EP0958345A2

EP0958345A2 - Activators for per compounds

Info

Publication number: EP0958345A2
Application number: EP98906909A
Authority: EP
Inventors: Elisabeth Kappes; Thomas Wehlage; Alfred Oftring; Dieter Boeckh
Original assignee: Oracle Corp
Current assignee: BASF SE
Priority date: 1997-02-04
Filing date: 1998-02-03
Publication date: 1999-11-24
Also published as: WO1998033878A2; DE19704143A1; JP2002518984A; WO1998033878A3; US6410497B1

Abstract

Disclosed are carbonates of general formula (I): A-O-CO-OR<3>, in which A is a radical (Ia) R<1>R<2>C=N- or a radical (Ib), or the hydromidesters of the general formula (I) or the polymer derivates thereof are used with radicals having the meaning of R<1> to R<5>, especially alkyl and aryl with or without substituents, R<1>/R<2> representing inter alia hydrogen or, jointly, an alkyl group, while R<4>/R<5> represent inter alia jointly an alkyl group and R<6>/R<7> a carbocycle, as activators for anorganic per compounds.

Description

Activators for inorganic per compounds

The invention relates to the use of carbonates, such as oxime carbonates and hydroximide carbonates, hydroximide esters and polymers thereof, as activators for inorganic per compounds, and also detergent formulations containing them.

The use of certain hydroximide esters as bleach activators is known. EP-A-0 267 046 describes bleaching compositions which contain peracid precursors. N-hydroximides, such as N-hydroxysuccinimide, N-hydroxymthalimide, N-hydroxyglutarimide, N-hydroxynaphthalimide, N-hydroxymaleimide, N-hydroxydiacetylimide and N-hydroxydipropionylimide, are listed as compounds. These N-hydroxylimides are used in the form of esters with carboxylic acids, in particular with octanoic acid. In addition, oxime esters are used which are formed from oximes of aldehydes or ketones with carboxylic acids, in particular octanoic acid. Preferred oximes are acetone oxime and methyl ethyl ketoxime.

The object of the present invention is to provide further activators for inorganic per-compounds which have an improved effect, in particular in the case of hydrophobic bleaching. According to the invention, the object is achieved by using carbonates of the general formula (I)

AO-CO-OR ³ (I)

in the

A a rest (Ia)

R ¹ R ² C = N- (Ia)

or A a residue (Ib)

wherein R ^1, R ^2, R ^3, R ⁴ and R ^{5 are} independently linear or branched C ^ _Q alkyl, C _2-30 alkenyl, C _18.5 cycloalkyl, C. ₇ ₁₈ aralkyl or

C ₆ _ ₁₈ aryl or heteroaryl, aliphatic radicals additionally having 1 to 5 hydroxyl groups, Amino groups, Cι. ₄ -alkylamino groups, Chlorine atoms, bromine atoms, nitro groups, cyano groups, carboxyl groups, sulfo groups, carboxy-Cι. ₄ -alkyl groups, carboxamide groups or phenyl, tolyl or benzyl radicals can be functionalized, where aromatic, cycloaliphatic and heteroaromatic structural units can also be substituted by the radicals mentioned, or by 1 to 8 non-adjacent oxygen atoms, amino groups, C -alkylamino groups or Carbonyl groups can be interrupted, and R ¹ and R ^{2 can} furthermore signify hydrogen or together form a 1, 3-, 1, 4-, 1, 5-, 1, 6-, 1, 7- or 1, 8-alkylene group with 3 to 33 C atoms , which additionally by 1 to 5 hydroxyl groups, Cι - alkylamino groups, di-C ,. ₄ -alkylamino groups, chlorine atoms, bromine atoms, nitro groups, cyano groups, carboxyl groups, sulfo groups, carboxy-

Cι. ₄ -alkyl groups, carboxamide groups or phenyl, tolyl or benzyl radicals can be functionalized, whereby aromatic radicals can in turn also be substituted by the radicals mentioned, or by 1 or 2 non-adjacent oxygen atoms, amino groups, C,. ₄ -alkylamino groups or carbonyl groups can be interrupted,

where, if A is a radical (Ia), R ^{3 is} not a vinyl radical which can be substituted by a carboxylic acid group, sulfonic acid group, phosphonic acid group or their alkali metal or ammonium salt, and no vinyloxy radical -O-CR ^1: = CHR ² , in which R ¹ and R ^{2 have} the meaning given above,

and R ^{3 can be} a radical (Ib) if A is a radical (Ib), in particular if R ⁴ and R ⁵ together form a 1,2-phenylene ring (phthalimide derivative), 1,2-ethylene ring (succinimide derivative) or Form 1, 2-ethylene ring,

and R ⁴ and R ⁵ further together can form a 1, 2-, 1, 3-, 1, 4-, 1, 5-, 1, 6-alkylene group having 2 to 30 C atoms, which are like the above Alkylene groups can be substituted, or

R ⁴ and R ⁵ together form a carbon 5-, -6-, -7-, -8-, or -9-ring, which is bonded to the carbonyl groups via 2 adjacent C atoms, one or more double bonds in the Ring can be present or the ring can be aromatically unsaturated, where one or more carbon atoms in the ring can be replaced by heteroatoms, and 2 C atoms in the ring can be connected via a hetero atom or a C ^ alkylene radical or C _2-3 alkenylene radical, or

R ⁴ and R ⁵ can form together from 2 carbonate molecules the above carbon ring, which is bonded via 2 adjacent C atoms to the carbonyl groups of the two imide structures (see, for example, the tricyclic diimide structures of structure VI below)

or hydroximide esters of the general formula (II)

wherein R ^{3 has} the meaning given above and R ⁶ and R ⁷ together form a carbon 5-, -6-, -7-, -8- or -9-ring, which has 2 adjacent C atoms on the carbonyl groups is bound, where one or more double bonds can be present in the ring, one or more ring positions can be replaced by heteroatoms and 2 carbon atoms in the ring via a heteroatom and a Cι. ₃ -alkylene radical or C _2- 3 -alkenylene radical, which is bonded via 2 adjacent C atoms to the carbonyl groups of the two imide structures,

or R ⁶ and R ⁷ can form together from 2 hydroximide ester molecules the above carbon ring, which is bonded to the carbonyl groups of the two imide structures via 2 adjacent C atoms (see, for example, the tricyclic diimide structures of structure VI below)

or polymers, which C may contain from ₂ _ ₈ -Olefincomonomerbausteine and basic building blocks of the general formulas (III), (IV) and / or (V) contain

where R ^{8 is} a radical R ³ or -OR ³ with the meaning given above,

as activators for inorganic per compounds.

The activators according to the invention can be used in washing, cleaning, bleaching and disinfecting agents, for example as cold bleach activators.

According to one embodiment of the invention, the compounds are oxime carbonates if A is a radical (Ia) R ¹ R ² C = N-. In addition to hydrogen, R ¹ and R ² are, for example, linear or branched C ₃₀ alkyl radicals, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl , tert-butyl, n-pentyl, i-pentyl, sec.-pentyl, tert.-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, n -Nonyl-, n-decyl-, n-undecyl-, n-dodecyl-, n-tredecyl-, n-tetradecyl-, n-pentadecyl-, n-hexadecyl-, n-heptadecyl-, n-octadecyl-, n -Nonadecyl or n-eicosyl residues. Preferred alkyl radicals are C ₂ alkyl radicals, particularly preferably C 1-4 alkyl radicals, in particular the radicals R ¹ and R ^{2 are} ethyl groups.

The radicals R ¹ and R ² can furthermore be linear or branched C ₂ , ₃₀ -alkenyl radicals, such as vinyl, allyl, 2-methylprop-2-enyl radicals or radicals derived from oleic acid, linoleic acid, linolenic acid. G _j .g alkenyl residues are preferred, as are C _6.22 alkenyl residues.

In addition, C _5.18 cycloalkyl radicals can be used, preferably C _5.10 cycloalkyl radicals, such as cyclopentyl, cyclohexyl, 2-, 3- or 4-methylcyclohexyl radicals, 2,3-, 2,4-, 2,5- or 2 , 6-Dimethylcyclohexylreste, Cycloheptylreeste or Cyclooctylreste. Further useful are C ₇ _ ₁₈ aralkyl, preferably C ₇ _ ₁₂ -Aralkylre- ste, in particular alkyl-substituted phenyl such as benzyl, 2-, 3- or 4- methylbenzyl, 2-phenylethyl, 3-phenylpropyl, 4 -Phenylbutyl, 2-, 3- or 4-ethylbenzyl, 3- or 4-isopropylbenzyl or 3- or 4-butylbenzyl radicals.

As C ₆ . _8- aryl groups are, for example, phenyl, 2-, 3- or 4-bisphenyl, alpha- or beta-naphthyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 3- or 4-isopropylphenyl, 3- or 4-butylphenyl or 3- or 4- (2'-ethylhexyl) phenyl radicals. C _6.14 aryl radicals, in particular phenyl radicals and alkyl-substituted phenyl radicals, are preferred.

C _6.18 heteroaryl radicals are preferably 5- or 6-membered C _6.12 heteroaryl radicals having one or two heteroatoms from the group consisting of nitrogen, oxygen or sulfur. Examples of suitable heterocycles are pyridine, furan, thiophene, pyrrole, imidazole, pyrazole, thiazole, pyrazine and pyrimidine. These residues can be attached via any of the ring carbon atoms. In addition, the ring structures on the carbon atoms which have free valences can be substituted by preferably Cι. ₄ -alkyl radicals, such as the methyl, ethyl, propyl and butyl radicals described above.

Examples of aliphatic radicals interrupted by oxygen or amino groups, in particular NH or N (CH ₃ ) groups, can for example be methylethylaminoethyl, dimethylaminomethyl, methoxymethyl, methoxyethyl, ethoxyethyl, hydroxyethyl, reacted with 1 to 8 ethylene oxide units, methoxybutyl, methoxypropyl, with 2-methoxy -l-methylethyl and 2-hydroxy-1-methylethyl, reacted with 1 to 5 propylene oxide units, can be used.

R ¹ and R ² together may preferably be a C ₃ . Form ₁₂ alkylene radical. Examples are propylene radicals which are substituted in the 1-, 2- or 3-position by methyl groups, ethyl groups, propyl groups or butyl groups, butylene radicals which can be substituted in the 1-, 2-, 1,2-, 1,3-, 1,4-position by methyl groups, ethyl groups, propyl groups or butyl groups, pentylene radicals which in 1-, 2-, 3-, 1,5-, 1,3-, 2,4-, 3,3-position can be substituted by methyl groups or in one of the positions by an ethyl group, propyl group or butyl group, n -Hexylene residues, n-heptylene residues or n-octylene residues. The alkylene radicals can have the functionalizations or interruptions described.

The aldoxime or ketoxime groups R ¹ RC = can be derived from the known aldehydes or ketones, thereby, such as formaldehyde, acetaldehyde, propionaldehyde, Bencaldehyd, vinyl acetaldehyde, acetone, ethyl methyl ketone, diethyl ketone, acetophenone, vinyl acetone, benzophenone, cyclopentanone, cyclohexanone or cycloheptanone.

The radicals R ⁴ and R ⁵ can together form a 1,2-, 1,3-, 1,4-, 1, 5- or 1,6-alkylene group with 2 to 30 C atoms. Preferred groups are C ₂ . ₁₀ -alkylene groups, such as ethylene, which can be substituted in positions 1, 2, or 1 and 2 by methyl, ethyl, propyl or butyl radicals, propylene, butylene, pentylene, hexylene, as described above. These residues can also be functionalized or interrupted.

The radical R ³ is preferably a C _j. ^ - alkyl, particularly preferably C _1. ₄ - alkyl radical or C _7.15 alkyl radical, which can be straight-chain or branched. Preferred residues are methyl and n-butyl residues, as well as residues which are derived from industrial alcohols or alcohol mixtures, in particular branched alcohols or alcohol mixtures. Examples of these are C _8/10 lorol, iso-C ₁₀ alcohol, C _{9 11} oxo alcohol, C _{11 13} oxo alcohol, 2-propylheptanol, 2-ethylhexanol. Aralkyl radicals are also preferred, in particular C ι ₄ alkyl radicals which are substituted by a phenyl radical. A particularly preferred radical is a benzyl radical.

In the carbonates of the general formula (I), in which the radical A is a radical (Ib), the radical R ^{3 can} also preferably be a phenyl radical which can optionally be substituted by the stated substituents.

R ⁴ and R ⁵ can together form a carbon -5-, -6-, -7-, -8- or -9- ring which is bonded to the carbonyl groups via 2 adjacent C atoms. It can thus be a cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclononyl ring which is connected to the carbonyl groups in the rest (Ib) on 2 adjacent C atoms. The ring can be substituted, as described above, or one or more of the C atoms in the ring can be replaced by heteroatoms. An example of such a compound is piperidine. Other known heterocyclic compounds can form this ring. The ring is preferably a 5- or 6-ring. The ring can contain one or more double bonds or be aromatically unsaturated. It can preferably be a 6-ring which has a double bond and is connected in the 4,5-position to the carbonyl groups. It is therefore a cyclohexene ring. The ring is likewise preferably an aromatically unsaturated ring, in particular a 6-ring. The compounds in this case are phthalic acid derivatives. Diterephthalhydroximide carbonates which are accessible by reacting terephthalohydimide with phosgene are preferred. The aromatic rings can also have substituents. Furthermore, 2 C atoms in the ring can be via a hetero atom or a C 1-4 alkylene radical or C ₂ . ₃ -Alkenylene radical may be connected. It is consequently a bicyclic radical. Oxygen is preferably used as the hetero atom for bridging, or a C 1-4 alkylene radical, in particular methylene radical. In this case, preferably none points of the rings has fewer than 5 ring atoms. The two ring carbon atoms which are adjacent to the carbon atoms and via which the ring is bonded to the carbonyl groups of the radical (Ib) are particularly preferably connected in a carbon 6 ring. It is preferably a cyclohexene ring in which the carbon atoms which are adjacent to the carbon atoms connected to the carbonyl groups are bridged via an oxygen atom or a methylene group. The double bond in the cyclohexene ring is between the two remaining carbon atoms.

R ⁴ and R ⁵ from two carbonate molecules can also together form the above carbon ring, which is thus bonded to four carbonyl groups. The radical R ³ has the meaning given above and is preferably a phenyl radical. Structures VI below have examples of suitable cyclic radicals

Preferably, the radicals R ¹ and R ² are independently C _{[_} ₄ alkyl, R ³ is C ₀ alkyl, phenyl or benzyl, and R ⁴ and R ⁵ together form a 1, 2-phenylene radical or 4,5-cyclohexenylene.

According to one embodiment of the invention, the activators for inorganic per compounds are hydroximide esters of the general formula (II)

where R ^{3 has} the meaning given above. R ⁶ and R ⁷ form a carbon 5-, -6-, -7-, -8- or -9-ring which, as above, for the compounds of the general formula (I) with the radical (Ib) as the radical A is bonded to the carbonyl groups via two adjacent C atoms. The preferred radicals R ⁶ and R ⁷ are the cyclic radicals from R ⁴ and R ⁵ listed above which are bonded to the carbonyl groups via 2 adjacent C atoms.

Polymers can also be used which have basic building blocks of the general formulas (III), (IV) and (V).

where R ^{8 is} a radical R ³ or -OR ³ with the meaning given above. These polymers contain per molecule at least two monomer units, such as those listed above, and may be C ^ _g -Olefinco- monomer included. It can thus be homopolymers from the stated basic building blocks, copolymers of the given basic building blocks with one another, as well as copolymers of the given basic building blocks with preferably ethene, propene, n-butene, isobutene, pentenes. The polymers which contain basic building blocks of the general formula (III) can be prepared on the basis of maleic anhydride (co) polymers, for example a maleic anhydride / isobutene copolymer. The number of basic building blocks of the general formulas (III), (IV) and (V) is at least 2, preferably 2 to 5,000, in particular 10 to 1,000. The number of olefinic comonomer units is 0 to 50,000, preferably 10 to 10,000, in particular 100 to 1,000.

The basic building blocks (IV), (V) can be based on polyketones, such as, for example, oligo (meth) acrolein or an ethylene / CO copolymer.

Bleach activators which are particularly preferred according to the invention are N- (2-propylheptyloxicarbonyl) oxiphthalimide, N- (vinyloxicarbonyl) oxicyclohex-4-en-1-dicarboximide, O- (methyloxicarbonyl) acetone oxime, O- (benzyloxicarbonyl) acetone oxide and O- (n-butyloxide carbonyl) acetone oxime.

The bleach activators according to the invention can preferably be used as activators for inorganic per compounds where a particular increase in the oxidizing effect of the inorganic per compounds at low temperatures is important, for example in the bleaching of textiles, hair or hard surfaces, in the oxidation of organic or inorganic Intermediates and disinfection. The activators are particularly advantageous when bleaching hydrophobic soils.

The bleach activators according to the invention are generally solid compounds which can be incorporated stably into powder or granular detergent, bleach or cleaning agent formulations.

When using the compounds, there are preferably conditions under which compounds containing active oxygen, for example hydrogen peroxide, and the activators react with one another, with secondary products having a stronger oxidizing effect being obtained. Such conditions are, for example, an aqueous alkaline solution which contains both reaction partners. Depending on the intended use, the conditions conditions can be varied within a wide range. In addition to pure aqueous solutions, mixtures of water and suitable organic solvents can also be used, for example for use in disinfection or in the oxidation of intermediates. The pH of the reaction medium can vary within wide limits from the acidic (pH 4) to a strongly alkaline range (pH 13). The pH is preferably from 8 to 11. The activators are preferably used together with a sodium perborate or with sodium carbonate perhydrate, which already have pH values in the range given above in their solutions. Examples of other suitable per compounds are phosphate perhydrates and urea perhydrate. It can sometimes be expedient to shift the pH of the medium again after the activation reaction by means of suitable additives, especially in the acidic range.

The amounts of per compounds are generally chosen so that the solutions contain between 10 and 10,000 ppm of active oxygen, preferably between 50 and 5,000 ppm of active oxygen. The amount of activator used depends on the application. Depending on the desired degree of activation, 0.03 to 1.0 mol, preferably 0.1 to 0.5 mol, of activator are used per mol of inorganic per-compound.

The activators according to the invention can be used for activation in pure form or, if this is expedient, for example, to increase the storage stability, in special formulations, such as tablets, granules or in finely divided form (so-called prills). They are preferably in those forms which are produced by agglomeration granulation. For machine dosing, the activators should be in dissolved or dispersed form. The activators are preferably used in pre-assembled agents in a mixture with the per compounds to be activated and, if appropriate, further components required for the bleaching, oxidation or cleaning process. The activators according to the invention can also be used in combination with known activators. Below are further components of detergents and bleaches according to the invention, bleach additives or dishwashing detergents and disinfectants.

The bleaching agents that can be used have already been described above.

BLEACH CATALYSTS

The bleach activators used according to the invention can be used together with suitable bleach catalysts. Examples of these are quaternized imines and sulfonimines, as are described, for example, in US Pat. No. 5,360,568, US Pat. No. 5,360,569 and EP-A-0 453 003, and also manganese complexes, as described, for example, in WO-A 94/21777 . Further usable metal-containing bleaching catalysts are described in EP-A-0 458 397, EP-A-0 458 398, EP-A-0 549 272. Secondary amines as described in the German patent application with the file number 19625908.8 are also suitable.

Bleach activators which, according to one embodiment of the invention, can be used in the compositions together with the activators according to the invention are, for example, compounds of the following substance classes:

Polyacylated sugar or sugar derivatives with C ^ o-acyl residues, preferably

Acetyl, propionyl, octanoyl, nonanoyl or benzoyl radicals, particularly preferably acetyl radicals, can be used as bleach activators. As sugar or sugar derivatives, mono- or disaccharides and their reduced or oxidized derivatives can be used, preferably glucose, mannose, fructose, sucrose, xylose or lactose. Particularly suitable bleach activators of this class of substances are, for example, pentaacetylglucose, xylose tetraacetate, l-benzoyl-2,3,4,6-tetraacetylglucose and l-octanoyl-2,3,4,6-tetraacetylglucose.

Another class of substances that can be used are the acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, where C _j. ^ Acyl residues can be used. Acetyl, propionyl, octanoyl, nonanoyl and benzoyl residues are preferred, in particular acetyl residues and nonanoyl residues. Particularly suitable bleach activators of this class of substances are acetyloxybenzenesulfonic acid, benzoyloxybenzenesulfonic acid and nonanoylbenzenesulfonic acid (NOBS) or isononanoylbenzenesulfonic acid (isoNOBS). They are preferably used in the form of their sodium salts.

O-acyl oxime esters such as e.g. O-acetylacetone oxime, O-benzoylacetone oxime, bis (propylimino) carbonate, bis (cyclohexylimino) carbonate. Acylated oximes which can be used according to the invention are described, for example, in EP-A-0 028 432. Oxime esters which can be used according to the invention are described, for example, in EP-A-0 267 046.

N-Acylcaprolactams such as, for example, N-acetylcaprolactam, N-benzoylcaprolactam, N-octanoylcaprolactam, carbonylbiscaprolactam can also be used.

Are still usable

N-diacylated and N, N'-tetracylated amines, for example N, N, N ', N'-tetraacetyl-methylenediamine and -ethylenediamine (TAED), 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, e.g. N-methyl-N-mesyl-acetamide or N-methyl-N-mesyl-benzamide;

N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. Monoacetyl maleic acid hydrazide;

- O, N, N-trisubstituted hydroxylamines, e.g. O-benzoyl-N, N-succinyl-hydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine or O, N, N-triacetyl-hydroxylamine;

N, N'-diacylsulfurylamides, e.g. N, N'-dimethyl-N, N'-diacetylsulfurylamide or N, N'-diethyl-N, N'-dipropionylsulfurylamide;

Triacylcyanurates, e.g. Triacetyl cyanurate or tribenzoyl cyanurate;

Carboxylic anhydrides, e.g. Benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;

1,3-diacyl-4,5-diacyloxyimidazolines, e.g. 1,3-diacetyl-4,5-diacetoxyimidazoline;

- tetraacetylglycoluril and tetrapropionylglycoluril;

diacylated 2,5-diketopiperazines, e.g. 1,4-diacetyl-2,5-diketopiperazine;

Acylation products of propylene diurea and 2,2-dimethylpropylene diurea, for example tetraacetyl propylene diurea; α-acyloxy-polyacyl-malonamides, for example o; -acetoxy-N, N'-diacetylmalonamide;

Diacyl-dioxohexahydro-l, 3,5-triazines, e.g. 1,5-diacetyl-2,4-dioxohexa- hydro-l, 3,5-triazine.

Likewise usable are 2-alkyl- or 2-aryl- (4H) -3, l-benzoxazin-4-ones, as described for example in EP-B1-0 332 294 and EP-B 0 502 013. In particular 2-Phenyl- (4H) -3, l-benzoxazin-4-one and 2-methyl- (4H) -3, l-benzoxazin-4-one can be used.

Cationic nitriles as described, for example, in EP 303 520 and EP 458 396 AI can also be used. Examples of suitable cation nitriles are the methosulfates or tosylates of trimethylammonium acetonitrile, N, N-dimethyl-N-octylammonium acetonitrile, 2- (trimethylammonium) propionitrile, 2- (trimethylammonium) -2-methyl-propionitrile, N-methylpipera - Zinium-N, N'-diacetonitrile and N-methylmorpholinium acetonitrile.

The bleach activators which can be used according to the invention are preferably in a solid state at room temperature, since intensive contact of the bleach catalyst with the bleach activator before use can be disadvantageous for achieving the optimum bleaching effect. Additional crystalline bleach activators particularly suitable according to the invention are tetraacetylethylene diamine (TAED), NOBS, isoNOBS, carbonyl biscaprolactam, benzoyl caprolactam, bis (2-propylimino) carbonate, bis (cyclohexylimino) carbonate, O-benzoylacetone oxime and 2-phenyl- (4H) -3, l benzoxazin-4-one, anthranil, phenylanthranil, N-octanoylcaprolactam (OCL) and N-methylpiperazin-N, N'-diacetonitrile as well as liquid or poorly crystallizing bleach activators in a form made up as a solid product. BLEACHING STABILIZERS

According to one embodiment of the present invention, the compositions which can be used, for example, in detergents and cleaning agents additionally contain one or more bleach stabilizers. These are additives that can adsorb, bind or complex heavy metal traces. Examples of additives with bleach-stabilizing action that can be used according to the invention are polyanionic compounds such as polyphosphates, polycarboxylates, polyhydroxypolycarboxylates, soluble silicates as fully or partially neutralized alkali or alkaline earth metal salts, in particular as neutral Na or Mg salts, which are relatively weak bleach stabilizers. Strong bleach stabilizers which can be used according to the invention are, for example, complexing agents, such as ethylenediaminetetraacetate (EDTA), nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA), β-alaninediacetic acid (ADA), ethylenediamine-N, N'-diesuccinate (EDDS) and phosphonates, such as ethylenediamine diaminephosphate, such as ethylenediamine diamine - Lentriamine pentamethylene phosphonate or hydroxyethylidene-1, 1-diphosphonic acid in the form of the acids or as partially or completely neutralized alkali metal salts. The complexing agents are preferably used in the form of their Na salts.

The detergents according to the invention preferably contain at least one bleach stabilizer, particularly preferably at least one of the abovementioned. strong bleach stabilizers.

In the field of textile washing, bleaching and cleaning in the household and in the commercial sector, the compositions described can contain almost all of the usual constituents of washing, bleaching and cleaning agents according to one embodiment of the invention. You can build up textile detergents in this way, for example especially suitable for textile treatment at low temperatures, and also those that are suitable in several temperature ranges up to the traditional area of hot laundry.

The main constituent of textile washing, bleaching and cleaning agents, in addition to the bleaching agent composition, consisting of bleaching agent, bleach activator according to the invention and optionally bleaching catalysts and bleach stabilizers, are builders, i.e. inorganic builders and / or organic cobuilders, and surfactants, especially anionic and / or nonionic surfactants. In addition, other customary auxiliaries and accompanying substances such as bulking agents, complexing agents, phosphonates, dyes, corrosion inhibitors, graying inhibitors and / or soil release polymers, color transfer inhibitors, bleaching catalysts, peroxide stabilizers, electrolytes, optical brighteners, enzymes, perfume oils, foam regulators and activating sub-regulators punch in these funds if this is appropriate.

INORGANIC BUILDER (SCAFFOLDING SUBSTANCES)

All conventional inorganic builders such as aluminosilicates, silicates, carbonates and phosphates are suitable as inorganic builder substances.

Suitable inorganic builders are, for example, aluminosilicates with ion-exchanging 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 partly replaced by other cations such as Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for example, in EP-A038 591, EP-A 021 491, EP-A 087 035, US-A 4 604 224, GB-A2 013 259, EP-A 522 726, EP-A 384 070 and WO- A 94/24 251. Other suitable inorganic builders are, for example, amorphous or crystalline silicates such as, for example, amorphous disilicates, crystalline disilicates such as the layered silicate SKS-6 (manufacturer Hoechst). The silicates can be used in the form of their alkali, alkaline earth or ammonium salts. Na, Li and Mg silicates are preferably used.

Anionic surfactants

Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having from 8 to 22, preferably 10 to 18 carbon atoms, for example C ₉ - to C _{ι r} alcohol sulfates, C ₁₂ - stylsulfat to _C13 alcohol sulphates, cetyl sulfate, myristic, palmityl, stearyl and Talgfettalkoholsulfat.

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, mol of ethylene oxide being used per mol 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 alkanesulfonates such as C _{8 to} C ₂₄ , preferably C ₁₀ to C ₁₈ alkanesulfonates 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). However, the compositions are preferably low in LAS or LAS-free.

Further suitable anionic surfactants are N-acyl sarcosinates with aliphatic saturated or unsaturated C ₈ to C ₂₅ acyl residues, preferably C ₁₀ to C ₂₀ acyl residues, for example N-oleoylsarcosinate.

The anionic surfactants are preferably added to the detergent in the form of salts. Suitable cations in these salts are alkali metal salts such as sodium, potassium and lithium and ammonium salts such as e.g. Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

NON-ionic 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, mol of at least one alkylene oxide are used per mole of alcohol. Ethylene oxide is preferably used as the alkylene oxide. The alcohols preferably have 10 to 18 carbon atoms. Another class of suitable nonionic surfactants are alkylphenol ethoxylates with C ₆ -C ₁₄ -alkyl chains and 5 to 30 mol 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.

Another class of nonionic surfactants are N-alkyl glucamides of the general structure II or III

R ⁷

R> 6 ° - rC-- TNU-. _ DR8 ^ö (mII) p R6 ° -NCR ^ö (III)

II II

OR ⁷ O

where R ^{6 is} C ₆ to C ₂₂ alkyl, R ⁷ H or C _r to C ₄ alkyl and R ^{8 is} a polyhydroxyalkyl radical having 5 to 12 C atoms and at least 3 hydroxyl groups. R ⁶ is preferably C ₁₀ to C ₁₈ alkyl, R ^{7 is} methyl and R ^{8 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

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 alkenyl succinic acids with C ₂ to C ₁₆ alkyl or alkenyl residues;

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

Aminopolycarboxylates such as e.g. Nitrilotriacetic acid, methylglycinediacetic acid, alaninediacetic acid, ethylenediaminetetraacetic acid and serinediacetic acid;

Salts of phosphonic acids such as e.g. Hydroxyethane diphosphonic acid, ethylenediaminetetra (methylenephosphonate) and diethylenetriaminepenta (methylenephosphonate).

Examples of suitable oligomeric or polymeric polycarboxylates as organic cobuilders are:

Oligomaleic acids as described, for example, in EP-A-451 508 and EP-A-396 303;

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. Acrylic acid and methacrylic acid from group (i) are preferably used.

Group (ii) includes monoethylenically unsaturated C ₂ -C ₂₂ olefins, vinyl alkyl ethers Styrene, vinyl ester of C _r 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 with C _r C ₄ alkyl groups, vinyl acetate and vinyl propionate.

Group (iii) includes (meth) acrylic esters of C _{r to} C ₈ alcohols, (meth) acrylonitrile, (meth) acrylamides of C _r C ₈ amines, N-vinylformamide and vinylimidazole.

If the polymers of group (ii) contain vinyl esters in copolymerized form, these can also be partially or completely hydrolyzed to vinyl alcohol structural units. Suitable copolymers and terpolymers are known, for example, from US Pat. No. 3,887,806 and DE-A43 13 909.

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 _r C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 5 (acrylic acid + vinyl ester), the weight ratio of acrylic acid increasing Vinyl esters can vary in the range from 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 -I- 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 5,227,446, DE-A-44 15 623, DE-A-43 13 909 are also suitable as organic cobuilders.

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 of acrylic acid and maleic acid which are grafted on in amounts of 40 to 95% by weight, based on the component to be grafted become. For modification, up to 30% by weight, based on the component to be grafted, of additional monoethylenically unsaturated monomers can be present in copolymerized form. Suitable modifying monomers are the above-mentioned monomers of groups (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 molar masses of up to M _w = 5,000 such as polyethylene glycols are suitable as the 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 _r C ₂₂ alcohols, cf. US-A 4,746,456.

From this group, grafted degraded or degraded reduced starches and grafted polyethylene oxides are preferably used, 20 to 80% by weight of monomers, based on the graft component, being used in the graft polymerization. A mixture of maleic acid and acrylic acid in a weight ratio of 90:10 to 10:90 is preferably used for the grafting.

Polyglyoxylic acids as organic cobuilders are described, for example, in EP-B-001 004, US-A 5,399,286, DE-A-41 06 355 and EP-A-656 914. The end groups of the polyglyoxylic acids can have different structures.

Polyamidocarboxylic acids and modified polyamidocarboxylic acids as organic cobuilders are known, for example, from EP-A-454 126, EP-B-511 037, WO-A 94/01486 and EP-A-581 452. Polyaspartic acid or cocondensates of aspartic acid with further amino acids, C ₄ -C ₂₅ -mono- or -dicarboxylic acids and / or C ₄ -C ₅ -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 condensates containing carboxyl groups usually have molecular weights of up to 10,000, preferably up to 5,000.

GRAYING INHIBITORS AND SOIL RELEASE POLYMERS

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 end capped on one side with di- and / or polyhydric alcohols and dicarboxylic acid.

Such polyesters are known, for example from US-A 3,557,039, GB-A 1 154 730, EP-A-185 427, EP-A-241 984, EP-A-241 985, EP-A-272 033 and US-A 5, 142.020. Other suitable soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides (cf. US Pat. No. 4,746,456, US Pat. No. 4,846,995, DE-A-37 11 299, US Pat. No. 4,904,408, US Pat. A 4,846,994 and US-A 4,849, 126) or modified celluloses such as methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.

Color transfer inhibitors

Color transfer inhibitors used are, for example, homopolymers and copolymers of vinylpyrrolidone, vinylimidazole, vinyloxazolidone and 4-vinylpyridine-N-oxide with molecular weights from 15,000 to 100,000 and crosslinked, finely divided polymers based on these monomers. The use of such polymers mentioned here is known, cf. DE-B-22 32 353, DE-A-28 14 287, DE-A-28 14 329 and DE-A-43 16 023.

Enzymes

According to one embodiment of the invention, the bleaching agent compositions containing at least one bleach activator are used in enzyme-containing washing and cleaning agents. Suitable enzymes are, for example, proteases, amylases, lipases and cellulases, in particular proteases. Several enzymes can be used in combination.

In addition to the use in detergents and cleaning agents for textile washing in the household, the bleaching agent compositions which can be used according to the invention can also be used in the field of commercial textile washing and cleaning. As a rule, peracetic acid is used as a bleaching agent in this area of application, which is added to the wash liquor as an aqueous solution. In this area of application, the activator used according to the invention can either be separated as a single component added in the washing or cleaning process or mixed together with other feedstocks in advance and then added together.

Bleaching additives according to the invention for textile washing contain 1 to 30% by weight, based on the total amount of the bleaching additive, of at least one activator according to the invention.

Dishwashing detergents according to the invention preferably contain 0.05 to 15% by weight, based on the total amount of dishwashing detergents, of at least one activator according to the invention.

Disinfectants according to the invention preferably contain 1 to 40% by weight, based on the total amount of disinfectant, of at least one activator according to the invention.

Detergents and bleaches according to the invention for textile washing preferably contain 0.1 to 20% by weight, based on the total amount of the detergent and bleach, of at least one activator according to the invention.

According to one embodiment, the at least one activator-containing textile detergent according to the invention with a bleaching system based on peroxy compounds and percarboxylic acids comprises 0.5 to 40% by weight, preferably 2.5 to 30% by weight, particularly preferably 5 to 25% by weight Peroxy compounds or peracids, 0 to 20% by weight, preferably 0.1 to 20% by weight, preferably 0.5 to 10% by weight, particularly preferably 0.5 to 6.0% by weight according to the invention Bleach activators and 0 to 5% by weight, preferably 0.05 to 2% by weight, particularly preferably 0.1 to 1% by weight, of at least one bleaching catalyst. When the activators according to the invention are used, the performance of bleaching agent compositions, in particular in the case of cold bleaching agent compositions and in particular in the case of hydrophobic soiling, can be considerably improved. Weaknesses of commercially available bleach activators can be specifically compensated for by using activators according to the invention, so that high-performance bleaching is possible at low temperatures.

The bleach activators to be used according to the invention are preferably used in powdered or granular detergents. It can be classic heavy-duty detergents or concentrated or compacted detergents.

A typical powder or granular heavy-duty detergent according to the invention can have the following composition, for example:

0.5 to 50% by weight, preferably 5 to 30% by weight, of at least one anionic and / or nonionic surfactant,

0.5 to 60% by weight, preferably 15 to 40% by weight, of at least one inorganic builder,

0 to 20% by weight, preferably 0.5 to 8% by weight, of at least one organic cobuilder,

2 to 35% by weight, preferably 5 to 30% by weight, of an inorganic bleaching agent, such as perborate or percarbonate 0.1 to 20% by weight, 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% by weight, 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, protease,

0 to 1.5% by weight, preferably 0.1 to 1.0% by weight, 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 that are preferably used in detergents are sodium carbonate, sodium hydrogen carbonate, zeolite A and P, and amorphous and crystalline sodium silicates.

Organic cobuilders preferably used in detergents are acrylic acid / maleic acid copolymers, acrylic acid / maleic acid / vinyl ester terpolymers 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 alkylbenzenesulfonates (LAS) and soaps, the proportion of LAS preferably being below 8% by weight, particularly preferably below 4% by weight.

According to one embodiment of the invention, the textile detergent according to the invention is essentially free of linear alkylbenzenesulfonates and preferably based on fatty alcohol sulfonates.

According to one embodiment of the invention, the textile detergent composition is essentially phosphate-free.

According to one embodiment of the invention, the textile detergent composition according to the invention contains at least one polycarboxylate, preferably in an amount of 0.1 to 7.5% by weight.

Nonionic surfactants preferably used in detergents are C _n - 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 with 1-4 propylene oxide or butylene oxide units alkoxylated ethoxylated fatty or oxo alcohols.

Enzymes which are preferably used in detergents are protease, lipase and cellulase. Of the commercially available enzymes, amounts of 0.05 to 2.0% by weight, preferably 0.2 to 1.5% by weight, of the made-up enzyme are generally added to the detergent. Suitable proteases are, for example, Savinase, Desazym and Esperase (manufacturer Novo Nordisk). A suitable lipase is, for example, Lipolase (manufacturer Novo Nordisk). A suitable cellulase is eg Celluzym (manufacturer Novo Nordisk). Graying inhibitors and soil release polymers preferably used in detergents are graft polymers of vinyl acetate on polyethylene oxide of molecular weight 2,500-8,000 in a weight ratio of 1.2: 1 to 3.0: 1, polyethylene terephthalates / oxyethylene terephthalates of molecular weight 3,000 to 25,000 made of polyethylene oxides of molecular weight 750 to 5,000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and block polycondensates according to DE-A-44 03 866.

Color transfer inhibitors preferably used in detergents are soluble vinylpyrrolidone and vinylimidazole copolymers with molar masses above 25,000 and finely divided crosslinked polymers based on vinylimidazole.

The powdered or granular detergents according to the invention can contain up to 60% by weight of inorganic fillers. Sodium sulfate is usually used for this. However, the detergents according to the invention are preferably low in adjusting agents and contain only up to 20% by weight, 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 1,200, in particular 500 to 950 g / l. Modern compact detergents generally have high bulk densities and show a granular structure.

In addition to combined detergents and bleaches, the form of the bleach activators described for textile washing can also be agents which are used as additives to peroxide-containing or peroxide-free detergents. They essentially contain the activator or a bleaching agent composition containing bleach, bleach activator according to the invention, and optionally further auxiliaries and Additives, in particular stabilizers, pH regulators, thickeners and surfactants.

The present invention furthermore also relates to bleach additives for textile washing, which contain 1 to 30% by weight, preferably 5 to

25% by weight, based on the total amount of bleach additives, contain one or more activators according to the invention.

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 at least one bleach activator according to the invention,

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.

The present invention also relates to dishwashing detergents which contain 0.05 to 15% by weight, preferably 0.1 to 10% by weight, in particular 0.5 to 5% by weight, in each case based on the total amount of dishwashing detergent or contain several bleach activators in addition to the usual ingredients.

Agents intended for cleaning hard surfaces generally contain, in addition to per compound and activator, in particular surfactants, builders and, Case of polishing and abrasive agents, abrasive components. Since these agents are often used at room temperature, the use of the activators according to the invention has a particularly advantageous effect on the bleaching and germicidal action.

Ready-made agents are of particular importance for use in disinfection, since there are generally increased demands on application safety. Disinfectants based on the activators described generally contain, in addition to these and inorganic per-compounds, further auxiliaries and additives, such as pH-regulating substances, stabilizers and surfactants. In special cases, they can additionally contain special microbicides which increase the very broad killing effect of the activated per-compound against certain germs.

The present invention also relates to disinfectants which contain 1 to 40% by weight, preferably 5 to 30% by weight, based on the total amount of the disinfectant, of one or more activators according to the invention.

Typical disinfectants of this type have the following composition:

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

1 to 40% by weight, preferably 5 to 30% by weight, of at least one activator according to the invention,

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 not limited to the use in a ready-made form, as described for example above. In the commercial sector, for example, the reagents are usually dosed individually, since this is often the cheaper method.

With the bleach activators according to the invention, a marked improvement in the bleaching, oxidation and cleaning action in the lower temperature range can be achieved in the technical applications described.

The invention also relates to a method for washing or cleaning or disinfecting objects or textiles with an aqueous, preferably 0.2 to 10% by weight, liquor of a detergent and bleach, dishwashing detergent or disinfectant as described above.

MANUFACTURING EXAMPLES

General manufacturing instructions for hydroximide carbonates (reaction of hydroximides with alkyl chloroformates):

0.2 mol of hydroximide are placed in about 150 ml of toluene at 10 to 15 ° C., 0.2 mol of dimethylcyclohexylamine in about 50 ml of toluene and 0.2 mol of alkyl chloroformate in 50 ml of toluene are added dropwise over half an hour with cooling and about 0 , Stirred for 5 to 4 hours at room temperature. One works on in which either the fancy Hydrochloride is suctioned off or removed by extraction with water. The toluene phase obtained is optionally dried with sodium sulfate and concentrated. The desired hydroximide carbonate is obtained in a yield of more than 90%.

General preparation instructions for hydroximide esters (reaction of hydroximides with acid chlorides):

0.2 mole of hydroximide and 0.2 mole of dimethylcyclohexylamine are placed in about 150 ml of toluene at room temperature, 0.2 mole of the desired acid chloride in 50 ml of toluene are added dropwise within half an hour, if necessary with cooling, and about 0.5 to 4 hours if necessary slightly elevated temperature (up to about 70 ° C) stirred. The progress of the reaction is checked by means of DC. The reaction is carried out by either suctioning off the precipitated hydrochloride or removing it by extraction with water. The toluene phase obtained is optionally dried with sodium sulfate and concentrated. The hydroximide ester is obtained in a yield of more than 90%. In particular, phosgene is used as the acid chloride for producing the carbonic acid esters.

The following bleach activators were obtained according to the above manufacturing instructions:

Example 1 N- (2-propylheptyloxicarbonyl) oxiphthalimide Example 2 N- (phenyloxicarbonyl) oxicyclohex-4-en- 1, 2-dicarboximide Example 3 O- (methyloxicarbonyl) acetone oxime Example 4 O- (benzyloxicarbonyl) acetone oxime Example 5 O- (n-butyloxycarbonyl) acetone oxime The bleach activators according to the invention can be formulated in the exemplary detergent compositions of heavy-duty detergents listed below.

Table 1: Detergent compositions of heavy duty detergents

Soil release polymer 1 = graft polymer of vinyl acetate on polyethylene glycol with a molecular weight of 6,000,

Molar mass of the graft polymer 24,000 (Sokalan ^® HP22 from BASF AG)

Soil release polymer 2 = polyethylene terephthalate / polyoxyethylene terephthalate with a molecular weight of 8,000 Dequest 2046 * = ethylenediamine-N, N, N ', N' -tetra (methylene lenphosphonate) SKS-6 »= commercially available layered silicate, manufacturer: Hoechst AG

The detergent composition III described above was used in the tests below. To check the effect of the bleach activators according to the invention, test soiling of tea on cotton, red wine on cotton, carotene micronisate in vegetable oil on cotton and chlorophyll / vegetable oil on cotton was produced and washing tests were carried out with detergent composition III. The washing operations were carried out in a Launder-O-meter, type Atlas Standard under the following conditions:

Table 2: Washing conditions

The bleaching effect of the detergent composition was determined by measuring the color strength of the test fabrics. This measurement was carried out photometrically. The reflectance values measured at the individual test tissues at 16 wavelengths in the range from 400 to 700 μm at a distance of 20 nm were converted according to the method described in A. Kud, Seifen, Öle, Fette, Wachsen H9, pp. 590 - 594 (1993) the respective color strengths of the test soils before and after washing are determined and from this the absolute bleaching effect A _{abs is} calculated in%. The absolute bleaching action A _abs is defined as follows:

Strong color (before washing) - Strong color (after washing) abs Strong color (before washing) - Strong color (white fabric) 100%

The amount of activator used in the examples below was 5.0% by weight. Comparative tests were also carried out without using a bleach activator and using TAED as a bleach activator.

The test results are summarized in Table 3 below:

Table 3: Results of washing tests with test soiling. Numerical values are absolute bleaching action A _abs in%

Bleach activator carotene tea red chlorophyll

22 ° C 38 ° 22 ° C 38 ° white 22 ° C 38 °

C C n C

22 ° C 38 °

C

^* TAED 49.9 50.8 47.5 71.5 68.3 81, 9 5.9 12, without assets 48.7 53.1 22.9 46.6 57.8 68.4 2 goal 6 4.5 1.1

Example No. 1 58.5 65.6 62.7 74.8 65.1 74.0 29.2 35,

Example No. 2 52.1 56.0 45.5 72.9 67.1 77.9 8

Example No. 3 54.7 79.0 70.0 83.5 9.9 18,

Example No. 4 70.2 79.3 69.0 81.8 2

Example No. 5 66.3 79.4 66.6 82.7 10.6 19.1

22.8 25.3

17.8 23.6

= Comparison tests The washing tests with the bleach activators according to the invention show that the bleach activators show a pronounced increase in the bleaching action, which is improved in comparison with the comparison bleach activator for some soils, in particular tea and chlorophyll.

Claims

claims

1. Use of carbonates of the general formula (I)

AO-CO-OR ³ (I)

in the

A a rest (Ia)

R ^! R ² C = N- (Ia)

or A a residue (Ib)

wherein R ^1, R ^2, R ^3, R ⁴ and R ^{5 are} independently linear or branched C ^ _Q alkyl, C _2.30 alkenyl, C. ₅ ₁₈ -cycloalkyl, C ₇ . ₁₈ aralkyl or

C ₆ . ₁₈ denotes aryl or heteroaryl, aliphatic radicals additionally comprising 1 to 5 hydroxyl groups, C 1-4 alkoxy groups, amino groups, C 1-4 alkylamino groups, di-C ₁ . ₄ -alkylamino groups, chlorine atoms, bromine atoms, nitro groups, cyano groups, carboxyl groups, sulfo groups, carboxy-C _ι.4 -alkyl groups, carboxamide groups or phenyl, to- Lyl or benzyl radicals can be functionalized, where aromatic, cycloaliphatic and heteroaromatic structural units can also be substituted by the radicals mentioned, or can be interrupted by 1 to 8 non-adjacent oxygen atoms, amino groups, C _j.4 -alkylamino groups or carbonyl groups, and

R ¹ and R ^{2 can} furthermore signify hydrogen or together form a 1, 3-, 1, 4-, 1, 5-, 1, 6-, 1, 7- or 1, 8-alkylene group with 3 to 33 C atoms , which additionally by 1 to 5 hydroxyl groups, C _l - alkylamino groups, di-C ^ -alkylamino groups, chlorine atoms, bromine atoms,

Nitro groups, cyano groups, carboxyl groups, sulfo groups, carboxy-C _j ^ -alkyl groups, carboxamide groups or phenyl, tolyl or benzyl radicals can be functionalized, wherein aromatic radicals in turn can also be substituted by the radicals mentioned, or by 1 or 2 non-adjacent oxygen atoms , Amino groups, C 1-4 alkylamino groups or carbonyl groups can be interrupted,

where, when A is a radical (Ia), R ^{3 is} not a vinyl radical which can be substituted by a carboxylic acid group, sulfonic acid group, phosphonic acid group or their alkali metal or ammonium salt, and none

Vinyloxy radical -O-CR ^{1 =} = CHR ² , in which R ¹ and R ^{2 have} the above meaning,

and R ^{3 can be} a radical (Ib) if A is a radical (Ib),

and R ⁴ and R ⁵ further together can form a 1,2-, 1,3-, 1,4-, 1,5-, 1,6-alkylene group with 2 to 30 C atoms, which are like the above Alkylene groups can be substituted, or R ⁴ and R ⁵ together form a carbon 5-, -6-, -7-, -8-, or -9-ring, which is bonded to the carbonyl groups via 2 adjacent C atoms, one or more double bonds in the Ring can be present or the ring can be aromatically unsaturated, where one or more carbon atoms in the ring can be replaced by heteroatoms, and

2 carbon atoms in the ring can be connected via a hetero atom or a C 1-4 alkyl learning group or C _2-3 alkenylene group, or

R ⁴ and R ⁵ can form the above carbon ring from 2 carbonate molecules, which is bonded to the carbonyl groups of the two imide structures via 2 adjacent C atoms,

or hydroximide esters of the general formula (II)

wherein R ^{3 has} the meaning given above and R ⁶ and R ⁷ together form a carbon 5-, -6-, -7-, -8- or -9-ring which is bonded to the carbonyl groups via 2 adjacent C atoms , where one or more double bonds can be present in the ring, one or more ring positions can be replaced by heteroatoms and 2

C atoms in the ring can be connected via a hetero atom and a C 1-4 alkylene radical or C ₂ , ₃ -alkenylene radical,

or R ⁶ and R ^{7 can form} from two hydroximide ester molecules together the above carbon ring, the one adjacent to each other C atoms are bonded to the carbonyl groups of the two imide structures,

or polymers which can contain C _2.8 olefin comonomer building blocks and contain basic building blocks of the general formulas (III), (IV) and / or (V)

where R ^{8 is} a radical R ³ or -OR ³ with the meaning given above,

as activators for inorganic per compounds.

Use according to claim 1, wherein R ¹ and R ^{2 are} independently C _i alkyl radicals, R ^{3 is} a C ^ _Q alkyl radical, phenyl radical or benzyl radical and R ⁴ and R ⁵ together are a 1,2-vinylene radical or 4,5-cyclohexene - form ylenrest.

3. Use according to claim 1 or 2 in detergents, cleaning agents, bleaching agents and disinfectants.

4. washing and bleaching agent for textile washing, containing 0.1 to 20% by weight of at least one compound as defined in claim 1 or 2.

5. Detergent containing

0.1 to 20% by weight of at least one compound as defined in claim 1 or 2, 5 to 30% by weight of at least one anionic and / or nonionic

Surfactants,

5 to 50% by weight of at least one inorganic builder,

5 to 30% by weight of at least one inorganic bleaching agent, 0.2 to 2.0% by weight of enzymes,

the total amount of detergent ingredients being 100% by weight.

6. Bleaching agent for textile washing, containing 1 to 30 wt .-%, based on the total amount of the bleaching agent, at least one compound as defined in claim 1 or 2.

7. Dishwashing detergent containing 0.05 to 5 wt .-%, based on the total amount of dishwashing detergent, at least one compound as defined in claim 1 or 2.

8. disinfectant containing 1 to 40 wt .-%, based on the total amount of disinfectant, of at least one compound as defined in claim 1 or 2.

9. A method for washing or cleaning or disinfecting objects or textiles, wherein the objects or textiles with an aqueous, preferably 0.2 to 10 wt .-% liquor of a detergent and bleach, dishwashing detergent or disinfectant according to any one of claims 4 , 5, 7 or 8 treated.

10. Carbonates of the general formula (I)

AO-CO-OR ³ (I) in the

A a rest (Ia)

R ¹ R ² C = N- (Ia)

or A a residue (Ib)

is, wherein R ¹ , R ² , R ³ , R ⁴ and R ^{5 are} independently straight-chain or branched Cι_ ₃₀ alkyl, C2. ₃₀ alkenyl, C ₅ . ₁₈ -cycloalkyl, C ₇ . ₁₈ aralkyl or

Cg. _{j is} g-aryl or heteroaryl, where aliphatic radicals are additionally represented by 1 to 5 hydroxyl groups, C 1-4 -alkoxy groups, amino groups, C -alkylamino groups, di-C -alkylamino groups, chlorine atoms, bromine atoms, nitro groups, cyano groups, carboxyl groups, sulfo groups, Carboxy-C 1-4 alkyl groups, carboxamide groups or phenyl, tolyl or benzyl radicals can be functionalized, where aromatic, cycloaliphatic and heteroaromatic structural units can also be substituted by the radicals mentioned, or by 1 to 8 non-adjacent oxygen atoms, amino groups, C _t ^ alkylamino groups or carbonyl groups can be interrupted, and

R ¹ and R ^{2 may} also be hydrogen or together a

1,3-, 1,4-, 1,5-, 1,6-, 1,7- or 1,8-alkylene group with 3 to 33 C-

Form atoms which are additionally formed by 1 to 5 hydroxyl groups, C _μ -alkylamino groups, di-C -alkylamino groups, chlorine atoms, bromine atoms, Nitro groups, cyano groups, carboxyl groups, sulfo groups, carboxy-Ci ^ -alkyl groups, carboxamide groups or phenyl, tolyl or benzyl radicals can be functionalized, wherein aromatic radicals in turn can also be substituted by the radicals mentioned, or by 1 or 2 not adjacent Oxygen atoms, amino groups, C _r ^ -alkylamino groups or carbonyl groups can be interrupted,

Vinyloxy radical -O-CR ^ CHR ² , in which R ¹ and R ^{2 have} the above meaning,

and R ^{3 can be} a radical (Ib) if A is a radical (Ib),

and R ⁴ and R ⁵ further together can form a 1,2-, 1,3-, 1,4-, 1,5-, 1,6-alkylene group with 2 to 30 C atoms, which are like the above Alkylene groups can be substituted, or

R ⁴ and R ⁵ together form a carbon F-5-, -6-, -7-, -8-, or -9-ring which is bonded to the carbonyl groups via 2 adjacent C atoms, one or more double bonds in the Ring can be present or the ring can be aromatically unsaturated, where one or more carbon atoms in the ring can be replaced by hetero atoms, and 2 carbon atoms in the ring are connected via a hetero atom or a C 1-4 alkylene radical or C ₂ _3-alkenylene radical can, or

R ⁴ and R ⁵ can form the above carbon ring from 2 carbonate molecules, which is bonded to the carbonyl groups of the two imide structures via 2 adjacent C atoms, or hydroximide esters of the general formula (II)

where R ^{3 has} the meaning given above and R ⁶ and R ⁷ together form a carbon 5-, -6-, -7-, -8- or -9-ring which is bonded to the carbonyl groups via 2 adjacent C atoms , where one or more double bonds can be present in the ring, one or more ring positions can be replaced by heteroatoms and 2 C atoms in the ring can be connected via a heteroatom and a C 1-4 alkylene radical or C ₂ _ ₃ -alkenylene radical,

or R ⁶ and R ⁷ can form together from 2 hydroximide ester molecules the above carbon ring, which is bonded to the carbonyl groups of the two imide structures via 2 adjacent C atoms,

or polymers which can contain C 1-6 olefin comonomer building blocks and basic building blocks of the general formulas (HI), (IV) and / or (V)

where R ^{8 is} a radical R ³ or -OR ³ with the meaning given above.