EP0826025B1 - Use of heterocyclic compounds as activators for inorganic peroxy compounds - Google Patents

Description

The present invention relates to the use of certain heterocyclic compounds based on cyclic carbamates, Lactones or lactams as activators for inorganic per compounds in detergents, cleaning agents and bleaches as well as in Disinfectants. The present invention further relates to certain technical preparations that these heterocyclic Connections included.

In an effort to save energy in washing, cleaning and bleaching processes have recently been gaining application temperatures in the lower Temperature range, for example in textile washing clearly below 60 ° C, especially below 45 ° C, more and more Importance. At such temperatures, the effect of the known Activators for inorganic per compounds, this System is responsible for the bleaching or cleaning effect, but already significantly behind. It therefore has no aspirations missing, more effective activators for this temperature range develop without a convincing success so far would have been.

Textile detergent formulations are known from EP-A 028 432, which include N-acyl lactams, e.g. N-acetylcaprolactam, included as a precursor for a bleaching organic peroxyacid.

WO-A 94/27970 and WO-A 94/28103 describe C ₂ to C ₇ acyl or C ₁₀ to C ₁₃ acyl caprolactams as bleach activators for inorganic per-compounds.

The object of the present invention was to improve the Bleaching, oxidation and cleaning effects of a system Activator and inorganic per-compounds in the lower Temperature range, in particular from 15 to 60 ° C, bring about.

(a) einen cyclischen Carbamatrest der Formel

(b) einen Lactonoxyrest der Formel

oder

(c) einen Lactamrest der Formel

steht, wobei

Z¹ bis Z³

1,2-, 1,3-, 1,4- oder 1,5-Alkylengruppen mit 2 bis 20 C-Atomen, welche zusätzlich durch ein bis drei Hydroxylgruppen, C₁- bis C₄-Alkoxygruppen, Aminogruppen, C₁- bis C₄-Alkylaminogruppen, Di-C₁- bis C₄-alkylaminogruppen, Chloratome, Bromatome, Nitrogruppen, Cyanogruppen, Carboxylgruppen, Sulfogruppen, Carboxy-C₁- bis C₄-alkylgruppen, Carboxamidgruppen oder Phenyl-, Tolyl- oder Benzylreste funktionalisiert, wobei aromatische Kerne ihrerseits ebenfalls durch die genannten Reste substituiert sein können, oder durch ein oder zwei nicht benachbarte Sauerstoffatome, Aminogruppen, C₁-bis C₄-Alkylaminogruppen oder Carbonylgruppen unterbrochen sein können, bezeichnen und

T

Wasserstoff oder C₁- bis C₄-Alkyl bedeutet,

X

eine sauerstoffhaltige Gruppe der Formel

bedeutet, wobei

Y

für Wasserstoff, Ammonium, welches gegebenenfalls durch organische Reste substituiert sein kann, oder C₁- bis C₄-Alkyl steht und

A

eine C₁- bis C₁₈-Alkylengruppe, eine C₂- bis C₁₈-Alkenylengruppe, eine C₅- bis C₃₂-Cycloalkylengruppe, eine C₇- bis C₃₀-Aralkylengruppe, eine C₆- bis C₁₈-Arylengruppe oder eine C₃- bis C₁₈-Heteroarylengruppe bezeichnet, wobei aliphatische Struktureinheiten zusätzlich durch ein bis fünf Hydroxylgruppen, C₁- bis C₄-Alkoxygruppen, Aminogruppen, C₁- bis C₄-Alkylaminogruppen, Di-C₁- bis C₄-alkylaminogruppen, Chloratome, Bromatome, Nitrogruppen, Cyanogruppen, Carboxylgruppen, Sulfogruppen, Carboxy-C₁-bis C₄-alkylgruppen, Carboxamidgruppen oder Phenyl-, Tolyl- oder Benzylreste funktionalisiert, wobei aromatische, cycloaliphatische und heteroaromatische Struktureinheiten ebenfalls durch die genannten Reste substituiert sein können, oder durch ein bis acht nicht benachbarte Sauerstoffatome, Aminogruppen, C₁- bis C₄-Alkylaminogruppen oder Carbonylgruppen unterbrochen sein können,

mit Ausnahme von Terephthaloyldivalerolactam und Terephthaloyldicaprolactam als Aktivatoren für anorganische Perverbindungen gefunden.Accordingly, the use of heterocyclic compounds of the general formula I L ― X ― L in which the two heterocyclic radicals L are the same and for

(a) a cyclic carbamate residue of the formula

(b) a lactoneoxy radical of the formula

or

(c) a lactam residue of the formula

stands, where

Z ¹ to Z ³

1,2-, 1,3-, 1,4- or 1,5-alkylene groups with 2 to 20 C atoms, which are additionally replaced by one to three hydroxyl groups, C ₁ - to C ₄ -alkoxy groups, amino groups, C ₁ - functionalized to C ₄ alkylamino groups, di-C ₁ to C ₄ alkylamino groups, chlorine atoms, bromine atoms, nitro groups, cyano groups, carboxyl groups, sulfo groups, carboxy-C ₁ to C ₄ alkyl groups, carboxamide groups or phenyl, tolyl or benzyl radicals , where aromatic nuclei can in turn also be substituted by the radicals mentioned, or can be interrupted by one or two non-adjacent oxygen atoms, amino groups, C ₁ -C ₄ -alkylamino groups or carbonyl groups, and

T

Is hydrogen or C ₁ -C ₄ -alkyl,

X

an oxygen-containing group of the formula

means where

Y

represents hydrogen, ammonium, which can optionally be substituted by organic radicals, or C ₁ - to C ₄ -alkyl and

A

a C ₁ to C ₁₈ alkylene group, a C ₂ to C ₁₈ alkenylene group, a C ₅ to C ₃₂ cycloalkylene group, a C ₇ to C ₃₀ aralkylene group, a C ₆ to C ₁₈ arylene group or denotes a C ₃ - to C ₁₈ -heteroarylene group, aliphatic structural units additionally having one to five hydroxyl groups, C ₁ - to C ₄ -alkoxy groups, amino groups, C ₁ - to C ₄ -alkylamino groups, di-C ₁ - to C ₄ - Functionalized alkylamino groups, chlorine atoms, bromine atoms, nitro groups, cyano groups, carboxyl groups, sulfo groups, carboxy-C ₁ -C ₄ -alkyl groups, carboxamide groups or phenyl, tolyl or benzyl radicals, aromatic, cycloaliphatic and heteroaromatic structural units also being substituted by the radicals mentioned can, or can be interrupted by one to eight non-adjacent oxygen atoms, amino groups, C ₁ - to C ₄ -alkylamino groups or carbonyl groups,

with the exception of terephthaloyldivalerolactam and terephthaloyldicaprolactam found as activators for inorganic per-compounds.

wobei bei unsymmetrischen Alkylengruppierungen prinzipiell beide Einbaumöglichkeiten in die Ringe möglich sind. Die Variablen Z¹ bis Z³ können wie angegeben funktionalisiert oder unterbrochen sein.The variables Z ¹ to Z ³ in the heterocyclic systems (a) to (c) can in particular mean C ₂ to C ₁₀ alkylene groups of the following structure:

with asymmetrical alkylene groups, in principle, both installation options are possible in the rings. The variables Z ¹ to Z ³ can be functionalized or interrupted as indicated.

• als lineare oder verzweigte C₁- bis C₁₈-Alkylengruppe, insbesondere C₆- bis C₁₂-Alkylengruppe, können Methylen, 1,2-Ethylen, 1,1-Ethylen, 1,3-Propylen, 1,2-Propylen, 1,1-Propylen, 2,2-Propylen, 1,4-Butylen, 1,2-Butylen, 2,3-Butylen, Pentamethylen, 3-Methyl-1,5-pentylen, Hexamethylen, Heptamethylen, Octamethylen, Nonamethylen, Decamethylen, Undecamethylen, Dodecamethylen, Tetradecamethylen, Hexadecamethylen oder Octadecamethylen auftreten;
• als lineare oder verzweigte C₂- bis C₁₈-Alkenylengruppe, insbesondere C₆- bis C₁₂-Alkenylengruppe, können Brückenglieder mit ein, zwei oder drei olefinischen Doppelbindungen oder auch acetylenischen Doppelbindungen auftreten, z.B. 1,2-Ethenylen, 1,3-Propenylen, 1,4-But-2-enylen, 1,6-Hex-3-enylen, 1,8-Oct-4-enylen oder 1,12-Dodec-6-enylen;
• als C₅ bis C₃₂-Cycloalkylengruppen, insbesondere C₅- bis C₁₀-Cycloalkylengruppen eignen sich 1,2- oder 1,3-Cyclopentylen, 1,2-, 1,3- oder 1,4-Cyclohexylen, 1,2-, 1,3- oder 1,4-Cycloheptylen, 1,2-, 1,3-, 1,4- oder 1,5-Cyclooctylen oder Gruppierungen der Formel
  
  
  
  
• als C₇- bis C₃₀-Aralkylengruppen, insbesondere gegebenenfalls alkylsubstituierte C₇- bis C₂₂-Phenylalkylen- und -Diphenylalkylengruppen kommen in Betracht Gruppierungen der Formel
  
  
  
  
  
• als C₆- bis C₁₈-Arylengruppen, insbesondere gegebenenfalls alkylsubstituierte Phenylen-, Bisphenylen- oder Naphthylengruppen eignen sich vor allem 1,4-, 1,3- und 1,2-Phenylen, aber auch Gruppierungen der Formel
  
  
  oder
  
• als C₃- bis C₁₈-Heteroarylengruppen, insbesondere fünf- oder sechsgliedrige C₃- bis C₁₂-Heteroarylengruppen mit ein oder zwei Heteroatomen aus der Gruppe Stickstoff, Sauerstoff und Schwefel kommen in Betracht Gruppierungen der Formel
  
  
  
  
• als durch Sauerstoff oder Amino-Gruppierungen, insbesondere NH- oder N(CH₃)-Gruppierungen, unterbrochene Strukturen kommen beispielsweise folgende Strukturen in Betracht:
  
  ―CH₂―O―CH₂― , ―CH₂CH₂―O―CH₂― ,
  
  
  
  oder
  
  mit n = 2 bis 8 und m = 2 bis 5.

Typical examples of bridge link A are as follows:

• as a linear or branched C ₁ to C ₁₈ alkylene group, in particular C ₆ to C ₁₂ alkylene group, methylene, 1,2-ethylene, 1,1-ethylene, 1,3-propylene, 1,2-propylene, 1,1-propylene, 2,2-propylene, 1,4-butylene, 1,2-butylene, 2,3-butylene, pentamethylene, 3-methyl-1,5-pentylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, Decamethylene, undecamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene or octadecamethylene occur;
• as linear or branched C ₂ - to C ₁₈ -alkenylene group, in particular C ₆ - to C ₁₂ -alkenylene group, bridge members with one, two or three olefinic double bonds or also acetylenic double bonds can occur, for example 1,2-ethenylene, 1,3- Propenylene, 1,4-but-2-enylene, 1,6-hex-3-enylene, 1,8-oct-4-enylene or 1,12-dodec-6-enylene;
• 1,2- or 1,3-cyclopentylene, 1,2-, 1,3- or 1,4-cyclohexylene, 1,2 are suitable as C ₅ to C ₃₂ cycloalkylene groups, in particular C ₅ to C ₁₀ cycloalkylene groups -, 1,3- or 1,4-cycloheptylene, 1,2-, 1,3-, 1,4- or 1,5-cyclooctylene or groupings of the formula
  
  
  
  
• as C ₇ to C ₃₀ aralkylene groups, in particular optionally alkyl-substituted C ₇ to C ₂₂ phenylalkylene and diphenylalkylene groups, groups of the formula come into consideration
  
  
  
  
  
• as C ₆ - to C ₁₈ -arylene groups, in particular optionally alkyl-substituted phenylene, bisphenylene or naphthylene groups, 1,4-, 1,3- and 1,2-phenylene are particularly suitable, but also groups of the formula
  
  
  or
  
• as C ₃ - to C ₁₈ -heteroarylene groups, in particular five- or six-membered C ₃ - to C ₁₂ -heteroarylene groups with one or two heteroatoms from the group consisting of nitrogen, oxygen and sulfur, are suitable groups of the formula
  
  
  
  
• The following structures can be considered as structures interrupted by oxygen or amino groups, in particular NH or N (CH ₃ ) groups:
  
  ―CH ₂ ―O ― CH ₂ -, ―CH ₂ CH ₂ ―O ― CH ₂ -,
  
  
  
  or
  
  with n = 2 to 8 and m = 2 to 5.

The variables Z ¹ to Z ³ and A defined above can additionally be functionalized by the specified groups. C ₁ - to C ₄ -alkoxy groups mean in particular methoxy, ethoxy, n-propoxy-iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy or tert-butoxy. Preferred amino groups are -NH ₂ , -NH (CH ₃ ), -NH (CH ₂ CH ₃ ), -N (CH ₃ ) ₂ and -N (CH ₂ CH ₃ ) ₂ . Carboxy-C ₁ - to C ₄ -alkyl groups are, for example, carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl or carboxy-tert-butyl.

The oxygen-containing group X, in which one or two oxygen atoms are bonded to carbon, sulfur or phosphorus atoms by a double bond, that is to say represent carbonyl or heterocarbonyl functionalities, preferably means

For the case R ¹ = L, the two heterocyclic radicals L bonded to the group X are preferably the same.

(12) N,N'-Carbonylbisoxazolidon der Formel

(13) N,N'-Carbonylbis-1,3-tetrahydrooxazinon der Formel

(14) Kohlensäurebis-γ-butyrolacton der Formel

(15) Kohlensäurebis-γ-valerolacton der Formel

(16) O,O'-Carbonylbispantolacton der Formel

(17) Kohlensäurebis-δ-valerolacton der Formel

(18) Kohlensäurebis-ε-caprolacton der Formel

(19) N,N'-Carbonylbis-γ-butyrolactam der Formel

(20) N,N'-Carbonylbis-δ-valerolactam der Formel

(21) N,N'-Carbonylbis-ε-caprolactam der Formel

(24) verdoppelte N-Acyloxazolidone der Formel

(25) verdoppelte N-Acyl-1,3-tetrahydrooxazinone der Formel

(26) verdoppelte Acyloxy-γ-butyrolactone der Formel

(27) verdoppelte Acyloxy-γ-valerolactone der Formel

(28) verdoppelte O-Acylpantolactone der Formel

(29) verdoppelte Acyloxy-δ-valerolactone der Formel

(30) verdoppelte Acyloxy-ε-caprolactone der Formel

(31) verdoppelte Acyl-γ-butyrolactame der Formel

(32) verdoppelte Acyl-δ-valerolactame der Formel

(33) verdoppelte N-Acyl-ε-caprolactame der Formel

The following structure types of the heterocyclic compounds I are preferably used:

(12) N, N'-carbonylbisoxazolidone of the formula

(13) N, N'-carbonylbis-1,3-tetrahydrooxazinone of the formula

(14) carbonic acid bis-γ-butyrolactone of the formula

(15) carbonic acid bis-γ-valerolactone of the formula

(16) O, O'-carbonyl bispantolactone of the formula

(17) carbonic acid bis-δ-valerolactone of the formula

(18) carbonic acid bis-ε-caprolactone of the formula

(19) N, N'-Carbonylbis-γ-butyrolactam of the formula

(20) N, N'-carbonylbis-δ-valerolactam of the formula

(21) N, N'-carbonylbis-ε-caprolactam of the formula

(24) doubled N-acyloxazolidones of the formula

(25) doubled N-acyl-1,3-tetrahydrooxazinones of the formula

(26) doubled acyloxy-γ-butyrolactones of the formula

(27) doubled acyloxy-γ-valerolactones of the formula

(28) doubled O-acylpantolactones of the formula

(29) doubled acyloxy-δ-valerolactones of the formula

(30) doubled acyloxy-ε-caprolactones of the formula

(31) doubled acyl-γ-butyrolactams of the formula

(32) doubled acyl-δ-valerolactams of the formula

(33) doubled N-acyl-ε-caprolactams of the formula

The bridge member A in the structure types (24) to (33) stands in particular for hexamethylene, octamethylene, decamethylene, dodecamethylene, 1,3- or 1,4-cyclohexylene or 1,4-, 1,3- or 1,2-phenylene; 1,4-phenylene is of particular interest for A (derived from terephthalic acid).

When using the heterocyclic described according to the invention Compounds I can now experience an unexpected increase the oxidation, bleaching and cleaning effects in inorganic Aqueous washing, bleaching and cleaning liquors containing per compounds in the temperature range from 10 to 80 ° C, especially 15 up to 60 ° C, especially 20 to 45 ° C, can be observed.

The compounds I can act as activators for inorganic per-compounds can be used wherever there is a special need Increasing the oxidation effect of the inorganic per-compounds arrives at low temperatures, e.g. in the Bleaching of textiles, hair or hard surfaces at which Oxidation of organic or inorganic intermediates and disinfection. Most of them outperform Activators in their properties the previously known Activators.

The compounds I are odorless or pleasant smelling substances that are therefore also without difficulties be used in such washing and cleaning agents can, which are intended for use in the household.

It is important for the use according to the invention, conditions to create, among which, for example, hydrogen peroxide and the compounds I can react with one another The aim is to obtain secondary products with a stronger oxidizing effect. Such Conditions exist in particular if both reactants meet in aqueous alkaline solution.

The conditions can vary widely depending on the intended use become. In addition to purely aqueous solutions, there are also mixtures from water and suitable organic solvents, e.g. For use in disinfection or in the oxidation of intermediates, as a reaction medium in question. The pH of the reaction medium can vary widely, from the weakly acidic range (pH 4) up to the strongly alkaline range (pH 13), depending on the application, to get voted. The alkaline range is preferred from pH 8 to pH 11 as it is used for the activation reaction and the stability of the per compound formed is particularly advantageous is.

For this reason, the activator described is also preferred together with a sodium perborate or with sodium carbonate perhydrate used in their solutions already pH values this Range. Examples of other suitable per-compounds are phosphate perhydrates and urea perhydrate. Occasionally it may also be useful to adjust the pH of the medium after the Activation reaction by suitable additives again, especially in the acidic area.

The amounts of per-compounds are generally chosen so that that in the solutions between 10 and 10000 ppm active oxygen, preferably between 50 and 5000 ppm active oxygen present are. The amount of activator used also depends on the application from. Depending on the desired level of activation 0.03 to 1.0 mole, preferably 0.1 to 0.5 mole of activator per mole inorganic per-compound used, but can in particular If these limits are exceeded or fallen short of.

The compounds I can be activated in pure form or if this is useful, for example, to increase the storage stability is, in special forms of supply such as tablets, granules or used in finely divided enveloped form (so-called prills) become. Such grainy is of particular importance Forms which are produced by agglomeration granulation. Liquid ones are suitable for machine dosing Activators as such or solutions in organic solvents or liquid dispersions containing the activator.

It is preferably used in pre-assembled products in the Mixture with the per compounds to be activated and optionally further for the desired bleaching, oxidation or cleaning process necessary components such as pH regulating Agents and stabilizers for per compounds. In addition to the compounds I also present other customary activators his. By mixing with selected amounts of per compounds and other additives, the application is facilitated and the user achieves the desired result more reliably, because when the funds are released, the set optimal conditions. Such means are in solid, preferably scatterable form, but also as liquids in front.

• polyacylierte Zucker, z.B. Pentaacetylglucose;
• Acyloxybenzolsulfonsäuren und deren Alkali- und Erdalkalimetallsalze, z.B. Natrium-p-isononanoyloxy-benzolsulfonat oder Natrium-p-benzoyloxy-benzolsulfonat;
• N-diacylierte und N,N'-tetracylierte Amine, z.B. N,N,N',N'-Tetraacetyl-methylendiamin und -ethylendiamin, N,N-Diacetylanilin, N,N-Diacetyl-p-toluidin oder 1,3-diacylierte Hydantoine wie 1,3-Diacetyl-5,5-dimethylhydantoin;
• N-Alkyl-N-sulfonyl-carbonamide, z.B. N-Methyl-N-mesyl-acetamid oder N-Methyl-N-mesyl-benzamid;
• N-acylierte cyclische Hydrazide, acylierte Triazole oder Urazole, z.B. Monoacetyl-maleinsäurehydrazid;
• O,N,N-trisubstituierte Hydroxylamine, z.B. O-Benzoyl-N,N-succinylhydroxylamin, O-Acetyl-N,N-succinyl-hydroxylamin oder O,N,N-Triacetylhydroxylamin;
• N,N'-Diacyl-sulfurylamide, z.B. N,N'-Dimethyl-N,N'-diacetylsulfurylamid oder N,N'-Diethyl-N,N'-dipropionyl-sulfurylamid;
• Triacylcyanurate, z.B. Triacetylcyanurat oder Tribenzoylcyanurat;
• Carbonsäureanhydride, z.B. Benzoesäureanhydrid, m-Chlorbenzoesäureanhydrid oder Phthalsäureanhydrid;
• 1,3-Diacyl-4,5-diacyloxy-imidazoline, z.B. 1,3-Diacetyl-4,5-diacetoxyimidazolin;
• Tetraacetylglycoluril und Tetrapropionylglycoluril;
• diacylierte 2,5-Diketopiperazine, z.B. 1,4-Diacetyl-2,5-diketopiperazin;
• Acylierungsprodukte von Propylendiharnstoff und 2,2-Dimethylpropylendiharnstoff, z.B. Tetraacetylpropylendiharnstoff;
• α-Acyloxy-polyacyl-malonamide, z.B. α-Acetoxy-N,N'-diacetylmalonamid;
• Diacyl-dioxohexahydro-1,3,5-triazine, z.B. 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin;
• Benz-(4H)1,3-oxazin-4-one mit Alkylresten, z.B. Methyl, oder aromatischen Resten, z.B. Phenyl, in der 2-Position.

Additional activators that can be used in combination with the compounds I are primarily:

• polyacylated sugars, for example pentaacetyl glucose;
• Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, for example sodium p-isononanoyloxy-benzenesulfonate or sodium p-benzoyloxy-benzenesulfonate;
• N-diacylated and N, N'-tetracylated amines, for example N, N, N ', N'-tetraacetyl-methylenediamine and -ethylenediamine, N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3- diacylated hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin;
• N-alkyl-N-sulfonyl-carbonamides, for example N-methyl-N-mesyl-acetamide or N-methyl-N-mesyl-benzamide;
• N-acylated cyclic hydrazides, acylated triazoles or urazoles, for example monoacetyl-maleic acid hydrazide;
• O, N, N-trisubstituted hydroxylamines, for example O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine or O, N, N-triacetylhydroxylamine;
• N, N'-diacylsulfurylamide, for example N, N'-dimethyl-N, N'-diacetylsulfurylamide or N, N'-diethyl-N, N'-dipropionylsulfurylamide;
• Triacyl cyanurates, for example triacetyl cyanurate or tribenzoyl cyanurate;
• Carboxylic anhydrides, for example benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;
• 1,3-diacyl-4,5-diacyloxy-imidazolines, for example 1,3-diacetyl-4,5-diacetoxyimidazoline;
• Tetraacetylglycoluril and tetrapropionylglycoluril;
• diacylated 2,5-diketopiperazines, for example 1,4-diacetyl-2,5-diketopiperazine;
• Acylation products of propylene diurea and 2,2-dimethylpropylene diurea, for example tetraacetylpropylene diurea;
• α-acyloxy-polyacyl-malonamides, for example α-acetoxy-N, N'-diacetylmalonamide;
• Diacyl-dioxohexahydro-1,3,5-triazines, for example 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;
• Benz- (4H) 1,3-oxazin-4-one with alkyl radicals, for example methyl, or aromatic radicals, for example phenyl, in the 2-position.

The use of the heterocyclic is of particular interest Compounds I as activators for inorganic per-compounds for the temperature range from 10 to 80 ° C in washing, cleaning and bleaches, especially in washing and bleaching agents and Bleach additives for textile washing, as well as in disinfectants.

In the field of textile laundry, the described Activators with almost all common components of washing and bleaches can be combined. You can do that Build up funds that are specifically for textile treatment at low Temperatures are suitable and also those in several temperature ranges all the way to the traditional area of cooked linen are suitable.

The main components of washing, bleaching and cleaning agents are in addition to per-compounds and activators, framework substances (Builder), i.e. inorganic builders and / or organic cobuilders, and surfactants, especially anionic and / or nonionic Surfactants. In addition, other usual auxiliary substances and accompanying substances such as adjusting agents, complexing agents, phosphonates, dyes, Corrosion inhibitors, graying inhibitors, bleaching catalysts, Peroxide stabilizers, electrolytes, optical brighteners, Enzymes, perfume oils, foam regulators and activators Substances are present in these agents if this is appropriate.

Inorganic builders (builders)

All customary inorganic are suitable as inorganic builder substances Builders such as aluminosilicates, silicates, carbonates and Phosphates.

Suitable inorganic builders are e.g. Aluminum silicates with ion exchange Properties such as Zeolites. Different types of zeolites are suitable, in particular zeolite A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially exchanged for other cations such as Li, K, Ca, Mg or ammonium are. Suitable zeolites are described, for example in EP-A 038 591, EP-A 021 491, EP-A 087 035, US-A 4 604 224, GB-A 2 013 259, EP-A 522 726, EP-A 384 070 and WO-A 94/24 251.

Other suitable inorganic builders are e.g. amorphous or crystalline silicates such as amorphous disilicates, crystalline Disilicates such as the layered silicate SKS-6 (manufacturer Hoechst). The Silicates can be in the form of their alkali, alkaline earth or ammonium salts be used. Na, Li and Mg silicates used.

Anionic surfactants

Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for example C ₉ to C ₁₁ alcohol sulfates, C ₁₂ to C ₁₃ alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are sulfated ethoxylated C ₈ to C ₂₂ alcohols (alkyl ether sulfates) or their soluble salts. Compounds of this type are prepared, for example, by first alkoxylating a C ₈ to C ₂₂ , preferably a C ₁₀ to C ₁₈ alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product. Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, moles of ethylene oxide being used per mole of fatty alcohol. However, the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide. Alkoxylated C ₈ to C ₂₂ alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide are also suitable. The alkoxylated C ₈ or to C ₂₂ alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution.

Other suitable anionic surfactants are alkane sulfonates such as C ₈ to C ₂₄ , preferably C ₁₀ to C ₁₈ alkane sulfonates and soaps such as the salts of C ₈ to C ₂₄ carboxylic acids.

Other suitable anionic surfactants are C ₉ to C ₂₀ linear alkylbenzenesulfonates (LAS).

The anionic surfactants are preferably in the detergent Form of salts added. Suitable cations in these salts are alkali metal salts such as sodium, potassium and lithium and Ammonium salts such as Hydroxethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

Nonionic surfactants

Suitable nonionic surfactants are, for example, alkoxylated C ₈ -C ₂₂ -alcohols such as fatty alcohol alkoxylates or oxalcohol alkoxylates. The alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant. Here too, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide are used per mole of alcohol. The alkylene oxide used is preferably ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms.

Another class of suitable nonionic surfactants are alkylphenol ethoxylates with C ₆ - to C ₁₄ -alkyl chains and 5 to 30 moles of ethylene oxide units.

Another class of nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the Alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5 glucoside units.

wobei R⁴ C₆- bis C₂₂-Alkyl, R⁵ H oder C₁- bis C₄-Alkyl und R⁶ ein Polyhydroxyalkyl-Rest mit 5 bis 12 C-Atomen und mindestens 3 Hydroxygruppen ist. Vorzugsweise ist R⁴ C₁₀- bis C₁₈-Alkyl, R⁵ Methyl und R⁶ ein C₅- oder C₆-Rest. Beispielsweise erhält man derartige Verbindungen durch die Acylierung von reduzierend aminierten Zuckern mit Säurechloriden von C₁₀-C₁₈-Carbonsäuren.Another class of nonionic surfactants are N-alkyl glucamides of general structure II or III

wherein R ^{4 is} C ₆ to C ₂₂ alkyl, R ⁵ H or C ₁ to C ₄ alkyl and R ^{6 is} a polyhydroxyalkyl radical having 5 to 12 C atoms and at least 3 hydroxy groups. R ⁴ is preferably C ₁₀ to C ₁₈ alkyl, R ^{5 is} methyl and R ^{6 is} a C ₅ or C ₆ radical. For example, such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C ₁₀ -C ₁₈ carboxylic acids.

The detergents according to the invention preferably contain C ₁₀ -C ₁₆ alcohols ethoxylated with 3-12 mol ethylene oxide, particularly preferably ethoxylated fatty alcohols as nonionic surfactants.

Organic cobuilder

C₄- bis C₂₀-Di-, -Tri- und -Tetracarbonsäuren wie z.B. Bernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure und Alkyl- und Alkylenbernsteinsäuren mit C₂- bis C₁₆-Alkyl- bzw. -Alkylen-Resten;

C₄- bis C₂₀-Hydroxycarbonsäuren wie z.B. Äpfelsäure, Weinsäure, Gluconsäure, Glutarsäure, Citronensäure, Lactobionsäure und Saccharosemono-, -di- und -tricarbonsäure;

Aminopolycarboxylate wie z.B. Nitrilotriessigsäure, Methylglycindiessigsäure, Alanindiessigsäure, Ethylendiamintetraessigsäure und Serindiessigsäure;

Salze von Phosphonsäuren wie z.B. Hydroxyethandiphosphonsäure, Ethylendiamintetra(methylenphoshponat) und Diethylentriaminpenta(methylenphosphonat).

Examples of suitable low molecular weight polycarboxylates as organic cobuilders are:

C ₄ - to C ₂₀ di-, tri- and tetracarboxylic acids such as succinic acid, propane tricarboxylic acid, butane tetracarboxylic acid, cyclopentane tetracarboxylic acid and alkyl and alkylene succinic acids with C ₂ to C ₁₆ alkyl or alkylene radicals;

C ₄ to C ₂₀ hydroxycarboxylic acids such as malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;

Aminopolycarboxylates such as nitrilotriacetic acid, methylglycinediacetic acid, alaninediacetic acid, ethylenediaminetetraacetic acid and serinediacetic acid;

Salts of phosphonic acids such as hydroxyethane diphosphonic acid, ethylenediaminetetra (methylene phosphonate) and diethylene triamine penta (methylene phosphonate).

Oligomaleinsäuren, wie sie beispielsweise in EP-A 451508 und EP-A 396303 beschrieben sind;

Co- und Terpolymere ungesättigter C₄-C₈-Dicarbonsäuren, wobei als Comonomere monoethylenisch ungesättigte Monomere

aus der Gruppe (i) in Mengen von bis zu 95 Gew.-%

aus der Gruppe (ii) in Mengen von bis zu 60 Gew.-%

Aus der Gruppe (iii) in Mengen von bis zu 20 Gew.-%

einpolymerisiert enthalten sein können. Examples of suitable oligomeric or polymeric polycarboxylates as organic cobuilders are:

Oligomaleic acids, as described for example in EP-A 451508 and EP-A 396303;

Copolymers and terpolymers of unsaturated C ₄ -C ₈ dicarboxylic acids, with monoethylenically unsaturated monomers as comonomers

from group (i) in amounts of up to 95% by weight

from group (ii) in amounts of up to 60% by weight

From group (iii) in amounts of up to 20% by weight

polymerized may be included.

Examples of suitable unsaturated C ₄ -C ₈ dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.

Group (i) includes monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid.

Group (ii) includes monoethylenically unsaturated C ₂ -C ₂₂ olefins, vinyl alkyl ethers with C ₁ -C ₈ alkyl groups, styrene, vinyl esters of C ₁ -C ₈ carboxylic acids, (meth) acrylamide and vinyl pyrrolidone. From group (ii), preference is given to using C ₂ -C ₆ olefins, vinyl alkyl ethers having C ₁ -C ₄ alkyl groups, vinyl acetate and vinyl propionate.

Group (iii) comprises (meth) acrylic esters of C ₁ to C ₈ alcohols, (meth) acrylonitrile, (meth) acrylamides of C ₁ -C ₈ amines, N-vinylformamide and vinylimidazole.

If the polymers of group (ii) polymerize vinyl esters contain, they can also partially or completely to vinyl alcohol structural units are hydrolyzed. Suitable Copolymers and terpolymers are known, for example, from US Pat. No. 3,887,806 and DE-A 43 13 909 known.

Copolymere von Maleinsäure und Acrylsäure im Gewichtsverhältnis 10:90 bis 95:5, besonders bevorzugt solche im Gewichtsverhältnis 30:70 bis 90:10 mit Molmassen von 10000 bis 150000;

Terpolymere aus Maleinsäure, Acrylsäure und einem Vinylester einer C₁-C₃-Carbonsäure im Gewichtsverhältnis 10 (Maleinsäure) : 90 (Acrylsäure + Vinylester) bis 95 (Maleinsäure) : 10 (Acrylsäure + Vinylester), wobei das Gew.-Verhältnis von Acrylsäure zu Vinylester im Bereich von 20:80 bis 80:20 variieren kann, und besonders bevorzugt

Terpolymere aus Maleinsäure, Acrylsäure und Vinylacetat oder Vinylpropionat im Gewichtsverhältnis 20 (Maleinsäure) : 80 (Acrylsäure + Vinylester) bis 90 (Maleinsäure) : 10 (Acrylsäure + Vinylester), wobei das Gew.-Verhältnis von Acrylsäure zum Vinylester im Bereich von 30:70 bis 70:30 variieren kann;

Copolymere von Maleinsäure mit C₂-C₈-Olefinen im Molverhältnis 40:60 bis 80:20, wobei Copolymere von Maleinsäure mit Ethylen, Propylen oder Isobutan im Molverhältnis 50:50 besonders bevorzugt sind.

Suitable copolymers of dicarboxylic acids as organic cobuilders are preferably:

Copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, particularly preferably those in a weight ratio of 30:70 to 90:10 with molecular weights of 10,000 to 150,000;

Terpolymers of maleic acid, acrylic acid and a vinyl ester of a C ₁ -C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester), the weight ratio of acrylic acid Vinylester can vary in the range of 20:80 to 80:20, and particularly preferred

Terpolymers of maleic acid, acrylic acid and vinyl acetate or vinyl propionate in a weight ratio of 20 (maleic acid): 80 (acrylic acid + vinyl ester) to 90 (maleic acid): 10 (acrylic acid + vinyl ester), the weight ratio of acrylic acid to vinyl ester in the range from 30: Can vary from 70 to 70:30;

Copolymers of maleic acid with C ₂ -C ₈ olefins in a molar ratio of 40:60 to 80:20, copolymers of maleic acid with ethylene, propylene or isobutane in a molar ratio of 50:50 being particularly preferred.

Graft polymers of unsaturated carboxylic acids on low molecular weight Carbohydrates or hydrogenated carbohydrates, cf. US-A 5227446, DE-A 4415623, DE-A 4313909 are also known as organic cobuilders suitable.

Suitable unsaturated carboxylic acids are, for example Maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, Methacrylic acid, crotonic acid and vinyl acetic acid and mixtures from acrylic acid and maleic acid, which in quantities of 40 to 95 wt .-%, based on the component to be grafted, grafted on become.

For modification, up to 30% by weight, based on the component to be grafted, further monoethylenically unsaturated Monomers are present in copolymerized form. Suitable modifying Monomers are the above group monomers (ii) and (iii).

Degraded polysaccharides such as acidic or enzymatically degraded starches, inulins or cellulose, reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides such as mannitol, sorbitol, aminosorbitol and glucamine and polyalkylene glycols with molecular weights up to M _w = 5000 such as polyethylene glycols are suitable as a graft base. Ethylene oxide / propylene oxide or ethylene oxide / butylene oxide block copolymers, statistical ethylene oxide / propylene oxide or ethylene oxide / butylene oxide copolymers, alkoxylated mono- or polybasic C ₁ -C ₂₂ alcohols, cf. US-A 4746456.

Grafted mined or mined from this group are preferred reduced starches and grafted polyethylene oxides are used, wherein 20 to 80 wt .-% monomers based on the graft component be used in the graft polymerization. For Grafting is preferably a mixture of maleic acid and Acrylic acid in a weight ratio of 90:10 to 10:90.

Polyglyoxylic acids as organic cobuilders are, for example described in EP-B 001004, US-A 5399286, DE-A 4106355 and EP-A 656914. The end groups of the polyglyoxylic acids can be different Have structures.

Polyamidocarboxylic acids and modified polyamidocarboxylic acids as Organic cobuilders are known from, for example EP-A 454126, EP-B 511037, WO-A 94/01486 and EP-A 581452.

Polyaspartic acid or co-condensates of aspartic acid with further amino acids, C ₄ -C ₂₅ mono- or dicarboxylic acids and / or C ₄ -C ₂₅ mono- or diamines are also preferably used as organic cobuilders. Are particularly preferred in phosphorus-containing acids used prepared with C ₆ -C ₂₂ -mono- or -dicarboxylic acids or with C ₆ -C ₂₂ -mono- or -diamines.

Condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds as organic cobuilders are e.g. known from WO-A 93/22362 and WO-A 92/16493. Such carboxyl groups containing condensates usually have molecular weights to 10,000, preferably up to 5,000.

Graying inhibitors and soil release polymers

Polyester aus Polyethylenoxiden mit Ethylenglycol und/oder Propylenglycol und aromatischen Dicarbonsäuren oder aromatischen und aliphatischen Dicarbonsäuren;

Polyester aus einseitig endgruppenverschlossenen Polyethylenoxiden mit zwei- und/oder mehrwertigen Alkoholen und Dicarbonsäure.

Suitable soil release polymers and / or graying inhibitors for detergents are, for example:

Polyesters of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids;

Polyester made of polyethylene oxides which are end group-capped with di- and / or polyhydric alcohols and dicarboxylic acid.

Such polyesters are known, for example from US-A 3557039, GB-A 1154730, EP-A 185427, EP-A 241984, EP-A 241985, EP-A 272033 and US-A 5142020.

Other suitable soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides (see US-A 4746456, US-A 4846995, DE-A 3711299, US-A 4904408, US-A 4846994 and US-A 4849126) or modified Celluloses such as Methyl cellulose, hydroxypropyl cellulose or Carboxymethyl cellulose.

Color transfer inhibitors

Color transfer inhibitors are, for example, homo- and Copolymers of vinyl pyrrolidone, vinyl imidazole, vinyl oxazolidone and 4-vinylpyridine-N-oxide with molecular weights of 15,000 to 100,000 and cross-linked, finely divided polymers based on of these monomers used. The use mentioned here Polymers is known, cf. DE-B 2232353, DE-A 2814287, DE-A 2814329 and DE-A 4316023.

Enzymes

Suitable enzymes are proteases, lipases, amylases and cellulases. The enzyme system can work on a single one of the enzymes be limited or include a combination of different enzymes.

Bleaching catalysts

Suitable bleaching catalysts are quaternized imines and sulfonimines (see US-A 5360568, US-A 5360569 and EP-A 453003) and Manganese complexes (cf. WO-A 94/21777).

Use in detergents and bleaches for textile washing

The present invention also relates to washing and Bleaching agents for textile washing, which 0.1 to 20 wt .-%, preferably 0.5 to 10% by weight, based on the total amount of the preparation, one or more heterocyclic compounds I contain as activators for inorganic per-compounds.

0,5 bis 20 Gew.-%, vorzugsweise 5 bis 15 Gew.-% anionische und/ oder nichtionische Tenside,

0,5 bis 60 Gew.-%, vorzugsweise 5 bis 40 Gew.-% Gerüstsubstanzen aus der Gruppe kondensierte Phosphate, Alkalisilicate, Alkalicarbonate, Natriumaluminiumsilicate und deren Mischungen,

0 bis 20 Gew.-%, vorzugsweise 0,5 bis 8 Gew.-% Gerüstsubstanzen aus der Gruppe Salze von Aminocarbonsäuren, Salze von Polyphosphonsäuren, Salze von Polycarbonsäuren und deren Mischungen,

2 bis 35 Gew.-%, vorzugsweise 5 bis 30 Gew.-% anorganische Perverbindungen,

0,1 bis 20 Gew.-%, vorzugsweise 0,5 bis 10 Gew.-% der Verbindungen I,

ad 100 % übliche Hilfs- und Begleitstoffe und Wasser. Typical textile detergents and bleaches of this type have the following composition:

0.5 to 20% by weight, preferably 5 to 15% by weight of anionic and / or nonionic surfactants,

0.5 to 60% by weight, preferably 5 to 40% by weight, of framework substances from the group of condensed phosphates, alkali silicates, alkali carbonates, sodium aluminum silicates and mixtures thereof,

0 to 20% by weight, preferably 0.5 to 8% by weight, of builder substances from the group consisting of salts of aminocarboxylic acids, salts of polyphosphonic acids, salts of polycarboxylic acids and mixtures thereof,

2 to 35% by weight, preferably 5 to 30% by weight, of inorganic per-compounds,

0.1 to 20% by weight, preferably 0.5 to 10% by weight of the compounds I,

ad 100% usual auxiliary and accompanying substances and water.

The activators I according to the invention are preferably in powder or granular detergents used. It can classic heavy-duty detergents or concentrated or act compacted detergent.

• 0,5 bis 50, vorzugsweise 5 bis 30 Gew.-% mindestens eines anionischen und/oder nichtionischen Tensids,
• 0,5 bis 60, vorzugsweise 15 bis 40 Gew.-% mindestens eines anorganischen Builders,
• 0 bis 20, vorzugsweise 0,5 bis 8 Gew.-% mindestens eines organischen Cobuilders,
• 2 bis 35, vorzugsweise 5 bis 30 Gew.-% eines anorganischen Bleichmittels, insbesondere Perborat oder Percarbonat,
• 0,1 bis 20, vorzugsweise 0,5 bis 10 Gew.-% eines erfindungsgemäßen Bleichaktivators, gegebenenfalls in Abmischung mit weiteren Bleichaktivatoren,
• 0 bis 1, vorzugsweise bis höchstens 0,5 Gew.-% eines Bleichkatalysators,
• 0 bis 5 Gew.-%, vorzugsweise 0 bis 2,5 % eines polymeren Farbübertragungsinhibitors,
• 0 bis 1,5 Gew.-%, vorzugsweise 0,1 bis 1,0 Gew.-% Protease,
• 0 bis 1,5 Gew.-%, vorzugsweise 0,1 bis 1,0 Gew.-% anderer Waschmittelenzyme, insbesondere Lipase,
• 0 bis 1,5 Gew.-%, vorzugsweise 0,2 bis 1,0 % Gew.-% eines Soil-Release-Polymers,

ad 100 % übliche Hilfs- und Begleitstoffe und Wasser.A typical powder or granular heavy-duty detergent according to the invention can have the following composition, for example:

• 0.5 to 50, preferably 5 to 30% by weight of at least one anionic and / or nonionic surfactant,
• 0.5 to 60, preferably 15 to 40% by weight of at least one inorganic builder,
• 0 to 20, preferably 0.5 to 8% by weight of at least one organic cobuilder,
• 2 to 35, preferably 5 to 30% by weight of an inorganic bleaching agent, in particular perborate or percarbonate,
• 0.1 to 20, preferably 0.5 to 10% by weight of a bleach activator according to the invention, optionally in a mixture with other bleach activators,
• 0 to 1, preferably up to at most 0.5% by weight of a bleaching catalyst,
• 0 to 5% by weight, preferably 0 to 2.5% of a polymeric color transfer inhibitor,
• 0 to 1.5% by weight, preferably 0.1 to 1.0% by weight of protease,
• 0 to 1.5% by weight, preferably 0.1 to 1.0% by weight, of other detergent enzymes, in particular lipase,
• 0 to 1.5% by weight, preferably 0.2 to 1.0% by weight, of a soil release polymer,

ad 100% usual auxiliary and accompanying substances and water.

Inorganic builders which are preferably used in detergents are sodium carbonate, sodium hydrogen carbonate, zeolite A and P and amorphous and crystalline Na silicates, in particular sheet silicates such as SKS-6 (manufacturer: Hoechst AG),
Organic cobuilders preferably used in detergents are acrylic acid / maleic acid copolymers, acrylic acid / maleic acid / vinyl ester terpolymers such as acrylic acid / maleic acid / vinyl acetate terpolymers, polyaspartic acid and citric acid.

Inorganic bleaching agents preferably used in detergents are sodium perborate and sodium carbonate perhydrate.

Inorganic surfactants preferably used in detergents are fatty alcohol sulfates, linear alkyl benzene sulfonates (LAS) and Soaps, the proportion of LAS preferably below 8% by weight, is particularly preferably less than 4% by weight.

Nonionic surfactants preferably used in detergents are C ₁₁ - to C ₁₇ -oxoalcohol ethoxylates with 3-13 ethylene oxide units, C ₁₀ - to C ₁₆ -fatty alcohol ethoxylates with 3-13 ethylene oxide units and additionally alkoxylated with 1-4 propylene oxide or butylene oxide units Fat or oxo alcohols.

Enzymes preferably used in detergents are protease, Lipase and cellulase. Of the commercially available enzymes Detergents usually amounts from 0.1 to 1.5 wt .-%, preferably 0.2 to 1.0 wt .-% of the compounded enzyme added. Suitable proteases are e.g. Savinase and Esperase (manufacturer Novo Nordisk). A suitable lipase is e.g. Lipolase (Manufacturer Novo Nordisk). A suitable cellulase is e.g. Celluzym (manufacturer Novo Nordisk).

Graying inhibitors preferably used in detergents and soil release polymers are graft polymers of vinyl acetate Polyethylene oxide with a molecular weight of 2500-8000 in weight ratio 1.2: 1 to 3.0: 1, polyethylene terephthalate / oxyethylene terephthalate the molecular weight 3000 to 25 000 from polyethylene oxides of the molecular weight 750 to 5000 with terephthalic acid and ethylene oxide and one Molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and block polycondensates according to DE-A 4403866.

Color transfer inhibitors preferably used in detergents are soluble vinyl pyrrolidone and vinyl imidazole copolymers with molecular weights over 25,000 and finely divided cross-linked polymers based on vinyl imidazole.

The detergents described preferably contain Phosphonates.

The powder or granular detergents according to the invention can contain up to 60% by weight of inorganic adjusting agents. Sodium sulfate is usually used for this. Preferably however, the detergents according to the invention are low in adjusting agents and contain only up to 20 wt .-%, particularly preferably only up to 8% by weight of adjusting agents.

The detergents according to the invention can have different bulk densities in the range from 300 to 1200, in particular 500 to 950 g / l have. Modern compact laundry detergents generally have high ones Bulk densities and show a granular structure.

In addition to combined detergents and bleaches, there are also formulations the activators described for textile washing also agents considered as additives to peroxide or peroxide-free detergents can be used. They contain in essential activator or a mixture of activator and per compound and, if appropriate, further auxiliaries and additives, in particular stabilizers, pH regulators, thickeners and surfactants.

The present invention also relates to bleach additives for textile washing, which is 1 to 30% by weight, preferably 5 to 25% by weight, based on the total amount of the additive preparation, one or more heterocyclic Compounds I as activators for inorganic per-compounds contain.

5 bis 50 Gew.-%, vorzugsweise 15 bis 35 Gew.-% anorganische Perverbindung,

1 bis 30 Gew.-%, vorzugsweise 5 bis 25 Gew.-% der Verbindungen I,

0 bis 5 Gew.-%, vorzugsweise 0,1 bis 3 Gew.-% Peroxidstabilisatoren,

0 bis 40 Gew.-%, vorzugsweise 5 bis 30 Gew.-% pH-regulierende Mittel,

ad 100 Gew.-% andere übliche Hilfs- und Zusatzstoffe.Typical bleach additives of this type have the following composition:

5 to 50% by weight, preferably 15 to 35% by weight, of inorganic per compound,

1 to 30% by weight, preferably 5 to 25% by weight, of the compounds I,

0 to 5% by weight, preferably 0.1 to 3% by weight, of peroxide stabilizers,

0 to 40% by weight, preferably 5 to 30% by weight of pH-regulating agents,

ad 100% by weight of other customary auxiliaries and additives.

In addition, agents intended for cleaning hard surfaces contain Per compound and activator in particular surfactants, builders and, in the case of polishing and abrasive agents, abrasive acting ingredients. Because these agents are often at room temperature are applied, the use of the invention has an effect here Activators particularly beneficial to the bleaching and germicidal effect.

Assembled agents are of particular importance when used in disinfection, since there are generally increased requirements be placed on application security. Disinfectant based on the activators described in addition to these and inorganic per compounds in general other auxiliary substances and additives such as pH regulating substances, Stabilizers and surfactants. In special cases you can they also contain special microbicides, which in themselves very broad killing effect of the activated per-compound reinforce certain germs.

The present invention also relates to disinfectants, which are 1 to 40% by weight, preferably 5 to 30% by weight, based on the total amount of the preparation or more heterocyclic compounds I as activators for contain inorganic per-compounds.

5 bis 40 Gew.-%, vorzugsweise 10 bis 20 Gew.-% anorganische Perverbindungen,

1 bis 40 Gew.-%, vorzugsweise 5 bis 30 Gew.-% der Verbindungen I,

0 bis 5 Gew.-%, vorzugsweise 0,1 bis 3 Gew.-% Peroxidstabilisatoren,

0,1 bis 20 Gew.-%, vorzugsweise 0,2 bis 5 Gew.-% Tenside,

ad 100 Gew.-% weitere Hilfs- und Zusatzstoffe.Typical disinfectants of this type have the following composition:

5 to 40% by weight, preferably 10 to 20% by weight, of inorganic per-compounds,

1 to 40% by weight, preferably 5 to 30% by weight of the compounds I,

0 to 5% by weight, preferably 0.1 to 3% by weight, of peroxide stabilizers,

0.1 to 20% by weight, preferably 0.2 to 5% by weight of surfactants,

ad 100% by weight of other auxiliaries and additives.

The use of the activators described according to the invention is but never on the application in a ready-made form described or limited other types. For example, it says in the commercial sector in general the single dosage of reagents in the foreground as they are often the less expensive Represents procedure.

The heterocyclic compounds I are predominantly known from the literature and syntheses for their preparation are described.

With the heterocyclic compounds I a clear one Improvement of the bleaching, oxidation and cleaning effects in the lower temperature range in the technical applications described achieve.

Typical preparation instructions for heterocyclic compounds I example 1 Preparation of N, N'-carbonylbis-ε-caprolactam

In a 2 l stirred flask were 1 mol (113 g) ε-caprolactam and 1.05 mol (133.3 g) dimethylcyclohexylamine (DMCA) in 700 ml toluene submitted. Within 45 minutes, 0.55 mol (54.5 g) of phosgene gasified into the reaction solution. The inside temperature was with Using an ice bath kept at about 20 ° C. After the end of the Phosgene addition, the reaction mixture was heated to 40 ° C and at this temperature was stirred for a further 2 h. The DMCA hydrochloride formed was filtered off and washed with toluene. The organic Phase was extracted with 250 ml of water and then constricted. - The title compound was obtained in one yield of 46% (58 g) with a melting point of 116 ° C.

Examples of use

With example 1, washing tests were carried out with test soiling performed by red wine, tea or grass on cotton fabric, at which in most cases have better bleaching effects could as with the state of the art Activator N, N, N ', N'-tetraacetylethylenediamine (TAED) (comparative example B). Examples 6 and B were used in addition to washing tests with a test soil From grass to cotton too those carried out with a colored fabric (EMPA 115). In which Colored fabrics can be seen that the undesirable fading of the color in the activators used according to the invention on a comparable or lower level compared to TAED.

The test was carried out in a Launder-O-meter, type Atlas Standard, using a phosphate-free detergent I under the following conditions:
Fleet volume 250 ml
Fabric: 4 x 2.5 g various test fabrics (bleached cotton soiled with red wine, tea or grass and color fabric EMPA 115)
Water hardness 3 mmol / l (17 ° dH)
Temperatures: 22 ° C and 38 ° C or 38 ° C and 60 ° C
Washing time: 30 min (including heating up time)
Rinse: 3 x 30 sec with tap water (14 ° dH)
Detergent dosage: 7.0 g / l Detergent composition I (% by weight): linear alkylbenzenesulfonate (Na salt) 6.25 C ₁₃ / C ₁₄ oxo alcohol, reacted with 7 mol ethylene oxide 4.7 Tallow soap 2.8 Zeolite A 25.0 sodium 12.0 Magnesium silicate 1.0 Sodium disilicate 4.5 Polycarboxylate (acrylic acid / methacrylic acid 60:40, M _w = 70000) 3.0 Carboxymethyl cellulose (60%) 1.0 Sodium perborate monohydrate 10.0 Activator (100% active ingredient) 0 or 4.0 Sodium sulfate to 100

The tests were evaluated by remission measurements on the dried tissues at a wavelength of 460 nm. The differences ΔR = R _A -R _{O of} the remission between the fabrics washed without activator and the fabrics washed with activator for the four test fabrics listed and the washing temperatures indicated are shown in Table 1 below. Activator Test fabric with Grass contamination Color fabric (EMPA 115) 38 ° C 60 ° C 38 ° C 60 ° C Example # 1 2.0 1.4 1.3 1.9 (B) for comparison: TAED 0.5 0.4 1.0 2.0 (EMPA 115: Test fabric No. 115 from the Swiss Federal Materials Testing Institute, Switzerland)

With example 1, further washing tests with test soiling were carried out performed by tea or red wine on cotton fabric, at which in most cases have better bleaching effects could than with TAED (Comparative Example C).

Table 2 below shows typical modern heavy-duty detergent formulation amounts II to VIII. The composition V was used in the washing tests. Detergent compositions of heavy duty detergents (% by weight) II III IV V VI VII VIII PVP (K value 30) 1.5 VI / VP copolymer (K value 30) 1.0 1.0 0.6 AS / MS (70000) 5.0 5.0 AS / MS / VAc terpolymer (20000) 5.0 Oligomaleic acid 5.0 Polyaspartic acid 7.5 Na perborate monohydrate 15 15 15 7.5 Na perborate 18th 15 18th N- (phenyloxycarbonyl) -γ-butyrolactam as an activator 3.8 5.0 4.2 2.0 Activator from example 1 4.0 5.0 2.9 Na lauryl sulfate 3.5 6.0 12.0 6.0 5.5 2.0 Linear alkyl benzene sulfonate sodium salt 1.7 0.8 4.5 Soap 2.8 0.6 0.4 2.5 1.5 2.4 C13 / C15 oxo alcohol * 3EO 3.0 C13 / C15 oxo alcohol * 7EO 4.7 4.7 13.5 4.0 6.5 C13 / C15 oxo alcohol * 10EO 3.0 C12 / C14 fatty alcohol * 7EO 10.0 Lauryl alcohol * 13EO 5.0 Zeolite A 25th 25th 15 30th 15 35 Zeolite P 40 SKS-6 14 15 Na disilicate 2.5 3.9 0.5 4.5 1.5 Mg silicate 1.0 0.8 1.0 1.0 0.6 Sodium sulfate 20th 2.5 3.2 2.0 1.5 5.5 3.4 Sodium bicarbonate 9.0 6.5 sodium 12.0 13.6 10.0 8.0 9.8 Soil release polymer 0.4 0.5 Polyethylene terephthalate / oxyethylene terephthalate 1.0 0.5 0.8 1.0 Carboxymethyl cellulose 0.6 1.3 0.6 1.0 0.6 0.6 0.5 Dequest® 2046 0.5 citric acid 6.8 5.0 2.5 3.8 Lipase 1.0 Protease 1.0 1.0 0.5 0.6 Cellulase 0.6 water to 100 to 100 to 100 to 100 to 100 to 100 to 100

SKS-6 =

handelsübliches Schichtsilikat (Hersteller: Hoechst AG)

Soil-Release-Polymer =

Pfropfpolymerisat von Vinylacetat auf Polyethylenglykol der Molmasse 6000, Molmasse des Pfropfpolymerisats 24000

Dequest® 2046 =

Ethylendiamin-N,N,N',N'-tetra(methylenphosphonat)

Examples III, V, VII and VIII do not fall within the claimed range.

SKS-6 =

commercially available layered silicate (manufacturer: Hoechst AG)

Soil release polymer

Graft polymer of vinyl acetate on polyethylene glycol of molecular weight 6000, molecular weight of graft polymer 24000

Dequest® 2046 =

Ethylenediamine-N, N, N ', N'-tetra (methylenephosphonate)

The test was carried out under the following washing conditions: device Launder-O-meter, type Atlas Standard Cycles 1 Duration 30 min Temperatures 22 ° C, 38 ° C and 60 ° C Water hardness 3.0 mmol / l Test fabric 5x2.5 g various test fabrics (bleached cotton or cotton nettle fabric soiled with red wine or tea) Fleet quantity 250 ml Fleet ratio 1:20 Detergent concentration 4.5 g / l

The color strength of the test fabric was measured photometrically. From the reflectance values measured at the individual test fabrics at 18 wavelengths in the range from 400 to 700 nm at a distance of 20 nm, the methods described in A. Kud, Seifen, Öle, Fette Wachsen 119, pp. 590-594 (1993) Determine the respective color strengths of the test soils before and after washing and use them to calculate the absolute bleaching effect A _abs in%. Results of washing tests with test soiling fabrics (numerical values are absolute bleaching effect A _abs in%) Bleach activator Detergent formulation tea red wine 22 ° C 38 ° C 22 ° C 38 ° C Example No. 1 V 31.3 61.4 68.4 74.9 (C) for comparison: TAED V 21.8 55.5 64.1 75.6 without activator V 4.4 10.9 55.3 56.8

The results in Table 3 show that the bleaching effect of the Carbonyllactam derivative to be used according to the invention from Example 1 TAED partly clear, especially at low temperatures surpasses. Carbonylcaprolactam derivatives are also with grass soiling mostly significantly more effective than TAED.

Claims (6)

1. The use of heterocyclic compounds of the general formula I L―X―L where the two heterocyclic radicals L are identical and are

   (a) a cyclic carbamate residue of the formula

   

   (b) a lactonoxy residue of the formula

   

   or

   (c) a lactam residue of the formula

   

   where

   Z¹ to Z³

   are 1,2-, 1,3-, 1,4- or 1,5-alkylene groups which have 2 to 20 carbon atoms and which can additionally be functionalized by one to three hydroxyl groups, C₁-C₄-alkoxy groups, amino groups, C₁-C₄-alkylamino groups, di-C₁-C₄-alkylamino groups, chlorine atoms, bromine atoms, nitro groups, cyano groups, carboxyl groups, sulfo groups, carboxy-C₁-C₄-alkyl groups, carboxamide groups or phenyl, tolyl or benzyl radicals, it being possible for aromatic nuclei in turn likewise to be substituted by the said radicals, or can be interrupted by one or two non-adjacent oxygen atoms, amino groups, C₁-C₄-alkylamino groups or carbonyl groups, and

   T

   is hydrogen or C₁-C₄-alkyl, and

   X

   is an oxygen-containing group of the formula

   

   where

   Y

   is hydrogen, ammonium which may be substituted by organic radicals, or C₁-C₄-alkyl, and

   A

   is a C₁-C₁₈-alkylene group, a C₂-C₁₈-alkenylene group, a C₅-C₃₂-cycloalkylene group, a C₇-C₃₀-aralkylene group, a C₆-C₁₈-arylene group or a C₃-C₁₈-hetarylene group, it being possible for aliphatic structural units additionally to be functionalized by one to five hydroxyl groups, C₁-C₄-alkoxy groups, amino groups, C₁-C₄-alkylamino groups, di-C₁-C₄-alkylamino groups, chlorine atoms, bromine atoms, nitro groups, cyano groups, carboxyl groups, sulfo groups, carboxy-C₁-C₄-alkyl groups, carboxamide groups or phenyl, tolyl or benzyl radicals, where aromatic, cycloaliphatic and heteroaromatic structural units can likewise be substituted by the said radicals, or to be interrupted by one to eight non-adjacent oxygen atoms, amino groups, C₁-C₄-alkylamino groups or carbonyl groups,

   with the exception of terephthaloyldivalerolactam and terephthaloyldicaprolactam,
   as activators for inorganic peroxy compounds.
2. The use of heterocyclic compounds I as claimed in claim 1, in which the oxygen-containing group X is

   
3. The use of heterocyclic compounds I as claimed in claim 1 or 2 as activators for inorganic peroxy compounds for the temperature range from 10 to 80°C in detergents, cleaners and bleaches.
4. A detergent or bleach for textile laundering, containing 0.1-20 % by weight, based on the total amount of the formulation, of one or more heterocyclic compounds I as activators for inorganic peroxy compounds as claimed in claim 1 or 2.
5. A bleach additive for textile laundering, containing 1-30 % by weight, based on the total amount of the additive formulation, of one or more heterocyclic compounds I as activators for inorganic peroxy compounds as claimed in claim 1 or 2.
6. A disinfectant containing 1 to 40 % by weight, based on the total amount of the formulation, of one or more heterocyclic compounds I as activators for inorganic peroxy compounds as claimed in claim 1 or 2.