WO2004087855A1

WO2004087855A1 - Bleach activator compound

Info

Publication number: WO2004087855A1
Application number: PCT/EP2004/002890
Authority: WO
Inventors: Maren Jekel; Ulrich Pegelow; Peter Schmiedel; Georg Assmann; Heike Schirmer-Ditze
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2003-03-31
Filing date: 2004-03-19
Publication date: 2004-10-14
Also published as: DE10314441A1

Abstract

Disclosed are compounds comprising i) at least one cationic nitrile of formula (I), wherein R1 represents -H, -CH3, a C2-24 alkyl radical or alkenyl radical, a substituted C2-24 alkyl radical or alkenyl radical containing at least one substituent from the group encompassing -CI, -Br, -OH, -NH2, -CN, an alkyl radical or alkenylaryl radical containing a C1-24 alkyl group, or a substituted alkyl radical or alkenylaryl radical containing a C1-24 alkyl group and at least one additional substituent on the aromatic ring, R2 and R3 are independently selected among -CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, and -(CH2CH2-O)nH, n being equal to 1, 2, 3, 4, 5, or 6 and X representing an anion, and ii) at least one polymer that is provided with at least one monomeric component having an acid functionality. The moiety of the polymer ranges between 5 and 99.99 percent by weight relative to the total weight of the compound. The inventive compounds are characterized by an increased shelf life.

Description

"Bleach activator compound"

The present invention relates to so-called nitrile quats, bleach activators, which are used, for example, in washing or cleaning agents. In particular, the invention relates to a special bleach activator compound containing nitrate, which is particularly suitable for use in automatic dishwashing detergents.

Detergent compositions for automatic dishwashing are described in a variety of forms and are represented on the market. Of particular importance are powdered or granular cleaners, liquids, gels etc. or compositions individually packaged in containers made of water-soluble film. Detergent tablets for machine dishwashing are of the greatest importance in the market because they are compact and easy to use.

To achieve an improved bleaching effect when cleaning at temperatures of 60 ° C and below, these cleaning agents can contain bleach activators. Compounds which release aliphatic peroxocarboxylic acids under perhydrolysis conditions, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), are used as bleach activators. Cleaning agents that contain TAED are the subject of numerous prior art publications.

Another group of bleach activators, the nitrile quat type bleach activators, has also been extensively described in the prior art. For example, European patent application EP 303 520 (Kao Corp.) discloses bleaching compositions which contain a peroxide and a peracid precursor which contain at least one group N ⁺ -CH ₂ -CN or one N ⁺ (CH ₂ CN) ₂ .

Cationic nitriles of the general formula R ¹ R ¹¹ R ¹¹¹ N ⁺ CR ¹ R ² -CN and their use as bleach activators are described in European patent application EP 464880 (Unilever).

European patent application EP 458 396 (Unilever) also describes bleaching agent compositions which contain a peroxy bleaching agent and a peracid precursor with at least one group N ⁺ -CH ₂ -CN or N ⁺ (CH ₂ CN) ₂ . A problem with the use of nitrile quats as bleach activators in detergents or cleaning agents is their poor storage stability. In an alkaline environment, these bleach activators rapidly decompose, especially when water is ingress. This problem can be reduced, for example, by the separate preparation of the bleach activators or by the application of protective coating layers, but such a procedure limits the freedom of formulation in the production of the nitrile quatein-containing cleaning agents and also leads to the use of additional coating materials which generally do not have a washing or cleaning activity Have an effect and thus increase the total weight of a dosing unit without any additional effect.

The present invention was based on the object of providing bidding forms for washing or cleaning agents containing nitrile quatium, in particular machine dishwashing detergents, which do not have the stability problems mentioned above. In particular, such forms of assembly should be provided that are stable in storage without the use of coating materials. Alternatively, such substances should be used as coating materials that are already an integral part of the formulation and therefore do not further increase the number of formulation components.

It has now been found that the long-term storage-stable incorporation of nitrile quats in washing or cleaning agents, in particular cleaning agents for automatic dishwashing, succeeds when the nitrile quats in compounded form in the presence of a polymer which has at least one acid functionality, that is to say has at least one monomer which is characterized by an acid functionality.

A first subject of the present application is therefore a compound comprising i) at least one cationic nitrile of the formula (I)

R ¹

R ² -N ⁽⁺⁾ - (CH ₂ ) -CN X ^(_) (I),

R ³

in which R ^{1 represents} -H, -CH ₃ , a C ₂ - ₂₄ alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical with at least one substituent from the group -CI, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a Cι. ₂₄ alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ³ are independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ - CH ₃ , -CH (CH ₃ ) -CH _3l -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, - CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -0) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion, and ii) at least one polymer which has at least one monomeric building block with an acid functionality, thereby characterized in that the weight fraction of the polymer in the total weight of the

Compounds is between 5 and 99.99% by weight.

General formula (I) includes a large number of cationic nitriles which can be used in the context of the present invention. The compounds according to the invention particularly advantageously contain cationic nitriles in which R ^{1 is} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n -Hexadecyl or n-octadecyl radical. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, where one or both radicals can advantageously also be a cyanomethylene radical. In the table below, preferred cationic nitriles of the formula (I) are characterized by their radicals R ¹ , R ² and R ³ :

For reasons of easier synthesis, compounds are preferred in which the radicals R to R ^{3 are} identical, for example (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO- CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" . A preferred subject of the present application is therefore a compound according to the invention, which is characterized in that it is a cationic nitrile of the formula (I) as a cationic nitrile of the formula (la) R ⁴

R ⁵ -N ⁽⁺⁾ - (CH ₂ ) -CN X ^H (la),

R ⁶

contains, in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ^{4 can} additionally be -H and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ^{( +)} CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{" are} particularly preferred.

Compounds according to the invention which contain a cationic nitrile of the formula (I), preferably of the formula (Ia), particularly preferably of the formula (CH ₃ ) ₃ N ^(+> CH ₂ -CN X ^" , where X ^{" is} an anion which from the group chloride, bromide, iodide, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate or xylene sulfonate or mixtures thereof are particularly preferred.

Of course, a compound according to the invention can contain several cationic nitriles of the structure described above. Compounds according to the invention which contain two, three, four or five different cationic nitriles of the formula (I) are technically feasible and preferred in the context of the present application.

The proportion by weight of the cationic nitriles in the total weight of the compound according to the invention can vary, the proportion by weight of the cationic nitrile being up to 60% by weight. In the context of the present application, however, those compounds according to the invention are preferred which have a weight fraction of cationic nitrile of between 0.01 to 40% by weight, preferably from 0.1 to 32% by weight, preferably from 0.2 to 28% by weight. -%, particularly preferably from 0.5 to 24 wt .-% and in particular from 1, 0 to 20 wt .-%, each based on the total weight of the compound.

In addition to one or more cationic nitrile (s), the compounds according to the invention furthermore contain at least one polymer which has at least one acid functionality. The proportion by weight of the polymer with the acid functionality is, based on the total weight, preferably more than 7% by weight, preferably more than 14% by weight, particularly preferably more than 20% by weight, very particularly preferably more than 25% by weight. -% and in particular more than 29 wt .-%. Compounds according to the invention particularly preferably have a proportion by weight of polymer between 15 and 99% by weight, preferably between 25 and 97% by weight, preferably between 35 and 95% by weight, particularly preferably between 45 and 92% by weight and in particular between 50 and 89% by weight .-%, each based on the total weight of the compound.

In principle, all polymers containing acid groups can be used as polymers. The polymers can be in non-neutralized, partially neutralized, or fully neutralized form. However, the use of partially neutralized or completely neutralized acids is preferred. Preferred polymers have at least one monomer from the group of the carboxylic acids and / or the sulfonic acids and / or the phosphonic acids.

The group of polymers which have at least one monomer from the group of the carboxylic acids includes, for example, the polycarboxylates, but also acid-modified polysaccharides such as carboxymethyl cellulose.

Polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins are also particularly suitable as polymers. Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

In the context of the present application, the compounds according to the invention particularly preferably comprise polymers which, as a monomer, comprise an ethylenically unsaturated, monomeric carboxylic acid of the general formula II

R ¹ (R ² ) C = C (R ³ ) COOH (II);

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

Further preferred polymers which contain at least one monomer from the group of the carboxylic acids are the amphoteric copolymers, which, as a monomer unit, in addition to an ethylenically unsaturated carboxylic acid, also the at least one ethylenically unsaturated monomer unit of the general formula III R ¹ (R ² ) C = C (R ³ ) R ⁴ (III),

in which R ¹ to R ⁴ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above, a heteroatomic group with at least one positively ended group, a quaternized nitrogen atom or at least one amine group with a positive charge in the pH range between 2 and 11 or for -COOH or -COOR ⁵ , where R ^{5 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Examples of the aforementioned (non-polymerized) monomer units of Formula III are diallylamine, methyldiallylamine, dimethyldimethylammonium salts,

Acrylamidopropyl (trimethyl) ammonium salts (R ¹ , R ² , and R ³ , = H, R ⁴ = C (0) NH (CH ₂ ) ₂ N ⁺ (CH ₃ ) ₃ X ^" ), methacrylamidopropyl (trimethyl) ammonium salts (R ¹ and R ² = H, R ³ = CH ₃ H, R ⁴ = C (0) NH (CH ₂ ) 2N ⁺ (CH ₃ ) 3 X ^" ).

Particularly preferred amphoteric polymers contain, as monomer units, derivatives of dialiylamine, in particular dimethyldiallylammonium salt and / or

Methacryamidopropyl (trimethyl) ammonium salt, preferably in the form of chloride, bromide, iodide, hydroxide, phosphate, sulfate, hydrosulfate, ethyl sulffasts, methyl sulfate, mesylate, tosylate, formate or acetate in combination with monomer units from the group of ethylenically unsaturated carboxylic acids.

Particularly preferred polymers contain at least one monomer from the group of the sulfonic acids.

Copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers can be used with particular preference as polymers containing sulfonic acid groups.

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

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

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

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula V

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (V),

in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas Va, Vb and / or Vc,

H ₂ C = CH-X-S0 ₃ H (Va),

H ₂ C = C (CH ₃ ) -X-S0 ₃ H (Vb),

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (Vc),

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _π - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH- CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₂ CH ₃ ) in formula Va), 2-acrylamido-2-propanesulfonic acid (X = -C ( 0) NH-C (CH ₃ ) ₂ in formula Va), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH- CH (CH ₃ ) CH ₂ - in formula Va), 2-methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₃ ) CH ₂ - in formula Vb), 3-methacrylamido -2-hydroxy-propanesulfonic acid (X = -C (0) NH- CH ₂ CH (OH) CH ₂ - in formula Vb), allylsulfonic acid (X = CH ₂ in formula Va), methallylsulfonic acid (X = CH ₂ in formula Vb ), Allyloxybenzenesulfonic acid (X = -CH ₂ -0-C ₆ H ₄ - in formula Va), methallyloxybenzenesulfonic acid (X = -CH ₂ -0-C ₆ H ₄ - in formula Vlb), 2-hydroxy-3- (2 - propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid (X = CH ₂ in formula Vb), styrene sulfonic acid (X = C ₆ H ₄ in formula Va), vinyl sulfonic acid (X not present in formula Va), 3-sulfopropyl acrylate (X = -C (0) NH-CH ₂ CH ₂ CH ₂ - in formula Va), 3-sulfopropyl methacrylate (X = - C (0) NH-CH ₂ CH ₂ CH ₂ - in formula VIb), sulfomethacrylamide (X = -C (0) NH- in formula Vb), sulfomethyl methacrylamide (X = -C (0) NH-CH ₂ - in formula Vb) and water-soluble salts of the acids mentioned.

Other suitable ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The group iii) monomer content of the polymers used according to the invention is preferably less than 20% by weight, based on the polymer. Polymers to be used with particular preference consist only of monomers of groups i) and ii).

In summary, copolymers are made of

i) unsaturated carboxylic acids of formula IV.

R (R ² ) C = C (R ³ ) COOH (IV),

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

ii) Monomers of the formula V containing sulfonic acid groups

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (V),

in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally available spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C ( 0) -NH-CH (CH ₂ CH ₃ ) -

iü) optionally further ionic or nonionic monomers

particularly preferred ingredients of the compounds according to the invention.

Particularly preferred copolymers consist of

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

ii) one or more monomers of the formulas XVI la, XVI Ib and / or XVI Ic containing sulfonic acid group:

H ₂ C = CH-X-S0 ₃ H (Va),

H ₂ C = C (CH ₃ ) -X-S0 ₃ H (Vb),

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (Vc),

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH- CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers.

The copolymers can contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii). Particularly preferred polymers have certain structural units, which are described below.

For example, compounds according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula VI - [CH ₂ -CHC00H] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VI),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -0- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the washing or cleaning agent compositions according to the invention is also preferred and is characterized in that the preferred compounds contain one or more copolymers which have structural units of the formula X.

- [CH ₂ -C (CH ₃ ) C00H] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VII),

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Compounds according to the invention which contain one or more copolymers which have structural units of the formula VIII

- [CH ₂ -CHC00H] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (VIII),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -0- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are also preferred, a preferred embodiment of the present invention, just like compounds are preferred, which are characterized in that they contain one or more copolymers having structural units of the formula IX - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] p- (IX),

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, washing or cleaning agent compositions which are preferred according to the invention and which are characterized in that they contain one or more copolymers, the structural units of the formula X, are obtained

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (X),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -0- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is preferred, and compounds which are characterized in that they contain one or more copolymers, the structural units of the formula XI

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (XI),

In summary, compounds according to the invention which contain one or more copolymers which have structural units of the formein VI and / or VII and / or VIII and / or IX and / or X and / or XI are preferred - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VI),

- [CH ₂ -C (CH ₃ ) C00H] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VII),

- [CH ₂ -CHC00H] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] p- (VIII),

- [CH ₂ -C (CH ₃ ) C00H] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (IX),

- [H00CCH-CHC00H] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (X),

- [H00CCH-CHC00H] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (XI),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -O- (C _β H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is preferred.

All or part of the sulfonic acid groups in the polymers can be in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. Corresponding compounds which are characterized in that the sulfonic acid groups in the copolymer are partially or completely neutralized are preferred according to the invention.

The monomer distribution of the copolymers used in the compounds according to the invention is preferably 5 to 95% by weight i) or ii), particularly preferably 50 to 90% by weight, in the case of copolymers which contain only monomers from groups i) and ii). % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

In the case of terpolymers, those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred ,

The molar mass of the sulfo copolymers described above used in the compounds according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Preferred washing or

Detergent compositions are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol ^"1 , preferably from 4000 to 25,000 gmol ^{" 1} and in particular from 5000 to 15,000 gmol ^"1 . Further particularly preferred polymers contain at least one monomer from the group of the carboxylic acids and furthermore at least one monomer from the group of the phosphonic acids.

The proportion by weight of the cationic nitrile in the total weight of the compounds according to the invention is preferably less than the proportion by weight of the polymer. In a preferred embodiment of the present invention, the ratio of the proportion by weight of the cationic nitrile to the proportion by weight of the polymer is between 1: 1 and 1:40, preferably between 1: 1, 5 and 1:36, preferably between 1: 2 and 1:32, particularly preferably between 1: 3 and 1:28 and in particular between 1: 4 and 1:24.

It is particularly preferred if the compounds according to the invention are in a coarser form. Preferred compounds according to the invention are characterized in that they contain at least 50% by weight, preferably at least 60% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight of the Particles of the compound have a particle size above 0.2 mm, preferably above 0.3 mm and particularly preferably above 0.4 mm.

The proportion of particles with sizes above 200 μm should preferably be more than 90% by weight, based on the total number of particles in the compound. In order to have an advantageous homogeneous particle size distribution, the compounds according to the invention should in particular be free of too fine or dust components, that is to say particularly preferably contain no particles of less than 0.2 mm diameter. Particularly preferred compounds are substantially free of particles with sizes below 0.2 mm. In the context of the present invention, “substantially free” means contents below 2% by weight, preferably below 1% by weight and in particular below 0.5% by weight, in each case based on the totality of the particles.

In a further particularly preferred embodiment, the particles of the compound according to the invention have an average particle size above 400 μm, preferably above 500 μm, particularly preferably above 600 μm and in particular above 700 μm.

The bulk density of compounds preferred according to the invention is between 0.8 and 2.0 g / cm ³ , preferably between 0.9 and 1.9 g / cm ³ , particularly preferably between 1.0 and 1.8 g / cm ³ and in particular between 1, 2 and 1, 8 g / cm ³ .

The water content of compounds preferred according to the invention is low and is below 10% by weight, preferably below 10% by weight, preferably below 9% by weight, particularly preferably between 1 and 9% by weight and in particular between 3 and 9% by weight. -%. This low water content has a particularly advantageous effect on the storage stability of the compounds. Compounds preferred according to the invention are characterized in that the compound has a layer structure of a polymer-containing core, a nitrile-containing first layer and optionally a further polymer-containing second layer.

The compounds according to the invention are distinguished by an improved storage stability compared to the prior art, in particular in alkaline environments. To further improve the storage stability, the compounds according to the invention can additionally be provided with a coating, preferably with a coating made of a polymeric material. Preferred compounds according to the invention are accordingly characterized in that the particles of the compound have a coating, the coating material being selected at least in part from a polymer or polymer mixture

a) water-soluble nonionic polymers from the group of

a1) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers a4) polyvinyl alcohol a5) polyalkylene glycol, in particular polyethylene glycol and / or polypropylene glycol

b) water-soluble amphoteric polymers from the group of

b1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalky | (meth) acrylic acid -

Copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate alkyl methacrylate

Copolymers b8) copolymers from b8i) unsaturated carboxylic acids bδii) cationically derivatized unsaturated carboxylic acids bδiii) optionally further ionic or nonionic monomers c) water-soluble zwitterionic polymers from the group of

d) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their

Alkali and ammonium salts c3) methacroylethyl betaine / methacrylate copolymers

d) water-soluble anionic polymers from the group of

d1) vinyl acetate-crotonic acid copolymers d2) vinylpyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid or acrylic acid Polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the non-ionic type, dδii) at least one monomer of the ionic type, dδiii) of polyethylene glycol and d5iv) a crosslinked d6) by copolymerization of at least one Monomers of each of the following three

Copolymers obtained in groups: dδi) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, dθii) unsaturated carboxylic acids, dδiii) esters of long-chain carboxylic acids and unsaturated alcohols and / or

Esters of the carboxylic acids of group d6ii) with saturated or unsaturated, linear or branched C ₈ ι ₈ alcohol d7) terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester d8) tetra- and pentapolymers of dδi) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate dδiii) branched allyl or methallyl esters dδiv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts d10) terpolymers from vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position

e) water-soluble cationic polymers from the group of

e1) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and

Amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate e6) vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol eδ) under the INCI names Polyquaternium 2, polyquaternium 2

Polyquaternium 1δ and Polyquaternium 27 indicated polymers.

A preferred method for coating the cationic nitriles or for producing the nitrile compounds according to the invention is the fluidized bed method, in which bleach activators of the formula (I) are present in solid, in particular powdery form, optionally in admixture with binder and / or solid filler or as Prefabricated granules, with simultaneous drying in a fluidized bed apparatus, sprayed with an acidic aqueous coating solution.

Alternatively, a polymer-containing primary grain can also be placed in a fluidized bed system and sprayed with a nitrile quat solution and / or a polymer solution. The spraying with the two solutions can be carried out at the same time but also at different times, with a shell-like structure of the granules being achieved when the different solutions are sprayed at different times. This latter procedure is particularly preferred in the context of the present application.

Of course, all devices with which coatings can be produced from an aqueous solution are also suitable for applying the coating to the cationic nitriles or nitrile compounds. For example, larger objects can be sprayed directly with spray nozzles, preferably two-substance nozzles, with a simultaneous or subsequent one Dried to be sprayed. Smaller objects can be sprayed in drum coaters, such as those commonly used in pharmacy, or coating pans.

The proportion by weight of the water-soluble or water-dispersible coating to the total weight of the particulate coated cationic nitrile / nitriles in the detergent or cleaning agent compositions according to the invention is preferably 0.03 to 80% by weight, particularly preferably 1.2 to 60% by weight and in particular 1, 6 to 40% by weight.

In addition to the polymers mentioned, inorganic salts are also suitable for coating the compounds according to the invention. The coating material is preferably selected at least in part from the group of water-soluble or water-dispersible inorganic salts, preferably from the group of sulfates, chlorides, phosphates and phosphonates, with in particular the alkali and alkaline earth salts and here in turn the sodium, potassium and / or Magnesium salts are particularly preferred. Acidic salts, which are optionally used in admixture with polymers, are particularly suitable.

Finally, a third group of preferred coating materials are meltable substances or substance mixtures, in particular substances or substance mixtures with a melting point above 40 ° C., such as fats and / or triglycerides and / or fatty acids and / or fatty alcohols and / or waxes and / or parrafins and / or polyalkylene glycols , preferably polyethylene glycol.

Fat (s) or triglyceride (s) is the name for compounds of glycerol in which the three hydroxyl groups of the glycerol are esterified by carboxylic acids. The naturally occurring fats are triglycerides, which usually contain different fatty acids in the same glycerin molecule. By saponification of the fats and subsequent esterification or reaction with acyl chlorides, synthetic triglycerides in which only one fatty acid is bound are also accessible (e.g. tripalmitin, triolein or tristearin). Natural and / or synthetic fats and / or mixtures of the two are preferred as coating material or part of the coating of cationic nitriles in the context of the present invention.

Aliphatic saturated or unsaturated, carboxylic acids with a branched or unbranched carbon chain are referred to as fatty acids in the present application. A large number of production methods exist for the production of the fatty acids. While the lower fatty acids are mostly based on oxidative processes based on alcohols and / or aldehydes and aliphatic or acyclic hydrocarbons, the higher ones are homologous Most of the time, the easiest way to do this is to saponify natural fats. Advances in the field of transgenic plants mean that there are almost unlimited possibilities for varying the fatty acid spectrum in the storage fats of oil plants. In the context of the present invention, preferred fatty acids have a melting point which allows these fats to be processed as coating material. Preferred coating materials or coating components are therefore capric acid and / or undecanoic acid and / or lauric acid and / or tridecanoic acid and / or myristic acid and / or pentadecanoic acid and / or palmitic acid and / or margaric acid and / or stearic acid and / or nonadecanoic acid and / or arachic acid and / or Erucic acid and / or elaeosteraric acid.

Fatty alcohol is a collective name for the linear, saturated or unsaturated primary alcohols with 6 to 22 carbon atoms that can be obtained by reducing the triglycerides, fatty acids or fatty acid esters. The fatty alcohols can be saturated or unsaturated depending on the manufacturing process. Myristyl alcohol and / or 1-pentadecanol and / or cetyl alcohol and / or 1-heptadecanl and / or stearyl alcohol and / or erucyl alcohol and / or 1-nonadecanol and / or arachidyl alcohol and / or 1-heneicosanol and / or behenyl alcohol and / or erucyl alcohol and / or brassidyl alcohol are preferred components of the coating of cationic nitriles in the context of the present invention.

It has also proven to be advantageous if the washing or cleaning agent compositions contain waxes as the coating material or as part of the coating. Preferred waxes have a melting range that is between approximately 45 ° C. and approximately 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. Waxes with such a melting range are on the one hand dimensionally stable at room temperature, but melt at temperatures of 30 ° C. to 90 ° C. which are typical for machine dishwashing and are therefore more readily water-dispersible at these temperatures.

'Waxing' is understood to mean a number of natural or artificially obtained substances which generally melt above 40 ° C without decomposition and which are relatively low-viscosity and non-stringy just above the melting point. They have a strongly temperature-dependent consistency and solubility.

The waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes. The natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

The chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated softening point requirements can also be used as meltable or softenable substances for the masses hardening by cooling. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or semi-synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ^® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Shellac, for example shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used according to the invention as a coating material.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ^® (Pamentier & Co).

Further advantageous constituents of the matrix of the above-mentioned coatings are wax alcohols, ie fatty alcohols with approx. 24-36 carbon atoms, which are the main constituent of many natural waxes in the form of wax esters of higher molecular weight fatty acids (wax acids). Examples of preferred wax alcohols are lignoceryl alcohol, ceryl alcohol, myricyl alcohol or melissyl alcohol. In summary, compounds according to the invention are preferred in which the particles of the compound have a coating, the coating material being selected at least in part from the group of meltable substances, preferably from the group of fats and / or triglycerides and / or fatty acids and / or fatty alcohols and / or Waxes and / or parrafins, and / or from the group of anionic surfactants.

In addition to the above-mentioned ingredients, the compounds according to the invention can have further washing or cleaning substances. Compounds preferred according to the invention are characterized in that the particles of the compound contain at least one further substance usually contained in washing or cleaning agents, preferably a substance from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, electrolytes, pH regulators, fragrances , perfume carriers, dyes, hydrotropes, foam inhibitors, antiredeposition agents, optical brighteners, graying inhibitors, shrink preventatives, anticrease agents, dye transfer inhibitors, antimicrobial active ingredients, germicides, fungicides, antioxidants, corrosion inhibitors, antistats, repellency and impregnation agents, swelling and antislip agents, nonaqueous solvents, plasticizers, Softener, protein hydrolyzate, and UV absorber, particularly preferably from the group of plasticizers, dyes or fragrances. For a detailed description, reference is made to the following explanations in order to avoid repetitions.

The present application also relates to detergent or cleaning composition which contain at least one compound according to the invention.

The proportion by weight of the compound according to the invention in the total weight of the detergent or cleaning agent composition is preferably between 0.01 and 30% by weight, preferably between 0.05 and 27% by weight, preferably between 0.1 and 24% by weight, particularly is preferably between 0.2 and 21% by weight and in particular between 0.4 and 1δ% by weight.

In addition to the compounds according to the invention, preferred washing or cleaning agent compositions further comprise at least one washing or cleaning-active substance from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, electrolytes, pH regulators, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, Anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, phobing and Impregnating agent, swelling and anti-slip agent, non-aqueous solvent, plasticizer, fabric softener, protein hydrolyzate, and UV absorber.

Detergent or cleaning agent compositions preferred in the context of the present invention are characterized in that these compositions comprise builders in amounts of from 1 to 100% by weight, preferably from 5 to 95% by weight, particularly preferably from 10 to 90% by weight and contains in particular from 20 to 85% by weight, in each case based on the weight of the detergent or cleaning composition.

The washing or cleaning agent compositions according to the invention can contain all of the builders usually used in washing or cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and — where there are no ecological prejudices against their use — also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSixO ^ -n Η ₂ 0, where M is 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 2, 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ 0 ₅ "yH ₂ 0 are preferred.

Amorphous sodium silicates with a module Na ₂ 0: Si0 ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred. Detergent or cleaning agent compositions preferred in the context of the present invention are characterized in that these silicate (s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in amounts of 10 to 60% by weight, preferably 15 to 50% by weight. % and in particular from 20 to 40 wt .-%, each based on the weight of the detergent or cleaning composition without the water-soluble or water-dispersible container.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ 0 ^■ (1-n) K ₂ 0 ^■ Al ₂ 0 ₃ ^■ (2 - 2.5) Si0 ₂ ^■ (3.5 - 5.5) H ₂ 0

can be described. The zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 13 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the summary name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ P0 _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance. Sodium dihydrogen phosphate, NaH ₂ P0 ₄ , exists as a dihydrate (density 1, 91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white powders, which are very easily soluble in water, lose the water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ 0 ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ 0 ₉ ) and Maddrell's salt (see below). NaH ₂ P0 _{4 is} acidic; it arises when 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), KH ₂ P0 ₄ , is a white salt with a density of 2.33 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 ₃ ) J and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HP0 ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1, 6δ gladly ^{" 3} , melting point 4δ ° with loss of 5 H ₂ 0) and 12 mol. Water ( Density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ 0), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ 0 ₇ when heated more. Disodium hydrogen phosphate is lost by neutralizing phosphoric acid with soda solution Using phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HP0 ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ P0, are colorless crystals which like dodecahydrate have a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ 0 ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ 0 ₅ ) a density of 2.536 like ^"3 . 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 three-base potassium phosphate), K ₃ P0 ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred in the cleaning agent industry over corresponding sodium compounds.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ 0 ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 9δδ °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like ^{" 3} , melting point 94 ° with water loss). For substances are colorless, in water with alkaline reaction soluble crystals. Na P ₂ 0 ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), KP ₂ 0 ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33, preferably ³ , which is soluble in water, the pH of the 1% solution being 25 ° is 10.4.

Condensation of NaH ₂ P0 or KH ₂ P0 ₄ produces higher mols. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ Oι ₀ (sodium tripolyphosphate), is an anhydrous or 6 H ₂ 0 crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _n -Na with n = 3. About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. 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. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P ₂ 0 ₅ , 25% K ₂ 0). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaP0 ₃ ) ₃ + 2 KOH - Na ₃ K ₂ P3θ ₁₀ + H ₂ 0

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; 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 can also be used according to the invention. Detergent or cleaning agent compositions preferred in the context of the present invention are characterized in that these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 20 to 80% by weight. -%, preferably from 25 to 75 wt .-% and in particular from 30 to 70 wt .-%, each based on the weight of the detergent or cleaning composition without the water-soluble or water-dispersible container.

Alkali carriers can be present as further constituents. Examples of alkali carriers include alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metal silicates and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquic acid being used for the purposes of this invention. A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.

Particularly preferred detergent or cleaning agent compositions contain carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular from 10 to 30% by weight, in each case based on the weight of the detergent or cleaning composition.

Organic cobuilders which can be used in the washing or cleaning agent compositions according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. 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 themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight. To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

Also particularly preferred are biodegradable polymers made up of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallyisulfonic acid and sugar derivatives as monomers ,

Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and are particularly preferred.

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both 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 molar masses in the range from 2000 to 30000 g / mol can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and at most two acid groups.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.

The amount of builder is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight, in each case based on the detergent or cleaning agent composition. Again, the amount of builders used is dependent on the intended use, so that bleaching agent compositions can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight) ), for example detergent compositions (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight). In addition to builders, the agents according to the invention can contain anionic, nonionic, cationic and / or amphoteric surfactants, nonionic surfactants being preferred due to their foaming power.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C ₉ . ₁₃ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained, for example, from C _12-18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, into consideration. Also suitable are alkanesulfonates, which are for example derived from C ₁₂ ι ₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as 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 sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₅ alkyl sulfates and C ₁ -C ₁ alkyl sulfates are preferred from a washing-technical point of view. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂ ι alcohols, such as 2-methyl-branched

with an average of 3.5 Moles of ethylene oxide (EO) or C _12-18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably δ to 1δ carbon atoms in the Al k (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 1 δ C atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to δ EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-1 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 3 EO, Cι _2-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci ₂ -ι alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution on (narrow ranks ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having δ to 22, preferably 12 to 1δ C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

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

R '

R-CO-N- [Z] (XV)

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for 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 which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (XVI) R ¹ -0-R ²

I

R-CO-N- [Z] (XVI)

in which R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical is 2 to δ carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this remainder.

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

Low-foaming nonionic surfactants are used as preferred surfactants. The cleaning agents according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-1 alcohol with 7 EO, C ₁₃ -i ₅ alcohols with 3 EO, 5 EO, 7 EO or δ EO , C _12- ι ₈ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12- ι ₄ alcohol containing 3 EO and C _12- ι ₈ alcohol containing 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Dishwashing detergents according to the invention which contain a nonionic surfactant which has a melting point above room temperature are particularly preferred. Accordingly, preferred dishwashing detergents are characterized in that they have nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, 3 ° C.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms, (Cι. ₆ ₂₀ alcohol), preferably a Cι ₈ alcohol and at least 12 mole, preferably at least 15 mol and recovered in particular at least 20 moles of ethylene oxide , Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred dishwashing detergents according to the invention contain ethoxylated nonionic surfactant (s) which consist of C _6-2 o-monohydroxyalkanols or C ₆ . ₂ o-alkylphenols or Cι _6-2 o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol was obtained. The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants. Preferred dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Make up surfactants.

Other nonionic surfactants with melting points above room temperature which are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight. -% 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 mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-16 from Olin Chemicals.

A further preferred dishwashing detergent according to the invention contains nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y [CH ₂ CH (OH) R ² ],

in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 1δ carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y stands for a value of at least 15.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (0H) [CH ₂ ] _j 0R ² in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or - CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x ≥ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

If the last statements are summarized, dishwashing detergents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² contain, in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

in which x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

In the context of the present invention, weakly foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants. Among these, surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Here, automatic dishwashing agents according to the invention are preferred which contain surfactants of the general formula XII as nonionic surfactant (s)

R ¹ -0- (CH ₂ -CH ₂ -0) _w - (CH ₂ -CH-0) _x - (CH ₂ -CH ₂ -0) _y - (CH ₂ -CH-0) _z -H (XII )

I I

R ² R ³

in R ¹ for a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . _{24 is} alkyl or alkenyl; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently represent integers from 1 to 6.

The preferred nonionic surfactants of the formula XII can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R in the above formula XII can vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is generally not shown, the linear radicals being of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow or Oleyl alcohol are preferred. Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or residues which are methyl-branched in the 2-position or linear and methyl-branched residues in a mixture, as are usually present in oxo alcohol residues. Regardless of the type of to produce the invention in Alcohol used in the agents containing nonionic surfactants are preferred dishwasher detergents according to the invention in which R ¹ in formula XII represents an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. But also other alkylene oxides in which R ² and R ³ are selected independently of one another from -

CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are suitable. Preferred automatic dishwashing agents are characterized in that R ² or R ³ for a radical -CH ₃ , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

In summary, nonionic surfactants which have a C ₉ . ₁₅ alkyl group having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used with particular preference according to the invention.

The specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation represent statistical mean values which can be an integer or a fractional number for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which can result in mean values and fractional numbers both for the C chain lengths and for the degrees of ethoxylation or alkoxylation.

Instead of the surfactants mentioned or in conjunction with them, cationic and / or amphoteric surfactants can also be used.

The agents according to the invention can contain, for example, cationic compounds of the formulas XIII, XIV or XV as cationic active substances: R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _π -TR ² (XIII)

(CH ₂ ) _n -TR ²

R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -CH-CH ₂ (XIV)

R ¹ TT

RR ^z

R ¹

R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (XV)

R ⁴

wherein each group R ^{1 is} independently selected from C _1-6 alkyl, alkenyl or

-2

hydroxyalkyl; each R group is independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O- CO- or -CO-O- and n is an integer from 0 to 5.

In summary, washing or cleaning agent compositions according to the invention are preferred which contain surfactant (s), preferably nonionic surfactant (s) and in particular nonionic surfactant (s) from the group of the alkoxylated alcohols, in amounts of 0.1 to 60% by weight .-%, preferably from 0.5 to 50 wt .-%, particularly preferably from 1 to 40 wt .-%, and in particular from 2 to 30 wt .-%, each based on the total agent. Particularly preferred machine washing or

Detergent compositions are characterized in that they contain 5 to 25% by weight, preferably 6 to 22.5% by weight, particularly preferably 7.5 to 20% by weight and in particular 8 to 17.5% by weight of nonionic ( s) contain surfactant (s).

In addition to the builders, bleaches, bleach activators, enzymes, silver preservatives, dyes and fragrances, etc. are preferred ingredients of the invention Detergent or cleaning agent compositions. In addition, other ingredients may be present, with detergent or cleaning agent compositions according to the invention being preferred which additionally contain one or more substances from the group of the acidifying agents or the chelating agents.

Both inorganic acids and organic acids are suitable as acidifiers, provided that these are compatible with the other ingredients. The solid mono-, oligo- and polycarboxylic acids can be used in particular for reasons of consumer protection and handling safety. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. The anhydrides of these acids can also be used as acidifying agents, maleic anhydride and succinic anhydride in particular being commercially available. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

Another possible group of ingredients are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, i. H. is at least "bidentate". In this case, normally elongated compounds are closed to form rings by complex formation via an ion. The number of ligands bound depends on the coordination number of the central ion.

Common chelate complexing agents preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and generally react with suitable metal atoms to form chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cycl.) Polyamino, mercapto, 1, 3-dicarbonyl - and Crown ether residues with z. T. very specific Activities against ions of different metals. The base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.

In the context of the present invention, particular preference is given to detergent or cleaning agent compositions, in particular detergents for machine dishwashing, which contain one or more chelating agents from the groups of

(i) polycarboxylic acids, in which the sum of the carboxyl and optionally

Hydroxyl groups is at least 5,

(ii) nitrogen-containing mono- or polycarboxylic acids,

(iii) geminal diphosphonic acids,

(iv) aminophosphonic acids,

(v) phosphonopolycarboxylic acids,

(vi) cyclodextrins

in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the Dishwashing detergent without the deep-drawn or cast container.

All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups. The following are preferably used individually or in a mixture:

a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5 such as gluconic acid, b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 3-nitridodiacetic acid, nitridodiacetic acid , N-di- (ß-hydroxyethyl) -glycine, N- (1,2-dicarboxy-2-hydroxyethyl) -glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA), c) geminal diphosphonic acids such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), their higher homologues with up to 8 carbon atoms as well as hydroxy or amino group containing derivatives thereof and 1-aminoethane-1, 1-diphosphonic acid, their higher homologues with up to 8 carbon atoms and hydroxyl- or amino group-containing derivatives thereof, d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri ( methylenephosphonic acid), e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1, 2,4-tricarboxylic acid and f) cyclodextrins.

In the context of this patent application, polycarboxylic acids a) are understood to mean carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

The automatic cleaning of dishes in household dishwashers usually comprises a pre-wash, a main wash and a rinse cycle, which are interrupted by intermediate wash cycles. In most machines, the pre-wash for heavily soiled dishes can be switched on, but is only selected by the consumer in exceptional cases, so that in most machines a main wash, an intermediate wash with pure water and a rinse cycle are carried out. The temperature of the main wash cycle varies between 40 and 65 ° C depending on the machine type and program level selection. In the rinse cycle, rinse aids are added from a dosing tank in the machine, which usually contain non-ionic surfactants as the main component. Such rinse aids are in liquid form and are widely described in the prior art. Your main task is to prevent limescale and deposits on the cleaned dishes. In addition to water and low-foaming nonionic surfactants, these rinse aids often also contain hydrotopes, pH adjusting agents such as citric acid or scale-inhibiting polymers.

The storage tank in the dishwasher must be filled with rinse aid at regular intervals, with one filling sufficient for 10 to 50 wash cycles, depending on the type of machine. If you forget to fill up the tank, glasses in particular become unsightly due to limescale and deposits. In the prior art there are therefore some proposed solutions for integrating a rinse aid into the detergent for machine dishwashing. "2in1" products, which combine detergent and rinse aid, are now also established on the market. Another development is to make it unnecessary to refill the regeneration salt container in the dishwasher. So-called "3-in-1" cleaners, which combine the three functions of cleaning, rinsing and water softening in a single detergent formulation, so that the refill of salt with water hardness levels of 1 to 3 is no longer necessary for the consumer. For water softening, these cleaners usually contain sodium tripolyphosphate and / or polymers which act as softeners.

Detergent or cleaning agent compositions according to the invention for machine dishwashing can therefore additionally contain polymers which act as softeners. The sulfonic acid group-containing polymers described in detail above are used with particular preference. To avoid repetition, reference is made here to the execution there.

Among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or

Diperdodecanedioic. Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid

[Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyacidacidacidacidacidacid Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in the washing or cleaning agent compositions according to the invention. Suitable materials releasing chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Preferred detergent or cleaning agent compositions according to the invention additionally contain bleaching agents in amounts of 1 to 40% by weight, preferably 2.5 to 30% by weight and in particular 5 to 20% by weight, in each case based on the total agent without the water-soluble or water-dispersible container.

According to the invention, cationic nitrile (s) are / are contained in the detergent or cleaning agent compositions as a bleach activator which supports the action of the bleaching agents. It is possible that the agents contain further bleach activator (s). Possible further bleach activators which have not already been described above as nitrile quats are, for example, compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1, 5-diacetyl-2,2-dioxohexahydro-1, 3,5-triazine DADHT and isatoic anhydride ISA.

As bleach activators it is also possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, ethylene glycol Diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxyllact and optionally octaacetyl and octaacetyl N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are also preferably used. Combinations of conventional bleach activators can also be used. The bleach activators are usually used in machine dishwashing detergents in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular 1 to 10% by weight, based in each case on the detergent. in the In the context of the present invention, the proportions mentioned relate to the weight of the composition without the water-soluble or water-dispersible container.

In addition to the conventional bleach activators or in their place, so-called blelch catalysts can also be incorporated into the active substance particles. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

If further bleach activators are to be used in addition to the nitrile quats, bleach activators from the group of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyloxy- or isononosulfonates, are preferred. n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and particularly preferably 2 to 6% by weight, based on the detergent or cleaning agent compositions, without the water-soluble or water-dispersible container.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetaf) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in customary amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent without the container used. But in special cases, more bleach activator can be used.

In order to facilitate the disintegration of solid detergent or cleaning agent compositions, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these agents in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of Pharmaceutical Technology" (6th edition, 19δ7, p. 1δ2-1δ4), tablet disintegrants or accelerators of disintegration are understood as auxiliary substances which are necessary for the rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in resorbable form. These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred detergent or cleaning agent compositions contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, of one or more disintegration auxiliaries, in each case based on the weight of the compositions without the water-soluble or water-dispersible Container. If only the composition contains disintegration aids, the information given relates only to the weight of this composition.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing or cleaning agent compositions contain such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ Hι ₀ O _s ) _n and, formally speaking, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant. The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above and described in more detail in the documents cited coarser Desintegrationshilfsmittei based on cellulose are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. Subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

Detergent or cleaning agent compositions preferred in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the composition without the water-soluble or water-dispersible container.

The detergent or cleaning agent compositions according to the invention can also contain a gas-developing shower system. The gas-developing shower system can consist of a single substance which releases a gas when it comes into contact with water. Among these compounds, magnesium peroxide should be mentioned in particular, which releases oxygen on contact with water. Usually, however, the gas-releasing bubble system itself consists of at least two components that react with one another to form gas. While a large number of systems are conceivable and executable here, which release nitrogen, oxygen or hydrogen, for example, the effervescent system used in the detergent or cleaning agent compositions according to the invention can be selected on the basis of both economic and ecological aspects. Preferred shower systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and hydrogen carbonates may be preferred.

In preferred detergent or cleaning agent compositions, 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular, are used as the effervescent system 3 to 10 wt .-% of an acidifying agent, based in each case on the detergent or cleaning agent composition.

Examples of acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are boric acid and alkali metal bisulfates,

Alkali metal dihydrogen phosphates and other inorganic salts can be used. However, organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred from this group. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

In the context of the present invention, preference is given to detergent or cleaning agent compositions in which a substance from the group of the organic di-, tri- and oligocarboxylic acids or mixtures thereof are used as acidifying agents in the effervescent system.

The cleaning agents according to the invention can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the area of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Especially benzotriazole and / or alkylaminotriazole are preferred. In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

Instead of or in addition to the silver protective agents described above, for example the benzotriazoles, redox-active substances can be used in the washing or cleaning agent compositions according to the invention. These substances are preferably inorganic redox-active substances from the group of the manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, the metals preferably in one of the oxidation states II, III , IV, V or VI are present.

The metal salts or metal complexes used are said to be at least partially soluble in water. The counterions suitable for salt formation include all customary one, two or three times negatively charged inorganic anions, e.g. B. oxide, sulfate, nitrate, fluoride, but also organic anions such. B. stearate.

For the purposes of the invention, metal complexes are compounds which consist of a central atom and one or more ligands and, if appropriate, additionally one or more of the abovementioned anions. The central atom is one of the metals mentioned in one of the oxidation states mentioned above. The ligands are neutral molecules or anions that are monodentate or multidentate; the term “ligands” in the sense of the invention is explained in more detail, for example, in “Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507”. If the charge of the central atom and the charge of the ligand (s) do not add up to zero in a metal complex, then depending on whether there is a cationic or an anionic excess of charge, either one or more of the above anions or one or more cations, e.g. B. sodium, potassium, ammonium ions for charge balance. Suitable complexing agents are, for example, citrate, acetylacetonate or 1-hydroxyethane-1, 1-diphosphonate. The common definition for "oxidation level" in chemistry is given, for example, in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3166".

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V ₂ 0 ₅ , V ₂ 0 ₄ , V0 ₂ , TiOS0 ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoS0 ₄ , Co (N0 ₃ ) ₂ , Ce (N0 ₃ ) ₃ and mixtures thereof., so that preferred automatic dishwashing agents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxy-ethane

1, 1 -diphosphonate], V ₂ 0 ₅ , V ₂ 0 ₄ , V0 ₂ , TiOS0 ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoS0 ₄ , Co (N0 ₃ ) ₂ , Ce (N0 ₃ ) ₃ .

These metal salts or metal complexes are generally commercially available substances which can be used in the agents according to the invention for the purpose of protecting against silver corrosion without prior cleaning. For example, it is from the S0 ₃ production

(Contact method) known mixture of pentavalent and tetravalent vanadium (V ₂ 0 ₅ , V0 ₂ , V ₂ 0) is suitable, as is the titanyl sulfate formed by diluting a Ti (S0 ₄ ) ₂ solution,

TiOS0 ₄ .

The inorganic redox-active substances, in particular metal salts or metal complexes, are preferably coated, i.e. completely covered with a waterproof material that is easily soluble at cleaning temperatures to prevent their premature decomposition or oxidation during storage. Preferred coating materials which are applied by known processes, for example melt coating processes according to Sandwik from the food industry, are paraffins, micro waxes, waxes of natural origin such as carnauba wax, candella wax, beeswax, higher-melting alcohols such as hexadecanol, soaps or fatty acids. The coating material, which is solid at room temperature, is applied in a molten state to the material to be coated, e.g. by throwing finely divided material to be coated in a continuous stream through a likewise continuously generated spray zone of the molten coating material. The melting point must be selected so that the coating material easily dissolves or melts quickly during the silver treatment. The melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.

The metal salts and / or metal complexes mentioned are in the inventive washing or cleaning agent compositions, in particular machine dishwashing agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, based on the agent without the water-soluble or water-dispersible container

Another important criterion for assessing a machine dishwashing detergent is, in addition to its cleaning performance, the visual appearance of the dry dishes after cleaning. Possible calcium carbonate deposits on crockery or in the machine interior can, for example, affect customer satisfaction and thus have a causal influence on the economic success of such a cleaning agent. Another long-standing problem with machine dishwashing is the corrosion of glassware, which can usually manifest itself through the appearance of cloudiness, streaks and scratches, but also through iridescence of the glass surface. The effects observed are essentially based on two processes, the emergence of alkali and alkaline earth ions from the glass in connection with hydrolysis of the silicate network, and on the other hand in the deposition of silicate compounds on the glass surface.

The problems mentioned can be solved with the detergent or cleaning agent compositions according to the invention if, in addition to the mandatory and optionally optional ingredients mentioned above, certain glass corrosion inhibitors are incorporated into the agents. Preferred cleaning agents according to the invention therefore additionally contain one or more magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

A preferred class of compounds which can be added to the agents according to the invention to prevent glass corrosion are insoluble zinc salts. These can accumulate on the glass surface during the dishwashing process and prevent metal ions from the glass network from dissolving and the hydrolysis of the silicates. In addition, these insoluble zinc salts also prevent silicate from being deposited on the glass surface, so that the glass is protected from the consequences described above.

Insoluble zinc salts in the sense of this preferred embodiment are zinc salts which have a solubility of at most 10 grams of zinc salt per liter of water at 20 ° C. Examples of insoluble zinc salts which are particularly preferred according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ COs), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (P0 ₄ ) ₂ ), and zinc pyrophosphate (Zn ₂ (P ₂ 0 ₇ )).

The zinc compounds mentioned are used in the agents according to the invention in amounts which contain zinc ions between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0% by weight, based in each case on the medium. The exact content of the zinc salt or zinc salts in the detergents naturally depends on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration in the detergents according to the invention.

Since the insoluble zinc salts remain largely unchanged during the dishwashing process, the particle size of the salts is a criterion to be observed so that the salts do not adhere to glassware or machine parts. Here, automatic dishwashing agents according to the invention are preferred, in which the insoluble zinc salts have a particle size below 1.7 millimeters.

If the maximum particle size of the insoluble zinc salts is below 1.7 mm, there is no fear of insoluble residues in the dishwasher. The insoluble zinc salt preferably has an average particle size which is significantly below this value in order to further minimize the risk of insoluble residues, for example an average particle size of less than 250 μm. This, in turn, is all the more the less the zinc salt is soluble. In addition, the glass corrosion inhibiting effectiveness increases with decreasing particle size. In the case of very poorly soluble zinc salts, the average particle size is preferably below 100 μm. For even more poorly soluble salts, it can be even lower; For example, average particle sizes below 100 μm are preferred for the very poorly soluble zinc oxide.

Another preferred class of compounds are magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid. These have the effect that even with repeated use the surfaces of glassware do not change corrosively, in particular no clouding, streaks or scratches but also no iridescence of the glass surfaces.

Although according to the invention all magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be present in the claimed agents, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids are obtained from the Groups of the unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred. Within the scope of the present invention, the acids mentioned below are again preferred within these groups:

From the group of unbranched saturated or unsaturated monocarboxylic acids: methanoic acid (formic acid), ethanoic acid (acetic acid), propanoic acid (propionic acid), Pentanoic acid (valeric acid), hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, pentadecanoic acid, pentadecanoic acid, , Heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotinic acid), triacotanoic acid (melissic acid), 9c-hexadecenoic acid (palmitoleic acid) (palmitoleic acid) (palmitol 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-octadecatreic acid (linolenic acid).

From the group of the branched saturated or unsaturated monocarboxylic acids: 2-methylpentanoic acid, 2-ethylhexanoic acid, 2-propylheptanoic acid, 2-butyloctanoic acid, 2-pentylnonanoic acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 2-octyldodecanoic acid, 2-nonyltridecanoic acid, 2 2- Undecylpentadecanoic acid, 2-dodecyl-hexadecanoic acid, 2-tridecylheptadecanoic acid, 2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid, 2-hexadecyleicosanoic acid, 2-heptadecylhenicosanoic acid.

From the group of unbranched saturated or unsaturated di- or tricarboxylic acids: propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid) (azelaic acid) Sebacic acid), 2c-butenedioic acid (maleic acid), 2t-butenedioic acid (fumaric acid), 2-butynedicarboxylic acid (acetylenedicarboxylic acid).

From the group of aromatic mono-, di- and tricarboxylic acids: benzoic acid, 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3.5 -Dicar- boxybenzoic acid (trimesionic acid).

From the group of the sugar acids: galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid, alginic acid.

From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), hydroxy succinic acid (malic acid), 2,3-dihydroxy-butanedioic acid (tartaric acid), 2-hydroxy-1, 2,3-propanetricarboxylic acid (citric acid) .

Ascorbic acid, 2-hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid). From the group of oxo acids: 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).

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

From the group of polymeric carboxylic acids: polyacrylic acid, polymethacrylic acid, alkyl acrylamide / acrylic acid copolymers, alkyl acrylamide / methacrylic acid copolymers,

Alkyl acrylamide / methyl methacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers.

The spectrum of the zinc salts of organic acids, preferably organic carboxylic acids preferred according to the invention, extends from salts which are sparingly or not soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, up to such salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, particularly preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C. water temperature). The first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate; the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate:

In a further preferred embodiment of the present invention, the washing or cleaning agent compositions according to the invention contain at least one zinc salt, but no magnesium salt of an organic acid, which is preferably at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group zinc stearate, zinc oleate, Zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

A preferred agent in the context of the present invention contains zinc salt in amounts of 0.1 to 5% by weight, preferably 0.2 to 4% by weight and in particular 0.4 to 3% by weight, or zinc in oxidized form (calculated as Zn ²⁺ ) in amounts from 0.01 to 1% by weight, preferably from 0.02 to 0.5% by weight and in particular from 0.04 to 0.2% by weight , each based on the total weight of the automatic dishwashing detergent without the water-soluble or water-dispersible container.

In addition to the constituents mentioned, builder, surfactant, disintegration aid, bleach and bleach activator, the washing or Detergent compositions further ingredients common in washing or cleaning agents from the group of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors,

Color transfer inhibitors and corrosion inhibitors included.

Detergent or cleaning agent compositions according to the invention can contain enzymes to increase the washing or cleaning performance, it being possible in principle for all enzymes established in the prior art to be used for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents or cleaning agents, which are accordingly preferred. Agents according to the invention preferably contain enzymes in total amounts of 1 x 10 ^" ⁶ to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and that which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ^® from Novozymes A / S, Bagsvserd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. The variants listed under the name BLAP ^{® are} derived from the protease from Bacillus lentus DSM 5463.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, which is sold under the trade name Protosol ^® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ^® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name Proleather ^® and Protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan. Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens or from ß. stearothermophilus and its further developments for use in detergents and cleaning agents. The enzyme from ß. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar ^® ST. Development products of this α- amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from ß. Amyloliquefaciens is sold by Novozymes under the name BAN ^® , and derived variants from the α-amylase from β. stearothermophilus under the names BSG ^® and Novamyl ^® , also from Novozymes.

Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12363) and the cyclodextrin glucanotransferase (CGTase) from ß. to highlight agaradherens (DSM 9948).

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae. Another commercial product is the Amylase-LT ^® .

Agents according to the invention can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^® , Lipolase ^® Ultra, LipoPrime ^® , Lipozyme ^® and Lipex ^® . Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. Lipase ^® , Lipase AP ^® , Lipase M-AP ^® and Lipase AML ^® available. For example, the Genencor company can use the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention, also the product Lumafast ^® from Genencor. Agents according to the invention can contain further enzymes, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 L from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA , The from ß. subtilis .beta.-glucanase obtained is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, washing and cleaning agent compositions according to the invention can contain oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain. Suitable commercial products are Denilite ^® 1 and 2 from Novozymes. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of greatly different redox potentials between the oxidizing enzymes and the soiling.

The enzymes used in agents according to the invention either originate from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.

The enzymes in question are advantageously purified by methods which are in themselves established, for example by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.

Agents according to the invention can be added to the enzymes in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers. Alternatively, the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural polymer, or in the form of capsules, for example those in which the enzymes are enclosed in a solidified gel are or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.

Furthermore, it is possible to assemble two or more enzymes together, so that a single granulate has several enzyme activities.

A protein and / or enzyme contained in an agent according to the invention can be protected, particularly during storage, against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage. When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Agents according to the invention can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.

A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters. Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.

Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders can additionally stabilize an enzyme contained.

Lower aliphatic alcohols, but above all polyols, such as, for example, glycerol, ethylene glycol, propylene glycol or sorbitol are further frequently used enzyme stabilizers. Likewise Calcium salts such as calcium acetate or calcium formate are used, and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, among other things, against physical influences or pH fluctuations. Polymers containing polyamine-N-oxide act as enzyme stabilizers. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds also act as enzyme stabilizers.

Reducing agents and antioxidants increase the stability of the enzymes against oxidative decay. A sulfur-containing reducing agent is, for example, sodium sulfite.

Combinations of stabilizers are preferably used, for example made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is increased by the combination with boric acid and / or boric acid derivatives and polyols and is further enhanced by the additional use of divalent cations, such as calcium ions.

Preferred automatic dishwashing agents according to the invention are characterized in that they additionally contain one or more enzymes and / or enzyme preparations, preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of 1 to 5% by weight, preferably of 1 , 5 to 4.5 and in particular from 2 to 4 wt .-%, each based on the total agent.

Dyes and fragrances can be added to the agents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensorially "typical and distinctive" product in addition to performance. As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate,

Dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate,

Ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals δ-1δ carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones, for example the jonones, α-isomethylionone and methylcedryl ketone, to the alcohols anethole, citronellol, eugenol, phenanolethylol alcohol, linalol , The hydrocarbons mainly include terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the washing or cleaning agent compositions according to the invention, but it can also be advantageous to apply the fragrances to carriers which ensure a long-lasting fragrance due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

In order to improve the aesthetic impression of the agents according to the invention, it (or parts thereof) can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to the substrates to be treated with the compositions, such as glass, ceramics or plastic dishes, so as not to stain them.

The detergent or cleaning agent compositions according to the invention dissolve completely in the washing or cleaning cycle, and - as mentioned above - it can be advantageous if the different regions have different dissolution rates. Due to the different dissolution rates, in addition to the release of certain ingredients, the properties of the washing or cleaning liquor can also be changed in a targeted manner. For example, detergent and cleaning agent compositions are preferred in which the pH of a 1% by weight solution of the detergent or cleaning agent composition in water is in the range from δ to 12, preferably from 9 to 11 and in particular from 9.5 to 10, lies. In addition to this, detergent and cleaning agent compositions are preferred in which the pH of a 1% by weight solution of the total detergent or cleaning agent composition in water is in the range from 7 to 11, preferably from 7.5 to 10 and in particular from δ to 9.5.

In a preferred embodiment, the washing or cleaning agent compositions according to the invention have a water-soluble or water-dispersible packaging which preferably comprises at least one water-soluble or water-dispersible container and at least one water-soluble or water-dispersible closure unit.

The nitrile quat-containing compounds described above are preferably introduced in solid preparation form into an injection-molded, deep-drawn or cast water-soluble or water-dispersible container.

The injection-molded, deep-drawn or cast water-soluble or water-disposable container can have any shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, pyramidal, dodecahedral, octahedral, octahedral, octahedral, octahedral, octahedral, octahedral, octahedral, octahedral, octahedral, octahedral, octahedral, octahedral, octahedral, octahedral ellipsoidal, pentagonal, hexagonal and octagonal prismatic and rhombohedral shapes are preferred. Containers with completely irregular bases such as arrow or animal shapes, trees, clouds etc. can also be realized. If the deep-drawn or cast containers have corners and edges, they are preferably rounded.

Of course, the deep-drawn or cast containers can also have devices for subdivision into receiving chambers. Detergent or cleaning agent compositions in which the water-soluble or water-dispersible packaging has at least two separate receiving chambers are preferred in the context of the present application. For optical or recipe reasons, it may be appropriate to divide the deep-drawn or cast container into more than two receiving chambers. Water-soluble or water-dispersible packaging with three, four, five, six, seven, eight, nine, ten, eleven, twelve or more receiving chambers are therefore further particularly preferred embodiments within the scope of the present invention.

If the water-soluble or water-dispersible container has two or more receiving chambers, it is within the scope of the present invention to avoid the disadvantageous interactions between cationic nitrile and one or several constituents of the detergent or cleaning composition preferably that at least one of the receiving chambers does not contain a compound according to the invention.

The separation of certain ingredients described is described in the following tables by way of example using selected active substances for washing or cleaning agent compositions according to the invention, which have a packaging with two (entries 1 to 9) or three receiving chambers.

The detergents or cleaning agents or detergent components contained in the receiving chamber (s) can be liquids, dispersions or solids. The following table shows exemplary distributions of such liquids, dispersions and solids to a container according to the invention with two (entries 1 to 6) and three receiving chambers:

The compounds in the compounds according to the invention can be part of the solids, the dispersion (s) and / or the solution (s). However, the compounds according to the invention are preferably part of the solid (s) and / or the dispersion (s).

Detergent or cleaning agent compositions which are particularly preferred in the context of the present application are characterized in that at least one receiving chamber contains a liquid and at least one further receiving chamber contains a solid, preferably in the form of a powder and / or an agglomerate and / or a compact and / or a casting , contains. The compounds according to the invention are preferably part of the solid in these preferred detergent or cleaning agent compositions. Detergent or cleaning agent compositions which are particularly preferred in the context of the present application are characterized in that at least one receiving chamber contains a meltable casting body and at least one further receiving chamber contains a solid, preferably in the form of a powder and / or an agglomerate and / or a compactate and / or one Casting body, contains. The compounds according to the invention are in these preferred washing or

Detergent compositions preferably part of the solid.

In the context of the present applications, liquids are referred to as single-phase substances or substance mixtures which have a viscosity (Brookfield viscometer LVT-II at 20 rpm and 20 ° C., spindle 3) of 500 to 100,000 mPas, preferably of 1000 to Have 50,000 mPas, particularly preferably from 1200 to 10,000 mPas and in particular from 1300 to 5000 mPas.

In addition to water, as one of the most common solvents, such liquids can also contain other non-aqueous solvents as a liquid matrix. These non-aqueous solvents originate, for example, from the groups of the mono-alcohols, diols, triols or polyols, the ethers, esters and / or amides. Non-aqueous solvents which are water-soluble are particularly preferred, "water-soluble" solvents for the purposes of the present application being solvents which are completely miscible with water at room temperature, i.e. without a miscibility gap.

Non-aqueous solvents which can be used in the agents according to the invention preferably come from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mononon-butyl ether, diethylene glycol methyl ether -ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene-glycol-t- butyl ether and mixtures of these solvents.

A liquid detergent or cleaning agent composition which is particularly preferred in the context of the present invention is characterized in that it particularly comprises non-aqueous solvents in amounts of 0.1 to 70% by weight, preferably 0.5 to 60% by weight preferably from 1 to 50% by weight, very particularly preferably from 2 to 40% by weight and in particular from 2.5 to 30% by weight, in each case based on the overall composition, contains, preferred non-aqueous solvent (s) being selected from the group of the nonionic surfactants which are liquid at room temperature, the polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol and n-propanol and / or iso-propanol.

In the context of the present application, dispersion is referred to as dispersion, which, in addition to a continuous phase (dispersing agent), has at least one further finely divided phase (dispersed phase, dispersant). The dispersions thus include, for example, the emulsions, aerosols and suspensions. In preferred embodiments of the present invention, the cationic nitrile (s) is in solid, particulate form, preferably in combination with a carrier material or a coating, suspended in a continuous liquid phase, the same being true for the liquid phases, for example can be the aforementioned non-aqueous solvents, as well as water or mixtures of these non-aqueous solvents with water.

Preferably, however, liquid, water-free formulations with coated or uncoated nitrile quats suspended therein are used as dispersions. In the context of the present application, “water-free” refers to formulations which have a water content below 5% by weight, preferably below 3% by weight and in particular below 1.5% by weight. In addition to the nitrile quats and Descriptions of some washing or cleaning-active substances preferred in the context of the present invention, such as surfactants, builders, etc., can be found further below in this description.

Both the liquids described above and the suspensions described can additionally contain one or more thickeners. Detergents or cleaning agents preferred in the context of the present invention are characterized in that they additionally contain 0.01 to 5% by weight, preferably 0.02 to 4% by weight, particularly preferably 0.05 to 3% by weight and in particular 0.1 to 1.5% by weight, of a thickener, preferably a polymeric thickener, wherein the thickener is hydroxyethyl cellulose and / or hydroxypropyl cellulose and / or thickener from the group of the polysaccharides, preferably xanthan, the polyurethane or the modified Polyacrylates with particular preference for thickeners of the formula R ^ύ

[-CH ₂ -C-] _n

I CXR ⁴

II o

in which R ^{3 is} H or a branched or unbranched C _1- alk (en) yl radical, X is NR ⁵ or O, R ^{4 is} an optionally alkoxylated branched or unbranched, possibly substituted C ₈ . ₂₂ -alk (en) yl radical, R ^{5 is} H or R ⁴ and n is a natural number, are preferred.

In the present application, solids in particular refer to powders, agglomerates, compactates and castings. Washing or cleaning agent compositions according to the invention which contain a powder and / or an agglomerate and / or a compact and / or a casting as a solid are particularly preferred.

Powder is a general term for a form of separation of solid substances and / or mixtures of substances which is obtained by comminution, i.e. grinding or crushing in the grinding bowl (pulverization), grinding in mills or as a result of atomization or freeze drying. A particularly fine division is often called atomization or micronization; the corresponding powders are called micro powders.

According to the grain size, the powders are roughly divided into coarse, fine and. Very fine powder common; A more precise classification of powdered bulk goods is based on their bulk density and by sieve analysis. However, powders preferred in the context of the present application have lower particle sizes of 500 μm, preferably 600 μm and in particular δOO μm. Methods for determining the lower particle size are usually based on the aforementioned sieve analysis and are described in detail in the prior art.

Powders can be compacted and agglomerated by extrusion, pressing, rolling, briquetting, pelleting and related processes. In principle, any of the methods known in the prior art for agglomeration of particulate mixtures is suitable for producing the solids contained in the agents according to the invention. In the context of the present invention, agglomerates which are preferably used as solid (s) are, in addition to the granules, the compactates and extrudates. Accumulations of granules are referred to as granules. A granulate is an asymmetrical aggregate of powder particles. Granulation processes are widely described in the prior art. Granules can be produced by wet granulation, by dry granulation or compacting and by melt solidification granulation.

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

If the granulation takes place in a spray tower, the starting materials used can be, for example, melts (melt solidification) or, preferably aqueous, slurries (spray drying) solid substances which are sprayed at the top of a tower in a defined droplet size, freeze or dry in free fall, and on Bottom of the tower accumulate as granules. Melt solidification is generally particularly suitable for shaping low-melting substances that are stable in the melting temperature range (e.g. urea, ammonium nitrate and various formulations such as enzyme concentrates, pharmaceuticals, etc.), the corresponding granules are also referred to as prills. Spray drying is used particularly for the production of detergents or detergent components.

Further agglomeration techniques described in the prior art are extruder or perforated roller granulation, in which powder mixtures optionally mixed with granulating liquid are plastically deformed when pressed by perforated disks (extrusion) or on perforated rollers. The products of extruder granulation are also called extrudates.

Compactates can be produced, for example, using dry granulation techniques such as tableting or roller compaction. Compacting in tablet presses enables single-phase or multi-phase tablets or briquettes to be produced. In addition to the multi-layer or sandwich tablets, the multi-phase tablets also include, for example, the coated tablets and the point tablets (BuIl-eye tablets). The briquettes can be just like the ones in Compaction rollers produced scraps are crushed after the compaction by opposing spiked rollers or beaten by sieves. The size of the particles obtained by compacting can vary.

In the context of the present application, casting bodies are solid substance particles which are produced by solidification and / or crystallization from melts or solutions. The solidification and / or crystallization preferably takes place in prefabricated matrices. Depending on the size of the die and the intended use of the casting body, the casting bodies released from the dies after solidification can subsequently be used in their original size or, if appropriate, after comminution, as solids in the water-soluble containers according to the invention.

In particular, meltable substances from the group of fats and / or triglycerides and / or fatty acids and / or fatty alcohols and / or waxes and / or parrafins are suitable as matrix material for castings which are produced by melt solidification. A detailed description of these substances can be found further below in this document in connection with the description in the context of this application of preferred coating materials for cationic nitriles. To avoid repetition, reference is made here to the explanations given there.

In summary, such washing or

Detergent compositions are particularly preferred in which the detergent or cleaning agent composition comprises at least one liquid and / or at least one dispersion and / or at least one solid. In a particularly preferred embodiment of the present invention, the washing or cleaning agent composition according to the invention has at least one receiving chamber which contains a liquid and at least one further receiving chamber which contains a solid.

The shapes of the receiving chambers can also be freely selected within wide limits. For the shape of the receiving chambers, what has already been said about the shape of the deep-drawn or cast container above in the text applies to special embodiments, to which reference is made here to avoid repetition. The shape of the receiving chambers must on the one hand adapt to the technical requirements, for example the size of the receiving chambers should be adapted to the volume fraction of the liquid or solid agents contained in these receiving chambers to avoid empty volumes. On the other hand, the subdivision of the water-soluble or water-dispersible containers into separate receiving chambers naturally also offers a possibility for the optical upgrading of the Total product. In this context, preference is given to those deep-drawn or cast water-soluble or water-dispersible containers which are subdivided into receiving chambers and which have a cuboid shape and in which the subdivision into receiving chambers takes place symmetrically. Particularly preferred are those containers whose subdivision into receiving chambers, in particular in the direction of the top or bottom, has a C ₂ symmetry.

The geometric implementation forms mentioned above can be combined with one another as desired. This means that containers with a rectangular or square base and circular holding chambers can be manufactured as well as round containers with octagonal holding chambers, whereby there are no limits to the variety of possible combinations. For reasons of process economy and aesthetic consumer perception, as well as in relation to the preferred use of agents according to the invention in dishwashers, rectangular containers are preferred.

The size of the receiving chamber (s) compared to the entire container depends on the desired use of the agents according to the invention. The size of the receiving chambers can vary depending on whether the receiving chamber (s) should be filled with further active substance and whether a smaller or larger amount of active substance should be contained. Regardless of the intended use, detergent or cleaning agent compositions according to the invention with two or more receiving chambers are preferred, in which the volume of each receiving chamber present is at least 2% by volume, preferably at least 5% by volume and in particular at least 10% by volume, particularly preferably between 15 to 90 vol .-% and very particularly between 20 and 80 vol .-%. The volume is calculated from the volume of the sealed container according to the invention, divided into receiving chambers.

Preferred containers according to the invention have a film as the closure unit, which is bonded to the container in an adherent manner, for example by gluing, partial melting or by chemical reaction. It is possible to apply the film to all container surfaces and to bond them firmly, so that the film constitutes a coating, a "coating" of the entire container. However, preferred detergent or cleaning agent compositions are characterized in that the film does not cover the entire container encloses.

For reasons of process economy and the aesthetic impression, it is preferred that the film is only applied to the container surfaces where it fulfills a function, ie serves to close receiving chambers. Agents according to the invention in which the film only the Areas of the container covered, in which openings of the receiving chambers are located, are therefore preferred.

The film closing the receiving chamber can of course also be a laminate of several differently composed films. By using individual film layers of different compositions, the opening of different receiving chambers can be released at certain times in the washing and cleaning cycle. In particular, the film material or film thickness is preferably chosen such that the closure unit of the deep-drawn or cast water-soluble or water-dispersible container has a dissolving behavior which differs from the dissolving behavior of the water-soluble or water-dispersible container.

In the context of the present application, “dissolution behavior” refers in particular to the time at which water, after introducing a container according to the invention into an aqueous liquor, penetrates the film or the container wall. Particularly preferred are embodiments in which the films used are surrounded by surrounding water more quickly is penetrated as the container.

Preferred water-soluble or water-dispersible materials are the polymers known from the prior art. In particular, washing or

Preferred detergent composition, in which the water-soluble or water-dispersible container and / or the water-soluble or water-dispersible closure unit consists of a polymer with 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.

Such preferred polymers can be synthetic or natural in origin. If native or partially native polymers are used as film material, detergent or cleaning agent compositions are preferred in which the water-soluble or water-dispersible container and / or the water-soluble or water-dispersible closure unit are one or more substances from the group carrageenan, guar, pectin, xanthan, cellulose and their derivatives, starch and their derivatives, and gelatin or consist entirely of these substances.

Carrageenan is an extract from North Atlantic red algae, which is one of the florid species, and is named after the Irish coastal town of Carragheen. The carrageenan precipitated from the hot water extract of the algae is a colorless to sand-colored Powder with a molecular weight of 100000-800000 and a sulfate content of approx. 25%, which is very easily soluble in warm water. There are three main components in carrageenan: The yellow-forming / fraction consists of D-galactose-4-sulfate and 3,6-anhydro-α-D-galactose, which are alternately glycosidically linked in the 1,3 and 1,4 positions (In contrast, agar contains 3,6-anhydro-α-L-galactose). The non-gelling l fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and is readily soluble in cold water. The i-carrageenan composed of D-galactose-4-sulfate in 1,3-bond and 3,6-anhydro-α-D-galactose-2-sulfate in 1,4-bond is both water-soluble and gel-forming. Other types of carrageenan are also designated with Greek letters: α, ß, γ, μ, v, ξ, π, ω, χ. The type of cations present (K, NH, Na, Mg, Ca) also influences the solubility of the carrageenans. Semi-synthetic products that contain only one type of ion and can also be used as film and / or container materials in the context of the present invention are also called Carrag (h) eenate.

The guar, also called guar flour, which can be used as film and / or container material in the context of the present invention, is an off-white powder which is obtained by grinding the endosperm of those originally endemic in the Indian and Pakistani regions, but now also in other countries, e.g. in the southern United States, cultivated guar beans (Cyamopsis tetragonobolus) belonging to the legume family. The main component of the guar is up to approx. 85% by weight of the dry substance guaran (guar gum, cyamopsis gum); Minor components are proteins, lipids and cellulose. Guaran itself is a polygalactomannan, i.e. a polysaccharide whose linear chain is composed of unsubstituted (see formula II) and substituted in the C6 position with a galactose residue (see formula (III) mannose units in a β-D (1-4) linkage.

galactose

Manno

The ratio of 11: 111 is approximately 2: 1; contrary to original assumptions, the Il units are not strictly alternating, but are arranged in pairs or triplets in the polygalactomannan molecule. Data on the molar mass of guaran vary significantly with values of approx. 2.2 - 10 ⁵ - 2.2 - 10 ⁶ g / mol depending on the degree of purity of the polysaccharide - the high value was determined on a highly purified product - and correspond to approx. 1350 -13500 sugar units / macromolecule. Guaran is insoluble in most organic solvents.

The pectins that can also be used as film and / or container material are high-molecular glycosidic plant substances that are very common in fruits, roots and leaves. The pectins consist essentially of chains of 1,4-α-glycoside. connected galacturonic acid units, the acid groups of which are esterified to 20-80% with methanol, a distinction being made between highly esterified (> 50%) and low-esterified pectins (<50%). The pectins have a sheet structure and are thus in the middle of starch and cellulose molecules. Your macromolecules still contain some glucose, galactose, xylose and arabinose and have weakly acidic properties.

Fruit pectin contains 95%, beet pectin to δ5% galacturonic acid. The molar masses of the different pectins vary between 10,000 and 500,000. The structural properties are also strongly dependent on the degree of polymerization; so form e.g. the fruit pectins in the dried state asbestos-like fibers, the flax pectins, on the other hand, fine, granular powders.

The pectins are produced by extraction with dilute acids, predominantly from the inner parts of citrus fruit peel, fruit residues or sugar beet pulp.

Xanthan can also be used according to the invention as a film and / or container material. Xanthan is a microbial anionic heteropolysaccharide that is produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular weight of 2 to 15 million Daltons. Xanthan is formed from a chain with ß-1, 4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, Glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan. Xanthan can be described by the following formula:

Basic unit of xanthan

The celluloses and their derivatives are also suitable as film materials. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, viewed formally, is a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used as film material based on cellulose in the context of the present invention. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. In addition to cellulose and cellulose derivatives, (modified) dextrins, starch and starch derivatives can also be used as film and / or container materials.

Suitable nonionic organic film and / or container materials are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 owns. Both 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 molar masses in the range from 2000 to 30000 g / mol can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.

Starch can also be used as film and / or container material for the detergent or cleaning agent compositions according to the invention. Starch is a homoglycan, with the glucose units linked α-glycosidically. Starch is made up of two components of different molecular weights: approx. 20-30% straight-chain amylose (MW. Approx. 50,000-150,000) and 70-δ0% branched-chain amylopectin (MW. Approx. 300,000-2,000,000), in addition there are only a few Contain quantities of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300-1200 glucose molecules due to the binding in the 1,4 position, the chain in the amylopectin branches after an average of 25 glucose units through 1,6 binding to form a knot-like structure with about 1500-12000 molecules of glucose. In addition to pure starch, starch derivatives which can be obtained from starch by polymer-analogous reactions are also suitable as film materials in the context of the present invention. Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches. Among the proteins and modified proteins, gelatin is of outstanding importance as a film and / or container material. Gelatin is a polypeptide (molecular weight: approx. 15,000-> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules.

Other polymers which can be used as film and / or container materials are synthetic polymers which are preferably water-swellable and / or water-soluble. Such synthetic-based polymers can be "tailor-made" for the desired permeability during storage and dissolution of the film. Particularly preferred washing or cleaning agent compositions according to the invention are distinguished in that the deep-drawn or cast water-soluble or water-dispersible container and / or the water-soluble or comprises a polymer or polymer mixture, the polymer or at least 50% by weight of the polymer mixture being selected from

a) water-soluble nonionic polymers from the group of

b) water-soluble amphoteric polymers from the group of

b1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers / Methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b7) alkyl acrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate

Copolymers bδ) copolymers from bδi) unsaturated carboxylic acids bδii) cationically derivatized unsaturated carboxylic acids bδiii) optionally further ionic or nonionic monomers

c) water-soluble zwitterionic polymers from the group of

Alkali and ammonium salts c3) methacroylethyl betaine / methacrylate copolymers

d) water-soluble anionic polymers from the group of

d1) vinyl acetate / crotonic acid copolymers d2) vinyl pyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate N-tert-butyl acrylamide terpolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid or acrylic acid Polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the non-ionic type, d5ii) at least one monomer of the ionic type, dδiii) of polyethylene glycol and d5iv) a crosslinked d6) by copolymerization of at least one Monomers of each of the following three

Copolymers obtained in groups: dδi) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain sucked alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, d6iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or

Esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C ₈ . ₁₈ alcohol d7) terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl - 7δ -

esters dδ) tetra- and pentapolymers from dδi) crotonic acid or allyloxyacetic acid dδii) vinyl acetate or vinyl propionate dδiii) branched allyl or methallyl esters dδiv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) with one or more copolymers of crotonic acid or copolymers

Ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts d10) Terpolymers from vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position

e) water-soluble cationic polymers from the group of

Polyquaternium 1δ and Polyquaternium 27 indicated polymers.

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

The films and / or containers of the detergent or cleaning agent compositions preferred according to the invention can be produced from individual polymers mentioned above, but mixtures or multilayered layers composed of the polymers can also be used. The polymers are described in more detail below.

Water-soluble polymers preferred according to the invention are nonionic. Suitable non-ionogenic polymers are, for example: Polyvinylpyrrolidones, such as those sold under the name Luviskol (BASF). Polyvinylpyrrolidones are preferred nonionic polymers in the context of the invention.

Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (IV)

which are produced by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Vinylpyrrolidone / Vinylester copolymers, as are marketed, for example under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone-vinyl acetate copolymers, are particularly preferred nonionic polymers.

The vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (V)

- CH ₉ - CH -

I o

I

O ^ ^ R ₍ v) as a characteristic basic building block of macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates as by far the most important representatives have the greatest technical importance.

The vinyl esters are polymerized by free radicals using various processes (solution polymerization, suspension polymerization, emulsion polymerization,

Bulk polymerization.). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (IV) and (V)

Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and

Methylhydroxypropylcellulose, such as are for example sold under the trademark Culminal® ^® and Benecel ^® (AQUALON).

Cellulose ethers can be described by the following general formula

in R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in the formula is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average. Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish white, odorless and tasteless powders in widely differing degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Polyvinyl alcohols, abbreviated as PVAL, are polymers of the general structure [-CH ₂ -CH (OH) -] _n

which in small proportions also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ ]

contain. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are prepared in solution via polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol). These technical processes also make PVAL accessible which contain a predeterminable residual proportion of acetate groups.

Commercial PVAL (eg Mowiol ^® types from Hoechst) are commercially available as white-yellowish powders or granules with degrees of polymerization in the range of approx. 500-2500 (corresponding to molar masses of approx. 20,000-100,000 g / mol) and have different degrees of hydrolysis from 9δ-99 and δ7-89 mol%. They are therefore partially saponified polyvinyl acetates with a residual acetyl group content of approx. 1-2 or 11-13 mol%.

The water solubility of PVAL can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjust to the desired values.

Other polymers suitable according to the invention are water-soluble amphopolymers. Under the generic term amphopolymers, amphoteric polymers, ie polymers which contain both free amino groups and free -COOH or S0 ₃ H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers which contain quaternary ammonium groups and -COO ^" in the molecule. - or -S0 ₃ ^" groups, and summarized such polymers that contain -COOH or S0 ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3- tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally further ionic or nonionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be seen. Terpolymers of acrylic acid, methyl acrylate and Methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat 2001 N, are particularly preferred amphopolymers according to the invention. Other suitable amphoteric polymers are for example those available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are available under the name Amersette® ^® (AMERCHOL).

Anionic polymers suitable according to the invention include a .:

Vinyl acetate / crotonic acid copolymers, such as are commercially available for example under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF).

In addition to monomer units of the aforementioned formula (V), these polymers also have monomer units of the general formula (VI):

[-CH (CH ₃ ) -CH (COOH) -] _n (VI)

Vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is that available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymers.

Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, which are sold, for example, under the name Ultrahold ^® strong (BASF).

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

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture with other copolymerizable compounds on polyalkylene glycols, are obtained by polymerization in the heat in a homogeneous phase by converting the polyalkylene glycols into the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, in Presented by radical generator. Suitable vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and as an ester of acrylic acid or methacrylic acid, those which have low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available.

Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol which have the general formula VII

H- (0-CH ₂ -CH ₂ ) _n -OH (VII)

are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula VII mentioned above. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG-9 , PEG-10, PEG-12, PEG-14 and PEG-16 can be used. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone - Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers.

Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula VIII

H- (0-CH-CH ₂ ) _n -OH (VIII)

I CH ₃

are sufficient, where n can take values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycol, ie the representatives with n = 2, 3 and 4 in formula VIII. In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.

grafted and crosslinked copolymers from the copolymerization of i) at least one monomer of the non-ionic type, ii) at least one monomer of the ionic type, iii) of polyethylene glycol and iv) a crosslinker

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

The nonionic monomers can be of very different types and the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.

The non-ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid, vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are particularly preferably contained in the graft polymers.

Ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule of saccharin are preferably used as crosslinkers.

The grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight of at least one monomer of the nonionic type, ii) 3 to 80% by weight of at least one monomer of the ionic type, iii) 2 to 50% by weight, preferably 5 to 30% by weight of polyethylene glycol and iv) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii) is.

copolymers obtained by copolymerization of at least one monomer of each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or

Esters of short-chain saturated alcohols and unsaturated carboxylic acids, - 35 -

ii) unsaturated carboxylic acids, iii) esters of long chain carboxylic acids and unsaturated alcohols and / or esters from the

Carboxylic acids of group ii) with saturated or unsaturated, linear or branched C ₈ alcohol _8- ι

Short-chain carboxylic acids or alcohols are to be understood as meaning those with 1 to δ carbon atoms, the carbon chains of these compounds optionally being interrupted by double-bonded hetero groups such as -O-, -NH-, -S_.

Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester

These terpolymers contain monomer units of the general formulas (V) and (VI) (see above) and monomer units from one or more allyl or methallyesters of the formula IX:

R ¹ R ³

I I

R ² -CC (0) -0-CH ₂ - C = CH ₂ (IX)

I CH ₃

wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight-chain or branched C- | .. ₆ -alkyl radical and the sum the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2.

The above-mentioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to δ6% by weight, preferably 71 to 63% by weight of vinyl acetate and δ to 20% by weight, preferably 10 to 17% by weight .-% Allyl or Methallylester of formula IX.

Tetra and penta polymers of i) crotonic acid or allyloxyacetic acid ii) vinyl acetate or vinyl propionate iii) branched allyl or methallyl esters iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters

Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts - δδ -

Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position.

In the case of the anionic polymers, particularly suitable film and / or container materials are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins, which are described below.

Usable organic film and / or container materials are, for example, the polycarboxylic acids which can be used in the form of their sodium salts but also in free form. Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers. Particularly preferred as film and / or container materials are also biodegradable polymers of more than two different monomer units, for example those which are salts of acrylic acid and maleic acid as monomers and vinyl alcohol or vinyl alcohol derivatives or which are salts of acrylic acid and monomers the 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymeric film and / or container materials are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred film and / or container materials are polymeric aminodicarboxylic acids, their salts or their precursors. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable film and / or container materials are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other polymers that can preferably be used as film and / or container materials are cationic polymers. The permanent cationic polymers are preferred among the cationic polymers. According to the invention, polymers which have a cationic group irrespective of the pH of the agent (ie both the film and the rest of the detergent or cleaning agent composition) are referred to as “permanently cationic”. These are generally polymers which have a quaternary nitrogen atom , for example in the form of an ammonium group.

Preferred cationic polymers are, for example

quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives.

Polysiloxanes with quaternary groups, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM -2059 (manufacturer: General Electric), SLM-55067 (Manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; di-quaternary polydimethylsiloxanes, Quaternium-80),

Cationic guar derivatives, such as in particular the products sold under the trade names Cosmedia ^® Guar and Jaguar ^® ,

Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers.

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.

Vinylpyrrolidone-methoimidazolinium chloride copolymers, such as those sold under the name Luviquat ^® , quaternized polyvinyl alcohol

as well as those under the designations

Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27

known polymers with quaternary nitrogen atoms in the main polymer chain. The polymers mentioned are named according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which express reference is made here becomes.

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

In preferred washing or cleaning agent compositions according to the invention, the film and / or container material is selected from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinylpyrrolidone, polyethylene oxide, Polyethylene glycol, gelatin, cellulose and their derivatives, in particular MC, HEC, HPC, HPMC and / or CMC, and / or copolymers and mixtures thereof. Optionally, plasticizers known to those skilled in the art can be added to the coverings to increase the flexibility of the material.

In the context of the present invention, polyvinyl alcohols are particularly preferred as water-soluble polymers. "Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure

which in small proportions (approx. 2%) also structural units of the type

contain.

Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups. The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. Polyvinyl alcohol is largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allows water vapor to pass through. Preferred detergent or cleaning agent compositions in the context of the present invention are characterized in that the water-soluble or water-dispersible container and / or the water-soluble or water-dispersible closure unit comprises polyvinyl alcohols and / or PVAL copolymers whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 Mol%, particularly preferably 81 to δ9 mol% and in particular 62 to δδ mol%.

Polyvinyl alcohols of a certain molecular weight range are preferably used, washing or cleaning agent compositions according to the invention being preferred in which the water-soluble or water-dispersible container and / or the water-soluble or water-dispersible closure unit comprises polyvinyl alcohols and / or PVAL copolymers, the molecular weight of which ranges from 3,500 to 100,000 gmol ^"1 , preferably from 10,000 to 90,000 gmol ^{" 1} , particularly preferably from 12,000 to 60,000 gmol ^"1 and in particular from 13,000 to 70,000 gmol ^{" 1} .

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1 δ90, particularly preferably between about 240 to about 16δ0 and in particular between about 260 to about 1500.

Detergent or cleaning agent compositions preferred according to the invention are characterized in that the water-soluble or water-dispersible container and / or the water-soluble or water-dispersible closure unit comprises polyvinyl alcohols and / or PVAL copolymers whose average degree of polymerization is between δO and 700, preferably between 150 and 400, particularly preferably between 1 δ0 to 300 and / or their molecular weight ratio MG (50%) to MG (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). Particularly suitable in the context of the present invention, polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^{® 4-8δ,} Mowiol ^® 5-δδ and Mowiol ^{® δ-88th}

Further polyvinyl alcohols which are particularly suitable as material for the water-soluble or water-dispersible film and / or containers can be found in the table below:

Further polyvinyl alcohols suitable as material for the water-soluble or water-dispersible films and / or containers are ELVANOL ^® 51-05, 52-22, 50-42, 85-δ2, 75-15, T-25, T-66, 90- 50 ( Trademark of Du Pont), ALCOTEX ^® 72.5, 7δ, B72, F80 / 40, F8δ / 4, Fδδ / 26, Fδδ / 40, Fδδ / 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 KK). ERKOL types from Wacker are also suitable.

Preferred detergent or cleaning agent compositions according to the invention are characterized in that the water-soluble or water-dispersible container and / or the water-soluble or water-dispersible closure unit comprises hydroxypropylmethyl cellulose (HPMC), which have a degree of substitution (average number of methoxy groups per anhydroglucose unit of cellulose) from 1.0 to 2.0, preferably from 1.4 to 1.9, and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of the cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25 ,

Irrespective of the chemical composition of the film, detergent and cleaning agent compositions according to the invention are preferred, which are characterized in that the film (s) which close / seal the receiving chamber (s) have a thickness of 1 to 150 μm, preferably 2 to 100 μm, particularly preferably from 5 to 75 μm and in particular from 10 to 50 μm.

The method used for the production of water-soluble or water-dispersible containers according to the invention is deep-drawing or casting.

In the context of the present application, “deep-drawing processes” refer to processes in which a first film-like wrapping material is deformed after being brought into contact with a receiving trough located in a die forming the deep-drawing plane and the shaping of the wrapping material into this receiving trough by the action of pressure and / or vacuum The wrapping material can be before or during molding by the action of heat and / or solvents and / or conditioning are pretreated by changing relative air humidity and / or temperature relative to ambient conditions. The pressure can be exerted by two parts of a tool, which behave like positive and negative to each other and deform a film placed between these tools when pressed together. However, the action of compressed air and / or the weight of the film and / or the weight of an active substance placed on the top of the film are also suitable as pressure forces.

After deep-drawing, the deep-drawn envelope materials are preferably fixed by using a vacuum within the receiving troughs and in the spatial shape achieved by the deep-drawing process. The vacuum is preferably applied continuously from deep drawing to filling, preferably to sealing and in particular to the separation of the receiving chambers. With comparable success, however, it is also possible to use a discontinuous vacuum, for example for deep-drawing the receiving chambers and (after an interruption) before and during the filling of the receiving chambers. The strength of the continuous or discontinuous vacuum can also vary and, for example, assume higher values at the beginning of the process (when deep-drawing the film) than at the end (when filling or sealing or separating).

As already mentioned, the wrapping material can be pretreated by the action of heat before or during molding into the receiving troughs of the dies. The coating material, preferably a water-soluble or water-dispersible polymer film, is kept at temperatures above 60 ° C. for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0.4 to 2 seconds. preferably heated above δ0 ° C, particularly preferably between 100 and 120 ° C and in particular to temperatures between 105 and 115 ° C. In order to dissipate this heat, but in particular also to dissipate the heat (e.g. melting) introduced by the means filled into the deep-drawn receiving chambers, it is preferred to cool the dies used and the receiving troughs located in these dies. The cooling is preferably carried out at temperatures below 20 ° C., preferably below 15 ° C., particularly preferably at temperatures between 2 and 14 ° C. and in particular at temperatures between 4 and 12 ° C. The cooling is preferably carried out continuously from the start of the deep-drawing process to the sealing and separation of the receiving chambers. Cooling liquids, preferably water, which are circulated in special cooling lines within the die are particularly suitable for cooling.

This cooling, like the continuous or discontinuous application of a vacuum described above, has the advantage of shrinking back the thermoformed containers prevent deep drawing, which not only improves the appearance of the process product, but at the same time also prevents the agents filled into the receiving chambers from escaping over the edge of the receiving chamber, for example into the sealing areas of the chamber. This prevents problems with the sealing of the filled chambers.

In the deep-drawing process, a distinction can be made between processes in which the wrapping material is fed horizontally into a molding station and from there in a horizontal manner for filling and / or sealing and / or singling, and processes in which the wrapping material is fed via a continuously rotating die-forming roller (optionally optionally with a counter-rotating male mold roll, which guides the shaping upper punches to the cavities of the female mold roll). The first-mentioned process variant of the flatbed process is to be operated both continuously and discontinuously; the process variant using a shaping roller is generally carried out continuously. All of the deep-drawing processes mentioned are suitable for producing the agents preferred according to the invention. The receiving troughs located in the matrices can be arranged “in series” or offset.

Another preferred method within the scope of the present application, which is suitable for producing the packaging, is injection molding. Injection molding refers to the shaping of a molding compound in such a way that the mass contained in a mass cylinder for more than one injection molding process plastically softens under the action of heat and flows under pressure through a nozzle into the cavity of a previously closed tool. The process is mainly used for non-hardenable molding compounds that solidify in the mold by cooling. Injection molding is a very economical, modern process for the production of non-cutting shaped objects and is particularly suitable for automated mass production. In practical operation, the thermoplastic molding materials (powder, granules, cubes, pastes, etc.) are heated to liquefaction (up to 130 ° C) and then injected under high pressure (up to 140 MPa) into closed, two-part, that is, from dies (formerly Matrix) and core (formerly patrix), preferably water-cooled hollow molds, where they cool and solidify. Piston and screw injection molding machines can be used. Suitable molding compounds (injection molding compounds) are water-soluble polymers such as, for example, the above-mentioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.

However, the shell materials can also be cast into hollow molds. The hollow form of the resulting water-soluble or water-dispersible portioned compositions according to the invention comprise at least one solidified melt. This melt can be a melted pure substance or a mixture of several substances. It is of course, it is possible to mix the individual substances of a multi-substance melt before melting or to produce separate melts which are then combined. Melting from mixtures of substances can be of advantage, for example, when eutectic mixtures are formed which melt significantly lower and thus lower the process costs.

Preferred agents according to the invention are characterized in that the hollow mold consists of at least one material or material mixture whose melting point is in the range from 40 to 1000 ° C, preferably from 42.5 to 500 ° C, particularly preferably from 45 to 200 ° C and in particular from 50 to 160 ° C.

The material of the melt preferably has a high water solubility, for example above 100 g / l, with solubilities above 200 g / l in distilled water at 20 ° C. being particularly preferred.

Such substances come from a wide variety of substance groups. In the context of the present invention, such melts have proven to be particularly suitable as material for the hollow mold which, in addition to the above-mentioned, in particular polymeric substance groups, substances from the groups of carboxylic acids, carboxylic acid anhydrides, dicarboxylic acids, dicarboxylic acid anhydrides, hydrogen carbonates, hydrogen sulfates,

Polyethylene glycols, polypropylene glycols contain sodium acetate trihydrate and / or urea. Agents according to the invention are particularly preferred here in which the material of the hollow form contains one or more substances from the groups of carboxylic acids, carboxylic anhydrides, dicarboxylic acids, dicarboxylic anhydrides, hydrogen carbonates, hydrogen sulfates,

Polyethylene glycols, polypropylene glycols, sodium acetate trihydrate and / or urea in amounts of at least 40% by weight, preferably at least 60% by weight and in particular at least 60% by weight, in each case based on the weight of the hollow mold.

In addition to the dicarboxylic acids, carboxylic acids and their salts are also suitable as materials for the production of the open hollow form. From this class of substances, citric acid and trisodium citrate as well as salicylic acid and glycolic acid have proven to be particularly suitable. It is also particularly advantageous to use fatty acids, preferably those with more than 10 carbon atoms, and their salts as material for the open hollow form. Carboxylic acids which can be used in the context of the present invention are, 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. The use of fatty acids such as Dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (Lignoceric acid), hexacosanoic acid (cerotinic acid), triacotanoic acid (melissic acid) and the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (9c-octadecenoic acid) Elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic acid (linolenic acid) .For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids as they are accessible from the fat hydrolysis. such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C _10, 4δ wt .-% C _12, 1δ% by weight of C _14, 10 wt .-% C _16, 2 wt .-% C ₁₈ wt .- δ% C ₁₈ - 1 wt .-% C ₁₈ -), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt % Cι _0, 50 wt .-% _C12, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% C ₁₈ - 1 wt .-% C ₁₈ -), tallow fatty acid (approx. 3% by weight C ₁₄ , 26% by weight C ₁₆ , 2% by weight C ₁₆ -, 2% by weight C ₁₇ , 17% by weight C ₁₈ , 44% by weight C ₁₈ -, 3% by weight C ₁₈ -, 1% by weight C ₁₈ -), hardened tallow fatty acid (approx. 2 wt% C ₄ , 2δ wt% C ₁₆ , 2 wt% C ₁₇ , 63 wt% C ₁₈ , 1 wt% C ₁₈ -), technical oleic acid (approx. 1 wt. - _12% C, 3 wt .-% C _14, 5 wt .-% C _16, 6 wt .-% C ₁₆ - 1 wt .-% C _17, 2 wt .-% C _18, 70 wt % C ₁₈ -, 10% by weight C ₁₈ -, 0.5% by weight C ₁₈ •••), technical palmitin / stearic acid (approx. 1% by weight C ₁₂ , 2% by weight C ₁₄ , 45 wt% C ₁₆ , 2 wt% C ₁₇ , 47 wt% C ₁₈ , 1 wt% C ₁₈ -) and soybean oil fatty acid (approx. 2 wt% C ₁₄ , 15 wt. -% C ₁₆ , 5% by weight C ₁₈ , 25% by weight C ₁₈ -, 45% by weight C ₁₈ -, 7% by weight C ₁₈ -).

The above-mentioned carboxylic acids are largely obtained industrially from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on an industrial scale that splits the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. The alkali metal salts of the abovementioned carboxylic acids or carboxylic acid mixtures can also be used for the preparation of the open hollow mold, if appropriate in a mixture with other materials. Salicylic acid and / or acetysalicylic acid or their salts, preferably their alkali metal salts, can also be used, for example.

Other suitable materials that can be processed into open hollow molds via the state of the melt are hydrogen carbonates, in particular the alkali metal hydrogen carbonates, especially sodium and potassium hydrogen carbonate, and the hydrogen sulfates, in particular alkali metal hydrogen sulfates, especially potassium hydrogen sulfate and / or sodium hydrogen sulfate. The eutectic mixture of potassium hydrogen sulfate and sodium hydrogen sulfate has also proven to be particularly suitable, which consists of 60% by weight of NaHS0 ₄ and 40% by weight of KHS0. Particularly suitable further melt materials can be found in the table below:

As can be seen in the table, sugars are also suitable materials for the melt. Also preferred are agents which are characterized in that the material of the hollow form contains one or more substances from the group of sugars and / or sugar acids and / or sugar alcohols, preferably from the group of sugars, particularly preferably from the group of oligosaccharides, Oligosaccharide derivatives, monosaccharides, disaccharides,

Monosacchariddenvate and disaccharide derivatives and mixtures thereof, particularly from the group of glucose and / or fructose and / or ribose and / or maltose and / or lactose and / or sucrose and / or maltodextrin and / or isomalt comprises ^®. Sugar, sugar acids and sugar alcohols have proven to be particularly suitable materials for the melt in the context of the present invention. These substances are generally not only sufficiently soluble, but are also characterized by low costs and good processability. For example, sugar and sugar derivatives, in particular the mono- and disaccharides and their derivatives, can be processed, for example, in the form of their melts, these melts having good solubility both for dyes and for many active washing and cleaning substances. The solid bodies resulting from the solidification of the sugar melts are also distinguished by a smooth surface and an advantageous appearance, such as a high surface brilliance or transparent appearance.

The group of preferred as the material for the melt in the context of the present application include sugar from the group of mono- and disaccharides, and derivatives of mono- and disaccharides in particular glucose, fructose, ribose, maltose, lactose, sucrose, maltodextrin, and isomalt, and mixtures ^® of two, three, four or more mono- and / or disaccharides and / or the derivatives of mono- and / or disaccharides. Mixtures of Isomalt ^® and glucose, Isomalt ^® and lactose, Isomalt ^® and fructose, Isomalt ^® and ribose, Isomalt ^® and maltose, glucose and sucrose, Isomalt ^® and maltodextrin or Isomalt ^® and sucrose are particularly preferred as materials for the melt. The weight fraction of ^{Isomalt® in} the total weight of the aforementioned mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight.

Mixtures of maltodextrin and glucose, maltodextrin and lactose, maltodextrin and fructose, maltodextrin and ribose, maltodextrin and maltose or maltodextrin and sucrose are also particularly preferred as the material for the melt. The proportion by weight of maltodextrin in the total weight of the aforementioned mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight.

In the context of the present application, maltodextrin refers to water-soluble carbohydrates (dextrose equivalents, DE 3-20) obtained by enzymatic degradation of starch with a chain length of 5-10 anhydroglucose units and a high proportion of maltose. Maltodextrin are used to improve the rheological and food. added caloric properties, taste little sweet u. do not tend to retrogradate. Commercial products, for example from Cerestar, are generally offered as spray-dried, free-flowing powders and have a water content of 3 to 5% by weight. As isomalt ^® in the context of the present application, a mixture of 6-O-α-D-glucopyranosyl-D-sorbitol (1, 6-GPS) and 1-O-α-D-glucopyranosyl-D-mannitol (1, 1 -GPM). In a preferred embodiment, the weight fraction of the 1,6-GPS in the total weight of the mixture is less than 57% by weight. Mixtures of this type can be prepared industrially, for example, by enzymatic rearrangement of sucrose into isomaltose and subsequent catalytic hydrogenation of the isomaltose obtained to form an odorless, colorless and crystalline solid.

In a further preferred embodiment, the present invention relates to a washing or cleaning agent which has a water-soluble or water-dispersible hollow mold which comprises at least one further solid body, the at least one further solid body being at least partially cast into the wall of the hollow mold.

In the context of the present invention, the term “hollow shape” denotes a shape enclosing at least one space, wherein the enclosed space can be filled or can be. In addition to the at least one enclosed space, the hollow shape can have further enclosed spaces and / or spaces that are not completely enclosed. In the context of the present invention, the hollow shape does not have to consist of a uniform wall material, but can also be composed of several different materials.

The inclusion of at least one solid in the wall of the hollow mold is possible, for example, by producing a hollow shell from a solidified melt, which at least partially encloses at least one solid. This hollow shell can then be filled and closed, for example by a melt with a different composition. The two solidified melts together form the hollow form of the agent preferred according to the invention.

Analogously, at least one solid can also be incorporated at least partially into the melt, which closes the hollow shell from solidified melt. Again, the hollow shell made of solidified melt and the solidified melt that forms the “lid” together form the hollow form of the agents according to the invention. In this embodiment, the hollow shell can at least partially enclose at least one solid (then the hollow form contains at least two solids), it can but also be completely free of a solid, because the solid, at least partially enclosed by the sealing melt, is at least partially cast into the wall of the hollow mold.

The agents according to the invention with a cast water-soluble or water-dispersible container comprise a hollow mold. This can be a hollow shell, for example, which is used for Recording the dispersion of the invention is suitable and can be closed if necessary. However, it is also possible (see above) to produce a hollow shell without inclusion of solid bodies and at least partially embed at least one solid body in a solidifying melt which closes the hollow mold. At least one additional solid body is at least partially cast into the wall of this hollow mold. In the context of the present invention, “solid body” means that the body or bodies do not themselves melt at the melting temperature of the melt and do not dissolve in the melt either. When processing into the agents according to the invention, the melt is therefore flowable before cooling After the melt has cooled, the solids still represent discrete areas of the hollow mold wall, but the entire hollow mold is naturally solid.

The present application further relates to a process for the preparation of compounds containing nitrile and polymer, characterized by the steps: a) introducing at least one solid in a mixer, b) spraying on a substance preparation of a cationic nitrile of the formula (I)

R ¹

R ² -N ⁽⁺⁾ - (CH ₂ ) -CN X ^H (I),

R ³

in which R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical with at least one substituent from the group -CI, -Br, - OH, - NH ₂ , -CN, an alkyl or alkenylaryl radical with a C _1-24 alkyl group, or for a substituted alkyl or alkenylaryl radical with a C _1-2 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) - CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , - CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -0) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion;

Solids in step a) of the process according to the invention are in particular all washing or cleaning-active substances or substance mixtures described above in the text, such as, for example, the solid builders or polymers. In a method according to the invention which is particularly preferred in the context of the present application, the solid presented in step a) contains at least one polymer, preferably a polymer which has at least one monomeric building block with an acid functionality. In a preferred embodiment, the weight fraction of the polymer with acid functionality in the total weight of the solid initially introduced in step a) is at least 5% by weight, preferably at least 10% by weight, preferably at least 20% by weight, particularly preferably at least 40% by weight. % and in particular at least δO% by weight. Particularly preferred are those processes in which the solid introduced in step a) consists entirely of a polymer which has at least one monomer with an acid function, particularly preferably at least one monomer from the group of the carboxylic acids, the sulfonic acids or the phosphonic acids. For a detailed description of these polymers, reference is made to the explanations above in the text in order to avoid repetition.

The substance preparation sprayed on in step b) of the process according to the invention is preferably a solution or a dispersion. For reasons of easier synthesis, solutions of such cationic nitriles are preferred in which the radicals R ¹ to R ^{3 are} identical, for example (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ^{( +)} CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" . A preferred subject of the pending application is therefore a process according to the invention in which in step b) the solution or dispersion of a cationic nitrile of the formula ( la)

R ⁴

R ⁵ -N ⁽⁺⁾ - (CH ₂ ) -CN X ^w (la),

R °

is used, in which R, R and R are independently selected from -CH ₃ , - CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ⁴ additionally can also be -H and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ( CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{" are} particularly preferred.

Compounds according to the invention which contain a cationic nitrile of the formula (I), preferably of the formula (Ia), particularly preferably of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^' , where X ^"is an anion which from the group chloride, bromide, iodide, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate or xylene sulfonate or mixtures thereof are particularly preferred. Solutions of a cationic nitrile of the formula (I) are used with particular preference. The content of cationic nitriles in these solutions, based on the total weight of the solution, is preferably at least 2% by weight, preferably at least 5% by weight, particularly preferably between 8 and 40% by weight, very particularly preferably between 10 and 35 % By weight and in particular between 12 and 30% by weight.

In addition to solutions of one or more cationic nitriles of the formula (I), dispersions which contain these nitriles can also be used in step b) of the process according to the invention, suspensions of the cationic nitriles of the formula (I) being particularly preferred. The cationic nitrile content of these suspensions, based on the total weight of the solution, is preferably at least 2% by weight, preferably at least 5% by weight, particularly preferably between 8 and 40% by weight, very particularly preferably between 10 and 35 % By weight and in particular between 12 and 30% by weight.

After spraying on a substance preparation containing nitrile quat, in a preferred embodiment of the process according to the invention, the resulting product is sprayed with a polymer-containing solution in a further step c).

The process according to the invention can generally be carried out in all mixers or granulators known to the person skilled in the art. For example, drum coaters equipped with spray nozzles, preferably two-substance nozzles, coating pans, high-speed mixers or fluidized bed apparatuses can be used. With particular preference, however, high-speed mixers or fluidized-bed apparatuses are used in the context of the present application to carry out this procedure.

A cleaning method for cleaning dishes in a dishwasher, which is characterized in that one or more washing or cleaning agent compositions according to the invention are placed in the dosing chamber of the dishwasher, preferably a dishwasher, and a washing program is run, in the course of which the Dosing chamber opens and the agent or agents are dissolved, another object of the present invention.

The dosing chamber can also be dispensed with in the cleaning process according to the invention and the compositions according to the invention can be placed, for example, in the cutlery basket. Of course, the use of a dosing aid, for example a basket, which is attached to the wash cabinet, is also possible without any problems. Accordingly, a cleaning method for cleaning dishes in a dishwasher is one in which place one or more detergent or cleaning agent compositions according to the invention with or without dosing aid in the wash cabinet of the dishwasher and run a washing program, in the course of which the detergent or cleaning agent compositions are dissolved, a further subject of the present invention.

Examples

Production of a compound from Acusol 915 and Cvanomethylen-Trimethylamiτionium methosulfate: CYMAS)

In a laboratory fluidised bed plant (Aeromatic) 400 g Acusol ^® 915 (acrylic sulfonic acid copolymer, sodium salt) were charged and in particulate form as a primary granules swirled. The fluidized material was sprayed simultaneously with 250 g of a solution of CYMAS (45% solution in water) and 670 g of a solution of Acusol ^® 915 (45% solution in water). Thereafter, the fluidized material was coated by spraying a Acusol ^® 915 solution (200 g Acusol 915 in water; 20%) coated. The resulting product was dried and fractionated.

The fraction with a grain size between 0, δ and 1.4 mm was analyzed: the nitrile quat (CYMAS) content of the resulting granules was therefore 9.1% by weight, the bulk density was 1525 g / l, and the water content was 8.6% .-%.

In storage tests, detergents or cleaning agents with a content of the previously described nitrile quat / acusol compounds were distinguished from agents with a content of conventionally made-up nitrile quats by an improved shelf life, that is, an improved bleaching effect even after a long storage period.

Claims

claims:

1. Compound comprising i) at least one cationic nitrile of the formula (I)

R ¹

I

R ² -N ^W - (CH ₂ ) -CN X ^w (I),

R ³

in which R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-2 alkyl or alkenyl radical with at least one substituent from the group -CI, - Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a Cι. ₂₄ alkyl group, or represents a substituted alkyl or alkenylaryl radical with a C _1-2 alkyl group and at least one further substituent on the aromatic ring, R ² and R ³ are selected independently of one another from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ - CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ - OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -0) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion, and ii) at least one polymer which has at least one monomeric unit with a

Has acid functionality, characterized in that the proportion by weight of the polymer in the total weight of the

Compounds is between 5 and 99.99% by weight.

2. Compound according to claim 1, characterized in that it is a cationic nitrile of the formula (Ia) as the cationic nitrile of the formula (I)

R ⁴

R ⁶

contains, in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ^{4 can} additionally be -H and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ^{( +)} CH2-CN X ^" , (CH ₃ CH ₂ ) ₃ N ^(+> CH ₂ -CN X ^' , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^"are particularly preferred.

3. Compound according to one of claims 1 or 2, characterized in that X ^"represents an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate or xylene sulfonate or whose mixtures is selected.

4. Compound according to one of claims 1 to 3, characterized in that the proportion by weight of the cationic nitrile between 0.01 to 40 wt .-%, preferably from 0.1 to 32 wt .-%, preferably from 0.2 to 2δ % By weight, particularly preferably from 0.5 to 24% by weight and in particular from 1.0 to 20% by weight, in each case based on the total weight of the compound.

5. Compound according to one of claims 1 to 4, characterized in that the polymer has at least one monomer from the group of carboxylic acids and / or sulfonic acids and / or phosphonic acids.

6. Compound according to one of claims 1 to 5, characterized in that the proportion by weight of the polymer with the acid functionality between 15 and 99 wt .-%, preferably between 25 and 97 wt .-%, preferably between 35 and 95 wt .-% , particularly preferably between 45 and 92% by weight and in particular between 50 and 39% by weight, in each case based on the total weight of the compound.

7. Compound according to one of claims 1 to 6, characterized in that the ratio of the proportion by weight of the cationic nitrile to the proportion by weight of the polymer is between 1: 1 and 1:40, preferably between 1: 1, 5 and 1:36, preferably between 1 : 2 and 1:32, particularly preferably between 1: 3 and 1:28 and in particular between 1: 4 and 1:24.

8. Compound according to one of claims 1 to 7, characterized in that the at least 50 wt .-%, preferably at least 60 wt .-%, preferably at least 70 wt .-%, particularly preferably at least 80 wt .-% and in particular at least 90% by weight of the particles of the compound have a particle size above 0.2 mm, preferably above 0.3 mm, and particularly preferably above 0.4 mm.

9. Compound according to one of claims 1 to δ, characterized in that the particles of the compound have an average particle size above 400 microns, preferably above of 500 μm, particularly preferably above 600 μm and in particular above 700 μm.

10. Compound according to one of claims 1 to 9, characterized in that the bulk density of the compound between 0.8 and 2.0 g / cm ³ , preferably between 0.9 and 1.9 g / cm ³ , particularly preferably between 1 , 0 and 1, 8 g / cm ³ and in particular between 1, 2 and 1, 8 g / cm ³ .

11. Compound according to one of claims 1 to 11, characterized in that the compound has a water content below 10% by weight, preferably below 9% by weight, particularly preferably between 1 and 9% by weight and in particular between 3 and 9 % By weight.

12. Compound according to one of claims 1 to 11, characterized in that the compound has a layer structure of a polymer-containing core, a nitrile-containing first layer and optionally a further polymer-containing second layer.

13. Compound according to one of claims 1 to 12, characterized in that the particles of the compound have a coating, wherein the coating material is at least partially selected from a polymer or polymer mixture

a) water-soluble nonionic polymers from the group of

b) water-soluble amphoteric polymers from the group of

b1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate

Copolymers b8) copolymers of bδi) unsaturated carboxylic acids bδii) cationically derivatized unsaturated carboxylic acids bδiii) optionally further ionic or nonionic monomers

c) water-soluble zwitterionic polymers from the group of

Alkali and ammonium salts c3) methacroylethyl betaine / methacrylate copolymers

d) water-soluble anionic polymers from the group of

d1) vinyl acetate / crotonic acid copolymers d2) vinylpyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, copolymerized with crotonic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the nonionic type, d5ii) at least one monomer of the ionic type, dδiii) of polyethylene glycol and d5iv) a crosslinked dδ) by copolymerization of a monomer each of the following three

Copolymers obtained in groups: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, dδiii) esters of long-chain carboxylic acids and unsaturated alcohols and / or

Esters from the carboxylic acids of group dδii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol d7) terpolymers from crotonic acid, vinyl acetate and an allyl or methallyl ester dδ) tetra- and pentapolymers from dδi) crotonic acid or allyloxyacetic acid dδii) vinyl acetate or vinyl propionate dδiii) branched allyl or methallyl esters dδiv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) crotonic acid copolymers with one or more monomers from the group

e) water-soluble cationic polymers from the group of

Polyquaternium 1δ and Polyquaternium 27 indicated polymers.

14. Compound according to one of claims 1 to 13, characterized in that the particles of the compound have a coating, wherein the coating material is at least partially selected from the group of water-soluble or water-dispersible inorganic salts, preferably from the group of sulfates, chlorides, phosphates and phosphonates, the alkali and alkaline earth salts in particular, and here in turn the sodium, potassium and / or magnesium salts, being particularly preferred.

15. Compound according to one of claims 1 to 14, characterized in that the particles of the compound have a coating, the coating material at least is selected in part from the group of meltable substances, preferably from the group of fats and / or triglycerides and / or fatty acids and / or fatty alcohols and / or waxes and / or parrafins, and / or from the group of anionic surfactants.

16. Compound according to one of claims 1 to 15, characterized in that the particles of the compound at least one further substance usually contained in washing or cleaning agents, preferably a substance from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes , Electrolytes, pH adjusters, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antifungal agents, anti-corrosive agents, anti-corrosive agents and anti-slip agents, non-aqueous solvents, plasticizers, fabric softeners, protein hydrolyzates, and UV absorbers, particularly preferably from the group of plasticizers, dyes or fragrances.

17. washing or cleaning composition comprising at least one compound according to any one of claims 1 to 16.

1δ. Detergent or cleaning agent composition according to claim 17, characterized in that the proportion by weight of the compound according to one of claims 1 to 17 of the total weight of the detergent or cleaning agent composition is between 0.01 and 30% by weight, preferably between 0.05 and 27% by weight. %, preferably between 0.1 and 24% by weight, particularly preferably between 0.2 and 21% by weight and in particular between 0.4 and 18% by weight.

19. Detergent or cleaning agent composition according to one of claims 16 or 17, characterized in that the detergent or cleaning agent composition has a water-soluble or water-dispersible packaging, which preferably comprises at least one water-soluble or water-dispersible container and at least one water-soluble or water-dispersible closure unit.

20. Detergent or cleaning agent composition according to one of claims 17 to 19, characterized in that the water-soluble or water-dispersible packaging has at least two separate receiving chambers.

21. Detergent or cleaning agent composition according to one of claims 17 to 20, characterized in that at least one of the receiving chambers contains no compound according to one of claims 1 to 17.

22. Detergent or cleaning agent composition according to any one of claims 17 to 21, characterized in that at least one receiving chamber contains a liquid and at least one further receiving chamber a solid, preferably in the form of a powder and / or an agglomerate and / or a compact and / or of a casting.

23. Detergent or cleaning agent composition according to one of claims 17 to 22, characterized in that the water-soluble or water-dispersible container and / or the water-soluble or water-dispersible closure unit comprises polyvinyl alcohols and / or PVAL copolymers, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 61 to δ9 mol% and in particular 82 to 88 mol%.

24. Detergent or cleaning agent composition according to one of claims 17 to 23, characterized in that the water-soluble or water-dispersible container and / or the water-soluble or water-dispersible closure unit comprises polyvinyl alcohols and / or PVAL copolymers whose molecular weight is in the range from 3,600 to 100,000 gmol ^{" 1} , preferably from 10,000 to 90,000 gmol ^"1 , particularly preferably from 12,000 to 80,000 gmol ^{" 1} and in particular from 13,000 to 70,000 gmol ^"1 .

2δ. Detergent or cleaning agent composition according to one of Claims 17 to 24, characterized in that the water-soluble or water-dispersible container and / or the water-soluble or water-dispersible closure unit comprises polyvinyl alcohols and / or PVAL copolymers whose average degree of polymerization is between 80 and 700, preferably between 160 and 400, particularly preferably between 180 to 300 and / or their molecular weight ratio MG (δ0%) to MG (90%) between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.4δ and 0, 6 lies.

26. Detergent or cleaning agent composition according to one of claims 17 to 2δ, characterized in that the water-soluble or water-dispersible container and / or the water-soluble or water-dispersible closure unit comprises hydroxypropylmethyl cellulose (HPMC), which has a degree of substitution (average number of methoxy groups per anhydroglucose unit) Cellulose) from 1.0 to 2.0, preferably from 1.4 to 1.9, and a molar substitution (average number of Hydroxypropoxyl groups per anhydroglucose unit of cellulose) from 0.1 to 0.3, preferably from 0.1 δ to 0.2δ.

27. Process for the production of compounds containing nitrile and polymer, characterized by the steps: a) introducing at least one solid in a mixer, b) spraying on a substance preparation of a cationic nitrile of the formula (I)

R ¹

R ² -N ⁽⁺⁾ - (CH ₂ ) -CN X ( ¹ -)

(I).

R ³

in which R ^{1 is} -H, -CH ₃ , a C _2-2 -alkyl or -alkenyl radical, a substituted C _2-2 -alkyl or -alkenyl radical with at least one substituent from the group -CI, -Br, - OH, - NH ₂ , -CN, an alkyl or alkenylaryl radical with a C _1-24 alkyl group, or for a substituted alkyl or alkenylaryl radical with a Cι _-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) - CH ₃ , -CH ₂ -OH , -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , - CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -0) nH with n = 1, 2, 3, 4, δ or 6 and X is an anion;

28. The method according to claim 27, characterized in that the solid submitted in step a) contains at least one polymer, preferably a polymer which has at least one monomeric building block with an acid functionality.

29. The method according to claim 28, characterized in that the proportion by weight of the polymer having acid functionality in the total weight of the solid introduced in step a) is at least δ% by weight, preferably at least 10% by weight, preferably at least 20% by weight, particularly is preferably at least 40% by weight and in particular at least 80% by weight.

30. The method according to any one of claims 27 to 29, characterized in that the substance preparation in step b) is a solution or a dispersion.

31. The method according to any one of claims 27 or 30, characterized in that a polymer-containing solution is sprayed on in a further step c).

2. The method according to any one of claims 27 to 31, characterized in that the method is carried out in a high-speed mixer or a fluidized bed apparatus.