GB2383773A

GB2383773A - Production of filled hollow bodies by rotary-table automatic injection moulding machines

Info

Publication number: GB2383773A
Application number: GB0224188A
Authority: GB
Inventors: Sandra Hoffman; Wilfried Raehse
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2001-10-20
Filing date: 2002-10-17
Publication date: 2003-07-09
Anticipated expiration: 2022-10-17
Also published as: GB0224188D0; DE10152266C1; GB2383773B

Abstract

The rapid large-scale industrial fabrication of filled and closed water-soluble hollow bodies is achieved by a process for the production of detergents, rinsing agents or cleaning agents in the form of filled hollow bodies, in which water-soluble hollow bodies are produced by injection moulding, filled, and then sealed. A hollow portion of the hollow body is injection moulded in an injection mould wherein the tool half of the injection mould accommodating the hollow portion is part of a rotary table that can be rotated about a vertical axis. An upper mould half of the injection mould is then removed from the hollow portion or portions, which is/are moved away from injection moulding nozzle(s) by rotating the rotary table and is/are filled, the hollow portion(s) being closed after the filling.

Description

"Production of Filled Hollow Bodies by Rotary-Table Automatic Injection Moulding Machines" The present invention relates to a process for the production of injection moulded hollow bodies of watersoluble material (s).

In virtually all areas of application of industrial products for domestic use, these products have to be suitably packaged in order to protect them against environmental influences and/or to facilitate their handling. Especially in the case of products that are added to water to produce aqueous, ready-for-use liquors (detergents or cleaning agents, fertilisers, medicaments, animal feedstuffs, vitamin preparations, colourants, disinfectants, etc. ) packagings produced from water-soluble materials have been found to be suitable as a user-friendly alternative since the user can add the packaged agents directly to the systems used to prepare the liquor (washing machine, measuring flask, vat/tub, injection device, etc.) without having to unpack the agents. In addition an exact metering can be achieved in this way since the user no longer has to measure out amounts of powder or liquid, but only has to use one or more packaged units.

Such water-soluble packagings comprise for example film bags of water-soluble polymers (so-called pouches) or,

particularly in the pharmaceutical sector, gelatin capsules.

Thermoformed water-soluble containers for agrochemicals such as plant protection agents are disclosed in recent publications in the prior art. In WO 92/17382 a non-planar sheet of water-dispersible material is filled and sealed with a"cover"of water-dispersible material by means of a circumferential sealing seam of water-soluble or waterdispersible material.

WOO1/36290 discloses injection-moulded hollow bodies of water-soluble polymers for detergents or cleaning agents, medicaments or fertilisers. This specification discloses wall thicknesses of the injection-moulded containers ranging from 100 pm up to 1 mm and injection pressures of less than 3 x 106 Pa (30 bar). This specification does not disclose any details of throughput rates in the production.

It has been shown that the production processes disclosed in the prior art are unsuitable for a large-scale industrial production of water-soluble hollow bodies since the number of hollow bodies produced per unit time is too low. Both in thermoforming processes as well as in the injection-moulding process large throughputs cannot be realised. In addition, limits are placed on large-scale production of the filled containers since the unfilled containers after their production have to be brought to the filling machine and then to the sealing machine. In the

ungraded packing of hollow bodies produced for example by thermoforming, bottle blowing or injection-moulding a grading has to be carried out before the filling; problems arise with graded stacking since the unfilled hollow bodies stick to one another and in this way sometimes several hollow bodies on top of one another are fed to the filling machine. During ejection from the filling and/or sealing machine these extra containers may fall off and cause stoppages in the plant. If filled containers with"multiple covers"reach the market, this can give rise to user frustration since the increased wall thickness does not provide the exactly adjusted solubility.

An object of the present invention is to provide a process

I that permits the rapid large-scale production of filled and sealed water-soluble hollow bodies.

The present invention provides a process for the production of filled hollow bodies, in which water-soluble hollow bodies are produced by injection-moulding, filled with a filler composition, and then sealed, wherein a) the tool half of an injection mould accommodating the moulding is part of a rotary table which is rotatable about a vertical axis; b) one or more mouldings is/are injection-moulded in the injection mould, and the upper mould half of the injection mould is then removed from the moulding (s);

c) the moulding (s) is/are moved away from the injection moulding nozzle (s) by rotating the rotary table and is/are filled ; d) the moulding (s) is/are sealed after having been filled.

The preferred procedure according to the invention can be briefly summarised as follows: in a vertically closeable injection moulding machine of conventional design and construction, the injection head of the injection moulding machine can be connected to an injection moulding tool that consists of an upper mould half and a mould upper part that can be raised and lowered and that is formed on guide pillars. In the injection moulding position the lower mould half and the mould upper part form a closed mould cavity into which thermoplastic water-soluble plastics material can be injected by means of the injection head, in order to produce a moulding or base body of the desired shape. After completing the injection moulding of the base body the injection head is moved away from the mould tool and the mould upper part is raised. The base body remains in the lower mould half of the mould tool, which can be rotated about a vertical axis on a carousel table. By rotation about a predetermined angle the lower mould half together with the optionally still unsolidified base, body is brought into a position in which it is located underneath a metering unit that meters the composition to be metered in, which is preferably a detergent, rinsing agent or cleaning agent composition, into the open hollow

body. In this connection the metering head may be lowered in the direction of the hollow body before the filling of the cavity; it is however also possible to carry out the filling process from a stationary metering head. After completion of the metering procedure the metering head is optionally moved away from the mould tool, in which the now filled hollow body is located. The filled hollow body remains in the lower mould half of the mould tool that can be rotated about a vertical axis on a carousel table. By rotation about a predetermined angle the lower mould half together with the filled hollow body is brought into a position in which it is situated underneath a sealing unit that effects the closure of the filled hollow body. This is accomplished in preferred embodiments of the present invention by sealing on a film of water-soluble material.

The individual process steps are described in more detail hereinafter.

In the first process step [b)] one or more moulding (s) is/are injection moulded in the injection mould, and the upper mould half of the injection mould is then removed from the moulding (s). In this connection the number of mould cavities may vary depending on the geometry of the injection moulded part and size of the apparatus. In the case of complicated, large hollow bodies and small machines there may be one mould cavity, whereas with smaller hollow bodies and larger machines up to 200 mould cavities are possible. Preferred processes utilise preferably at most 100, particularly preferably at most 80 and especially 5 to

60 mould cavities per injection moulding station.

Processes according to the invention that are characterised in that 1 to 100, preferably 2 to 60 and in particular 10 to 30 mouldings are injection moulded in the injection mould are furthermore preferred. The injection-moulded parts (hollow bodies) may in this connection be fabricated in different spatial shapes, for example hemispherical or hemi-ellipsoidal, cubical, right-parallelepiped or trapezoidal, trough-shaped, etc. Also, completely irregular shapes such as Santa Claus figures, Easter Rabbits, as well as flora and fauna shapes can be produced without any problem. The mouldings may in this connection be formed as an individual metering unit, but it is however also possible to join the hollow bodies together via their edge to form multiple metering units. Such"blister"packs are similarly used for example for coffee creamers or yoghurt, although in these cases they are made of waterinsoluble materials. The consumer accordingly has a coherent structure of a plurality of filled hollow bodies, from which he or she can, depending on the particular use, detach one or more portions and use as appropriate.

Depending on the size and number of the mould cavities, the injection moulding unit requires a specific area on the rotary table. In this connection processes according to the invention are preferred that are characterised in that the tool half of the injection mould accommodating the moulding makes up 40 to 180 , preferably 50 to 120 and in particular 60 to 90 of the rotary table.

The advantages of the procedure for the production of the dimensionally stable hollow bodies by injection-moulding lie in the sophisticated technology of this procedure, the high degree of flexibility with regard to the materials that can be used, the possibility of exactly obtaining desired wall thicknesses of the moulding and/or dimensionally stable hollow body, and the possibility of producing a dimensionally stable hollow body in one step with a high degree of reproducibility using one or more integral compartmentalisation devices.

In preferred processes according to the invention the injection pressure in the injection moulding is 1.5 x 107 Pa to 5 x 108 Pa, preferably 2.5 X 107 Pa to 4 x 108 Pa, particularly preferably 5 x 107 Pa to 2.5 x 108 Pa and especially 1 x 108 Pa to 1.5 x 108 Pa.

The temperature of the material that is to be injection moulded is preferably above the melting point or softening point of the material and therefore depends also on the type of material for the hollow body. In preferred processes according to the invention step b) is carried out

at temperatures between 100 and 250 C, preferably between 120 and 200 C and in particular between 140 and 180 C.

The tools that accommodate the materials are preferably subjected to preliminary heat treatment and are at temperatures above room temperature, temperatures between

25 and 60 C and in particular from 35 to 50 C being preferred.

Particularly preferably the injection moulds are fabricated from materials or coated with materials that facilitate a subsequent release of the filled and closed containers from the mould. Such a coating must on the one hand be both hard and resistant to high surface stresses, but on the other hand must also have a friction-reducing or lubricating property. To this end, nickel-containing surface coatings in which very fine PTFE particles (Teflon) are incorporated have proved particularly suitable. These particles impart anti-stick and material abrasion prevention properties to the coating. As an alternative, an embodiment in which the base coating material consists of a nickel-phosphorus alloy instead of nickel has also proved convenient for the adhesion-reducing coating.

As a further alternative to the surface coating having at least an adhesion-reducing action, but which also satisfies the requirements as regards hardness and strength, a coating of graphite containing diamond particles has also proved effective. For this, the surface of the injection mould is coated with a graphite layer that is known to have a lubricating or slip-promoting action and that here serves at the same time as a binder for fixing diamond particles, which in turn impart the necessary hardness to the surface.

Particularly preferred are plasma coatings, for example those with titanium nitride (TiN), which can be applied by

gas phase deposition (chemical vapour deposition) to the surfaces of the tools, and for example form there coatings 2 to 3 pm thick ; titanium carbide (TiC) as well as titanium carbonitride are also suitable; chromium nitride coatings are also particularly suitable. Tests with these surface coatings on the injection moulds have shown that, even with very long service lives of the moulds, no sticking of the material was observed. Processes according to the invention which are characterised in that the injection

moulds are provided with coatings preferably 0. 5 to 600 Am thick, particularly preferably 1 to 100 jum and especially 1 to 20 jum thick, are preferred embodiments of the present invention.

I It is particularly preferred to use water-soluble polymers as material for the hollow bodies. In this connection processes that have proved suitable are characterised in that the injection moulding composition comprises one or more materials from the group comprising (optionally acetalised) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives and mixtures, particularly preferably (optionally acetalised) polyvinyl alcohol (PVAL).

Within the scope of the present invention polyvinyl alcohols are particularly preferred as coating materials.

"Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) denotes polymers of the general structure

that also contain in small proportions (ca. 2%) structure units of the type

Commercially available polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerisation in the range from ca. 100 to 2500 (molecular weights of ca. 4000 to 100,000 g/mol) have a degree of hydrolysis of 98-99 mol% and 87-89 mol%, and thus still contain a residual content of acetyl groups. The polyvinyl alcohols are characterised by the manufacturers in terms of the degree of polymerisation of the initial polymer, degree of hydrolysis, saponification no. and the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and in a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); they are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classed as toxicologically harmless and are at least partially biodegradable. The water solubility may be

reduced by post-treatment with aldehydes (acetalisation), by complexing with Ni or Cu salts, or by treatment with dichromates, boric acid or borax. The polyvinyl alcohol coatings are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but however are permeable to water vapour.

Preferred processes within the scope of the present invention are characterised in that the injection moulding composition comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and especially 82 to 88 mol%.

Polyvinyl alcohols of a specific molecular weight range are preferably used as materials for the hollow bodies, wherein processes according to the invention are preferred in which the injection-moulding composition comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000

to 100, 000 mol-1, preferably 11, 000 to 90, 000 mol-1, particularly preferably 12, 000 to 80, 000 mol-l and especially 13,000 to 70,000 mol-1.

The degree of polymerisation of such preferred polyvinyl alcohols is between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to

rOX4 approximately 1680 and especially between approximately 260 to approximately 1500.

The aforedescribed polyvinyl alcohols are commercially widely available, for example under the trademark Mowiol# (Clariant). Particularly suitable polyvinyl alcohols within the scope of the present invention are for example mowiol 3-83, Mowiol# 4-88, Mowiol# 5-88 as well as Mowiol# 8-88.

Further polyvinyl alcohols that are particularly suitable as material for the hollow bodies are given in the following table:

Name Degree of Molecular Melting Hydrolysis Weight [kDa] Point [ C] [%] Airvol 205 88 15 - 27 230 Vineux 2019 88 15 - 27 170 Vinex 2144 88 44 - 65 205 Vinex 1025 99 15 - 27 170 Vinex 2025 88 25 - 45 192 Gohsefimer@ 30 - 28 23,600 100 5407 Gohsefimere 41 - 51 17,700 100 LL02

t Further polyvinyl alcohols suitable as material for the hollow body include ELVANOL 51-05,52-22, 50-42,85-82, 75-15, T-25, T-66,90-50 (trademark of Du Pont), ALCOTEX 72.5, 78, B72, F80/40, F88/4, F88/26, F88/40, F88/47

(trademark of Harlow Chemical Co.), Gohsenol NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei K. K.).

The hollow bodies according to the invention can be produced particularly advantageously if the proportion of the water-soluble polymers in the total mass of the hollow bodies is high. Preferably the overall hollow body consists only of the water-soluble polymers and optionally auxiliary substances (see below). Here processes according to the invention are preferred in which the injection moulding composition contains the aforementioned polymers in amounts of at least 50 wt. %, preferably of at least 70 wt. %, particularly preferably of at least 80 wt. % and especially of at least 90 wt. %, in each case referred to the weight of the injection moulding composition.

In order to facilitate the injection moulding process (i. e. their production) the hollow bodies may contain plasticiser auxiliary substances. This may be especially advantageous if polyvinyl alcohol or partially hydrolysed polyvinyl acetate has been chosen as material for the hollow bodies.

The proportion of the plasticiser auxiliary substances (referred to the polymer) is normally up to 15 wt. %, values of between 5 and 10 wt. % being preferred. Glycerol, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine have proved particularly suitable as plasticiser auxiliary substances.

Apart from the plasticiser auxiliary substances mould release additives are also important auxiliary substances

that can be used in the injection moulding compositions.

From the groups comprising fatty substances and finely particulate substances, within the scope of the present invention stearic acid and/or stearates as well as pyrogenic silicic acids (Aerosil&commat;) and also talcum have proved especially suitable. The proportion of mould release additives (referred to the polymer) is normally up to 5 wt. %, values between 0.5 and 2.5 wt. % being preferred.

Further substances that may be used as mould release additives are derived in particular from the group comprising fatty substances. The term fatty substances is understood within the scope of this application to mean substances that are liquid to solid at normal temperature (20 C) selected from fatty alcohols, fatty acids and fatty acid derivatives, in particular fatty acid esters.

Reaction products of fatty alcohols with alkylene oxides are counted as surfactants (see above) within the scope of the present invention and are not fatty substances within the meaning of the invention. As fatty substances there can preferably be used according to the invention fatty alcohols and fatty alcohol mixtures, fatty acids and fatty acid mixtures, fatty acid esters with alkanols or diols or polyols, fatty acid amides, fatty amines, etc.

The following alcohols obtainable from natural fats and

oils are for example used as fatty alcohols : 1-hexanol (hexyl alcohol), 1-heptanol (heptyl alcohol), 1-octanol (capryl alcohol), 1-nonanol (pelargonic alcohol), 1-decanol (caprin alcohol), 1-undecanol, 10-undecen-l-ol, 1-dodecanol (lauryl alcohol), 1-tridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), 1-heptadecanol, 1-octadecanol (stearyl alcohol),

9-cis-octadecen-1-ol (oleyl alcohol), 9-trans-octadencen-1-ol (erucyl alcohol), 9-cisoctadecen-1, 12-diol (ricinol alcohol), all-cis-9, 12-octadecadien-l-ol (linoleyl alcohol), allcis-9,12, 15-octadecatrien-l-ol (linolenyl alcohol), 1-nonadecanol, 1-eicosanol (arachidyl alcohol), 9-cis-eicosen-1-ol (gadoleyl alcohol), 5, 8, 11, 14-eicosatetraen-1-ol, 1-heneicosanol, 1-docosanol (behenyl alcohol), 1, 3-cis-docosen-1-ol (erucyl alcohol), 1, 3-trans-docosen-1-ol (brassidyl alcohol) as well as mixtures of these alcohols. According to the invention guerbet alcohols and oxoalcohols, for example Cl3-IS oxoalcohols or mixtures of C12-i8 alcohols with C12-14 alcohols may also be used without any problem as fatty substances.

Mixtures of alcohols may however obviously also be used, for example those Gig-is alcohols produced by ethylene polymerisation according to the Ziegler process.

Particular examples of alcohols that may be used as component b) are the alcohols already mentioned above, as well as lauryl alcohol, palmityl alcohol and stearyl alcohol, and mixtures thereof.

Preferred mould release additives are Ciao-30 fatty alcohols, preferably C12-24 fatty alcohols, and particularly preferably 1-hexadecanol, 1-octadecanol, 9-cis-octadecen-1ol, allcis-9, 12-octadecadien-l-ol, all-cis-9,12, 15-octadecatrien-

1-or, 1-docosanol and their mixtures.

I Fatty acids can also be used as mould release additives.

These are obtained industrially for the most part from natural fats and oils by hydrolysis. Whereas alkaline saponification carried out over the last hundred years led directly to the alkali salts (soaps), nowadays industrially

only water is used for the splitting reaction, which splits the fats into glycerol and free fatty acids. Industrially used processes include for example splitting in autoclaves or continuous high-pressure splitting. Carboxylic acids that may be used as fatty substance within the scope of the present invention include for example hexanoic acid (caproic acid), heptanoic acid (oenanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. Within the scope of the present invention it is preferred to use fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachinic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignocerin acid), hexacosanoic acid (cerotic acid), triacontanoic acid (melissic acid) as well as the unsaturated acids 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatrienoic acid (linolenic acid).

Obviously tridecanoic acid, pentadecanoic acid, margaric acid, nonadecanoic acid, erucic acid, elaeostearic acid and arachidonic acid may also be used. For reasons of cost it is preferred not to use the pure compounds but instead industrial mixtures of the individual acids, such as are available from the splitting of fats. Such mixtures include for example coconut oil fatty acid (ca. 6 wt. % Cg, 6 wt. % Ciao, 48 wt. % C12, 18 wt. % C14, 10 wt. % Cig, 2 wt. % Cis, 8 wt. % Cls', 1 wt. % C18"), palm kernel oil fatty acid (ca. 4 wt. % Cs, 5 wt. % C1O, 50 wt. % C12, 15 wt. % C14, 7 wt. % Cig, 2

wt. % C18, 15 wt. % C18', 1 wt. % CIS"), tallow fatty acid (ca.

3 wt. % C14, 26 wt. % C16, 2 wt. % C16', 2 wt. % C17, 17 wt. % C18, 44 wt. % Cis', 3 wt. % Gig", 1 wt. % Ci8'"), hardened tallow fatty acid (ca. 2 wt. % C14, 28 wt. % C16, 2 wt. % C, 63 wt. % Cis, 1 wt. % Ci8'), industrial oleic acid (ca. 1 wt. % C12, 3 wt. % C14, 5 wt.% C16, 6 wt. % Cri6', 1 wt.% C17, 2 wt. % C18, 70 wt. % C18', 10 wt. % Ci8", 0.5 wt. % C18''') industrial palmitic/stearc acids (ca. 1 wt. % C12, 2 wt.% C14, 45 wt. % C16, 2 wt. % Ci7, 47

wt. % Ci8, 1 wt. % Ci8') as well as soya bean oil fatty acid (ca. 2 wt. % C14, 15 wt. % Gig, 5 wt. % Ci8, 25 wt. % Cite', 45 wt. % C18", 7 wt. % Cive'").

The esters of fatty acids with alkanols, diols or polyols can be used as fatty acid esters, fatty acid polyol esters being, preferred. Suitable fatty acid polyol esters are monoesters and/or diesters of fatty acids with specific polyols. The fatty acids that are esterified with the polyols are preferably saturated or unsaturated fatty acids with 12 to 18 C atoms, for example lauric acid, myristic acid, palmitic acid or stearic acid, the industrially occurring mixtures of the fatty acids preferably being used, for example the acid mixtures derived from coconut oil, palm kernel oil or tallow fat. In particular acids or mixtures of acids with 16 to 18 C atoms, such as for example tallow fatty acid, are suitable for the esterification with the polyhydric alcohols. Suitable polyols within the scope of the present invention that are esterified with the aforementioned fatty acids include sorbitol, trimethylolpropane, neopentyl glycol, ethylene glycol, polyethylene glycols, glycerol and polyglycerols.

Preferred embodiments of the present invention envisage using glycerol as the polyol that is esterified with fatty acid or acids. Accordingly fatty substances from the group comprising fatty alcohols and fatty acid glycerides are preferred as mould release additives. Particularly preferred mould release additives are fatty substances from the group comprising fatty alcohols and fatty acid monoglycerides. Examples of such preferably used fatty substances are glycerol monostearate and/or glycerol monopalmitate.

In order to prevent undesirable changes in the injection moulding compositions caused by the action of oxygen and other oxidative processes, these may contain antioxidants.

This class of compounds includes for example substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

In preferred processes according to the invention the material of the mould, the wall thickness and the size of the mould are chosen so that the hollow body dissolves and/or releases the contents of the filling in less than 300 seconds, preferably in less than 60 seconds, in unstirred water at 20 C. In this connection it is not necessary for the whole of the moulded article to dissolve spontaneously. Instead, it is sufficient if all the constituents dissolve, within the specified time under the conditions of use. For normal washing or rinsing processes this means temperatures of 20 C and above, mechanical action as well as times of less than 200 minutes, preferably less than 60 minutes, in particular less than 20 minutes. The release of the contents of at least one

compartment should however preferably take place in less than 300 seconds, in particular in less than 60 seconds.

This may be accomplished by the use of disintegration auxiliary substances, by sealing one compartment with a thin, water-soluble film, by dissolution of a"plug"closing an opening, or by any other appropriate means.

The wall thickness of the injection-moulded hollow bodies produced by the preferred processes according to the invention is 200 to 1500 jum, preferably 300 to 1000 am and in particular 400 to 600 jum.

In the next process step the injection-moulded hollow bodies of water-soluble material are filled with the desired compositions. The hollow bodies produced according to the invention may in every case be filled with a filler composition, i. e. all compositions that can be packed in water-soluble casings. Areas of use include for example the production of portions of agrochemicals (fertilisers and plant protection agents, etc. ), foodstuffs ("degradable" beverage packagings, packaged foodstuffs and foodstuffs additives, etc. ), animal feedstuffs, pharmaceuticals, colourants and fragrances, adhesives, cosmetics, or other industrial applications. The hollow bodies produced according to the invention are particularly preferably filled with detergents, rinsing agents or cleaning agents, with the result that preferred processes are characterised in that the injection-moulded hollow bodies are filled, after rotation of the rotary table, with one or more liquid detergent, rinsing agent or cleaning agent compositions.

The details given hereinafter refer to this particularly preferred delivery form of the present invention, though

they also apply in a completely similar way to other industrial areas of application.

The individually portioned detergents, rinsing agents or cleaning agents according to the invention may be formulated as detergents, as cleaning agents or as rinsing agents depending on which constituents are contained in the casing. Apart from textile detergents there may for example be produced cleaning agents for dishwashers or handwashing of dishes (washing-up liquids), all-purpose domestic cleaning agents, WC cleaning agents, glass cleaning agents, etc. Depending on the intended use, the choice of the constituents in the detergent, rinsing agent or cleaning agent compositions contained in the casing may vary. Important constituents of these compositions are described hereinafter.

I The detergent, rinsing agent or cleaning agent compositions preferably contain surfactant (s), in which connection anionic, non-ionic, cationic and/or amphoteric surfactants may be employed. In the case of textile detergents mixtures of anionic and non-ionic surfactants are preferred from the application technology aspect, in which connection the proportion of the anionic surfactants should be greater than the proportion of non-ionic surfactants. The overall surfactant content of the detergent, rinsing agent or cleaning agent composition is preferably below 30 wt. % referred to the whole agent.

As non-ionic surfactants there are preferably used alkoxylated, more preferably ethoxylated, in particular primary alcohols with preferably 8 to 18 C atoms and with on average 1 to 12 moles of ethylene oxide (EO) per mol of

alcohol, in which the alcohol radical may be linear or preferably methyl-branched in the 2-position, and/or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxoalcohol radicals.

Particularly preferred however are alcohol ethoxylates with linear radicals of alcohols of natural origin with 12 to 18 C atoms, for example coconut butter, palm oil, tallow oil or oleyl alcohol, with on average 2 to 8 EO per mol of alcohol. These preferred ethoxylated alcohols include for

example C12-14 alcohols with 3 EO, 4 EO or 7 EO, C9-11 alcohol with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 alcohols with 3 EO, 5 EO or 7 EO, and mixtures of the latter such as mixtures of C12-14 alcohol with 3 EO and C12-18 alcohol with 7 EO. The specified degrees of ethoxylation represent statistical average values, which for a particular product may be a whole number or a fraction.

Preferred alcohol ethoxylates have a narrow homologue distribution range (narrow range ethoxylates, NRE). In addition to these non-ionic surfactants, there may also be used fatty alcohols with more than 12 EO. Examples of these include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Also, non-ionic surfactants that contain the EO and PO groups together in the molecule may be used according to the invention. In this connection block copolymers with EO-PO block units and/or PO-EO block units may be used, as well as EO-PO-EO copolymers and/or PO-EO-PO copolymers. Mixed alkoxylated non-ionic surfactants in which EO and PO units are distributed not in blocks but randomly may obviously also be used. Such products are obtainable by the simultaneous action of ethylene oxide and propylene oxide on fatty alcohols.

In addition there may be used as further non-ionic surfactants also alkyl glycosides of the general formula RO (G) x in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched in the 2position, aliphatic radical with 8 to 22 C atoms, preferably 12 to 18 C atoms, and G is the symbol for a glycose unit with 5 or 6 C atoms, preferably glucose. The degree of oligomerisation x which specifies the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1.2 to 1.4.

A further class of preferably used non-ionic surfactants, which are employed either as the sole non-ionic surfactant or in combination with other non-ionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.

Non-ionic surfactants of the type comprising amine oxides, for example N-coconut-alkyl-N, N-dimethylamine oxide and Ntallow-alkyl-N, N- dihydroxyethylamine oxide and fatty acid alkanolamides may also be suitable. The amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, and in particular is not more than half of the latter.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula I

in which RCO denotes an aliphatic acyl radical with 6 to 22 carbon atoms, R1 denotes hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] denotes a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances that may normally be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine followed by acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group comprising polyhydroxy fatty acid amides also includes compounds of the formula II

in which R denotes a linear or branched alkyl or alkenyl radical with 7 to 12 carbon atoms, R1 denotes a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms, and R2 denotes a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical with 1 to 8 carbon atoms, Cl-4 alkyl or phenyl radicals being preferred, and [Z] denotes a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups ; or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

[Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy-substituted or N-aryloxy-substituted compounds may then be converted by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired polyhydroxy fatty acid amides.

The content of non-ionic surfactants in the preferred individually portioned detergent, rinsing agent or cleaning agent compositions according to the invention that are suitable for textile washing is 5 to 20 wt. %, preferably 7 to 15 wt. % and in particular 9 to 14 wt. %, in each case referred to the total agent.

Weakly foaming non-ionic surfactants are preferably used in dishwasher detergents. Dishwasher detergents according to the invention particularly preferably contain a non-ionic surfactant that has a melting point above room temperature.

Accordingly, preferred agents are characterised in that they contain non-ionic surfactant (s) with a melting point above 20 C, preferably above 25 C, particularly preferably between 25 and 60 C, and especially between 26. 6 and 43. 3 C.

Suitable non-ionic surfactants that have melting points or softening points in the aforementioned temperature range are for example weakly foaming non-ionic surfactants that may be solid or highly viscous at room temperature. If non-ionic surfactants that are highly viscous at room temperature are used, then it is preferred that these have a viscosity above 20 Pas, preferably above 35 Pas and in

particular above 40 Pas. Non-ionic surfactants that have a waxy consistency at room temperature are also preferred.

Non-ionic surfactants solid at room temperature that are preferably used are derived from the groups comprising alkoxylated non-ionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) surfactants. Such (PO/EO/PO) non-ionic surfactants are moreover characterised by a good foaming behaviour.

In a preferred embodiment of the present invention the nonionic surfactant with a melting point above room temperature is an ethoxylated non-ionic surfactant that is obtained by reacting a monohydroxyalkanol or alkylphenol with 6 to 20 C atoms with preferably at least 12 moles, particularly preferably at least 15 moles, especially at least 20 moles of ethylene oxide per mol of alcohol or alkylphenol.

A particularly preferred non-ionic surfactant solid at room temperature that may be used is obtained from a straight-

chain fatty alcohol with 16 to 20 carbon atoms (Cl6-20 alcohol), preferably a Cig alcohol, and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide. Of these, the so-called"narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred agents according to the invention contain ethoxylated non-ionic surfactant or surfactants that has/have been obtained from C6-20

monohydroxyalkanols or C6-20 alkylphenols or C16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mol of alcohol.

The non-ionic surfactant preferably additionally contains propylene oxide units in the molecule. Preferably such PO units make up to 25 wt. %, particularly preferably up to 20 wt. % and especially up to 15 wt. % of the total molecular weight of the non-ionic surfactant. Particularly preferred non-ionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols that additionally contain polyoxyethylene/polyoxypropylene block copolymer units.

The alcohol part and/or alkylphenol part of such non-ionic surfactant molecules then preferably makes up more than 30 wt. %, particularly preferably more than 50 wt. % and especially more than 70 wt. % of the total molecular weight of such non-ionic surfactants. Preferred clear rinsing agents (rinse aids) are characterised in that they contain ethoxylated and propoxylated non-ionic surfactants in which the propylene oxide units in the molecule make up to 25 wt. %, preferably up to 20 wt. % and in particular up to 15 wt. % of the total molecular weight of the non-ionic surfactant.

Further particularly preferred non-ionic surfactants that may be used and that have melting points above room temperature contain 40 to 70% of a, polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend that consists of 75 wt. % of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide, and 25 wt. % of a block copolymer of polyoxyethylene and

polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mol of trimethylolpropane.

Non-ionic surfactants that may particularly preferably be used are obtainable for example under the name Poly Tergent SLF-18 from Olin Chemicals.

A further preferred individually portioned detergent, rinsing agent or cleaning agent according to the invention contains non-ionic surfactants of the formula RIO[CH2CH (CH3) 0]x[CH2CH20]y[CH2CH (OH) R2], in which RI denotes a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof, and x denotes values between 0.5 and 1.5 and y has a value of at least 15.

Further non-ionic surfactants that may preferably be used are the terminal group-closed poly (oxyalkylated) non-ionic surfactants of the formula

RO [CH2CH (R3) 0] x [CH2] kCH (OH) [CH2] jOR in which Ri and R2 denote linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R3 denotes H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x denotes values between 1 and 30, k and j denote values between 1 and 12, preferably between 1 and 5. If

the value x # 2, then each R3 in the above formula may be different. R1 and R2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 6'to 22 carbon atoms, radicals with 8 to 18 C

3 atoms being particularly preferred. For the radical R3, H, - CH3 or-CH2CH3 are particularly preferred. Particularly preferred values for x lie in the range from 1 to 20, in particular from 6 to 15.

As described above, each R3 in the above formula may be different if x > 2. The alkylene oxide unit in the square brackets may thus vary. If x is for example 3, then the radical R3 may be chosen so as to form ethylene oxide (R3 =

3 H) or propylene oxide ( (R == CHs) units, which may be arranged in any sequence, for example (EO) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO) (PO). The value 3 for x has been chosen as an example in this connection and may of course be larger, in which case the variation width increases with increasing x values and for example covers a large number of (EO) groups combined with a small number of (PO) groups, or vice versa.

Particularly preferred terminal group-closed poly (oxyalkylated) alcohols of the formula given above have values of k = 1 and j = 1, with the result that the above formula simplifies to RO [CH2CH (R) 0] XCH2CH (OH) CH2OR2 In this formula R, R2 and R3 are as defined above and x denotes numbers from 1 to 30, preferably 1 to 20 and in particular 6 to 18. Particularly preferred are surfactants

in which the radicals R and R have 9 to 14 carbon atoms, R3 denotes H, and x has values from 6 to 15.

To summarise the information given above, individually portioned detergents, rinsing agents or cleaning agents according to the invention are preferred that contain the terminal group-closed poly (oxyalkylated) non-ionic surfactants of the formula

RO [CH2CH (R3) 0] x [CHs] KCH (OH) [CH2] JOR2 in which R and R denote linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R3 denotes H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x denotes values between 1 and 30, k and j denote values between 1 and 12, preferably between 1 and 5, wherein surfactants of the type RO [CH2CH (R3) 0]xCH2CH(OH)CH2OR2 in which x denotes numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are especially preferred.

Anionic, cationic and/or amphoteric surfactants may also be used in conjunction with the aforementioned surfactants, and if so are employed only in minor amounts on account of their foaming behaviour in dishwasher detergents, and generally only in amounts below 10 wt. %, generally even below 5 wt. %, for example 0.01 to 2.5 wt. %, in each case referred to the agent. The agents according to the

invention may thus also contain anionic, cationic and/or amphoteric surfactants as surfactant components.

The agents according to the invention may for example contain as cationic active substances, cationic compounds of the formulae III, IV or V

wherein each group R1 is selected independently of one another from Cl-6-alkyl, -alkenyl or -hydroxyalkyl groups ; each group R2 is selected independently of one another from Cs-2s-alkyl or-alkenyl groups ; R = R or (CHn-T-R ; R"= R or R2 or (CH2) n-T-R2 ; T = -CH2-, -O-CO- or -CO-O- and n is a whole number from 0 to 5.

As anionic surfactants there are used for example those of the type comprising sulfonates and sulfates. Suitable surfactants of the sulfonate type are preferably C9-13alkylbenzenesulfonates, olefin sulfonates, i. e. mixtures of

alkene sulfonates and hydroxyalkane sulfonates as well as disulfonates, such as are obtained for example from C12-18 monoolefins with terminal-position or internal-position double bonds by sulfonation with gaseous sulfur trioxide followed by alkaline or acid hydrolysis of the sulfonation products. Also suitable are alkane sulfonates that are obtained from C12-18 alkanes by for example sulfochlorination or sulfoxidation followed by hydrolysis and/or neutralisation. The esters of a-sulfo fatty acids (ester sulfonates), for example the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are likewise suitable.

Further suitable anionic surfactants are sulfonated fatty acid glycerol esters. The term fatty acid glycerol esters is understood to mean the monoesters, diesters and triesters as well as their mixtures, as are obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfonated fatty acid glycerol esters are the sulfonated products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates, the alkali metal salts and in particular the sodium salts of the sulfuric acid semiesters of C12-18 fatty alcohols, for example of cocoa butter alcohol, tallow fat alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or of C10-20 oxoalcohols and those semiesters of secondary alcohols of these chain lengths, are preferred. Also preferred are alk (en) yl sulfates of

the aforementioned chain length that contain a synthetic straight-chain alkyl radical produced from petrochemicals, and that have a similar degradation behaviour as the suitable compounds based on raw materials in fat chemistry. From the detergent aspect, the C12-16 alkyl sulfates and C12-15 alkyl sulfates as well as C14-15 alkyl sulfates are preferred. Suitable anionic surfactants also include 2,3alkyl sulfates that are produced for example according to US patent specifications 3,234, 258 or 5,075, 041, and that may be obtained as commercial products under the name DAN from the Shell Oil Company.

Also suitable are the sulfuric acid monoesters of straightchain or branched C7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-11 alcohols with on average 3. 5 moles of ethylene oxide (EO) or C12-18 fatty alcohols with 1 to 4 EO. On account of their high foaming behaviour, these monoesters are employed only in relatively small amounts in detergents, for example in amounts of 1 to 5 wt. %.

Further suitable anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also termed sulfosuccinates or sulfosuccinic acid esters, and which constitute monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols, and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8-18 fatty alcohol radicals or mixtures of the latter. Particularly preferred sulfosuccinates contain a fatty alcohol radical that is derived from ethoxylated fatty alcohols that, considered per se, constitute nonionic surfactants (for description see below). In this connection sulfosuccinates whose fatty alcohol radicals are

derived from ethoxylated fatty alcohols with a narrow homologue distribution are in turn particularly preferred.

Similarly, it is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain, or its salts.

Soaps in particular are also suitable as further anionic surfactants. Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, as well as in particular soap mixtures derived from natural fatty acids, for example coconut acid, palm kernel acid, olive oil acid or tallow fat acid.

The anionic surfactants including the soaps may be present in the form of their sodium, potassium or ammonium salts, as well as in the form of soluble salts of organic bases such as monoethanolamine, diethanolamine or triethanolamine. Preferably the anionic surfactants are present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The content of anionic surfactants in the preferred textile detergents according to the invention is 5 to 25 wt. %, preferably 7 to 22 wt. % and in particular 10 to 20 wt. %, in each case referred to the total agent.

Within the scope of the present invention preferred agents contain in addition one or more substances from the group comprising detergent builders, bleaching agents, bleaching activators, enzymes, electrolytes, non-aqueous solvents, pH adjustment agents, fragrances, perfume carriers,

fluorescence agents, colourants, hydrotopes, foam inhibitors, silicone oils, anti-redeposit agents, optical brighteners, greying inhibitors, anti-shrink agents, crease prevention agents, colour transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatics, ironing auxiliary agents, phobing and impregnating agents, anti-swelling and non-slip agents, as well as UV absorbers.

As detergent builders that may be contained in the agents according to the invention, there should in particular be mentioned phosphates, silicates, aluminium silicates (in particular zeolites), carbonates, salts of organic dicarboxylic acids and polycarboxylic acids, as well as mixtures of these substances.

The use of the generally known phosphates as builder substances is possible according to the invention as long as such a use should not be avoided for ecological reasons.

Among the multiplicity of commercially available phosphates, the alkali metal phosphates, particularly preferably pentasodium and pentapotassium triphosphate (sodium and potassium tripolyphosphate), have proved most important in the detergent and cleaning agent industry.

Alkali metal phosphates is the generic description for the alkali metal (in particular sodium and potassium) salts of the various phosphoric acids, in which there may be distinguished metaphosphoric acids (HP03) n and orthophosphoric acid H3PO4, in addition to higher molecular weight members. The phosphates combine several advantages: they act as alkali carriers, prevent calcium carbonate deposits on machinery parts and/or calcium carbonate

incrustations in fabrics, and contribute overall to the cleaning performance.

Sodium dihydrogen phosphate, NaH2PO4, exists as the dihydrate (density 1.91 g/cm3, melting point 60 C) and as the monohydrate (density 2.04 g/cm3). Both salts are white powders very readily soluble in water that lose their water

of crystallisation on heating, and that at 200 C are converted into the weakly acidic diphosphate (disodium hydrogen diphosphate, NaEOy), and at higher temperatures into sodium trimetaphosphate (Na3P309) and Maddrell salt (see below). NaH2PO4 reacts acidically and is formed if phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH2PO4, is a white salt of density 2.33 g/cm3, which has a melting point of 253 C decomposition with the formation of potassium polyphosphate (KPOs) ] and is readily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na2HP04, is a colourless crystalline salt, very readily soluble in water. It exists in the anhydrous form and also combines with 2 moles of water (density 2.066 g/cm3, loss of water at 95 C), 7 moles of water (density 1.68 g/cm3, melting point 48 C with loss of 5 H2O) and 12 moles of water (density 1.52 g/cm3, melting point 350C with loss of 5 H2O),

becomes anhydrous at 100 C, and under strong heating transforms into the diphosphate Na4P207. Disodium hydrogen phosphate is produced by neutralising phosphoric acid with sodium carbonate solution using phenolphthalein as indicator. Dipotassium hydrogen phosphate (secondary or

dibasic potassium phosphate), KzHP04'is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na3PO4, exists as colourless crystals, which as the dodecahydrate has a density of 1.62 g/cm3 and a melting point of 73-76 C (decomposition), as the decahydrate (corresponding to 19- 20% P20s) has a melting point of 100 C, and in the anhydrous form (corresponding to 39-40% Pros) has a density of 2.536 g/cm3. Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K3PO4, is a white deliquescent

3 granular powder of density 2. 56 g/cm3, which has a melting point of 13400C and is readily soluble in water with an alkaline reaction. It is formed for example by heating basic slag with coal and potassium sulfate. Despite their higher price, the more readily soluble and therefore more effective potassium phosphates are greatly preferred in the detergents industry to the corresponding sodium compounds.

Tetrasodium disphosphate (sodium pyrophosphate), NaPh, 3 exists in anhydrous form (density 2. 534 g/cm3, melting point 988 C, also given as 880 C), and as the decahydrate (density 1. 815-1. 836 g/cm3, melting point 940C with loss of water). Both substances are colourless crystals soluble in water with an alkaline reaction. Na4P207, is formed by heating disodium phosphate to > 200 C or by reacting phosphoric acid with sodium carbonate in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness forming agents and thereby reduces the water hardness.

Potassium diphosphate (potassium pyrophosphate), K4P207, exists in the form of the trihydrate and forms a colourless, hygroscopic powder with a density of 2.33 g/cm3 that is soluble in water, the pH value of a 1% solution at 25 C being 10.4. By condensation of NaHzP04 or KH2PO4, higher molecular weight sodium and potassium phosphates are formed, in which there may be distinguished cyclic representatives, namely sodium and potassium metaphosphates, and chain-type representatives, namely sodium and potassium polyphosphates. A large number of trivial names are employed, especially for the latter phosphates: melt phosphates or annealing phosphates, Graham's salt, Kurrol's salt and Maddrell salt. All higher sodium phosphates and potassium phosphates are generically termed condensed phosphates.

I The industrially important pentasodium triphosphate, Nap3010 (sodium tripolyphosphate), is an anhydrous, or crystallising with 6 H2O, non-hygroscopic, white, water-

soluble salt of the general formula NaO- [P (O) ONa)-Oln-Na where n=3. In 100 g of water about 17 g of the salt free of water of crystallisation dissolve at room temperature, ca. 20 g at 60 C, and around 32 g at 100 C ; after heating the solution for 2 hours at 100 C, about 8% of orthophosphate and 15% of diphosphate are formed by hydrolysis. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Like Graham's salt and sodium diphosphate, pentasodiumtriphosphate dissolves many insoluble metal compounds (also lime soaps, etc.).

Pentapotassium triphosphate, KsPgOic (potassium tripolyphosphate), is commercially available for example in

the form of a 50 wt. % solution ( > 23% P205, 25% K2O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. Furthermore sodium/potassium tripolyphosphates also exist, which may likewise be used within the scope of the present invention. These are formed for example by hydrolysing sodium trimetaphosphate with KOH:

(NaP03) 3 + 2 KOH- NaECio + H2O These may be used according to the invention exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; according to the invention there may also be used mixtures of sodium tripolyphosphate and sodium/potassium tripolyphosphate, or mixtures of potassium tripolyphosphate and sodium/potassium tripolyphosphate, or mixtures of sodium tripolyphosphate and potassium

tripolyphosphate and sodium/potassium tripolyphosphate.

Suitable crystalline, stratiform sodium silicates have the general formula NaMSix02x+l. H2O, where M denotes sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, and preferred values for x are 2,3 or 4.

Preferred crystalline layer silicates of the specified formula are those in which M denotes sodium and x has the values 2 or 3. Particularly preferred are ss-sodium as well as 6-sodium disilicates, Na2SI20s'yH2O.

There may also be used amorphous sodium silicates with an Na20 : Si02 ratio of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which exhibit a delayed dissolution and secondary wash properties. The delayed

dissolution compared to conventional amorphous sodium silicates may have been brought about in various ways, for example by surface treatment, compounding, compacting/consolidation or by overdrying. Within the scope of the present invention the term"amorphous"is also understood to mean"X-ray amorphous". This means that the silicates do not provide sharp X-ray reflections in X-ray diffraction experiments, as are typical of crystalline substances, but instead display one or more maxima of the scattered X-ray radiation that exhibit a width of several units of degree of the angle of diffraction. This may however very well even lead to particularly good builder properties if the silicate particles yield overlapping or even sharp diffraction maxima in electron diffraction experiments. This should be interpreted as meaning that the products have microcrystalline regions of the size of 10 to a few hundred nm, values of up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Such so-called X-ray amorphous silicates likewise exhibit a delayed dissolution compared to conventional water glasses.

Particularly preferred are consolidated and compacted amorphous silicates, compounded amorphous silicates, and overdried X-ray amorphous silicates.

The finely crystalline synthetic zeolite containing bound water that is used is preferably zeolite A and/or zeolite P. MAP"zeolite (commercial product available from Crosfield) is particularly preferred. However, zeolite X as well as mixtures of A, X and/or P are also suitable. A co-crystallisate of zeolite X and zeolite A (ca. 80 wt. % zeolite X) that is commercially available and may for example preferably be used within the scope of the present

invention is marketed by CONDEA Augusta S. p. A. under the trade name VEGOBOND AX and may be described by the formula nNa20- (l-n) K2O. A1203. (2 - 2. 5) SiO2-(3. 5-5. 5) H20 The zeolite may be used as a spray-dried powder or also as an undried stabilised suspension that is still wet from the production. In the case where the zeolite is used as a suspension, this may contain minor additions of non-ionic surfactants as stabilisers, for example 1 to 3 wt. %, referred to zeolite, of ethoxylated C12-18 fatty alcohols with 2 to 5 ethylene oxide groups, C12-14 fatty alcohols with 4 to 5 ethylene oxide groups, or ethoxylated isotridecanol. Suitable zeolites have a mean particle size of less than 10 pm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22 wt. %, in particular 20 to 22 wt. %, of bound water.

Further important detergent builders are in particular carbonates, citrates and silicates. Trisodium citrate and/or pentasodium tripolyphosphate and/or sodium carbonate and/or sodium bicarbonate and/or gluconates and/or silicate builders from the class comprising disilicates and/or metasilicates are preferably used.

Alkali carriers may preferably be added as further constituents. Alkali carriers include alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metasilicates, and mixtures of the aforementioned substances, wherein within the context of the present invention alkali carbonates, in particular

sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, are preferably used.

A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.

Also particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.

In addition, further constituents may be added, wherein according to the invention detergents, rinsing agents or cleaning agents are preferred which additionally contain one or more substances from the group comprising acidification agents, chelate complex-forming agents or deposit-inhibiting polymers.

i As acidification agents there may be used inorganic acids as well as organic acids, provided that these are compatible with the other constituents. For reasons of user protection and handling safety, the solid monocarboxylic, oligocarboxylic and polycarboxylic acids may in particular be used. Of this group, the following are in turn preferred: citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid as well as polyacrylic acid. The anhydrides of these acids may also be used as acidification agents, in which connection in particular maleic anhydride and succinic anhydride are commercially available. Organic sulfonic acids such as amidosulfonic acid may also be used.

Sokalan DCS (trademark of BASF), which is a mixture of succinic acid (max. 31 wt. %), glutaric acid (max. 50 wt. %) and adipic acid (max. 33 wt. %) and is commercially

available, may preferably also be used as acidification agent within the scope of the present invention.

Chelate complex-forming agents represent a further possible group of constituents. Chelate complex-forming agents are substances that form cyclic compounds with metal ions, in which an individual ligand occupies more than one coordination site on a central atom, i. e. is at least "bidentate". In this case normally stretched compounds are thus closed by complex formation via an ion to form rings.

The number of bound ligands depends on the co-ordination number of the central ion.

Conventional chelate complex-forming agents that are preferred within the scope of the present invention include for example polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, i. e. polymers that carry functional groups either in the main chain itself or in side positions relative to the latter, which may act as ligands and react with appropriate metal atoms as a rule with the formation of chelate complexes, may also be used according to the invention. The polymer-bound ligands of the resultant metal complexes may in this connection be derived from only one macromolecule or however may belong to various polymer chains. The latter case leads to the crosslinking of the material as long as the complex-forming polymers have not previously been crosslinked via, covalent bonds.

Complexing groups (ligands) of conventional complex-forming polymers include iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid,

amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and crown ether radicals having in some cases very specific activities with respect to ions of different metals. Base polymers of many, also commercially important, complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Complex-forming polymers also include natural polymers such as cellulose, starch or chitin. Moreover, these may be provided with further ligand functionalities by means of polymer-like conversions.

Particularly preferred within the scope of the present invention are detergents, rinsing agents or cleaning agents that contain one or more chelate complex-forming agents from the following groups (i) polycarboxylic acids in which the sum total of carboxyl and optionally hydroxyl groups is at least 5, (ii) nitrogen-containing monocarboxylic acids or polycarboxylic acids, (iii) geminal diphosphonic acids, (iv) aminophosphonic acids, (v) phosphonopolycarboxylic acids, (vi) cyclodextrins in amounts above 0.1 wt. %, preferably above 0.5 wt. %, particularly preferably above 1 wt. % and especially above 2.5 wt. %, in each case referred to the weight of the dishwasher detergent.

All complex-forming agents of the prior art may be used within the scope of the present invention. These may

belong to various chemical groups. The following are preferably used, either individually or mixed with one another: a) polycarboxylic acids in which the sum total of carboxyl groups and optionally hydroxyl groups is at least 5, such as gluconic acid, b) nitrogen-containing monocarboxylic acids or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N- hydroxyethylethylenediaminetriacetic acid, diethylentriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-

3-propionic acid, isoserindiacetic acid, N, N-di- (sshydroxyethyl) -glycine, N- (1, 2-dicarboxy-2hydroxyethyl)-glycine, N- (l, 2-dicarboxy-2hydroxyethyl)-aspartic acid or nitrilotriacetic acid (NTA), c) geminal diphosphonic acids such as 1-hydroxyethane- 1, 1-diphosphonic acid (HEDP), its higher homologues with up to 8 carbon atoms, as well as hydroxy group- containing or amino group-containing derivatives thereof and l-aminoethane-l, l-diphosphonic acid, its higher homologues with up to 8 carbon atoms, as well as hydroxy group-containing or amino group-containing derivatives thereof, d) aminophosphonic acids such as ethylenediaminetetra (metheylenephosphonic acid), diethylentriaminepenta (methyelenephosphonic acid) or nitrilotri (methyelenephosphonic acid), e) phosphonopolycarboxylic acids such as 2- phosphonobutane-l, 2,4-tricarboxylic acid, as well as f) cyclodextrins.

Polycarboxylic acids a) are understood within the scope of this patent application to mean carboxylic acidsincluding monocarboxylic acids-in which the sum total of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5. Complex-forming agents from the group comprising nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. With the alkaline pH values of the treatment solutions that are necessary according to the invention, these complex-forming agents are present at least partially as anions. It is not important whether they are employed in the form of the acids or in the form of salts. In the case where salts are used, then alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

I Deposit-inhibiting polymers may also be contained in the agents according to the invention. These substances, which may be built up in various chemical ways, are derived for example from the groups comprising low molecular weight polyacrylates with molecular weights between 1,000 and 20,000 Daltons, polymers with molecular weights below 15,000 Daltons being preferred.

Deposit-inhibiting polymers may also exhibit co-builder properties. As organic co-builders there may in particular be used in the dishwasher detergents according to the invention polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic co-builders (see below) as well as phosphonates. These classes of substances are described hereinafter.

Usable organic detergent builder substances are for example polycarboxylic acids that may be employed in the form of their sodium salts, the term polycarboxylic acids being understood to denote those carboxylic acids that carry more than one acidic function. Examples include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such a use is not undesirable for ecological reasons, as well as mixtures of the latter. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids per se may also be used. In addition to their builder action, the acids typically also have the property of an acidification component and thus also serve for establishing a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and arbitrary mixtures thereof may in particular be mentioned in this connection.

Furthermore, as builders and/or deposit inhibitors polymeric polycarboxylates are suitable, which include for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those with a relative molecular weight of 500 to 70000 g/mole.

The molecular weights given for polymeric polycarboxylates are, within the context of this specification, weightaverage molecular weights Mw of the respective acid form, that were in principle determined by means of gel permeation chromatography (GPC), a UV detector being used

in this connection. The measurement was carried out against an external polyacrylic acid standard, which on account of its structural relationship to the investigated polymers yields realistic molecular weight values. These figures deviate markedly from the molecular weight data in which polystyrenesulfonic acids are used as standard. The molecular weights measured against polystyrenesulfonic acids are as a rule significantly higher than the molecular weights given in this specification.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 500 to 20000 g/mole.

On account of their superior solubility, of this group there may in turn be preferred the short-chain polyacrylates that have molecular weights of 1000 to 10000

g/mole, and particularly preferably 1000 to 4000 g/mole.

I Polyacrylates as well as copolymers of unsaturated carboxylic acids, sulfonic acid group-containing monomers as well as optionally further ionic or non-ionogenic monomers are particularly preferably employed in the agents according to the invention. The sulfonic acid groupcontaining copolymers are furthermore described in detail hereinafter.

Copolymeric carboxylates, in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid, are furthermore suitable.

Copolymers of acrylic acid with maleic acid that contain 50 to 90 wt. % of acrylic acid and 50 to 10 wt. % of maleic acid have proved particularly suitable. Their relative molecular weight, referred to free acids, is in general

2000 to 70000 g/mole, preferably 20000 to 50000 g/mol and in particular 30000 to 40000 g/mole.

The (co) polymeric polycarboxylates may be used either as powder or as aqueous solution. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20 wt. %, in particular 3 to 10 wt. %.

Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those that contain as monomers salts of acrylic acid and maleic acid as well as vinyl alcohol and/or vinyl alcohol derivatives, or those that contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives. Further preferred copolymers are those that contain as monomers preferably acrolein and acrylic acid/acrylic acid salts and/or acrolein and vinyl acetate.

Further preferred builder substances that should also be mentioned include polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids and/or their salts and derivatives, which besides having co-builder properties also exhibit a bleach-stabilising action.

Further suitable builder substances include polyacetals, which may be obtained by reacting dialdehydes with pplyolcarboxylic acids containing 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde as well as their mixtures, and from polyolcarboxylic acids such as gluconic acid and/or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers and/or polymers of carbohydrates, which may be obtained by partial hydrolysis of starches.

The hydrolysis may be carried out according to conventional, for example acid-catalysed or enzymecatalysed methods. The hydrolysis products preferably have mean molecular weights in the range from 400 to 500000 g/mole. In this connection a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, the DE index being a conventional measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100.

Maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30000 g/mol may be used.

Oxidised derivatives of such dextrins comprise their reaction products with oxidising agents that are able to oxidise at least one alcohol group in the saccharide ring to a carboxylic acid group. A product oxidised on C6 of the saccharide ring may be particularly advantageous.

Also, oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable co-builders. In this connection ethylenediamine-N, N'-disuccinate (EDDS) is used, preferably in the form of its sodium or magnesium salts. Furthermore, glycerol disuccinates and glycerol trisuccinates are also preferred in this connection. Suitable amounts for use in zeolite-containing and/or silicate-containing formulations are 3 to 15 wt. %.

Further organic co-builders that may be used include for example acetylated hydroxycarboxylic acids and/or their salts, which optionally also may be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxy group as well as at most two acidic groups.

Phosphonates constitute a further class of substances having co-builder properties. Suitable phosphonates are in particular hydroxyalkane phosphonates and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1- hydroxyethane-1, l-diphosphonate (HEDP) is particularly important as a co-builder. It is preferably used as the sodium salt, the disodium salt giving a neutral reaction and the tetrasodium salt giving an alkaline reaction (pH 9). Suitable aminoalkane phosphonates are preferably ethylenediaminetetramethylene phosphonates (EDTMP), diethylenetriaminepentamethylene phosphonate (DTPMP) as well as their higher homologues. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the heptasodium and octasodium salt of DTPMP. In this connection, from the class of phosphonates HEDP is preferably used as builder. The aminoalkane phosphonates also have an excellent ability to bind heavy metals.

Accordingly it may be preferred, especially if the agents also contain bleach, to use aminoalkane phosphonates, in particular DTPMP, or to employ mixtures of the aforementioned phosphonates.

In addition to the substances from the aforementioned classes, the agents according to the invention may contain further conventional constituents of detergents, rinsing

agents or cleaning agents, in particular bleaching agents, bleaching activators, enzymes, silver protective agents, colourants and fragrances. These substances are described hereinafter.

Among the compounds serving as bleaching agents and that release H202 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important.

Further bleaching agents that may be used include for example sodium percarbonate, peroxy pyrophosphates, citrate perhydrates as well as peracid salts or peracids releasing H202, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.

In order to achieve an improved bleaching action when washing at temperatures of 60 C and below, bleaching activators may be incorporated into the detergent and cleaning agent moulded articles. As bleaching activators there may be used compounds that under perhydrolysis conditions produce aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and/or optionally substituted perbenzoic acid. Substances that carry 0-acyl groups and/or N-acyl groups having the aforementioned number of C atoms and/or optionally substituted benzoyl groups are suitable. Multiply acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1, 5-diacetyl-2,4-dioxohexahydro- 1,3, 5-triazine (DADHT), acylated glycoluriles, especially tetraacetylglycolurile (TAGU), N-acylimides, especially Nnonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl-or isononanoyloxybenzenesulfonate (n-and iso-NOBS), carboxylic acid anhydrides, especially

phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleaching activators or instead of the latter, so-called bleaching catalysts may also be incorporated into the moulded bodies. These substances are bleach-intensifying transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo Salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogencontaining tripod ligands, as well as Co, Fe, Cu and Ru ammine complexes may also be used as bleach catalysts.

Suitable enzymes include in particular those from the classes of hydrolases such as proteases, esterases, lipases and/or lipolytically acting enzymes, amylases, cellulases and/or other glycosyl hydrolases and mixtures of the aforementioned enzymes. All these hydrolases contribute in the wash process to the removal of spots and stains such as protein-containing, grease-containing or starch-containing stains and grey discolourations. Cellulases and other glycosyl hydrolases may moreover contribute, by removing pill and microfibrils, to the colour retention and enhancement of the softness of the textile material.

Oxireductases may also be used for bleaching and/or to inhibit colour transfer (bleeding). Enzymatic active substances obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable.

Proteases of the subtilisin type and in particular proteases that are obtained from Bacillus lentus are preferably used. In this connection enzyme mixtures,

for example of protease and amylase or protease and lipase and/or lipolytically acting enzymes or protease and cellulase, or of cellulase and lipase and/or lipolytically acting enzymes, or of protease, amylase and lipase, and/or lipolytically acting enzymes or protease, lipase and/or lipolytically acting enzymes and cellulase, but in particular protease and/or lipase-containing mixtures and/or mixtures with lipolytically acting enzymes, are of particular interest. Examples of such lipolytically acting enzymes are the known cutinases. Also, peroxidases or oxidases have in some cases proved suitable. Suitable amylases include in particular a-amylases, iso-amylases, pullulanases and pectinases. As cellulases there are preferably used cellobiohydrolases, endoglucanases and glucosidases, which are also termed cellobiases, and/or mixtures thereof. Since the various types of cellulase differ as regards their CMCase and avicelase activities, the desired activities can be adjusted by specific mixtures of cellulases.

The enzymes may be adsorbed on carrier substances or embedded in envelope substances in order to protect them against premature degradation. The proportion of the enzymes, enzyme mixtures or enzyme granules may for example be about 0.1 to 5 wt. %, preferably 0.12 to about 2 wt. %.

The cleaning agents according to the invention used for dishwashers may contain corrosion inhibitors to protect the items being washed or the dishwasher, silver protection agents being particularly important in connection with dishwasher use. The substances known from the prior art may be used. In general there may be used in particular silver protection agents selected from the group comprising

triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes. It is particularly preferred to use benzotriazole and/or alkylaminotriazole. Cleaning agent formulations moreover frequently include agents containing active chlorine, which can significantly reduce corrosion of silver surfaces. Chlorine-free cleaning agents comprise in particular oxygen-containing and nitrogen-containing organic redox-active compounds such as dihydroxy and trihydroxy phenols, e. g. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol and/or derivatives of these classes of compounds. Salt-type and complex-type inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred in this connection are transition metal salts that are selected from the group comprising manganese and/or cobalt salts and/or complexes, particularly preferred being cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt or manganese, and manganese sulfate.

Zinc compounds may also be used to prevent corrosion on articles being washed.

As electrolytes from the group comprising inorganic salts there may be used a large number of widely different salts.

Preferred cations include the alkali metals and alkaline earth metals, and preferred anions include the halides and sulfates. For production technology reasons it is preferred to use NaCl or MgClz in the agents according to the invention. The amount of electrolytes in the agents according to the invention is normally 0.5 to 5 wt. %.

Non-aqueous solvents that may be used in the agents according to the invention are chosen for example from the group comprising monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration ranges.

The solvents are preferably selected from ethanol, n-or ipropanol, butanols, glycol, propanediol or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol monon-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or monoethyl ether, di-isopropylene glycol monomethyl or monoethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy- 2-propanol, 3-methyl-3-methoxybutanol, propylene glycol tbutyl ether, as well as mixtures of these solvents. Nonaqueous solvents may be used in the liquid washing agents according to the invention in amounts between 0.5 and 10 wt. %, but preferably less than 5 wt. % and in particular less than 3 wt. %.

In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjustment agents may be indicated. All known acids or alkalis may be used for this purpose as long as their use is not prohibited for application technology or ecological reasons and/or on grounds of user safety. Normally the amount of these adjustment agents should not exceed 5 wt. % of the overall formulation.

In order to improve the aesthetic impression of the agents according to the invention, they may be coloured using

suitable colourants. Preferred colourants, the choice of which will not present any difficulty to the person skilled in the art, have a high storage stability and insensitivity to the remaining constituents of the agents and to light, and also do not exhibit any pronounced substantivity towards textile fibres, so that they do not dye the latter.

Suitable foam inhibitors that may be used in the agents according to the invention include for example soaps, paraffins or silicone oils, which may if necessary be applied to carrier materials. Suitable anti-redeposition agents, which are also termed soil repellents, include for example non-ionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups ranging from 15 to 30 wt. % and of hydroxypropyl groups ranging from 1 to 15 wt. %, in each case referred to the non-ionic cellulose ethers, as well as polymers of phthalic acid and/or terephthalic acid and/or their derivatives, known from the prior art, in particular polymers of ethylene terephthalate and/or polyethylene glycol terephthalates or anionically and/or non-ionically modified derivatives of the latter. Particularly preferred of these are the sulfonated derivatives of phthalic acid polymers and terephthalic acid polymers.

Optical brighteners (so-called"white toners") may be added to the agents according to the invention in order to prevent greying and yellowing of the treated textiles.

These substances bind to the fibres and produce a brightening and imaginary bleaching action by converting invisible ultraviolet radiation into visible light of longer wavelength, the ultraviolet light absorbed from the sunlight being re-emitted as a pale bluish fluorescence and

producing a pure white impression with the yellow shade of the grey and/or discoloured wash. Suitable compounds are obtained for example from the classes of substances comprising 4,4'-diamino-2, 2'-stilbenedisulfonic acids (flavone acids), 4,4'-distyrylbiphenylene, methyl umbelliferones, cumarins, dihydroquinolinones, 1,3diarylpyrazolines, naphthalic acid imides, benzoxazole, benzisoxasole and benzimidazole systems, as well as pyrene derivatives substituted by heterocyclic compounds. The optical brighteners are normally used in amounts of between 0.05 and 0.3 wt. % referred to the final agent.

Greying inhibitors have the task of maintaining the dirt dissolved from the fibre suspended in the wash liquor and thereby preventing the dirt being readsorbed. Watersoluble colloids generally of an organic nature are suitable for this purpose, for example size, gelatin, salts of ether sulfonic acids of starch or of cellulose, or salts of acidic sulfuric acid esters of cellulose or of starch.

Water-soluble polyamides containing acidic groups are also suitable for this purpose. Furthermore soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone may also be used. However, cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and their mixtures are preferably used in amounts of 0.1 to 5 wt. % referred to the agents.

If the agents according to the invention are formulated for use in dishwashers, then further constituents may be included. Nowadays more stringent requirements are often placed on dishes washed by machine than on dishes washed by hand. Thus, an item of crockery from which food residues have been completely removed is not regarded as satisfactorily cleaned if, after having been washed in the dishwasher, it also exhibits whitish spots caused by water hardness or other mineral salts that are left behind because of the lack of wetting agent, after water droplets have dried. In order to obtain glass-clear and spotless dishes, rinse aids are therefore nowadays successfully used. The addition of rinse aids at the end of the rinse program ensures that the water runs off as fully as possible from the washed dishes so that the various surfaces are free of residues and appear spotless and shining at the end of the rinse program. The cleaning of dishes in domestic dishwashers normally includes a preliminary rinse stage, a main wash stage and a clear rinse stage, which are interrupted by intermediate rinse procedures. In most dishwashers the preliminary rinse program can be selected for highly soiled dishes, but is chosen only in exceptional cases by the user, so that most dishwashers perform a main wash stage, an intermediate rinse stage with pure water, and a clear rinse stage. The temperature of the main wash stage varies depending on the type of dishwasher and program stage selection, and is between 40 and 65 C. In the clear rinse stage rinse aid is added to the dishwasher from a metering device; the rinse aid normally contains non-ionic surfactants as the main constituent. Such rinse aids are in liquid form and are widely described in the prior art. Their task is

principally to prevent spots of calcium carbonate and deposits on the dishes.

The agents according to the invention may be formulated as "normal"dishwasher detergents, which are employed together with commercially available supplementary agents (rinse aids, regenerating salt). However, the additional metering of rinse aids may particularly advantageously be dispensed with in the products according to the invention. These socalled"2inl"products simplify handling and save the user the task of having to add two different products (dishwasher detergent and rinse aid).

Even when using"2inl"products, two metering procedures at specified time intervals are required in the operation of a domestic dishwasher, since after a certain number of wash cycles the regenerating salt in the water hardness removal system of the dishwasher has to be replenished. These water hardness removal systems consist of ion exchange polymers which remove the hardness constituents in the water flowing into the dishwasher and are regenerated by flushing with salt water at the end of the rinse program.

However, products according to the invention can also be formulated that combine, in the form of so-called"3inl" products, the conventional dishwasher detergent, rinse aid and a salt replacement function. To this end dishwasher detergents according to the invention are preferred that additionally contain 0.1 to 70 wt. % of copolymers of i) unsaturated carboxylic acids

ii) monomers containing sulfonic acid groups L--L-L-Ld groups

iii) optionally further ionic or non-ionogenic monomers.

These copolymers act in such a way that dishes treated with such agents become significantly cleaner in subsequent cleaning procedures than dishes that have been rinsed with conventional agents.

An additional positive effect is a reduction in the drying time of the dishes treated with the cleaning agent, i. e. the user can after the end of the wash program remove the dishes earlier from the dishwasher and use them again.

The invention is characterised by an improved"cleanability" of the treated substrates during subsequent cleaning procedures and by a considerable reduction in the drying time compared to comparable agents without the addition of polymers containing sulfonic acid groups.

Within the scope of the teaching according to the invention the term"drying time"is generally understood to have the literal meaning, i. e. the time that elapses until a surface of a dish washed in a dishwasher is dry, but in particular the time that elapses until 90% of a surface treated with a dishwasher detergent or rinse aid in concentrated or dilute form is dry.

Within the scope of the present invention unsaturated carboxylic acids of the formula VI are preferred as monomers, R1 (R2) C=C (R3) COOH (VI),

in which R1 to R3 independently of one another denote-H, - CH3, a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, singly or multiply unsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals as defined above substituted with -NH2, -OH or -COOH, or denote-COOH or - COOR, where R4 is a saturated or unsaturated, straightchain or branched hydrocarbon radical with 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids that can be

described by the formula VI, acrylic acid (R1 = R2 = R3 = H), methacrylic acid (R = R = H; R3 = CH3) and/or maleic acid (Rl = COOH; R2 = R3 = H) are particularly preferred.

Of the monomers containing sulfonic acid groups, those of I the formula VII are preferred, R5 (R6) C=C (R7)-X-SO3H (VII), in which R5 to R7 independently of one another denote-H, -CH3, a straight-chain or branched saturated alky radical with 2 to 12 carbon atoms, a straight-chain or branched, singly or multiply unsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals as defined above substituted with-NHz,-OH or-COOH, or denote-COOH or - COOR, where R is a saturated or unsaturated, straightchain or branched hydrocarbon radical with 1 to 12 carbon atoms, and X denotes an optionally present spacer group that is selected from- (CH2) n- where n = 0 to 4, -COO- (CH2) K- where k = 1 to 6,-C (O)-NH-C (CH3) 2- and-C (O)-NH-CH (CH2CH3)-.

Among these monomers, those of the formulae VIla, VIIb and/or VIIc are preferred, H2C=CH-X-S03H (VIla) H2C=C (CH3)-X-S03H (VIIb) H03S-X- (R6) C=C (R7) -X-S03H (Vllc)

in which R6 and R7 independently of one another are selected from-H,-CH3,-CH2CH3,-CH2CH2CH3,-CH (CH3) 2 and X denotes an optionally present spacer group that is selected from -(CH2)n- where n = 0 to 4,-COO- (CH2) K- where k = 1 to 6, -C(O)-NH-C(CH3)2- and -CO(O)-NH-CH(CH2CH3)-.

Particularly preferred monomers containing sulfonic acid

groups are 1-acrylamido-l-propanesulfonic acid (X = - C (O) NH-CH (CH2CH3) in formula VIIa), 2-acrylamido-2- propanesulfonic acid (X =-C (0) NH-C (CH3) 2-in formula VIIa), 2-acrylamido-2-methyl-l-propanesulfonic acid (X =-C (O) NHCH (CH3) CH2- in formula VIla), 2-methacrylamido-2-methyl-l- propanesulfonic acid (X =-C (O) NH-CH (CH3) CH2- in formula VIIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (O) NH-CH2CH (OH) CH2- in formula VIIb), allylsulfonic acid (X = CH2 in formula VIla), methallylsulfonic acid (X = CH2 in formula VIIb), allyloxybenzenesulfonic acid (X =-CH2-0C6H4-in formula VIla), methallyloxybenzenesulfonic acid (X

=-CH2-O-C6H4-in formula VIIb), 2-hydroxy-3- (2propenyloxy) propanesulfonic acid, 2-methyl-2-propene-l- sulfonic acid (X = CH2 in formula VIIb), styrenesulfonic acid (X = C6H4 in formula VIla), vinylsulfonic acid (X not

present in formula VIIa), 3-sulfopropyl acrylate (X = - C (O) NH-CH2CH2CH2- in formula VIIa), 3-sulfopropyl methacrylate (X = -C (O) NH-CH2CH2CH2- in formula VIIb), sulfomethacrylamide (X =-C (O) NH- in formula VIIb),

sulfomethylmethacrylamide (X =-C (0) NH-CH2- in formula VIIb) as well as water-soluble salts of the aforementioned acids.

Further suitable ionic or non-ionic monomers are in particular ethylenically unsaturated compounds. Preferably the content of monomers of group iii) in the polymers employed according to the invention is less than 20 wt. %, referred to the polymer. Particularly preferred polymers that are used simply comprise monomers of the groups i) and ii).

To summarise, particularly preferred are copolymers of

i) unsaturated carboxylic acids of the formula VI, R1 (ruz) C=C (R3) COOH (VI), in which R1 to R3 independently of one another denote - H,-CH3, a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, singly or multiply unsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals as defined above substituted with-NH,-OH or

4 4 - COOH, or denote-COOH or-COOR, where R4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1 to 12 carbon atoms, ii) monomers containing sulfonic acid groups, of the formula VII R5 (R6) C=C (R7)-X-S03H (VII), in which R5 to R7 independently of one another denote-H,

- CH3, a straight-chain or branched saturated alky radical with 2 to 12 carbon atoms, a straight-chain or branched, singly or multiply unsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals as defined above substituted with-NH2,-OH or-COOH, or denote-COOH or - COOR, where R is a saturated or unsaturated, straightchain or branched hydrocarbon radical with 1 to 12 carbon atoms, and X denotes an optionally present spacer group that is selected from- (CH2) n- where n = 0 to 4, -COO- (CH2) K- where k = 1 to 6,-C (O)-NH-C(CH3)2- and -C(O)-NH-CH(CH2CH3)-, iii) optionally further ionic or non-ionogenic monomers.

Particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group comprising acrylic acid, methacrylic acid and/or maleic acid ii) one or more monomers containing sulfonic acid groups, of the formulae VIIa, VIIb and/or VIIc : H2C=CH-X-S03H (VIIa) H2C=C (CH3)-X-S03H (VIIb) H03S-X- (R) C=C (R) -X-S03H (VIIc)

in which R6 and R7 independently of one another are selected from-H,-CH3,-CH2CH3,-CH2CH2CH3,-CH (CH3) 2 and X denotes an optionally present spacer group that is selected from - (CH2) n- where n = 0 to 4,-COO- (CH2) K-where k = 1 to 6, - C (0)-NH-C (CH3) 2- and-C (0)-NH-CH (CH2CH3)- iii) optionally further ionic or non-ionogenic monomers.

The copolymers contained according to the invention in the agents may contain the monomers of the groups i) and ii) as well as optionally iii) in varying amounts, in which connection all representatives of the group i) may be combined with all representatives of the group ii) and with all representatives of the group iii). Particularly preferred polymers have specific structural units, which are described hereinafter.

Thus, for example, agents according to the invention are preferred that are characterised in that they contain one or more copolymers that contain structural units of the formula VIII - [CH2-CHCOOH] m-[CH2-CHC (O)-Y-SO3HJp- (VIII), in which m and p in each case denote a whole natural number between 1 and 2000, and Y denotes a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals with 1 to 24 carbon atoms, spacer groups in which Y denotes-0- (CH2) nwhere n = 0 to 4, or denotes -O- (C6H4) -, -NH-C (CH3) 2- or-NHCH (CH2CH3)- being preferred.

These polymers are produced by copolymerisation of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerised with methacrylic acid, then another polymer is obtained whose use in the agents according to the invention is also preferred, and which is characterised in that the agents contain one or

more copolymers that contain structural units of the formula IX - [CH2-C (CH3) COOH] m- [CH2-CHC (0)-Y-S03H] p- (IX), in which m and p in each case denote a whole natural number between 1 and 2000, and Y denotes a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals with 1 to 24 carbon atoms, spacer groups in which Y denotes-0- (CH2) n" where n = 0 to 4, or denotes -O- (C6H4) -, -NH-C (CH3) 2- or-NH- CH (CH2CH3)- being preferred.

Acrylic acid and/or methacrylic acid can also be copolymerised in a completely analogous manner with methacrylic acid derivatives containing sulfonic acid groups, whereby the structural units in the molecule are altered. Thus, agents according to the invention are preferred that contain one or more copolymers which include structural units of the formula X - [CH2-CHCOOH] m- [CH2-C (CH3) C (0)-Y-S03H] p- (X), in which m and p in each case denote a whole natural number between 1 and 2000, and Y denotes a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals with 1 to 24 carbon atoms, spacer groups in which Y denotes-0- (CH2) n" where n = 0 to 4, or denotes -O- (C6H4) -, -NH-C (CH3) 2- or -NHCH (CH2CH3)- being preferred, and similarly according to a preferred embodiment of the present invention, in exactly the same way agents are also preferred that are

characterised in that they contain one or more copolymers that contain structural units of the formula XI - [CH2-C (CH3) COOH]m-[CH2-C (CH3) C (0)-Y-S03H] p- (XI), in which m and p in each case denote a whole natural number between 1 and 2000, and Y denotes a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals with 1 to 24 carbon atoms, spacer groups in which Y denotes-0- (CH2) nwhere n = 0 to 4, or denotes -O- (C6H4) -, -NH-C (CH3) 2- or-NH- CH (CH2CH3)- being preferred.

Instead of acrylic acid and/or methacrylic acid and/or in addition to the latter, maleic acid may also be used as a particularly preferred monomer from the group i). In this way preferred agents according to the invention are obtained that are characterised in that they contain one or more copolymers which contain structural units of the formula XI

- [HOOCCH-CHCOOH] m- [CH2-CHC (0)-Y-S03H] p- (XI), in which m and p in each case denote a whole natural number between 1 and 2000, and Y denotes a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals with 1 to 24 carbon atoms, spacer groups in which Y denotes -O- (CH2) n- where n = 0 to 4, or denotes -O- (C6H4) -, -NH-C (CH3) 2- or-NHCH (CH2CH3) - being preferred, and agents are obtained that are characterised in that they contain one or more copolymers that comprise structural units of the formula

XII

- [HOOCCH-CHCOOH]m-[CH2-C (CH3) C (O) O-Y-SOsH] ?- (XII), in which m and p in each case denote a whole natural number between 1 and 2000, and Y denotes a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals with 1 to 24 carbon atoms, spacer groups in which Y denotes-0- (CH2) nwhere n = 0 to 4, or denotes -O-(C6H4)-, -NH-C (CH3) 2- or -NHCH (CH2CH3)- being preferred.

To summarise, dishwasher detergents according to the invention are preferred that contain as constituent b) one or more copolymers that comprise structural units of the formulae VII and/or VIII and/or IX and/or X and/or XI and/or XII - [CH2-CHCOOH] m- [CH2-CHC (0)-Y-S03H] p- (VII), - [CH2-C (CH3) COOH]m-[CH2-CHC(O)-Y-SO3H]p- (VIII), - [CH2-CHCOOH] m- [CH2-C (CH3) C (0)-Y-S03H] p- (IX), - [CH2-C (CH3) COOH] - [CH2-C (CH3) C (0)-Y-S03H] p- (X),

- [HOOCCH-CHCOOHJm-[CHz-CHC (O) -Y-S03HJp- (XI), - [HOOCCH-CHCOOH] - [CH2-C (CH3) C (O) O-Y-S03H]p- (XII), in which m and p in each case denote a whole natural number between 1 and 2000, and Y denotes a spacer group that is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals with 1 to 24 carbon atoms, spacer groups in which Y denotes-0- (CH2) nwhere n = 0 to 4, or denotes -O- (C6H4) -, -NH-C (CH3) 2- or -NHCH (CH2CH3)- being preferred.

In the polymers the sulfonic acid groups may be present wholly or partially in neutralised form, i. e. the acidic hydrogen atom of the sulfonic acid group may be replaced in some or all sulfonic acid groups by metal ions, preferably alkali metal ions and in particular by sodium ions.

Corresponding agents that are characterised in that the sulfonic acid groups in the copolymer are present in partially or fully neutralised form are preferred according to the invention.

The monomer distribution of the copolymers used in the agents according to the invention is, in the case of copolymers that contain only monomers from the groups i) and ii), preferably in each case 5 to 95 wt. % of i) and/or ii), particularly preferably 50 to 90 wt. % of monomers from the group i) and 10 to 50 wt. % of monomers from the group ii), in each case referred to the polymer.

In the case of terpolymers, those are particularly preferred that contain 20 to 85 wt. % of monomers from the group i), 10 to 60 wt. % of monomers from the group ii) as well as 5 to 30 wt. % of monomers from the group iii).

The molecular weight of the polymers used in the agents according to the invention may be varied in order to match the properties of the polymers to the desired intended use.

Preferred dishwasher detergents are characterised in that the copolymers have molecular weights of 2000 to 200,000 mole-1, preferably 4000 to 25,000 gnole-l and in particular

1 5000 to 15, 000 gnole-.

The content of one or more copolymers in the agents according to the invention may vary depending on the

intended use and desired product performance, dishwasher detergents according to the invention being preferred that are characterised in that they contain the copolymer or copolymers in amounts of 0.25 to 50 wt. %, preferably 0.5 to 35 wt. %, particularly preferably 0.75 to 20 wt. % and especially 1 to 15 wt. %.

As already mentioned above, in the agents according to the invention there are particularly preferably used polyacrylates as well as the aforedescribed copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups, as well as optionally further ionic or nonionogenic monomers. The polyacrylates have been described in detail above. Particularly preferred are combinations of the aforedescribed copolymers containing sulfonic acid groups with polyacrylates of low molecular weight, for example in the range between 1000 and 4000 Dalton. Such polyacrylates are commercially obtainable under the trade names Sokalan PA15 and Sokalan PA25 (BASF).

The agents according to the invention may also be formulated as textile softeners or wash additives. They may also contain further constituents depending on the desired intended use. Textile softener compositions for the rinsing stage in washing machines are widely described in the prior art. Normally these compositions contain as active substance a cationic quaternary ammonium compound that is dispersed in water. Depending on the content of active substance in the finished textile softener composition, the latter are described either as dilute, ready-for-use products (active substance contents less than 7 wt. %) or so-called concentrates (active substance content greater than 7 wt. %). On account of the smaller volume and

consequently the reduced packaging and transport costs, textile softener concentrates have advantages in ecological terms and have achieved an increasing market penetration.

On account of the inclusion of cationic compounds, which have only a very low water solubility, normal softener compositions exist in the form of dispersions, have a milky-cloudy appearance, and are not transparent. For reasons of product aesthetics it may however also be desirable to make available to the consumer transparent, clear softeners that stand out optically from the known products.

Individually portioned softeners according to the invention preferably contain cationic surfactants as textilesoftening active substance, which have already been described in detail above (formulae XII, XIII and XIV).

"Softener portions"according to the invention particularly preferably contain so-called esterquats. Whereas there exist a large number of possible compounds from this class of substances, according to the invention esterquats are particularly preferably used that can be produced in a manner known per se by reacting trialkanolamines with a mixture of fatty acids and dicarboxylic acids, optionally followed by alkoxylation of the reaction product and quaternisation, as is described in DE 195 39 846.

The esterquats produced in this way are particularly suitable for producing"portions"according to the invention that may be used as softeners. Depending on the choice of the trialkanolamine, fatty acids and dicarboxylic acids as well as the quaternisation agent, a large number of suitable products can be produced and employed in the agents according to the invention ; a description of the

esterquats that are preferably used according to the invention in terms of their production process is more informative than merely giving a general formula.

The aforementioned components, which react with one another to form the esterquats that are preferably used, may be mixed with one another in varying quantitative ratios.

Within the scope of the present invention individually portioned softeners are preferred in which a reaction product of trialkanolamines with a mixture of fatty acids and dicarboxylic acids in a molar ratio of 1: 10 to 10: 1, preferably 1: 5 to 5: 1, which has optionally been alkoxylated and then quaternised in a manner known per se, is contained in amounts of 2 to 60 wt. %, preferably 3 to 35 wt. % and in particular 5 to 30 wt. %. It is particularly preferred in this connection to use triethanolamine, so that further preferred individually portioned softeners according to the present invention contain a reaction product of triethanolamine with a mixture of fatty acids and dicarboxylic acids in a molar ratio of 1: 10 to 10: 1, preferably 1: 5 to 5: 1, which has optionally been alkoxylated and then quaternised in a manner known per se, in amounts of 2 to 60 wt. %, preferably 3 to 35 wt. % and in particular 5 to 30 wt. %.

*As fatty acids there may be used in the reaction mixture for the production of the esterquats, all acids obtained from vegetable or animal oils and fats. In this connection there may be used as fatty acid throughout in the reaction mixture, also a fatty acid that is not solid, i. e. is pasty to liquid, at room temperature.

The fatty acids may be saturated or singly to multiply unsaturated irrespective of their state of aggregation.

Obviously there may be used not only"pure"fatty acids, but also industrial fatty acid mixtures obtained in the splitting of fats and oils, these mixtures in turn clearly being preferred from the economic aspect.

Accordingly, individual species or mixtures of the following acids can for example be used in the reaction mixtures for the production of the esterquats for the clear aqueous softeners according to the invention: caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecanol acid, arachinic acid, behenic acid, lignoceric acid, cerotinic acid, melissic acid, 10-undecanoic acid, petroselinic acid, petroselaidic acid, oleic acid, elaidinic acid, ricinoleic acid, linolaidic acid, a- and -elaeostearic acid, gadoleic acid, erucic acid and brassidic acid. Fatty acids with an odd number of C atoms may obviously also be used, for example undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoic acid, tricosanoic acid, pentacosanoic acid and heptacosanoic acid.

Within the scope of the present invention it is preferred to use fatty acids of the formula XIII in the reaction mixture for the production of the esterquats, so that preferred individually portioned softeners contain a reaction product of trialkanolamines with a mixture of fatty acids of the formula XIII R1-CO-OH (XIII)

in which R1-CO- denotes an aliphatic, linear or branched acyl radical with 6 to 22 carbon atoms and 0 and/or 1,2 or 3 double bonds and dicarboxylic acids in a molar ratio of 1: 10 to 10: 1, preferably 1: 5 to 5: 1, which has optionally been alkoxylated and then quaternised in a manner known per se, in amounts of 2 to 60 wt. %, preferably 3 to 35 wt. % and in particular 5 to 30 wt. % in the agents.

Suitable as dicarboxylic acids for the production of the esterquats to be used in the agents according to the invention are in particular saturated or singly or multiply unsaturated a, ro-dicarboxylic acids. By way of example there may be mentioned the saturated acids oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic and dodecanoic acids, brassylic acid, tetradecanoic and pentadecanoic acids, thapsic acid as well as heptadecanoic, octadecanoic and nonadecanoic acids, eicosanoic and heneicosanoic acids, and also phellogenic acid.

Dicarboxylic acids that have the general formula XXIII are preferably used in the reaction mixture, so that individually portioned agents according to the invention are preferred that contain a reaction product of trialkanolamines with a mixture of fatty acids and dicarboxylic acids of the formula XIV HO-OC-[X]-CO-OH (XIV) in which X denotes an optionally hydroxy-substituted alkenyl group with 1 to 10 carbon atoms, in a molar ratio of 1: 10 to 10: 1, preferably 1: 5 to 5: 1, which has optionally been alkoxylated and then quaternised in a

manner known per se, in amounts of 2 to 60 wt. %, preferably 3 to 35 wt. % and in particular 5 to 30 wt. %.

Among the large number of esterquats that may be produced and may be used according to the invention, in turn those esterquats have proved particularly suitable in which the alkanolamine is triethanolamine and the dicarboxylic acid is adipic acid. Accordingly, within the scope of the present invention agents are particularly preferred that contain a reaction product of triethanolamine with a mixture of fatty acids and adipic acid in a molar ratio of 1: 5 to 5: 1, preferably 1: 3 to 3: 1, which has then been quaternised in a manner known per se, in amounts of 2 to 60 wt. %, preferably 3 to 35 wt. % and in particular 5 to 30 wt. %.

The agents according to the invention may-irrespective of whether they are formulated as textile detergents, wash auxiliary substances or softeners-also contain further additives. Compositions preventing colour transfer (bleeding), agents with"anti-grey formulations", agents to facilitate ironing, agents with special fragrance release properties, agents with improved dirt dissolution properties and/or that prevent re-soiling, antibacterial agents, UV protection agents, colour fresheners, etc. may for example be formulated. Some examples are discussed in more detail hereinafter.

Since textile fabrics, in particular of rayon, viscose stable fibre, cotton and their mixtures may have a tendency to crease since the individual fibres are sensitive to bending, folding, compression and squeezing transverse to the fibre direction, the agents according to the invention

may contain synthetic anti-crease agents. These include for example synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol esters, fatty acid alkylol amides or fatty alcohols, which are generally reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

In order to control microorganisms the agents according to the invention may contain antimicrobial active constituents. In this connection a distinction is made, depending on antimicrobial spectrum and action mechanism, between bacteriostatics and bacteriocides, fungistatics and fungicides, etc. Important substances from these groups include for example benzalkonium chlorides, alkylaryl sulfonates, halogenated phenols and phenol mercury acetate, though the use of these compounds in the agents according to the invention may be dispensed with completely.

In order to prevent undesirable changes to the agents and/or to the treated textiles caused by the action of oxygen and other oxidative processes, the agents may contain antioxidants. This class of compounds includes for example substituted phenols, hydroquinones, pyrocatechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

An increased wear, comfort can also be achieved by the additional use of antistatics, which are added to the agents according to the invention. Antistatics increase the surface conductivity and thus permit an improved discharge of static charges that have built up. External antistatics are as a rule substances with at least one

hydrophilic molecule ligand and impart a more or less hygroscopic film to the surfaces. These for the most part interface-active antistatics can be subdivided into nitrogen-containing antistatics (amines, amides, quaternary ammonium compounds), phosphorus-containing antistatics (phosphoric acid esters) and sulfur-containing antistatics (alkyl sulfonates, alkyl sulfates). Lauryl (and/or stearyl) dimethylbenzylammonium chlorides are suitable as antistatics for textiles and/or as an additive to detergents, a softening effect in addition being achieved.

In order to improve the water absorption capacity, the rewettability of the treated textiles and to facilitate ironing of the treated textiles, the agents according to the invention may for example contain silicone derivatives.

These improve in addition the rinsing out behaviour of the agents according to the invention due to their foaminhibiting properties. Preferred silicone derivatives are for example polydialkyl siloxanes or alkylaryl siloxanes, in which the alkyl groups contain 1 to 5 C atoms and are wholly or partially fluorinated. Preferred silicones are polydimethyl siloxanes, which may optionally be derivatised and are then amino-functional or quaternised, and/or contain Si-OH-, Si-H-and/or Si-Cl bonds. The viscosities of the preferred silicones at 25 C are in the range between 100 and 100,000 centistokes, in which connection the silicones may be employed in amounts between 0.2 and 5 wt. % referred to the overall agent.

Finally, the agents according to the invention may also contain UV absorbers that bond to the treated textiles and improve the light stability of the fibres. Compounds that exhibit these desired properties include for example the

compounds and derivatives of benzophenone with substituents in the 2-position and/or 4-position, which are active through radiationless deactivation. Furthermore substituted benzotriazoles, acrylates phenyl-substituted in the 3-position (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes, as well as natural substances such as umbelliferone and endogenic urocanic acid are also suitable.

After they have been filled the injection-moulded and filled hollow bodies are rotated further on the rotary table about a vertical axis and passed to a sealing unit.

The closure of the filled hollow bodies is preferably carried out by sealing with a water-soluble film, though other process variants, for example closure by means of a plug, sealing or adhesion with a three-dimensional moulded body (for example a further filled and closed hollow body), the application of a solidifying cover layer, etc. may also be employed. Preferred processes are those in which the injection-moulded and filled hollow bodies are closed by sealing with a water-soluble film.

Such films are known from the prior art and are obtained for example from the group comprising (acetalised) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin and mixtures thereof.

Polyvinyl alcohols have already been described in detail above as materials for the injection-moulded hollow bodies.

Polyvinylpyrrolidones, abbreviated as PVPs, can be represented by the general formula

PVPs are produced by free-radical polymerisation of 1vinylpyrrolidone. Commercially available PVPs have molecular weights in the range from ca. 2500 to 750,000 g/mol and are available as white, hygroscopic powders or as aqueous solutions.

Polyethylene oxides, abbreviated as PEOXs, are polyalkylene glycols of the general formula H- [0-CH2-CH2] n-OH which may be produced industrially by base-catalysed polyaddition of ethylene oxide (oxiran) in systems generally containing minor amounts of water, using ethylene glycol as starter molecule. They have molecular weights in the range from ca. 200 to 5,000, 000 g/mole, corresponding to degrees of polymerisation n of ca. 5 to > 100,000.

Polyethylene oxides have an extremely low concentration of reactive hydroxy terminal groups and exhibit only weak glycol properties.

Gelatin is a polypeptide (molecular weight ca. 15,000 to 250,000 g/mole), which is principally obtained by

4 hydrolysis of collagen contained in animal skin and bone, under acid or alkaline conditions. The amino acid

composition of the gelatin corresponds largely to that of the collagen from which it has been obtained, and varies depending on its origin. The use of gelatin as a watersoluble encasing material is extremely widespread, especially in pharmacy, in the form of hard gelatin or soft gelatin capsules. Gelatin is used only to a minor extent in the form of films on account of its high price compared to the aforementioned polymers.

Also preferred within the scope of the present invention are processes in which the injection-moulded and filled hollow bodies are closed with a water-soluble film of at least one polymer from the group comprising starch and starch derivatives, cellulose and cellulose derivatives, in particular methylcellulose and mixtures thereof.

Starch is a homoglycan, the glucose units being a-glycosidically coupled. Starch is built up from two components of different molecular weights. Starch contains 20-30% straight-chain amylose (molecular weight ca. 50,000 to 150,000) and 70-80% branched-chain amylopectin (molecular weight ca. 300,000 to 2,000, 000), in addition to minor amounts of lipids, phosphoric acid and cations.

Whereas amylose, on account of the bonding in the 1,4position, forms long, helical, intertwined chains containing about 300-1200 glucose molecules, the amylopectin chain branches after on average 25 glucose structural units due to 1,6-bonding to form a dentriticlike structure containing about 1500-12000 glucose molecules. In addition to pure starch, starch derivatives that can be obtained from starch by polymer-like reactions are also suitable within the scope of the present invention for the production of water-soluble sachets. Such

chemically modified starches include for example products obtained from esterifications and/or etherifications, in which hydroxy hydrogen atoms have been replaced. However starches in which the hydroxy groups have been replaced by functional groups that are not bound via an oxygen atom can be used as starch derivatives. This group of starch derivatives includes for example alkali starches, carboxymethyl starch (CMS), starch esters and ethers, as well as aminostarches.

Pure cellulose has the empirical formula (C6H1OOS) n and in formal terms is a -1, 4-polyacetal of cellobiose, which in turn is built up from two molecules of glucose. Suitable celluloses consist of ca. 500 to 5000 glucose units and accordingly have average molecular weights of 50,000 to 500, OpO. As cellulose-based disintegration agents there may also be used within the scope of the present invention cellulose derivatives that can be obtained by polymer-like reactions from cellulose. Such chemically modified celluloses include for example products of esterifications and/or etherifications in which hydroxy hydrogen atoms have been replaced. However, celluloses in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom can also be used as cellulose derivatives. Such cellulose derivatives include for example alkali celluloses, carboxymethyl celluloses (CMC), cellulose esters and ethers, as well as aminocelluloses.

Preferred closure films consist of a polymer having a molecular weight between 5000 and 500,000 Daltons, preferably between 7500 and 250,000 Daltons, and in particular between 10,000 and 100,000 Daltons. The watersoluble film that forms the closure preferably has a

thickness of 1 to 150 Jm, preferably of 2 to 100 pm, particularly preferably of 5 to 75 jum and especially of 10 to 50 pun.

The closure of the injection-moulded and filled hollow bodies may alternatively also be effected with other closure parts. It is for example possible and preferred to produce further injection-moulded parts (preferably on separate injection moulding machines) and to feed these to the rotary-table automatic injection moulding machine for the closure of the filled hollow bodies. These further injection-moulded parts (hereinafter also called closure parts) may be flat, i. e. may exist as"closure plates", but they may however also have a spatial shape in which they themselves are capable of accommodating the volume. In this connection processes according to the invention are preferred in which the injection-moulded and filled hollow bodies are closed by applying an upper closure part capable of accommodating the volume.

This closure part may together with the opening for filling the already filled hollow body either be mounted on the latter, leading to the formation of a larger closed hollow space in which the previously poured-in detergent, rinsing agent or cleaning agent composition can move as long as it is flowable or movable. It is however also possible to form a closure part that can itself be refilled. In this way"multilevel"filled individually portioned detergent, rinsing agent or cleaning agent compositions can be produced if the freely accessible hollow space of the closure part is subsequently refilled and then closed.

This principle can obviously also be extended to three,

four, five, six, seven, eight, nine, etc. closure parts capable of accommodating the volume. Particularly preferred in this connection are processes in which the upper closure parts capable of accommodating the volume are fabricated on a separate injection moulding machine.

Further preferred processes are characterised in that the filled and closed hollow bodies are filled with one or more further detergent, rinsing agent or cleaning agent compositions and are then closed.

The closure of the filled hollow bodies may also be effected by sticking on a film or another injection-moulded part (see above), though other closure mechanisms may also be chosen. For example it is possible by means of a snapfit, notch, bayonet or insert connection to mount upper closure parts capable of accommodating the volume, on the filled hollow bodies. As further mechanisms for joining the injection-moulded parts to one another there may for example be mentioned plasma welding, adhesion of the edge/flange with adhesives or hotmelts, wetting the edge/flange with water or polymer solutions, etc.

With the"multilevel"and multiply filled portions, the various fillings can be released at different times if the wall thickness and/or the material composition (for example the degree of hydrolysis of the polyvinyl alcohol) and/or the proportion of auxiliary substances (plasticiser and/or cellulose ether content) are varied.

Claims

Claims 1. A process for the production of filled hollow bodies, in which water-soluble hollow bodies are produced by injection moulding, filled with a filler composition, and then sealed, wherein a) the tool half of an injection mould accommodating the moulding is part of a rotary table which is rotatable about a vertical axis; b) one or more mouldings is/are injection-moulded in the injection mould, and the upper mould half of the injection mould is then removed from the moulding (s); c) the moulding (s) is/are moved away from the injection moulding nozzle (s) by rotating the rotary table and is/are filled; d) the moulding (s) is/are sealed after having been filled.
2., The process according to claim 1, wherein the tool half of the injection mould accommodating the moulding makes up 40 to 180 , preferably 500 to 120 and in particular 600 to 900, of the rotary table.
3. The process according to claims 1 or 2, wherein 1 to 100, preferably 2 to 60 and in particular 10 to 30 mouldings, are injection-moulded in the injection mould.
4. The process according to any one of claims 1 to 3, wherein the injection pressure in the injection moulding is 1.5 x 107 Pa to 5 x 108 Pa, preferably 2.5 x 107 Pa to 4 x 108 Pa, particularly preferably 5 x 107 Pa

<Desc/Clms Page number 85>

to 2.5 x 108 Pa, and especially 1 x 108 Pa to 1. 5 x 108 Pa.
5. The process according to any one of claims 1 to 4, wherein the injection moulds are coated, the thickness of the coating preferably being 0.5 to 600 um, particularly preferably 1 to 100 m and especially 1 to 20 m.
6. The process according to any one of claims 1 to 5, wherein the injection moulding composition comprises one or more materials selected from (optionally acetalised) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives and their mixtures, particularly preferably (optionally acetalised) polyvinyl alcohol (PVAL).
7. The process according to claim 6, wherein the injection moulding composition comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and especially 82 to 88 mol%.
8. The process according to claims 6 or 7, wherein the injection moulding composition comprises a polyvinyl alcohol whose molecular weight is from 10,000 to

100, 000 mol-1, preferably from 11, 000 to 90, 000 mol-1, particularly preferably from 12, 000 to 80, 000 gmol' and especially from 13, 000 to 70, 000 mol-1.

<Desc/Clms Page number 86>
9. The process according to any one of claims 6 to 8, wherein the injection moulding composition contains the aforementioned polymers in amounts of at least 50 wt. %, preferably of at least 70 wt. %, particularly preferably of at least 80 wt. % and especially of at least 90 wt. %, in each case referred to the weight of the injection moulding composition.
10. The process according to any one of claims 1 to 9, wherein the wall thickness of the injection-moulded hollow bodies is 200 to 1500 urn, preferably 300 to 1000 am and in particular 400 to 600 urn.
11. The process according to any one of claims 1 to 10 ; wherein the injection-moulded hollow bodies are filled, after rotating the rotary table, with one or more liquid detergent, rinsing agent or cleaning agent compositions.
12. The process according to claim 11, wherein the injection-moulded and filled hollow bodies are closed by sealing with a water-soluble film.
13. The process according to claim 11, wherein the injection-moulded and filled hollow bodies are closed by application of an upper closure part capable of accommodating the volume.
14. The process according to claim 13, wherein the upper closure parts capable of accommodating the volume are fabricated on a separate injection moulding machine.

<Desc/Clms Page number 87>
15. The process according to any one of claims 12 to 14, wherein the filled and closed hollow bodies are filled with one or more further detergent, rinsing agent or cleaning agent compositions and then closed.