CA2297861A1 - The use of phosphonic-acid-modified polyacrylates as sequestering agents - Google Patents

Abstract

The invention relates to the use of phosphoric-acid-modified polyacrylates as sequestrants for the production of water-based bleaching compositions. Together in particular with other polyelectrolytes, buffers and chlorine-stable surfactants, preparations which reliably protect textiles from yellowing, preferably chlorine bleaching liquors, are obtained.

Description

The Use of Phosphonic-acid-modified Polyacrylates as Sequestering Agents Field of the Invention This invention relates to the use of phosphonic-acid-modified polyacrylates as sequestering agents (sequestrants) for the production of water-containing bleaching compositions.
Prior Art In the cold washing of soiled textiles, liquid bleaching compositions, preferably based on hypochlorite, are used in addition to a detergent for removing particularly difficult stains. These liquid bleaching compositions have to be compatible with textiles, i.e. the removal of stains by the treatment with hypochlorite, an aggressive chemical, should take place without any adverse effect on the textile. In addition, since skin contact with the bleaching compositions cannot be ruled out, the preparations have to be as dermatologically safe as possible. One particular problem is that hypochlorite solutions are capable of dissolving iron and manganese ions from the walls of the washing machine during the washing process. These iron and manganese ions subsequently catalyze photochemical reactions and lead to yellowing of the washing. Although commercially available compositions attempt to prevent this redeposition through the use of polyacrylates [DE 19730650 A1 (Henkel)], this measure has not always proved satisfactory in practice.
Accordingly, the complex problem addressed by the present invention was to prevent the yellowing of washing through the deposition of metal traces on the washing and to provide sequestrants with which it would be possible to produce water-based bleaching compositions, more particularly chlorine bleaching liquors, which at one and the same time would be chlorine-stable, kind to fabrics and dermatologically safe while developing high stain removing power and which would have a sufficiently high viscosity.
Description of the Invention The present invention relates to the use of phosphonic-acid-modified polyacrylates as sequestrants for the production of water-based bleaching compositions.
It has surprisingly been found that the addition of small quantities of phosphonic-acid-modified polyacrylates to water-based bleaching composi-tions, more particularly to hypochlorite solutions, significantly reduces the deposition of metal traces on the laundry during the washing process and, in doing so, counteracts yellowing of the fibers. The invention includes the observation that the use of other polyelectrolytes, buffers and optionally chlorine-stable surfactants and optical brighteners leads to a further improvement in stabilization against yellowing, in cleaning performance and in dermatological compatibility.
Phosahonic-acid-modifiedJ~ol~acrylates Polyacrylates are polymers based on esters of acrylic acid with a characteristic chain unit corresponding to formula (I):
-[CHZ-CH(COOR~)]- (I) in which R' is hydrogen or a linear or branched hydrocarbon radical containing 1 to 22, preferably 2 to 12 and more preferably 3 to 8 carbon atoms. Typical examples are polymers of acrylic acid and esters thereof with methanol, ethanol, propanol, isopropyl alcohol, n-butanol, isobutanol, sec.-butanol, tert.-butanol, pentanol, caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and the technical mixtures thereof obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis. Homopolymers or copolymers of acrylic acid and methyl, tert.-butyl or 2-ethylhexyl esters thereof are preferably used. The resulting polyacrylates are modified with phosphonic acid, the point of attachment of the phosphonic acid group being situated on the carbon chain. The polymers obtained can have average molecular weights of the order of 300 to 50,000, preferably in the range from 1000 to 30,000 and more preferably in the range from 5000 to 10,000 dalton.
Polyelectrolytes In one particular embodiment of the invention, the phosphonic-acid-modified polyacrylates are used in combination with other already known polyelectrolytes. These other electrolytes support the sequestering effect of the polyacrylates according to the invention.
(a) Low molecular weight dicarboxylic acids. In the most simple case, the polyelectrolytes used may be low molecular weight dicarboxylic acids corresponding to formula (II):
R200C(CH2)~OOCR3 (II) in which R2 and R3 represent hydrogen, an alkali metal and/or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammo-nium and n is a number of 0 to 64. Typical examples are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid and the dimer and trimer fatty acids based on unsaturated fatty acids, namely oleic acid, elaidic acid, gadoleic acid and erucic acid. The dicarboxylic acids may be mono- or polyunsaturated and/or may have an aromatic ring instead of the alkylene groups. Typical examples are malefic acid, fumaric acid, sorbic acid, phthalic acid and terephthalic acid. When the acids mentioned are introduced into the alkaline bleaching composition, neutralization takes place. However, they may also be directly used in the form of their salts, preferably sodium salts.
In one particularly preferred embodiment, adipic acid or sodium adipate is used as the polyelectrolyte.
(b) Low molecular weight polybasic hydroxycarboxylic acids. Typical examples of suitable polybasic hydroxycarboxylic acids are malic acid, tartaric acid and in particular citric acid. These acids may also be used in the form of their alkali metal and/or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium salts. In one parti-cularly preferred embodiment, citric acid or sodium citrate is used as the polyelectrolyte.
(c) Homopolymers and copolymers of unsaturated dicarboxylic acids and derivatives thereof. Unsaturated dicarboxylic acids suitable as mon-omers have already been mentioned under (a). However, malefic anhy-dride is preferably used by virtue of its high reactivity and its low price.
The products obtainable, for example, by hydrolysis of polymaleic anhydride have a high charge intensity. Ring structures formed by secondary reactions during the polymerization reaction additionally provide the molecules with a certain chain stiffness which has a favorable effect on sequestering. Polymaleic anhydrides (PMAs) with molecular weights of 300 to 5000 dalton are known, for example, from US 3,810,835 (Ciba). Co-polymers of PMA and poly(meth)acrylic acid with molecular weights of 1000 to 50,000 are mentioned in DE 242926 AS (Ciba). US 3,650,970 (Atlantic Richfield) describes copolymers of malefic anhydride and styrene which have been subjected to ring opening with polyethylene glycol (molecular weight 300 to 1000) and which also have a favorable sequester-ing effect. The same applies to copolymers of malefic anhydride with sulfonated styrene [FR2322831 A (Betz)], vinyl acetate [US 3,755,264 5 (Amicon]), methacrylic acid/styrene [US 4,065,607(Pfitzner)], allyl acetate [US 4,001,134 (Grace)] and/or acrolein [DE 2404192 AS (Ciba)].
(d) Homopolymers and copolymers of unsaturated monocarboxylic acid amides and derivatives thereof. This group of substances are preferably compounds which are obtained either by (co)polymerization of the monomers or by polymer-analog hydrolysis of poly(meth)acrylamide or poly(meth)acrylonitrile. The production of a polyacrylamide with a molecular weight of 500 to 5000 dalton by using thioglycolic acid as regulator and alkaline hydrolysis of 60 to 90% of the amide groups is described, for example, in US 4,001,161 (Cyanamid). A polymer of similar composition is obtained in accordance with US 3,492,240 (Nalco). The product contains 20 to 50% amide groups and 50 to 80% carboxyl groups and has a molecular weight of 20,000 to 40,000. In addition, CA 982341 (Nalco) describes a hydrolyzed polyacrylonitrile which contains 20 to 30%
amide groups and 70 to 80% acid groups and has a molecular weight of 5000 to 40,000. Graft polymers of acrylamide or acrylonitrile on starch or vinyl alcohol and hydrolysis products thereof [cf. NL 6615265 (ICI)] are also suitable.
(e) Other anionic and cationic polyelectrolytes. Besides the compounds mentioned, the following compounds are also suitable polyelectrolytes: poly-(N,N-bis-carboxymethylene acrylamide) [cf. GB
1,310,613 A (Chemed)], copolymers of fumaric acid and vinyl sulfonic acid [cf. US 3,879,288, US 3,706,717 (Siegele)], polymers of 3-acylamido-3-methylpropane sulfonic acid (cf. US 3,709,815, US 3,928,916 (Calgon)], copolymers of acrylic acid and styrene sulfonic acid [cf. US 4,048,066 (Chemed)], copolymers of acrylic acid with 2-hydroxyethyl methacrylate monophosphate [cf. JA 76/112447 A (Sanyo)], homopolymers and copolymers of 3-acrylamido-3-methyl butyl trimethyl ammonium chloride [cf. US 3,752,761 (Calgon)], copolymers of diallyl glycinamide hydrochloride and acrylic acid [cf. US 3,574,175 (Grace)], copolymers of dimethyl allyl ammonium chloride with acrylamide [cf. GB 1,287,489 A], polyethylene and/or polypropylene imines [cf. GB 1,015,612 A (Grace)] and mixtures thereof.
Alkali metal ~pochlorites Although the water-based bleaching compositions may contain hydrogen peroxide, they are preferably chlorine bleaching liquors containing alkali metal hypochlorite. Alkali metal hypochlorites in the context of the present invention are understood to be lithium, potassium and, in particular, sodium hypochlorite. The hypochlorites may be used in quantities of 1.5 to 10% by weight, preferably in quantities of 2 to 8% by weight and more preferably in quantities of 4 to 6% by weight, based on the composition.
B uffe rs In one preferred embodiment of the invention, the phosphonic-acid-modified polyacrylates are used in combination with buffers which are alkali metal and/or alkaline earth metal silicates, carbonates, phosphonates or mixtures thereof. The salts support the sequestering effect of the poly-electrolytes and ensure that the preparations always have a highly alkaline pH in the range from 10 to 14. Typical examples are sodium silicate, potassium silicate, sodium carbonate, potassium carbonate and - from the group of phosphonates - above all the amine oxide phosphonic acids marketed, for example, under the name of Sequion~ by Bozetto, Italy, for example the aminotrimethylene phosphonic acid-N-oxide (ATMP-N-oxide) obtainable as Sequion~ CLR. The buffers may be used individually or in the form of mixtures in quantities of 0.01 to 5% by weight, preferably in quantities of 0.1 to 2% by weight and more preferably in quantities of 0.5 to 1 % by weight, based on the composition.
Chlorine-stable surfactants (a) Alkyl ether sulfates are known anionic surfactants which are obtained by sulfation of nonionic surfactants of the alkyl polyglycol ether type and subsequent neutralization. The alkyl ether sulfates suitable for use in the compositions according to the invention correspond to formula (111):
R4O-(CH2CH2O)qSO3X (III) in which R4 is an alkyl group containing 12 to 18 and more particularly 12 to 14 carbon atoms, q is a number of 2 to 5 and, more particularly, 2 to 3 and X is sodium or potassium. Typical examples are the sodium salts of sulfates of the C~2,~4 cocoalcohol 2, 2.3 and 3 EO adduct. The alkyl ether sulfates may have a conventional or narrow homolog distribution. The alkyl ether sulfates are used in quantities of preferably 1 to 8% by weight, more preferably 1.5 to 6% by weight and most preferably 2 to 4% by weight, based on the composition.
(b) Amine oxides are also known compounds which are occasionally classified as cationic surfactants, but generally as nonionic surfactants.
They are produced from tertiary fatty amines which normally have either one long and two short alkyl chains or two long and one short alkyl chain by oxidation in the presence of hydrogen peroxide. The amine oxides suitable for use in the compositions according to the invention correspond to formula (IV):

Rs Rs_N_>O . (IV) R' in which R5 is a linear or branched alkyl group containing 12 to 18 carbon atoms and Rs and R' independently of one another have the same meaning as R5 or represent an optionally hydroxy substituted alkyl group containing 1 to 4 carbon atoms. Amine oxides of formula (IV), in which R5 and R6 represent C~2,~a or C~2,~s cocoalkyl groups and R' is a methyl or hydroxyethyl group, are preferably used. Amine oxides of formula (IV), in which R5 is a C~2,~a or C~2,~a cocoalkyl group and Rs and R' represent a methyl or hydroxyethyl group, are also preferred. The amine oxides are preferably used in quantities of 1.5 to 6% by weight and preferably 2 to 4%
by weight, based on the composition.
(c) Alkyl and/or alkenyl oligoglycosides are known nonionic surfactants corresponding to formula (I):
Ra0-[G]p (V) in which R8 is an alkyl and/or alkenyl group containing 4 to 22 carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms and p is a number of 1 to 10. They may be obtained by the relevant methods of preparative organic chemistry. EP 0 301 298 A1 and WO 90103977 are cited as representative of the extensive literature available on the subject. The alkyl and/or alkenyl oligoglycosides may be derived from aldoses or ketoses containing 5 or 6 carbon atoms, preferably glucose. Accordingly, the preferred alkyl and/or alkenyl oligoglycosides are alkyl and/or alkenyl oligoglucosides. The index p in general formula (V) indicates the degree of oligomerization (DP), i.e. the distribution of mono- and oligoglycosides, and is a number of 1 to 10. Whereas p in a given compound must always be an integer and, above all, may assume a value of 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined calculated quantity which is generally a broken number. Alkyl and/or alkenyl oligo-glycosides having an average degree of oligomerization p of 1.1 to 3.0 are preferably used. Alkyl and/or alkenyl oligoglycosides having a degree of oligomerization of less than 1.7 and, more particularly, between 1.2 and 1.4 are preferred from the applicational point of view. The alkyl or alkenyl radical R8 may be derived from primary alcohols containing 4 to 11 and preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and the technical mixtures thereof obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides having a chain length of C$ to Coo (DP = 1 to 3), which are obtained as first runnings in the separation of technical C8_~8 coconut oil fatty alcohol by distillation and which may contain less than 6% by weight of C~2 alcohol as an impurity, and also alkyl oligo-glucosides based on technical C9,» oxoalcohols (DP = 1 to 3) are preferred. In addition, the alkyl or alkenyl radical R$ may also be derived from primary alcohols containing 12 to 22 and preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and technical mixtures thereof which may be obtained as described above. Alkyl oligoglucosides based on hydrogenated C,2,~4 cocoalcohol with a DP of 1 to 3 are preferred. The glycosides are preferably used in quantities of 1.5 to 6% by weight and more preferably in quantities of 2 to 4% by weight.

(d) The compositions according to the invention may contain as further surfactants fatty acid salts corresponding to formula (VI):
R9C0-OX (VI) in which R9C0 is an acyl group containing 12 to 22 carbon atoms and X is an alkali metal. Typical examples are the sodium and/or potassium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, iso-stearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic 10 acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and the technical mixtures thereof obtained in the pressure hydrolysis of technical fats and oils. Salts of technical cocofatty acid or tallow fatty acid are preferably used. Since the compositions according to the invention are highly alkaline, the salts may even be replaced by the fatty acids which are neutralized in situ on introduction into the mixture.
Compositions according to the invention which are required to be particularly low-foaming preferably contain fatty acid salts as an optional component. The soaps are used in quantities of preferably 1.5 to 6% by weight and more preferably 2 to 4% by weight, based on the composition.
Commercial Apa~lications The bleaching compositions obtainable using polyacrylates in accordance with the invention generally have a non-aqueous component of 5 to 35% by weight and preferably 8 to 15% by weight and are particularly suitable for the treatment of textiles such as, for example, yarns, webs and, in particular, fabrics. They are normally used at low temperatures, i.e. at cold wash temperatures (ca. 15 to 25°C). Not only are the compositions distinguished by excellent stain removal, they also reliably prevent the deposition of metal traces on the fibers and thus prevent yellowing.
Although the actual use of the compositions is directed at the removal of stains during washing, they are also suitable in principle for other applications where hypochlorite solutions are used, for example for the cleaning and disinfection of hard surfaces.
Additional auxiliaries and additives which may be used include, for example, other chlorine-stable surfactants or hydrotropes such as, for example, alkyl sulfates, alkyl sulfonates, alkyl benzenesulfonates, xylene sulfonates, sarcosinates, taurides, isethionates, sulfosuccinates, betaines, sugar esters, fatty alcohol polyglycol ethers and fatty acid-N-alkyl glucamides. In one preferred embodiment, all the surfactants together make up at most 10 to 15% by weight of the total quantity of ingredients in the composition. The compositions according to the invention may contain alkali metal compounds, preferably sodium hydroxide or potassium hydroxide, with which the pH of the compositions can be adjusted to an optimal value of 10 to 14 and preferably 12.5 to 13.5.
Typical examples of suitable optical brighteners are derivatives of diaminostilbene disulfonic acid and alkali metal salts thereof. Suitable optical brighteners are, for example, derivatives of 4,4'-diamino-2,2'-stilbene disulfonic acid (flavonic acid), such as in particular the salts of 4,4'-bis-(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)-stillbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the morpholino group, contain a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Other brighteners which may be present are those of the substituted diphenyl styryl type, for example alkali metal salts of 4,4'-bis-(2-sulfostyryl)-Biphenyl, 4,4'-bis-(4-chloro-2-sulfo-styryl)-Biphenyl or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-Biphenyl, methyl umbelliferone, coumarin, dihydroquinolinone, 1,3-diaryl pyrazoline, naphthalic acid amide, benzoxazole, benzisoxazole and benzimidazole systems linked by CH=CH bonds, heterocycle-substituted pyrene derivatives and the like. Mixtures of the brighteners mentioned above may also be used. The potassium salt of 4,4'-bis-(1,2,3-triazolyl)-(2)-stilbine-2,2-sulfonic acid marketed under the name of Phorwite~ BHC 766 is preferred. The compositions generally contain the optical brighteners in quantities of 1 to 5% by weight and preferably in quantities of 2 to 3% by weight. In addition, blue dyes may also be present in small quantities. A
particularly preferred dye is Tinolux~ (Ciba-Geigy).
Typical examples of suitable perfumes stable to active chlorine are: citronellol (3,7-dimethyl-6-octen-1-ol), dimethyl octanol (3,7-dimethyl-1-octanol), hydroxycitronellol (3,7-dimethyloctane-1,7-diol), mugol (3,7-dimethyl-4,6-octatrien-3-ol), myrcenol (2-methyl-6-methylene-7-octen-2-ol), terpinolene (p-mentho-1,4-(8)-diene), ethyl-2-methyl butyrate, phenyl propyl alcohol, galaxolide (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclo-pental-2-benzopyran), tonalide (7-acetyl-1,1,3,4,4,6-hexamethyl tetrahydro-naphthalene), rose oxide, linalol oxide, 2,6-dimethyl-3-octanol, tetra-hydroethyl linalool, tetrahydroethyl linalyl acetate, o-sec.-butyl cyclohexyl acetate and isolone diphorenepoxide and also isoborneal, dihydroterpineol, isobornyl acetate, dihydroterpenyl acetate). Other suitable perfumes are the substances mentioned columns 3 and 4 of European patent application EP 0622451 A1 (Procter & Gamble).
Suitable pigments are inter alia green chlorophthalocyanines (Pigmosol~ Green, Hostaphine~ Green) or yellow Solar Yellow BG 300 (Sandoz). The compositions according to the invention are prepared by stirring. The product obtained may optionally be decanted or filtered to remove foreign bodies and/or agglomerates. In addition, the compositions have a viscosity below 100 mPas and preferably below 50 mPas, as measured at 20°C in a Brookfield viscosimeter (spindle 1, 10 r.p.m.).
Examples In order to test the bleaching effect, soiled fabrics were treated with various bleaching solutions. Yellowing was photochemically determined using the starting value of the soiled fabric as standard (100%). The measurements were carried out in a liquor with a metal ion content of 300 ppb iron and 100 ppb manganese; the water hardness was 1000 ppm CaCl2; the hydrogen carbonate content was 0.013% by weight. The liquor ratio of fabric to water was 1:50 and the contact time was 30 minutes at a temperature of 40°C. The results are set out in Table 1.
Table 1 Bleaching effect (quantities in % by weight) E
~orrii a~i~i~~rt~' ~t~~rrn~~~~'t 2~, .. ~~~ ' -.~2 ' v .-..
... ....~......_..... .. .._ ...__ Sodium hypochlorite 5.0 5.0 5.0 5.0 5.0 Sodium hydroxide 0.7 0.5 0.5 0.5 0.5 Sodium silicate 0.1 0.1 0.1 0.1 0.1 Polyacrylic acid, phosphonic-acid-0.055 0.2 0.3 - -modified~~

Polyacrylic acid2~ - - - 0.3 -Amine oxide phosphonic acid3~0.1 0.1 0.1 0.1 0.1 Yellowing [%-rel.] 86 82 79 90 93 Norasol~ 470 N (Rohm & Haas / DE) Carbopol~ EX 497 (BF Goodrich / BG) Sequion~ (Bozetto / IT)

Claims (10)

1. The use of phosphonic-acid-modified polyacrylates as sequestrants for the production of water-based bleaching compositions.

2. The use claimed in claim 1, characterized in that polyelectrolytes selected from the group consisting of (a) low molecular weight dicarboxylic acids, (b) low molecular weight polybasic hydroxycarboxylic acids, (c) homopolymers and copolymers of unsaturated dicarboxylic acids and derivatives thereof and/or (d) homopolymers and copolymers of unsaturated monocarboxylic acid amides and derivatives thereof are additionally used.

3. The use claimed in claims 1 and 2, characterized in that poly-electrolytes selected from the group consisting of poly-(N,N-bis-carboxy-methylene acrylamides), copolymers of fumaric acid and vinyl sulfonic acid, polymers of 3-acrylamido-3-methyl propane sulfonic acid, copolymers of acrylic acid and styrene sulfonic acid, copolymers of acrylic acid with 2-hydroxyethyl methacrylate monophosphate, homo- and copolymers of 3-acrylamido-3-methyl butyl trimethyl ammonium chloride, copolymers of diallyl glycine amide hydrochloride and acrylic acid, copolymers of dimethyl allyl ammonium chloride with acrylamide and/or polyethylene and/or polypropylene imines are additionally used.

4. The use claimed in at least one of claims 1 to 3, characterized in that the polyacrylates are used with a molecular weight in the range from 300 to 50,000.

5. The use claimed in at least one of claims 1 to 4, characterized in that the polyacrylates are used in quantities of 0.01 to 5% by weight, based on the water-containing bleaching composition.

6. The use claimed in at least one of claims 1 to 5, characterized in that the polyacrylates are used in hypochlorite-containing bleaching compositions.

7. The use claimed in at least one of claims 1 to 6, characterized in that the polyacrylates are used together with buffers selected from the group consisting of alkali metal and/or alkaline earth metal silicates, carbonates and/or phosphonates.

8. The use claimed in at least one of claims 1 to 7, characterized in that the polyacrylates are used together with chlorine-stable surfactants selected from the group consisting of alkyl ether sulfates, amine oxides, alkyl and/or alkenyl oligoglycosides and/or fatty acid salts.

9. The use claimed in at least one of claims 1 to 8, characterized in that the polyacrylates are used together with chlorine-stable optical brighteners.

10. The use claimed in at least one of claims 1 to 9, characterized in that the polyacrylates are used together with chlorine-stable perfumes.