EP3342846B1 - Selbstlösliche capsule zur vorbereitung von waschlösungen - Google Patents
Selbstlösliche capsule zur vorbereitung von waschlösungen Download PDFInfo
- Publication number
- EP3342846B1 EP3342846B1 EP16207662.4A EP16207662A EP3342846B1 EP 3342846 B1 EP3342846 B1 EP 3342846B1 EP 16207662 A EP16207662 A EP 16207662A EP 3342846 B1 EP3342846 B1 EP 3342846B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- washing
- sodium
- capsule
- chosen
- following
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000005406 washing Methods 0.000 title claims description 120
- 239000002775 capsule Substances 0.000 title claims description 99
- 238000002360 preparation method Methods 0.000 title claims description 5
- 239000006041 probiotic Substances 0.000 claims description 74
- 235000018291 probiotics Nutrition 0.000 claims description 74
- 230000000529 probiotic effect Effects 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 241000894006 Bacteria Species 0.000 claims description 37
- 244000005700 microbiome Species 0.000 claims description 35
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 22
- 239000003205 fragrance Substances 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 18
- 229920002125 Sokalan® Polymers 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 241000193749 Bacillus coagulans Species 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 159000000000 sodium salts Chemical class 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 239000002736 nonionic surfactant Substances 0.000 claims description 14
- -1 C8 alkyl glucoside Chemical class 0.000 claims description 13
- 102000004190 Enzymes Human genes 0.000 claims description 13
- 108090000790 Enzymes Proteins 0.000 claims description 13
- 239000003945 anionic surfactant Substances 0.000 claims description 13
- 229940088598 enzyme Drugs 0.000 claims description 13
- 239000003755 preservative agent Substances 0.000 claims description 13
- 230000002335 preservative effect Effects 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000004014 plasticizer Substances 0.000 claims description 12
- 229920005646 polycarboxylate Polymers 0.000 claims description 12
- 235000011187 glycerol Nutrition 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 229940054340 bacillus coagulans Drugs 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 239000013538 functional additive Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 9
- 229940071160 cocoate Drugs 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229930182478 glucoside Natural products 0.000 claims description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 6
- 229920001202 Inulin Polymers 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 6
- 229940029339 inulin Drugs 0.000 claims description 6
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000600 sorbitol Substances 0.000 claims description 6
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 claims description 6
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 claims description 5
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 5
- 235000013922 glutamic acid Nutrition 0.000 claims description 5
- 239000004220 glutamic acid Substances 0.000 claims description 5
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 claims description 5
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- 108091005804 Peptidases Proteins 0.000 claims description 4
- 239000004365 Protease Substances 0.000 claims description 4
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 4
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- KLMGMPDXSPSCOC-UHFFFAOYSA-N 2-undecoxyethanol Chemical compound CCCCCCCCCCCOCCO KLMGMPDXSPSCOC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004382 Amylase Substances 0.000 claims description 3
- 102000013142 Amylases Human genes 0.000 claims description 3
- 108010065511 Amylases Proteins 0.000 claims description 3
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- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 235000019418 amylase Nutrition 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
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- 229920001577 copolymer Polymers 0.000 claims description 3
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- 229940057402 undecyl alcohol Drugs 0.000 claims description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 2
- CRWPSVYQTNMIPY-UHFFFAOYSA-N 1-octanoylpyrrolidin-2-one Chemical compound CCCCCCCC(=O)N1CCCC1=O CRWPSVYQTNMIPY-UHFFFAOYSA-N 0.000 claims description 2
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 claims description 2
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- 241001249119 Bacillus vallismortis Species 0.000 claims description 2
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- JDRSMPFHFNXQRB-CMTNHCDUSA-N Decyl beta-D-threo-hexopyranoside Chemical compound CCCCCCCCCCO[C@@H]1O[C@H](CO)C(O)[C@H](O)C1O JDRSMPFHFNXQRB-CMTNHCDUSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
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- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 claims description 2
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 claims description 2
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- OAGFCEDIUISLRL-UHFFFAOYSA-L disodium;3-[2-carboxylatoethyl(2-ethylhexyl)amino]propanoate Chemical compound [Na+].[Na+].CCCCC(CC)CN(CCC([O-])=O)CCC([O-])=O OAGFCEDIUISLRL-UHFFFAOYSA-L 0.000 claims description 2
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- RVRONQZKSCNZRS-UHFFFAOYSA-M potassium;4-propan-2-ylbenzenesulfonate Chemical compound [K+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 RVRONQZKSCNZRS-UHFFFAOYSA-M 0.000 claims description 2
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- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 claims description 2
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- WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/045—Multi-compartment
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/381—Microorganisms
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Definitions
- the invention relates to a self-dissolving capsule for preparation of washing solutions, containing chemical materials and probiotic microorganisms.
- Structure - the capsule is comprised of two or more cavities, wherein one of them is filled with a tablet composed partially of microorganisms.
- Known household chemistry formulations appearing on the market in form of capsules enclosed in self-dissolving films, and formulations containing microorganisms are mono- and multi-cavity self-dissolving capsules in liquid/liquid, liquid/powder, powder/liquid phase, used for laundry washing, dishwashing, cleaning of hard surfaces such as floors or windows (to a small extent). They contain concentrated, active chemical substances.
- the formulations containing microorganisms are products in bottles with an atomizer (trigger) containing nonionic surfactants of natural origin, soaps of natural origin and probiotic strains. These formulations are usually very expensive and directed towards environmentally-friendly households, mainly for cleaning of hard surfaces.
- the object of the invention is improving the available cleaning agents by providing formulations preventing harmful changes in composition of the microbial flora resulting from using aggressive detergents as cleaning agents that firstly cause sterilisation of cleaned surfaces and appliances, which later leads to uncontrolled colonisation of such ecological niches by undesirable microorganisms. This often leads to arising of hard to remove, unpleasant odours (biofilms), e.g. in spaces of washing or laundry washing devices.
- Another technological problem directly involving the invention is providing a cleaning agent of this type in a form fit to apply in currently used washing and laundry washing appliances, especially in dishwashers and automatic washing machines, which are usually configured to use a cleaning agent in a form having a particular tablet shape or self-dissolving capsule containing a cleaning agent.
- self-dissolving capsules they are currently manufactured, generally, with a film dissolving in water, containing polyvinyl alcohol (PVOH), and the cleaning agent contained within is usually in liquid form.
- PVOH film is known to people skilled in the art, e.g. from the application WO2014110356 .
- the liquid part and eventual tablet part of the capsule should be compatible with the self-dissolving PVOH film.
- the cleaning agent formula should be stable (not subjected to physicochemical changes), and the product should be effective at the same time.
- the invention relates to a self-dissolving capsule for preparation of washing solutions, characterised in that it contains washing agents and probiotic microorganisms, wherein the capsule consists of two separate, sealed cavities, the first of which contains the washing agent, whereas the second one contains a lyophilised or concentrated liquid formulation of the probiotic microorganisms, wherein the washing agent is a composition containing the following components: a nonionic surfactant, a polycarboxylate, an anionic surfactant, a complexing agent aiding the washing process and providing gloss, a plasticiser, a phosphonate, a hydrolytic enzyme, a preservative, a fragrance, a functional additive, and water, and wherein the probiotic microorganism is Bacillus species probiotic bacteria, forming spores and displaying growth in temperature up to 65°C.
- the capsule contains probiotic bacteria chosen from the following: Bacillus subtilis, Bacillus pumilus, Bacillus vallismortis, Bacillus coagulans, Bacillus lactis, and Bacillus mojavensis, preferably spores of Bacillus coagulans PCM 1843 strain.
- probiotic bacteria chosen from the following: Bacillus subtilis, Bacillus pumilus, Bacillus vallismortis, Bacillus coagulans, Bacillus lactis, and Bacillus mojavensis, preferably spores of Bacillus coagulans PCM 1843 strain.
- the washing agent contained in the capsule contains the following: a nonionic surfactant in amount of 5 to 30 wt%, a polycarboxylate in amount below 7 wt%, an anionic surfactant in amount of 0 up to 35 wt%, a complexing agent in amount of 50 to 75 wt%, a plasticiser in amount below 20 wt%, a phosphonate in amount below 3 wt%, a hydrolytic enzyme in amount below 1 wt%, a preservative in amount below 1 wt%, a fragrance in amount below 1 wt%, a functional additive in amount below 1 wt%, and water in amount below 4 wt%.
- a nonionic surfactant in amount of 5 to 30 wt%
- a polycarboxylate in amount below 7 wt%
- an anionic surfactant in amount of 0 up to 35 wt%
- a complexing agent in amount of 50 to 75 wt%
- a plasticiser in
- the nonionic surfactant is chosen from the group containing the following: C12-C14 ethoxylated alcohols, C8 alkyl glucoside, capryl decyl glucoside, alkyldimethylamine oxide solution, sorbitan sesquioctanoate, alkoxylated fatty alcohol, 2-propylheptanol ethoxilate, 2-ethylhexyl glucoside, alcohol alkoxylate, C8/10 methyl ester, preferably chosen from the group containing: C12-C14 ethoxylated alcohols and C8 alkyl glucoside.
- the anionic surfactant is chosen from the group containing the following: sodium p-cumenesulphonate; potassium 4-isopropylbenzenesulphonate; sodium 2-ethylhexyliminodipropionate; sodium cocopropylenediamine propionate; decyl phosphoric acid; potassium salt, sodium alkyl sulphate; sodium 2-ethylhexyl sulphate; C12-C14 ethoxylated alcohols, sulphates, sodium salts; MEA cocoate; TEA cocoate, preferably chosen from the group consisting of: C12-C14 ethoxylated alcohols, sulphates, sodium salts; MEA cocoate; TEA cocoate.
- the complexing agent is chosen from the group containing the following: sodium carboxymethyl inulin; tetrasodium EDTA; N,N-bis(carboxymethyl)alanine trisodium salt; glutamic acid, N,N-diacetic acid tetrasodium salt; sodium citrate, preferably chosen from the group containing: sodium carboxymethyl inulin; glutamic acid, N,N-diacetic acid tetrasodium salt.
- the polycarboxylate is chosen from the group containing the following: aqueous solution of partially neutralised polycarboxylic acid; aqueous solution of a polyacrylic acid sodium salt; preferably is an aqueous solution of partially neutralised polycarboxylic acid.
- the functional additive is chosen from the group containing the following: vinylpyrrolidone/vinylimidazole copolymer; sodium metasilicate; acylamide carboxylic acid, alkanolamine salt; Fluorescent Brightener 28; Undeceth-5, undecyl alcohol, sodium lauryl sulphate, caprylyl pyrrolidone.
- the plasticiser is chosen from the group containing the following: glycerine, propylene glycol, and sorbitol.
- the phosphonate is chosen from the group containing the following: proprietary mixture of organophosphonic acid, sodium salts; aqueous solution of aminophosphonic acid salt.
- the preservative is chosen from the group containing the following: 2-bromo-2-nitropropane-1,3-diol, methylchloroisothiazolinone, methylisothiazolinone; methylisothiazolinone, benzisothiazolinone.
- the hydrolytic enzyme is chosen from the group containing the following: protease, lipase, amylase, and cellulase.
- the invention relates also to a method for cleaning soiled surfaces, characterised in that the soiled surface is washed with an aqueous solution obtained by dissolving the self-dissolving capsule as defined above in 2 to 10 litres volume of water, wherein, after finishing the washing process, the cleaned surface is left to dry.
- a substance from the following table is chosen as a dye, wherein the particularly preferred substances are underlined.
- Dye name Dysol Turquoise AXN50 Liquid Brilliant Blue E133 Violet 656271 Dysol Red 4B Rhodamine conc.
- a commercially available substance from the following table is chosen as a fragrance, wherein the particularly preferred substances are underlined.
- the invention relates to a self-dissolving capsule for cleaning soiled hard surfaces characterised in that, the soiled surface is washed with an aqueous solution obtained by diluting the capsule of the present invention, defined above, in 2 to 10 litres of water, wherein the cleaned surface is left to dry, after the washing process.
- microorganisms enable isolating the components acting antagonistically in separate cavities, and thus maintaining their high activity and effectiveness.
- the product protects the microorganisms from the influence of concentrated materials during the step of enclosing inside the capsule and under practical conditions (administration routes of biocomponents).
- Product according to the invention contains a tablet, which allows obtaining a maximal concentration of substances contained therein.
- microorganisms' technology enables introducing microorganisms along with chemical substances in a single washing bath, also in automatic washing systems (dishwashers, washing machines), by which they aid the cleaning cycle, and by colonisation of outlets and surfaces of the device, they promote the hygiene maintenance.
- the natural microbial enzymes carry out decomposition of organic substances, which provides a possibility of decreasing the amount of chemical substances in the cleaning agents - environmental aspect.
- microorganisms aid the cleaning processes by extending the washing cycle.
- colonisation of the washing surface the 'good microbes' compete with pathogenic microorganisms present on the washing surface, driving them out and ultimately improving the microflora of the cleaning surface.
- capsules according to the invention have a corresponding level to that of available traditional products. Their advantage is performing a microbiological cleaning process. In comparison to products not containing microorganisms, in case of capsules according to the invention, a biofilm reduction and improvement of bacterial flora by eliminating pathogenic microorganisms are observed. Applying the capsule with probiotic on hard surfaces reduced survival of potentially pathogenic Gram+ bacteria including Staphylococcus aureus and Enterococcus faecalis.
- Capsules according to the invention induce a change in the flora in direction of eliminating pathogenic microbes.
- a multi-cavity capsule of self-dissolving film was formed, in liquid/liquid liquid/tablet (12 mm dimeter) phase according to the following criteria: capsule size 30 mm ⁇ 40 mm or approximate, total tablet mass not exceeding 24 g.
- a multi-cavity capsule of self-dissolving film was formed, in liquid/liquid liquid/tablet (16 mm dimeter or approximate) phase according to the following criteria: capsule size 30 mm ⁇ 40 mm or approximate, total tablet mass shout not exceed 24 g.
- Introducing the tablet also provides a possibility of higher concentration of the compounds, introducing peroxide substances into the formula, mutual separation of peroxide compound and probiotics, which are negatively affected by them, and possible introduction of probiotics in pressed form into the product.
- Single-cavity capsule the formula basis and biocomponents are encapsulated in the same cavity.
- the components and the basis are applied jointly from a single cavity. There is no possibility of enclosing the water suspension of biocomponents available on the market in a self-dissolving film - dissolving of the film occurs.
- probiotic in powder form should be enclosed in a self-dissolving film.
- Multi-cavity capsule (liquid/liquid)
- a multi-cavity liquid/12 mm diameter tablet capsule allows using an about 2 g tablet and obtaining a liquid part volume of about 12 ml in the first, and 17 ml in the second case.
- the total mass of the capsule with a cavity of 12 ml volume is 16 g, and of the capsule with 17 ml cavity is 21 g.
- Both sachet types fit into the dishwasher detergent cup.
- the tablet position inside the capsule is suitable for its shape.
- the tablet placement in subsequent samples in relation to the liquid cavity is constant.
- the film is sealed.
- the mass in relation to the assumed capsule size in both cases is below 24 g.
- the capsule with a cavity of 17 ml volume looks 'bulgy', the capsule does not touch the table with the whole surface. Folds are forming around the tablet - further development on flattening them is required.
- the cavity having 12 ml volume for the liquid and 12 mm for the tablet has been assessed as too small to contain the proper biocomponent dose.
- Liquid/tablet (16 mm) capsule Increasing the tablet diameter allows obtaining a more stable tablet while cutting the heat-seal. A smaller cavity required for the tablet/liquid is less cone-like, which positively affects the stage of enclosing the tablet/liquid in a film. The amount of active substance that can be contained in a capsule of this form was increased to 3 g and corresponds to the recommended dose.
- Figures 3-5 illustrate different views of the capsule according to the invention, having a coating made of PVOH
- the capsule is filled with an aqueous solution containing: nonionic surfactants, polycarboxylates, anionic surfactants, phosphonates, enzymes, a preservative, a fragrance composition and microorganisms (preferably about 1 wt%).
- Microorganisms are contained in the tablet portion.
- the capsule is made of a PVOH self-dissolving film.
- the method of administering the microorganisms in dry form ensures their stability in the system.
- Microorganisms contained in the tablet in form of spores are activated by contact with water.
- the capsule manufacture process proceeds in two steps.
- the first step is preparing the tablet. This stage involves the process of ingredient mixing, and next pressing on the device to a tablet form.
- the pressing step is carried out under pressure, which ensures intactness of cell wall structures.
- the second step involves a process of forming the capsule, in which the dosing step of the liquid part and tablet incorporation is achieved at the same time.
- the process is carried out under strictly controlled conditions of about 23°C and 45% humidity. Performed tests of film stability confirm the stability of its structure, and therefore the stability of the capsule under these formulating conditions.
- the capsule can be applied in appliances for dishwashing, laundry washing, and, after diluting, also for cleaning other hard surfaces.
- the tablet contained in the capsule displayed a change of parameters - bulging (about 1 mm height change, which consequently results in tearing of the film.
- the liquid part penetrates into the tablet part, which consequently leads to exposure of the microorganisms on aggressive chemical substances and their elimination.
- a dishwasher capsule with an addition of a peroxide substance (comparative example):
- the peroxide substances are desired in the formula systems due to the fact that they enhance their effectiveness and efficiency.
- the tests employed sodium percabonate.
- peroxide substances are highly hygroscopic.
- One of the stages of forming the capsule involves binding (gluing) the upper and lower self-dissolving film by spraying it with water.
- the tablet with an addition of a peroxide compound displayed a strong bulging effect and was tearing the film.
- Product was not stable in time. The negative effect was observed already 2 weeks after the product manufacture.
- washing agent formulas capsules for the preparation of washing solutions not containing the probiotic microorganisms and the washing agents listed in claim 1 are not according to the current invention
- Glycerine 15-30 Stabilizes the bacteria / utilized as carbon and energy source 4.
- Dodecylbenzene sulfonic acid 15-30 Highly bactericidal 5.
- Water ⁇ 15 In low concentration (9%) increases the effectiveness of bactericidal components 6.
- Example 4 Influence of physicochemical parameters, changing environment and washing agent formula components on biocomponent activity in changing environments
- Tests of pH influence on microbial survival in the probiotic were performed.
- the maximum survival temperature of microbes isolated from the probiotic was determined - the maximum temperature growth for probiotics was 58°C, as well as the thermal death time of the probiotics in temperature of 100°C.
- test of probiotics' survival in different washing agent formulas were performed. It has been determined that washing mixture components in high concentrations totally inhibit probiotic growth, displaying very high bactericidal properties towards them.
- the tests demonstrated a possibility of survival, especially in spore form, of chosen Bacillus sp. bacteria constituting the probiotic during washing process using the washing agent diluted to the working concentration. For this reason, in the finished product, microbes should be contained in a separate cavity.
- Table 1 A summary report of thermostability, pH influence and microbial survivability tests in concentrated washing agents (so called formulas) and washing baths in working dilutions. No. Tested strain pH Temperature Survivability in the formula Survivability in the washing bath 1
- Commercial liquid probiotic Badlox R XL100x Ospray Biotechnics Inc. (mixture of Bacillus sp. probiotic strains) Bacteria incubated in a growth medium, as well as in the tap water, are resistant to a wide range of pH, at least 4-10. Bacteria are highly thermostable, exhibiting cell division up to the temperature of 58°C.
- Lactococcus lactis strain- live bacteria Polish Collection of Microorganisms access number PCM 476
- the bacterial strain exhibits good survivability in pH 5, 7, and 8, in temperatures of 30, 40, and 50°C. In temperature of 60°C, a satisfactory survivability was recorded only in pH 8. Higher temperatures act bactericidally on tested bacteria. Test were not performed - bacteria strains died out already in diluted solutions. The washing gel exhibits a highly bactericidal effect on tested bacteria strains. No satisfactory survivability of bacterial cells was observed in any tested conditions (pH and temperature) in the presence of washing gel.
- Bacillus coagulans - spores Polish Collection of Microorganisms access number PCM 1843 Bacillus coagulans spores are characterised by a good survivability in tested washing and cleaning formulas, in tested pH and temperature range. Not performed Tested temperature did not exhibit an inhibiting effect on spore count, except for the temperature of 100°C. However, even after incubation in temperature of 100°C, bacterial spores capable of growing were found.
- 1:10 was arbitrarily chosen as maximal possible probiotic dilution in the tested medium, which equals a 10% content of the microbial medium in the tested formula (10+90).
- two approaches were applied in order to verify the survivability of the microbes in this environment in comparison with the double control: a 1:10 dilution of probiotic in the growth medium and an inoculation immediately after mixing with the tested medium (washing liquid or laundry washing liquid). The inoculations were performed at time: 0, 1 h, 2 h, 3 h, 6 h, 20 h, accordingly.
- the obtained results were verified in a subsequent experiment in liquid growth media.
- the tested samples were inoculated in liquid growth media by means of an inoculation loop, thus transporting about 10 microlitres of the tested sample into 5 ml of the growth medium (1:500 dilution). This approach would enable catching even individual microbial cells surviving in the laundry washing/washing liquid formula or their spores, and effective growth under optimal conditions, which would by demonstrated by turbidity of the liquid growth medium.
- the culture samples in the liquid growth medium were also analysed by a spectrophotometric method (absorbance change for 600 nm light wavelength). Obtained results confirmed lack of bacterial growth.
- the concentrated laundry washing liquid and washing liquid fully eliminate the microbial growth, displaying very high bactericidal properties.
- Probiotic survivability (pos. 1 and 2) in dilutions used in the washing process.
- the mixture was incubated at time: 0 (inoculation immediately after mixing), 1 h, 2 h, 3 h, 6 h, 24 h. Each time after the incubation time in the tested medium has elapsed, microbiological inoculations on a plate (0.1 ml), on optimal growth media were performed, and incubated at optimal temperature.
- the tests employed cell suspension of chosen bacteria having a cell count of an order of 10 6 cells/ml.
- An appropriate volume of the suspension was taken and transported to a laundry washing bath with a given pH, prepared beforehand.
- the final cell count in the bath was 10 4 cells/ml.
- the bath along with the cells were placed in a defined temperature for 30 minutes. After this time, 1 ml of the suspension was taken and a pour plate prepared, using an earlier developed, best growing mixture as a growth medium.
- Table 2 Lactococcus lactis bacteria cell count after 30 minutes incubation in the laundry washing bath under the tested conditions.
- the tests were performed under the so called dirty conditions, that is with an addition of 3 g of lecithin for 1 litre of the mixture (the added lecithin simulates the organic matter load, similarly to the organic contaminations).
- the originally prepared suspension contained 1.5 ⁇ 10 7 of bacterial spores. Subsamples were taken from this suspension, and introduced to the reaction mixtures (washing and laundry washing formulas with various pH values).
- the final spore count in the laundry washing formula was of order 10 5 , whereas in the washing formula it was 10 6 .
- washing tests were performed.
- Tested dilutions of the laundry washing liquid and the washing liquid enable bacterial survivability. 167/2016 Probiotic in a tablet milk - 93.02% yolk - 79.14% plates/cereal - 92.49% The probiotics inhabit sides and hard to read areas of the appliances. Tested dilutions of the laundry washing liquid and the washing liquid enable bacterial survivability.
- the capsule is filled with a mixture containing the following: nonionic surfactants, polycarboxylates, anionic surfactants, complexing compounds, plasticisers, phosphonates, enzymes, a preservative, a fragrance composition, functional additives, water, and microorganisms (preferably about 1 wt%).
- a mixture containing the following: nonionic surfactants, polycarboxylates, anionic surfactants, complexing compounds, plasticisers, phosphonates, enzymes, a preservative, a fragrance composition, functional additives, water, and microorganisms (preferably about 1 wt%).
- nonionic surfactants chosen in the first step of the formula development have not led to obtaining stable systems, they had low effectiveness in the washing process. Attempts to additionally introduce anionic surfactants into the formula also did not yield good results.
- the obtained formulation were characterised by excessively high foam, which is not recommended for automatic washing systems.
- a compound for wetting the surface was sought that would maintain compatibility with the other elements of the formula.
- a difficulty in developing a stable formulation of the liquid part of the capsule was posed by its compatibility with the self-dissolving PVOH (polyvinyl alcohol) film, having a natural, desired capability of dissolving in water.
- PVOH polyvinyl alcohol
- the research led to reduction of the water content introduced directly to the formula from 7% to below 4%.
- a method of reducing the water content in the formula in a form contained in the materials was investigated, by means of replacing them with materials having a higher concentration or introducing thickeners and complexing compounds that bond water.
- plasticisers As part of the development; the next group of compounds found, having influence on the film structure, were plasticisers. Their amount in the final formulas, in comparison with the starting formulas, was lowered by about 50% and was on a level ⁇ 20%. The starting, high content of plasticisers originated from their additional function as a solvent, which allowed introducing of thickeners into the formulas. Analysing the water content and the plasticisers' share in the formulation was an essential element for capsules functionality of keeping and maintaining its shape and proper properties during the whole shelf life. Decision not to use the glucose-fructose syrup, as well as reduction of glycerine and propylene glycol content in the formula, resulted in an improvement of elasticity and reduction of plasticity of the capsule surface.
- Formulation numbers 43, 46, 51, 77, 128, 146 and 160 are comparative examples, not according to the current invention.
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Claims (13)
- Sich selbst auflösende Kapsel zur Herstellung von Waschlösungen, dadurch gekennzeichnet, dass sie Waschmittel und probiotische Mikroorganismen enthält, wobei die Kapsel aus zwei getrennten, versiegelten Hohlräumen besteht, von denen der erste das Waschmittel enthält, während das zweite eine lyophilisierte oder konzentrierte flüssige Zubereitung der probiotischen Mikroorganismen enthält,
wobei das Waschmittel eine Zusammensetzung ist, die die folgenden Komponenten enthält: ein nichtionisches Tensid, ein Polycarboxylat, ein anionisches Tensid, einen Komplexbildner, der den Waschvorgang unterstützt und für Glanz sorgt, einen Weichmacher, ein Phosphonat, ein hydrolytisches Enzym, einen Konservierungsstoff, einen Duftstoff, ein funktionelles Additiv und Wasser;
und wobei die probiotischen Mikroorganismen probiotische Bakterien einer Bacillus-Spezies sind, die Sporen bilden und bei Temperaturen bis zu 65 °C Wachstum zeigen. - Kapsel gemäß Anspruch 1, dadurch gekennzeichnet, dass sie probiotische Bakterien enthält, die aus folgenden ausgewählt sind: Bacillus subtilis, Bacillus pumilus, Bacillus vallismortis, Bacillus coagulans, Bacillus lactis und Bacillus mojavensis, vorzugsweise Sporen des Bacillus-coagulans-Stamms PCM 1843.
- Kapsel gemäß Anspruch 1, dadurch gekennzeichnet, dass das Waschmittel Folgendes enthält: ein nichtionisches Tensid in einer Menge von 5 bis 30 Gew.-%, ein Polycarboxylat in einer Menge von unter 7 Gew.-%, ein anionisches Tensid in einer Menge von bis zu 35 Gew.-%, einen Komplexbildner in einer Menge von 50 bis 75 Gew.-%, einen Weichmacher in einer Menge von unter 20 Gew.-%, ein Phosphonat in einer Menge von unter 3 Gew.-%, ein hydrolytisches Enzym in einer Menge von unter 1 Gew.-%, einen Konservierungsstoff in einer Menge von unter 1 Gew.-%, einen Duftstoff in einer Menge von unter 1 Gew.-%, ein funktionelles Additiv in einer Menge von unter 1 Gew.-% und Wasser in einer Menge von unter 4 Gew.-%.
- Kapsel gemäß Anspruch 1, dadurch gekennzeichnet, dass das nichtionische Tensid aus der Gruppe ausgewählt ist, die die folgenden enthält: C12-C14-ethoxylierte Alkohole, C8-Alkylglucosid, Capryldecylglucosid, Alkyldimethylaminoxid-Lösung, Sorbitansesquioctanoat, alkoxylierten Fettalkohol, 2-Propylheptanolethoxylat, 2-Ethylhexylglucosid, Alkoholalkoxylat, C8/10-Methylester, vorzugsweise aus der Gruppe ausgewählt ist, die C12-C14-ethoxylierte Alkohole und C8-Alkylglucosid enthält.
- Kapsel gemäß Anspruch 1, dadurch gekennzeichnet, dass das anionische Tensid aus der Gruppe ausgewählt ist, die die folgenden enthält: Natrium-p-cumensulfonat; Kalium-4-isopropylbenzolsulfonat; Natrium-2-ethylhexyliminodipropionat; Natriumcocopropylendiaminpropionat; Kaliumsalz von Decylphosphorsäure; Natriumalkylsulfat; Natrium-2-ethylhexylsulfat; Natriumsalze von C12-C14-ethoxylierten Alkohol-Sulfaten; MEA-Cocoat; TEA-Cocoat, vorzugsweise aus der Gruppe ausgewählt ist, die aus n, Natriumsalzen von C12-C14-ethoxylierten Alkohol-Sulfaten; MEA-Cocoat; TEA-Cocoat besteht.
- Kapsel gemäß Anspruch 1, dadurch gekennzeichnet, dass der Komplexbildner aus der Gruppe ausgewählt ist, die die folgenden enthält: Natriumcarboxymethylinulin; Tetranatrium-EDTA; N,N-Bis(carboxymethyl)alanin-Trinatriumsalz; Glutaminsäure, N,N-Diessigsäure-Tetranatriumsalz; Natriumcitrat, vorzugsweise aus der Gruppe ausgewählt ist, die Natriumcarboxymethylinulin; Glutaminsäure, N,N-Diessigsäure-Tetranatriumsalz enthält.
- Kapsel gemäß Anspruch 1, dadurch gekennzeichnet, dass das Polycarboxylat aus der Gruppe ausgewählt ist, die die folgenden enthält: wässrige Lösung von teilweise neutralisierter Polycarbonsäure, wässrige Lösung eines Natriumsalzes von Polyacrylsäure, vorzugsweise eine wässrige Lösung von teilweise neutralisierter Polycarbonsäure ist.
- Kapsel gemäß Anspruch 1, dadurch gekennzeichnet, dass das funktionelle Additiv aus der Gruppe ausgewählt ist, die die folgenden enthält: Vinylpyrrolidon/Vinylimidazol-Copolymer; Natriummetasilicat; Alkanolaminsalz von Acylamidcarbonsäure,; Fluorescent Brightener 28 (optischer Aufheller); Undeceth-5, Undecylalkohol, Natriumlaurylsulfat, Caprylylpyrrolidon.
- Kapsel gemäß Anspruch 1, dadurch gekennzeichnet, dass der Weichmacher aus der Gruppe ausgewählt ist, die die folgenden enthält: Glycerin, Propylenglycol und Sorbit.
- Kapsel gemäß Anspruch 1, dadurch gekennzeichnet, dass das Phosphonat aus der Gruppe ausgewählt ist, die die folgenden enthält: proprietäres Gemisch von Natriumsalzen von Organophosphonsäure; wässrige Lösung von Aminophosphonsäuresalz.
- Kapsel gemäß Anspruch 1, dadurch gekennzeichnet, dass der Konservierungsstoff aus der Gruppe ausgewählt ist, die die folgenden enthält: 2-Brom-2-nitropropan-1,3-diol, Methylchlorisothiazolinon, Methylisothiazolinon; Methylisothiazolinon, Benzisothiazolinon.
- Kapsel gemäß Anspruch 1, dadurch gekennzeichnet, dass das hydrolytische Enzym aus der Gruppe ausgewählt ist, die die folgenden enthält: Protease, Lipase, Amylase und Cellulase.
- Verfahren zum Reinigen verschmutzter Oberflächen, dadurch gekennzeichnet, dass die verschmutzte Oberfläche mit einer wässrigen Lösung gewaschen wird, die man dadurch erhält, dass man die den Ansprüchen 1-12 definierte, sich selbst auflösende Kapsel in einem Volumen von 2 bis 10 Litern Wasser auflöst, wobei die gereinigte Oberfläche nach Beendigung des Waschvorgangs trocknen gelassen wird.
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CN114686319B (zh) * | 2022-04-01 | 2023-07-14 | 威莱(广州)日用品有限公司 | 一种稳定高效的机用洗碗剂 |
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WO2012112718A1 (en) | 2011-02-15 | 2012-08-23 | Novozymes Biologicals, Inc. | Mitigation of odor in cleaning machines and cleaning processes |
WO2016000128A1 (en) | 2014-06-30 | 2016-01-07 | The Procter & Gamble Company | Water-soluble pouch |
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WO2002008371A2 (en) * | 2000-02-17 | 2002-01-31 | The Procter & Gamble Company | Cleaning composition |
DE102009003027A1 (de) * | 2009-05-12 | 2010-12-02 | Henkel Ag & Co. Kgaa | Probiotischer Reiniger für harte Oberflächen |
GB2484134B (en) * | 2010-10-01 | 2013-01-30 | Cleveland Biotech Ltd | Cleaning compositions |
US10829621B2 (en) | 2013-01-11 | 2020-11-10 | Monosol, Llc | Edible water-soluble film |
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WO2012112718A1 (en) | 2011-02-15 | 2012-08-23 | Novozymes Biologicals, Inc. | Mitigation of odor in cleaning machines and cleaning processes |
WO2016000128A1 (en) | 2014-06-30 | 2016-01-07 | The Procter & Gamble Company | Water-soluble pouch |
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