WO1997041197A1

WO1997041197A1 - Detergent components protected against exothermic decomposition by oxidation

Info

Publication number: WO1997041197A1
Application number: PCT/EP1997/002118
Authority: WO
Inventors: Jürgen HUFF; Gunnar Schornick; Hans-Ulrich JÄGER; Jürgen Alfred LUX; Ulrich Bröckel; Ulrich LÖFFLER
Original assignee: Basf Aktiengesellschaft
Priority date: 1996-04-25
Filing date: 1997-04-24
Publication date: 1997-11-06
Also published as: DE19616570A1; EP0902830A1

Abstract

Detergent components contain: (a) at least one dirt-removing amphiphilic polyester; (b) at least one antioxidant agent selected among the phenols, bisphenols and thiobisphenols substituted with sterically hindered groups, aromatic amines, preferably secondary aromatic amines and substituted p-phenylene diamines, phosphine, phosphite and phosphonite compounds, esters of 3,3'-thiodipropionic acid, reductones and metal ion disactivators; and (c) a carrier.

Description

Detergent components protected from exothermic decomposition by oxidation

description

The present invention relates to detergent components protected from exothermic decomposition by oxidation.

Oxidation reactions of oxidizable organic materials with large surfaces pose a problem both with regard to the loss of effectiveness of the ingredients and with regard to safety problems in the production and storage in the presence of oxygen. In certain cases, it can occur especially at elevated temperatures and persistent access to oxygen uncontrollable exothermic decomposition occur. Such conditions occur in particular when the organic materials are used in combination with supports which have large surfaces. Mixtures of organic materials with inorganic supports are often e.g. used for packaging detergents.

The use of antioxidants to prevent or delay various oxidation processes, such as Autooxidation is known for a large number of organic substrates, see for example Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, 5th ed., vol. 3, pp. 91-111.

NL-A-7411994 describes the use of 2,6-di-tert. -butyl-4-methylphenol as an antioxidant in detergents containing enzymes to increase storage stability. NL-A-6708730 describes the use of 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene for stabilizing soaps against oxidative decomposition.

US Pat. No. 3,369,304 describes the stabilization, by antioxidants, of water-soluble alkyl (polyoxyalkylene) ethers and detergent formulations which contain these polyethers and which are used as washing substances, before the oxidative decomposition as a result of heat and the presence of oxygen. Such stabilization is necessary in order to be able to subject the polyethers or the detergent formulations to spray drying, in which conditions of this type generally occur. Sterically hindered substituted phenols, bisphenols, thiobisphenols, aromatic amines and substituted quinolines are used as antioxidants. The US-A-3, 436, 351 describes detergent based on alkyl benzene sulphonates, which antioxidants are added to improve the ^'heat as well as color and odor stability. Substituted aromatic amines, substituted phenols and bisphenols in combination with water-soluble inorganic salts are used as anti-oxidants. The method is used both for stabilization against elevated temperatures during production and during storage.

Modern detergents, especially those for fabrics made of synthetic fibers, such as Polyesters generally contain water-soluble polymers with a graying-inhibiting and / or soil-release-promoting effect. These include e.g. the polyoxyalkylene ethers disclosed in US Pat. Nos. 3,369,304, and the graft copolymers of polyalkylene oxides and vinyl acetate described in EP-A-0 219 048 with a graying-inhibiting effect.

Copolyesters made from dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units are known, particularly effective dirt-removing agents. DE 4 408 360 e.g. describes a process for the preparation of dirt-dissolving, free-flowing and free-flowing granules which contain polymers with ethylene terephthalate and polyoxyethylene terephthalate groups. WO-A-95/21880 describes processes for the production of amphiphilic polyesters with blocks which are produced using aromatic dicarboxylic acids and blocks which are produced using aliphatic carboxylic acids and their use as additives for detergents, other detergent additives and Laundry after-treatment agents. The advantage over the polyesters of purely aromatic carboxylic acids disclosed in DE 4 408 360 lies in their better biodegradability.

Due to the carriers with large surfaces, such as e.g., used in the assembly of detergents and detergent additives containing the aforementioned polyester, crystalline alkali alumosilicates (zeolites), the problem of decomposition and, in particular, the uncontrolled exothermic decomposition by oxidation occurs increasingly as a result of the large surfaces and / or catalytic effect of the support materials.

The present invention is based on the object of providing detergent additives which comprise amphiphilic polyesters and carrier materials with large internal surfaces and which prevent exothermic decomposition by oxidation, even at elevated temperatures. temperatures are protected in the presence of oxygen or with prolonged storage.

Surprisingly, it has now been found that this object is achieved if the specified components are used in combination with a suitable antioxidant.

The invention therefore relates to a detergent component comprising: a) at least one dirt-removing amphiphilic polyester; b) at least one antioxidant which is selected from phenols, bisphenols and thiobisphenols which are substituted with sterically hindering groups, aromatic amines, preferably secondary aromatic amines, and substituted p-phenylenediamines,

Phosphine, phosphite and phosphonite compounds, esters of 3, 3 'thiodipropionic acid, reductones and

Metal ion deactivators and c) a carrier.

Suitable amphiphilic polyesters are known to the person skilled in the art. They preferably have a molecular weight M _w of 1500 to 60,000 and contain, as hydrophilic units, polyethylene glycol, block copolymers of ethylene oxide and propylene oxide and / or butylene oxide with molecular weights M _n of 500 to 8000 and / or mono- or polybasic containing sulfo groups Carboxylic acids and blocks of aromatic polybasic carboxylic acids condensed as hydrophobic units, optionally in combination with aliphatic polybasic carboxylic acids and C ₂ -C ₄ -alkylene glycols and / or trihydric or polyhydric alcohols.

Such polyesters are e.g. in US-A-3,557,039, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 and US-A-5 142 020 .

A preferred class of partially crystalline, amphiphilic polymers are polyesters, the units of

(1) ethylene terephthalate and

(2) Polyoxyethylene terephthalate of polyethylene glycols with molar masses M _n from 1000 to 7500

in the weight ratio (1): (2) from 1: 1 to 1:25. Another preferred class of amphiphilic polymers are the polyesters described in US Pat. No. 5,142,020, which are obtainable "by condensation of

(1) carboxylic acids with at least 2 carboxyl groups, their esters, anhydrides or mixtures,

(2) at least dihydric alcohols and / or addition products of 1 to 5 mol of at least one alkylene oxide having 2 or 3 carbon atoms on 1 mol of an at least dihydric alcohol or mixtures and

(3) water-soluble adducts of 5 to 80 mol of at least one alkylene oxide with 1 mol of Cg to C ₂₄ alcohols, Cg to Cis alkylphenols or C _ß to C ₂₄ alkylamines

in the molar ratio (1): (2): (3) of 100: (25 to 2500): (5 to 110) at temperatures of at least 120 ° C. up to molar masses M _w of 4000 to 50,000.

Particularly preferred are polyesters which contain (a) ester units from polyalkylene glycols with a molecular weight of 500 to 7500 and aliphatic dicarboxylic acids and / or monohydroxymonocarboxylic acids and (b) ester units from aromatic dicarboxylic acids and polyhydric alcohols and molecular weights from 1500 to 60,000 , especially 1500 to 25000. Such polyesters are described in WO-A-95/21880.

Suitable carrier materials are preferably amorphous or crystalline alkali silicates, such as sodium orthosilicate or metasilicate, crystalline alkali alumosilicates (zeolites), such as sodium aluminum silicates, phosphates and polyphosphates, alkali carbonates, such as sodium carbonate, polycarboxylates (polyvinyl carboxylic acids), alkali metal silicates Cellulose derivatives, such as carboxymethyl cellulose, alkyl cellulose or hydroxyalkyl cellulose and alkali metal sulfates, such as Sodium sulfate. They can be used individually or in mixtures of two or more.

Preferred carriers are synthetic, crystalline alkali alumosilicates (Wessalith® types from Degussa, e.g. Wessalith P or SKS® types from Hoechst ;.

Suitable antioxidants are phenols, bisphenols and thiobisphenols substituted by sterically hindering groups; aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines; Phosphorus compounds with trivalent phosphorus, such as phosphines, phosphites and phosphonites; Endiol Group-containing compounds, so-called reductones, such as ascorbic acid and its derivatives; Organosulfur compounds, such as "the esters of 3, 3 'thiodipropionic acid with C 1 -C ₈ alkanols, in particular Cio-Cig alkanols; metal ion deactivators which are capable of metal ions catalyzing the autooxidation, such as copper, for example complex, such as EDTA, nitrilotriacetic acid etc .; and their mixtures.

Certain antioxidants, e.g. those which contain hydroxyl groups can optionally also be bonded chemically to the amphiphilic polyester or the carrier via functional groups which react with one another. For polyesters with free carboxyl end groups, the bond can e.g. by direct reaction of the antioxidant with the polyester with the formation of an ester. After reaction with a di- or polyisocyanate, dicarboxylic acid chloride or bisglycidyl ether, polyesters or carriers with free hydroxyl end groups can be coupled to the hydroxyl groups of the anti-oxidant.

The detergent component according to the invention preferably comprises one or more of the following antioxidants: 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-4 -aminophenol, 4-hydroxymethyl-2, 6-di-tert. - butylphenol, 2-tert. -Butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, 2-tert-butyl-4-methylphenol, 2, 4, 6-tri-tert-butylphenol, 2, 3, 6-tri-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-4-nonylphenol, 2,4-di-tert-butyl-6-nonylphenol, gallic acid, a butylated product of p-cresol and dicyclopentadiene (Wingstay® LT 40, Goodyear), 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (4, 6 -dimethylphenol), 2,2'-methylenebis [4-methyl-6- (1-methylcyclohexyl) phenol], 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 1, 1 -Bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 4,4'-methylenebis- {3-methyl-6-tert-butylphenol), 4,4'-ethylidenebis - (3-methyl-6-tert-butylphenol), 4,4'-methylene-bis- (2-methyl-6-tert-butylphenol), 4,4'-thiobis- (2, 6-di- tert-butylphenol), 4,4'-thiobis- (3-methyl-6-tert-butylphenol), 4,4'-thiobis- (2-methyl-6-tert-butylphenol), 4,4'-methylene-bis- (2,6-di-tert-butylphenol), 4,4'-butylidene-bis- (2,6-di-t ert.-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, 5-trimethyl-2,4, 6-tris - (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N'-bis [(3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl] hexamethylene diamine, N , N'-di-isopropyl-p-phenylenediamine, N, N'-di- (naphthyl-2) -p-phenylene-diamine, 4- (p-toluenesulfonamido) -diphenylamine and (o-tolyl) -biguanide , Triphenylphosphine, diethylphosphite, triphenylphosphite, tris-nonylphenylphosphite, tris- (monononylphenylphosphite), tris- (dinonylphenylphosphite), tridecylphosphite, triisodecylphosphite, octyl- diphenylphosphite, 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid ^' di-n-octadecyl ester, dilauryl, dimyristyl, distearyl esters of 3 , 3 '-Thiodipropionic acid, ascorbic acid, 5, 6-diacetylascorbic acid, 6-palmitoylascorbic acid and hydroquinone monomethyl ether.

One or more of the following anti-oxidants are particularly preferred: gallic acid, a butylated product of p-cresol and dicyclopene

10 tadiene (Wingstay® LT 40, Goodyear), N, N'-bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hexamethylene diamine, ascorbic acid, triphenylphosphine, hydroquinone monomethyl ether and in particular ¬ special 4,4'-thiobis [3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl] butane and / or

15 1,3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene.

The mixing ratio by weight of amphiphilic polyester to carrier is, according to the invention, in the range from 5:95 to 20 95: 5%, preferably 10:90 to 80: 20% and particularly preferably 15:85 to 70: 30%.

The amount of antioxidant, based on the mixture of carrier and polyester, for the mixtures 25 according to the invention is in the range from 0.0001 to 10% by weight, preferably 0.002 to 5% by weight.

The invention also relates to detergents which optionally contain a detergent component according to the invention with white

30 other detergent and cleaning agent ingredients included. These agents can be prepared in a manner known to the person skilled in the art and then contain the detergent constituents in such an amount that the amphiphilic polyester in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, in particular preferably 0.5

35 to 2 wt .-%, based on the total weight of the detergent, is present. Suitable detergent and cleaning agent ingredients are known to the person skilled in the art, see e.g. can Ulimann's Enzyklopä¬ die der technical chemistry, VCH, Weinheim 1983, 4th ed., pp. 63-160. These include, among other things, adjusting devices, such as Sodium-

40 sulfate, soaps, alkalis, e.g. Soda, plasticizers, defoamers, perfume oils, optical brighteners, enzymes, bleach activators and color transfer inhibitors.

The invention also relates to the use of the abovementioned 45 antioxidants of the detergent constituents defined above for protection against exothermic decomposition by oxidation as a result of high lower temperatures during production or storage in the presence of oxygen.

The detergent ingredients are preferably in the form of pourable and free-flowing granules. A method for producing the detergent components according to the invention comprises melting the amphiphilic polyester, preferably under a nitrogen atmosphere, and mixing it with the antioxidant and, if appropriate, further auxiliaries. After cooling, the mixture is then ground with the carrier to produce a free-flowing formulation.

However, the preparation is preferably carried out by applying a molten mixture of the amphiphilic polyester and the antioxidant to the support in a mixer or in the fluidized bed. In mixer granulation, the mixture temperature is at least as high as the softening temperature of the polyester, while in fluidized bed granulation it is at most as high as the softening temperature of the polyester. The grain size of the low-dust granules obtained is preferably 3 mm and less.

The preparation and the use of the detergent components according to the invention are explained with the aid of the following non-limiting examples.

The "soil-release" polyester used was a copolyester with a molecular weight of about 9000 from terephthalic acid, adipic acid, ethylene glycol and polyethylene glycol (molecular weight about 4000), as described in WO-A-95/21880.

a) Preparation of mixtures of polyester and antioxidants

The polyester mentioned above is melted under a nitrogen atmosphere at 120 ° C. and mixed with the amounts of antioxidant given in Table 1, column 4. Mixing with the carrier material takes place according to one of the two following mixing processes, designated 1 and 2.

Mixing method 1:

After the above mixture has cooled, 30 parts by weight of the mixture are intimately milled with 70 parts by weight of a crystalline alkali aluminum silicate (Wessalith® P from Degussa). Mixing method 2:

The compounding is carried out in an intensive mixer from the company ^" Eirich Type R02 in an air atmosphere, the carrier material (Wessalith® P) with 75% by weight being introduced as a fluidized bed. The molten mixture (25% by weight) consisting of the poly ester and antioxidant is injected into the mixer via a nozzle lance, preferably at 130 ° C. and 15 bar, the speed of the plate is 42 min ^-1 , that of the vortex 2500 min ^-1, after 3 to 5 minutes the granulation results free-flowing granules, the grain size of which is below 1.5 mm and which can be described as low-dust.

b) measurement of the effect of the antioxidants

The effectiveness of the added antioxidants was checked by means of DSC (differential scanning calorimetry). DSC diagrams were made in the presence of air (platinum crucible, reference A1 ₂ 0 ₃ , temperature range 0 to 350 ° C, air flow 70 ccm / min, heating rate 5 ° C / min). The effectiveness of the additives was compared by comparing the temperatures at which the first exothermic maxima could be seen in the DSC diagrams. The results are shown in Table 1. The higher the temperatures, the better the effectiveness of the antioxidants.

3 o

Table 1 vβ

vo

OH

vβ

©

It can be seen that the mixtures in which the antioxidants of invention ^{'contemporary} be used possess in comparison to the reference (Examples 1 and 2) a higher DSC maximum. This means that the oxidative decomposition only begins at a significantly higher temperature.

In order to test the effect of the added antioxidants even when storing the detergent components, adiabatic heat build-up measurements were carried out on samples in 100 ml wire baskets at a heating rate of 0.01 to 0.02 K / min. Such adiabatic warm storage tests reproduce the conditions in large containers, as they occur, for example, under the production conditions, particularly well. As a measure of the efficacy of the antioxidative tion medium, the following Table 2 gives the temperature T _onset wie¬ that at which a heat production caused by exothermic oxidation of the sample is measurable for the first time.

3

Table 2: adiabatic heat accumulation measurements O vs

VO -4

² > Topanol® CA from ICI

³⁾ Santonox® R from Monsanto to

Cl

H

VO δ oe

The values from the tests under adiabatic hot storage conditions, which are well suited for representing the conditions in large containers, show that the additives according to the invention are also effective in the storage of large quantities of products.

c) Description of the washing tests

The influence of the antioxidant additive was checked in a series of washing tests.

The dirt-removing properties of the polymers were combined in one

Wash test determined.

For this purpose, the test fabrics were prewashed three times (washing conditions see table 3).

The test fabrics were soiled with used engine oil. This was left to act for 20 h and the reflectance of these tissues was determined using a photometer from Data Color (Rl). It was then washed again and the remission was measured (R2). The dirt detachment S in% was calculated using the formula S = (R3-R2) / (R1-R2) x 100.

Table 3: Washing conditions

Launder-o-meter washing machine

Persil® Color detergent (Henkel KGaA)

Detergent liquor 250 ml detergent dosage 6 g / 1 washing time 30 min. Washing temperature 60oC prewash cycles 3 test fabrics 10 g cotton, 5 g polyester / cotton,

5 g polyester soiling 0.2 g used motor oil polymer additive 1% (100% active substance) the amount of polymer refers to the amount of detergent used

The results in Table 4 show that when polymer is added, dirt removal of over 70% is achieved in all cases.

3

VoO

VO

² > Topanol® CA from ICI

³⁾ SantonoxCD R from Monsanto u

i

o H

• from β

The graying-inhibiting effect was tested as follows: The test fabric was subjected to standard soiling in a series of 3 washes. The dirty fabric was renewed after each wash, with the test fabric becoming more soiled with each wash. The degree of whiteness of the test fabric after the 3rd wash was used to assess the degree of soiling. The photometric measurement of the reflectance in percent was measured with a photometer from Datacolor at the wavelength 460 nm (barium primary white standard according to DIN 5033). The test detergent used in the tests had the following composition:

Table 5: Composition of the test detergent

(%)

Na-Cι-Cχ ₃ alkylbenzenesulfonate 9, 0

Cι ₃ -Cι ₅ fatty alcohol + 7 EO 6.6

Zeolite A 45, 0

Na carbonate 7.0 Mg silicate 0.8

Na citrate 12.0

Soap 1.8

The formula was mathematically supplemented with H ₂ 0 to 100%.

Table 6: Test conditions

Launder-o-meter washing machine

Wash liquor 250 ml detergent dosage 6 g / 1

Water hardness 16.8 ° d

Fleet ratio 1: 12.5

Wash temperature 60 ° C

Wash duration 30 min Wash cycles 3

Test fabric 5 g cotton, 2.5 g polyester / cotton,

2.5 g polyester

Test fabric 10 g WFK IOC (standard contamination of the

Laundry research institute Krefeld) renewed with every cycle

Polymer addition 1.0% (active substance)

Table 7 shows the significant increase in the reflectance of polyester after addition of 1% polymer (active substance) 3

O

Table 7: Graying-inhibiting effect VO unwashed PES fabric: R = 75.4% ve

² > Topanol® CA from ICI

³ > Santonox® R from Monsanto o

3 v -βα o

00

The effect on the wash cycle has been tested tongues at 8 Standardanschmut- ^".

The following test fabrics were tested: EMPA 101, EMPA 104, EMPA 112, EMPA 116 from the Swiss Material Testing and Testing Institute (St. Gallen, Switzerland);

WFK 10D, WFK 20D, WFK 30D, WFK IOC from the Krefeld laundry research institute.

Table 8: Washing conditions

Launder-o-meter washing machine

Persil Color detergent (Henkel KGaA)

Detergent dosage 6 g / 1 water hardness 16.8 ° d

Washing time 30 min.

Wash temperature 60 ° C

Fleet ratio 1: 12.5

Ballast fabric 10 g cotton Test fabric combination: 5 g EMPA 101, 5 g WFK 10D

5 g EMPA 104, 5 g WFK 20D 5 g EMPA 112, 5 g EMPA 116 5 g WFK IOC, 5 g WFK 30D

Table 9: Washing results

The results from Table 9 show that the addition of 1% polymer (active substance) improves the primary washing power. For this purpose, the washed test fabrics were measured with a photometer from Datacolor (Elrepho® 2000) at a wavelength of 460 nm. The total values of the mean reflectance values obtained on the individual test fabrics by multiple measurements are given in the result table.

3O

M VO

² > Topanol® CA from ICI

³⁾ Santonox® R from Monsanto

OH vβ δ

It can be seen that compounds of dirt-removing ^" polyesters on inorganic supports are not impaired in their dirt-removing or graying-inhibiting or in their primary washing effectiveness by the use of antioxidants.

Claims

claims

1. A detergent component comprising: a) at least one dirt-releasing amphiphilic polyester; b) at least one antioxidant which is selected from phenols, bisphenols and thiobisphenols which are substituted with sterically hindering groups, aromatic amines, preferably secondary aromatic amines, and substituted p-phenylenediamines,

Phosphine, phosphite and phosphonite compounds,

Esters of 3, 3'-thiodipropionic acid,

Reductones and

Metal ion deactivators and c) a carrier.

2. Detergent component according to claim 1, wherein the antioxidant is one of the following compounds:

2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-4-aminophenol, 4-hydroxymethyl-2,6-di - tert-butylphenol, 2-tert-butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, 2-tert-butyl-4-methylphenol, 2,4, 6-tri-tert.- butylphenol, 2,3,6-tri-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-4-nonylphenol, 2,4-di-tert-butyl-6-nonylphenol , Gallic acid, a butylated product of p-cresol and dicyclopentadiene, 2,2 'methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (4,6-dimethylphenol), 2,2 'methylenebis [4-methyl-6- (1-methylcyclohexyl) phenol], 2,2' methylenebis (4-ethyl-6-tert-butylphenol), 1,1-bis ( 5-tert-butyl-4-hydroxy-2-methylphenly) butane,

4,4'-methylenebis (3-methyl-6-tert-butylphenol), 4,4'-ethylidibis (3-methyl-6-tert-butylphenol), 4,4'-methylene bis - (2-methyl-6-tert-butylphenol), 4,4'-thiobis (2, 6-di-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert. -butylphenol), 4,4'-thiobis- (2-methyl-6-tert-butylphenol),

4,4'-methylene-bis- (2,6-di-tert-butylphenol), 4,4'-butylidene-bis- (2,6-di-tert-butylphenol), 1,1,3- Tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,4-tris (3,5-di-tert. -butyl-4-hydroxybenzyl) -benzene, N, N'-bis- ((3,5-di-tert-butyl-4-hydroxyphenol) propionyl] -hexamethylene diamine, N, N'-di-isopropyl- p-phenylenediamine, N, N'-di- (naphthyl-2) -p-phenylenediamine, 4- (p-toluenesulfonamido) -diphenylamine and (o-tolyl) biguanide, triphenylphosphine, diethylphosphite, triphenylphosphite, tris -nonylphenylphosphite, tris (monononylphenylphosphite), tris- (dinonylphenylphosphite), tridecylphosphite, triisodecylphosphite, octyl-diphenylphosphite, 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl- esters, 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid di-octadecyl ester, dilauryl, dimyristyl and distearyl esters of 3, 3 '-thiodipropionic acid, ascorbic acid, 5, 6-diacetyl-ascorbic acid, 6-palmitoylascorbic acid and Hydroquinone monomethyl ether.

3. Detergent ingredient according to claim 1 or 2, wherein the antioxidant is one of the following compounds: gallic acid, a butylated product of p-cresol and dicyclopentadiene, 4, 4 '-Thiobis- (3-methyl-6-tert-butylphenol , 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenol) butane, N, N'-bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] -hexa- methylenediamine, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, ascorbic acid, triphenylphosphine and hydroquinone monomethyl ether.

4. Detergent component according to one of the preceding claims, wherein the antioxidant 4,4'-thiobis- [3-methyl-6-tert. -butylphenol), 1, 1, 3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl] butane and / or 1,3, 5-trimethyl-2, 4, 6-tris- (3rd , 5-di-tert-butyl-4-hydroxy-benzyl) benzene.

5. Detergent component according to one of the preceding claims, wherein the dirt-removing polyester blocks

Ester units from polyalkylene glycols with a molecular weight of 500 to 7500 and aliphatic dicarboxylic acids and / or monohydroxycarboxylic acids and

Has ester units from aromatic dicarboxylic acids and polyhydric alcohols and has a molecular weight of 1500 to 60,000.

6. Detergent component according to one of the preceding claims, in which the carrier is selected from amorphous or crystalline alkali silicates, crystalline alkali alumosilicates, phosphates and polyphosphates, alkali carbonates, polycarboxylates, alkali citrates, cellulose derivatives, and mixtures thereof.

7. Detergent component according to one of the preceding claims, the weight-based mixing ratio of polyester to carrier being 5:95 to 95: 5%, preferably 10:90 to 80:20% and in particular 15:85 to 70:30% is.

8. Detergent component according to one of the preceding claims, wherein the antioxidant b), based on the mixture of carrier and polyester, is 0.0001 to 10% by weight, preferably 0.002 to 5% by weight.

5

9. Detergent containing a detergent component according to one of claims 1 to 8, optionally together with further detergent and cleaning agent components.

10. Use of an antioxidant as defined in one of claims 1 to 5 for protecting a detergent component which comprises a dirt-releasing amphiphilic polyester and a carrier, prior to exothermic decomposition by oxidation in the preparation or storage in the presence of

15 oxygen.

11. A process for the preparation of a detergent component according to any one of claims 1 to 8, characterized in that the polyester a) is mixed in the liquid state with the antioxidant agent 20 b) and the mixture is ground after cooling with the carrier c).

12. A process for the preparation of a detergent component according to one of claims 1 to 8, characterized in that 25 a molten mixture of polyester a) and Antioxidida¬ tion agent b) is applied to the carrier.

30

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40

45