CLEANING AGENTS INCLUDING ENZYME

Abstract

Cleaning agents, such as dishwasher detergents, in particular dishwashing machine detergents, may include at least one gel-like phase having a low content of water, such as a substantially anhydrous gel-like phase having at least one enzyme, such as at least one enzyme granulate.

Claims

1. A cleaning agent comprising: at least one gel phase comprising at least one enzyme therein.

2. The cleaning agent according to claim 1, wherein the proportion by weight of the at least one enzyme, based on the amount of active enzyme protein, in the at least one gel phase, based on the total weight of the at least one gel phase ranges from 0.0005 to 20.0 wt. %.

3. The cleaning agent according to claim 1, wherein the at least one enzyme is selected from the group of proteases amylases, or both.

4. The cleaning agent according to claim 1, wherein the at least one enzyme comprises at least one protease; wherein the at least one protease comprises: a) an amino acid sequence having at least 70% sequence identity with the amino acid sequence given in SEQ ID NO:1 over its entire length and has an amino acid substitution at at least one of the positions corresponding to positions 212, 12, 43, 122, 127, 154, 156, 160, 211, or 222, each based on the numbering according to SEQ ID NO: 1; b) an amino acid sequence which is at least 80% identical to the amino acid sequence specified in SEQ ID NO:2 over the entire length thereof and has at least one amino acid substitution at one positions 9, 15, 66, 212, and 239 in the numbering according to SEQ ID NO: 2; c) an amino acid sequence which is at least 80% identical to the amino acid sequence specified in SEQ ID NO:2 over the entire length thereof and has an amino acid substitution at position 97 and an insertion of an amino acid between the amino acids at positions 97 and 98 in the numbering according to SEQ ID NO:2; d) an amino acid sequence which is at least 80% identical to the amino acid sequence specified in SEQ ID NO:3 over the entire length thereof and has at least one amino acid substitution at one of the following positions 32, 33, 48-54, 58-62, 94-107, 116, 123-133, 150, 152-156, 158-161, 164, 169, 175-186, 197, 198, and 203-216 in the numbering according to SEQ ID NO:3; e) an amino acid sequence having an amino acid sequence which is at least 80% identical to the amino acid sequence specified in SEQ ID NO:4 over the entire length thereof and has at least one amino acid substitution at one or more of the following positions 3, 4, 99, and 199 in the numbering according to SEQ ID NO:4; f) and combinations thereof.

5. The cleaning agent according to claim 3, wherein the proportion by weight of the at least one protease, based on the amount of active enzyme protein of the at least one proteases with respect to the total weight of the cleaning agent, ranges from 0.005 to 5 wt. %.

6. The cleaning agent according to claim 3, wherein the proportion by weight of the at least one protease, based on the amount of active enzyme protein in the at least one gel phase based on the total weight of the at least one gel phase is ranges from 0.0005 to 20.0 wt. %.

7. The cleaning agent according to claim 3, wherein the amount of the at least one protease, based on the amount of active enzyme protein added per wash cycle ranges from 0.001 to 1,000 mg/job.

8. The cleaning agent according to claim 1, wherein the at least one enzyme comprises one or more alpha-amylases; selected from the group consisting of a) an α-amylase having an amino acid sequence which is at least 80% identical to the amino acid sequence specified in SEQ ID NO:5 over the entire length thereof and has at least one amino acid substitution at one of the positions 172, 202, 208, 255, and 261 in the numbering according to SEQ ID NO:5; b) an α-amylase having an amino acid sequence which is at least 60% identical to the amino acid sequence specified in SEQ ID NO:6 over the entire length thereof and has at least one amino acid substitution at one of the positions 9, 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 195, 202, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 320, 323, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 458, 461, 471, 482, and 484 and/or a deletion at one of the positions 183 and 184 in the numbering according to SEQ ID NO:6; c) an α-amylase having an amino acid sequence which is at least 90% identical to the amino acid sequence specified in SEQ ID NO:7 over the entire length thereof and has at least one substitution and/or deletion at one of the positions 93, 116, 118, 129, 133, 134, 140, 142, 146, 147, 149, 151, 152, 169, 174, 183, 184, 186, 189, 193, 195, 197, 198, 200, 203, 206, 210, 212, 213, 235, 243, 244, 260, 262, 284, 303, 304, 320, 338, 347, 359, 418, 431, 434, 439, 447, 458, 469, 476, and 477 in the numbering according to SEQ ID NO:7; d) and combinations thereof.

9. The cleaning agent according to claim 1, further comprising a gelling agent, amount ranging from 4 to 40 wt. %, in each case based on the total weight of the gel phase.

10. The cleaning agent according to claim 1, wherein the at least one gel phase further comprises at least one organic solvent selected from the group consisting of 1,2-propanediol, 1,3-propanediol, glycerol, 1,1,1-trimethylolpropane, triethylene glycol, dipropylene glycol, polyethylene glycols, and/or mixtures thereof.

11. The cleaning agent according to claim 10, wherein the at least one organic solvent is present in the at least one gel phase in an amount ranging from 30 to 90 wt. %, based on the total weight of the at least one gel phase.

12. The cleaning agent according to claim 1, wherein the gel phase further comprises a sulfonic acid group-containing monomer.

13. The cleaning agent according to claim 1, further comprising at least one solid phase.

14. A packaging comprising a water-soluble wrapping having one or more chambers/compartments comprising the cleaning agent according to claim 1.

15. The cleaning agent according to claim 13, wherein the at least one gel phase is contained in direct contact; with the at least one solid phase.

16. (canceled)

Description

EMBODIMENTS

[0268] Cleaning agents were prepared that comprise a solid phase and a gel phase. Different geometries were produced in the process. In addition, cleaning agents were prepared that comprise two solid phases and a gel phase. Cleaning agents were also prepared that comprise a solid phase and three, four and five gel phases (having the same or different composition). The following quantities refer to wt. % of active substance based on the total weight of the relevant phase (unless indicated otherwise).

TABLE-US-00001 TABLE 1 The solid granular mixtures of a solid composition, in particular powdery and free-flowing phases, had the following preferred composition: wt. % Citrate, Na salt 15-20 Phosphonate (esp. HEDP) If permitted by regulation 0-7.5 (2.5-7.5) MGDA, Na salt  0-25 Disilicate, Na salt  5-35 Soda 10-25 Silver protection (especially cysteine) 0.0-1.0 Percarbonate, Na salt 10-15 Bleach catalyst (preferably Mn-based) 0.02-0.5  Bleach activator (esp. TAED) 1-3 Non-ionic surfactant(s), e.g., fatty alcohol alkoxylate, 2.5-10  preferably 20-40 EO, optionally end-capped Polycarboxylate  4-10 Cationic copolymer   0-0.75 Disintegrant - (esp. Crosslinked PVP) .sup. 0-1.5 Protease preparation (tq) 0-5 Amylase preparation (tq) 0-3 Perfume 0.05-0.25 Dye solution 0.0-1.sup.  Zn salt (e.g. acetate) 0.1-0.3 Sodium sulfate 0.0-10  Water 0.0-1.5 pH adjuster (e.g., citric acid) .sup. 0-1.5 Processing aids 0-5

TABLE-US-00002 TABLE 2 The gel phases used had the following compositions (quantities in each case based on the total amount of the gel phase): wt. % Enzyme granulate (protease), based on active protein 0.01-7.5  content Enzyme granulate (amylase), based on active protein  0-5.0 content Water-soluble zinc salt (preferably zinc acetate anhydrate) 0.1-2.4  Glycerol 10-50  Propanediol (preferably 1,3-propanediol) 10-50  Polycarboxylate copolymer having sulfonic acid-containing 0-30 groups, preferably Acusol ® 588 or Acusol ® 590 Non-ionic surfactant(s), e.g., fatty alcohol alkoxylate, 0-40 preferably 20-40 EO, optionally end-capped Polyethylene glycol avg. molar mass 200-600 (for example 8-26 PEG 400 (INCI)) PVOH 8-22 Processing aids 0-10 Dye solution 0.0-1.5  Misc., other active substances, organic solvents, perfume, To make up to 100

[0269] The solid and gel phases could be combined as desired. The spatial configuration of the gel phase, which was liquid after mixing of the ingredients and dimensionally stable within a setting time of a maximum of 10 minutes, was predetermined by the spatial configuration of the solid phase and by molds that are commercially available or self-designed. A water-soluble wrapping in the form of an open pouch was produced by thermoforming a PVOH-containing film. A liquid composition was poured into said open cavity and resulted in the gel phase after curing, then solid phases in the form of a free-flowing solid were poured into a pouch comprising polyvinyl alcohol, and the open pouch was then sealed by applying a second film and sealing by heat sealing.

TABLE-US-00003 TABLE 3 Compositions of the gel phase in wt. % G1 G2 G3 G4 G5 G6 Water-free zinc acetate 0.5 0.5 1.0 1.0 2.0 2.0 Polymer comprising acrylic acid- 11 0 0 11 11 0 containing and amidopropyl sulfonic acid-containing monomers, Acusol ® 588 Polymer comprising acrylic acid- 0 11 11 0 0 11 containing and amidopropyl sulfonic acid-containing monomers, Acusol ® 590 Glycerol 25 25 25 25 25 25 1,3-propanediol 30 30 30 30 30 30 PEG 400 15 15 15 15 15 15 PVOH (Mowiol 4-88) 15 15 15 15 15 15 Misc. (including processing To To To To To To aids, pH make make make make make make adjuster, perfume, dye) up to up to up to up to up to up to 100 100 100 100 100 100

[0270] Corresponding formulations have been prepared according to table 3. The gel phases were stirred at temperatures of 110° C. Shortly before dosing the gel phases, protease granulates 1 or 2 were dosed into the still-hot compositions.

[0271] The corresponding gel phases (1.5 g) were then packaged as described under Table 2 together with a solid phase according to Table 4 (17.0 g) in single portions (pouches) with a total weight of 18.5 g.

TABLE-US-00004 TABLE 4 Composition of the gel phase: wt. % of active substance Citrate, Na salt 35 Soda 25 Percarbonate, Na salt 10 Bleach catalyst (Mn-TACN) 0.05 Bleach activator (TAED) 1 Non-ionic surfactants 2.5 Polycarboxylate, (Acusol ® 588) 5 Amylase preparation (tq) 1.5 Sodium sulfate, dye, perfume To make up to 100

[0272] Cleaning Performance:

[0273] Using the single portions prepared in this way (gel phase G1, solid phase, Table 4), the cleaning performance of the compositions was determined according to the IKW method in a Miele GSL, Eco 45° program, at 21° dH.

TABLE-US-00005 TABLE 5 Creme Egg Cleaning performance brûlée yolk Spaghetti E1 G1 + protease granulate 1 (30 mg/job) 7.2 4.7 3.5 E2 G1 + protease granulate 2 (30 mg/job) 8.4 8.0 4.5

[0274] Both protease granulates each contain 30 mg of active protein/job (corresponding to the active enzyme protein content per single portion, suitable for a cleaning application).

[0275] The protease granulate 1 contains a combination of protease 1a (protease according to SEQ ID NO:6 from WO2016000973) and protease 1b (Ovozyme®, ex Novozymes) in a ratio of 1.5:1.

[0276] The protease granulate 2 contains a protease according to SEQ ID NO:5 from WO2017215925.

[0277] Surprisingly, it was found that the proteases were able to withstand the remaining high temperatures of the gel preparation before it solidified (>90° C.). Furthermore, it was surprisingly found that when protease granulate 2 is used, in addition to a particularly good cleaning performance on protein-containing stains, an effect on the starch-based stain spaghetti can also be observed.

[0278] In a corresponding further experiment with the same parameters, only lower amounts of protease were used in the gel phase (see Table 6):

TABLE-US-00006 TABLE 6 Burnt-on Cleaning performance minced meat Egg yolk E3 G1 + protease granulate 1 (15 mg/job) 4.2 3.2 E4 G1 + protease granulate 2 (15 mg/job) 6.9 5.6

[0279] Both protease granules each contain 15 mg of active protein/job (corresponding to the content of active enzyme protein per single serving, suitable for a cleaning application).

[0280] The protease granulate 1 contains a combination of protease 1a (protease according to SEQ ID NO:6 from WO2016000973) and protease 1b (Ovozyme®, ex Novozymes) in a 1:1 ratio.

[0281] The protease granulate 2 contains a protease according to SEQ ID NO:5 from WO2017215925.

[0282] Here, too, it was surprisingly found that both proteases gave good results on protease-sensitive stains, in particular when using protease granulate 2, particularly good cleaning performance can be observed, in particular on egg yolk and burnt-on minced meat.