FORMULATIONS, THE PRODUCTION AND USE THEREOF, AND SUITABLE COMPONENTS

Abstract

A solid, liquid, or gel formulation including: (A) alkali metal sulfite or alkali metal bisulfite, and (B) at least one graft copolymer formed from: at least one graft base selected from nonionic monosaccharides, disaccharides, oligosaccharides, and polysaccharides, and side chains obtainable by grafting of at least one ethylenically unsaturated mono- or dicarboxylic acid and at least one compound of the general formula (I),

##STR00001##

where the variables are each defined as follows:

R.sup.1 is chosen from methyl and hydrogen,

A.sup.1 is chosen from C.sub.2-C.sub.4-alkylene,

R.sup.2 are the same or different and chosen from C.sub.1-C.sub.4-alkyl,

X.sup.− is chosen from halide, mono-C.sub.1-C.sub.4-alkylsulfate and sulfate,

where alkali metal (bi)sulfite (A) and graft copolymer (B) are present in a weight ratio in the range from 1:100 to 10:1.

Claims

1. A solid, liquid, or gel formulation comprising: (A) ammonium sulfite or ammonium bisulfite or alkali metal sulfite or alkali metal bisulfite, and (B) at least one graft copolymer formed from (a) at least one graft base selected from nonionic monosaccharides, disaccharides, oligosaccharides, and polysaccharides, and (b) side chains obtainable by grafting of (1) at least one ethylenically unsaturated mono- or dicarboxylic acid, and (2) at least one compound of the general formula (I), ##STR00009## where the variables are each defined as follows: R.sup.1 is chosen from methyl and hydrogen, A.sup.1 is chosen from C.sub.2-C.sub.4-alkylene, R.sup.2 are the same or different and chosen from C.sub.1-C.sub.4-alkyl, X.sup.− is chosen from halide, mono-C.sub.1-C.sub.4-alkylsulfate and sulfate, where (bi)sulfite (A) and graft copolymer (B) are present in a weight ratio in the range from 1:100 to 10:1.

2. The formulation according to claim 1, which is free of enzymes.

3. The formulation according to claim 1, which is free of phosphates and polyphosphates.

4. The formulation according to claim 1, wherein (bi)sulfite (A) is chosen from alkali metal sulfite and alkali metal bisulfite.

5. The formulation according to claim 1, wherein compound (2) is chosen from w-trimethylaminoethyl (meth)acrylatochloride.

6. The formulation according to claim 1, which further comprises at least one complexing agent (C) chosen from alkali metal salts of methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), and citric acid, and combinations of at least two of the above.

7. The formulation according to claim 1, further comprising at least one polymeric builder (F).

8. The formulation according to claim 1, which is in liquid or gel form at 20° C.

9. The formulation according to any claim 1, which comprises: a total in the range from 0.005% to 2% by weight of (bi)sulfite (A), and a total in the range from 0.05% to 4% by weight of graft copolymer (B), based in each case on the solids content of the formulation.

10. A method of using formulations according to claim 1, the method comprising using the formulations for washing of dishware and kitchen utensils.

11. A method of using formulations according to claim 1, the method comprising using the formulations for washing of articles having at least one glass surface that is decorated or undecorated.

12. The method according to claim 10, wherein the washing is a washing operation with a machine dishwasher.

13. A process for producing formulations according to claim 1, the method comprising mixing at least one (bi)sulfite (A) and at least one graft copolymer (B) and optionally one or more further ingredients (F) and optionally polymeric builders (F) with one another in one or more steps in the presence of water.

Description

EXAMPLES

I. Production of Formulations of the Invention and of Comparative Formulations

[0203] In the context of the present application, figures in % are percent by weight, unless explicitly stated otherwise.

[0204] Graft copolymer (B.1) corresponds to graft copolymer (B.4) from WO 2015/197379. It was pre-pared as follows:

[0205] Preparation of Graft Copolymer (B.1)

[0206] A stirred reactor was initially charged with 220 g of (c.1) in 618 g of water and heated to 80° C. while stirring. At 80° C., the following solutions were metered in simultaneously and via separate feeds as follows:

[0207] a) an aqueous solution of 40.6 g of (a.1) in 149 g of water, within 4 hours.

[0208] b) a solution of 9.85 g of sodium peroxodisulfate in 68.0 g of water within 5 h, commencing simultaneously with the metered addition of a).

[0209] c) a solution of 32.8 g of (b.1) and 36.5 g of sodium hydroxide solution (50% in water), diluted with 139 g of water, within 2 hours, commencing 2 hours after commencement of metered addition of a).

[0210] On completion of addition of solutions a) to c), the reaction mixture was stirred at 80° C. for one hour. Subsequently, a solution of 0.73 g of sodium peroxodisulfate in 10.0 g of water was added and the mixture was stirred at 80° C. for a further 2 hours. This was followed by cooling to 20° C. and addition of 8 g of biocide. This gave a 22.4% by weight solution of graft copolymer (B.1).

[0211] The biocide used was a 9% by weight solution of 1,2-benzisothiazolin-3-one in water-propylene glycol mixture, commercially available as Proxel™ XL2 Antimicrobial. Stated amounts for biocide are tel quel.

[0212] The liquid base detergent formulation below was produced, with the starting weights each based on the solids content.

TABLE-US-00001 TABLE 1 Base detergent formulation Substance Active ingredient or solids [g] Glycerol 50 (C.1) 150 (C.2) 50 (E.1) 50 HEDP, Na salt 10 Citric acid See below Graft copolymer (B.1) 2.5

[0213] 350 mL of demineralized water was first initially charged and then the substances according to table 1 were added while stirring.

[0214] (C.1): MGDA-Na.sub.3 as 40% aqueous solution

[0215] (C.2): trisodium citrate.2 H.sub.2O

[0216] (E.1): polyacrylic acid, M.sub.w 2000 g/mol, fully neutralized with NaOH

[0217] Subsequently, addition according to table 2 was added and the mixture was made up to one liter with demineralized water.

[0218] If required, sufficient citric acid was added here to establish a pH of 6, 7 or 8. Pale yellow detergent formulations were obtained.

[0219] The formulations thus obtainable were stored at +40° C. over a period of 10 weeks. Subsequently, the color was determined. Formulations without polymer (B.1) did show comparatively good color values, but showed unsatisfactory cleaning results.

TABLE-US-00002 TABLE 2 inventive formulations and comparative formulations, and storage tests Formulation (B.1) Addition pH Color after storage test C-F.1 — — 8 pale yellow C-F.2 1.0 — 8 yellow C-F.3 1.0 0.4% (D.1) 8 yellow F.4 1.0 0.4% (A.1) 8 pale yellow C-F.5 1.0 0.4% vitamin C 8 amber C-F.6 — — 7 pale yellow C-F.7 1.0 — 7 yellow C-F.8 1.0 0.4% (D.1) 7 yellow F.9 1.0 0.4% (A.1) 7 pale yellow C-F.10 1.0 0.4% vitamin C 7 dark red C-F.11 — — 6 yellow C-F.12 1.0 — 6 yellow C-F.13 1.0 0.4% (D.1) 6 yellow F.14 1.0 0.4% (A.1) 6 pale yellow C-F.15 1.0 0.4% vitamin C 6 dark red-brown (A.1): Na.sub.2SO.sub.3 (D.1): H.sub.2O.sub.2

[0220] Percentages are % by weight and relate to the solids content, i.e. without water and without glycerol.