DE10314441A1 - Bleach activator compounds - Google Patents

Abstract

Compounds comprising i) at least one cationic nitrile of the formula (I), DOLLAR F1 in the R · 1 · for -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 -Cl, -Br, -OH, -NH¶2¶, -CN, an alkyl or alkenyl radical with a C¶1-24¶- Alkyl group or a substituted alkyl or alkenylaryl radical with 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¶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¶-O) ¶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, the proportion by weight of the polymer in the total weight of the compound being between 5 and 99.99% by weight is characterized by increased storage stability.

Description

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

Detergent compositions for the machine dishwashing are described in various forms of offer and represented in the market. Of particular importance are powder or granular cleaners, liquids, Gels etc. or individually in containers from water soluble Film packaged compositions. Have the greatest importance in the market Detergent tablets for machine dishwashing, because they are compact and easy to use.

Around improved when cleaning at temperatures of 60 ° C and below Can achieve bleaching effect these detergents contain bleach activators. As bleach activators For example, compounds are used under perhydrolysis conditions aliphatic peroxocarboxylic acids release, such as, for example, multi-acylated alkylenediamines, especially tetraacetylethylenediamine (TAED). Cleaning supplies, which contain TAED are the subject of numerous publications the state of the art.

Another group of bleach activators, the nitrile quat type bleach activators, has also been extensively described in the prior art. So the European patent application reveals EP 303 520 (Kao Corp.) Bleaching compositions containing a peroxide and a peracid precursor containing 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 the European patent application EP 464 880 (Unilever).

The European patent application EP 458 396 (Unilever) also describes bleaching compositions which contain a peroxy bleach and a peracid precursor with at least one group N ⁺ -CH ₂ -CN or N ⁺ (CH ₂ CN) ₂ .

On Problem when using nitrile quats as bleach activators in washing or cleaning agents, is their low storage stability. In alkaline The surrounding area quickly decomposes, especially when water enters of these bleach activators. This problem can be solved, for example the separate assembly of the bleach activators or by applying protective Reduce coating layers, but such an approach limits the freedom of formulation in the production of those containing nitrile quat Detergent and leads Moreover to use additional Coating materials that are generally not active in washing or cleaning Have effect and thus the total weight of a dosing unit enlarge without any additional effect.

The The present invention was based on the object of quotation forms for nitrile quat Detergents or cleaning agents, especially machine dishwashing detergents, to provide which the stability problems mentioned above do not have. In particular, such types of clothing should be provided which are stable in storage without the use of coating materials. Alternatively, such substances should be used as coating materials which are already an integral part of the recipe and the number of recipe components are not further enlarge.

It it has now been found that the Long-term storage stable incorporation of nitrile quats in washing or Detergents, in particular detergents for machines Wash the dishes succeeds when the nitrile quats are present in compounded form of a polymer which has at least one acid functionality, the is called has at least one monomer, which is characterized by an acid functionality is present.

• i) mindestens ein kationisches Nitril der Formel (I)
  
  in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -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, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist, sowie
• ii) mindestens ein Polymer, welches mindestens einen monomeren Baustein mit einer Säurefunktionalität aufweist,

dadurch gekennzeichnet, daß der Gewichtsanteil des Polymers am Gesamtgewicht des Compounds zwischen 5 und 99,99 Gew.% beträgt.A first subject of the present application is therefore a compound comprising

• i) at least one cationic nitrile of the formula (I)
  
  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 -Cl, -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 _1-24 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 -O) _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,

characterized in that the proportion by weight of the polymer in the total weight of the compound is between 5 and 99.99% by weight.

Aus Gründen der leichteren Synthese sind Verbindungen bevorzugt, in denen die Reste R¹ bis R³ identisch sind, beispielsweise (CH₃)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^–, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^–. Ein bevorzugter Gegenstand der vorliegenden Anmeldung sind daher ein erfindungsgemäßes Compound, welches dadurch gekennzeichnet ist, daß es als kationisches Nitril der Formel (I) ein kationisches Nitril der Formel (Ia)

enthält, in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH(CH₃))₃N⁽⁺⁾CH_Z-CN X^–, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^– besonders bevorzugt sind.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 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 present application are 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 (I)

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 _Z -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 Chloride, bromide, iodide, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate or xylene sulfonate group or mixtures thereof are particularly preferred.

Of course you can a compound according to the invention contain several cationic nitriles of the structure described above. Technically feasible and within the scope of the present application Compounds according to the invention are preferred, the two, three, four or five contain various cationic nitriles of the formula (I).

The Weight fraction 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 to can be up to 60% by weight. Within the scope of the present application However, those compounds according to the invention are preferred which a weight percentage of cationic nitrile 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% by weight and in particular from 1.0 to 20% by weight, based in each case on the total weight of the Compounds.

Next The compounds of the invention further contain one or more cationic nitrile (s) at least one polymer which has at least one acid functionality. The proportion by weight of the polymer with the acid functionality is based based on the total weight, preferably more than 7% by weight more than 14% by weight, particularly preferably more than 20% by weight, entirely particularly preferably more than 25% by weight and in particular more than 29% by weight. 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 preferred between 45 and 92% by weight and in particular between 50 and 89% by weight, in each case based on the total weight of the compound.

As Polymers are fundamental all containing acid groups Polymers can be used. The polymers can be used in non-neutralized, partially neutralized or complete in neutralized form. However, use is preferred of partial re-registrations or complete neutralized acids. Preferred polymers have at least one monomer from the group of carboxylic acids and / or the sulfonic acids and / or the phosphonic acids on.

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

As Polymers are furthermore, in particular, polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, polyaspartic acid, Suitable for polyacetals and dextrins. Polymeric polycarboxylates are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a 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 with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical with 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH ₂ , -OH or -COOH as defined above, a heteroatomic group with at least one positive group found, 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 , contains.

Examples of the aforementioned (non-polymerized) monomer units of the formula III are diallylamine, methyldiallylamine, dimethyldimethylammonium salts, acrylamidopropyl (trimethyl) ammonium salts (R ¹ , R ² , and R ³ , = H, R ⁴ = C (O) 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 (O) NH (CH ₂ ) ₂ N ⁺ (CH ₃ ) ₃ X ^- ).

Especially preferred amphoteric polymers contain derivatives as monomer units of diallylamine, especially dimethyldiallylammonium salt and / or Methacrylamidopropyl (trimethyl) ammonium salt, preferably in the form of chloride, bromide, iodide, hydroxide, phosphate, sulfate, hydrosulfate, Ethyl sulffasts, methyl sulfates, mesylates, tosylates, formates or Acetates in combination with monomer units from the group of the ethylenic unsaturated Carboxylic acids.

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

Especially preferably as sulfonic acid group-containing Copolymers of unsaturated carboxylic acids containing sulfonic acid groups can be used as polymers Monomers and optionally other ionic or nonionic Monomers.

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-SO 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 (O) -NH-C (CH ₃ ) ₂ - and -C (O) -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-SO ₃ H (Va), H ₂ C = C (CH ₃ ) -X-SO ₃ H (Vb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO 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 ) with n = 0 to 4, -COO- (CH ₂ ) k- with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C ( O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH ₂ CH ₂ CH ₃ ) in formula Va), 2-acrylamido-2-propanesulfonic acid (X _ -C ( O) NH-C (CH ₃ ) ₂ in formula Va), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula Va), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula Vb), 3-methacrylamido-2-hydroxy-propanesulfonic acid (X = -C (O) 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 -OC ₆ H ₄ - in formula Va), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula VIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenisulfonic 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 (O) NH-CH ₂ CH ₂ CH ₂ - in Formula Va), 3-sulfopropylme thacrylate (X = -C (O) NN-CH ₂ CH ₂ CH ₂ - in formula VIb), sulfomethacrylamide (X = -C (O) NH- in formula Vb), sulfomethyl methacrylamide (X = -C (O) NH- CH ₂ - in formula Vb) and water-soluble salts of the acids mentioned.

As other ionic or nonionic monomers come in particular ethylenically unsaturated compounds into consideration. Preferably is the content of those used according to the invention Polymers to monomers of group iii) less than 20 wt .-%, based on the polymer. Polymers to be used with particular preference only from monomers of groups i) and ii).

• i) ungesättigten Carbonsäuren der Formel IV. R¹(R²)C=C(R³)COOH (IV), in der R¹ bis R³ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• ii) Sulfonsäuregruppen-haltigen Monomeren der Formel V R⁵(R⁶)C=C(R⁷)-X-SO₃H (V),in der R⁵ bis R⁷ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren besonders bevorzugte Inhaltsstoffe der erfindungsgemäßen Compounds.

In summary, copolymers are made of

• i) unsaturated carboxylic acids of formula IV. 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,
• ii) Monomers of the formula V containing sulfonic acid groups R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO 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 (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -
• iii) optionally further ionic or nonionic monomers, particularly preferred ingredients of the compounds according to the invention.

• i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln XVIIa, XVIIb und/oder XVIIc: H₂C=CH-X-SO₃H (Va), H₂C=C(CH₃)-X-SO₃H (Vb), HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H (Vc),in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂)CH₃)-
• iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.

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 XVIIa, XVIIb and / or XVIIc containing sulfonic acid groups: H ₂ C = CH-X-SO ₃ H (Va), H ₂ C = C (CH ₃ ) -X-SO ₃ H (Vb), HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO 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 (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ ) CH ₃ ) -
• iii) optionally further ionic or nonionic monomers.

The Copolymers can the monomers from groups i) and ii) and, if appropriate, iii) Contained in varying amounts, with all representatives from the group i) with all Representatives from group ii) and all representatives from the Group iii) can be combined. 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 -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO 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 -O- (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 ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p (VII), 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 -O- (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.

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 -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO 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 -O- (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 ) - is, 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 (O) -Y-SO ₃ H] _p (IX), 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 -O- (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.

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 (O) -Y-SO 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 -O- (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 ) - 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 (O) OY-SO 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 represents -O- (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.

In summary, compounds according to the invention which contain one or more copolymers which have structural units of the formulas 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 (O) -Y-SO ₃ H] _p (VI), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p (VII), - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p (VIII), - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p (IX), - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p (X), - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO 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 represents -O- (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.

In the polymers can the sulfonic acid groups are wholly or partly in neutralized form, i.e. that the acid Hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular can be exchanged for sodium ions. Corresponding compounds, which are characterized in that the sulfonic acid groups partially or completely neutralized in the copolymer, are preferred according to the invention.

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

at Terpolymers are particularly preferred those that 20 to 85 wt .-% Monomer from group i), 10 to 60% by weight monomer from the group ii) and 5 to 30% by weight of monomer from group iii).

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 detergent or cleaning agent 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 the group of 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 above In 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 especially between 1: 4 and 1:24.

Especially it is preferred if the compounds according to the invention are in a coarser form available. Preferred compounds according to the invention are characterized in that that this at least 50% by weight, preferably at least 60% by weight, preferred 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 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 more than 90 wt .-%, based on the total of Particles of the compound. To an advantageous homogeneous particle size distribution the compounds of the invention should in particular have be free of too fine or dust components, so particularly preferred contain no particles under 0.2 mm in diameter. Especially preferred compounds are substantially free of particles with sizes below 0.2 mm. Under "substantial become free in Contents of the present invention Contents below 2 wt .-%, preferably below 1% by weight and in particular below 0.5% by weight, in each case based to the entirety of the particles.

In Another particularly preferred embodiment has the particles of the compound of the invention an average particle size above of 400 μm, preferably above 500 μm, particularly preferably above 600 μm and in particular above of 700 μm on.

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 more preferred according to the invention Compounds is low and is preferably below 10% by weight below 10% by weight, preferably below 9% by weight, particularly preferred 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 storage stability of the compounds.

Preferred according to the invention Compounds are characterized in that the compound has a layer structure from a polymer-containing core of a nitrile-containing first layer and optionally has a further polymer-containing second layer.

• a) wasserlöslichen nichtionischen Polymeren aus der Gruppe der
• a1) Polyvinylpyrrolidone,
• a2) Vinylpyrrolidon/Vinylester-Copolymere,
• a3) Celluloseether
• a4) Polyvinylalkohol
• a5) Polyalkylenglycol, insbesondere Polyethylenglycol und/oder Polypropylenglycol
• b) wasserlöslichen amphoteren Polymeren aus der Gruppe der
• bi ) Alkylacrylamid/Acrylsäure-Copolymere
• b2) Alkylacrylamid/Methacrylsäure-Copolymere
• b3) Alkylacrylamid/Methylmethacrylsäure-Copolymere
• b4) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere
• b5) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure- Copolymere
• b6) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere
• b7) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymere
• b8) Copolymere aus b8i) ungesättigten Carbonsäuren b8ii) kationisch derivatisierten ungesättigten Carbonsäuren b8iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
• c) wasserlöslichen zwitterionischen Polymeren aus der Gruppe der
• c1) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• c2) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• c3) Methacroylethylbetain/Methacrylat-Copolymere
• d) wasserlöslichen anionischen Polymeren aus der Gruppe der
• d1) Vinylacetat/Crotonsäure-Copolymere
• d2) Vinylpyrrolidon/Vinylacrylat-Copolymere
• d3) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere
• d4) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen
• d5) gepropften und vernetzten Copolymere aus der Copolymerisation von d5i) mindesten einem Monomeren vom nicht-ionischen Typ, d5ii) mindestens einem Monomeren vom ionischen Typ, d5iii) von Polyethylenglycol und d5iv) einem Vernetzter
• d6) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere: d6i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesätigter Alkohole und ungesättigter Carbonsäuren, d6ii) ungesättigte Carbonsäuren, d6iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols
• d7) Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester
• d8) Tetra- und Pentapolymere aus d8i) Crotonsäure oder Allyloxyessigsäure d8ii) Vinylacetat oder Vinylpropionat d8iii) verzweigten Allyl- oder Methallylestern d8iv) Vinylethern, Vinylesterrn oder geradkettigen Allyl- oder Methallylestern
• d9) Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze
• d10) Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in α-Stellung verzweigten Monocarbonsäure
• e) wasserlöslichen kationischen Polymeren aus der Gruppe der
• e1) quaternierten Cellulose-Derivate
• e2) Polysiloxane mit quaternären Gruppen
• e3) kationischen Guar-Derivate
• e4) polymeren Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure
• e5) Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats
• e6) Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere
• e7) quaternierter Polyvinylalkohol
• e8) unter den INCI-Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 angegeben Polymere.

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) vinyl pyrrolidone / vinyl ester copolymers,
• a3) Cellulose ether
• a4) Polyvinyl alcohol
• a5) Polyalkylene glycol, in particular polyethylene glycol and / or polypropylene glycol
• b) water-soluble amphoteric polymers from the group of
• bi) 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
• b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
• b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers
• b8) copolymers of b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids b8iii) optionally further ionic or nonionic monomers
• c) water-soluble zwitterionic polymers from the group of
• c1) Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali and ammonium salts
• c2) Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts
• c3) methacroylethylbetaine / 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 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
• 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, d5iii) of polyethylene glycol and d5iv) a crosslinker
• d6) copolymers obtained by copolymerizing at least one monomer of each of the following three groups: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, d6iii) esters of long-chain carboxylic acids and unsaturated alcohols and / / or esters 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 ester
• d8) tetra- and pentapolymers from d8i) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate d8iii) branched allyl or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
• d9) crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts
• d10) terpolymers of 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) vinyl pyrrolidone-methoimidazolinium chloride copolymers
• e7) quaternized polyvinyl alcohol
• e8) polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

On preferred method for coating the cationic nitriles or for the production of the nitrile compounds according to the invention Fluid bed process, in which in solid, in particular powdery form present bleach activators of formula (I), optionally in Mix with binder and / or solid filler or as a pre-made Granules, with simultaneous drying in a fluidized bed apparatus sprayed with an acidic aqueous coating solution.

alternative can also be a polymer-containing one in a fluidized bed system primary particle submitted and sprayed with a nitrile quat solution and / or a polymer solution. The spraying with the two solutions can be done at the same time but also at different times, whereby if spraying is staggered with the different solutions a shell-like structure of the granules is achieved. The latter The procedure is special in the context of the present application prefers.

To the Application of the coating on the on the cationic nitriles or nitrile compounds are of course still all suitable Devices with which coatings from an aqueous solution can be produced. So can larger objects for example directly with spray nozzles, preferably two-substance nozzles, under can be sprayed simultaneously or subsequently drying. Smaller objects can in drum coaters, such as those commonly used in pharmacy are sprayed or coating pans become.

The Percentage by weight of water soluble or water-dispersible coating on the total weight of the particulate coated cationic nitriles / nitriles in the washing or Detergent compositions are preferably 0.8 to 80 % By weight, particularly preferably 1.2 to 60% by weight and in particular 1.6 up to 40% by weight.

Next The polymers mentioned are also inorganic salts for coating of the compounds according to the invention suitable. At least the coating material is preferred partly selected from the group of water-soluble or water-dispersible inorganic salts, preferably of the group of sulfates, chlorides, phosphates and phosphonates, where especially the alkali and alkaline earth salts and here again the Sodium, potassium and / or magnesium salts are particularly preferred. In particular acidic salts are suitable, which may be mixed with Polymers are used.

A third group of preferred coating materials are finally meltable Substances or mixtures of substances, in particular substances or mixtures of substances 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.

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

As fatty acids are aliphatic saturated or unsaturated, carboxylic acids labeled with branched or unbranched carbon chain. For the Production of the fatty acids exist a variety of manufacturing methods. While the lower fatty acids mostly on oxidative processes based on alcohols and / or aldehydes as well as aliphatic or acyclic hydrocarbons, are the higher homologues are mostly still easiest today by saponification more natural Fat accessible. Due to advances in transgenic plants are now almost unlimited possibilities to vary the fatty acid spectrum in the storage fats of oil plants given. Preferred fatty acids have a melting point in the context of the present invention, which allows these fats to be processed as coating material. Preferred coating materials or 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 arachidic acid and / or erucic acid and / or Elaeosterarinsäure.

fatty alcohol is a collective name for by reducing the triglycerides, fatty acids or fatty acid esters available linear, saturated or unsaturated primary Alcohols with 6 to 22 carbon atoms. The fatty alcohols can be found in dependence saturated by the manufacturing process or unsaturated his. 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 frame 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. On the one hand, waxes with such a melting range are dimensionally stable at room temperature, however, melt at temperatures of 30 ° C. to 90 ° C. typical for machine dishwashing and are therefore more readily water-dispersible at these temperatures.

Under "Grow" there is a series naturally or artificial understood substances that usually melt above 40 ° C without decomposition and a little above the melting point, relatively low viscosity and not are stringy. They have a strongly temperature-dependent consistency and solubility on.

To In terms of their origin, the waxes are divided into three groups, the natural ones Waxes, chemically modified waxes and synthetic waxes.

To the natural Counting growth for example vegetable waxes such as candelilla wax, carnauba wax, Japan 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, walrus, lanolin (wool wax), or uropygial fat, Mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

To The chemically modified waxes include hard waxes, for example such as Montanester 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 Argowaz ^® (Pamentier & Co).

Further advantageous components of the matrix of the above-mentioned coatings are wax alcohols, i.e. fatty alcohols with approx. 24-36 carbon atoms, those in the form of wax esters of higher molecular weight Fatty acids (wax acids) main ingredient many natural Are waxes. Exemplary for preferred wax alcohols here are lignoceryl alcohol, ceryl alcohol, Myricyl alcohol or melissyl alcohol called.

In summary are compounds according to the invention preferred, in which the particles of the compound have a coating have, wherein the coating material at least partially is selected 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, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, anti-swelling agents and anti-phobic agents fasteners, non-aqueous solvents, plasticizers, fabric softeners, protein hydrolyzates, and UV absorbers, 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.

On further subject of the present application are washing or Detergent composition comprising at least one compound according to the invention contain.

The Weight fraction of the compound according to the invention on 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 preferably between 0.2 and 21% by weight and in particular between 0.4 and 18 % By weight.

Next the compounds of the invention contain preferred detergent or cleaning agent compositions furthermore at least one washing or cleaning active substance from the group of bleaching agents, bleach activators, polymers, builders, Surfactants, enzymes, electrolytes, pH adjusting agents, 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 agents, Swelling and anti-slip agents, non-aqueous solvents, plasticizers, fabric softeners, protein hydrolyzate, as well as UV absorbers.

in the Preferred detergent or cleaning agent compositions within the scope of the present invention are characterized in that these Compositions builders in amounts of 1 to 100% by weight, preferably 5 to 95% by weight, particularly preferably from 10 to 90% by weight and in particular from 20 to 85 wt .-%, each based on the weight of the washing or Detergent composition contains.

In the washing machine according to the invention or detergent compositions can all typically be found in laundry or Builders used detergents may be included, in particular So zeolites, silicates, carbonates, organic cobuilders and - where no ecological There are prejudices against their use - including phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} H ₂ O, 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 O ₅ .yH ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 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 the sharp X-ray reflections that are typical of 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 deliver 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.

in the Preferred detergent or cleaning agent compositions within the scope 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 from 15 to 50% by weight and in particular from 20 to 40% by weight, in each case based on the weight of the detergent or cleaning composition without the water-soluble or water-dispersible container, contains.

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 n Na ₂ O · (1-n) K ₂ O · Al ₂ O ₃ · (2–2.5) SiO ₂ · (3.5–5.5) H ₂ O 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 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It goes without saying it is also possible to use the generally known phosphates as builder substances, provided that such use is not avoided for ecological reasons should be. Among the variety of commercially available The alkali metal phosphates have a particular preference for phosphates Pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) of greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid HP ₃ O _{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 PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{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 PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to the diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

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

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , enamel point 94 ° with water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O 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), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH of which is 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. 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 O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -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% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). 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: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

This are accurate according to the invention such as sodium tripolyphosphate, potassium tripolyphosphate or mixtures usable from these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and are potassium tripolyphosphate and sodium potassium tripolyphosphate usable according to the invention.

in the Preferred detergent or cleaning agent compositions within the scope of the present invention are characterized in that these Phosphate (s), preferably alkali metal phosphate (s), particularly preferred Pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 20 to 80% by weight, preferably 25 to 75% by weight us in particular from 30 to 70 wt .-%, each based on the weight the detergent or cleaning agent composition without the water-soluble or water-dispersible container, contain.

As other components can alkali carriers be present. As an alkali carrier apply, for example, alkali metal hydroxides, alkali metal carbonates, Alkali metal bicarbonates, alkali metal sesquicarbonates, the aforementioned Alkali silicates, alkali metasilicates, and mixtures of the aforementioned Substances, in the sense of this invention preferably the alkali carbonates, especially sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate be used. A builder system is particularly preferred a mixture of tripolyphosphate and sodium carbonate. Likewise a builder system containing a mixture is particularly preferred from tripolyphosphate and sodium carbonate and sodium disilicate.

Especially contain preferred detergent or cleaning agent compositions Carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably from 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.

useful organic builders are, for example, those that can be used in the form of their sodium salts polycarboxylic being under polycarboxylic acids such carboxylic acids can be understood that 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), unless such use for ecological reasons objectionable, and mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, sugar acids and mixtures of these.

Also the acids can in itself be used. The acids In addition to their builder effect, they typically also have the property an acidifying component and thus also serve to set a lower and milder one pH value of detergents or cleaning agents. In particular, here are citric acid, Succinic acid, glutaric, adipic acid, gluconic and to name any mixtures of these.

As Polymeric polycarboxylates are also suitable, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a 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 Have 2000 to 20,000 g / mol. Because of their superior solubility can from this group, in turn, the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, have, be preferred.

Suitable are also copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been particularly suitable maleic proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative molecular mass, 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 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 can the polymers also allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

In particular biodegradable polymers of more than two are also preferred various monomer units, for example those used as monomers Acrylic acid salts and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Acrylic acid salts and 2-alkylallylsulfonic acid as well as sugar derivatives.

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

As well are further preferred builder substances are polymeric aminodicarboxylic acids Salts or their precursors to call. Polyaspartic acids or their salts and.

Other suitable builder substances are polyacetals, which are reacted with dialdehydes Polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained. 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.

Further Suitable organic builder substances are dextrins, for example Oligomers or polymers of carbohydrates by partial Hydrolysis of starches can be obtained. The hydrolysis can be carried out according to the usual for example acid or enzyme-catalyzed processes. Preferably acts are hydrolysis products with average molecular weights in the range from 400 to 500000 g / mol. There is a polysaccharide with one Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, are preferred, where DE is a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which a DE of 100 has. Both maltodextrins can be used 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.

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

Also Oxydisuccinates and other derivatives of disuccinates, preferably Ethylene diamine disuccinate are other suitable cobuilders. there becomes ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates are also preferred in this context and glycerol trisuccinates. Suitable amounts are those containing zeolite and / or silicate-containing formulations at 3 to 15% by weight.

Further Organic cobuilders that can be used are, for example, acetylated ones hydroxy or their salts, which may also be in lactone form can and which have at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.

A phosphonates represent another class of substances with cobuilder properties It is particularly hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferred used as the sodium salt, the disodium salt being neutral and the tetrasodium salt is alkaline (pH 9). As aminoalkane phosphonates come preferably ethylenediaminetetramethylene phosphonate (EDTMP), Diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and octa sodium salt the DTPMP. As a builder, the class becomes the Phosphonates preferably used HEDP. The aminoalkane phosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agent also bleach contain, be preferred, aminoalkanephosphonates, in particular DTPMP, to use, or to use mixtures of the phosphonates mentioned.

Furthermore can all compounds capable of complexes with alkaline earth ions train as cobuilders.

The Amount of builders is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50 wt .-%, each based on the detergent or cleaning agent composition. Again it is Amount of builders used depending on the intended use, so bleaching compositions higher Amounts of builders can have (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 wt .-%, preferably 12.5 to 45 wt .-% us in particular between 17.5 and 37.5% by weight).

Next Builders) can the agents according to the invention anionic, nonionic, cationic and / or amphoteric surfactants contain, with non-ionic surfactants preferred due to their foaming power are.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sweat field trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Further suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters are the mono-, di- and triesters and their mixtures to understand how they in the manufacture by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved. Preferred sulfonated fatty acid glycerol esters are included the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or Behenic acid.

As alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -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 ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 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 the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol 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 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As other anionic surfactants are particularly suitable for soaps. Saturated fatty acid soaps are suitable, like the salts of lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and especially from natural ones fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The including anionic surfactants the soaps can in the form of their sodium, potassium or ammonium salts and as soluble salts organic bases, such as mono-, di- or triethanolamine, are present. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially 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 18 carbon atoms, for example from coconut, palm, tallow fat 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 _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 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 ethoxy latex has 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.

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 8 to 22, preferably 12 to 18, 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.

A another class of preferred nonionic surfactants used, the either as the sole nonionic surfactant or in combination used 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.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can 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 from that.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (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.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder Propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (XVI)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} 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 by reductive amination of a reduced sugar obtained, for example glucose, fructose, maltose, lactose, galactose, Mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds can be reacted with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

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 is usually the case in oxo alcohol radicals In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 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 (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.

In particular dishwashing detergents according to the invention are preferred, which contain a nonionic surfactant that has a melting point above room temperature. Accordingly, preferred dishwashing detergents characterized in that they nonionic surfactants) 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, contain.

suitable non-ionic surfactants, the melting or softening points in the above Temperature range are, for example, low-foaming nonionic Surfactants that can be solid or highly viscous at room temperature. Become used at room temperature highly viscous nonionic surfactants, it is preferred that these a viscosity above 20 Pas, preferably above 35 Pas and in particular above Have 40 Pas. Also nonionic surfactants, which are waxy at room temperature Have consistency are preferred.

Prefers nonionic surfactants to be used as solid at room temperature originate from the groups of alkoxylated nonionic surfactants, especially ethoxylated ones primary Alcohols and mixtures of these surfactants with structurally complicated built-up surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants stand out beyond that through good foam control.

In a preferred embodiment The present invention is the nonionic surfactant with a Melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferred at least 15 moles, especially at least 20 moles of ethylene oxide per Mol alcohol or alkylphenol has emerged.

A particularly preferred nonionic surfactant which is solid at room temperature is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide , Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred dishwashing agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol has been 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 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 additionally Have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes preferably more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight such non-ionic surfactants. Preferred dishwashing detergents are characterized in that that she 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 make up 15% by weight of the total molecular weight of the nonionic surfactant, contain.

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 inverse block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethyl lenoxide and 44 moles 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-18 from Olin Chemicals.

A further preferred dishwashing detergent according to the invention contains nonionic surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ], in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 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 O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 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 throws 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 O (CH ₂ CH (R ³ ) O] _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 O [CH ₂ CH (R ³ ) O] _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 O [CH ₂ CH (R ³ ) O] _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 der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C_6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus -CH₃; -CH₂CH₃, -CH₂CH₂-CH₃, CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.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 (s) surfactants

in which R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; 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 ¹ in formula XII above 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 from alcohols of native origin with 12 to 18 carbon atoms, for example from 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. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, preferred dishwasher detergents according to the invention are those in which R ¹ in formula XII for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 is up 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. However, other alkylene oxides in which R ² or R ³ are selected independently of one another from -CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are also 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 radical with 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, are particularly preferred for use in the agents according to the invention. 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 are statistical Mean values for a special product can be an integer or a fractional number can. Due to the manufacturing process, there are commercial products for the above Formulas are usually not from an individual representative, but rather from mixtures, which affects both the C chain lengths and the degrees of ethoxylation or degrees of alkoxylation and consequently fractional values Numbers can result.

On Site of the surfactants mentioned or in connection with them can also cationic and / or amphoteric surfactants are used.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.The agents according to the invention can contain, for example, cationic compounds of the formulas XIII, XIV or XV as cationic active substances:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 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 are washing according to the invention or detergent compositions preferred, the surfactant (s), preferably nonionic) surfactants) and especially nonionic) Surfactants) from the group of alkoxylated alcohols, in quantities of 0.1 to 60% by weight, preferably from 0.5 to 50% by weight, particularly preferably from 1 to 40% by weight, and in particular from 2 to 30% by weight, in each case based on the total composition. Particularly preferred machine according to the invention Detergent or cleaning agent compositions are characterized in that that she 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 surfactants) contain.

Next the builders are in particular bleaches, bleach activators, enzymes, silver preservatives, Dyes and fragrances, etc. preferred ingredients of inventive washing or detergent compositions. In addition, other Ingredients be present, washing or cleaning agent compositions according to the invention are preferred that additionally one or more substances from the group of acidifying agents or contain the chelating agent.

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 com Plexing agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, ie being 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 and chelate complex images preferred within the scope of the present invention are for example polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Also complex-forming polymers, i.e. polymers that are either in the Main chain itself or sideways contribute to this functional groups that can act as ligands and with suitable metal atoms, usually with the formation of chelate complexes react, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can come from only one macromolecule or belong to different polymer chains. The latter leads to Cross-linking of the material, unless the complex-forming polymers already before covalent bonds were cross-linked.

complexing Groups (ligands) more common 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 towards ions different metals. Many base polymers are also commercially available important complex-forming polymers are polystyrene, polyacrylates, Polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethylene imines. Even natural Polymers such as cellulose, starch or chitin are complex-forming polymers. In addition, this provided with further ligand functionalities by polymer-analogous conversions become.

• (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• (iii) geminalen Diphosphonsäuren,
• (iv) Aminophosphonsäuren,
• (v) Phosphonopolycarbonsäuren,
• (vi) Cyclodextrine

in Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.-%, jeweils bezogen auf das Gewicht des Geschirrspülmittels ohne den tiefgezogenen oder gegossenen Behälter, enthalten.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.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
• b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-asparaginsäure oder Nitrilotriessigsäure (NTA),
• c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
• d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),
• e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
• f) Cyclodextrine.

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, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di- (β-hydroxyethyl) 1,2-glycine 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, and derivatives thereof containing hydroxyl or amino groups, and 1-aminoethane-1,1-diphosphonic acid, their higher homologues with up to 8 carbon atoms as well as derivatives thereof containing hydroxyl or amino groups,
• 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 includes a pre-wash, a main wash and a rinse aid, which are interrupted by intermediate rinse cycles. Most machines have a pre-wash for heavily soiled dishes switchable, but is only selected by the consumer in exceptional cases, so that in Most machines have a main wash, an intermediate wash pure water and a rinse aid carried out become. The temperature of the main wash cycle varies depending on Machine type and program level selection between 40 and 65 ° C. Be in the rinse aid Rinse aid added from a dosing tank in the machine, which is usually contain non-ionic surfactants as the main ingredient. Such rinse aids lie in liquid Form before and are widely described in the prior art. Your task consists primarily of lime stains and deposits on the cleaned dishes to prevent. In addition to water and low-foaming nonionic surfactants this rinse aid often also hydrotopes, pH regulators such as citric acid or scale inhibitors Polymers.

The Storage tank in the dishwasher must in at regular intervals rinse aid filled be a filling depending on the machine type for 10 to 50 rinse cycles are sufficient. Will filling up the Forget tanks, especially glasses become unsightly due to limescale stains and deposits. In the prior art, there are therefore some proposed solutions, one rinse aid in the detergent for machine dishwashing to integrate. "2in1" products which Detergent and rinse aid unite, are now also established in the market.

A further development goes there, also the filling of the regeneration salt container of the dishwasher to make it unnecessary. Also called "3in1" cleaners, which have the three functions of cleaning, rinsing and water softening combine in a single cleaner formulation so that for the consumer also refilling of salt in water hardness from 1 to 3 becomes superfluous, are now in the market. For water softening, these cleaners usually contain Sodium tripolyphosphate and / or polymers effective as softeners.

Washing according to the invention or detergent compositions for automatic dishwashing can therefore additionally as a softener contain effective polymers. With particular preference the already detailed above described sulfonic acid group-containing Polymers used. To avoid repetitions on this Place on the execution there directed.

Among the compounds which serve as bleaching agents and supply in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. 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, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the 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-phthalimidthanoic acid paproacidaproacidoxyhexanoic acid , o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic acid, diperoxyphthalic acids, the 2-decyldiperoxybutane-1,4- diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

As Bleaching agents in the washing or cleaning agent compositions according to the invention can chlorine or bromine-releasing substances can also be used. Under the appropriate chlorine or bromine releasing materials come for example heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric, tribromoisocyanuric, dibromoisocyanuric and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. 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 Lich bleaches in amounts of 1 to 40 wt .-%, preferably from 2.5 to 30 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent without the water-soluble or water-dispersible container.

As Bleach activator that supports the action of the bleaching agents is / are according to the invention in the washing or detergent compositions cationic nitrile (s) contain. It is possible, that the means contain further bleach activators). Possible other bleach activators, which have not already been described as nitrile quats, are, for example, compounds that contain one or more N or Contain O-acyl groups, such as substances from the anhydride class, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylene diamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

As Bleach activators can continue compounds that are aliphatic under perhydrolysis conditions peroxycarboxylic with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid result can be used. Suitable substances are the O- and / or N-acyl groups of the above C number of carbon atoms and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine, are preferred (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl morpholinium acetonitrile methyl sulfate (MMA) and acetylated sorbitol and mannitol or their Mixtures (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. hydrophilic Substituted acylacetals and acyl lactams are also preferred used. Combinations of conventional bleach activators can also be used become. The bleach activators are commonly used in automatic dishwashing detergents in amounts from 0.1 to 20% by weight, preferably from 0.25 to 15% by weight and in particular from 1 to 10% by weight, in each case based on the composition, used. In the context of the present invention, the mentioned proportions on the weight of the agent without the water-soluble or water-dispersible container.

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

Provided in addition to the nitrile quats, other bleach activators can be used are preferred, bleach activators from the group of multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (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 up to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 up to 6% by weight based on the detergent or cleaning agent compositions without the water-soluble or water-dispersible container, used.

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 of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate in usual Amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01 % By weight to 0.25% by weight, in each case based on the total agent without the container, used. But in special cases more bleach activator can also 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 (9. Edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, pp. 182-184) understood auxiliary substances which are necessary for the rapid disintegration of tablets in water or gastric juice and for the release of Provide pharmaceuticals in an absorbable form.

This Substances, which are also referred to as "explosives" due to their effect, enlarge when water enters their volume, on the one hand increasing their own volume (swelling), on the other hand also about the Release of gases creates a pressure on the tablet can disintegrate into smaller particles. Well-known Disintegration aids include carbonate / citric acid systems, taking other organic acids can be used. Swelling disintegration aids are, for example, synthetic Polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or modified Natural substances 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. contains refer only to the composition of 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 H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetate 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 disintegration aids, 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.

As further disintegrant based on cellulose or as a component this component can use microcrystalline cellulose. This microcrystalline cellulose is obtained by partial hydrolysis of Celluloses obtained under such conditions that only the amorphous Attack areas (approx. 30% of the total cellulose mass) of the celluloses and complete dissolve, leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the hydrolysis microfine celluloses provide the microcrystalline celluloses, the primary particle sizes of approx. 5 μm have and compactible for example to granules with an average particle size of 200 microns are.

in the Preferred detergent or cleaning agent compositions within the scope of the present invention included in addition a disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, co-granulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the composition without the water-soluble or water-dispersible Container.

The inventive washing or detergent compositions can also be a gas evolving Shower system included. The gas-developing shower system can consist of a single substance that comes into contact with water Releases gas. Among these compounds is magnesium peroxide in particular to be mentioned, which releases oxygen on contact with water. Usually However, the gas-releasing bubble system consists of itself at least two components that form gas together react. While a variety of systems is conceivable and executable here, for example nitrogen, Release oxygen or hydrogen, the will in the washing according to the invention or bubbling system used in detergent compositions both based on economic as well as ecological Select points of view to let. Preferred shower systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent that is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

at the alkali metal carbonates or bicarbonates are the sodium and potassium salts for cost reasons across from clearly preferred to the other salts. Of course you don't have to the relevant pure alkali metal carbonates or bicarbonates be used; rather can Mixtures of different carbonates and hydrogen carbonates are preferred his.

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

Acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts. 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).

Prefers are detergent or cleaning agent compositions within the scope of the present invention, where a substance is used as an acidifying agent in the shower system the group of organic di-, tri- and oligocarboxylic acids or Mixtures of these are used.

The cleaning agents according to the invention can to protect the dishes or the machine contain corrosion inhibitors, especially Silver protective agents in the field of automatic dishwashing have special meaning. The known substances can be used the state of the art. In general, silver protection agents in particular selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. To be used particularly preferably are benzotriazole and / or alkylaminotriazole. One finds in cleaner formulations about that out often Active chlorine-containing agents that clearly corrode the silver surface can reduce. Chlorine-free cleaners contain oxygen and nitrogen in particular organic redox-active compounds, such as di- and trihydric phenols, z. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers here are the transition metal salts, the selected are from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Likewise can Zinc compounds are used to prevent corrosion on the wash ware become.

Instead of of or in addition to the silver protection agents described above, for example the Benzotriazoles in the washing machine according to the invention or detergent compositions used redox-active substances become. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, Contains cobalt and cerium salts and / or complexes, the metals preferably are in one of the oxidation states II, III, IV, V or VI.

The Metal salts or metal complexes used should at least partially soluble in water his. The counterions suitable for salt formation include all the usual ones one, two or three times negatively charged inorganic anions, z. B. oxide, sulfate, nitrate, fluoride, but also organic anions such as B. stearate.

metal complexes For the purposes of the invention, compounds are those which have a central atom and one or more ligands and optionally additionally one or more of the above Anions exist. The central atom is one the above Metals in one of the above Oxidation states. The ligands are neutral molecules or anions that are monodentate or multidentate; the term "ligand" in the sense of the invention is e.g. in "Römpp Chemie Lexicon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, Page 2507 "explained in more detail. Complement each other the charge of the central atom and the charge in a metal complex of the ligand (s) is not zero, depending on whether a or there is an anionic excess 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 e.g. Citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The common in chemistry Definition for "oxidation level" is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168 "reproduced.

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 O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ and mixtures thereof, see above 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-hydroxyethane-1,1-diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce ( NO 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, the mixture of pentavalent and tetravalent vanadium (V ₂ O ₅ , VO ₂ , V ₂ O ₄ ) known from SO ₃ production (contact process) is suitable, as is that by diluting a Ti (SO ₄ ) ₂ - Solution of titanyl sulfate, TiOSO ₄ .

The inorganic redox-active substances, especially metal salts or metal complexes are preferably coated, i.e. completely with a waterproof but easily soluble at cleaning temperatures Material covered, to prevent their premature decomposition or oxidation during storage prevent. Preferred coating materials, which are produced by known processes, such as Sandwik melt coating processes from the food industry, are applied, paraffins, micro waxes, waxes are natural Origin such as carnauba wax, candella wax, beeswax, higher melting Alcohols such as hexadecanol, soaps or fatty acids. there the coating material, which is solid at room temperature, is melted State applied to the material to be coated, e.g. by fine-grained material to be coated in a continuous stream through a likewise continuously generated spray zone of the molten coating material is thrown. The melting point must be like this chosen be that yourself the coating material during the Silver treatment easily dissolves or melts quickly. The melting point should ideally be in Range between 45 ° C and 65 ° C and preferably in the range of 50 ° C up to 60 ° C lie.

The mentioned metal salts and / or metal complexes are in the inventive washing or detergent compositions, especially mechanical Dishwashing detergents, preferably in an amount of 0.05 to 6% by weight, preferably 0.2 to 2.5 wt .-%, based on the agent without the water-soluble or water-dispersible container, included Another important criterion for assessing a machine dishwashing detergent is, in addition to its cleaning performance, the visual appearance dry dishes after cleaning. Possibly occurring Calcium carbonate deposits on dishes or inside the machine can For example, affect customer satisfaction and thus have causal Influence on the economic success of such a cleaning agent. Another longstanding problem with machine dishwashing is the corrosion of glassware, which is usually characterized by the appearance of cloudiness, streaks and scratches but can also manifest by iridescence of the glass surface. They watched Effects are essentially based on two processes, the exit of alkali and alkaline earth ions from the glass in combination with a Hydrolysis of the silicate network, on the other hand in a deposit 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. He 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 used to prevent glass corrosion the agents according to the invention can be added are insoluble Zinc salts. these can yourself during the dishwashing process on the glass surface accumulate and prevent metal ions from dissolving there from the glass network as well as the hydrolysis of the silicates. Prevent additionally these insoluble Zinc salts also the deposit of silicate on the glass surface, so that this 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 CO ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (PO ₄ ) 2), and zinc pyrophosphate (Zn ₂ (P ₂ O ₇ )).

The Zinc compounds mentioned are in the agents according to the invention used in amounts that contain zinc ions between the agents 0.02 and 10 wt .-%, preferably between 0.1 and 5.0 wt .-% and in particular between 0.2 and 1.0 wt .-%, each based on the Means, effect. The exact content of the agent in the zinc salt or the zinc salts are naturally dependent on the type of zinc salts - each less soluble the zinc salt used, the higher its concentration should be in the agents according to the invention his.

There the insoluble Zinc salts during of the dishes cleaning process for the most part unchanged remain is the particle size of the salts a criterion to be observed so that the salts are not on glassware or machine parts stick. Here are machine according to the invention Dishwashing liquid preferred where the insoluble Zinc salts one particle size below Have 1.7 millimeters.

If the maximum particle size of the insoluble Zinc salts below 1.7 mm are insoluble residues in the dishwasher not to fear. Preferably has the insoluble Zinc salt has an average particle size that is well below this value is in order to further minimize the risk of insoluble residues, for example an average particle size smaller 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. at very poorly soluble Zinc salts, the average particle size is preferably below 100 μm. For yet less soluble Salts can be even lower; for example, are very for that poorly soluble Zinc oxide mean particle sizes below of 100 μm prefers.

A further preferred class of compounds are magnesium and / or Zinc salts) of at least one monomeric and / or polymeric organic Acid. These also cause with repeated use, the surfaces of the glassware do not change corrosively, especially no cloudiness, Streaks or scratches but also no iridescence on the glass surfaces become.

Even though according to the invention all magnesium and / or zinc salts) of monomeric and / or polymeric organic acids in the claimed agents may be included, as above described, the magnesium and / or zinc salts monomeric and / or polymeric organic acids from the groups of 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, of oxo acids, of amino acids and / or of polymeric carboxylic acids prefers. Within these groups, within the scope of the present According to the invention, the acids mentioned below are preferred: from the group the unbranched saturated or unsaturated Monocarboxylic acids: Methansäure (Formic acid), Ethansäure (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 (tetranoic acid) Myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic 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), meliacid acid (9) ), 6c-octadecenoic acid (petroselinic 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 (linolaid) 9c, 12c, 15c-octadecatreic acid (linolenic acid).

Out the group of 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-decyltetradecanoic acid, 2-undecyladecanoic acid, 2-undecyladecanoic acid, 2-undecylacid Tridecylheptadecanoic acid, 2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid, 2-hexadecyleicosanoic acid, 2-heptadecylheneicosanoic acid contains.

Out the group of unbranched saturated or unsaturated Di- or tricarboxylic acids: propanedioic (Malonic acid), Butandisäure (Succinic acid), pentanedioic (Glutaric acid), hexanedioic (Adipic acid), heptanedioic (Pimelic acid), octanedioic (Suberic acid), nonanedioic (Azelaic acid), decanedioic (Sebacic acid), 2c-butenedioic (Maleic acid), 2t-butenoic acid (fumaric acid), 2-butynedicarboxylic acid (acetylenedicarboxylic acid).

Out 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-dicarboxybenzoic acid ( Trimesionsäure).

Out the group of sugar acids: galactonic, Manno acid, Fructonsäure, arabinonic, xylonic, ribonic, 2-deoxy-ribonic, Alginic acid.

Out the group of hydroxy acids: hydroxyphenylacetic (Mandelic acid), 2-hydroxypropanoic (Lactic acid), malic (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).

Out the group of oxo acids: 2-oxopropionic (Pyruvic acid), 4-oxo-pentanoic acid (Levulinic acid).

Out 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.

Out the group of polymeric carboxylic acids: polyacrylic acid, polymethacrylic Alkylacrylamide / acrylic acid copolymers, Alkylacrylamide / methacrylic acid copolymers, Alkyl acrylamide / methyl methacrylic acid copolymers, Copolymers of unsaturated Carboxylic acids, Vinyl acetate / crotonic acid copolymers, Vinylpyrrolidone / 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 cleaning agent compositions according to the invention can contain further ingredients customary 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 agents tion 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 × 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, Bagsværd, 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 5483.

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 B. amyloliquefaciens or from B. stearothermophilus and their further developments which are improved for use in detergents and cleaning agents. The enzyme from B. 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 B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

Furthermore are for for this purpose the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. 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 ^φ, 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 Genen cor.

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 β-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 obtained from B. subtilis β-glucanase 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 in agents according to the invention the enzymes used are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or according to known biotechnological processes produced by suitable microorganisms, such as transgenic Expression hosts of the genera Bacillus or filamentous fungi.

The Purification of the enzymes in question is conveniently done per se established processes, for example via 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 the enzymes are added in any form established in the prior art become. This includes for example by granulation, extrusion or lyophilization obtained solid preparations or, especially with liquid or gel-shaped Means, solutions the enzymes, advantageously if possible concentrated, low in water and / or mixed with stabilizers.

alternative can the enzymes for both the fixed as well for the liquid Dosage form are encapsulated, 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 as in enclosed in a solidified or in the core-shell type, in which an enzyme-containing core with a water, air and / or Chemikalienundurchlässigen Protective layer covered is. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or Dyes are applied. Such capsules are after known methods, for example by shaking or Roll granulation or applied in fluid-bed processes. Are advantageous granules of this type, for example by applying polymeric film formers, low dust and storage stable due to the coating.

Farther Is it possible, to assemble two or more enzymes so that a single Granulate multiple enzyme activities having.

On in an agent according to the invention contained protein and / or enzyme can be particularly during the Storage against damage such as inactivation, denaturation or decay, for example through physical influences, Oxidation or proteolytic cleavage are protected. With microbial Obtaining the proteins and / or enzymes is an inhibition of Proteolysis is particularly preferred, especially if the agents Proteases included. Agents according to the invention can stabilizers for this purpose contain; the provision of such means is preferred embodiment of the present invention.

A Group of stabilizers are reversible protease inhibitors. Become frequent Benzamidine hydrochloride, Borax, boric acids, boronic acids or their salts or esters are used, especially derivatives with aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their Salts or esters. As peptide protease inhibitors are among mention other ovomucoid and leupeptin; 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.

low aliphatic alcohols, but especially polyols, such as Glycerin, ethylene glycol, propylene glycol or sorbitol are further frequently Enzyme stabilizers used. Calcium salts are also used, such as calcium acetate or calcium formate, 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. Cross-linked N-containing compounds also act as enzyme stabilizers.

reducing agent and increase antioxidants the stability of the enzymes oxidative decay. A sulfur-containing reducing agent is, for example Sodium sulphate.

Prefers combinations of stabilizers are used, for example from 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 Salt. The effect of peptide-aldehyde stabilizers is due to the combination with boric acid and / or boric acid derivatives and polyols increased and by the additional use of divalent Cations, such as calcium ions further enhanced.

preferred machine according to the invention Dishwashing liquid are characterized in that they also have a 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 from 1.5 to 4.5 and in particular from 2 to 4% by weight, in each case based on the entire average.

color and fragrances can the agents according to the invention be added to the aesthetic impression to improve the emerging products and consumer in addition the performance a visually and sensory "typical and distinctive" product available put. As perfume oils or Fragrances can individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type be used. Fragrance compounds are of the ester type e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example Benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, α-isomethylionone and Methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limes and pinene. However, mixtures are preferred different fragrances, which together have an appealing fragrance produce. Such perfume oils can also natural Contain fragrance mixtures as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Likewise 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 directly into the washing or detergent compositions are incorporated but can also be advantageous to apply the fragrances to carriers, which ensure a long-lasting fragrance due to a slower fragrance release. As such carrier materials Cyclodextrins have proven themselves, for example, the cyclodextrin-perfume complexes additionally can be coated with other 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 are insensitive to the others Ingredients of the agents and against light as well as no pronounced substantivity towards the substrates to be treated with the agents, such as glass, ceramics or plastic dishes, so as not to stain them.

The inventive washing or detergent compositions dissolve in the washing or cleaning cycle Completely on, where it - like mentioned above - advantages can have if the different regions are different dissolution rates exhibit. Due to the different release speeds, besides the release of certain ingredients at certain times also target the properties of the washing or cleaning liquor changed become. For example, detergent and cleaning agent compositions preferred, in which the pH of a 1 wt .-% solution of Detergent or cleaning agent composition in water in the area from 8 to 12, preferably from 9 to 11 and in particular from 9.5 to 10.

In addition to this detergent and detergent compositions are preferred which the pH of a 1 wt .-% solution of the total washing or Detergent composition in water in the range of 7 to 11, preferably from 7.5 to 10 and in particular from 8 to 9.5, lies.

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

The Compounds containing nitrile quath described above are preferred in solid preparation form in an injection molded, deep drawn or poured water-soluble or water-dispersible container brought in.

The injection molded, thermoformed or cast water soluble or water-disposable containers can have any shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five, hexagonal and octagonal prismatic and rhombohedral shapes are preferred. Containers too with totally irregular base areas like arrow or animal shapes, trees, Clouds etc. will be realized. Assign the deep-drawn or cast container corners and edges, they are preferably rounded.

Of course they can deep-drawn or cast containers also facilities for Have subdivision into reception chambers. Detergent or cleaning agent composition where the water soluble or water-dispersible packaging at least two separate Containing chambers are within the scope of the present application prefers. For optical or recipe reasons it can be indicated the deep-drawn or cast container in more than two receiving chambers to divide. water-soluble or water-dispersible packaging with three, four, five, six, seven, eight, nine, ten, eleven, twelve or more receiving chambers are therefore within the scope of the present invention further particularly preferred embodiments.

has the water soluble or water-dispersible containers two or more reception chambers, so it is within the scope of the present Invention to avoid the adverse interactions described above between cationic nitrile and one or more components 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 in the compounds according to the invention can both constituent of the / the solids, the dispersions) and / or of solutions) his. However, the compounds according to the invention are preferably a constituent of the solids) and / or the dispersion (s).

in the Particularly preferred washing or Detergent compositions are characterized in that at least a receiving chamber contains a liquid and at least another receiving chamber a solid, preferably in the form a powder and / or an agglomerate and / or a compactate and / or a casting. The compounds according to the invention are in these preferred detergent or cleaning compositions preferably part of the solid.

in the Particularly preferred washing or Detergent compositions are characterized in that at least a receiving chamber contains a meltable casting body and at least one further Receiving chamber 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 detergent or cleaning compositions preferably part of the solid.

As liquids will be single-phase within the scope of the present applications Substances or mixtures of substances, which have a viscosity (Brookfield viscometer LVT-II at 20 rpm and 20 ° C, Spindle 3) from 500 to 100,000 mPas, preferably from 1000 to 50,000 mPas, particularly preferably from 1200 to 10000 mPas and in particular from 1300 to 5000 mPas.

such liquids can as a liquid Matrix except Water, as one of the most common Solvent, also other non-aqueous solvents contain. These non-aqueous solvents come, for example, from the groups of the mono-alcohols, diols, Triols or polyols, the ethers, esters and / or amides. Especially non-aqueous solvents are preferred, the water soluble are, "water-soluble" solvents in the sense of the present application are solvents which are at room temperature with water completely, i.e. without miscibility gap, are miscible.

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, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, di-ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol, ethoxy or methoxy, or methyl or 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.

A liquid washing detergents particularly preferred in the context of the present invention or detergent composition is characterized in that she non-aqueous solvent (s) in amounts from 0.1 to 70% by weight, preferably from 0.5 to 60% by weight, particularly 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 total composition, with preferred non-aqueous (s) solvent selected is / are from the group of non-ionic liquids which are liquid at room temperature Surfactants, the polyethylene glycols and polypropylene glycols, glycerin, Glycerol carbonate, triacetin, ethylene glycol, propylene glycol, propylene carbonate, Hexylene glycol, ethanol and n-propanol and / or iso-propanol.

As Dispersion are multiphase in the context of the present application Systems which, in addition to a continuous phase (dispersant) at least. another finely divided phase (dispersed phase, Dispergens) have. The dispersions include, for example Emulsions, aerosols and suspensions. In preferred embodiments of the present invention is the cationic nitrile (s) in solid, particulate Form, preferably in combination with a carrier material or a coating suspended in a continuous liquid phase before taking it yourself at the liquid phases for example also the aforementioned non-aqueous solvents, as well as water or mixtures of these non-aqueous solvents can trade with water.

Preferably However, dispersions are liquid, water-free formulations with coated or uncoated nitrile quats suspended therein used. As "water-free" in the frame of the present application designates formulations which have a water content below 5% by weight, preferably below 3% by weight and in particular have below 1.5 wt .-%. Such suspensions can in addition to mentioned nitrile quats and the dispersant further wash or contain cleaning-active substances. Descriptions for some preferred washing or cleaning active in the context of the present invention Substances such as surfactants, builders etc. can be found below in this description.

in der R³ für H oder einen verzweigten oder unverzweigten C_1-4-Alk(en)ylrest, X für N-R⁵ oder O, R⁴ für einen gegebenenfalls alkoxylierten verzweigten oder unverzweigten, evtl. substituierten C_8-22-Alk(en)ylrest, R⁵ für H oder R⁴ und n für eine natürliche Zahl steht, bevorzugt sind.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

in which R ^{3 represents} H or a branched or unbranched C _1-4 alk (en) yl radical, X represents NR ⁵ or O, R ^{4 represents} 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.

As In the present application, solids are in particular powders, Agglomerates, compactates and castings called. Washing according to the invention or detergent compositions which are a solid Powder and / or an agglomerate and / or a compactate and / or one Moldings are included particularly preferred.

powder is a general term for a form of division solid substances and / or mixtures of substances that are obtained by crushing, this means Grate or crush 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 designated.

To the grain size is one rough classification of the powders into coarse, fine and Very fine powder common; a more precise Classification of powder Bulk goods are made via their bulk density and through sieve analysis. Preferred in the context of the present application However, powders have lower particle sizes of 500 μm, preferably of 600 μm and in particular of 800 μm on. Methods for determining the lower particle size are supported usually on the aforementioned sieve analysis and are described in detail in the prior art.

powder can be by extrusion, pressing, rolling, briquetting, pelleting and agglomerate related processes. Each of the in State-of-the-art method for agglomeration of particulate mixtures is in principle suitable in the agents according to the invention to contain contained solids. As part of the present Invention preferably used as solids) are agglomerates in addition to the granules, the compactates and extrudates.

As Granules become piles of granules designated. A granulate is an asymmetrical aggregate from powder particles. Granulation processes are state of the art broadly described. Granules can by wet granulation, by dry granulation or compacting and produced by melt solidification granulation.

The common Granulation technology is wet granulation because this technology least restrictions is subjected and most safely to granules with cheap Properties leads. 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 used in mixers, fluidized beds or spray towers, where said mixer equipped for example with stirring and kneading tools could be. For the However, granulation are also combinations of fluidized beds) and Mixer (s) or combinations of different mixers can be used. The granulation is dependent of the starting material and the desired product properties under the influence of low to high shear forces.

He follows granulation in a spray tower so can as starting materials, for example, melting (melt solidification) or, preferably aqueous, slurries (Spray drying) solid substances are used, which are at the top of a Sprayed tower in a defined droplet size, solidify or dry in free fall and as at the bottom of the tower Granules accumulate. Melt solidification is generally suitable especially for shaping low-melting materials in the area the melting temperature are stable (e.g. urea, ammonium nitrate u. various formulations such as enzyme concentrates, pharmaceuticals etc.), the corresponding granules are also referred to as prills. Spray drying will especially for the production of detergents or detergent components used.

Further agglomeration techniques described in the prior art are Extruder or perforated roll granulation, where optional with granulating staggered powder mixtures when pressing through perforated disks (extrusion) or plastically deformed on perforated rollers. The products of Extruder granulation is also called extrudate.

compacts can be, for example, by dry granulation techniques such as produce the tableting or roller compaction. Through the Compacting in tablet presses can be single or multi-phase tablets or briquettes getting produced. The multi-phase tablets include the multi-layer or sandwich tablets, for example Coated tablets and the point tablets (bull-eye tablets). The Briquettes can just like the slugs produced in compacting rollers after the compacting through opposing Spiked rollers are crushed or struck by sieves. The Size of by Compaction particles obtained may 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. The castings released from the dies after solidification can then be used depending on the size of the die and the intended use of the casting body are used in their original size or, if appropriate, after comminution as solids in the water-soluble containers according to the invention.

As Matrix material for Casting body, which produced by melt solidification are particularly suitable fusible substances from the group of fats and / or triglycerides and / or fatty acids and / or Fatty alcohols and / or waxes and / or parrafins. A detailed one A description of these substances can be found below in this Document in connection with the description in the context of this application preferred coating materials for cationic nitriles. to Avoiding repetitions is at this point on those there versions directed.

In summary are such inventive washing or detergent compositions particularly preferred in which the detergent or cleaning agent composition contains at least one liquid and / or at least one dispersion and / or at least one solid includes. In a particularly preferred embodiment of the present The inventive washing or cleaning agent composition has the invention at least one receiving chamber, which is a liquid contains and at least one further receiving chamber, which is a solid contains.

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 the possibility of optically upgrading the overall 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 forms of implementation mentioned above can be combine as desired. So containers with rectangular or square base and circular receiving chambers as well as round ones container with octagonal compartments, the variety of possible combinations there are no limits. For reasons of process economy and the aesthetic Consumer sensibility, as well as in terms of preferred use means according to the invention in dishwashers are cuboid container prefers.

The Size of the receiving chamber (s) compared to the entire container depends on the desired Intended use of the agents according to the invention. It depends on the receiving chamber (s) are filled with further active substance should and whether a smaller or larger amount of active substance may contain the size of the receiving chambers vary. Independently detergent or cleaning agent compositions according to the invention are of use preferred with two or more receiving chambers where the volume each existing receiving chamber at least 2 vol .-%, preferably at least 5% by volume and in particular at least 10% by volume, particularly preferred between 15 to 90% by volume and very particularly between 20 and 80 Vol .-% is. The volume is calculated from the volume of the closed according to the invention container divided into receiving chambers.

preferred Containers according to the invention as a locking unit a film which, for example, by gluing, partial Melt or firmly bonded to the container by chemical reaction is. It is possible, apply the film to all container surfaces and bond firmly to them so that the film has a coating, constitutes a "coating" of the entire container. However, preferred detergent or cleaning agent compositions are characterized in that the Do not foil the entire container encloses.

Out establish process economics and the aesthetic It is impressively preferred that the Foil only applied to the container surfaces where it fulfills a function i.e. closing from reception chambers. Agents according to the invention in which the film only the areas of the container covered in which there are openings of the receiving chambers are preferred.

at the film closing the receiving chamber can of course also be a laminate of several differently composed foils act. about the use of individual film layers of different compositions can the opening different reception chambers at certain times in the washing and cleaning cycle are released. In particular, the film material or the film thickness, however, is preferably chosen so that the closure unit of deep-drawn or cast water-soluble or water-dispersible container a dissolution behavior which differs from the dissolution behavior of water soluble or water-dispersible container different.

In the context of the This application specifically designates the time at which water after introducing a container according to the invention into an aqueous liquor the film or the container wall penetrates. In particular, such embodiments are preferred in which the used foils from surrounding water faster is penetrated as the container.

preferred water-soluble or water-dispersible materials are those from the prior art Polymers known in the art. In particular, are detergent or cleaning agent compositions preferred, in which the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible sealing unit made of a polymer with a molecular weight between 5000 and 500,000 daltons, preferably between 7,500 and 250,000 daltons and especially between 10,000 and 100,000 daltons.

Such preferred polymers can synthetic or natural Be of origin. Are polymers on a native or part-native basis used as film material are detergent or cleaning agent compositions preferred, in which the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible closure unit one or more Substances from the group carrageenan, guar, pectin, xanthan, cellulose and their derivatives, starch and their derivatives as well as gelatin comprises or consists 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 molar masses 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 f 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 I 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, β, γ, μ, ν, ξ, π, ω, χ. The type of cations present (K, NH ₄ , 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 in the context of the present invention as film and / or container material usable guar, also called guar flour, is an off-white powder, that by grinding the endosperm originally in Indian and Pakistani Endemic space, now also in other countries, e.g. in the southern United States, cultivated guar beans (Cyamopsis tetragonobolus) is obtained. The main component of the guar is with up to approx. 85% by weight of the dry substance guaran (guar gum, cyamopsis gum); Minor components are proteins, lipids and cellulose. Guaran himself is a polygalactomannan, i.e. a polysaccharide whose linear Chain of unsubstituted (see Formula II) and in the C6 position with a galactose residue substituted (see formula (III) mannose units in β-D (1 → 4) linkage built is.

The ratio of II: III is approximately 2: 1; Contrary to original assumptions, the II units are not strictly alternating, but are arranged in pairs or triplets in the polygalactomannan molecule. Information about the molar mass of guaran varies 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 corresponds 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 20-80% esterified 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 up to 85% galacturonic acid. The molecular weights of the various pectins vary between 10,000 and 500000. The structural properties are also strongly dependent on the degree of polymerization dependent; so form e.g. the fruit pectins are asbestos-like when dry Fibers, the flax pectins, on the other hand, fine, granular powders.

The Pectins are mainly extracted from the inside by extraction with dilute acids Portions of citrus fruit peel, leftovers or beet pulp manufactured.

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 β-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:

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, formally speaking, is a β-1,4-polyacetate 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.

Next Cellulose and cellulose derivatives can also (modified) dextrins, Strength and starch derivatives as foil and / or container materials be used.

As nonionic organic film and / or container materials are suitable Dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The Hydrolysis can be carried out according to the usual for example acid or enzyme-catalyzed processes. Preferably acts are hydrolysis products with average molecular weights in the range from 400 to 500000 g / mol. There is a polysaccharide with one Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, are preferred, where DE is a common one Measure of the reducing effect of a polysaccharide compared to dextrose, which have a DE of 100 owns. Both maltodextrins with one can be used 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.

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

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 70-80% branched-chain Amylopectin (MW. Approx. 300,000-2,000,000), in addition, it also contains small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300-1200 glucose molecules as a result of the binding in the 1,4-position, the chain in the amylopectin branches to an ast-like structure after an average of 25 glucose units through 1,6-binding 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 hydroxy 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.

Under The proteins and modified proteins have gelatin as a foil and / or container material outstanding importance. Gelatin is a polypeptide (molecular weight: approx.15,000 → 250,000 g / mol), mainly by hydrolysis of the skin and bones collagen from animals under acidic or alkaline conditions is won. The amino acid composition The gelatin largely corresponds to that of the collagen from which it is made and varies depending on its provenance. The The use of gelatin as a water-soluble coating material is particularly important extremely wide in pharmacy in the form of hard or soft gelatin capsules common.

• a) wasserlöslichen nichtionischen Polymeren aus der Gruppe der
• a1) Polyvinylpyrrolidone,
• a2) Vinylpyrrolidon/Vinylester-Copolymere,
• a3) Celluloseether
• a4) Polyvinylalkohol
• a5) Polyalkylenglycol, insbesondere Polyethylenglycol und/oder Polypropylenglycol
• b) wasserlöslichen amphoteren Polymeren aus der Gruppe der
• b1) Alkylacrylamid/Acrylsäure-Copolymere
• b2) Alkylacrylamid/Methacrylsäure-Copolymere
• b3) Alkylacrylamid/Methylmethacrylsäure-Copolymere
• b4) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere
• b5) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere
• b6) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere
• b7) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymere
• b8) Copolymere aus b8i) ungesättigten Carbonsäuren b8ii) kationisch derivatisierten ungesättigten Carbonsäuren b8iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
• c) wasserlöslichen zwitterionischen Polymeren aus der Gruppe der
• c1) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• c2) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• c3) Methacroylethylbetain/Methacrylat-Copolymere
• d) wasserlöslichen anionischen Polymeren aus der Gruppe der
• d1) Vinylacetat/Crotonsäure-Copolymere
• d2) Vinylpyrrolidon/Vinylacrylat-Copolymere
• d3) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere
• d4) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen
• d5) gepropften und vernetzten Copolymere aus der Copolymerisation von d5i) mindesten einem Monomeren vom nicht-ionischen Typ, d5ii) mindestens einem Monomeren vom ionischen Typ, d5iii) von Polyethylenglycol und d5iv) einem Vernetzter
• d6) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere: d6i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesätigter Alkohole und ungesättigter Carbonsäuren, d6ii) ungesättigte Carbonsäuren, d6iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols
• d7) Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester
• d8) Tetra- und Pentapolymere aus d8i) Crotonsäure oder Allyloxyessigsäure d8ii) Vinylacetat oder Vinylpropionat d8iii) verzweigten Allyl- oder Methallylestern d8iv) Vinylethern, Vinylesterrn oder geradkettigen Allyl- oder Methallylestern
• d9) Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze
• d10) Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in α-Stellung verzweigten Monocarbonsäure
• e) wasserlöslichen kationischen Polymeren aus der Gruppe der
• e1) quaternierten Cellulose-Derivate
• e2) Polysiloxane mit quaternären Gruppen
• e3) kationischen Guar-Derivate
• e4) polymeren Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und AmiAcrylsäure und Methaden von crylsäure
• e5) Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats
• e6) Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere
• e7) quaternierter Polyvinylalkohol
• e8) unter den INCI-Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 angegeben Polymere.

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
• a1) polyvinylpyrrolidones,
• a2) vinyl pyrrolidone / vinyl ester copolymers,
• a3) Cellulose ether
• 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 / alkylaminoalkyl (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 of b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids b8iii) optionally further ionic or nonionic monomers
• c) water-soluble zwitterionic polymers from the group of
• c1) Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali and ammonium salts
• c2) Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts
• c3) methacroylethylbetaine / 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 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
• 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, d5iii) of polyethylene glycol and d5iv) a crosslinker
• d6) copolymers obtained by copolymerizing at least one monomer of each of the following three groups: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, d6iii) esters of long-chain carboxylic acids and unsaturated alcohols and / / or esters 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 ester
• d8) tetra- and pentapolymers from d8i) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate d8iii) branched allyl or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
• d9) crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts
• d10) terpolymers of 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 amiacrylic acid and methades of crylic acid
• e5) copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate
• e6) vinyl pyrrolidone-methoimidazolinium chloride copolymers
• e7) quaternized polyvinyl alcohol
• e8) polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

Water soluble polymers For the purposes of the invention, such polymers are those that operate at room temperature are more than 2.5% by weight soluble in water.

The Foils and / or containers the preferred according to the invention Detergent or cleaning agent compositions can be made from individual ones polymers mentioned above, but it can also mixtures or multilayered layers made of the polymers be used. The polymers are described in more detail below.

• – Polyvinylpyrrolidone, wie sie beispielsweise unter der Bezeichnung Luviskol^® (BASF) vertrieben werden. Polyvinylpyrrolidone sind bevorzugte nichtionische Polymere im Rahmen der Erfindung. Polyvinylpyrrolidone [Poly(1-vinyl-2-pyrrolidinone)], Kurzzeichen PVP, sind Polymere der allg. Formel (IV)
  
  die durch radikalische Polymerisation von 1-Vinylpyrrolidon nach Verfahren der Lösungs- oder Suspensionspolymerisation unter Einsatz von Radikalbildnern (Peroxide, Azo-Verbindungen) als Initiatoren hergestellt werden. Die ionische Polymerisation des Monomeren liefert nur Produkte mit niedrigen Molmassen. Handelsübliche Polyvinylpyrrolidone haben Molmassen im Bereich von ca. 2500-750000 g/mol, die über die Angabe der K-Werte charakterisiert werden und – K-Werfabhängig – Glasübergangstemperaturen von 130-175° besitzen. Sie werden als weiße, hygroskopische Pulver oder als wäßrige. Lösungen angeboten. Polyvinylpyrrolidone sind gut löslich in Wasser und einer Vielzahl von organischen Lösungsmitteln (Alkohole, Ketone, Eisessig, Chlorkohlenwasserstoffe, Phenole u.a.).
• – Vinylpyrrolidon/Vinylester-Copolymere, wie sie beispielsweise unter dem Warenzeichen Luviskol^® (BASF) vertrieben werden. Luviskol^® VA 64 und Luviskol^® VA 73, jeweils Vinylpyrrolidon/Vinylacetat-Copolymere, sind besonders bevorzugte nichtionische Polymere.

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

• - polyvinylpyrrolidones, as, for example, 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. Commercially available 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-Werf, 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 with the grouping that are accessible from vinyl esters of the formula

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

• – Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal^® und Benecel^® (AQUALON) vertrieben werden.

The vinyl esters are polymerized by free radicals using different 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 methylhydroxypropyl cellulose, such as are for example sold under the trademark Culminal® ^® and Benecel ^® (AQUALON).

in R für H oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in Formel für -CH₂CH₂CH₂-OH oder -CH₂CH₂-OH. Celluloseether werden technisch durch Veretherung von Alkalicellulose (z.B. mit Ethylenoxid) hergestellt. Celluloseether werden charakterisiert über den durchschnittlichen Substitutionsgrad DS bzw. den molaren Substitutionsgrad MS, die angeben, wieviele Hydroxy-Gruppen einer AnhydroglucoseEinheit der Cellulose mit dem Veretherungsreagens reagiert haben bzw. wieviel mol des Veretherungsreagens im Durchschnitt an eine Anhydroglucose-Einheit angelagert wurden. Hydroxyethylcellulosen sind ab einem DS von ca. 0,6 bzw. einem MS von ca. 1 wasserlöslich. Handelsübliche Hydroxyethyl- bzw. Hydroxypropylcellulosen haben Substitutionsgrade im Bereich von 0,85-1,35 (DS) bzw. 1,5-3 (MS). Hydroxyethyl- und -propylcellulosen werden als gelblichweiße, geruch- und geschmacklose Pulver in stark unterschiedlichen Polymerisationsgraden vermarktet. Hydroxyethyl- und -propylcellulosen sind in kaltem und heißem Wasser sowie in einigen (wasserhaltigen) organischen Lösungsmitteln löslich, in den meisten (wasserfreien) organischen Lösungsmitteln dagegen unlöslich; ihre wäßrigen Lösungen sind relativ unempfindlich gegenüber Änderungen des pH-Werts oder Elektrolyt-Zusatz.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 the cellulose have reacted with the etherification reagent or how many moles of the 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. Commercial 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 98-99 and 87-89 mol%. They are therefore partially saponified polyvinyl acetates with a residual acetyl group content of approx. 1-2 or 11-13 mol%.

The Water PVAL can be treated with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, Reduce borax and adjust it to the desired values.

Other polymers suitable according to the invention are water-soluble amphopolymers. The term amphopolymers includes amphoteric polymers, ie polymers which contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers which contain quaternary ammonium groups and -COO ^- - or -SO3 ^- groups, and summarized those polymers which contain -COOH or SO 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. Also 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 other ionic or non-ionic monomers, such as 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).

• – Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen Resyn^® (NATIONAL STARCH), Luviset^® (BASF) und Gafset^® (GAF) im Handel sind. Diese Polymere weisen neben Monomereinheiten der vorstehend genannten Formel (V) auch Monomereinheiten der allgemeinen Formel (VI) auf: [-CH(CH₃)-CH(COOH)-]_n (VI)
• – Vinylpyrrolidon/Vinylacrylat-Copolymere, erhältlich beispielsweise unter dem Warenzeichen Luviflex^® (BASF). Ein bevorzugtes Polymer ist das unter der Bezeichnung Luviflex^® VBM-35 (BASF) erhältliche Vinylpyrrolidon/Acrylat-Terpolymere.
• – Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere, die beispielsweise unter der Bezeichnung Ultrahold^® strong (BASF) vertrieben werden.
• – Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Acrylsäure oder MethaGemisch, copolymerisiert mit Crotonsäure, crylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen

Anionic polymers suitable according to the invention include:

• - 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 from vinyl esters, esters of acrylic acid or methacrylic acid alone or in acrylic acid or metha mixture, copolymerized with crotonic acid, acrylic 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 by heat polymerization obtained in a homogeneous phase by the polyalkylene glycols in the monomers of vinyl esters, esters of acrylic acid or methacrylic acid, in the presence of radical formers.

Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid, those which are used with 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, be endures.

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

genügen, wobei n Werte zwischen 1 (Propylenglycol) und mehreren tausend annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d.h. die Vertreter mit n=2, 3 und 4 in Formel VIII.Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula VIII

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.

• – gepropfte und vernetzte Copolymere aus der Copolymerisation von i) mindesten einem Monomeren vom nicht-ionischen Typ, ii) mindestens einem Monomeren vom ionischen Typ, iii) von Polyethylenglycol und iv) einem Vernetzter Das verwendete Polyethylenglycol weist ein Molekulargewicht zwischen 200 und mehreren Millionen, vorzugsweise zwischen 300 und 30.000, auf. Die nicht-ionischen Monomeren können von sehr unterschiedlichem Typ sein und unter diesen sind folgende bevorzugt: Vinylacetat, Vinylstearat, Vinyllaurat, Vinylpropionat, Allylstearat, Allyllaurat, Diethylmaleat, Allylacetat, Methylmethacrylat, Cetylvinylether, Stearylvinylether und 1-Hexen. Die nicht-ionischen Monomeren können gleichermaßen von sehr unterschiedlichen Typen sein, wobei unter diesen besonders bevorzugt Crotonsäure, Allyloxyessigsäure, Vinylessigsäure, Acrylsäure und MethaMaleinsäure, crylsäure in den Pfropfpolameren enthalten sind. Als Vernetzer werden vorzugsweise Ethylenglycoldimethacrylat, Diallylphthalat, ortho-, meta- und para-Divinylbenzol, Tetraallyloxyethan und Polyallylsaccharosen mit 2 bis 5 Allylgruppen pro Molekül Saccharin. Die vorstehend beschriebenen gepfropften und vernetzten Copoymere werden vorzugsweise gebildet aus: i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ, ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ, iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglycol und iv) 0,1 bis 8 Gew.-% eines Vernetzters, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.
• – durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltene Copolymere: i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren, ii) ungesättigte Carbonsäuren, iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols Unter kurzkettigen Carbonsäuren bzw. Alkoholen sind dabei solche mit 1 bis 8 Kohlenstoffatomen zu verstehen, wobei die Kohlenstoffketten dieser Verbindungen gegebenenfalls durch zweibindige Heterogruppen wie -O-, -NH-, -S_ unterbrochen sein können.
• – Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester Diese Terpolymere enthalten Monomereinheiten der allgemeinen Formeln (V) und (VI) (siehe oben) sowie Monomereinheiten aus einem oder mehreren Allyl- oder Methallyestern der Formel IX:
  
  worin R³ für -N oder -CH₃, R² für -CH₃ oder -CH(CH₃)₂ und R¹ für -CH₃ oder einen gesättigten geradkettigen oder verzweigten C_1-6-Alkylrest steht und die Summe der Kohlenstoffatome in den Resten R¹ und R² vorzugsweise 7, 6, 5, 4, 3 oder 2 ist. Die vorstehend genannten Terpolymeren resultieren vorzugsweise aus der Copolymerisation von 7 bis 12 Gew.-% Crotonsäure, 65 bis 86 Gew.-%, vorzugsweise 71 bis 83 Gew.-% Vinylacetat und 8 bis 20 Gew.-%, vorzugsweise 10 bis 17 Gew.-% Allyl- oder Methallylester der Formel IX.
• – Tetra- und Pentapolymere aus i) Crotonsäure oder Allyloxyessigsäure ii) Vinylacetat oder Vinylpropionat iii) verzweigten Allyl- oder Methallylestern iv) Vinylethern, Vinylesterrn oder geradkettigen Allyl- oder Methallylestern
• – Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze
• – Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in α-Stellung verzweigten Monocarbonsäure.

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, acrylic acid and methamaleic acid, acrylic 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, 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, straight-chain or branched C _8-18 alcohol. Short-chain carboxylic acids or alcohols are understood to mean those with 1 to 8 carbon atoms, the carbon chains of these compounds may optionally be 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 of one or more allyl or methallyesters of the formula IX:
  
  wherein R ^{3 is} -N 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 _1-6 alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2. The above-mentioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% Allyl or 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
• - Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position.

As Foil and / or container materials In the case of anionic polymers, polycarboxylates / polycarboxylic acids and polymers are particularly suitable Polycarboxylates, polyaspartic acid, Polyacetates and dextrins, which are described below.

useful organic film and / or container materials are for example those in the form of their sodium salts but also in Free form usable polycarboxylic acids. Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a 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 Have 2000 to 20,000 g / mol. Because of their superior solubility can from this group, in turn, the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, have, be preferred.

Suitable are also copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been particularly suitable maleic proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative molecular mass, 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.

to Improve water solubility can the polymers also allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

In particular as foil and / or container materials biodegradable polymers of more than two are also preferred various monomer units, for example those used as monomers Acrylic acid salts and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Acrylic acid salts and 2-alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymeric film and / or container materials are those the preferred monomers are acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

As well are further preferred film and / or container materials are polymeric aminodicarboxylic acids, the Salts or their precursors to call. Polyaspartic acids or their salts and derivatives.

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

Further, preferably usable as film and / or container materials Polymers are cationic polymers. Among the cationic polymers the permanently cationic polymers are preferred. As "permanent become cationic " according to the invention such Polymers referred to independently the pH of the agent (i.e. both the film and the other washing or detergent composition) have a cationic group. These are usually polymers that have a quaternary nitrogen atom, for example in the form of an ammonium group.

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

bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette. Die genannten Polymere sind dabei nach der sogenannten INCI-Nomenklatur bezeichnet, wobei sich detaillierte Angaben im CTFA International Cosmetic Ingredient Dictionary and Handbook, 5^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, finden, auf die hier ausdrücklich Bezug genommen wird.Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . 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; diquaternary polydimethylsiloxanes, Quaternium-80),
• Cationic guar derivatives, such as, in particular, the products marketed under the trade names Cosmedia ^® Guar and Jaguar ^® ,
• - Polymers dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat ^® 100 (poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are sold under the names Gafquat ^® 734 and Gafquat 755 ° in the trade.
• - Vinylpyrrolidone-methoimidazolinium chloride copolymers, as are offered under the name Luviquat ^® .
• - Quaternized polyvinyl alcohol and those under the names
• - 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 machine according to the invention or detergent compositions is the film and / or container material selected from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinyl pyrrolidone, polyethylene oxide, Polyethylene glycol, gelatin, cellulose and their derivatives, in particular MC, NEC, HPC, HPMC and / or CMC, and / or copolymers and their Mixtures. If necessary, you can the wrappings Plasticizers known to those skilled in the art to increase the flexibility of the material be added.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten.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, the as white-yellowish Powder or granules with degrees of polymerization in the range of approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol) are offered are, have degrees of hydrolysis of 98-99 and 87-89 mol% so there is still a residual content of acetyl groups. Be characterized the polyvinyl alcohols from the manufacturer by specifying the Degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

polyvinyl alcohols are dependent soluble in the degree of hydrolysis in water and a few strongly polar organic solvents (Formamide, dimethylformamide, dimethyl sulfoxide); from (chlorinated) They do not attack hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be achieved by post-treatment with aldehydes (acetalization) Complexing with Ni or Cu salts or by treatment with dichromates, boric acid or reduce borax. Polyvinyl alcohol is largely impenetrable for gases such as Oxygen, nitrogen, helium, hydrogen, carbon dioxide, however, leaves Pass water vapor through.

in the Preferred detergent or cleaning agent compositions are within the scope of the present invention characterized in that the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible closure unit polyvinyl alcohols and / or PVAL copolymers, whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol% is.

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 80,000 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 1890, more preferably between about 240 to about 1680 and especially between about 260 to about 1500th

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, the Average degree of polymerization is between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 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). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

Weitere als Material für die wasserlösliche oder wasserdispergierbaren Folien und/oder Behälter geeignete Polyvinylalkohole sind ELVANOL^® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (Warenzeichen der Du Pont), ALCOTEX^® 72.5, 78, B72, F80/40, F88/4, F88/26, F88/40, F88/47 (Warenzeichen der 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 (Warenzeichen der Nippon Gohsei K.K.). Auch geeignet sind ERKOL-Typen von Wacker.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:

Other polyvinyl alcohols suitable as material for the water-soluble or water-dispersible films and / or containers are ELVANOL ^® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 ( Trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A- 300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ- 06 (trademark of Nippon Gohsei KK). ERKOL types from Wacker are also suitable.

preferred washing machine according to the invention or detergent composition are characterized that the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible closure unit hydroxypropylmethyl cellulose (HPMC) comprises 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 cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25.

Independent of the chemical composition of the film are washing according to the invention and detergent compositions preferred, which are characterized are that the Foil (s) which closes the receiving chamber (s), a Thickness from 1 to 150 μm, preferably from 2 to 100 μm, particularly preferably from 5 to 75 μm and in particular from 10 to 50 μm, having.

at that for the production of water-soluble according to the invention or water-dispersible container used The process involves deep drawing or casting.

As a "deep drawing process" are in the frame referred to such methods in the present application which a first film-like wrapping material after spending over a receiving trough located in a die forming the deep-drawing plane and molding the wrapping material into this receiving trough by the action of pressure and / or vacuum is deformed. The wrapping material can be done before or during molding by exposure to heat and / or solvent and / or conditioning by changes compared to environmental conditions relative humidity and / or temperatures are pretreated. The pressure can be exerted by two parts of a tool, which are related to each other like positive and negative and one deformed film between these tools deform when compressed. As pressure forces however, the action of compressed air and / or that is also suitable Dead weight of the film and / or the dead weight of one on the top the active substance.

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).

How already mentioned, can the wrapping material before or during of molding into the receiving recesses of the matrices by the action of warmth be pretreated. The wrapping material, preferably a water soluble or water-dispersible polymer film, are used for up to 5 seconds, preferably for 0.1 up to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0.4 up to 2 seconds at temperatures above 60 ° C, preferably above 80 ° C, particularly preferably between 100 and 120 ° C and especially heated to temperatures between 105 and 115 ° C. to removal this warmth, but especially also for removal of the means filled in the deep-drawn receiving chambers brought in warmth (e.g. melting), it is preferred to use the matrices and to cool the receiving troughs located in these matrices. The cooling is preferably carried out at temperatures below 20 ° C., preferably below 15 ° C, particularly preferably to temperatures between 2 and 14 ° C and in particular to temperatures between 4 and 12 ° C. This is preferably done cooling continuously from the beginning of the deep-drawing process to the sealing and isolation of the reception chambers. Are particularly suitable for cooling Coolants, preferably water, which in special cooling lines within the die be circulated.

This cooling has like the previously described continuous or discontinuous Applying a vacuum has the advantage of shrinking the deep-drawn containers after deep drawing to prevent not only the appearance of the Process product is improved, but at the same time the leakage the filled in the receiving chambers Means about the edge of the receiving chamber, for example in the sealing areas the chamber is avoided. Problems with the sealing of the filled chambers are avoided.

at the deep drawing process can between procedures 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 Is performed individually and methods in which the wrapping material has a Continuously rotating die forming roller (optionally optional with an opposite out Male forming roll, which forms the upper punch to the cavities of the Guide die forming roller) guided will distinguish. The first-mentioned process variant of the The flatbed process is both continuous and discontinuous to operate the process variant using a form roller usually takes place continuously. All of the deep-drawing processes mentioned are suitable for the preparation of the agents preferred according to the invention. The receiving troughs located in the matrices can be arranged “in series” or offset his.

On further preferred within the scope of the present application, for the production A suitable process for packaging is injection molding. Injection molding thereby shaping a molding compound in such a way that the in a mass cylinder for more as an injection molding process contained mass under the influence of heat plastically softened and under pressure through a nozzle into the cavity of a previously flows into the closed tool. The process is mainly used for non-curable Molding compounds applied that solidify in the mold by cooling. The injection molding is a very economical modern process for the production without cutting shaped objects and is particularly suitable for automated mass production. One heats up in practical operation the thermoplastic molding compounds (powder, granules, cubes, pastes, etc.) up to liquefaction (up to 180 ° C) and then injects them under high pressure (up to 140 MPa) into closed, two-part, this means from die (formerly Matrix) and core (formerly Patrix) existing, preferably water-cooled molds, where they cool and solidify. Piston and screw injection molding machines can be used. As molding compounds (injection molding compounds) are water-soluble Polymers such as the cellulose ethers, pectins, Polyethylene glycols, polyvinyl alcohols, polyvinyl pyrrolidones, alginates, gelatin or strength.

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 possible to mix the individual substances of a multi-substance melt before melting, or to produce separate melts which then separate be inclined. 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, especially preferably from 45 to 200 ° C and in particular from 50 to 160 ° C, lies.

Preferably the material of the melt exhibits high water solubility on, for example, above 100 g / l, with solubilities above 200 g / l in distilled water at 20 ° C. is particularly preferred are.

Such Substances come from a wide variety of substance groups. As part of Such melts have been found in particular in the present invention as material for the hollow shape has proven suitable, in addition to the above-mentioned, in particular polymeric groups of substances from the groups of carboxylic acids, carboxylic anhydrides, dicarboxylic acids, dicarboxylic Hydrogen carbonates, hydrogen sulfates, polyethylene glycols, polypropylene glycols Contain sodium trihydrate and / or urea. Here are agents according to the invention particularly preferred in which the material of the hollow form is one or several substances from the groups of carboxylic acids, carboxylic anhydrides, dicarboxylic acids, dicarboxylic 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 80 wt .-%, based in each case 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) and meltsiacetic acid (9) Hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9tecadienoic acid, 9tecadienoic acid, 9tecadienoic acid, 9tecadienoic acid, linadic acid, 9tecadienoic acid, 9tecadienoic acid ) and 9c, 12c, 15c-octadecatreic acid (linolenic acid) It is preferred not to use the pure species, but rather technical mixtures of the individual acids, as are accessible from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _{C18 ',} 1 wt .-% C _18''), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt _12% C, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _{C18 ',} 1 wt .-% C _18''), tallow ( approx. 3 wt% C ₁₄ , 26 wt% C ₁₆ , 2 wt% C _{16 '} , 2 wt% C ₁₇ , 17 wt% C ₁₈ , 44 wt% C ₁₈ , 3 wt% C _{18 ''} , 1 wt% C _{18 '''} ), hardened tallow fatty acid (approx. 2 wt% C ₁₄ , 28 wt% C ₁₆ , 2 wt% C _17, 63 wt .-% C _18: 1 wt .-% C _{18 '),} technical grade oleic acid (about 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _16, 6 % By weight C _{16 '} , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18' , 10% by weight C _{18 ''} , 0.5% by weight C _{18 '''),} technical palmitic / stearic acid (about 1 wt .-% C _12, 2 wt .-% C ₁₄ 45 wt .-% C _16, 2 wt .-% C _17, 47 wt % C ₁₈ , 1% by weight C _{18 '} ) and soybean oil fatty acid (approx. 2% by weight C ₁₄ , 15% by weight C ₁₆ , 5% by weight C ₁₈ , 25% by weight C _{18 '} , 45% by weight C _18'' , 7% by weight C18''').

The the aforementioned carboxylic acids are technically mostly from native fats and oils Hydrolysis won. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps) is now used on an industrial scale only water is used for cleavage, which the fats in glycerol and the free fatty acids splits. Industrially processes used are, for example, cleavage in the autoclave or continuous high pressure fission. Also the alkali metal salt of the above carboxylic acids or carboxylic acid mixtures can - if necessary in a mixture with other materials - for the production of the open Use hollow form. Salicylic acid and / or, for example, can also be used acetylsalicylic acid or their salts, preferably their alkali metal salts.

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 has also proven particularly suitable A mixture of potassium hydrogen sulfate and sodium hydrogen sulfate has been proven, which consists of 60% by weight of NaHSO ₄ and 40% by weight of KHSO ₄ .

Wie der Tabelle zu entnehmen ist, sind auch Zucker geeignete Materialien für die Schmelze. Weiter bevorzugt sind daher auch Mittel, die dadurch gekennzeichnet sind, daß das Material der Hohlform einen oder mehrere Stoffe aus der Gruppe der Zucker und/oder Zuckersäuren und/oder Zuckeralkohole, vorzugsweise aus der Gruppe der Zucker, besonders bevorzugt aus der Gruppe der Oligosaccharide, Oligosaccharidderivate, Monosaccharide, Disaccharide, Monosaccharidderivate und Disaccharidderivate sowie deren Mischungen, insbesondere aus der Gruppe Glucose und/oder Fructose und/oder Ribose und/oder Maltose und/oder Lactose und/oder Saccharose und/oder Maltodextrin und/oder Isomalt^® umfaßt.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, monosaccharide derivatives and disaccharide derivatives and mixtures thereof, in particular from the group consisting of glucose and / or fructose and / or ribose and / or maltose and / or lactose and / or sucrose and / or maltodextrin and / or Isomalt ^® .

As Particularly suitable materials for the melt have been found in the Within the scope of the present invention the sugar, sugar acids and Sugar alcohols proven. These substances are generally not only sufficiently soluble but are also characterized by low costs and good processability out. This is how sugar and sugar derivatives, especially those Mono- and disaccharides and their derivatives, for example in the form process their melts, these melts having good solvent power both for dyes as also for have many washing and cleaning-active substances. From solidification resulting from the solidification of the sugar melts is also characterized by a smooth surface and an advantageous look, like high surface brilliance or transparent appearance.

To the group of the preferred material for the melt in the context of the present application Sugar count from the group of mono- and di-saccharides and derivatives of mono- and di-saccharides in particular glucose, fructose, ribose, maltose, lactose, sucrose, maltodextrin and isomalt ^® and mixtures of two, three, four or more mono- and / or di-saccharides 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.

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

As Maltodextrin are used in the context of the present application by enzymatic Breakdown of starch won water soluble Carbohydrates (dextrose equivalents, DE 3-20) with a chain length of 5-10 anhydroglucose units and a high proportion of maltose designated. Maltodextrin is used to improve foods rheological and added caloric properties, taste only a little sweet u. tend not for retrogradation.

Commercial products, for example from Cerestar, are usually spray-dried free flowing Powder offered and have a water content of 3 to 5 wt .-% on.

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 is ) designated. In a preferred embodiment, the weight proportion 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.

object The present invention is in a further preferred embodiment a detergent or cleaning agent, which is a water-soluble or has water-dispersible hollow form, the at least one other solid comprise, wherein the at least one further solid at least partially is cast into the wall of the hollow mold.

in the In the context of the present invention, the term “hollow shape” denotes at least one enclosing a room Form, whereby the enclosed space can be filled or can be. In addition to the at least one enclosed space, the hollow shape further enclosed spaces and / or not completely enclosed spaces exhibit. The hollow shape must be in Within the scope of the present invention not from a uniform Wall material exist, but can also be several different Materials.

The Inclusion at least of a solid in the wall of the hollow mold is possible, for example, by using a hollow shell is produced from a solidified melt, which at least a solid at least partially encloses. This hollow shell can then filled and - for example by a differently composed melt - be closed. The the two solidified melts together form the hollow form of the preferred ones according to the invention Agent.

Analogous can be at least one solid are also at least partially incorporated into the melt, which closes the hollow shell from solidified melt. In turn form the hollow shell from solidified melt and the solidified Melt that forms the "lid" together the hollow form of the agent according to the invention. In this embodiment can the hollow shell at least partially a solid enclose (then contains the hollow form at least two solids), but it can also be completely free of a solid be because of the sealing melt at least partially enclosed solid bodies is at least according to the invention partly 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 to hold the inventions dispersion according to the invention is suitable and can optionally be sealed. 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.

• a) Vorlegen mindestens eines Feststoffs in einem Mischer,
• b) Aufsprühen einer Stoffzubereitung eines kationische Nitrils der Formel (I)
  
  in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CN₃, -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, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist;

Another object of the present application is a process for producing nitrile and polymer-containing compounds characterized by the steps:

• a) placing at least one solid in a mixer,
• b) spraying on a preparation of a cationic nitrile of the formula (I)
  
  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 -Cl, -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 _1-24 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 -CN 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 -O) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion;

As Solids in step a) of the process according to the invention are suitable in particular all washing or washing described above cleaning-active substances or substance mixtures, such as the solid builders or polymers. In particular in the context of the present application preferred method according to the invention contains the solid submitted in step a) preferably at least one polymer a polymer which has at least one monomeric building block with a Has acid functionality.

The Weight fraction of polymer with acid functionality in the total weight of the solid presented in step a) is in a preferred embodiment at least 5% by weight, preferably at least 10% by weight, preferred at least 20% by weight, particularly preferably at least 40% by weight and is in particular at least 80% by weight. Be particularly preferred such processes in which the solid submitted in step a) Completely consists of a polymer which has at least one monomer with a Acid function, particularly preferably at least one monomer from the group of carboxylic acids, sulfonic acids or of phosphonic acids, having. For a detailed description of these polymers is used to avoid of repetitions on the executions referenced above in the text.

eingesetzt wird, in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^– , (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^–, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^– besonders bevorzugt sind.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 preceding 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 (Ia)

is used 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 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 (1), 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.

With Solutions are particularly preferred a cationic nitrile of the formula (I) used. The salary of these solutions of cationic nitriles, based on the total weight of the solution, 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.

Next solutions one or more cationic nitriles of the formula (I) can be in step b) of the method according to the invention also use dispersions containing these nitriles, in particular Suspensions of the cationic nitriles of the formula (I) are preferred. The content of cationic nitriles in these suspensions is based on the total weight of the solution, 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.

To spraying The result is a substance preparation containing nitrile quat Product in a preferred embodiment of the method according to the invention sprayed in a further step c) with a polymer-containing solution.

The inventive method can generally in all mixers or granulators known in the art carried out become. So can for example with spray nozzles, preferred Two-fluid nozzles, provided drum coater, coating pan, high speed mixer or fluidized bed apparatus can be used. With special Preference will be given within the scope of the present application for carrying out this procedure however, high speed mixers or fluidized bed equipment used.

On Cleaning process for cleaning dishes in a dishwasher, which is characterized in that one or more washing (s) according to the invention or detergent compositions in the dosing chamber of the dishwasher, preferably a dishwasher, and a washing program runs out in its The metering chamber opens and the means or means dissolved are another object of the present invention.

Also in the cleaning process according to the invention one can do without the metering chamber and the composition or compositions according to the invention place in the cutlery basket, for example. It goes without saying but also here the use of a dosing aid, for example one the basket, the attached in the washroom is easily possible. Accordingly, there is a cleaning method for cleaning dishes in a dishwasher, in which one or more detergent or cleaning agent compositions according to the invention with or without dosing aid in the dishwasher's wash cabinet and a washing program runs out in its Course of the detergent or cleaning agent compositions disbanded are another object of the present invention.

Examples

Production of a compound from Acusol 915 and cyanomethylene trimethylammonium methosulfate; CYMAS)

In a laboratory fluidized bed system (Aeromatic), 400 g of Acusol ^® 915 (acrylic acid-sulfonic acid copolymer, sodium salt) were placed in particulate form as primary granules and 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 0.8 and 1.4 mm was analyzed: the content of the resulting granules of nitrile quat (CYMAS) was therefore 9.1% by weight, the bulk density 1525 g / l, the water content 8.6% by weight.

In Storage test distinguished themselves with a detergent or cleaning agent Content of the previously described nitrile quat / acusol compounds compared to agents containing conventional assembled nitrile quats due to an improved shelf life, this means, an improved bleaching effect even after a long period of storage.

Claims (32)

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

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 -Cl, -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 _1-24 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 -O) _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, characterized in that the proportion by weight of the polymer in the total weight of the compound is between 5 and 99.99% by weight. 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)

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. 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 mixtures thereof is selected. Compound according to one of claims 1 to 3, characterized in that that the Percentage by weight of the cationic nitrile between 0.01 and 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% by weight and in particular from 1.0 up to 20% by weight, based on the total weight of the compound, is. Compound according to one of claims 1 to 4, characterized in that that this Polymer, at least one monomer from the group of carboxylic acids and / or of sulfonic acids and / or the phosphonic acids. Compound according to one of claims 1 to 5, characterized in that that the Weight fraction of polymer with acid functionality between 15 and 99% by weight, preferably between 25 and 97% by weight, is preferred between 35 and 95% by weight, particularly preferably between 45 and 92 % By weight and in particular between 50 and 89% by weight, in each case based on the total weight of the compound. Compound according to one of claims 1 to 6, characterized in that this relationship the proportion by weight of the cationic nitrile to the proportion by weight of the polymer 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. Compound according to one of Claims 1 to 7, characterized in that that this at least 50% by weight, preferably at least 60% by weight, preferred 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 Particle size above 0.2 mm, preferably above 0.3 mm, and particularly preferably above 0.4 mm. Compound according to one of claims 1 to 8, characterized in that that the Particles of the compound an average particle size above 400 microns, preferably above 500 μm, particularly preferably above 600 μm and in particular above of 700 μm exhibit. Compound according to one of Claims 1 to 9, characterized in that the bulk density of the compound 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 . Compound according to one of Claims 1 to 11, characterized in that that this Compound a water content below 10 wt .-%, preferably below 9% by weight, particularly preferably between 1 and 9% by weight and in particular has between 3 and 9 wt .-%. Compound according to one of Claims 1 to 11, characterized in that that this Compound a layer structure of a polymer-containing core, one nitrile-containing first layer and optionally another polymer-containing second layer. Compound according to one of claims 1 to 12, 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 of a) water-soluble nonionic polymers from the group of a1) polyvinylpyrrolidones, a2) vinylpyrrolidone / Vinyl ester copolymers, a3) cellulose ether a4) polyvinyl alcohol a5) polyalkylene glycol, in particular polyethylene glycol and / or polypropylene glycol b) water-soluble amphoteric polymers from the group of b1) alkylacrylamide / acrylic acid copolymers b2) alkylacrylamide / methacrylic acid copolymers b3) alkylacrylic acid Copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b7) alkyl acrylamide / alkymethacrylate / Alkyl methacrylate copolymers b8) copolymers of b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids b8iii) optionally further ionic or nonionogenic monomers c) water-soluble zwitterionic polymers from the group of c1) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts c2) acrylamidoalkyltrialkylammonium / Methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine / 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 made of vinyl) d4) graft 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 polykalkylene 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 Type, d5iii) of polyethylene glycol and d5iv) a crosslinker d6) copolymers obtained by copolymerizing at least one monomer from each of the three following 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 saturated 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 ester d8 ) Tetra- and pentapolymers from d8i) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate d8iii) branched allyl or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) crotonic acid or copolymers with a group of one or more copolymers with one or more copolymers of one or more copolymers with a group of one or more copolymers of one or more copolymers with a group of one or more copolymers of one or more copolymers with a group of one or more copolymers of one or more copolymers with one or more copolymers of a group of one or more copolymers with a group of one or more copolymers of one or more copolymers with a group of one or more copolymers of one or more copolymers with one or more copolymers of a group of one or more copolymers of a group of one or more copolymers of a group of one or more copolymers with one or more copolymers of a group of one or more copolymers of a group of one or more copolymers of a group of one or more copolymers of a group of copolymers with one another , Vinymethyl ether, acrylamide and their water-soluble salts d10) Terpolymers of 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) kati onical 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 copolymers e7 Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 indicated polymers. Compound according to one of claims 1 to 13, characterized in that that the Particles of the compound have a coating, the coating material is 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, in particular the alkali and alkaline earth salts and here again the sodium, potassium and / or magnesium salts are particularly preferred. Compound according to one of claims 1 to 14, characterized in that that the Particles of the compound have a coating, the coating material is 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. Compound according to one of claims 1 to 15, 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 adjusting agents, 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 inhibitors, antistatic agents, phobing and impregnating agents, swelling 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. Containing detergent or cleaning composition at least one compound according to any one of claims 1 to 16. Detergent or cleaning agent composition according to Claim 17, characterized in that the weight fraction of the compound according to one of the claims 1 to 17 of the total weight of the detergent or cleaning composition 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 wt .-% and in particular between 0.4 and 18 wt .-%. Detergent or cleaning agent composition according to one of the claims 16 or 17, characterized in that the detergent or cleaning composition a water soluble or water-dispersible packaging, which preferably at least one water soluble or water-dispersible container and at least one water-soluble or water-dispersible closure unit. Detergent or cleaning agent composition according to one of the claims 17 to 19, characterized in that the water-soluble or water-dispersible packaging at least two separate Has receiving chambers. Detergent or cleaning agent composition according to one of the claims 17 to 20, characterized in that at least one of the receiving chambers contains no compound according to any one of claims 1 to 17. Detergent or cleaning agent composition according to one of the claims 17 to 21, characterized in that at least one receiving chamber a liquid contains and at least one further receiving chamber, preferably a solid in the form of a powder and / or an agglomerate and / or one Kompaktats and / or a casting, contains. Detergent or cleaning agent composition according to one of the claims 17 to 22, characterized in that the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible closure unit polyvinyl alcohols and / or PVAL copolymers comprises whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol% is. 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 3,500 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 . Detergent or cleaning agent composition according to one of the claims 17 to 24, characterized in that the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible closure unit polyvinyl alcohols and / or PVAL copolymers comprises their average degree of polymerization between 80 and 700, preferably between 150 and 400, particularly preferably between 180 to 300 and / or their molecular weight ratio MG (50%) to MG (90%) between 0.3 and 1, preferably between 0.4 and 0.8 and in particular is between 0.45 and 0.6. Detergent or cleaning agent composition according to one of the claims 17 to 25, characterized in that the water-soluble or water-dispersible containers and / or the water soluble or water-dispersible closure unit hydroxypropylmethyl cellulose (HPMC) comprises 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 cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25. Process for producing nitrile and polymer-containing compounds characterized by the steps: a) placing at least one solid in a mixer, b) spraying on a substance preparation of a cationic nitrile of the formula (I)

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 -Cl, -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 _1-24 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 CN ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion; A method according to claim 27, characterized in that the in step a) submitted solid at least one polymer, preferably a polymer which has at least one monomeric building block with an acid functionality, contains. A method according to claim 28, characterized in that the Weight fraction of polymer with acid functionality in the total weight of the solid submitted in step a) 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 80% by weight is. Method according to one of claims 27 to 29, characterized in that that it the substance preparation in step b) is a solution or is a dispersion. Method according to one of claims 27 or 30, characterized in that that in a further step c) a polymer-containing solution is sprayed on. Method according to one of claims 27 to 31, characterized in that that this Process in a high speed mixer or fluidized bed apparatus carried out becomes.