x is between 1.2 and 1.4.

Other class of non-ionic surfactants, to be preferably employed, which are used well as the only ones nonionic surfactants or in combination with others nonionic surfactants, are alkyl esters of acids alkoxylated fatty acids, preferably ethoxylated or ethoxylated and propoxylated, preferably with 1 to 4 carbon atoms in the alkyl chain.

Agents may also be suitable. nonionic surfactants of the type of amine oxides, by example, the oxide of N-cocoalkyl-N, N-dimethylamine and the oxide of N-tallowalkyl-N, N-dihydroxyethylamine, and fatty acid alkanolamides. Preferably, the amount of these nonionic surfactants is not greater than that of ethoxylated fatty alcohols, especially is not greater than Half of it.

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

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

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

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

--- [Z]

in which RCO means a remainder aliphatic acyl with 6 to 22 carbon atoms, R1 means hydrogen, an alkyl or hydroxyalkyl moiety with 1 to 4 atoms carbon, and [Z] means a linear polyhydroxyalkyl moiety or branched with 3 to 10 carbon atoms, and with 3 to 10 groups hydroxyl The polyhydroxy fatty acid amides are known substances, which can usually be obtained by amination by reduction of a reducing sugar with ammonia, with a alkylamine or with an alkanolamine and then acylation with a fatty acid, with an alkyl ester of fatty acids, or a acid chloride fatty

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To the group of acid amides polyhydroxygreases also belong to the compounds of the formula

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

--- [Z]R --- CO ---

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

--- [Z]

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

Preferably [Z] is obtained by amination by reduction of a reducing sugar, for example glucose,  fructose, maltose, lactose, galactose, mannose or xylose. The compounds substituted with N-alkoxy or with N-aryloxy can be transformed by reaction with fatty acid methyl esters in the presence of a Alkoxide as a catalyst in the acid amides desired polyhydroxygreases.

Preferred surfactants will be used nonionic surfactants, with low foam generation. By way of especially preferred, cleaning agents, according to the invention, for machine washing of dishes, contain nonionic surfactants, especially nonionic surfactants of group of alkoxylated alcohols.

Especially preferred agents, according to the invention, are those that have a softening point above room temperature. Therefore the agents for preferred dishwashing, they are characterized because they contain one or more nonionic surfactants with a point of melting above 20 ° C, preferably above 25 ° C, of especially preferred between 25 and 60 ° C, 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, surfactants non-ionic with low foam generation, which can be solid or highly viscous at room temperature. When used highly viscous nonionic surfactants at room temperature, it will be preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and, especially, by over 40 Pas. Also preferred are non-surfactants. ionics that have a waxy type consistency at temperature ambient.

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 of these surfactants with structurally configured surfactants in a more complicated such as surfactants of polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO). Such Surfactants (PO / EO / PO) are also characterized by good control of the foam.

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 for Especially preferred, solid at room temperature, is obtained from a linear chain fatty alcohol with 16 to 20 carbon atoms (alcohol with 16-20 atoms of carbon), preferably from an alcohol with 18 atoms of carbon and at least 12 moles, preferably at least 15 moles and, especially, at least 20 moles of ethylene oxide. Between these are especially preferred so-called "ethoxylates narrow range ethoxylates "(see more above).

Therefore, the agents for scrubbing the Especially preferred dishes according to the invention contain one or more ethoxylated nonionic surfactants, which have been obtained from monohydroxyalkanoles with 6 to 20 atoms of carbon or from alkylphenols with 6 to 20 carbon atoms or at from 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.

The nonionic surfactant, solid at temperature ambient, preferably also has 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, ethylene polyoxide polyoxide units of propylene. The alcoholic or alkylphenolic ratio of such molecules of non-ionic surfactants in this case assume preferably more than 30% by weight, especially preferably more than 50% by weight and, especially, more than 70% in set weight of the molecular weight of such surfactants not ionic Preferred dishwashing agents will be characterized in that they contain ethoxylated nonionic surfactants and propoxylates, in which the propylene oxide units in the molecule accounts for up to 25% by weight, preferably up to 20% by weight and, especially, up to 15% by weight of molecular weight Total non-ionic surfactant.

Other non-ionic surfactants to be used especially preferably with melting points above of the room temperature, they contain from 40 to 70% in weight of a mixture of block copolymers of polyoxypropylene / polyoxyethylene / polyoxypropylene, which contain a 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 24 moles of ethylene oxide and 99 moles of oxide of propylene 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 Tergent® SLF-18 of the firm Olin Chemicals.

Another agent for dishwashing preferred, according to the invention, contain non-ionic surfactants of the formula (VI)

(VI) R 1 O [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] y [CH 2 CH (OH ) R2]

in which R1 means a aliphatic, linear or branched hydrocarbon moiety, with 4 to 18 carbon atoms or mixtures thereof, R2 means a hydrocarbon moiety, linear or branched, 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 surfactants that can be used in a manner Preferred are non-ionic 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 hydrocarbon residues, linear or branched, saturated 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 may be different in the formula indicated above. Preferably R1 and R2 are hydrocarbon moieties, linear or branched, saturated or unsaturated, aliphatic or aromatic, with 6 to 22 carbon atoms, being especially preferred residues with 8 to 18 carbon atoms. The remainder R3 it means, especially preferably, H, -CH 3 or -CH 2 CH 3. Especially preferred values for x are found in the range from 1 to 20, especially from 6 until fifteen.

As described above, each R 3 can 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 minor groups (PO) or the
inverse

Poly (oxyalkylated) alcohols, closed in the especially preferred end groups of the formula indicated above 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 last quoted formula, 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. 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 hydrocarbon residues, linear or branched, saturated 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 non-ionic surfactants, especially preferred, have been accredited, within the scope of this invention, surfactants with low foam generation, which present units of ethylene oxide and units of oxides of alternating alkylene. Among these are preferred, in turn, the surfactants with blocks formed by EO-AO-EO-AO, being linked to each other respectively from one to ten EO groups or AO, before a block consisting of the others is presented respective groups. In this case, agents are preferred for the machine scrubbing of the dishes, according to the invention, which contain as one or more nonionic surfactants, those surfactants of the general formula (VII)

\delm{C}{\delm{\para}{R ^{2} }}

H -- O)_{x} -- (CH_{2} -- CH_{2} -- O)_{y} -- (CH_{2} --

\delm{C}{\delm{\para}{R ^{3} }}

H -- O)_{z} -- H(VII) R 1 - O - (CH 2 - CH 2 - O) w - (CH 2 -

 \ delm {C} {\ delm {\ para} {R2}} 

H-O) x - (CH 2 - CH 2 - O) y - (CH 2 -

 \ delm {C} {\ delm {\ para} {R3}} 

H-O) z -H

in which R1 means a alkyl or alkenyl moiety with 6 to 24 chain carbon atoms linear or branched chain, saturated or mono or polyunsaturated; each group R 2 or R 3 being chosen, independently of each other, enter -CH3; -CH 2 CH 3, -CH 2 CH 2 -CH 3, -CH (CH 3) 2 and the indices w, x, y, z mean, independently of each other, whole numbers from 1 until 6.

Preferred non-ionic surfactants of the Formula VII can be prepared by known procedures from the corresponding alcohols R 1 -OH and ethylene oxide or alkylene The R 1 moiety in the preceding formula VII may vary according to the origin of the alcohol. When sources are used natural, the remainder R1 will have an even number of atoms of carbon and, as a rule, will not be branched, being preferred linear residues of alcohols of natural origin with 12 to 18 carbon atoms, for example, chosen from the coconut alcohol, palm alcohol, tallow alcohol or oleyl alcohol Alcohols accessible from sources Synthetic are, for example, Guerbet alcohols or remains branched by methyl in position 2 or linear residues and branched by methyl in mixture, such as those presented usually in the remains of oxoalcohols. Regardless of alcohol used to obtain non-ionic surfactants contained in the agents, according to the invention, are preferred those agents for machine washing of dishes, according to the invention, in which R 1, in formula VII, means a alkyl moiety with 6 to 24, preferably with 8 to 20, of especially preferred with 9 to 15 and, especially with 9 to 11 carbon atoms.

As alkylene oxide units, which are contents alternately in relation to the oxide unit of ethylene in the preferred non-ionic surfactants, enters consideration, in addition to propylene oxide, especially the butylene oxide However, other oxides of alkylene, in which R 2 or R 3 are chosen independently of each other between -CH 2 CH 2 -CH 3 or -CH (CH 3) 2. Preferred agents for machine scrubbing of the dishes are characterized in that R2 or either R 3 means a residue -CH 3, taking w and x, independently of each other, values of 3 or 4 and taking and, as well as z, values independently from each other of 1 or 2.

In summary, they are preferred for the use of the active products or in the preparations of active products, in the process, according to the invention, especially the nonionic surfactants having an alkyl moiety with 9 to 15 carbon atoms with 1 to 4 units of ethylene oxide, followed by 1 to 4 units of propylene oxide, followed by 1 up to 4 units of ethylene oxide, followed by 1 to 4 units of propylene oxide. These surfactants present in solution low viscosity aqueous, required, and are employable, according to the invention, in a particularly preferred way.

Other surfactants that can be used in a manner Preferred are non-ionic surfactants poly (oxyalkylated) closed at the end groups, of the formula (VIII)

(VIII) R 1 O [CH 2 CH (R 3) O] x R 2

in which R1 means moieties hydrocarbons, linear or branched, saturated or unsaturated, aliphatic or aromatic, with 1 to 30 carbon atoms, R2 means hydrocarbons, linear or branched, saturated or unsaturated, aliphatic or aromatic, with 1 to 30 atoms of carbon, which preferably have between 1 and 5 hydroxy groups and that are preferably also functionalized with a group ether, 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 40

In the case of non-ionic surfactants, especially preferred, of the preceding formula (VIII), R 3 means H. In the case of non-ionic surfactants resulting poly (oxyalkylated), closed in groups ends, of the formula (IX)

(IX) R 1 O [CH 2 CH 2 O] x R 2

they are especially preferred those nonionic surfactants in which R1 means linear or branched, saturated or saturated hydrocarbon moieties unsaturated, aliphatic or aromatic, with 1 to 30 atoms of carbon, preferably with 4 to 20 carbon atoms, R2 means linear or branched, saturated hydrocarbon moieties or unsaturated, aliphatic or aromatic, with 1 to 30 atoms of carbon, which preferably have between 1 and 5 hydroxy groups y x means values between 1 and 40

Especially, those will be preferred poly (oxyalkylated) surfactants, closed in groups extremes, which, according to formula (X)

(X) R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2

in addition to a R 1 residue, which means linear or branched, saturated or saturated hydrocarbon moieties unsaturated, aliphatic or aromatic with 1 to 30 atoms of carbon, preferably with 4 to 20 carbon atoms, present, in addition, a linear or branched hydrocarbon moiety, saturated or unsaturated, aliphatic or aromatic with 1 to 30 atoms of carbon R2, which is adjacent to an intermediate group monohydroxy -CH 2 CH (OH) -. In this formula x means a value between 1 and 40. Such surfactants do not Poly (oxyalkylated) ions closed at the end groups they can be obtained, for example, by reaction of an epoxide located at the end of the formula R 2 CH (O) CH 2 with an ethoxylated alcohol of the formula R 1 O [CH 2 CH 2 O] x-1 CH 2 CH 2 OH.

The lengths of the carbon chains, indicated, as well as the degrees of ethoxylation or the degrees of alkoxylation of the aforementioned nonionic surfactants represent statistical average values that for a product Special can be an integer or a fractional number. Due to the manufacturing process the commercial products of the formulas cited are not constituted, in most of the cases, by an individual representative, but are mixtures, with what which average values are obtained for both the lengths of the carbon chains as well as for degrees of ethoxylation or well for the degrees of alkoxylation and as a consequence they can Provide fractional numbers.

Washing or cleaning agents, according to the invention, especially preferred, contain, as agent dispersant, at least one nonionic surfactant, preferably at minus a closed poly (oxyalkylated) nonionic surfactant in the extreme groups, the proportion by weight being included of the non-ionic surfactant on the total weight of all agents dispersants preferably between 1 and 60% by weight, so especially preferred between 2 and 50% by weight and, especially, between 3 and 40% by weight. According to the invention, they are especially preferred washing or cleaning agents in the which the total weight of the non-ionic surfactants on the total weight of the agent, according to the invention, is comprised between 0.5 and 40% by weight, preferably between 1 and 30% by weight, especially preferably between 2 and 25 and, especially, between 2.5 and 23% by weight.

Preferred washing or cleaning agents, according to the invention, they are characterized in that at least one agent dispersant has a melting point above 25 ° C, preferably above 35 ° C and, especially, above 40 ° C The employment of agents is especially preferred dispersants with a melting point or with a melting range between 30 and 80 ° C, preferably between 35 and 75 ° C, especially preferably between 40 and 70 ° C and, especially, between 45 and 65 ° C, presenting this dispersing agent, in relation to the total weight of the agents dispersants used, a proportion by weight above 10% by weight, preferably above 40% by weight, so especially preferred above 70% by weight and, especially, between 80 and 100% by weight.

Preferred agents, according to the invention, are geometrically stable at 20 ° C. They are considered to be geometrically stable agents, according to the invention, which have their own geometric stability that is capable of acquire a form in non-disintegrable space under the usual conditions of manufacture, storage, transport and handling by the user, without modify this geometric shape under the conditions cited even for a prolonged period of time, preferably of 4 weeks, especially preferably 8 weeks and, especially, 32 weeks, that is to say that it stays in shape geometric in the manufacturing dependent space under the usual conditions of manufacture, storage, transport and handling by the user, that is to say It does not crumble.

The water content of the dispersions previously mentioned supposes, referred to its total weight, preferably a proportion less than 30% by weight, preferably less than 23% by weight, preferably less than 19% by weight, especially preferably less than 15% by weight and, especially, less than 12% by weight. The agents of washing or cleaning, preferred according to the invention, are poor in water or are anhydrous. Washing or cleaning agents especially preferred, according to the invention, are characterized because the dispersion, in relation to its total weight, presents a free water content below 10% by weight, preferably below 7% by weight, especially preferably by below 3% by weight and, especially, below 1% in weight.

The density at 20 ° C of the dispersing agent used, preferably between 0.8 and 1.4 g / cm3. As dispersing agents they will be especially preferred water soluble or water dispersible polymers with a density (20 ° C) above 1,040 g / cm 3, preferably with a density between 1,040 and 1,670 g / cm3, preferably between 1,120 and 1,610 g / cm3, especially preferably between 1,210 and 1,570 g / cm3, very particularly preferably between 1,290 and 1,510 g / cm3 and, especially, between 1,340 and 1,480 g / cm3.

Preferred washing or cleaning agents, according to the invention, they are characterized in this case because they dissolve in water (40 ° C) in less than 12 minutes, preferably in less than 10 minutes, preferably in a time less than 9 minutes, especially preferably in a time less than 8 minutes and, especially, in a time less than 7 minutes For the determination of solubility, they have 20 g of the dispersion in the internal cavity of a machine for dishwashing (Miele G 646 PLUS). Phase begins main scrubbing of a standardized scrubbing program (45 ° C). The determination of solubility is carried out in this case with aid of the conductivity measurement, which is marked by a conductivity sensor The dissolution procedure has concluded when maximum conductivity is reached. At Conductivity diagram this maximum corresponds to a plateau. The conductivity measurement begins with the application of the pump of recirculation in the main phase of scrubbing. The amount of Water used is 5 liters.

A description of the components that may be contained in the portions coated with the aid of the process according to the invention:

Portions of washing agents or Coated cleaning using the method according to the invention,  they can contain all the usual components of the agents of washing or cleaning, which are briefly described to continuation.

Portions of washing agents or cleaning coated with the process according to the invention, preferably contain one or more surfactants, being able to use anionic, nonionic, cationic and / or surfactants amphoteric From the point of view of industrial application in the Textile washing mixtures consisting of anionic surfactants and non-ionic surfactants, owing the proportion of anionic surfactants being greater than the proportion of nonionic surfactants. The total content of the portions of the washing or cleaning agents are found preferably below 30% by weight, based on the whole from the people. Nonionic surfactants have already been described. formerly as optional plasticizers for coating. The same substances can also be used in the agents as substances with washing activity.

In addition, they can be used as others nonionic surfactants also the alkyl glycosides of the formula general RO (G) x, where R means a remainder primary aliphatic, straight chain or branched with methyl, in special branched with methyl in position 2, with 8 to 22, preferably 12 to 18 carbon atoms, and G is the symbol which means a glycosal unit with 5 or 6 carbon atoms, preferably means glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10, preferably x is between 1.2 and 1.4.

Other class of non-ionic surfactants, to be preferably employed, which are used well as the only ones nonionic surfactants or in combination with others nonionic surfactants, are alkyl esters of acids alkoxylated fatty acids, preferably ethoxylated or ethoxylated and propoxylated, preferably with 1 to 4 carbon atoms in the alkyl chain, especially methyl esters of acids  fatty

Agents may also be suitable. nonionic surfactants of the type of amine oxides, by example, the oxide of N-cocoalkyl-N, N-dimethylamine and the oxide of N-tallowalkyl-N, N-dihydroxyethylamine, and fatty acid alkanolamides. Preferably, the amount of these nonionic surfactants is not greater than that of ethoxylated fatty alcohols, especially is not greater than Half of it.

Other suitable surfactants are the polyhydroxy fatty acid amides of the formula VIII,

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

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

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

--- [Z]

in which RCO means a remainder aliphatic acyl with 6 to 22 carbon atoms, R1 means hydrogen, an alkyl or hydroxyalkyl moiety with 1 to 4 atoms carbon, and [Z] means a linear polyhydroxyalkyl moiety or branched with 3 to 10 carbon atoms, and with 3 to 10 groups hydroxyl The polyhydroxy fatty acid amides are known substances, which can usually be obtained by amination by reduction of a reducing sugar with ammonia, with a alkylamine or with an alkanolamine and then acylation with a fatty acid, with an alkyl ester of fatty acids, or a acid chloride fatty

To the group of acid amides polyhydroxygreases also belong to the compounds of the formula IX

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

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

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

--- [Z]

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

Preferably [Z] is obtained by amination by reduction of a reducing sugar, for example glucose,  fructose, maltose, lactose, galactose, mannose or xylose. The compounds substituted with N-alkoxy or with N-aryloxy can be transformed by reaction with fatty acid methyl esters in the presence of a Alkoxide as a catalyst in the acid amides desired polyhydroxygreases.

The preferred content for the casting of textiles from portions of suitable washing or cleaning agents, manufactured with the aid of the process, according to the invention, in nonionic surfactants are between 5 and 20% by weight, preferably between 7 and 15% by weight and, especially, between 9 and 14% by weight, referring respectively to the whole of the agent.

In the agents for machine scrubbing of the tableware preferably non-ionic surfactants with Low foam generation

In combination with the surfactants mentioned anionic, cationic and / or surfactants can also be used amphoteric, having these only a subordinate meaning due to its behavior for the generation of foam in the agents for machine scrubbing of dishes and, in most cases, used only in amounts below 10% by weight, in most cases even below 5% by weight, of Example way from 0.01 to 2.5%, referred respectively to the agent. These surfactants have in the washing agents, on the contrary, a meaning clearly higher. The portions of the washing or cleaning agents, manufactured according to the invention may therefore contain as surfactant components also anionic, cationic components and / or amphoteric.

The agents according to the invention may contain as cationic active substances, for example, compounds cationic formulas X, XI or XII:

\melm{\delm{\para}{\hskip-0,1cm(CH _{2} ) _{n} 
--- T --- R ^{2} }}{N}{\uelm{\para}{R ^{1} }}

^{(+)} --- (CH_{2})_{n} --- T --- R^{2}(X) R1 ---

 \ melm {\ delm {\ para} {\ hskip-0,1cm (CH2) n 
--- T --- R 2}} {N} {\ uelm {\ para} {R 1}} 

^ (+)} --- (CH 2) n --- T --- R 2

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

^{(+)} --- (CH_{2})_{n} ---

\delm{C}{\delm{\para}{\delm{T}{\delm{\para}{R ^{2} }}}}

H ---

\delm{C}{\delm{\para}{\delm{T}{\delm{\para}{R ^{2} }}}}

H_{2}(XI) R1 ---

 \ melm {\ delm {\ para} {R 1}} {N} {\ uelm {\ para} {R 1}}} 

^ (+)} --- (CH2) n ---

 \ delm {C} {\ delm {\ para} {\ delm {T} {\ delm {\ para} {R2}}}}} 

H ---

 \ delm {C} {\ delm {\ para} {\ delm {T} {\ delm {\ para} {R2}}}}} 

H2

\melm{\delm{\para}{R ^{4} }}{N}{\uelm{\para}{R ^{1} }}

^{(+)} --- (CH_{2})_{n} --- T --- R^{2}(XII) R3 ---

 \ melm {\ delm {\ para} {R 4}} {N} {\ uelm {\ para} {R 1}}} 

^ (+)} --- (CH 2) n --- T --- R 2

in which each R1 group is independently choose between the alkyl groups, alkenyl or hydroxyalkyl with 1 to 6 carbon atoms; each group R2 is chosen, independently from each other, between the groups alkyl or alkenyl with 8 to 28 carbon atoms; R 3 = R 1 or (CH 2) n -T-R 2; R 4 = R 1 or R 2 or (CH 2) n -T-R 2; T = -CH_ {2} -, -O-CO- or -CO-O- and n means an integer from 0 to 5.

As anionic surfactants they will be used, by example, those of the type of sulphonates and sulfates. As sulphonate surfactants are considered, in this case, preferably alkyl benzenesulfonates with 9 to 13 carbon atoms, olefin sulfonates, that is, mixtures constituted by alkene and hydroxyalkane sulfonates, as well as disulfonates, such as those obtained, by way of example, from of monoolefins with 12 to 18 carbon atoms with double bond in terminal or internal position, by sulfonation with trioxide gaseous sulfur, and subsequent alkaline or acid hydrolysis of sulfonation products. Sulfonates are also suitable of alkane, which are obtained from alkanes with 12 to 18 atoms of  carbon, by way of example, by sulfocloration or sulfoxidation, with subsequent hydrolysis, or neutralization. Similarly, acid esters are also suitable. α-sulfograms (estersulfonates), by example, α-sulphonated methyl esters of coconut, palm kernel or tallow fatty acids, hydrogenated

Other suitable surfactants are those glyceride esters of sulfonated fatty acids. It is understood by Glycerin esters of mono-, di- and fatty acids tri-esters, as well as their mixtures, such as those formed in the obtained by esterification with a monoglycerin with 1 to 3 moles of fatty acid, or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin. In this case, the esters of Glycerin of the preferred sulfonated fatty acids are those sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, by way of example of capronic acid, of acid caprilic, caprinic acid, myristic acid, acid lauric, palmitic acid, stearic acid or acid Behenic

As alkyl (en) ilo sulfates are preferred are alkaline salts, and especially sodium salts, of the half esters of sulfuric acid with fatty alcohols with 12 at 18 carbon atoms, by way of example from alcohols coconut fatty, tallow fatty alcohols, lauric alcohol, myristic, cetyl or stearic, or oxoalcohols with 10 to 20 carbon atoms, and those semi esters of secondary alcohols With these chain lengths. In addition, sulfates of alky with the aforementioned chain lengths, which contain a synthetic straight chain alkyl moiety, obtained on a petrochemical basis, that have a behavior at degradation analogous to that of suitable compounds based on Raw materials of fat chemistry. They are preferred, for interest of washing technology, alkyl sulfates with 12 at 16 carbon atoms and alkyl sulfates with 12 to 15 atoms carbon, as well as alkyl sulfates with 14 to 15 atoms of carbon. Also 2,3-alkyl sulfates are suitable anionic surfactants, which are obtained, by way of example, according to US patent applications US 3,234,258 or 5,075,041, and which can be purchased by way of commercial products in the Shell Oil Company under the name DAN®.

Acid monsters are also suitable sulfuric acid with straight or branched chain alcohols, with 7 to 21 carbon atoms, ethoxylated with 1 to 6 moles of ethylene oxide, such as alcohols with 9 to 11 branched carbon atoms with 2-methyl, with an average of 3.5 moles of oxide of ethylene (OE), or fatty alcohols with 12 to 18 atoms of carbon with 1 to 4 OE. Due to its behavior with high foam generation, these are used in cleaning agents only in relatively small quantities, as an example in amounts from 1 to 5% by weight.

Other suitable anionic surfactants they are also the salts of the alkylsulfosuccinic acids, which They are also called sulfosuccinates or acid esters sulfosuccinic, and acid monoesters and / or diesters sulfosuccinic with alcohols, preferably fatty alcohols, and in Special with ethoxylated fatty alcohols. Sulphosuccinates Preferred contain fatty alcohol residues with 8 to 18 atoms of carbon, or mixtures of these. Sulfosuccinates especially Preferred contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which, considered in themselves, represent nonionic surfactants (see description later). In this case they are especially preferred, in turn, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with homolog distribution narrowed Similarly, it is also possible to use acids alkylsuccinic, preferably with 8 to 18 carbon atoms in the alkyl (en) yl chains, or Your salts

As other anionic surfactants enter in consideration, especially soaps. Soaps of saturated and unsaturated fatty acids, such as acid salts lauric, myristic acid, palmitic acid, acid stearic, erucic acid (hydrogenated) and behenic acid, as well as, in particular, mixtures of soaps derived from fatty acids natural, for example, from coconut fatty acids, from seeds of palm, olive or tallow.

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

The anionic surfactant content of the preferred agents for washing textiles, according to invention is between 5 and 25% by weight, preferably between 7 and 22% by weight and, especially, between 10 and 20% by weight, referring respectively to the whole of the agent.

Within the scope of the present invention, the preferred agents also contain one or more products chosen from the group of structuring substances, of the bleaching agents, bleaching activators, enzymes, electrolytes, non-aqueous solvents, agents for adjusting the pH, of the odorizing products, of the perfume holders, fluorescence agents, dyes, of the hydrotopes, of the foam inhibitors, of silicone oils, of anti-redeposition compounds, of optical brighteners, grating inhibitors, agents to prevent shrinkage of protective agents against the formation of folds, of the inhibitors of the run of the colors, of the antimicrobial active products, of the germicides, fungicides, antioxidants, corrosion inhibitors, antistatics, agents auxiliaries for ironing, foaming agents and impregnation, swelling agents and agents Non-slip as well as UV absorbers.

As structuring substances, which can be contained in the agents, according to the invention, should be mentioned, especially, phosphates, silicates, aluminosilicates (especially zeolites), carbonates, salts of organic dicarboxylic and polycarboxylic acids as well as mixtures of these products.

According to the invention, it is possible to use the phosphates generally known as adjuvant substances, as insofar as such employment should not be avoided for ecological reasons. Among the large amount of phosphates that can be acquired commercially, in the industry of washing agents and cleaning agents have the highest importance phosphates of alkali metals, with triphosphate being especially preferred pentasodium or pentapotassium triphosphate (tripolyphosphate of sodium or potassium).

Phosphates of alkali metals in this case they represent a general denomination for the salts of alkali metals (especially sodium and potassium) of various phosphoric acids, in which one can distinguish between metaphosphoric acid (HPO3) n and acid orthophosphoric H_ {3} PO_ {4} plus senior representatives molecular weight. Phosphates have several advantages in this case: these act as alkali carriers, prevent coatings of lime and 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 they transform at 200ºC 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, It dissolves very easily in water. It exists in anidium state and with 2 moles (density 2,066 gcm -3, loss of water 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), melting point 35 °, with loss of 5 H 2 O), at 100 ° it becomes anhydrous and 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 ° C and in form 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 molecular weight, 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 are produced, 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; 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.

Crystalline sodium silicates, stratified, suitable, 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. The silicates stratified, preferred crystals 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 disilicates Na_ {2} Si_ {2} O_ {5} \ cdotyH_ {2}.

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 are of delayed dissolution and have properties secondary wash. In this case, the delay in dissolution, versus traditional amorphous sodium silicates, there may be been produced in different ways, for example, through surface treatment, kneading, compaction / compression or by means of an overestimate. In the scope of the present invention, the term "amorphous" will also be understood as "amorphous for X-rays. "This means that silicates, in the case of X-ray diffraction experiments, do not provide reflections crisp x-rays, such as those typical for crystalline substances, but, at most, have one or more  maximum scattered x-ray radiation, which have a Diffraction angle width of several units of degrees. Without However, good properties of adjuvant, if silicate particles provide maximums of diffraction unclear or even sharp in the experiments of the electronic diffraction This should be interpreted in such a way that microcrystalline products have areas with a size from 10 to a few hundred nm, values up to a maximum of 50 nm and especially up to a maximum of 20 nm. They are especially preferred amorphous silicates compacted / compressed, kneaded amorphous silicates and amorphous x-ray silicates, overdone.

The zeolite used, finely crystalline, synthetic, which contains bound water, is preferably the zeolite A and / or P. As zeolite P, the zeolite MAP® (commercial product of Crosfield). Without However, zeolite X is also suitable, as well as mixtures of A, X and / or P. A product that can be obtained commercially and preferably used within the scope of the present invention, is  also a co-crystallized product of zeolite X and zeolite A (approximately 80% by weight of zeolite X), marketed by the CONDEA Augusta S.p.A. under the trade name VEGOBOND AX®, and which can be described by the formula

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

The zeolite can be used as a powder spray drying or also as a non-dried suspension, stabilized, still wet as a result of its manufacture. In the case in which the zeolite is used as a suspension, this may contain small additions of nonionic surfactants, stabilizers, for example, from 1 to 3% by weight, referred to zeolite, ethoxylated fatty alcohols with 12 to 18 carbon atoms with 2 to 5 ethylene oxide groups, fatty alcohols with 12 to 14 carbon atoms with 4 to 5 groups of ethylene oxide or ethoxylated isotridecanoles. Zeolites suitable have an average particle size less than 10 um (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, especially 20 to 22% by weight of bound water.

Other important structuring products are, especially carbonates, citrates and silicates. Preferably, trisodium citrate and / or the pentasodium tripolyphosphate and / or sodium carbonate and / or the sodium bicarbonate and / or gluconates and / or type adjuvants silicate of the class of disilicates and / or metasilicates.

As other components you can add the alkali carriers. As alkali carriers, the hydroxides of alkali metals, carbonates of metals alkaline, alkali metal bicarbonates, sesquicarbonates of alkali metals, alkali silicates, alkaline metasilicates, and product mixtures cited above, being used in the sense of this invention preferably alkali carbonates, especially the sodium carbonate, sodium bicarbonate or sesquicarbonate sodium.

An especially preferred adjuvant system It contains a mixture of tripolyphosphate and sodium carbonate.

In the same way a system is preferred adjuvant containing a mixture of tripolyphosphate and carbonate of sodium and sodium disilicate.

In addition, other components may be added, being preferred, according to the invention, the washing, scrubbing or cleaning agents, which additionally contain one or more products of the group formed by the acidifying agents, of the chelate complexers or of the inhibitor polymers of the formations of
deposits

As acidifying agents both inorganic acids, such as organic acids, as far as these are compatible with the remaining components. With the object of protect users and to give security to manipulation especially mono-, oligo- and acids can be used solid polycarboxylic. Among this group are preferred, to their time, citric acid, tartaric acid, succinic acid, Malonic acid, adipic acid, maleic acid, acid numerical, oxalic acid as well as polyacrylic acids. Of the in the same way the anhydrides of these acids will be used as agents of acidification, being commercially available so special maleic acid anhydride and acid anhydride succinic In the same way sulfonic acids can be used organic Within the scope of this invention they can be purchased at market and also be used as acidifying agents, preferably, the product Sokalan® DCS (registered trademark of the signature BASF), which is a mixture of succinic acid (at most one 31% by weight), of glutaric acid (maximum 50% by weight) and of adipic acid (at most 33% by weight).

Another possible group of components is represented by the chelate complex formers. Chelate complexers are products that form cyclic compounds with metal ions, occupying a single ligand more than one coordination point in a central atom, that is to say that it has at least "two teeth." In this case, the normally rectilinear compounds will therefore be closed by the formation of complexes through an ion to give rings. The number of bound ligands depends on the ion coordination index
central.

The usual chelate complexers and Preferred in the scope of the present invention are, for example, polyoxycarboxylic acids, polyamines, acid ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) Polymers according to the invention can also be used complexing agents, ie polymers that behave well in the own main chain or laterally to it, groups functional, that can act as ligands and react with suitable metal atoms as a rule with formation of chelate complexes The ligands bound with the polymer of the formed metal complexes can proceed in this case only from a macromolecule or they can belong to various polymer chains. The latter leads to the crosslinking of the material in both when complex forming polymers have not already been previously crosslinked by covalent bonds.

The complex-forming groups (ligands) of the usual complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, polyamine (cyclic) moieties, of mercapto, 1,3-dicarbonyl and crown ethers with partly very specific activities against the ions of the various metals. The basic polymers of many complex-forming polymers, also important commercially, are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Also complex polymers are natural polymers such as cellulose, starch or chitin. In addition, they may be provided with other ligand functionalities by transformations similar to polymerization.
tion.

In the scope of the present invention are especially preferred tablets of washing agents or cleaning, containing one or more complex formers of chelate chosen from the groups of

(i)

polycarboxylic acids, in which the sum of the carboxyl groups and, where appropriate, of the groups hydroxyl be at least 5,

(ii)

               monocarboxylic or polycarboxylic acids nitrogen,

(iii)

             geminal diphosphonic acids,

(iv)

             aminophosphonic acids,

(v)

              phosphonopolycarboxylic acids,

(saw)

             cyclodextrins,

in amounts above 0.1% by weight, preferably above 0.5% by weight, especially preferably above 1% and, especially, above 2.5%, respectively referring to the weight of the
agent.

       \ newpage
    

Within the scope of the present invention they can employ all complex trainers of the state of the technique. These may belong to different chemical groups. They will preferably be used individually or in a mixture between yes:

to)

        polycarboxylic acids, in which the sum of the groups carboxyl and, if appropriate, of the hydroxyl groups be 5 as minimum, such as gluconic acid,

b)

        monocarboxylic acids or nitrogenous polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), the acid N-hydroxyethylethylenediaminetriacetic acid diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, the acid nitrilodiacetic-3-propionic, the isoserinadiacetic acid, the N, N-di - (β-hydroxyethyl) -glycine,  the N- (1,2-dicarboxy-2-hydroxyethyl) -glycine, the acid N- (1,2-dicarboxy-2-hydroxyethyl) -asparagine or nitrilotriacetic acid (NTA),

C)

        geminal diphosphonic acids such as acid 1-hydroxyethane-1,1-diphosphonic (HEDP), its superior counterparts with up to 8 carbon atoms as well such as derivatives containing hydroxy groups or containing amino groups thereof and the acid 1-aminoethane-1,1-diphosphonic, their higher counterparts with up to 8 carbon atoms as well as the derivatives containing hydroxy groups or amino groups of the themselves,

d)

        aminophosphonic acids such as acid ethylenediaminetetra- (methylene phosphonic), acid diethylenetriaminopenta (methylene phosphonic), or acid nitrilotri (methylene phosphonic),

and)

        phosphonopolycarboxylic acids such as acid 2-phosphonobutan-1,2,4-tricarboxylic as well as

F)

         cyclodextrins

As polycarboxylic acids a) will be understood as the scope of this patent application carboxylic acids -even monocarboxylic acids- in which the sum of carboxyl groups and hydroxyl groups contained in the molecule be at least 5. The trainers of complexes of polycarboxylic acid groups nitrogen, especially EDTA. At alkaline pH values, necessary, according to the invention, of the treatment solutions, these complex formers are presented, at least partially, in the form of anions. It does not matter that they are incorporated into of acids or in the form of salts. In the case of incorporation as salts are preferred alkali metal, ammonium or alkylammonium, especially preferred sodium salt.

Formation inhibitor polymers of deposits may also be contained in the agents, according to the invention. These products, which may be constituted in different ways, from the chemical point of view, they proceed, for example, of the low weight polyacrylamide groups molecular with molecular weights between 1,000 and 20,000 Daltons, polymers with molecular weights being preferred by under 15,000 Daltons.

Formation inhibitor polymers of Deposits may also have adjuvant properties. As organic adjuvants they can be used in the agents for machine scrubbing of the dishes, according to the invention, especially polycarboxylates / polycarboxylic acids, polycarboxylates polymers, asparagine acid, polyacetals, dextrins, others organic adjuvants (see below), as well as phosphonates. These kinds of products are described below.

Suitable 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.

Acids can also be used per se . In addition, of their adjuvant effect, acids also typically have the property of an acidification component and, thus, also serve to adjust a low and gentle pH value of the washing agents and cleaning agents. In this case, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixture thereof should be especially mentioned.

In addition, as an adjuvant or as inhibitors of the deposit formations polycarboxylates are suitable polymers, these are, for example, alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those with a relative molecular weight of 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 an external standard of polyacrylic acid, which provides molecular weight values similar to the real ones due to their structural affinity with the polymers analyzed. These dates they differ markedly from molecular weight data for which uses a pattern of polystyrene sulfonic acids. The molecular weights measured against polystyrene sulfonic acids they are generally markedly higher than molecular weights indicated in this document.

Suitable polymers are especially polyacrylates, which preferably have a molecular weight from  500 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 1,000 to 10,000 g / mol, and especially preferably from 1,000 to 4,000 g / mol

In the agents, according to the invention, they will be used especially preferably both polyacrylates and also copolymers consisting of unsaturated carboxylic acids, monomers containing sulfonic groups as well as, where appropriate, other ionic or non-ionic monomers. The copolymers that contain sulfonic groups will be described in detail below.

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, which contain from 50 up to 90% acrylic acid and 50 to 10% acid Maleic Its relative molecular weight, based on free acid, is generally 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. The content  of polycarboxylates (co) polymers in the agents is preferably from 0.5 to 20% by weight, especially from 3 to 10% by weight.

Also especially preferred are biodegradable polymers consisting of more than two units of different monomers, for example, those that contain 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 have as monomers preferably acrolein and acrylic acid / salt of Acrylic acid or acrolein and vinyl acetate.

They should also be cited as other substances preferred adjuvants polymeric aminodicarboxylic acids, its salts or its precursor substances, for example, acids poliasparagine or its salts and derivatives, which have in addition to the properties of adjuvants, also, an effect bleaching stabilizer.

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

Other suitable organic adjuvant substances they are dextrins, for example, oligomers or polymers of hydrates of carbon, which can be obtained by partial hydrolysis of starches. Hydrolysis can be carried out according to usual procedures, by for example, catalyzed by acids or enzymes. Preferably deals with hydrolysis products with average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with an equivalent of dextrose (ED) in the range of 0.5 to 40, especially 2 to 30, being ED is a usual measure for the reducing effect of a polysaccharide compared to the dextrose, which has an ED of 100. Both the maltodextrins with an ED between 3 and 20 and syrups of dry glucose with an ED between 20 and 37, as well as the so-called yellow dextrins and white dextrins with older molecular weights, in the range from 2,000 to 30,000 g / mol

As for oxidized derivatives of this type of dextrins is their reaction products with agents oxidizers, which are capable of oxidizing at least one alcohol function of the saccharide ring to give a carboxylic acid function. An oxidized product in the atom of carbon 6 of the saccharide ring.

Other suitable adjuvants are also those oxidisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. In this case it will be used ethylenediamine-N, N'-disuccinate (EDDS) preferably in the form of its sodium or magnesium salts. In this context, glycerin disuccinates are also preferred. and glycerin trisuccinates. The quantities used, suitable, are from 3 to 15% by weight, in the formulations containing zeolite and / or silicate.

Other suitable 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 a maximum of two acid groups.

Another class of substances with properties of adjuvant are phosphonates. In this case it is specially treated of phosphonates of hydroxyalkanes or aminoalkanes. Among the phosphonates of hydroxyalkanes has a special importance, as an adjuvant, 1,1-hydroxyethane 1,1-diphosphonate (HEDP). It is preferably used as sodium salt, having the disodium salt a neutral reaction and alkaline tetrasodium salt (pH 9). As aminoalkane phosphonates come into consideration, preferably, ethylenediaminetetramethylene phosphonate (EDTMP),  diethylenetriaminepentamethylene phosphonate (DTPMP), as well as its superior counterparts. They will preferably be used in the form of neutral reaction sodium salts, for example, such as salt hexasodium of EDTMP or as a heptasodium and octasodium salt of DTPMP. In this case, it will be used as an adjuvant to the class of phosphonates, preferably, HEDP. In addition, phosphonates of aminoalkane have a strong binding power to metals heavy Correspondingly, it may be preferred when agents also contain bleaching agents, the use of phosphonates of aminoalkane, especially DTPMP, or mixtures of cited phosphonates.

In addition to the products of the cited classes, the agents, according to the invention, may contain other components usual of washing, scrubbing or cleaning agents, being significant, especially bleaching agents, bleaching activators, enzymes, protective agents of the silver, dyes and odor products. These products They described below.

Among the compounds that serve as agents of bleaching, which supply H2O2 in water, have a special meaning sodium perborate tetrahydrate and the sodium perborate monohydrate. Other bleaching agents employable are, for example, sodium percarbonate, the peroxypyrophosphates, citrateperhydrates as well as peracid salts or peracids suppliers of H 2 O 2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperácids or diperdodecanedioic acid.

In order to achieve a whitening effect improved when washing at temperatures of 60 ° C and below this value, activators of bleaching in the molded bodies of the washing agents and cleaning. As bleaching activators, compounds can be used that generate under the conditions of perhydrolysis, acids aliphatic peroxocarboxylic acids preferably with 1 to 10 atoms carbon, especially with 2 to 4 carbon atoms, and / or substituted perbenzoic acids. The substances bearing O- and / or N-acyl groups with the indicated number of carbon atoms and / or benzoyl groups replaced, if necessary. Alkylene diamines are preferred polycylated, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially the 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine  (DADHT), acylated glycolurils, especially the tetraacetylglycoluryl (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, especially the n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acid anhydrides carboxylic, especially phthalic acid anhydride, acylated polyvalent alcohols, especially triacetin, the ethylene glycol diacetate and the 2,5-diacetoxy-2,5-dihydrofuran.

Other bleaching activators, preferred, are cationic nitriles of the formula,

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

^{(+)} --- (CH_{2}) --- CN {}\hskip2cm X^{(-)},R2 ---

 \ melm {\ delm {\ para} {R 3}} {N} {\ uelm {\ para} {R 1}}} 

^ {(+)} --- (CH_2) --- CN {} \ hskip2cm X ^ (-)},

in which R1 means -H, -CH 3, an alkyl or alkenyl moiety with 2 to 24 atoms of carbon, an alkyl or alkenyl moiety with 2 to 24 atoms of carbon substituted with at least one substituent chosen from the group formed by -Cl, -Br, -OH, -NH2, -CN, an alkyl moiety- or alkenylaryl with an alkyl group with 1 to 24 carbon atoms, or means an alkyl- or alkenylaryl moiety substituted with a group alkyl with 1 to 24 carbon atoms and at least one other substituent is on the aromatic ring, R2 and R3 are choose, independently of each other, between -CH_ {2} -CN, -CH_ {3}, -CH_ {2} -CH_ {3}, -CH_ {2} -CH_ {2} -CH_ {3}, -CH (CH 3) - CH 3, -CH2 -OH, -CH2 -CH2 -OH, -CH (OH) -CH 3, -CH2 -CH2 -CH2 -OH,  -CH 2 -CH (OH) -CH 3, -CH (OH) -CH 2 -CH 3, - (CH 2 CH 2 -O) n H with n = 1, 2, 3, 4, 5 or 6 and X is a anion.

Under this general formula it is covered covers a plurality of cationic nitriles, which can be used in the scope of the present invention. In a way especially preferably the agents according to the invention contain in this case nitriles, in which R1 means methyl, ethyl, propyl, isopropyl or an n-butyl moiety, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or a n-octadecyl residue. Preferably, R2 and R 3 are chosen from methyl, ethyl, propyl, isopropyl e hydroxyethyl, being one of the two residues advantageously also a cyanomethylene residue. The following table has characterized preferred cationic nitriles, according to the invention, of the formula (I) by means of its radicals R 1, R 2 and R3:

7

8

9

10

In order to facilitate the synthesis are Preferred are those compounds in which the R 1 moieties up to R3 are identical, for example, (CH 3) 3 N (+) CH 2 -CN X -, (CH 3 CH 2) 3 N (+) CH 2 -CN X <->, (CH 3 CH 2 CH 2) 3 N (+)} CH 2 -CN X <->, (CH 3 CH (CH 3)) 3 N (+) CH 2 -CN  X-, or (HO-CH 2 -CH 2) 3 N (+)} CH 2 -CN X <->. Especially preferred are cationic nitriles of the following formula,

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

^{(+)} --- (CH_{2}) --- CN {}\hskip2cm X^{(-)},R5 ---

 \ melm {\ delm {\ para} {R 6}} {N} {\ uelm {\ para} {R 4}}} 

^ {(+)} --- (CH_2) --- CN {} \ hskip2cm X ^ (-)},

in which R 4, R 5 and R 6 are chosen, independently of each other, from -CH 3, -CH_ {2} -CH_ {3}, -CH 2 -CH_ {2-} CH 3, -CH (CH 3) - CH 3, and may also be R 4, also, -H and X is an anion, complying, preferably, that R 5 = R 6 = -CH 3 and, especially, that R 4 = R 5 = R 6 = -CH 3, are especially preferred, according to invention,

Preferred anions X (-) come from group consisting of chloride, bromide, iodide, hydrogen sulfate, Metosulfate, p-toluenesulfonate (tosylate), cumolsulfonate or xylenesulfonate.

In addition to bleach activators conventional, or instead, can also be incorporated into molded bodies, the so-called bleaching catalysts. These products consist of transition metal salts or by transition metal complexes, which intensify the bleaching, such as, for example, exit complexes or complexes carbonyl of Mn, Fe, Co, Ru or Mo. As bleaching catalysts Mn, Fe, Co, Ru, Mo, Ti, complexes can also be used V and Cu with tripod ligands, containing N, as well as amino complexes of Co, Fe, Cu and Ru.

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 the washing to the removal of stains such as stains containing protein, fat or starch, and from the gray. Cellulases and other glycosylhydrolases can contribute, by eliminating skinning and microfibrils, to maintaining colors and increasing the softness of textiles. Oxidoreductases can also be used for bleaching or for the inhibition of color flow. Enzyme active products obtained from bacterial or fungal strains, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens, are particularly suitable. Preferably, proteases of the subtilisin type and, especially, proteases that are obtained from Bacillus lentus will be employed. In this case, enzymatic mixtures, for example, constituted by proteases and amylases or by proteases and lipases, or by enzymes of lipolytic action or proteases and cellulases or by cellulases and lipases, or by enzymes of lipolytic action or by proteases are of particular interest. , amylases and lipases either enzymes of lipolytic action or proteases, lipases or enzymes of lipolytic action and cellulases, especially, however, mixtures containing proteases and / or lipases or mixtures with enzymes of lipolytic action. Examples of such enzymes of lipolytic action are the known cutinases. Peroxidases or oxidases have also been found suitable in some cases. Suitable amylases belong, especially α-amylases, iso-amylases, pululanases and pectinases. As cellulases, cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, will preferably be used. Since the different types of cellulases are distinguished by their CMCase and Avicelasa activities, the desired activities can be adjusted by specific mixtures of cellulases.

Enzymes may be adsorbed on support materials and / or may be embedded in substances coating for protection against decomposition early. The proportion of enzymes, of enzymatic mixtures or of the enzymatic granules may be comprised, by example, from about 0.1 to 5% by weight, preferably from 0.12 to about 2% by weight.

Cleaning agents tablets, according to the invention, for machine washing of dishes, can contain corrosion inhibitors for the protection of scrubbed or machine objects, having a special meaning Special agents for the protection of silver in the sector of machine washing of dishes. You can use the substances known from the state of the art. In general, they can employed, above all, chosen silver protective agents between the group of triazoles, of benzotriazoles, of 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 the chlorine-free cleaners they find  frequently application, in particular, organic compounds, with Redox activity, which contain oxygen and nitrogen, such as divalent and trivalent phenols, for example, hydroquinone, pyrocatechin, hydroxyhydroquinone, gallic acid, floroglucin, pyrogallol or derivatives of these kinds of compounds. Compounds also find frequent application inorganic saline and complex type, such as salts of the Mn, Ti, Zr, Hf, V, Co and Ce metals. In this case, the salts of transition metals, which are chosen from the group of salts and / or manganese and / or cobalt complexes, so Especially preferred for cobalt (amine) complexes of cobalt complexes (acetate), of the complexes of cobalt- (carbonyl), cobalt or manganese chlorides and of manganese sulfate as well as manganese complexes. Of the similarly zinc compound can be used to prevent corrosion of scrubbed objects.

As electrolytes of the salt group inorganic a large number of the most diverse can be used you go out. Preferred cations are alkali metals and alkaline earth metals, the preferred anions are halides and sulfates From the point of view of industrial manufacturing, it is preferably the use of NaCl or MgCl2 in the agents, according to the invention. The proportion of electrolytes in the agents, according to the The invention usually amounts to 0.5 to 5% by weight.

To bring the pH value of the agents, according to the invention, up to the desired range, it may be suitable the use of agents to adjust the pH. In this case they can all known acids or lyes are used, insofar as its use is not prohibited from the point of view of the application industrial or for ecological reasons or for reasons of User protection Usually the amount of this agent for the adjustment does not exceed 5% by weight of the whole of the formulation.

To improve the aesthetic impression of agents, according to the invention, these can be colored with dyes adequate. Preferred dyes, whose selection does not cause no difficulty to the technician in the field, they have a high storage stability and insensitivity to remaining components of the agents and facing the light, and not they have a marked substantivity against textile fibers, so as not to cause its coloration.

As foam inhibitors, which can used in the agents, according to the invention, enter consideration, by way of example, soaps, paraffins or oils of silicone, which can be applied, if appropriate, on materials support. Suitable anti-redeposition agents, which are called also dirt repellents, are, by way of example, ethers of non-ionic cellulose, such as methylcellulose and methylhydroxypropylcellulose, with a proportion of methoxy groups from 15 to 30% by weight, and hydroxypropyl groups from 1 to 15% by weight, referred respectively to the ethers of non-ionic cellulose, as well as polymers of phthalic acid and / or Terephthalic acid known to the state of the art, or its derivatives, especially polymers of ethylene terephthalates and / or modified polyethylene glycol terephthalates, or derivatives thereof in an anionic and / or non-ionic way. Among these are preferred in special sulfonated derivatives of phthalic acid polymers and of terephthalic acid.

The optical brighteners (the so-called "bleaches") can be added to the agents, depending on the invention, to prevent graying and yellowing of textiles treated. These products are absorbed by the fibers, and cause a rinse and a simulated bleaching effect, by transformation the invisible ultraviolet radiation in light with longer wavelength, visible, radiating ultraviolet light, absorbed from the sunlight, such as slightly bluish fluorescence, and providing a pure white with the yellow shade of gray clothes, or yellowish Suitable compounds proceed, by way of example, of acid substance classes 4,4'-diamino-2,2'-stilbenedisulfonic (flavonic acids), 4,4'-diethyrylbiphenylene, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole, benzoisoxazole and benzimidazole systems, as well as the pyrene derivatives substituted by heterocycles. I usually know they use optical brighteners in quantities between 0.05 and a 0.3% by weight, based on the finished agent.

Grating inhibitors have the task keep suspended dirt in the bathroom fibers, and thus prevent the reabsorption of dirt. Such Effect water-soluble colloids are suitable, in most of cases of an organic nature, by way of example cola, gelatin, starch or cellulose ethersulfonic acid salts, or salts of Acid cellulose or starch sulfates. They are also suitable for  this purpose water soluble polyamides, which contain acid groups. In addition, water-soluble starch preparations can be used, and starch products other than those mentioned above, by example, degraded starch, aldehyde starches, etc. It is also useful polyvinylpyrrolidone. However, they are used preferably cellulose ethers, such as carboxymethyl cellulose (salt sodium), methylcellulose, hydroxyalkylcellulose, and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methyl carboxymethyl cellulose, and mixtures thereof, in amounts from a 0.1 to 5% by weight, based on agents.

The agents, according to the invention, can be provided also with other useful additives. In this case they can be formulated, for example, color-inhibiting compositions, agents with "antiagrisado formula", agents to facilitate the ironing, agents with a special odor release, agents with improved soil shedding or preventing dirt redeposition, antibacterial agents, agents UV protectors, agents to bring colors to life, etc. Some examples are explained below:

Since surface structures textiles, especially consisting of rayon, viscose fiber, cotton, and mixtures thereof, may tend to wrinkle, since insulated fibers are sensitive to bending, buckling, pressing and crushing transversely to the direction of the fibers, the agents according to the invention may contain agents synthetic wrinkles. To these belong, by way of example, synthetic products based on fatty acids, acid esters fatty, amides, alkyl polyesters, fatty acid alkylamides, or fatty alcohols, which have been transformed with ethylene oxide in the most cases, or products based on lecithin or acid phosphoric modified.

For the fight against microorganisms, agents, according to the invention, may contain active products antimicrobials In this case it differs, according to spectrum antimicrobial and mechanism of action, between bacteriostatic and bactericides, fungistatics and fungicides, etc. The products of these groups are, by way of example, benzalkonium chlorides, alkylarylsulfonates, halogenated phenols and mercury phenol, being able to also completely dispense with these compounds in the agents according to the invention.

To prevent undesirable processes, caused by the action of oxygen and other oxidative processes in the agents and / or treated textile materials, the agents may contain antioxidants To this class of compounds belong, by way of example, substituted phenols, hydroquinones, pyrocatechins and aromatic amines, as well as organic sulphides, polysulfides, dithiocarbamates, phosphites and phosphonates.

It may be more convenient to use from the additional use of antistatics, which are added in addition to the agents, according to the invention. Antistatic increase the surface conductivity, and thus enable a Improved output of formed loads. External antistatic they are generally substances with at least one molecular ligand hydrophilic, and provide a more or less hygroscopic film on the surfaces. These antistatics, in most of cases with interfacial activity, can be subdivided into nitrogen antistatic agents (amines, amides, ammonium compounds quaternaries), phosphorous (phosphates) and sulfur (alkyl sulfonates, alkyl sulfates). Lauryl Chlorides- (or Stearyl-) dimethylbenzylammonium disclosed herein are suitable as antistatic for textile materials, or as an addition to washing agents, additionally achieving an effect of revival

For the improvement of water absorption power, the re-wettability of treated textile materials, and for facilitate ironing of treated textile materials, it they can use, by way of example, silicone derivatives in the agents according to the invention. These further improve the rinse behavior of the agents, according to the invention, to through its foam inhibitory properties. The derivatives of  Preferred silicone are, by way of example, polydialkyl- or alkylarylsiloxanes, in which the alkyl groups have one to five carbon atoms, and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can be derivatized if necessary, and then they are aminofunctional or are quaternized, or have links Si-OH, Si-H and / or Si-Cl. The viscosities of the preferred silicones  they are located at 25 ° C in the range between 100 and 100,000 mPas, being able to use silicones in amounts between 0.2 and 5% by weight, referred to the agent as a whole.

Finally, the agents, according to the invention, they can also contain UV absorbers, which are absorbed on treated textile materials, and improve stability to The light of the fibers. The compounds that present these desired properties are, by way of example, the active compounds by deactivation without radiation, and benzophenone derivatives with substituents in position 2 and / or 4. In addition, they are also suitable substituted benzotriazoles, phenyl acrylates substituted in position 3 (cinnamic acid derivatives), if necessary with cyano groups in position 2, salicylates, organic Ni complexes, as well as natural substances, such as umbelliferone, and urocanic acid endogenous.

When cleaning agents are manufactured for tableware machine, with the help of the procedure, according to the invention, these will preferably contain other substances, which improve the results of cleaning and / or exercise other functions. In this case, a particularly preferred component for the agents for machine washing of dishes, is a polymer, containing sulfonic groups. The compositions preferred, according to the invention, are therefore characterized because they cover at least one copolymer consisting of acids unsaturated carboxylic, monomers containing sulfonic groups and, where appropriate, other ionic or non-ionic monomers.

In the scope of the present invention are Preferred, as monomers, are unsaturated carboxylic acids of formula XIII,

(XIII), R 1 (R 2) C = C (R 3) COOH

where R 1 to R 3 mean, independently of each other, -H, -CH_ {3}, a remainder linear or branched chain alkyl saturated with 2 up to 12 carbon atoms, a straight chain alkenyl moiety or branched chain, mono or polyunsaturated, with 2 to 12 atoms of carbon, alkyl moieties or alkenyl moieties such as those defined above, substituted by -NH2, -OH or -COOH or mean -COOH or -COOR 4, where R 4 means a moiety saturated or unsaturated hydrocarbon, straight chain or chain branched, with 1 to 12 atoms of carbon.

Among the unsaturated carboxylic acids, which can be described by means of formula I, they are especially Preferred are acrylic acid (R 1 = R 2 = R 3 = H), the methacrylic acid (R 1 = R 2 = H; R 3 = CH 3) and / or maleic acid (R 1 = COOH; R 2 = R 3 = H).

Among the monomers containing groups sulphonic ones are preferred those of the formula XIV,

(XIV), R 5 (R 6) C = C (R 7) - X-SO 3 H

in which R 5 to R 7 mean, independently of each other, -H, -CH_ {3}, a remainder linear or branched chain alkyl, saturated, with 2 up to 12 carbon atoms, a straight chain alkenyl moiety or branched chain, mono or polyunsaturated, with 2 to 12 atoms of carbon, alkyl moieties or alkenyl moieties such as those defined above, substituted by -NH2, -OH or -COOH or mean -COOH or -COOR 4, where R 4 means a moiety saturated or unsaturated hydrocarbon, straight chain or chain branched, with 1 to 12 carbon atoms, and X means a group spacer, optionally present, which is chosen between - (CH 2) n - with n = 0 to 4, -COO- (CH 2) k - with k = 1 to 6, -C (O) -NH-C (CH 3) 2 - and -C (O) -NH-CH (CH 2 CH 3) -.

Among these monomers, those are preferred. of the formula XIVa, XIVb and / or XIVc,

H 2 C = CH-X-SO 3 H

(XIVa),

H 2 C = C (CH 3) - X-SO 3 H

(XIVb),

HO 3 S-X- (R 6) C = C (R 7) - X-SO 3 H

(XIVc),

in which R 6 and R 7 are choose, independently of each other, between -H, -CH_ {3}, -CH 2 CH 3, -CH 2 CH 2 CH 3, -CH (CH 3) 2 and X means a spacer group, optionally present, which is chosen between - (CH 2) n - with n = 0 to 4, -COO- (CH 2) k - with k = 1 to 6, -C (O) -NH-C (CH 3) 2 -  and -C (O) -NH-CH (CH 2 CH 3) -

Monomers containing sulfonic groups Especially preferred are, in this case, the acid 1-Acrylamido-1-Propanesulfonic  (X = -C (O) NH-CH (CH 2 CH 3) in formula XIVa), the acid 2-acrylamido-2-propanesulfonic (X = -C (O) NH-C (CH 3) 2  in formula XIVa), the acid 2-acrylamido-2-methyl-1-propanesulfonic (X = -C (O) NH-CH (CH 3) CH 2 - in formula XIVa), the acid 2-methacrylamido-2-methyl-1-propanesulfonic (X = -C (O) NH-CH (CH 3) CH 2 - in formula XIVb), the acid 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (O) NH-CH 2 CH (OH) CH 2 -  in formula XIVb), allylsulfonic acid (X = CH2 in the formula XIVa), the metalylsulfonic acid (X = CH2 in the formula XIVb), allyloxybenzenesulfonic acid (X = -CH_ {2} -O-C6 {H4} - in the formula XIVa), the metalyloxybenzenesulfonic acid (X = -CH_ {2} -O-C6 {H4} - in the formula XIVb), the acid 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, the acid 2-methyl-2-propene-1-sulfonic (X = CH2 in formula XIVb), styrenesulfonic acid (X = C 6 H 4 in formula XIVa), vinylsulfonic acid (X no is present in formula XIVa), the acrylate of 3-sulfopropyl (X = -C (O) NH-CH 2 CH 2 CH 2 - en formula XIVa), 3-sulfopropyl methacrylate (X = -C (O) NH-CH 2 CH 2 CH 2 - in formula XIVb), sulfomethacrylamide (X = -C (O) NH- in formula XIVb), the sulfomethylmethacrylamide (X = -C (O) NH-CH2 - in formula XIVb) as well as the water soluble salts of the acids mentioned.

How other ionic or non-ionic monomers enter especially considering ethylenically compounds unsaturated Preferably the content of the polymers employed, according to the invention, in monomers of group iii) is smaller than 20% by weight, based on the polymer. The polymers to be especially preferred employees are constituted only by monomers of groups i) and ii).

In summary, those are especially preferred copolymers consisting of

i)

         unsaturated carboxylic acids of the formula XII,

(XII), R 1 (R 2) C = C (R 3) COOH

in which R 1 to R 3 means, independently of each other, -H, -CH 3, a straight chain or branched chain alkyl moiety saturated with 2 to 12 carbon atoms, an alkenyl moiety of linear or branched chain, mono or polyunsaturated, with 2 up to 12 carbon atoms, alkyl moieties or alkenyl moieties such as those defined above, substituted by -NH2, -OH or -COOH or mean -COOH or -COOR 4, where R 4 means a saturated or unsaturated hydrocarbon moiety, chain linear or branched chain, with 1 to 12 atoms of carbon,

ii)

        monomers containing sulfonic groups of the formula XIV,

(XIV), R 5 (R 6) C = C (R 7) - X-SO 3 H

in which R 5 to R 7 means, independently of each other, -H, -CH 3, a straight chain or chain alkyl moiety branched, saturated, with 2 to 12 carbon atoms, a remainder straight chain or branched chain alkenyl, mono or polyunsaturated, with 2 to 12 carbon atoms, alkyl moieties or alkenyl moieties as defined above, substituted by -NH2, -OH or -COOH or means -COOH or -COOR 4, where R 4 means a hydrocarbon moiety saturated or unsaturated, straight chain or branched chain, with 1 to 12 carbon atoms, and X means a spacer group, optionally present, which is chosen between - (CH 2) n - with n = 0 to 4, -COO- (CH 2) k - with k = 1 to 6, -C (O) -NH-C (CH 3) 2 - and -C (O) -NH-CH (CH 2 CH 3) -,

iii)

       if necessary, other ionic or non-ionic monomers.

       \ vskip1.000000 \ baselineskip
    

Copolymers are especially preferred. constituted by

i)

         one or more unsaturated carboxylic acids of the acid group acrylic, methacrylic acid and / or maleic acid,

ii)

        one or more monomers containing sulfonic groups of the XIVa, XIVb and / or XIVc formulas:

H 2 C = CH-X-SO 3 H

(XIVa),

H 2 C = C (CH 3) - X-SO 3 H

(XIVb),

HO 3 S-X- (R 6) C = C (R 7) - X-SO 3 H

(XIVc),

in which R 6 and R 7 are chosen, independently of each other, from -H, -CH 3, -CH 2 CH 3, -CH 2 CH 2 CH 3, -CH (CH 3) 2 and X means a spacer group, optionally present, which is chosen between - (CH 2) n - with n = 0 to 4, -COO- (CH 2) k - with k = 1 to 6, -C (O) -NH-C (CH 3) 2 -  and -C (O) -NH-CH (CH 2 CH 3) -

iii)

       if necessary, other ionic or non-ionic monomers.

The copolymers, used according to the invention, they may contain the monomers of groups i) and ii) as well as in given case iii) in variable quantities, all of which can be combined the representatives of the group i) with all the representatives of the group ii) and with all the representatives of group iii). The Especially preferred polymers have certain units structural, which are described below.

Thus, for example, the compositions, according to the invention, characterized in that they contain one or more copolymers, which contain the structural units of formula XV,

(XV), - [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p -

in which m and p mean, respectively, a natural integer between 1 and 2,000 as well as Y means a spacer group, which is chosen from substituted or unsubstituted hydrocarbon moieties, aliphatic, aromatic or araliphatic with 1 to 24 atoms of carbon, the spacer groups in which Y is preferred means -O- (CH2) n - with n = 0 to 4, means -O- (C 6 H 4) -, means -NH-C (CH 3) 2 - or -NH-CH (CH 2 CH 3) -.

These polymers are prepared by copolymerization of acrylic acid with an acid derivative Acrylic containing sulfonic groups. If copolymerized Acrylic acid derivatives, containing sulfonic groups, with methacrylic acid will reach another polymer, whose use in compositions, according to the invention, is equally preferred and that It is characterized in that the compositions contain one or more copolymers, containing structural units of the formula XVI

(XVI), - [CH 2 -C (CH 3) COOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p -

in which m and p mean, respectively, a natural integer between 1 and 2,000 as well as Y means a spacer group, which is chosen from the substituted or unsubstituted hydrocarbon moieties, aliphatic, aromatic or araliphatic with 1 to 24 atoms of carbon, the spacer groups in which Y is preferred means -O- (CH2) n - with n = 0 to 4, means -O- (C 6 H 4) -, means -NH-C (CH 3) 2 - or -NH-CH (CH 2 CH 3) -.

In a completely analogous way they can copolymerize acrylic acid and / or methacrylic acid also with derivatives of methacrylic acid containing sulfonic groups, thereby modifying the structural units in the molecule. Of this, the compositions are preferred, according to the invention, comprising one or more copolymers, containing structural units of formula XVII

(XVII), - [CH 2 -CHCOOH] m - [CH 2 -C (CH 3) C (O) -Y-SO 3 H] p -

in which m and p mean, respectively, a natural integer between 1 and 2,000 as well as Y means a spacer group, which is chosen from the substituted or unsubstituted hydrocarbon moieties, aliphatic, aromatic or araliphatic with 1 to 24 atoms of carbon, the spacer groups in which Y is preferred means -O- (CH2) n - with n = 0 to 4, means -O- (C 6 H 4) -, means -NH-C (CH 3) 2 - or -NH-CH (CH2CH3) -, being preferred, also, a preferred embodiment of the present invention, as well as the compositions, which are characterized because they contain or several copolymers, which contain units structural formula XVIII

(XVIII), - [CH 2 -C (CH 3) COOH] m - [CH 2 -C (CH 3) C (O) -Y-SO 3 H ] p -

in which m and p mean, respectively, a natural integer between 1 and 2,000 as well as Y means a spacer group, which is chosen from the substituted or unsubstituted hydrocarbon moieties, aliphatic, aromatic or araliphatic with 1 to 24 atoms of carbon, the spacer groups in which Y is preferred means -O- (CH2) n - with n = 0 to 4, means -O- (C 6 H 4) -, means -NH-C (CH 3) 2 - or -NH-CH (CH 2 CH 3) -.

Instead of acrylic acid and / or acid methacrylic or as a complement to them can be used also maleic acid as a particularly preferred monomer of group i). In this way, preferred compositions are reached, according to the invention, characterized in that they contain one or several copolymers containing structural units of the formula XIX

(XIX), - [HOOCCH-CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p -

in which m and p mean, respectively, a natural integer between 1 and 2,000 as well as Y means a spacer group, which is chosen from the substituted or unsubstituted hydrocarbon moieties, aliphatic, aromatic or araliphatic with 1 to 24 atoms of carbon, the spacer groups in which Y is preferred means -O- (CH2) n - with n = 0 to 4, means -O- (C 6 H 4) -, means -NH-C (CH 3) 2 - or -NH-CH (CH2CH3) - and to compositions, which are characterized in that they contain one or more copolymers, which contain structural units of the formula XX

(XX), - [HOOCCH-CHCOOH] m - [CH 2 -C (CH 3) C (O) O-Y-SO 3 H] p -

in which m and p mean, respectively, a natural integer between 1 and 2,000 as well as Y means a spacer group, which is chosen from the substituted or unsubstituted hydrocarbon moieties, aliphatic, aromatic or araliphatic with 1 to 24 atoms of carbon, the spacer groups in which Y is preferred means -O- (CH2) n - with n = 0 to 4, means -O- (C 6 H 4) -, means -NH-C (CH 3) 2 - or -NH-CH (CH 2 CH 3) -.

In summary, the compositions, according to the invention, containing one or more copolymers, containing the structural units of the formulas III and / or IV and / or V and / or VI and / or VII and / or VIII

- [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p -

(XV),

- [CH 2 -C (CH 3) COOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p -

(XVI),

- [CH 2 -CHCOOH] m - [CH 2 -C (CH 3) C (O) -Y-SO 3 H] p -

(XVII),

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- [CH 2 -C (CH 3) COOH] m - [CH 2 -C (CH 3) C (O) -Y-SO 3 H] p } -

(XVIII),

- [HOOCCH-CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p -

(XIX),

- [HOOCCH-CHCOOH] m - [CH 2 -C (CH 3) C (O) O-Y-SO 3 H] p -

(XX),

in which m and p mean, respectively, a natural integer between 1 and 2,000 as well as Y means a spacer group, which is chosen from substituted or unsubstituted hydrocarbon moieties, aliphatic, aromatic or araliphatic with 1 to 24 atoms of carbon, the spacer groups in which Y is preferred mean -O- (CH2) n - with n = 0 to 4, means -O- (C 6 H 4) -, means -NH-C (CH 3) 2 - or -NH-CH (CH 2 CH 3) -.

Sulfonic groups can occur in the polymers in total or partially neutralized form, ie the acidic hydrogen atoms of the sulfonic groups can be exchanged in some or all sulfonic groups by metal ions, preferably alkali metal ions and, especially against sodium ions. They are preferred, according to the invention, the corresponding compositions, which characterize because sulfonic groups are present in the partially or completely neutralized copolymer.

The distribution of monomers in polymers used in the compositions, according to the invention, suppose  in the case of copolymers containing only monomers of groups i) and ii), preferably, in each case, from a up to 95% by weight of i) or ii), especially preferably from 50 to 90% by weight of monomers of the groups i) and from 10% to 50% by weight of monomers of the group ii), referred, respectively, to the polymer.

In the case of terpolymers they are especially Preferred are those containing from 20 to 85% by weight of monomers of group i), from 10 to 60% by weight of monomers of group ii) as well as from 5 to 30% by weight of monomers of group iii).

The molecular weight of sulfonic polymers, previously described, used in the compositions, according to the invention, can be modified to adapt the properties of the polymers to the desired application purposes. The Preferred compositions are characterized in that the copolymers they have molecular weights from 2,000 to 200,000 gmol -1, preferably from 4,000 to 25,000 gmol -1 and, especially, from 5,000 to 15,000 gmol -1.

Other preferred components of the agents for machine washing of dishes, manufactured according to the invention, are agents that are capable of protecting the corrosion of glassware during cleaning processes and / or scrubbing in a machine for dishwashing. These they come preferably from the group of zinc compounds, of aluminum, silicon, tin, magnesium, calcium,  strontium, titanium, zirconium, manganese and / or lanthanum. Among the compounds mentioned are especially preferred the oxides.

A preferred agent to provide a corrosion protection to glassware during the cleaning and / or scrubbing processes in a machine for Dishwashing is zinc in oxidized form, ie zinc compounds, in which zinc is present in the state cationic Likewise, salts of magnesium. In this case, zinc compounds or soluble magnesium as well as of poor solubility or insoluble. The Preferred compositions, according to the invention, contain one or several magnesium and / or zinc salts of at least one organic acid monomer and / or polymer.

The corresponding acids come in this preferably case of the group of monocarboxylic acids not branched, saturated or unsaturated, of monocarboxylic acids branched, saturated or unsaturated, of dicarboxylic acids saturated and unsaturated, of mono-, di- and tricarboxylic acids aromatic, of saccharic acids, of hydroxy acids, of oxoacids, amino acids and / or carboxylic acids polymers, of unbranched or branched fatty acids, unsaturated or saturated, mono or polyhydroxylated with at least 8 carbon atoms and / or resin acids.

Even if, according to the invention, they may be containing all magnesium and / or zinc salts of acids organic monomers and / or polymers, however, will be preferred, as described above, magnesium salts and / or zinc of the monomeric acids and / or organic polymers from from the group of saturated, unbranched monocarboxylic acids or unsaturated, of branched monocarboxylic acids, saturated or unsaturated, of saturated dicarboxylic acids or unsaturated, of aromatic mono-, di- and tricarboxylic acids, of saccharic acids, of hydroxy acids, of oxoacids, of amino acids and / or polymeric carboxylic acids. Within This group will be preferred, within the scope of this invention, in turn, the acids mentioned below:

from the group of monocarboxylic acids unsaturated, saturated or unsaturated: methanoic acid (acid formic). ethanoic acid (acetic acid), propanoic acid (propionic acid), pentanocio acid (valerianic acid), the hexanoic acid (capronic acid), heptanoic acid (acid enanthoic acid), octanoic acid (caprylic acid), acid nonanoic acid (pelargonic acid), decanoic acid (caprinic acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid (margarinic acid), octadecanoic acid (stearic acid), the Eicoxanoic acid (arachidic acid), docosanoic acid (acid behenic), tetracosanic acid (lignocerinic acid), acid hexacosanic (cerotinoic acid), triacotanoic acid (acid melisinic acid), 9c-hexadecenoic acid (acid palmitoleic acid), 6c-octadecenoic acid, (acid petroselinic), 6t-octadecenoic acid (acid petroselaidinic acid), 9c-octadecenoic acid (acid oleic), 9t-octadecenoic acid (acid elaidinic), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidinic acid) and acid 9c, 12c, 15c-octadecatreinic (linolenic acid).

Among the group of monocarboxylic acids branched, saturated or unsaturated: the acid 2-methylpentanoic acid 2-ethylhexanoic acid 2-propylheptanoic acid 2-Butyloctanoic acid 2-pentilnonanoic acid 2-hexyldecanoic acid 2-Heptylundecanoic acid 2-octyldodecanoic acid 2-nonyltridecanoic acid 2-decyltetradecanoic acid 2-undecylpentadecanoic acid 2-dodecyl hexadecanoic acid 2-tridecylheptadecanoic acid 2-tetradecyloctadecanoic acid 2-pentadecylonadecanoic acid 2-hexadecylecosanoic acid 2-heptadecylheneicosanoic.

From the group of di- or tricarboxylic acids not branched, saturated or unsaturated: propanedioic acid (acid malonic), butanedioic acid (succinic acid), acid Pentanedioic acid (glutaric acid), hexanedioic acid (acid adipic acid), heptanedioic acid (pimelinic acid), acid octanedioic (subic acid), nonanodioic acid (acid azelaic), decanodioic acid (sebacic acid), acid 2c-butenodioic (maleic acid), acid 2t-butenodioic (fumaric acid), acid 2-butindicarboxylic acid acetylenedicarboxylic acid).

From the group of mono-, di- and acids aromatic tricarboxylic acids: benzoic acid, acid 2-carboxybenzoic acid (phthalic acid), acid 3-carboxybenzoic acid (isophthalic acid), acid 4-carboxybenzoic acid (terephthalic acid), acid 3,4-dicarboxybenzoic acid (trimellitic acid), acid 3,5-dicarboxybenzoic acid (trimesionic acid).

From the group of saccharic acids: acid galactonic, manic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, acid 2-deoxy-ribonic acid Alginic

The hydroxy acid group: acid hydroxyphenylacetic acid (mandelic acid), acid 2-hydroxypropionic (lactic acid), acid hydroxysuccinic (malic acid), acid 2,3-dihydroxybutanedioic acid (tartaric acid), acid 2-hydroxy-1,2,3-propanotricarboxylic (citric acid), ascorbic acid, acid 2-hydroxybenzoic acid (salicylic acid), acid 3,4,5-trihydroxybenzoic acid (gallic acid).

From the group of oxoacids: acid 2-oxopropionic (pyrocatechinic acid), acid 4-oxopentanoic (levulinic acid).

From the group of amino acids: alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, asparagine acid, glutamine acid, lysine, arginine, histidine

From the group of polymeric carboxylic acids: polyacrylic acid, polymethacrylic acid, copolymers of alkylacrylamide / acrylic acid, copolymers of alkylacrylamide / methacrylic acid, the copolymers of alkylacrylamide / methyl methacrylic acid, copolymers constituted by unsaturated carboxylic acids, the copolymers consisting of vinyl acetate / crotonic acid, the copolymers of vinyl pyrrolidone / vinyl acrylate.

The spectrum of zinc salts of acids organic, preferred according to the invention, preferably of the Organic carboxylic acids, ranging from salts that are hardly soluble in water or that does not dissolve in water, it is say that they have a solubility below 100 mg / l, preferably below 10 mg / l, especially preferably that have no water solubility, up to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, especially preferably above 1 g / l and, especially, above 5 g / l (all solubilities at a water temperature of 20 ° C). To the first group of zinc salts belong, for example, the zinc citrate, zinc oleate and zinc stearate, to the group of the soluble zinc salts belong, for example, the formate zinc, zinc acetate, zinc lactate and gluconate zinc.

In another preferred embodiment of the In the present invention, the compositions according to the invention contain  at least one zinc salt, but they do not contain any magnesium salt of an organic acid, preferably being at least one zinc salt of an organic carboxylic acid, so especially preferred of a zinc salt of the group formed by zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate. further zinc ricinoleate, the abietato of zinc and zinc oxalate.

Claims (8)

1. Process for manufacturing portions of washing or cleaning agents coated with water soluble coatings, characterized in that it comprises the phases of

to)

        application of a water soluble bottom sheet on a chain of transport or on a tool with one or several molds;

b)

        application of one or more portions of washing agents or cleaning on the bottom sheet, without, in the case where step a) use a tool with one or several molds, the one or more portions of the washing or cleaning agents do not make up or make up with the upper side of the mold after application of the bottom sheet, but protrude or protrude from it, of such that it is inside the mold at most the 50%, preferably at most 40% and especially at most 30% of the maximum height of the agent portion (s) washing or cleaning;

C)

        application of a water soluble top sheet on the or portions of the washing or cleaning agents on the sheet lower;

d)

        fixing the upper sheet on the lower sheet with occlusion of the portion or portions of the washing agents or cleaning;

and)

        sealing and, optionally, cutting of the sheets.

2. Method according to claim 1, characterized in that the lower sheet is molded by applying a vacuum and / or by heating. 3. Method according to claim 1, characterized in that the lower sheet is completely flat during steps b) to e). 4. Method according to one of claims 1 to 3, characterized in that the one or more portions of the washing or cleaning agents, which are applied or applied in step b) on the lower sheet, are or are one or more washing or cleaning agent tablets. 5. Method according to one of claims 1 to 4, characterized in that the upper sheet is molded, as a previous step to the application in step c), by applying a vacuum and / or by heating in a mandrel. Method according to claim 5, characterized in that step c) is initiated by prior ventilation from above. Method according to one of claims 1 to 6, characterized in that the working stages c) and / od) are favored by evacuating the intermediate cavities located between the upper sheet and the lower sheet and / or by applying pressure. on the top sheet. Method according to one of claims 1 to 7, characterized in that, as water soluble foil or sheets, previously stretched sheets, which shrink in stage e) or after the same, are used in steps a) to c). on the or the portions of the washing or cleaning agents.