Bleaching-agent co-granules, method for producing said bleaching-agent co-granules, and use of said bleaching-agent co-granules

Abstract

The invention relates to a bleaching-agent co-granule containing a bleach activator, a metal-containing bleach catalyst comprising at least one ligand from the group consisting of di- or trimethyltriazacyclononane and derivatives of these, and a homo- or copolymeric polycarboxylate or its salts or partial neutralizates having a pH in the range from 3 to 9. The bleaching-agent co-granule is obtained in an anhydrous granulating process, preferably by compaction at a temperature below 100 C. The invention also relates to the method of using the bleaching-agent co-granule in dishwasher detergents and to a detergent comprising said bleaching-agent co-granule.

Claims

1. A storage-stable and odor-free bleaching-agent co-granule containing, in each case relative to the overall weight of the co-granule, a) 50 to 90 wt % of one or more bleach activators; b) 0.01 to 10 wt % of one or more metal-containing bleach catalysts having at least one ligand selected from the group consisting of di- or trimethyltriazacyclononane and derivatives thereof; and c) 5 to 40 wt % of a binder of one or more room temperature solid polymers or copolymers of acrylic acid and/or methacrylic acid or their salts or partial neutralizates with a pH in the range from 3 to 9, measured as 1 wt % solution in water characterized in that it is obtained in an anhydrous granulating process and the temperature in the anhydrous granulating process is maintained below 100 C.

2. The bleaching-agent co-granule as claimed in claim 1, characterized in that it is free from alcohol ethoxylate or derivatives of ethylene oxide or of propylene oxide.

3. The bleaching-agent co-granule as claimed in claim 1, characterized in that the binder is a homo- or copolymer based on methacrylic acid.

4. The bleaching-agent co-granule as claimed in claim 1, characterized in that relative to the overall weight of the co-granule it contains in each case a) 65 to 85 wt % of one or more bleach activators; b) 0.05 to 6 wt % of one or more metal-containing bleach catalysts having at least one ligand selected from the group consisting of di- or trimethyltriazacyclononane and derivatives thereof; and c) 10 to 30 wt % of one or more binders which are room temperature solid polymers or copolymers of acrylic acid and/or methacrylic acid or their salts with a pH in the range from 3 to 9, measured on a 1 wt % solution in water.

5. The bleaching-agent co-granule as claimed in claim 1, characterized in that the bleach activator component a) is selected from the group consisting of polyacylated alkylenediamines, acylated triazine derivatives, acylated glycolurils, N-acylimides, acylated phenolsulfonates, acylated phenolcarboxylic acids, carboxylic anhydrides, acylated polyhydric alcohols, acylated sugar derivatives, N-acylated lactams, and mixtures thereof.

6. The bleaching-agent co-granule as claimed in claim 1, characterized in that the bleach catalyst is selected from the group consisting of manganese complexes comprising at least one ligand of formula A or B ##STR00002## where R=H, CH.sub.3, C.sub.2H.sub.5, or C.sub.3H.sub.7.

7. The bleaching-agent co-granule as claimed in claim 1, characterized in that the metal-containing bleach catalyst is selected from the group consisting of: [Mn.sup.III.sub.2(-O).sub.1(-OAc).sub.2(Me-TACN).sub.2](PF.sub.6).sub.2, [Mn.sup.IV.sub.2(-O).sub.3(Me-TACN).sub.2](PF.sub.6).sub.2.H.sub.2O, [Mn.sup.IV.sub.2(-O).sub.2(-OAc)(Me4-DTE)]Cl.sub.2, [Mn.sup.IV(Me-TACN)(OCH.sub.3).sub.3]PF.sub.6 and [Mn.sup.IV(Me-TACN)(acac)OCH.sub.3]PF.sub.6.

8. The bleaching-agent co-granule as claimed in claim 1, characterized in that by way of said binder component c) it contains a polymer or copolymer of methacrylic acid, in the form of its salts or in partially neutralized form, wherein a 1% solution of the binder in water has a pH in the range from 3.5 to 8.5.

9. The bleaching-agent co-granule as claimed in claim 1, characterized in that the binder is selected from (i) a copolymer of maleic acid and acrylic acid or (ii) polymethacrylic acid having an average molar mass in the range from 500 to 70 000 g/mol.

10. A method of producing bleaching-agent co-granule material as claimed in claim 1, which method comprises an anhydrous granulating process including mixing the recited components as pulverulent actives and then compacting the mixture, wherein the temperature in the anhydrous granulating process is maintained below 100 C.

11. A method of making washing and cleaning compositions comprising utilizing a bleaching-agent co-granule as claimed in claim 1 in the manufacture of the washing and cleaning compositions.

12. A washing and cleaning composition incorporating a bleaching-agent co-granule as claimed in claim 1.

13. The washing and cleaning composition as claimed in claim 12, characterized in that it incorporates the bleaching-agent co-granule in an amount ranging from 0.1 to 10 wt %, relative to the overall weight of said washing and cleaning composition.

14. The washing and cleaning composition as claimed in claim 13, characterized in that it incorporates i) 15 to 65 wt % of a water-soluble builder component, ii) 5 to 25 wt % of a peroxygen compound, iii) 0.5 to 6 wt % of a bleaching-agent co-granule as claimed in claim 1, and iv) 0 to 50 wt % of further, adjunct components selected from the group consisting of enzymes, alkali carriers, surfactants, pH regulators, organic solvents, glass corrosion inhibitors, silver corrosion inhibitors and foam regulators, all relative to the overall weight of the washing and cleaning composition.

15. The method of producing bleaching-agent co-granule material as claimed in claim 10, which method comprises mixing the recited components as pulverulent actives and then compacting the mixture, thereafter grinding the compacted mixture with or without subsequent sieving into individual particle size fractions, wherein the temperature in the anhydrous granulating process is maintained below 100 C.

16. The method of producing bleaching-agent co-granule material as claimed in claim 15, wherein the compacting is effected on roll compactors.

17. The method of making washing and cleaning compositions as claimed in claim 11 comprising utilizing the bleaching-agent co-granule as claimed in claim 1 in the manufacture of dishwasher detergents.

18. The bleaching-agent co-granule as claimed in claim 1, characterized in that the bleach activator component a) is selected from the group consisting of tetraacetylethylenediamine, 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, tetraacetylglycoluril, N-nonanoylsuccinimide, N-nonanoyloxy- or n-lauroyloxybenzenesulfonate, nonanoyloxy- or decanoyloxybenzoic acid, phthalic anhydride, triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, acetylated sorbitol, mannitol, pentaacetylglucosc, pentaacetylfructose, tetraacetylxylose, octaacetyllactose, acetylated, optionally N-alkylated glucamine, gluconolactone, N-acylated lactams, and mixtures thereof.

19. The washing and cleaning composition as claimed in claim 12, characterized in that it incorporates the bleaching-agent co-granule in an amount ranging from 0.2 to 8 wt %, relative to the overall weight of said washing and cleaning composition.

20. The bleaching-agent co-granule as claimed in claim 1, characterized in that it has a coating in the form of a protective layer.

Description

EXAMPLES

(1) In the examples which follow, % ages are weight percent (wt %) unless specifically stated otherwise. As regards the reported relative humidities, the % ages have the usual meaning.

Comparative Example 1

Preparation of TAED-MnTACN Co-Granules as Per WO 2010/115581, Example 1

(2) 700 g of TAED powder and 20 g of [Mn.sup.IV.sub.2(-O).sub.3(Me-TACN).sub.2](PF.sub.6).sub.2.H.sub.2O and 80 g of citric acid were initially charged to a laboratory mixer, mixed therein and heated therein to the requisite starting temperature of T>40 C. Then, the binder in melt form200 g of Genapol T 500 (fatty alcohol polyglycol ether, commercial product from Clariant based on cetearyl alcohol with on average 50 ethylene oxide units in the molecule)was added at a temperature of T=70-75 C. under intensive agitation. The mixture was post-granulated for some minutes, then cooled down to room temperature and sieved to remove coarse and fine fractions from 200-1600 m.

(3) Storage Test of Co-Granule in Base Laundry Detergent Powder

(4) To test the chemical and physical stability of the co-granule thus obtained, its storage behavior was investigated in a typical laundry detergent powder formulation. To this end, the co-granule was incorporated in IEC-A base laundry detergent powder such that the final formulation contained 2% of co-granule. The mixture was transferred into a glass bottle and stored for several days with a closed lid under climatic conditions (T=40 C., 75% relative humidity). After just one day of storage, an amine-type odor was very conspicuous on opening the glass bottle.

Comparative Example 2

Preparation of Co-Granules Example 2

(5) 800 g of TAED powder and 20 g of [Mn.sup.IV.sub.2(-O).sub.3(Me-TACN).sub.2](PF.sub.6).sub.2.H.sub.2O were initially charged to a laboratory mixer and mixed therein. Then, an aqueous solution of a polyacrylate (Sokalan CP 13, commercial product from BASF) was added under intensive agitation and the mixture was granulated. The moist co-granule material was in a laboratory moving-bed dryer at about 60-80 C. and subsequently sieved to remove coarse and fine fractions from 200-1600 m.

(6) Even in its as-produced state, the co-granule material already had an unpleasant odor which further intensified to a significant degree following storage in a base laundry detergent.

Examples 1 to 4 (Inventive)

Preparation of Inventive Co-Granules 1 to 4

(7) The co-granules were produced under anhydrous conditions with the binders being employed in the form of their granules. The commercially available binder granules were initially ground down to a particle size of 200 to 1000 m.

(8) Bleach activator TAED, bleach catalyst 1-3 and solid binder were mixed in an Eyrisch mixer in the amounts reported in table 1 and the mixture was subsequently compacted using a Bepex laboratory compactor. The resulting sheet compacts were comminuted in an Alexanderwerk sieve mill to 1.25 mm and fractionally sieved at 200 to 1040 m using a Sweco sieve. Batch size: 5 to 7 kg.

(9) The table shows an overview of inventive co-granules 1 to 4

(10) TABLE-US-00001 Co-granule 1 2 3 4 Substances Bleach activator TAED TAED TAED TAED Bleach catalyst *) complex 1 complex 1 complex 2 complex 3 Binder Sokalan Sokalan Sokalan Sokalan CP 45 G CP 5 G CP 45 G CP 5 G Organic acid oxalic acid added Composition Bleach activator % 85 75 79 80 Bleach catalyst % 3 2 1 2 Binder % 12 23 20 17 Organic acid % 1 TAED tetraacetylethylenediamine *) complex 1 [Mn.sup.IV.sub.2(-O).sub.3(Me-TACN).sub.2](PF.sub.6).sub.2H.sub.2O, prepared as per EP 0 458 397 *) complex 2 [Mn.sup.IV.sub.2(-O).sub.3(Me-TACN).sub.2](OAc).sub.2, prepared as per WO 2006/125517 *) complex 3 [Mn.sup.IV(Me-TACN)](OCH.sub.3).sub.2(PF.sub.6), prepared as per EP 0 544 519 Sokalan CP copolymers of acrylic acid, commercial product from BASF
Storage Test of Co-Granule in Base Laundry Detergent Powder

(11) To test the chemical and physical stability of the co-granule thus obtained, its storage behavior was investigated in a typical laundry detergent powder formulation. To this end, the co-granule was incorporated in IEC-A base laundry detergent powder such that the final formulation contained 2% of co-granule. The mixture was transferred into a glass bottle and stored for several days with a closed lid under climatic conditions (T=40 C., 75% relative humidity). After 28 days of storage, the formulations were free-flowing, undiscolored and odor-neutral.