ES2246070T3 - DETERGENT STRUCTURES WITH IMPROVED DISSOLUTION PROPERTIES. - Google Patents

Abstract

The problems of disintegration of the molded bodies of detergent and cleaning agents containing an effervescent agent can be solved by the additional application of a water insoluble disintegration aid that is capable of swelling to the molded bodies. The molded bodies consist of a detergent molded from dense particles and a composition of cleaning agents containing between 1 and 10% of their weight of a water-insoluble disintegration aid that is capable of swelling, in addition to 3 and 60% of its weight of an effervescent gas generator system.

Description

Detergent structures with properties of Improved dissolution.

The present invention is related to the sector of compact structures, which offer detergent properties and active cleaning. Above all, they are interesting to the invention detergent structures such as tablets of detergent, dishwasher tablets, salt tablets Stain remover or water softening tablets for use domestic, especially for machine use.

The compact detergent structures and cleaning products are widely described in the current state of technique and enjoy growing popularity among consumers due to its simple dosage. Detergents and tablet cleaning products present in front of the way Powder a number of advantages: they are easier to dose and to handle and have advantages of storage and transport because of its compact structure. Therefore, also in the forms of patents are broadly described detergent structures and Cleaning products. A problem that always reappears with the application of detergent and cleaning active structures, is the excessively low decomposition and dissolution rate of the structures under the conditions of application. Since I only know they can make quite stable structures, that is structures hard and friable, by relatively high pressures, a strong compaction of the constituents of the structures and with it a successive late disintegration of structures in aqueous wash liquors and at an excessively slow release of active substances in phenomena detergent and cleaning.

The problem of excessive decomposition times of highly compacted structures is especially known in pharmacy, where certain disintegration aids, the so-called tablet dispersion media, have been used for a long time to shorten decomposition times. Under the generic term of dispersion in pads or decomposition accelerators, the auxiliaries compliant with Römpp (9th Edition, Volume 6, page 4440) and Voigt are collected in " Manual of Pharmaceutical Technology " (6th Edition, 1987, pages 182-184) , which are responsible for the rapid decomposition of the pills in water or gastric juices and the release of the drug in a resorbable manner.

The " Hager Manual of Pharmaceutical Practice " (5th Edition, 1991, page 942) classifies decomposition accelerators or disintegration aids according to their operating mechanism in different classes of substances, the most important decomposition mechanisms being the swelling mechanism ( "swelling"), the deformation mechanism ("deformation"), the initiation mechanism ("wicking"), the repulsion mechanism ("repulsion"), as well as the development of gas bubbles by contact with water (effervescent tablets) ). In the swelling mechanism, the particles swell with the incoming water and increase their volume. Local tensions arising from this appear, which extend far across the entire tablet and thus lead to the decomposition of the compressed structures. The deformation mechanism differs from the swelling mechanism in that the swollen particles were compacted before by compression in the preparation of tablets and now again reach their initial size with the entry of water. In the initiation mechanism, water is absorbed inside the structure by means of the decomposition accelerator and the binding forces between the particles are weakened, which also leads to the decomposition of the structures. The repulsion mechanism further differs in that the particles released by the water absorbed in the pores repel each other as a result of the electric forces. Another fundamental mechanism is based on the "effervescent tablets", which contain active ingredients or their system that emit gaseous substances when they come into contact with water, which causes the structures to burst. In addition, the consumption of hydrophilic auxiliaries is known, which are responsible for the better wetting of the tablet particles in water and for faster decomposition.

While the substances, which act according to the last two mechanisms mentioned, are easily delimited from other respective decomposition mechanisms, it does not always result evident to separate the effects that are based on the mechanisms of swelling and deformation as well as the mechanisms of initiation and repulsion, from each other, so it is reasonable for reasons practical a classification in hydrophilic auxiliaries, systems gas liberators and disintegrating swollen auxiliaries.

The consumption of these different auxiliaries of disintegration alone or in combination is well known in pharmaceutical applications Thus reveals the EP-B-0 396 335 (Beecham Group PLC) the existence of chewable tablets, which contain between 1 and 30% by weight of an effervescence system with 0.5 to 20% in weight of citric, tartaric, adipic, fumaric or maleic acid and of 0.5 to 30% by weight of hydrogen carbonate of Na-, K- or Ca or Sodium glycine carbonate in addition to 5 to 30% by weight of a disintegration aid such as cellulose (modified), polyvinylpyrrolidone or starch glycolate. The advantage of said chewable tablets are, according to the descriptions of the document, in a pleasant application for patients and a pleasant Feeling during intake.

Granulate combinations are also known. effervescent and disintegrating aids swollen thanks to the JP 06 024 959 (BAYER YAKUHIN KK, Derwent Abstract). Describe pharmaceutical compounds in the form of tablets, where they are mixed the active substances with a disintegrator (methylcellulose, carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone) and se partially covered with disintegration aids, which contain a swollen and gel-shaped polymer (sodium alginate, carrageenan, polyethylene oxide) as well as a system of Effervescence CO2 generator. These tablets are praised as carriers of the active ingredients with late release to despite the consumption of two disintegration systems. Those cited Dissolution recommendations lead to the desired result in the Preparation of drug pills. Although in the field of detergents and cleaning products undoubtedly contribute to a improvement of the decomposition properties of the tablets of detergents or active cleaning products; still not sufficient improvement achieved in many cases. This is effective especially when the content of organic substances increases viscous tablets, for example in anionic surfactants and / or non-ionic. In addition, the use of auxiliary decomposition in active structures of detergents and products of Cleaning can lead to specific problems, completely unknown to the drugs.

Thus, for example, the insertion of a system of Effervescence in detergent tablets does not lead to the desired rapid disintegration, often employs known first effervescence and decomposition effects of tablets conventional effervescent, but then, after a short time, it stops again and the tablet doesn't break down anymore. Often form, outside the aforementioned detergent ingredients and cleaning products and after a short period of time, a layer waterproof, which prevents water penetration into the tablet and its subsequent decomposition.

That is why it describes for example the European patent EP-A-0 466 484 (Unilever) tablets of particulate compressed detergent, where appropriate in addition to surfactant (s) and material (s) structural (s), other detergent ingredients, preferring swollen auxiliaries in cases where they contain adhesion / disintegration aids.

DE 35 35 516 (Bucher) describes Effervescent tablets of detergents and cleaning products. These tablets contain 2 to 6% by weight of surfactants, of 40 to 60% by weight of hydrogen carbonate, from 33 to 53% by weight of a solid organic acid (especially a mixture 2: 3 citric and tartaric acid), 1.5 to 2.5% by weight of polyvinylpyrrolidone in addition to colloidal silicon dioxide. Without However, these tablets do not correspond to any textile detergent, but they are preferably applied in areas such as tunnels vehicle window washing or cleaning and maintenance of floors.

With the use of conventional swollen auxiliaries of decay such as starch and cellulose or its derivatives or polymers such as polyvinylpyrrolidone or polyvinyl alcohol are they get pills in textile detergents, which break down into water more or less fast; however, such auxiliaries of disintegration lead, in the required size ratio for a rapid disintegration, to a problem of waste in the laundry treated.

Consequently, it was the duty of the invention prepare detergent and cleaning products structures that contain effervescent compound, which on the one hand decomposes fast in the operation wash liquor and on the other hand not originate any problem related to the formation of waste in textiles

It was discovered then, that they can be avoided from this way the problems of disintegration of structures of detergents and cleaning products containing compound effervescent, which in addition to the effervescence system contributes to structures a non-water soluble disintegrating agent, suitable for the inflation.

Object of the invention is therefore in a first mode of operation, a structure of detergents and products of cleaning from detergents and cleaning products in the form of compacted particles, comprising surfactant (s), structural materials as well as other constituents of detergents and cleaning products, where structures shaped contain

to)

from 1 10% by weight of one or more disintegrating agents not water soluble, suitable for inflation, transformed into grains thick by a spray drying process, granulated, chipboard, compacted, pelletized or extrusion and

b)

of 3 60% by weight of an effervescent generator system gas.

In the context of the present invention, abbreviate the contents of the medium in a) or b) as a "component a) "or" component b) "The concept" component "must understood in this context as pure construction of language. Especially the effervescence system b) may consist of several compounds, which do not necessarily have to exist in the form of a single compound Rather it is determined arithmetically the overall proportion of the respective compounds, which can also present in raw materials or completely isolated compounds different, and is described as "component b)". Neither do the non-water-soluble and suitable for disintegration agents inflation must necessarily be presented in the form of a single compound Also here you can present, where appropriate, more disintegration auxiliaries of said type in the different raw materials and / or isolated compounds, which is added arithmetically to "component a)".

As a non-water soluble disintegrating agent and suitable for inflation {component a)} mainly used polymeric substances with molar masses of between a few tens and hundreds of thousands of gmol -1. Together with synthetic polymers such as, for example, polyvinylpyrrolidone and polyvinyl alcohol, they are especially considered as component a) natural as well as chemically modified biopolymers, which they can select for example from the group of alginates, starches and cellulose. Preferably, component a) is selected from natural and synthetic polysaccharides and their derivatives.

To these groups belong, for example, the pure polysaccharides starch and cellulose, but also the products of esterifications or etherifications, in which they were replaced the hydrogen atoms of the hydroxy group. They were also left use celluloses or starches as polysaccharide derivatives, in which hydroxy groups were replaced by functional groups that They are not linked by an oxygen atom. To the group of cellulose derivatives belong, for example, celluloses alkaline, carboxymethyl cellulose (CMC), ester and ether of cellulose, as well as aminocelluloses. To the group of derivatives of Cotton belong, for example, carboxymethyl starch (CMS).

Of course, it can also be used as an agent non-water soluble and suitable for inflation microcrystalline cellulose. This cellulose has particle sizes primary of approximately 5 mm and can be compacted, for example, in granules with an average particle size of 200 mm. Such compacted are stable and allowed to mix with other substances, without decomposing into the primary particles.

Non-water soluble and disintegrating agents suitable for inflation are not used in the form of fine powder, but transformed into coarse grains by a drying process by atomization, granulated, agglomerated, compacted, pelletized or extrusion. To these "granulated" disintegration aids do not only granular disintegration aids belong, but by example also the disintegration aids in form cogranulated or otherwise compacted.

In preferred detergent structures and Cleaning products are used as component a) from 1 to 10% in weight, preferably from 2 to 7% by weight and especially from 3 to 5% by weight, based on the overall structure, of a cellulose or derived from it. The effervescent gas generator system {component b)} may consist of a single substance, which in Contact with water releases a gas. Under these compounds cited especially the already indicated magnesium peroxide, which in Contact with water releases oxygen. Usually the system of effervescence releasing gas consists of at least two constituents, which react with each other under the formation of gas. While here you can imagine and make a large number of systems, which for example release nitrogen, oxygen or hydrogen, the effervescence system used in the structures is selected of detergents and cleaning products according to the invention both economically and ecologically. The b) preferred constituents consist of carbonates and / or alkali metal hydrogen carbonates as well as an acidifier, which is appropriate for releasing dioxide from carbon from alkali metal salts in aqueous solution.

Among the carbonates or alkali metal hydrogen carbonates are manifestly prefer sodium or potassium salts, as opposed to other salts, for cost reasons. Of course, they cannot be used. the respective carbonates or hydrogen carbonates alkali metal cigars; Rather, mixtures of different carbonates and hydrogen carbonates by technical interests of washing.

In preferred detergent structures and Cleaning products are used as component b) from 2 to 20%, preferably 3 to 15% and especially 5 to 10% by weight of an alkali metal carbonate or hydrogen carbonate as well as 1 to 15%, preferably 2 to 12% and especially from 3 to 10% by weight of an acidifier, referred in each case to the global structure

As an acidifier that releases carbon dioxide of the alkali metal salts in aqueous solution can be use for example boric acid as well as alkali metal hydrogen sulfates, alkali metal and other dihydrogen phosphates inorganic salts On the other hand, it is preferred to employ organic acidifiers, citric acid being an acidifier especially preferred. In addition, they can be used especially the other mono-, oligo- and polycarbon solid acids. Of this group, again, tartaric, succinic, malonic acids are preferred, adipic, maleic, fumaric, oxalic as well as polyacrylic. You can also use organic sulfonic acids such as acid amidosulfonic In the context of the present invention, it is preferred use the commercially obtainable product as acidifier Sokalan® DCS (BASF brand), a mixture of acid succinic (maximum 31% by weight), glutaric (maximum 50% in weight) and adipic (maximum 33% by weight).

They are preferred in the context of the present. invention structures of detergents and cleaning products, in the which is used as an acidifier in component b) a substance of the group of di-, tri- and oligocarboxylic organic acids or mixtures of these.

The detergent structures and products of cleaning of the present invention preferably also contain other common ingredients in detergents and cleaning products from the group of surfactants, structural materials, bleaches, bleach activators, enzymes, lighteners optics, foam inhibitors, perfumes and dyes. These Substances are specified below.

In the structures of detergents and products of cleaning according to the invention surfactants can be used anionic, nonionic, cationic and / or amphoteric. They are preferred by reasons of industrial implantation mixtures of surfactants anionic and nonionic, where the surfactant content anionics must be greater than the non-surfactant content ionic The total surfactant content of the structures is is between 5 and 60% by weight, based on the weight of the structure, with surfactant contents being preferred over 15% by weight.

As anionic surfactants are used for example some of the sulphonate and sulfate type. Surfactants from sulfonate type are preferably considered alkylbenzenesulfonates C 9-13, olefinsulfonates, that is mixtures of alkene- and hydroxy-alkanesulfonates, and disulfonates, such as those obtained, for example, from monolefins C_ {12-18} with a double terminal or inner link by sulfonation with gaseous sulfur trioxide followed by alkaline or acid hydrolysis of sulfonation products. Also suitable are alkanesulfonates, which are obtained at from C 12-18 alkanes for example by sulphochlorination or sulfoxidation followed by hydrolysis or neutralization, respectively. In the same way they also result suitable α-sulfo acid esters fatty (estersulfonates), such as α-sulfo methyl esters of fatty acids hydrogenated coconut, palm nut or tallow.

Other suitable anionic surfactants are those glycerol esters of sulfated fatty acids. They are esters of mono-, di- and tri-ester fatty acid glycerol as well as their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or by transesterification of triglycerides with between 0.3 and 2 moles of glycerin. Glycerol esters of sulfated fatty acids Preferred are fatty acid sulfonation products saturated with 6 to 22 carbon atoms, for example acids Capric, caprylic, capric, myristic, lauric, palmitic, stearic, or behenic.

How alkylsulfates are preferred alkali metal salts and, in particular, the sodium salts of sulfuric monoesters of fatty alcohols C 12 -C 18, for example fatty alcohols coconut, tallow, lauric, myristic, cetyl or stearic or C 10 -C 20 oxoalcohols and those monoesters of secondary alcohols with that chain length. In addition, alkylsulfates of the mentioned chain length containing a linear alkyl radical synthetic, made from petrochemical bases, having a similar tolerance of the environment to that of the corresponding Compounds based on fatty chemical raw materials. From the point of view of detergents, the C 12 -C 16 alkyl sulfates and the C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates. They are also suitable anionic surfactants the 2,3-alkyl sulfates that can be made from agreement, for example, with US patents 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Compani under the name DAN®.

Sulfuric monoesters are also suitable of the C 7-21 linear ethoxylated alcohols or branched with 1 to 6 moles of ethylene oxide, such as 2-methyl branched alcohols C 9-11 with an average of 3.5 moles of oxide of ethylene (EO) or C 12-18 fatty alcohols with 1 to 4 EO. In cleaning products they are used only in one relatively small amount, due to its highly behavior sparkling, for example in concentrations between 1 and 5% in weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, called also sulphosuccinates or esters of alkylsulfosuccinic acid and constituting the monoesters and / or diesters of the acid alkylsulfosuccinic with alcohols, preferably alcohols fatty and in particular ethoxylated fatty alcohols. The ones are preferred sulfosuccinates containing C 8-18 radicals fatty alcoholics or mixtures of them. In particular they are preferred sulfosuccinates containing a fatty alcoholic radical, derived from ethoxylated fatty alcohols, which by themselves constitute non-ionic surfactants (for description, see down). Particularly preferred are sulfosuccinates, whose fatty alcoholic radicals derived from ethoxylated fatty alcohols with reduced homologous distribution. Similarly, it is also possible to use alkylsulfosuccinic acid with preferably from 8 to 18 carbon atoms in the chain alkylic or its salts.

How additional anionic surfactants enter particularly soaps in consideration. They are soaps suitable those of saturated fatty acids, such as salts of lauric, myristic, palmitic, stearic, hydrogenated erucic acids and behenic, as well as in particular mixtures of derived soaps of natural fatty acids, such as coconut, palm or of tallow

Anionic surfactants, including soaps, can be found in the form of their sodium, potassium or ammonium as well as soluble salts of organic bases, such as mono-, di- or triethanolamines. The anionic surfactants are preferably found in the form of sodium or potassium salts, especially in the form of sodium salts.

As nonionic surfactants are used preferably alkoxylated alcohols, preferably ethoxylated and in particular primary with preferably from 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 radical can be linear or, preferably, with a methyl branch in the second position and / or may contain a mixture of linear radicals and with methyl branches, such as those normally found in oxoalcoholic radicals. Particularly preferred are ethoxylates. alcoholics with linear radicals of naturally occurring alcohols containing from 12 to 18 carbon atoms (for example alcohols fatty or oleic coconut, palm or tallow), and an average of 2 to 8 EO per mole of alcohol. They belong to these ethoxylated alcohols preferred, for example, C 12-14 alcohols containing 3 or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3, 5, 7 or 8 EO, C 12-18 alcohols with 3, 5 or 7 EO and the mixtures of these, such as alcohol mixtures C 12-14 with 3 EO and alcohol C 12-18 with 5 EO. The indicated degrees of ethoxylation represent statistical mean values, which can be a whole quantity or a fraction for a specific product. The Preferred alcoholic ethoxylates show a homologous distribution reduced (narrow range ethoxylates, NREs). In addition to these nonionic surfactants can also be used fatty alcohols with more than 12 EO. Examples of this are tallow fatty alcohols with 14, 25, 30 or 40 EO.

Another class of non-ionic surfactants that You can use advantageously, they are alkyl polyglycosides (APG). Usable alkyl polyglycosides conform to the general formula RO (G) z, in which R is a linear aliphatic radical or branched (in particular with a methyl branching in the second position) saturated or unsaturated, containing 8-22 atoms carbon, preferably 12-18 carbon atoms and G is the symbol representing the unit of glycosa with 5 or 6 atoms of carbon, preferably glucose. The degree or glycosidation z ranges from 1 to 10; x preferably ranges from 1.2 to 1.4.

An additional class surfactants not ionic agents used preferably, which can be used as agents non-ionic surfactant only or in combination with others nonionic surfactants, collects acid alkyl esters alkoxylated fatty acids, preferably ethoxylated or ethoxylated and propoxylated, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described in Japanese patent JP 58/217598, or those preferably prepared according to the procedure described in the international patent WO-A-90/13533.

Agents may also be suitable nonionic surfactants of the aminoxide type (for example the N-cocoalkyl-N, N-dimethylaminoxide and the N-tallowalkyl-N, N-dihydroxyethylamino oxide) and of the fatty acid alkanolamide type. The concentration of these nonionic surfactants is preferably less than that of ethoxylated fatty alcohols, in particular not greater than Half of these.

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

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

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

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

--- [Z]

in which RCO is an acyl radical aliphatic with from 6 to 22 carbon atoms, R1 is hydrogen or an alkyl or hydroxyalkyl radical with 1 to 4 atoms of carbon and [Z] a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and between 3 and 10 hydroxyl groups. The Polyhydroxy fatty acid amides are known substances that they can be commonly obtained by reductive tuning of a reducing sugar with ammonia, an alkylamine or an alkanolamine and its subsequent acylation with a fatty acid, an acid alkyl ester fatty or an acid chloride fatty.

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

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

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

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

--- [Z]

in which R is an alkyl radical or linear or branched al (en) il with 7 to 12 atoms of carbon, R 1 is a linear, branched or branched alkyl radical cyclic or an aryl radical with 2 to 8 carbon atoms and R2 is a linear, branched or cyclic alkyl radical, a aryl radical or an oxyalkyl radical with 1 to 8 atoms of carbon, with alkyl radicals being preferred C_ {1-4} or phenolics and [Z] a radical linear polyhydroxyalkyl, whose alkyl chain is replaced by at least two hydroxy groups, or alkoxylated derivatives, preferably ethoxylated or propoxylated said radical.

[Z] is preferably obtained by amidation reducing a reducing sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The compounds N-alkoxy or N-aryloxy substituted they can then, for example as learned in the specification International WO-A-95/07331, become the desired polyhydroxy fatty acid amide by reaction with fatty acid methyl esters in the presence of a Alkoxide as catalyst.

As structural materials that can be find contents in detergent and product structures of cleaning according to the invention, are especially mentioned silicates, aluminum silicates (especially zeolites), carbonates, salts of di- and polycarboxylic organic acids as well As the mixture of these substances.

Crystalline and layered sodium silicates suitable possess the general formula NaMSi_ {O} {2x + 1} • H2O, where M is sodium or hydrogen, x a number from 1.9 to 4 e and a number from 0 to 20. The values Preferred of x are 2, 3 or 4. Such crystalline phyllosilicates are described for example in the European patent EP-A-0 164 514. Philosilicates Preferred crystals of the indicated formula are those, in the that M is sodium and x takes the values 2 or 3. In particular, it prefers both β- and δ-silicate sodium Na2 {Si} {2} O_ {5} \ cdotyH_ {2}, obtaining the sodium?-silicate for example by procedure described in the international patent WO-A-91/08171.

The use of sodium silicates is also possible amorphous with a Na 2 O: SiO 2 module from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which they are of delayed dissolution and have detergent properties high schools. Delayed dissolution compared to Conventional amorphous sodium silicates may be caused by various modes, for example by surface treatment, compound formation, compaction / condensation or by overestimated Within the framework of this invention it is also called under the term "amorphous" to substances "amorphous under rays X ". This means that in diffraction experiments of X-rays silicates do not provide clear reflections of rays X, which are typical of crystalline substances, but in all case show one or more scattered maximum X radiation, having a width of more units degree of diffraction angle. But nevertheless, it may very well lead even to especially good properties structural, when silicate particles provide a maximum diffraction blurred or even sharp in the experiments of electron diffraction. The interpretation of this is that products have microcrystalline areas of the size between 10 and a few hundred nm, with values up to a maximum of 50 being preferred nm and in particular up to a maximum of 20 nm. Such calls amorphous silicates under X-rays, which also show a solution delayed compared to conventional sodium silicates, are described for example in the German patent DE-A- 44 00 024. In particular, compressed amorphous silicates are preferred / compacted, compound amorphous silicates and low amorphous silicates X-rays overdone.

The finely crystalline, synthetic zeolite and that It contains water, used is preferably zeolite A and / or P. As zeolite P is especially preferred zeolite MAP® (product commercial of the Crosfield house). However, they also result suitable zeolite X as well as mixtures of A, X and / or P. The zeolite can be consumed as a stabilized powder suspension spray dried or also not dry, still wet after elaboration. In case the zeolite is used as a suspension, may contain a low supplement of non-ionic surfactants such as stabilizers, for example 1 to 3% by weight, based on zeolite, of C 12 -C 18 fatty alcohols ethoxylated with 2 to 5 ethylene oxide groups, fatty alcohols C 12 -C 14 with 4 to 5 oxide groups of ethylene or ethoxylated isotridecanoles. The right zeolites show an average particle size of less than 10 mm (volumetric distribution; measurement method: Coulter counter) and preferably contain 18 to 22% by weight, in particular of 20 to 22% by weight of combined water.

Of course, it is also possible to use the phosphates generally known as structural substances, while such use should not be avoided for ecological reasons. Result particularly suitable orthophosphate sodium salts, pyrophosphates and especially tripolyphosphates.

Usable organic structural substances they are, for example, the polycarboxylic acids that can be used in the form of its sodium salts, such as citric, adipic acids, succinic, glutaric, tartaric, glucinic, aminocarboxylic, nitrilotriacetic (NTA), while such uses are not rejected by ecological motifs, as well as mixtures of these. The preferred salts are those of polycarbonic acids such as citric acid, adipic acid, succinic, glutaric, tartaric, glucinic and mixtures thereof. These salts are used because of their structural properties and should not be consider as constituents of the effervescent system; especially they are not suitable, for example, to release carbon dioxide from hydrogen carbonates

Among the compounds that serve as agents of bleached and that provide H2O2 in water, have special meaning sodium perborate tetrahydrate and the sodium perborate monohydrate. Other bleaching agents Usable are, for example, sodium percarbonate, peroxypyrophosphates, citric perhydrates, as well as salts perished H 2 O 2 or peracids, such as perbenzoate, peroxophthalates, diperazellic acid, phthaloiminic acid or acid diperdodecanedioic.

To achieve during washing or cleaning a temperatures of 60 ° C and below an improved bleaching action, bleach activators may be included. As activators of bleached compounds may be used, which under conditions of perhydrolysis result in aliphatic peroxocarbonic acids with preferably 1 to 10 carbon atoms, in particular 2 at 4 carbon atoms, and / or, if necessary, perbenzoic acid substituted or unsubstituted. Suitable substances are those that carry O- and / or N-acyl groups with the aforementioned number of carbon atoms and / or, if necessary, benzoyl groups substituted or unsubstituted. Multiple preference is given acylated alkylenediamines, in particular to the tetraacetylethylenediamine (TAED); acylated triacin derivatives, in particular the 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triacin (DADHT); acylated glycolurils, in particular the tetraacetylglycoluril (TAGU); N-acylimides, in particularly N-Nonanoylsuccinimide (NOSI); acylated phenolsulfonates, in particular the n-Nonanoil- or the Iso-nonanoyl-oxybenzenesulfonate (n- or iso-NOBS); carbonic anhydrides, in particular the phthalic anhydride; acylated polyvalent alcohols, in particular the triacetin the ethylene glycol diacetate and the 2,5-diacetoxy-2,5-dihydrofuran.

In addition to conventional activators bleached or instead may also include the so-called bleaching catalysts. These substances are salts or complexes of bleached reinforcing transition metals, as per example complexes of salts of Mn-, Fe-, Co-, Ru- or Mo-, or complexes carbonyl They can also be used as catalysts for bleached complexes of Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V- and Cu- con tripod ligands containing N-; as well as the amino complexes of Co-, Fe-, Cu- and Ru-.

As foam inhibitors that can be constituents of component b), which are used as isolated component b), for example, soaps of natural or synthetic origin, offering a high acid content C 18 -24 fatty acids. Examples of inhibitors of Suitable non-surfactant foam are organopolysiloxanes and their mixtures with silicic acid or microfine bistethylethylenediamide and, when appropriate, silanized. They can also be used with advantages mixtures of different foam inhibitors, for example such as silicones, paraffins or waxes. Especially the inhibitors bind from foam to a granular, soluble or dispersible carrier substance in water Above all, the use of paraffin mixtures and bisiletiletilendiamidas.

Additionally they can also be used constituents that positively influence ease with that oil and grease are removed from the tissues by washing (called "stain repellents" -soil repellents-). This effect is especially evident when a tissue gets dirty which has been washed several times before with a washing detergent according to the invention, which includes these Solvent constituents of oil and grease. They belong to preferred oil and grease solvent constituents, for For example, non-ionic cellulose ethers such as methyl cellulose and the Methyl hydroxypropyl cellulose with a content in methoxy groups of 15 to 30% by weight and in groups hydroxy-propoxy from 1 to 15% by weight, relative in each case to non-ionic cellulose ethers; as well as the known polymers of phthalic acid of the state of the art and / or of terephthalic acid or its derivatives, especially polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic derivatives and / or non-ionic modified thereof. Of these are preferred, in in particular, sulfonated derivatives of acid polymers phthalic and terephthalic acid polymers.

Enzymes are considered those of the class of proteases, lipases, amylases, cellulases or mixtures thereof. Especially suitable are the enzymatic active ingredients obtained from a variety of bacteria and fungi, such as bacillus subtilis, bacillus licheniformis and streptomyces griseus. Are used especially subtilisin type proteases and, in particular, proteases obtained from bacillus lentus. In addition, they are special interest in this context enzymatic mixtures, for example of protease and amylase, protease and lipase, protease and cellulase, of cellulase and lipase; of protease, amylase and lipase or of protease, lipase and cellulase; but especially the mixtures that contain cellulase Also suitable in some cases are peroxidases or oxidases. Enzymes may be adsorbed on carrier substances and / or embedded in wrapping materials, for protect them from premature decomposition. The content in enzymes, enzymatic mixtures or enzymatic granules in the structures according to the invention can contribute for example with approximately 0.1 to 5% by weight, preferably 0.1 to approximately 2% by weight.

The structures may contain as lightening optics derived from diaminoestylbenodisulfonic acid or its salts of alkali metals. For example, salts of the acid 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) -tylbeno-2,2'-disulfonic acid or compounds of similar structure, which instead of the morpholino group they carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. They can also be found present clarifiers of the type of substituted diphenyl styryls: for example, alkaline salts of 4,4'-bis ( 2-sulfoestiryl) -diphenyl, del 4,4'-bis (4-chloro-3-sulfoestyryl) -diphenyl, or of 4- (4-Chlorostyril) -4 '- (2-sulfoestyryl) -diphenyl. You can also use mixtures of those already mentioned lightening

In another mode of operation the invention is of interest a procedure for the elaboration of the structures of detergents and cleaning products according to the invention by pressing a detergent and cleaning particulate agent, comprising surfactant (s), structural materials as well as, where appropriate, other constituents of detergents and products of cleaning, where shaped structures contain

to)

from 1 10% by weight of one or more disintegrating agents not water soluble, suitable for inflation, transformed into grains thick by a spray drying process, granulated, chipboard, compacted, pelletized or extrusion and

b)

of 3 60% by weight of an effervescent generator system gas.

referred in each case to original structures, constituents a) or b) being able to both composting with other constituents of detergents and products of cleaning as well as incorporated by separated.

The particulate mixture to be compacted may be present in constituents a) and b) as a mixture of pure powders, but it is preferred that isolated raw materials be provided, pretreated and especially previously pressed, in the mixture. Above all, the disintegration auxiliaries are added to the mixture Preferably preferably in the form of granules, pellets, compacted or extruded. The same also applies to certain others constituents as surfactants, which are added to the mixture in form of particles that conveniently contain materials structural, obtainable by spray drying, granulated, pelletized, compacted or extrusion.

In the preferred modes of operation of the process according to the invention, the particulate mixture of detergents and cleaning agents is pressed at temperatures below 30 ° C and pressing forces below 15 N / cm 2. The only possibility of elaboration of the structures according to the invention is verified at the moment by the dry mixing of the constituents, which can be totally or partially pregranulated, and then shaped, especially pressed into tablets, being able to resort to the conventional procedure (by example as in conventional patent forms for the preparation of tablets, especially in the area of detergents and washing products, especially as described in the aforementioned patents and the article "Preparation of Tablets: Current State of the Art" , SÖFW-Journal, 122. Year (1996), pages 1016-
1021).

The structures can be finished in Default spatial conformations and default size. How spatial conformations come into consideration practically all reasonably manipulable flow facilitators, by example the formation of plates, bars or ingots, dice, ashlars and the corresponding spatial elements with surfaces smooth sides as well as especially cylindrical shapes with cross section in the form of a cross or oval. This last conformation includes presentation forms from the tablet to compact cylindrical pads with a relationship height / diameter greater than 1.

Portion presses can be formed respectively as isolated elements separated from each other, which correspond to predetermined dosages of the detergent agent and / or cleaning. But it is also possible to form presses, which unite a greater amount of such mass units in a press, aiming at the easy separation of fragmented smaller units especially through previously given break positions. For the consumption of textile detergent in machines of the common types in Europe with horizontal mechanics may be convenient formation of presses in portions such as pads, cylinders or ashlars, depending on each case, preferring the relationship diameter / height in the range of about 0.5: 2 to 2: 0.5 Commercial hydraulic presses, eccentric presses or roller presses are suitable mechanisms, especially for the elaboration of similar presses.

In another mode of operation the spatial conformation of structures in their dimensions at drum of common household washing machines, so that the structures can be applied without a dispenser directly to the drum, where It dissolves during the rinsing phenomenon. Of course it turns out also possible and preferred in the context of the present invention the hassle-free consumption of detergent structures with dispenser

Another preferred structure, which could be elaborate, has a structure in plates or plates with segments thick and long and thin and short alternatives, so that isolated segments of these "bars" can be broken by desired break points, which offer thin and short segments, and Enter them in the machine. This principle of structures "bar" detergents can also be carried out with other geometric shapes, for example straight triangles, that only They are attached to each other on one of their sides.

However, it is also possible that different constituents do not press on a uniform tablet, but structures are obtained that have more layers, minimum two layers. It is also possible that these different layers offer Different dissolution rates. This may result advantageous properties of industrial implantation of the structures In cases where, for example, the structures contain constituents that influence each other negatively, then it is possible to integrate a constituent into the fast dissolving layer and the other constituent in the layer of slow dissolution, so that the first constituent already has reacted, when the second enters into solution. Construction of the layers of the structures can be done both in a way stacked, resulting in a dissolution phenomenon of the inner layer (s) at the edges of the structures, when the outer layers have not yet dissolved by full. But you can also achieve a total coating of the inner layer (s) through the respective and successive layers deposited externally, which entails an impediment to the precipitated dissolution of constituents of the layer (s) interior (s).

Another preferred mode of operation of the invention it consists of structures of at least three layers, that is to say two external and at least one inner layer, containing at least one of the layers internal a bleaching peroxi (while in the structures stacked both layers of cover, and in rolled structures the outermost layers are still free of peroxy bleach). In addition it is also possible to spatially separate into a structure peroxy bleach and, if applicable, bleach activators and / or enzymes present. Such multilayer structures offer the advantage, that can not only be used in the dispenser drawer or in the dispenser, which are added to the wash liquor; rather it is also possible in such cases, put the structures in direct contact with the textiles in the machine, without having to fear stains of bleaches and the like.

Similar effects can be obtained as well. by coating a constituent isolated from total detergents and cleaning products or from all The structure to be pressed. For this you can atomize the bodies to coat for example with aqueous solutions or emulsions, or get a wrap with the coating procedure with enamel.

The structures according to the invention, especially detergent and bleaching structures that up now they had a bad decomposition and bad dissolution, show thanks to the disintegration aid content insoluble in water, capable of swelling and effervescent system {constituents a) and b)} excellent decomposition properties. This can be verified, for example, under critical conditions in a common household washing machine (direct application in the liquor of washing by conventional dispensers, clothing program delicate or colored clothes, maximum washing temperature of 40ºC).

In another mode of operation of the invention, therefore requires a washing procedure, in which the structures are introduced into the drawer wash liquor Dispenser of a domestic washing machine. The dissolution times of the structures in the washing machine preferably amount to less than 8 minutes and especially less than 5 minutes. Another way of operation of the invention requires a washing procedure in the that the structures - where appropriate with a dispenser - are introduced directly with the laundry found in the drum of a domestic washing machine With this the structures can be added directly advantageously, that is without a dispenser, to the laundry; although the use of known dosers such as bags, bags, plastic containers or the like is also possible without problem any.

Examples

By pressing a particulate composition of detergents and cleaning products were made according to the invention the structures of detergents and cleaning products 1 and 2 as well as comparative examples 3 and 4, which show a composition according to Table 1.

The comparative examples contained either component a) (Example 3) or no component b) (Example 4), having used small amounts of Na2CO3 as structural material

TABLE 1 Detergent and cleaning products structures [% by weight of]

Detergent structures and products of cleaning one 2 3 4 C9-13-Alkylbenzenesulfonate 11.4 10.0 10.6 10.0 C12-18 fatty alcohol sulfated - 6.6 2.4 6.8 C12-18 Alcohol Fat with 7EO 5.8 - 4.8 6.2 Soap 0.7 2.1 1.6 1.8 Tripolyphosphate sodium - 23.5 - - Zeolite 4A (referred to the substance free of Water) 18.5 3.5 20.0 20.0 Perborate sodium 18.2 - 18.6 18.6 Percarbonate sodium - 23.0 - - Tetraacetyl ethylenediamine (TAED) 6.4 3.4 5.8 5.8 Cellulose {component to)} 3.4 4.0 - 6.0 Citric acid {constituent of the component b)} * 3.2 3.5 3.5 - Na_ {2} CO_ {3} {constituent of the component b)} * 8.6 - 8.1 6.3 NaHCO_ {{constituent of the component b)} * 6.4 7.0 6.8 - Sodium silicate amorphous 3.3 2.1 3.0 3.4 Acrylic Acid Acid Copolymer maleic 2.7 2.5 2.5 2.6 Enzymes 2.3 4.0 2.7 2.7 Lightening 0.2 0.2 0.2 0.2 Polyethylene glycol (dry molar mass: 4000 g / mol) - - 0.5 - Salts / water Residual Residual Residual Residual *) mixed by separated

The hardness of the pills was measured by deformation of the tablet until it breaks, the force acting on the lateral surfaces of the tablet and the tablet resistance.

For the determination of the decomposition of pills the tablet was placed in a beaker with water (600 ml of water, temperature: 30 ° C) and the time was measured until Total decomposition of the pills.

For the rinse test 3 were placed 40 g tablets in the rinse chamber of the respective washing machine. After the rinsing phenomenon, it dried and stabilized the residue in the chamber.

Table 2 shows the experimental data:

TABLE 2

Detergent tablets [Physical data] Tablet Example 1 Example 2 Example 3 Example 4 Hardness 33 N 25 N 30-35 N 30-35 N Time of decomposition 5-10 sec 5-10 sec > 5 min 3 min Residue - - 34 g 12 g

Claims (10)

1. Structures of detergents and cleaning products from detergents and cleaning products in the form of compacted particles, comprising surfactant (s), structural materials as well as, where appropriate, other constituents of detergents and cleaning products, characterized in that shaped structures contain

to)

from 1 10% by weight of one or more disintegrating agents not water soluble, suitable for inflation, transformed into grains thick by a spray drying process, granulated, chipboard, compacted, pelletized or extrusion and

b)

of 3 60% by weight of an effervescent generator system gas.

2. Detergent and cleaning products structures according to claim 1, characterized in that component a) is selected from natural or synthetic polysaccharides and their derivatives. 3. Detergent and cleaning products structures according to one of claims 1 or 2, characterized in that component b) consists of alkali metal carbonates and / or hydrogen carbonates as well as an appropriate acidifier for releasing carbon dioxide from the salts of alkali metals in aqueous solution. 4. Detergent and cleaning products structures according to one of claims 1 to 3, characterized in that as component a) 1 to 10% by weight, preferably 2 to 7% by weight, and especially 3 to 5% are used in weight, referred to the entire structure, of a cellulose or a derivative thereof. 5. Detergent and cleaning products structures according to one of claims 1 to 4, characterized in that as component b) 2 to 20% by weight, preferably 3 to 15% by weight and especially 5 to 10% are used by weight of carbonates or hydrogen carbonates of alkali metals as well as from 1 to 15, preferably from 2 to 12 and especially from 3 to 10% by weight of an acidifier, referred in each case to the overall structure. 6. Structures of detergents and cleaning products according to one of claims 3 to 5, characterized in that, as an acidifier in component b), a substance from the group of dihydric and oligocarboxylic organic acids or mixtures thereof is used. 7. Procedure for the development of detergent and cleaning products structures by pressing detergents and particulate cleaning products, comprising surfactant (s), structural materials as well as, where appropriate, other detergent constituents and cleaning products, characterized in that detergents and cleaning products to be pressed additionally contain

to)

from 1 10% by weight of one or more disintegrating agents not water soluble, suitable for inflation, transformed into grains thick by a spray drying process, granulated, chipboard, compacted, pelletized or extrusion and

b)

of 3 60% by weight of an effervescent generator system gas,

referred in each case to original structures, constituents a) or b) being able to both composting with other constituents of detergents and products of cleaning as well as incorporated by separated. Method according to claim 7, characterized in that the composition of the detergent or particulate cleaning product is pressed at temperatures below 30 ° C and pressures below 15 N / cm 2. 9. Washing procedure using the structure according to one of claims 1 to 6, characterized in that the structure is introduced into the washing liquor of the dispensing drawer of a domestic washing machine. 10. Washing procedure using the structure according to one of claims 1 to 6, characterized in that the structure is introduced directly with the laundry into the drum of a domestic washing machine.