EP1740690B2 - Method for producing detergent or cleaning products - Google Patents

Description

The present invention is in the field of detergents or cleaners. In particular, the present invention relates to a process for the preparation of detergents or cleaners, in particular dosing of detergents or cleaners.

Detergents or cleaners are now available to the consumer in a variety of forms. In addition to washing powders and granules, this offer also includes, for example, detergent concentrates in the form of extruded or tabletted compositions. These fixed, concentrated or compressed forms of supply are characterized by a reduced volume per dosing unit and thus reduce the costs for packaging and transport. In particular, the washing or cleaning agent tablets additionally meet the consumer's desire for simple dosing. The corresponding means are comprehensively described in the prior art. However, in addition to the advantages listed, compacted detergents or cleaners also have a number of disadvantages. Especially tableted supply forms are characterized by their high compression often by a delayed disintegration and thus a delayed release of their ingredients. In order to resolve this "conflict" between sufficient tablet hardness and short disintegration times, numerous technical solutions have been disclosed in the patent literature, reference being made by way of example to the use of so-called tablet disintegrating agents at this point. These disintegrants are added to the tablets in addition to the washing or cleaning-active substances, and as a rule have no washing or cleaning-active properties, and thus increase the complexity and the costs of these agents. A further disadvantage of the tabletting of mixtures of active substances, in particular mixtures containing washing or cleaning substances, is the inactivation of the active substances contained by the compaction pressure which occurs during tableting. Inactivation of the active substances can also take place due to the increased contact area of the ingredients due to the tableting due to chemical reaction.

As an alternative to the particulate or compacted detergents or cleaners described above, solid or liquid detergents or cleaners which have a water-soluble or water-dispersible packaging are increasingly being described in recent years. These agents are characterized as the tablets by a simplified dosage, since they can be dosed together with the outer packaging in the washing machine or dishwasher, but on the other hand they also allow the preparation of liquid or powdered detergents or cleaners, which compared to the Kompaktaten characterized by a better resolution and faster effectiveness.

For example, the EP 1 314 664 A2 (Unilever) a dome-shaped pouch with a receiving chamber containing a liquid

Subject of the WO 01/83657 A2 (Procter & Gamble), on the other hand, are pouches which contain in a receiving chamber two particulate solids, each present in fixed regions and not intermingled.

In addition to the packages, which have only one receiving chamber, the prior art has also disclosed molds which comprise more than one receiving chamber or more than one ready-made form.

Subject of the European application EP 1 256 623 A1 (Procter & Gamble) is a kit of at least two bags with different composition and different optics, The bags are separated and not as a compact single product before:

A method for producing multi-chamber bags by gluing second Elnzelkammem describes the International Application WO 02/85736 A1 (Reckitt Benckiser).

The object of the present application was to provide a process for the preparation of detergents or cleaners with water-soluble or water-dispersible packaging, by which the amounts of the water-soluble or water-dispersible material used can be minimized, wherein the water-soluble or water-dispersible packaging is stable even without the use of conventional adhesives or adhesion promoters Should have sealing seams. The resulting process products should further enable the co-packaging of solid and liquid or flowable detergent compositions in separate areas of a compact dosing unit. The final process product should be characterized by an attractive appearance.

These objects were achieved by a washing or cleaning agent in which a detergent or cleaning product molding and the water-soluble or water-dispersible packaging material are adhesively bonded together by a heat seal and the detergent tablets a coating with a water-soluble or water-dispersible organic polymer on its entire surface having.

A first subject of the present application is therefore a washing or cleaning agent, comprising at least one detergent or cleaning product molding and at least one water-soluble or water-dispersible film material, characterized in that the washing or cleaning agent molded body and the film material are adhesively bonded together by a heat-sealing seam and the Detergent or detergent tablet has a coating with a water-soluble or water-dispersible organic polymer on its entire surface . In contrast to conventional cleaning agents, the sealing seam in the cleaning agents according to the invention does not bind two film materials, for example for sealing a bag or pouch containing a washing or cleaning agent, but instead bonds the film material directly to the washing or cleaning agent. The adhesive bond of the film material and detergent tablets preferably leads to the formation of a cavity bounded by this film material and this body, which cavity in turn can be filled, preferably with another washing or cleaning agent. In such an embodiment, it is preferred that the composition of the detergent tablets differs from the composition of the detergent or cleaning agent filled in the cavity.

The heat-sealing seam of the compositions according to the invention preferably has the form of a circumferential sealed seam, that is, a self-contained sealed seam. The thickness of the sealing seam is preferably between 0.1 and 5 mm, preferably between 0.5 and 3 mm and particularly preferably between 1 and 2 mm. The heat seal is formed by bringing the film material and the molded body into contact with one another and then heating them in a spatially defined region.

The heat-sealing is preferably carried out at a temperature above 40 ° C, more preferably above 60 ° C, most preferably above 80 ° C and especially above 100 ° C. Preferably, the film material and the adjacent region of the shaped body for a maximum of 5 seconds, preferably for 0.1 to 4 seconds, more preferably for 0.2 to 3 seconds and especially for 0.4 to 2 seconds to temperatures above 60 ° C, preferably above 80 ° C, more preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C.

The heat-sealing of the washing or cleaning agent shaped article with the water-soluble or water-dispersible film material can be effected not only by the action of hot air or the action of a laser beam but also by means of heated sealing tools. When sealed by sealing tools ("sealing jaws"), the film material and the molded body are heated in the area of the later sealed seam. In this case, the sealing tool can be guided to the surface of the molding and support the sealing process by additional pressure. For this reason, preferred washing or cleaning agents are characterized in that the shaped body has a breaking pressure above 1 bar, preferably above 2.5 bar and in particular above 4 bar.

The breaking pressure is determined by placing the shaped body between two plane-parallel surfaces and moving them towards each other. The pressing force of the plates acts orthogonal to the plane of the heat-sealing seam. The fracture pressure then results taking into account the area of the plates used from the force at which the shaped body breaks.

A first constituent of the agents according to the invention is a detergent or cleaner tablet. Such shaped bodies are obtainable, for example, by compaction methods such as tableting, by extrusion, such as extrudate extrusion or by casting. In the context of the present application, moldings which are produced by tabletting or by casting are particularly preferred. The moldings contain or consist of washing or cleaning-active substances or substance mixtures.

The preparation of washing or cleaning agent tablets is carried out in a manner known to those skilled in the art by compressing particulate starting substances. To prepare the tablets, the premix is compressed in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection. The tabletting is preferably carried out on so-called rotary presses.

• Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• Geringe Umdrehungszahl des Rotors
• Große Füllschuhe
• Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• Füllschuh mit konstanter Pulverhöhe
• Entkopplung von Füllschuh und Pulvervorlage

When tableting with rotary presses, it has proven to be advantageous to carry out the tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness of the tablet can be reduced. Small variations in weight can be achieved in the following ways:

• Use of plastic inserts with small thickness tolerances
• Low number of revolutions of the rotor
• Big filling shoes
• Tuning of the filling paddle speed to the speed of the rotor
• Filling shoe with constant powder height
• Decoupling of filling shoe and powder template

To reduce Stempelanbackungen offer all known from the art non-stick coatings. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.

In the context of the present invention preferred methods are characterized in that the compression at pressing pressures of 0.01 to 50 kNcm ^-2 , preferably from 0.1 to 40 kNcm ^-2 and in particular from 1 to 25 kNcm ^-2 .

The production of preferred casting bodies according to the invention is carried out, for example, by casting a washing or cleaning-active preparation into a mold and subsequently demolding the solidified cast body to form a (mold) shaped body. As a "mold" are preferably tools that have cavities that can be filled with pourable substances. Such tools may be formed, for example, in the form of individual cavities but also in the form of plates having a plurality of cavities. The single cavities or cavity plates are preferably mounted on horizontally circulating conveyor belts in industrial processes which allow continuous or discontinuous transport of the cavities, for example along a number of different workstations (e.g., casting, cooling, filling, sealing, demolding, etc.).

The washing or cleaning active preparations are potted in the preferred method and solidify subsequently to a dimensionally stable body. In the context of the present invention, "solidification" characterizes any curing mechanism which delivers a body which is solid at room temperature from a deformable, preferably flowable mixture or such substance or mass, without the need for pressing or compacting forces. "Solidification" in the context of the present invention is therefore, for example, the curing of melts of solid substances at room temperature by cooling. "Solidification processes" in the context of the present application are also the curing of formable materials by time-delayed water binding, by evaporation of solvents, by chemical reaction, crystallization, etc. and the reactive curing of flowable powder mixtures to form stable hollow bodies.

1. i) 10 bis 85 Gew.-% Dispersionsmittel und
2. ii) 15 bis 90 Gew.-% dispergierte Stoffe

enthalten, besonders bevorzugt werden.For processing are generally all washing or cleaning active preparations that can be processed by casting techniques. With particular preference, however, washing or cleaning active preparations are used in the form of dispersions. In a particularly preferred embodiment of the present application, the washing or cleaning-active preparation poured into the receiving recess of the molding tool is a dispersion of solid particles in a dispersion medium, dispersions based on their total weight

1. i) from 10 to 85% by weight of dispersant and
2. ii) 15 to 90% by weight of dispersed substances

contain, are particularly preferred.

As dispersion in this application a system of several phases is referred to, one of which is dispersed continuously (dispersion medium) and at least one further (dispersed substances).

Suitable dispersants in the context of the present invention are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers. The dispersant may be both a single polymer and mixtures of various water-soluble or water-dispersible polymers. In a further preferred embodiment of the present invention, the dispersant or at least 50% by weight of the polymer mixture consists of water-soluble or water-dispersible nonionic polymers from the group consisting of polyvinylpyrrolidones, vinylpyrrolidone-vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.

Particular preference is given to using dispersions which contain, as dispersants, a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, the weight fraction of the poly (ethylene) glycol being based on the total weight of all dispersing agents is preferably between 10 and 90% by weight, more preferably between 30 and 80% by weight and in particular between 50 and 70% by weight. Particular preference is given to dispersions in which the dispersant contains more than 92% by weight, preferably more than 94% by weight, more preferably more than 96% by weight, very particularly preferably more than 98% by weight. and in particular to 100 wt .-% of a poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular consists poly (ethylene) glycol. Dispersing agents which also contain poly (propylene) glycol in addition to poly (ethylene) glycol preferably have a ratio of the weight proportions of poly (ethylene) glycol to poly (propylene) glycol between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, more preferably between 10: 1 and 1.5: 1 and in particular between 7: 1 and 2: 1 on.

Further preferred dispersants are the nonionic surfactants, which are used alone, but particularly preferably in combination with a nonionic polymer. Detailed information on the usable nonionic surfactants can be found in the description of washing or cleaning-active substances below.

For the purposes of the present application, all substances which are solid or wash-active at room temperature are suitable as dispersed substances, but especially washing or cleaning substances from the group of builders (builders and co-builders), the washing or cleaning-active polymers, the bleaching agent Bleach activators, the glass corrosion inhibitor, the silver protectant and / or the enzymes. A more detailed description of these ingredients can be found below in the text.

Dispersions preferably used as detergent tablets according to the invention are characterized in that they are dissolved in water (40 ° C.) in less than 9 minutes, preferably less than 7 minutes, preferably less than 6 minutes, more preferably less than 5 minutes and in particular dissolve in less than 4 minutes. To determine the solubility, 20 g of the dispersion are introduced into the interior of a dishwashing machine (Miele G 646 PLUS). The main wash cycle of a standard rinse program (45 ° C) is started. Solubility is determined by measuring the conductivity, which is recorded by a conductivity sensor. The dissolution process is completed when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau. The conductivity measurement starts with the replacement of the circulation pump in the main wash cycle. The amount of water used is 5 liters.

The moldings produced, for example, by tableting or casting may take any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal , pentagonal, octagonal and octagonal prismatic as well as rhombohedral forms are preferred. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can be realized. If the shaped bodies according to the invention have corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and bevelled ("touched") edges is preferred.

Of course, the moldings can also be produced in multiple phases. For reasons of process economy, two-layered or three-layered shaped bodies, in particular two-layered or three-layered tablets, have proven particularly useful here.

Within the scope of the present application, detergents or cleaners according to the invention which are in the form of a washing or cleaning agent tablet are single-phase or multi-phase detergents or cleaning tablets are particularly preferred.

In a particularly preferred embodiment, tablets and / or compacts, for example roll compacts, and / or extrudate and / or cast bodies are used as shaped bodies in step a) of the process according to the invention.

The detergent tablets according to the invention may be completely or partially coated by the water-soluble or water-dispersible film material. The film material, which is adhesively bonded to the shaped body by a heat-sealing seam, can therefore cover both the entire molded body and individual regions of the shaped body. Particularly preferred detergent tablets according to the invention are covered with a film material over their entire surface. Moldings in which the film material only covers parts of the surface of the molding, for example individual side surfaces, in particular those side surfaces with a cavity, are also preferred.

The coating of the shaped body can contribute to the improvement of its shaped body optics and / or to influence its dissolution behavior. The coating covers the entire molded body. According to the invention, moldings which have a coating on their entire surface.

The coating materials used in the present application are the water-soluble or water-dispersible natural or synthetic organic polymers.

1. a) wasserlöslichen nichtionischen Polymeren aus der Gruppe der
   • a1) Polyvinylpyrrolidone,
   • a2) Vinylpyrrolidon/Vinylester-Copolymere,
   • a3) Celluloseether
2. b) wasserlöslichen amphoteren Polymeren aus der Gruppe der
   • b1) Alkylacrylamid/Acrylsäure-Copolymere
   • b2) Alkylacrylamid/Methacrylsäure-Copolymere
   • b3) Alkylacrylamid/Methylmethacrylsäure-Copolymere
   • b4) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymere
   • b5) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymere
   • b6) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere
   • b7) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymere
   • b8) Copolymere aus
     • b8i) ungesättigten Carbonsäuren
     • b8ii) kationisch derivatisierten ungesättigten Carbonsäuren
     • b8iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
3. c) wasserlöslichen zwitterionischen Polymeren aus der Gruppe der
   • c1) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
   • c2) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
   • c3) Methacroylethylbetain/Methacrylat-Copolymere
4. d) wasserlöslichen anionischen Polymeren aus der Gruppe der
   • d1) Vinylacetat/Crotonsäure-Copolymere
   • d2) VinylpyrrolidonNinylacrylat-Copolymere
   • d3) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere
   • d4) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen
   • d5) gepfropften und vernetzten Copolymere aus der Copolymerisation von
     • d5i) mindesten einem Monomeren vom nicht-ionischen Typ,
     • d5ii) mindestens einem Monomeren vom ionischen Typ,
     • d5iii) von Polyethylenglycol und
     • d5iv) einem Vernetzter
   • d6) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere:
     • d6i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
     • d6ii) ungesättigte Carbonsäuren,
     • d6iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols
   • d7) Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester
   • d8) Tetra- und Pentapolymere aus
     • d8i) Crotonsäure oder Allyloxyessigsäure
     • d8ii) Vinylacetat oder Vinylpropionat
     • d8iii) verzweigten Allyl- oder Methallylestern
     • d8iv) Vinylethern, Vinylestern oder geradkettigen Allyl- oder Methallylestern
   • d9) Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinylmethylether, Acrylamid und deren wasserlöslicher Salze
   • d10) Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in α-Stellung verzweigten Monocarbonsäure
5. e) wasserlöslichen kationischen Polymeren aus der Gruppe der
   • e1) quaternierten Cellulose-Derivate
   • e2) Polysiloxane mit quaternären Gruppen
   • e3) kationischen Guar-Derivate
   • e4) polymeren Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure
   • e5) Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats
   • e6) Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere
   • e7) quaternierter Polyvinylalkohol
   • e8) unter den INCI-Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 angegeben Polymere.

As coating materials or as a constituent of the coating, in particular polymers or polymer mixtures, wherein the polymer or at least 50 wt .-% of the polymer mixture is selected from

1. a) water-soluble nonionic polymers from the group of
   • a1) polyvinylpyrrolidones,
   • a2) vinylpyrrolidone / vinyl ester copolymers,
   • a3) cellulose ethers
2. b) water-soluble amphoteric polymers from the group of
   • b1) alkylacrylamide / acrylic acid copolymers
   • b2) alkylacrylamide / methacrylic acid copolymers
   • b3) alkylacrylamide / methylmethacrylic acid copolymers
   • b4) Alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
   • b5) Alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
   • b6) Alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
   • b7) Alkylacrylamide / Alkymethacrylate / Alkylaminoethylmethacrylate / Alkylmethacrylate Copolymers
   • b8) copolymers
     • b8i) unsaturated carboxylic acids
     • b8ii) cationically derivatized unsaturated carboxylic acids
     • b8iii) optionally further ionic or nonionic monomers
3. c) water-soluble zwitterionic polymers from the group of
   • c1) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts
   • c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts
   • c3) Methacroylethylbetaine / methacrylate copolymers
4. d) water-soluble anionic polymers from the group of
   • d1) vinyl acetate / crotonic acid copolymers
   • d2) vinylpyrrolidone-vinyl acrylate copolymers
   • d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
   • d4) graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
   • d5) grafted and crosslinked copolymers from the copolymerization of
     • d5i) at least one nonionic type monomer,
     • d5ii) at least one ionic-type monomer,
     • d5iii) of polyethylene glycol and
     • d5iv) a networked one
   • d6) copolymers obtained by copolymerization of at least one monomer of each of the following three groups:
     • d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
     • d6ii) unsaturated carboxylic acids,
     • d6iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 -alcohols
   • d7) terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester
   • d8) tetra- and pentapolymers from
     • d8i) crotonic acid or allyloxyacetic acid
     • d8ii) vinyl acetate or vinyl propionate
     • d8iii) branched allyl or methallyl esters
     • d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
   • d9) crotonic acid copolymers with one or more monomers selected from the group consisting of ethylene, vinylbenzene, vinylmethyl ether, acrylamide and their water-soluble salts
   • d10) terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic α-branched monocarboxylic acid
5. e) water-soluble cationic polymers from the group of
   • e1) quaternized cellulose derivatives
   • e2) polysiloxanes with quaternary groups
   • e3) cationic guar derivatives
   • e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid
   • e5) Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate
   • e6) vinylpyrrolidone-methoimidazolinium chloride copolymers
   • e7) quaternized polyvinyl alcohol
   • e8) polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

Water-soluble polymers in the context of the invention are those polymers which are soluble in water at room temperature in excess of 2.5% by weight.

The moldings are preferably coated with a polymer or polymer mixture, wherein the polymer (and accordingly the entire coating) or at least 50% by weight of the polymer mixture (and thus at least 50% of the coating) is selected from certain polymers. The coating consists entirely or at least 50% of its weight of water-soluble polymers from the group of nonionic, amphoteric, zwitterionic, anionic and / or cationic polymers.

Preferred polymers from these groups have been listed above and are described in more detail below.

• Polyvinylpyrrolidone, wie sie beispielsweise unter der Bezeichnung Luviskol^® (BASF) vertrieben werden. Polyvinyl-pyrrolidone sind bevorzugte nichtionische Polymere im Rahmen der Erfindung.
  Polyvinylpyrrolidone [Poly(1-vinyl-2-pyrrolidinone)], Kurzzeichen PVP, sind Polymere der allg. Formel
  
  die durch radikalische Polymerisation von 1-Vinylpyrrolidon nach Verfahren der Lösungs- oder Suspensionspoly-merisation unter Einsatz von Radikalbildnern (Peroxide, AzoVerbindungen) als Initiatoren hergestellt werden. Die ionische Polymerisation des Monomeren liefert nur Produkte mit niedrigen Molmassen. Handelsübliche Polyvinylpyrrolidone haben Molmassen im Bereich von ca. 2500-750000 g/mol, die über die Angabe der K-Werte charakterisiert werden und - K-Wert-abhangig - Glasübergangstemperattiren von 130-175° besitzen. Sie werden als weiße, hygroskopische Pulver oder als wäßrige. Lösungen angeboten. Polyvinylpyrrolidone sind gut löslich in Wasser und einer Vielzahl von organischen Lösungsmitteln (Alkohole, Ketone, Eisessig, Chlorkohlenwasserstoffe, Phenole u.a.).
• VinylpyrrolidonNinylester-Copolymere, wie sie beispielsweise unter dem Warenzeichen Luviskol^® (BASF) vertrieben werden. Luviskol^® VA 64 und Luviskol^® VA 73, jeweils VinylpyrrolidonNinylacetat-Copolymere, sind besonders bevorzugte nichtionische Polymere. Die Vinylester-Polymere sind aus Vinylestern zugängliche Polymere mit der Gruppierung der Formel
  
  als charakteristischem Grundbaustein der Makromoleküle. Von diesen haben die Vinylacetat-Polymere (R = CH₃) mit Polyvinylacetaten als mit Abstand wichtigsten Vertretern die größte technische Bedeutung.
  Die Polymerisation der Vinylester erfolgt radikalisch nach unterschiedlichen Verfahren (Lösungspolymerisation, Suspensionspolymerisation, Emulsionspolymerisation, Substanzpolymerisation.).
• Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal^® und Benecel^® (AQUALON) vertrieben werden. Celluloseether lassen sich durch die allgemeine Formel beschreiben,
  
  in R für H oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in der vorstehenden Formel für -CH₂CH₂CH₂-OH oder - CH₂CH₂-OH. Celluloseether werden technisch durch Veretherung von Alkalicellulose (z.B. mit Ethylenoxid) hergestellt. Celluloseether werden charakterisiert über den durchschnittlichen Substitutionsgrad DS bzw. den molaren Substitutionsgrad MS, die angeben, wieviele Hydroxy-Gruppen einer Anhydroglucose-Einheit der Cellulose mit dem Veretherungsreagens reagiert haben bzw. wieviel mol des Veretherungsreagens im Durchschnitt an eine Anhydroglucose-Einheit angelagert wurden. Hydroxyethylcellulosen sind ab einem DS von ca. 0,6 bzw, einem MS von ca. 1 wasserlöslich. Handelsübliche Hydroxyethyl- bzw. Hydroxypropylcellulosen haben Substitutionsgrade im Bereich von 0,85-1,35 (DS) bzw. 1,5-3 (MS). Hydroxyethyl- und -propylcellulosen werden als gelblich-weiße, geruch- und geschmacklose Pulver in stark unterschiedlichen Polymerisationsgraden vermarktet. Hydroxyethyl- und -propylcellulosen sind in kaltem und heißem Wasser sowie in einigen (wasserhaltigen) organischen Lösungsmitteln löslich, in den meisten (wasserfreien) organischen Lösungsmitteln dagegen unlöslich; ihre wäßrigen Lösungen sind relativ unempfindlich gegenüber Änderungen des pH-Werts oder Elektrolyt-Zusatz.

Water-soluble polymers preferred according to the invention are nonionic. Suitable nonionic polymers are, for example:

• Polyvinylpyrrolidones, as sold for example under the name Luviskol ^® (BASF). Polyvinylpyrrolidones are preferred nonionic polymers in the invention.
  Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula
  
  which are prepared by free-radical polymerization of 1-vinylpyrrolidone by methods of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer provides only low molecular weight products. Commercially available polyvinylpyrrolidones have molar masses in the range of about 2500-750000 g / mol, which are characterized by the specification of the K values and - depending on K value - Glasübergangstemperattiren 130-175 ° possess. They are called white, hygroscopic powder or aqueous. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).
• VinylpyrrolidonNinylester copolymers, such as for example, under the trade name Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone-vinyl acetate copolymers, are particularly preferred non-ionic polymers. The vinyl ester polymers are vinyl ester-accessible polymers having the moiety of the formula
  
  as a characteristic building block of the macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates as by far the most important representatives of the greatest technical importance.
  The polymerization of the vinyl esters is carried out free-radically by different processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization).
• Cellulose ethers, such as hydroxypropylcellulose, hydroxyethylcellulose and methylhydroxypropylcellulose, as sold, for example, under the trademarks Culminal ^® and Benecel ^® (AQUALON). Cellulose ethers can be described by the general formula
  
  R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in the above formula is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose reacted with the etherifying reagent or how many moles of the etherifying agent were attached on average to an anhydroglucose unit. Hydroxyethylcelluloses are water-soluble from a DS of about 0.6 or, respectively, an MS of about 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS), respectively. Hydroxyethyl and propylcelluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propylcelluloses are soluble in cold and hot water as well as in some (hydrous) organic solvents but insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Further inventively preferred polymers are water-soluble amphopolymers. Amphoteric polymers, ie polymers which contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers which contain quaternary ammonium groups in the molecule and amphoteric polymers. COO ^- - or -SO ₃ ^- groups, and summarized those polymers containing -COOH or SO ₃ H groups and quaternary ammonium groups. An example of an inventively employable Am phopolymer is the available under the name Amphomer ^® acrylic resin containing a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group acrylic acid , Methacrylic acid and their simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (for example acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and, if appropriate, further ionic or nonionic monomers, as described, for example, in the German Offenlegungsschrift 39 29 973 and the cited prior art. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium as they are commercially available under the name Merquat ^® 2001 N, are inventively particularly preferred amphopolymers. Other suitable amphoteric polymers are for example sold under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) available octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

Suitable zwitterionic polymers are, for example, acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts. Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, sold under the name Amersette ^® (AMER-CHOL) are commercially available.

• Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen Resyn^® (NATIONAL STARCH), Luviset^® (BASF) und Gafset^® (GAF) im Handel sind. Diese Polymere weisen Monomereinheiten der allgemeinen Formel
  
          [-CH(CH₃)-CH(COOH)-]_n
  
  auf.
• VinylpyrrolidonNinylacrylat-Copolymere, erhältlich beispielsweise unter dem Warenzeichen Luviflex^® (BASF). Ein bevorzugtes Polymer ist das unter der Bezeichnung Luviflex^® VBM-35 (BASF) erhältliche Vinylpyrrolidon/Acrylat-Terpolymere.
• Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere, die beispielsweise unter der Bezeichnung Ultrahold^® strong (BASF) vertrieben werden.
• Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen Solche gepfropften Polymere von Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch mit anderen copolymerisierbaren Verbindungen auf Polyalkylenglycolen werden durch Polymerisation in der Hitze in homogener Phase dadurch erhalten, daß man die Polyalkylenglycole in die Monomeren der Vinylester, Ester von Acrylsäure oder Methacrylsäure, in Gegenwart von Radikalbildner einrührt.
  Als geeignete Vinylester haben sich beispielsweise Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylbenzoat und als Ester von Acrylsäure oder Methacrylsäure diejenigen, die mit aliphatischen Alkoholen mit niedrigem Molekulargewicht, also insbesondere Ethanol, Propanol, Isopropanol, 1-Butanol, 2-Butanol, 2-Methy-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, erhältlich sind, bewährt.
  Als Polyalkylenglycole kommen insbesondere Polyethylenglycole und Polypropylenglycole in Betracht. Polymere des Ethylenglycols, die der allgemeinen Formel
  
          H-(O-CH₂-CH₂)_n-OH
  
  genügen, wobei n Werte zwischen 1 (Ethylenglycol) und mehreren tausend annehmen kann. Für Polyethylenglycole existieren verschiedene Nomenklaturen, die zu Verwirrungen führen können. Technisch gebräuchlich ist die Angabe des mittleren relativen Molgewichts im Anschluß an die Angabe "PEG", so daß "PEG 200" ein Polyethylenglycol mit einer relativen Molmasse von ca. 190 bis ca. 210 charakterisiert. Für kosmetische Inhaltsstoffe wird eine andere Nomenklatur verwendet, in der das Kurzzeichen PEG mit einem Bindestrich versehen wird und direkt an den Bindestrich eine Zahl folgt, die der Zahl n in der oben genannten Formel V entspricht. Nach dieser Nomenklatur (sogenannte INCI-Nomenklatur, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997 ) sind beispielsweise PEG-4, PEG-6, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14 und PEG-16 einsetzbar. Kommerziell erhältlich sind Polyethylenglycole beispielsweise unter den Handelsnamen Carbowax^® PEG 200 (Union Carbide), Emkapol^® 200 (ICI Americas), Lipoxol^® 200 MED (HÜLS America), Polyglycol^® E-200 (Dow Chemical), Alkapol^® PEG 300 (Rhone-Poulenc), Lutrol^® E300 (BASF) sowie den entsprechenden Handelsnamen mit höheren Zahlen.
  Polypropylenglycole (Kurzzeichen PPG) sind Polymere des Propylenglycols, die der allgemeinen Formel
  
  genügen, wobei n Werte zwischen 1 (Propylenglycol) und mehreren tausend annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d.h. die Vertreter mit n=2, 3 und 4 in der vorstehenden Formel.
  Insbesondere können die auf Polyethylenglycole gepfropften Vinylacetatcopolymeren und die auf Polyethylenglycole gepfropften Polymeren von Vinylacetat und Crotonsäure eingesetzt werden.

• gepfropfte und vernetzte Copolymere aus der Copolymerisation von
  1. i) mindesten einem Monomeren vom nicht-ionischen Typ,
  2. ii) mindestens einem Monomeren vom ionischen Typ,
  3. iii) von Polyethylenglycol und
  4. iv) einem Vernetzter

According to the invention suitable anionic polymers include:

• Vinyl acetate / crotonic acid copolymers, such as those sold under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF) are commercially available. These polymers have monomer units of the general formula
  
  [-CH (CH ₃ ) -CH (COOH) -] _n
  
  on.
• Vinyl pyrrolidone copolymers, available, for example under the trade name Luviflex ^® (BASF). A preferred polymer is the VBM-35 (BASF) under the name Luviflex ^® available vinylpyrrolidone / acrylate terpolymers.
• Acrylic acid / ethyl acrylate / N-tert.butyl acrylamide terpolymers, for example, under the name Ultrahold ^® strong (BASF).
• Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols. Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on polyalkylene glycols Polymerization in the heat in the homogeneous phase obtained by stirring the polyalkylene glycols in the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, in the presence of radical generator.
  Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and esters of acrylic acid or methacrylic acid, those with aliphatic alcohols of low molecular weight, ie in particular 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, are proven.
  Suitable polyalkylene glycols are, in particular, polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol, those of the general formula
  
  H- (O-CH ₂ -CH ₂ ) _n -OH
  
  satisfy, where n can assume values between 1 (ethylene glycol) and several thousand. For polyethylene glycols there are various nomenclatures that can lead to confusion. Technically common is the indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. For cosmetic ingredients, a different nomenclature is used in which the abbreviation PEG is hyphenated and directly followed by the hyphen followed by a number corresponding to the number n in formula V above. According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997 For example, PEG-4, PEG-6, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, and PEG-16 are useful. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone -Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers.
  Polypropylene glycols (abbreviated PPG) are polymers of propylene glycol, those of the general formula
  
  satisfy, where n can assume values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycols, ie the representatives with n = 2, 3 and 4 in the above formula.
  In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.

• grafted and crosslinked copolymers from the copolymerization of
  1. i) at least one nonionic type monomer,
  2. ii) at least one ionic-type monomer,
  3. iii) of polyethylene glycol and
  4. iv) a networked person

The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000. The nonionic monomers may be of very different types and of these preferred are: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allylaurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.

Likewise, the ionic monomers may be of very different types, among which particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the grafting polymers. The crosslinking agents used are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho, meta and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose with 2 to 5 allyl groups per molecule of saccharin.

1. i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ,
2. ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ,
3. iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglycol und
4. iv) 0,1 bis 8 Gew.-% eines Vernetzers, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.
   • durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltene Copolymere:
     1. i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
     2. ii) ungesättigte Carbonsäuren,
     3. iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols
     Unter kurzkettigen Carbonsäuren bzw. Alkoholen sind dabei solche mit 1 bis 8 Kohlenstoffatomen zu verstehen, wobei die Kohlenstoffketten dieser Verbindungen gegebenenfalls durch zweibindige Heterogruppen wie -O-, -NH-, -S_ unterbrochen sein können.
   • Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester
     Diese Terpolymere enthalten neben weiteren Monomereinheiten Monomereinheiten aus einem oder mehreren Allyl- oder Methallyestern der Formel
     
     worin R³ für -H oder-CH₃, R² für -CH₃ oder -CH(CH₃)₂ und R¹ für -CH₃ oder einen gesättigten geradkettigen oder verzweigten C_1-6-Alkylrest steht und die Summe der Kohlenstoffatome in den Resten R¹ und R² vorzugsweise 7, 6, 5, 4, 3 oder 2 ist.
     Die vorstehend genannten Terpolymeren resultieren vorzugsweise aus der Copolymerisation von 7 bis 12 Gew.-% Crotonsäure, 65 bis 86 Gew.-%, vorzugsweise 71 bis 83 Gew.-% Vinylacetat und 8 bis 20 Gew.-%, vorzugsweise 10 bis 17 Gew.% Allyl- oder Methallylestern der vorstehenden Formel.
   • Tetra- und Pentapolymere aus
     1. i) Crotonsäure oder Allyloxyessigsäure
     2. ii) Vinylacetat oder Vinylpropionat
     3. iii) verzweigten Allyl- oder Methallylestern
     4. iv) Vinylethern, Vinylestern oder geradkettigen Allyl- oder Methallylestern
   • Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinylmethylether, Acrylamid und deren wasserlöslicher Salze
   • Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in □-Stellung verzweigten Monocarbonsäure.

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

1. i) from 5 to 85% by weight of at least one nonionic type monomer,
2. ii) from 3 to 80% by weight of at least one ionic-type monomer,
3. iii) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
4. iv) 0.1 to 8 wt% of a crosslinker, wherein the percentage of crosslinker is formed by the ratio of the total weights of i), ii) and iii).
   • Copolymers obtained by copolymerization of at least one monomer of each of the following three groups:
     1. i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
     2. ii) unsaturated carboxylic acids,
     3. iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 -alcohols
     Short-chain carboxylic acids or alcohols are to be understood as meaning those having 1 to 8 carbon atoms, it being possible for the carbon chains of these compounds to be interrupted, if appropriate, by divalent hetero groups such as -O-, -NH-, -S--.
   • Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester
     These terpolymers contain, in addition to further monomer units, monomer units of one or more allyl or methallyl esters of the formula
     
     wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight or branched C _1-6 alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2.
     The abovementioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight % Allyl or methallyl esters of the above formula.
   • Tetra and pentapolymers from
     1. i) crotonic acid or allyloxyacetic acid
     2. ii) vinyl acetate or vinyl propionate
     3. iii) branched allyl or methallyl esters
     4. iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
   • Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinylmethyl ether, acrylamide and their water-soluble salts
   • Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic □-position branched monocarboxylic acid.

Further, preferably used as part of the coating polymers are cationic polymers. Among the cationic polymers, the permanent cationic polymers are preferred. According to the invention, "permanently cationic" refers to polymers which have a cationic group, irrespective of the pH of the agent (ie both the coating and the shaped body). These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.

• quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^© im Handel erhältlich sind. Die Verbindungen Celquat^® H 100, Celquat^® L 200 und Polymer JR^® 400 sind bevorzugte quaternierte Cellulose-Derivate.
• Polysiloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Coming; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning^® 929 Emulsion (enthaltend ein hydroxylamino-modifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil^®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; diquaternäre Polydime- thylsiloxane, Quaternium-80),
• Kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia^®Guar und Jaguar^® vertiebenen Produkte,
• Polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unterden Bezeichnungen Merquat^®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat^®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^®734 und Gafquat^®755 im Handel erhältlich.
• Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat^® angeboten werden.
• quaternierter Polyvinylalkohol
  sowie die unter den Bezeichnungen
• Polyquaternium 2,
• Polyquaternium 17,
• Polyquaternium 18 und
• Polyquaternium 27

bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkelfe. Die genannten Polymere sind dabei nach der sogenannten INCI-Nomenklatur bezeichnet, wobei sich detaillierte Angaben im CTFA International Cosmetic Ingredient Dictionary and Handbook, 6th Edition. The Cosmetic, Toiletry and Fragrance Association, Washington, 1997 , finden, auf die hier ausdrücklich Bezug genommen wird.Preferred cationic polymers are, for example

• quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^© commercially. The compounds Celquat ^® H 100, Celquat L 200 and Polymer JR ^{® ®} 400 are preferred quaternized cellulose derivatives.
• Polysiloxanes having quaternary groups, such as the commercially available products Q2-7224 (manufactured by Dow Coming, a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary thylsiloxane Polydime-, quaternium-80).,
• Cationic guar derivatives, in particular the vertiebenen under the trade names Cosmedia® ^® Guar and Jaguar ^® products,
• Polymers Dimethyldiallylammoniumsalze and their copolymers with esters and amides of acrylic acid and methacrylic acid. The unterden names Merquat ^® (poly (dimethyldiallylammonium chloride)) and Merquat 100 ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers.
• Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminomethacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially.
• Vinylpyrrolidone methoimidazolinium chloride copolymers, as offered under the name Luviquat.RTM ^®.
• quaternized polyvinyl alcohol
  as well as those under the designations
• Polyquaternium 2,
• Polyquaternium 17,
• Polyquaternium 18 and
• Polyquaternium 27

known polymers with quaternary nitrogen atoms in the polymer Hauptkelfe. The polymers mentioned are designated according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 6th Edition. The Cosmetic, Toiletry and Fragrance Association, Washington, 1997 , which are expressly incorporated herein by reference.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the commercial product ^Polymer® JR 400, are very particularly preferred cationic polymers.

A particularly preferred coating material for shaped bodies in the context of the present application is polyvinyl alcohol (PVA). With regard to the degree of hydrolysis and the molecular weight of the polyvinyl alcohols preferably used for the coating, the statements made below in the description with regard to the preferred container materials apply, to which reference is made at this point in order to avoid repetitions.

The detergent tablets may have a cavity. The term "cavity" in the context of the present invention, both troughs and through the molding through holes or holes, which connect two sides of the molding, preferably opposite sides of the molding, for example, the bottom and roof surface of the molding together.

The shape of the cavity, which is preferably a well, may be chosen freely, with tablets being preferred in which at least one well is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral , conical, pyramidal, ellipsoidal, pentagonal, pentagonal, octagonal, prismatic and rhombohedral shapes. Completely irregular shapes such as arrow or animal shapes, trees, clouds etc. can also be realized. As with the basic moldings, wells with rounded corners and edges or with rounded corners and chamfered edges are preferred. The bottom surface of the trough can be flat or inclined.

The well opening surface may be planar. In such a trough opening, all boundary points of the trough opening lie in one plane. In a preferred embodiment, the surface forming the trough opening is not planar. Such an embodiment can be realized for example by a shaped body having an uneven surface. Alternatively, a shaped body can be provided, whose depression opening extends over at least two boundary surfaces of a shaped body.

In a further preferred embodiment, the cavity is an opening which connects two opposite sides of the molding together. If a tablet is used as the shaped body, then the shaped body with such a breakthrough corresponds to a so-called ring tablet. Breakthrough shaped moldings are particularly preferably used in which the opening areas of the opening on the opposite sides of the molded body are less than 80%, preferably less than 60%, preferably less than 40%, based on the larger of the two opening areas. more preferably differ by less than 20% and in particular by less than 10%. The cross-section of the aperture may be angular or round. Cross sections with one, two, three, four, five, six or more corners are feasible, but such moldings are in Particularly preferred frame of the present application, which have a breakthrough without corners, preferably a breakthrough with a round or oval cross-section. In this case, a "cross section" refers to a surface which is perpendicular to a straight connecting line between the center points of the two opposite opening surfaces of the shaped body.

Of course, the molding may have more than one cavity. Moldings having two, three, four, five, six, seven, eight, nine, ten, eleven, twelve or more cavities are particularly preferred in the present application. If the shaped body has more than one cavity, these cavities can be both the wells described above and the breakthroughs described above. Shaped bodies which have more than one cavity, wherein at least one of the cavities is a trough and at least one further of the cavities is a breakthrough, are particularly preferred in the context of the present application.

The volume of the cavity is preferably between 2 and 20 ml, preferably between 2 and 15 ml, more preferably between 2 and 10 ml and in particular between 2 and 7 ml.

In the context of the present application, detergent tablets or detergent tablets which have a cavity are particularly preferred. Very particular preference is given to detergents or cleaners according to the invention in which the shaped body has a cavity which is at least partly closed by the film material which is adhesively bonded to the shaped body by a heat-sealing seam.

In a particularly preferred embodiment of the present invention, the cavity of the washing or cleaning agent shaped body is filled. With preference, flowable washing and cleaning active preparations, preferably liquid (s), in particular melts, and / or gel (s) and / or powder and / or granules (e) and / or extrudate (s) and / or Kompaktat (e ) filled in the cavity of the washing or cleaning agent shaped body.

The term "liquid" in the present application denotes substances or substance mixtures as well as solutions or suspensions which are in the liquid state of matter.

Powder is a general term for a form of division of solids and / or mixtures obtained by comminution, that is, grinding or crushing in the mortar (pulverization), grinding in mills or as a result of atomization or freeze-drying. A particularly fine division is often called atomization or micronization; the corresponding powders are called micro-powders.

After the grain size is a rough division of the powder in coarse, fine u. Very fine powder usual; A more detailed classification of powdery bulk solids is made by their bulk density and sieve analysis. In the context of the present application, however, preferred powders have lower particle sizes below 5000 .mu.m, preferably less than 3000 .mu.m, preferably less than 1000 .mu.m, very particularly preferably between 50 and 1000 .mu.m and in particular between 100 and 800 .mu.m.

Powders can be compacted and agglomerated by extrusion, pressing, rolling, briquetting, pelleting and related processes. Each of the methods known in the prior art for the agglomeration of particulate mixtures is in principle suitable for producing the solids contained in the agents according to the invention. In the context of the present invention, preferably agglomerates used as solid (s) are, in addition to the granules, the compacts and extrudates.

Granules are aggregates of granules. A granule (granule) is an asymmetric aggregate of powder particles. Granulation methods are widely described in the art. Granules can be prepared by wet granulation, by dry granulation or compaction and by melt solidification granulation.

The most common granulation technique is wet granulation, since this technique is subject to the fewest restrictions and leads most safely to granules with favorable properties. The wet granulation is carried out by moistening the powder mixtures with solvents and / or solvent mixtures and / or solutions of binders and / or solutions of adhesives and is preferably carried out in mixers, fluidized beds or spray towers, said mixer can be equipped, for example, with stirring and kneading tools. However, combinations of fluidized bed (s) and mixer (s) or combinations of different mixers can also be used for the granulation. The granulation is dependent on the starting material and the desired product properties under the action of low to high shear forces.

If the granulation in a spray tower so as starting materials, for example, melting (melt solidification) or, preferably aqueous, slurries (spray drying) of solid substances are used, which are sprayed at the top of a tower in a defined droplet size, solidify in free fall or dry and on Floor of the tower incurred as granules. Melt solidification is generally particularly suitable for shaping low-melting substances which are stable in the melting temperature range (eg urea, ammonium nitrate and various formulations such as enzyme concentrates, pharmaceuticals etc.), the corresponding granules are also referred to as prills. Spray drying is used especially for the production of detergents or detergent ingredients.

Other agglomeration techniques described in the prior art are the extruder or perforated roll granulations in which powder mixtures optionally mixed with granulating liquid are pressed during perforating through perforated disks (Extrusion) or plastically deformed on perforated rolls. The products of extruder granulation are also referred to as extrudates.

Enzymes, bleaches, bleach activators, bleach catalysts, silver protectants or glass corrosion inhibitors are particularly suitable as constituents of the washing or cleaning-active preparations filled into the cavity of the detergent or cleaner body. Bleaches, in particular peroxygen compounds such as percarbonates or perborates, bleach activators or silver protectants, are particularly preferably introduced. These ingredients are preferably filled into the cavity as part of solid washing or cleaning active preparations between steps a) and b). These ingredients are described in more detail later in the text. To avoid repetition, reference is made at this point to the comments there.

A further preferred subject matter of the present application is therefore a washing or cleaning agent comprising at least one detergent or cleaning product body and at least one water-soluble or water-dispersible film material, characterized in that the washing or cleaning agent shaped body has a cavity in the form of a cavity which is active with a washing or cleaning agent Substance filled and sealed with a film material, wherein the film material is adhesively bonded by a heat seal with the detergent or Reinigugnsmittelformkörper.

Of course, the molding may also have a breakthrough instead of a trough, with particular preference molded body in the form of a ring tablet are used. Such shaped bodies can be produced, for example, by casting or by extrusion extruding, in addition to the tabletting described above. The present application therefore further relates to a washing or cleaning agent comprising at least one washing or cleaning agent shaped body in the form of a ring tablet and at least one water-soluble or water-dispersible sheet material, characterized in that the cavity of the washing or cleaning agent shaped body with a washing or cleaning-active substance is filled, wherein the film material is adhesively bonded by a heat-sealing seam with the washing or cleaning agent molding and preferably at least one, particularly preferably both openings of the cavity of the molding sealed.

In the above-described embodiments of the present invention, a laundry detergent or detergent tablet was adhesively bonded to a water-soluble or water-dispersible film material by means of a heat seal, wherein the water-soluble or water-dispersible film material was used in the form of a commercial film. In a further preferred embodiment, the water-soluble or water-dispersible film material is shaped into a hollow body which is an injection-molded and / or blow-molded and / or deep-drawn part.

In the context of the present application, "deep-drawn part" refers to such containers which are obtained by deep-drawing a first film-like wrapping material. The deep drawing is preferably carried out by bringing the wrapping material over a receiving trough located in a die forming the deep-drawing tray and shaping the wrapping material into this receiving trough by the action of pressure and / or vacuum. The shell material may be pre-treated before or during the molding by the action of heat and / or solvent and / or conditioning by relative to ambient conditions changed relative humidity and / or temperatures. The pressure action can be carried out by two parts of a tool, which behave as positive and negative to each other and deform a spent between these tools film when squeezed. However, the action of compressed air and / or the weight of the film and / or the weight of an active substance applied to the upper side of the film is also suitable as pressure forces.

The deep-drawn shell materials are preferably fixed after deep drawing by using a vacuum within the receiving wells and in their achieved by the deep-drawing process space shape. The vacuum is preferably applied continuously from deep drawing to filling until sealing and in particular until the separation of the receiving chambers. With comparable results, however, the use of a discontinuous vacuum, for example, for deep drawing of the receiving chambers and (after an interruption) before and during the filling of the receiving chambers, possible. Also, the continuous or discontinuous vacuum can vary in its thickness and, for example, take higher values at the beginning of the process (during deep drawing of the film) than at its end (during filling or sealing or singulation).

As already mentioned, the shell material can be pre-treated by the action of heat before or during the molding into the receiving troughs of the matrices. The shell material, preferably a water-soluble or water-dispersible polymer film, is heated to temperatures above 60 ° C. for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0.4 to 2 seconds , preferably above 80 ° C, more preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C. In order to dissipate this heat, but in particular also to dissipate the heat introduced by the means filled into the deep-drawn receiving chambers (eg melting), it is preferable to cool the dies used and the receiving troughs located in these dies. The cooling is preferably carried out at temperatures below 20 ° C, preferably below 15 ° C, more preferably at temperatures between 2 and 14 ° C and in particular at temperatures between 4 and 12 ° C. Preferably, the cooling takes place continuously from the beginning of the deep-drawing process to the sealing and separation of the receiving chambers. to Cooling is particularly suitable cooling fluids, preferably water, which are circulated in special cooling lines within the die.

This cooling, as well as the previously described continuous or discontinuous application of a vacuum has the advantage of preventing shrinkage of the deep-drawn containers after deep drawing, which not only improves the appearance of the process product, but also at the same time the escape of the filled into the receiving chambers means over the Edge of the receiving chamber, for example, in the sealing areas of the chamber, is avoided. Problems with the sealing of the filled chambers are thus avoided.

In the deep-drawing process can be between methods in which the shell material is guided horizontally in a forming station and from there in a horizontal manner for filling and / or sealing and / or separating and methods in which the shell material via a continuously rotating Matrizenformwalze (optionally optionally with a counter-guided Patrizenformwalze, which lead the forming upper punch to the cavities of the Matrizenformwalze) is different. The first-mentioned process variant of the flat bed process is to operate both continuously and discontinuously, the process variant using a molding roll is usually continuous. All of the mentioned deep drawing methods are suitable for the production of the inventively preferred means. The receiving troughs located in the matrices can be arranged "in series" or staggered.

The deep drawing bodies may have one, two, three or more receiving chambers. These receiving chambers can be arranged side by side and / or one above the other in the deep-drawn part. In a preferred embodiment of the present application, the agent according to the invention, in particular automatic dishwashing detergent, is formulated in a water-soluble or water-dispersible thermoformed body which, in addition to the solid detergent and / or cleaning agent according to the invention, in particular automatic dishwashing detergent, in a separate receiving chamber further comprises a liquid or gel detergent or detergent mixture contains.

The water-soluble or wasseridispergierbaren container can be prepared by injection molding in addition to deep drawing. Injection molding refers to the forming of a molding material such that the mass contained in a mass cylinder for more than one injection molding plastically softens under heat and flows under pressure through a nozzle into the cavity of a previously closed tool. The method is mainly applied to non-hardenable molding compounds which solidify in the tool by cooling. Injection molding is a very economical modern process for producing non-cutting shaped articles and is particularly suitable for automated mass production. In practical operation, the thermoplastic molding compounds (powders, granules, cubes, pastes, etc.) are heated to liquefaction (up to 180 ° C) and injected under high pressure (up to 140 MPa) in closed, two-piece, that is from Gesenk (earlier Die) and core (formerly male) existing, preferably water-cooled molds, where they cool and solidify. Can be used piston and screw injection molding machines. Suitable molding compositions (injection molding compounds) are water-soluble polymers, for example the abovementioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.

Detergents or cleaning agent tablets and molds are preferably adhesively bonded together along a circumferential sealing seam. Alternatively, the adhesive connection can of course also take place along a simple sealed seam, which is not self-contained and makes it possible to fold the shaped body and the hollow mold along this sealing seam. Such particularly preferred embodiments of the invention agents are characterized by an advantageous appearance and high flexibility in the dosage, in particular the dosage of the dispensing or dosing of washing machines or dishwashers.

Finally, the molded body and the hollow body may be adhesively bonded together along two or more separate sealing seams.

In a further embodiment, however, the washing or cleaning agent shaped body has a cavity which at least partially surrounds the hollow body. Wells are in turn wells as well as breakthroughs, in other words, washing or cleaning tablets are in the form of a well tablet as well as detergent tablets in the form of a ring tablet. The water-soluble or water-dispersible hollow bodies, which are adhesively bonded to the shaped body by a heat-sealing seam, are located at least partially in the cavity. The hollow body may for example be inserted into the cavity, but may also be secured in this cavity by an additional adhesive, snap or snap connection. In order to minimize the total volume of the washing or cleaning agent according to the invention, it is preferred that the hollow body has the cavity at least 50% by volume, preferably at least 70% by volume, more preferably at least 80% by volume and in particular at least 90 vol .-% fills.

The hollow body preferably has a filling, more preferably a liquid filling. Very particular preference is given to those liquid fillings which, based in each case on the total weight of the liquid filling, are at least 10% by weight, preferably at least 20% by weight, more preferably at least 40% by weight and in particular at least 80% by weight have multiple surfactants.

It has been found that the stability and quality of the heat-sealing seam, which the washing or cleaning agent molding connects with the water-soluble or water-dispersible film material can be influenced by the composition of the washing or cleaning agent molded body. It has proven to be advantageous if the shaped body or the shaped body phase, which is adhesively bonded to the water-soluble or water-dispersible film material by a heat-sealing seam, has a surfactant content below 20% by weight, preferably below 16% by weight, preferably below 12 wt .-%, more preferably below 8 wt .-% and in particular below 4 wt .-%.

As well as the surfactant content, the enzyme content, bleach content and bleach activator content in the molded article or molded article phase adhesively bonded to the water-soluble or water-dispersible film material by the heat-sealing seam are also kept within narrow limits.

Preference is given to washing or cleaning agents, characterized in that the shaped body or the shaped body phase, which is adhesively bonded to the water-soluble or water-dispersible film material by a heat-sealing seam, has an enzyme content below 6% by weight, preferably below 4.5% by weight. -%, preferably below 3.0 wt .-% and in particular below 1.0 wt .-%.

Preference is furthermore given to washing or cleaning agents, characterized in that the shaped body or the shaped body phase, which is adhesively bonded to the liquid-filled hollow body by a heat-sealing seam, has a bleaching agent content below 15% by weight, preferably below 12% by weight, preferably below 9 wt .-%, more preferably below 6 wt .-% and in particular below 3 wt .-%.

Finally, washing or cleaning agents are also particularly advantageous in that the shaped body or the shaped body phase, which is adhesively bonded to the water-soluble or water-dispersible film material by a heat-sealing seam, has a bleach activator content below 5% by weight, preferably below 3. 5 wt .-%, more preferably below 2.0 wt .-% and in particular below 1.0 wt .-%.

It has further been found that the quality and stability of the heat-sealing seam between detergent tablets and water-soluble or water-dispersible film material can be increased by increasing the builder content and / or the polymer content of the shaped body or the molded body phase having the heat-sealing seam ,

Preference is therefore given to washing or cleaning agents according to the invention in which the shaped body or the shaped body phase which is adhesively bonded to the liquid-filled hollow body by a heat-sealing seam has a builder content of more than 10% by weight, preferably more than 15% by weight. preferably above 20 wt .-%, more preferably above 25 wt .-% and in particular above 30 wt .-%.

Detergents or cleaning agents have furthermore proved to be advantageous, characterized in that the shaped body or the shaped body phase, which is adhesively bonded to the liquid-filled hollow body by a heat-sealing seam, has a polymer content above 0.5% by weight, preferably above 1 , 0 wt .-%, more preferably above 2.0 wt .-% and in particular above 4 wt .-%.

1. a) Herstellung von Wasch- oder Reinigungsmittelformkörpem, wobei die Wasch-oder
   Reinigungsmittelformkörper eine Beschichtung mit einem wasserlöslichen oder wasserdispergierbaren organischen Polymer auf ihrer gesamten Oberfläche aufweisen;
2. b) Bereitstellen eines wasserlöslichen oder wasserdispergierbaren Folienmaterials;
3. c) Haftende Verbindung mindestens eines Produktes aus Schritt a) mit dem wasserlöslichen oder wasserdispergierbaren Folienmaterial aus Schritt b) durch eine Heißsiegelnaht.

Another object of the present application is a process for the preparation of detergents or cleaning agents according to the invention, comprising at least one detergent or cleaner tablet and at least one water-soluble or water-dispersible film material, characterized by the steps

1. a) Preparation of washing or Reinigungsmittelformkörpem, wherein the washing or
   Detergent tablets have a coating with a water-soluble or water-dispersible organic polymer on its entire surface ;
2. b) providing a water-soluble or water-dispersible film material;
3. c) Adhesive connection of at least one product from step a) with the water-soluble or water-dispersible film material from step b) by means of a heat-sealed seam.

For heat sealing of molded articles and film material, a number of different tools and processes are available to the person skilled in the art.

In a first preferred embodiment, the heat seal is effected by the action of heated sealing tools.

In a second preferred embodiment, the heat seal is effected by the action of a laser beam.

In a third preferred embodiment, the heat seal is effected by the action of hot air.

The heat sealing is preferably carried out at a temperature above 40 ° C, more preferably above 60 ° C, even more preferably above 80 ° C and especially above 100 ° C.

6 seconds, preferably for 0.1 to 4 seconds, more preferably for 0.2 to 3 seconds and especially for 0.4 to 2 seconds at temperatures above 60 ° C, preferably above 80 ° C, particularly preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C.

It is further preferred that the water-soluble or water-dispersible film material provided in step b) is shaped into a hollow body which is an injection-molded and / or blow-molded and / or deep-drawn part,

The detergents or cleaners according to the invention can be used for textile cleaning as well as for Cleaning hard surfaces or dishes.

In addition to the abovementioned substances which are active in washing or cleaning, the detergents or cleaners according to the invention preferably comprise further washing and cleaning substances, in particular washing and cleaning substances from the group of bleaches, bleach activators, builders, surfactants, enzymes, polymers, disintegration aids, electrolytes, pH Surfactants, perfumes, perfume carriers, dyes, hydrotropes, foam inhibitors, corrosion inhibitors and glass corrosion inhibitors.

polymers

The group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.

Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.

Particularly preferably used as Suldonsauregruppen-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.

In the context of the present invention are as unsaturated monomer carboxylic acids of the formula

R ¹ (R ² ) C = C (R ³ ) CCOH

in which R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with --NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is - COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the above formula are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is preferred.

In the sulfonic acid-containing monomers are those of the formula

R ⁵ (R ⁶ ) CC (R ⁷ ) -X-SO ₃ H

in which R ⁶ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with --NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is - COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, geradkettigLer or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional Spacer group which is selected from - (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 ) -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , - CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (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 ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, melhallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3 -Sulfopropylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.

In particular ethylenically unsaturated β compounds are used as further ionic or nonionogenic monomers into consideration.

disintegration aid

In order to facilitate the disintegration of preformed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times. Under tablet proliferation agents or Decay accelerators are prepared according to Römpp (9th edition, Vol. 6, p. 4440 ) and Voigt " Textbook of Pharmaceutical Technology "(6th edition, 1987, pp. 182-184 ) Excipients, which ensure the rapid disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in resorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles decays. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Claims (17)

1. A washing or cleaning agent encompassing at least one washing- or cleaning-agent shaped element and at least one water-soluble or water-dispersible film material, characterised in that the washing- or cleaning-agent tablet and the film material are adherently joined to one another by a heat-sealed seam, and the washing- or cleaning-agent shaped element comprises a coating with a water-soluble or water-dispersible polymer over its entire surface.
2. The washing or cleaning agent according to Claim 1, characterised in that the shaped element comprises a cavity that is at least in part closed off by the film material.
3. The washing or cleaning agent according to Claim 2, characterised in that the cavity of the shaped element is filled.
4. The washing or cleaning agent according to one of Claims 1 to 3, characterised in that the water-soluble or water-dispersible film material is shaped into a hollow element that is an injection-moulded and/or blow-moulded and/or deep-drawn part.
5. The washing or cleaning agent according to Claim 4, characterised in that the washing- or cleaning-agent shaped element comprises a cavity that at least in part encompasses the hollow element.
6. The washing or cleaning agent according to one of Claims 1 to 5, characterised in that the washing- or cleaning-agent shaped element is a single- or multiple-phase washing- or cleaning-agent tablet.
7. The washing or cleaning agent according to one of Claims 4 to 6, characterised in that the hollow body comprises a filling, preferably a liquid filling.
8. The washing or cleaning agent according to one of Claims 1 to 7, characterised in that the shaped element or the shaped-element phase that is adherently joined by a heat-sealed seam to the water-soluble or water-dispersible film material has a surfactant content below 20 wt%, by preference below 16 wt%, preferably below 12 wt%, particularly preferably below 8 wt%, and in particular below 4 wt%.
9. The washing or cleaning agent according to one of Claims 1 to 8, characterised in that the shaped element or the shaped-element phase that is adherently joined by a heat-sealed seam to the water-soluble or water-dispersible film material has an enzyme content below 6 wt%, by preference below 4.5 wt%, preferably below 3.0 wt%, and in particular below 1.0 wt%
10. The washing or cleaning agent according to one of Claims 1 to 9, characterised in that the shaped element or the shaped-element phase that is adherently joined by a heat-sealed seam to the liquid-filled hollow element has a bleaching-agent content below 15 wt%, by preference below 12 wt%, preferably below 9 wt%, particularly preferably below 6 wt%, and in particular below 3 wt%.
11. The washing or cleaning agent according to one of Claims 1 to 10, characterised in that the shaped element or the shaped-element phase that is adherently joined by a heat-sealed seam to the water-soluble or water-dispersible film material has a bleach-activator content below 5 wt%, preferably below 3.5 wt%, particularly preferably below 2.0 wt%, and in particular below 1.0 wt%.
12. The washing or cleaning agent according to one of Claims 1 to 11, characterised in that the shaped element or the shaped-element phase that is adherently joined by a heat-sealed seam to the liquid-filled hollow element has a builder content above 15 wt%, preferably above 20 wt%, particularly preferably above 25 wt%, and in particular above 30 wt%.
13. The washing or cleaning agent according to one of Claims 1 to 12, characterised in that the shaped element or the shaped-element phase that is adherently joined by a heat-sealed seam to the liquid-filled hollow element has a polymer content above 0.5 wt%, by preference above 1.0 wt%, particularly preferably above 2.0 wt%, and in particular above 4 wt%.
14. The washing or cleaning agent according to one of Claims 1 to 13, characterised in that the tablet and the hollow element are adherently joined to one another along a peripheral sealed seam.
15. The washing or cleaning agent according to one of Claims 1 to 14, characterised in that the shaped element and the hollow element are adherently joined to one another along two or more sealed seams separated from one another.
16. The washing or cleaning agent according to one of Claims 1 to 15, characterised in that the tablet has a breaking pressure above 1 bar, by preference above 2.5 bar, and in particular above 4 bar.
17. A method for manufacturing a washing or cleaning agent made up of at least one washing- or cleaning-agent shaped element and at least one water-soluble or water-dispersible film material, characterised by the steps of:

    a) manufacturing washing- or cleaning-agent shaped elements that comprise a coating with a water-soluble or water-dispersible organic polymer over its entire surface;

    b) providing a water-soluble or water-dispersible film material;

    c) adherently joining at least one product of step a) to the water-soluble or water-dispersible film material of step b) by means of a heat-sealed seam.