EP0975721B1 - Gelled cleaning agent for flush toilets - Google Patents
Gelled cleaning agent for flush toilets Download PDFInfo
- Publication number
- EP0975721B1 EP0975721B1 EP98921455A EP98921455A EP0975721B1 EP 0975721 B1 EP0975721 B1 EP 0975721B1 EP 98921455 A EP98921455 A EP 98921455A EP 98921455 A EP98921455 A EP 98921455A EP 0975721 B1 EP0975721 B1 EP 0975721B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- amounts
- cleaning
- composition according
- particularly preferably
- 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.)
- Expired - Lifetime
Links
- 239000012459 cleaning agent Substances 0.000 title abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 29
- 239000004094 surface-active agent Substances 0.000 claims abstract description 28
- 239000000975 dye Substances 0.000 claims abstract description 25
- -1 scale preventives Substances 0.000 claims abstract description 25
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 19
- 150000004676 glycans Chemical class 0.000 claims abstract description 18
- 239000005017 polysaccharide Substances 0.000 claims abstract description 18
- 239000004615 ingredient Substances 0.000 claims abstract description 4
- 239000006096 absorbing agent Substances 0.000 claims abstract description 3
- 239000003381 stabilizer Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000000203 mixture Substances 0.000 claims description 49
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 239000002304 perfume Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 229920001285 xanthan gum Polymers 0.000 claims description 18
- 239000000230 xanthan gum Substances 0.000 claims description 14
- 235000010493 xanthan gum Nutrition 0.000 claims description 14
- 229940082509 xanthan gum Drugs 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 9
- 229920002907 Guar gum Polymers 0.000 claims description 8
- 239000000665 guar gum Substances 0.000 claims description 8
- 235000010417 guar gum Nutrition 0.000 claims description 8
- 229960002154 guar gum Drugs 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 5
- 229960004889 salicylic acid Drugs 0.000 claims description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical class C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- 150000003873 salicylate salts Chemical class 0.000 claims description 3
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 150000001860 citric acid derivatives Chemical class 0.000 claims 1
- 239000000645 desinfectant Substances 0.000 abstract description 7
- 239000003205 fragrance Substances 0.000 abstract description 3
- 230000003449 preventive effect Effects 0.000 abstract 1
- 239000012744 reinforcing agent Substances 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 55
- 238000004519 manufacturing process Methods 0.000 description 19
- 239000003921 oil Substances 0.000 description 14
- 238000005191 phase separation Methods 0.000 description 13
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 11
- 229930195729 fatty acid Natural products 0.000 description 11
- 150000002191 fatty alcohols Chemical class 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 9
- 235000002639 sodium chloride Nutrition 0.000 description 9
- 239000006260 foam Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 6
- 229920000151 polyglycol Polymers 0.000 description 5
- 239000010695 polyglycol Substances 0.000 description 5
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 241000207199 Citrus Species 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 4
- 235000020971 citrus fruits Nutrition 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical group C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 229940038773 trisodium citrate Drugs 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241000589636 Xanthomonas campestris Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- IAJILQKETJEXLJ-QTBDOELSSA-N aldehydo-D-glucuronic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-QTBDOELSSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 229940097043 glucuronic acid Drugs 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- FFQQCJGNKKIRMD-UHFFFAOYSA-N methyl n-(3-hydroxyphenyl)carbamate Chemical compound COC(=O)NC1=CC=CC(O)=C1 FFQQCJGNKKIRMD-UHFFFAOYSA-N 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920001522 polyglycol ester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial 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
- 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
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
-
- 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
- C11D3/50—Perfumes
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D1/662—Carbohydrates or derivatives
Definitions
- the present invention relates to a gel detergent, which is preferred can be used in flush toilets.
- solid detergents in piece form become automatic Keeping toilets clean. These are either in the toilet bowl or attached in the water tank.
- the moldings are with everyone Flushing process overflows with water, where they gradually dissolve and release their active cleaning agents during this time.
- these cleaning tablets also contain perfume for room scenting or disinfectant agents for hygiene optimization.
- the described lumpy detergent tablets are in suitable for this Containers partially applied with special refill options.
- the moldings described are usually after casting, pressing, Extruding or pelletizing processes that have a high technical Effort and often due to the temperature load (casting / extrusion process) suffer undesirable loss of perfume.
- Such a shaped body is described, for example, in the British patent application GB 2 288 186 A. It is a "gel cleaning block", which should contain surfactants, guar gum and monovalent ions. The production takes place at 90 ° C, then the block is poured into a mold and solidifies. Individual refilling of any quantities is therefore not possible.
- the object of the invention was to develop a system which described the Does not have disadvantages. Surprisingly, it was found that special gel-like preparations with pseudoplastic properties the effort of Reduce production considerably and, because of the simple technology, it is cheaper are to be produced. Also the problem of individual refill options can be solved by such pseudoplastic active substance preparations.
- a special container for the gel-shaped according to the invention Detergent is particularly suitable, is described in DE-A-195 201 45 described.
- the invention relates to a stable, gel-like and shear-thinning cleaning agent which, in addition to a polysaccharide, contains a C 8 -C 22 -alkyl polyglycoside as the surfactant system and perfume components, the agent as the polysaccharide xanthan gum and / or guar gum in amounts between 1 and 5 %
- a component of the surfactant system a C 8 to C 22 alkyl polyglucoside in amounts of between 3 and 25% by weight
- the perfume component (s) in amounts of 2 to 15% by weight and optionally further ingredients such as cosurfactants, lime-dissolving agents, dyes, germ-inhibiting agents, pearlescent agents, stabilizers, cleaning enhancers and odor absorbers and has a viscosity of 30,000 to 150,000 mPas; the viscosity was measured using a Brookfield rotary viscometer, type RVT with Helipath device and the spindle TA at 1 rpm and 23 ° C.
- Another advantage is that with increasing shear rate the viscosity decreases and a filling in the production process as well as an easy one Handling at the consumer during dosing / refilling results
- the size of the air bubbles that z. B. on the stirring speed in the production process and the viscosity of the agents can be controlled, neither too large still be too small; moreover, the amount of air bubbles should also only be in a preferred range. So should the presence of Air bubbles should be desired, so should not contain more than 30 vol% air, preferably between 2 and 25% by volume of air and very particularly preferably between 5 and 20 vol .-% air. The most preferred embodiments contain air bubbles between 0.1 mm and 20 mm in diameter, extremely preferably between 1 mm and 15 mm in diameter.
- the viscosity of the agents according to the invention also allows the Production process of air bubbles already entered by brief application a negative pressure that is in an area just below room pressure to close vacuum.
- the duration of the vacuum treatment depending on the strength of the negative pressure. With stronger negative pressure the Treatment should not be carried out for so long.
- the specialist also knows that undesirable side effects can occur if the vacuum is too strong, such as B. the increased evaporation of volatile perfume components and u. U. Problems with the stirrability of the system. Degassing the agents according to the invention by treatment in a centrifuge or by ultra-fast stirring is possible, but less preferred.
- the skilled person avoids according to the present Invention excessive exposure to shear forces on the invention Means during and after the production process, otherwise the properties of the invention are often lost in the short to medium term and can only be recovered after long waiting times.
- the surfactant alkyl polyglycoside
- the surfactant alkyl polyglycoside
- the other components are then added. If a bubble-free gel is to be ensured, the mixture, as already described above, is generally to be placed in a suitable container, depending on the viscosity, for a short time, for example 15 minutes, under reduced pressure or under a vacuum.
- Viscosity determination the common methods of Viscosity determination can be used.
- Brookfield viscometers worked, which is a spindle intended for gels ready.
- Helipath spindle the invention Viscosities measured.
- a polysaccharide e.g. B. a xanthan gum or a guar gum or mixtures of the same xanthan is formed from a chain with ⁇ -1,4-linked glucose (cellulose) with side chains.
- the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate.
- Xanthane is produced by Xanthomonas campestris under aerobic conditions with a molecular weight of 2-15 X 10 6 .
- Xanthan is produced in batch cultures and dried and ground with propanol after killing the culture and cases. Other suitable methods are also described in the literature.
- the polysaccharide, in particular xanthan gum is preferably present in the compositions in amounts of between 1 and 4% by weight, in particular between 1.5 and 3.5% by weight and most preferably between 1.8 and 3% by weight ,
- Alkyl polyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols according to the relevant methods of preparative organic chemistry, with a mixture of monoalkylated, oligomeric or polymeric sugars depending on the type of preparation.
- Preferred alkyl polyglycosides can be alkyl polyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol with alkyl chain lengths between C 8 and C 22 , preferably between C 8 and C 16 and particularly preferably between C 8 and C 12 or being a mixture of long-chain fatty alcohols.
- the degree of oligomerization of the sugars which is a calculated and therefore generally not an integer size, is between 1 and 10, preferably between 1.1 and 5 and very particularly preferably between 1.2 and 3 and extremely preferably between 1.3 and 2 ; 5.
- the agents contain C 8 to C 22 alkyl polyglycosides, preferably in amounts of 4 to 20% by weight, in particular 5 to 17% by weight and extremely preferably 5 to 15% by weight, with amounts of up to 12% by weight also .-% can be advantageous.
- Anionic co-surfactants according to the present invention can be aliphatic Sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, Ether sulfonates, n-alkyl ether sulfonates, ester sulfonates, and lignin sulfonates.
- aliphatic Sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, Ether sulfonates, n-alkyl ether sul
- fatty acid cyanamides sulfosuccinic acid esters, fatty acid isethionates are preferred, Acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, Ether carboxylic acids and alkyl (ether) phosphates.
- Fatty alcohol sulfates are preferred and fatty alcohol ether sulfates are used. Less good results were made previously achieved with alkylbenzenesulfonates.
- the weight ratio is Alkyl polyglycoside to co-surfactants, especially to fatty alcohol ether sulfate and / or fatty alcohol sulfate, at least 1, with ratios between 50: 1 and 1: 1, particularly preferably between 10: 1 and 1.5: 1 and very particularly preferably between 5: 1 and 1.8: 1, are particularly advantageous.
- Non-ionic co-surfactants can also be used.
- nonionic Surfactants in the context of the present invention can alkoxylated alcohols such as polyglycol ether, fatty alcohol polyglycol ether, alkylphenol polyglycol ether, End group capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and be fatty acid polyglycol esters.
- Ethylene oxide can also be used Propylene oxide, block polymers, fatty acid alkanolamides and Fatty acid polyglycol.
- alkoxylated alcohols as Reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferred in the sense of the present invention, the longer-chain alcohols. In usually arises from n moles of ethylene oxide and one mole of alcohol, depending a complex mixture of addition products from the reaction conditions different degrees of ethoxylation.
- the formulations described can preferably be used as descaling agents inorganic or organic acids such as citric acid, acetic acid, Lactic acid or its water-soluble salts in an amount of 1-12% by weight contain. Contents of 2-5% by weight are particularly preferred.
- inorganic or organic acids such as citric acid, acetic acid, Lactic acid or its water-soluble salts in an amount of 1-12% by weight contain. Contents of 2-5% by weight are particularly preferred.
- the agents according to the invention preferably contain dye, either for the Coloring of the product or for coloring the container playing around liquid.
- the content of water-soluble is preferably Dyes ⁇ 1 wt .-% and serves to improve the appearance of the product.
- the Content of water-soluble dyes up to 5 wt .-%.
- the content is up to 3% by weight. in particular up to 2% by weight and most preferably up to 1% by weight.
- the gels according to the invention are already without this component can have an excellent cleaning effect, the hygienic effect be reinforced by the addition of germ-inhibiting agents.
- the amount of this Medium depends heavily on the effectiveness of the particular compound and can last up to amount to 5% by weight. Preferably at least 0.01 wt .-% in the Gels incorporated. The range between 0.01% by weight is particularly preferred. and 3% by weight.
- Isothiazoline mixtures are particularly suitable, Sodium benzoate or salicylic acid or salicylates. More preferred Amounts used are 0.01 to 2% by weight, in particular 0.01 to 1% by weight.
- solubilizers for example for dyes and perfume oils, for example Alkanolamines, polyols such as ethylene glycol, representatives of the lower alcohols such as Propylene glycol, glycerin and other mono- and polyhydric alcohols, as well as alkylbenzenesulfonates serve with 1 to 3 carbon atoms in the alkyl radical.
- group of lower alcohols is preferred, very particularly ethanol.
- Preferred amounts are up to 5% by weight, in particular 0.01 to 4 % By weight, advantageously 0.1 to 4% by weight and very particularly preferably at 0.5 to 3% by weight.
- thickeners which are also available if required could be used include urea, sodium chloride, sodium sulfate, Magnesium sulfate, ammonium chloride and magnesium chloride and the Combination of these thickeners. The use of this additional However, thickener is not preferred.
- Water-soluble and water-insoluble builders may be included. Then there are water-soluble builders preferred because they tend to be less prone to to form insoluble residues.
- Usual builders or complexing agents which in the The low molecular weight can be present within the scope of the invention Polycarboxylic acids and their salts, the homopolymers and copolymers Polycarboxylic acids and their salts, the citric acid and its salts, the Carbonates, phosphates and silicates.
- Water-insoluble builders include Zeolites, which can also be used, as well as mixtures of the aforementioned builder substances. The group of is particularly preferred Citrate.
- the agents according to the invention preferably contain builders or Complexing agents in amounts up to 10% by weight, in particular 0.1 to 8% by weight, particularly preferably 1 to 6% by weight and very particularly preferably 2 to 5 Wt .-%.
- compositions are intended to illustrate some of the preferred ones of the invention Describe compositions. The performance was included following methods.
- the viscosity in the examples listed was measured using a Brookfield Roto viscometer, rotary viscometer, type RVT with Helipath device and the spindle TA at 1 rpm and 23 ° C.
- the measurement is carried out on an automatically controlled toilet system that is in Dispenses the contents of the water box and the box every 1 hour new with 9 l tap water with 17 ° d and a water temperature of 15 - 16 ° C crowded.
- the average results are from 5 Parallel experiments determined.
- Pre-weighed white Carrara marble slabs measuring 75 x 150 x 5 mm are completely immersed in the gel in a plexiglass cell. This happens for a time of 10 sec. Then the plate is removed and placed vertically in a tripod intended for this purpose. This has to happen that adhering product can run off. The exposure time of the adhesive Product is another 10 min. The plate is then rinsed off with water and after drying at 105 ° C the weight loss is determined.
- the measurement was carried out electrochemically in the concentrate.
- the storage took place in electrically controlled heating chambers.
- the production can be carried out in the most varied batch sizes up to the ton scale.
- water is in a commercial mixer, such as. B. submitted to a Beco mix system, and the dye stirred.
- the xanthan gum used is slurried separately with solvent, preferably ethanol and the desired perfume oil.
- the suspension is added to the aqueous receiver and stirred at low speeds, for example 30 rpm.
- solvent preferably ethanol
- the suspension is added to the aqueous receiver and stirred at low speeds, for example 30 rpm.
- the surfactant alkyl polyglycoside
- the citric acid was then added.
- the mixture should, as a rule, be placed in a suitable container depending on the viscosity for a short time, for example 15 minutes under reduced pressure or under a vacuum.
- the filling in the suitable storage container can then, for. B. via a suitable commercially available tube filler.
- Wt .-% Wt .-% sodium chloride 1.0 5.0 C 12 - 14 fatty alcohol ether sulfate + 2 EO 5.6 6.0 Fatty acid amide with betaine structure Dehyton K 3.3 3.5 Citrus perfume 1.0 6.0 water ad 100 100 viscosity 60,000 mPas 18,000 mPas PH value 9.0 9.0 Gel structure / appearance clear, slightly cloudy Shelf life dilutes heavily with water when rinsed off. Not a stable viscosity. Flows out of the container after filling.
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Abstract
Description
Die vorliegende Erfindung betrifft ein gelförmiges Reinigungsmittel, das bevorzugt in Spültoiletten eingesetzt werden kann.The present invention relates to a gel detergent, which is preferred can be used in flush toilets.
Bekanntermaßen werden feste Reinigungsmittel in Stückform zur automatischen Reinhaltung von Toiletten eingesetzt. Diese werden entweder in der WC-Schüssel oder im Wasserkasten angebracht. Die Formkörper werden bei jedem Spülvorgang von Wasser überströmt, wobei sie sich allmählich auflösen und während dieser Zeit ihre reinigungsaktiven Wirkstoffe freisetzen. Üblicherweise enthalten diese Reinigungsformkörper zusätzlich Parfüm zur Raumbeduftung oder desinfizierende Wirkstoffe zur Hygieneoptimierung. Die beschriebenen stückförmigen Reinigungsmittelformkörper werden in dafür geeigneten Behältnissen teilweise mit speziellen Nachfüllmöglichkeiten appliziert.As is known, solid detergents in piece form become automatic Keeping toilets clean. These are either in the toilet bowl or attached in the water tank. The moldings are with everyone Flushing process overflows with water, where they gradually dissolve and release their active cleaning agents during this time. Usually these cleaning tablets also contain perfume for room scenting or disinfectant agents for hygiene optimization. The described lumpy detergent tablets are in suitable for this Containers partially applied with special refill options.
Die beschriebenen Formkörper werden in der Regel nach Gieß-, Preß-, Extrudier- oder Granulierverfahren gefertigt, die einen hohen technischen Aufwand erfordern und häufig durch die auftretende Temperaturbelastung (Gieß/Extrudierverfahren) unerwünschte Parfümverluste erleiden.The moldings described are usually after casting, pressing, Extruding or pelletizing processes that have a high technical Effort and often due to the temperature load (casting / extrusion process) suffer undesirable loss of perfume.
Als nachteilig erweist es sich auch, daß die aus ökologischen Gründen verbreiteten Nachfülleinheiten nur nach vollständigem Verbrauch des stückförmigen Körpers eingesetzt werden können. Eine wünschenswerte beliebige Nachfüllung, z.B. zur stärkeren Wirkstoffreisetzung oder insbesondere der intensiveren Duftentfaltung, ist nicht möglich.It also proves disadvantageous that the for ecological reasons widespread refill units only after complete consumption of the piece-shaped body can be used. A desirable one any refill, e.g. for stronger drug release or in particular the more intense fragrance development is not possible.
Ein solcher Formkörper wird beispielsweise in der britischen Patentanmeldung GB 2 288 186 A beschrieben. Es handelt sich um einen "Gel-Reinigungsblock", welches Tenside, Guar Gum und einwertige Ionen enthalten soll. Die Herstellung erfolgt bei 90°C, anschließend wird der Block in eine Form gegossen und erstarrt. Individuelles Nachfüllen beliebiger Mengen ist daher nicht möglich.Such a shaped body is described, for example, in the British patent application GB 2 288 186 A. It is a "gel cleaning block", which should contain surfactants, guar gum and monovalent ions. The production takes place at 90 ° C, then the block is poured into a mold and solidifies. Individual refilling of any quantities is therefore not possible.
Aufgabe der Erfindung war es, ein System zu entwickeln, das die beschriebenen Nachteile nicht aufweist. Überraschenderweise wurde gefunden, daß spezielle gelförmige Zubereitungen mit strukturviskosen Eigenschaften den Aufwand der Herstellung erheblich verringem und aufgrund einfacher Technik kostengünstiger zu produzieren sind. Auch das Problem der individuellen Nachfüllmöglichkeit kann durch derartige strukturviskose Wirkstoffzubereitungen gelöst werden. Ein spezielles Behältnis, das für die erfindungsgemäßen gelförmigen Reinigungsmittel besonders geeignet ist, wird in der DE-A- 195 201 45 beschrieben.The object of the invention was to develop a system which described the Does not have disadvantages. Surprisingly, it was found that special gel-like preparations with pseudoplastic properties the effort of Reduce production considerably and, because of the simple technology, it is cheaper are to be produced. Also the problem of individual refill options can be solved by such pseudoplastic active substance preparations. A special container for the gel-shaped according to the invention Detergent is particularly suitable, is described in DE-A-195 201 45 described.
Gegenstand der Erfindung ist ein stabiles gelförmiges und scherverdünnendes Reinigungsmittel, welches außer einem Polysaccharid ein C8- bis C22-Alkylpolyglycosid als Tensidsystem und Parfümkomponenten enthält, wobei das Mittel als Polysaccharid Xanthan-Gum und/oder Guar-Gum in Mengen zwischen 1 und 5 Gew.-%, als eine Komponente des Tensidsystems ein C8- bis C22-Alkylpolyglucosid in Mengen zwischen 3 und 25 Gew.-%, die Parfümkomponente(n) in Mengen von 2 bis 15 Gew.-% sowie ggf. weitere Inhaltsstoffe wie Cotenside, kalklösende Mittel, Farbstoffe, keimhemmende Mittel, Perlglanzmittel, Stabilisatoren, Reinigungsverstärker und Geruchsabsorber enthält und eine Viskosität von 30 000 bis 150 000 mPas aufweist; die Viskosität wurde dabei mit einem Brookfield Rotationsviskosimeter, Typ RVT mit Helipath-Einrichtung und der Spindel TA bei 1 Upm und 23°C gemessen.The invention relates to a stable, gel-like and shear-thinning cleaning agent which, in addition to a polysaccharide, contains a C 8 -C 22 -alkyl polyglycoside as the surfactant system and perfume components, the agent as the polysaccharide xanthan gum and / or guar gum in amounts between 1 and 5 % By weight, as a component of the surfactant system, a C 8 to C 22 alkyl polyglucoside in amounts of between 3 and 25% by weight, the perfume component (s) in amounts of 2 to 15% by weight and optionally further ingredients such as cosurfactants, lime-dissolving agents, dyes, germ-inhibiting agents, pearlescent agents, stabilizers, cleaning enhancers and odor absorbers and has a viscosity of 30,000 to 150,000 mPas; the viscosity was measured using a Brookfield rotary viscometer, type RVT with Helipath device and the spindle TA at 1 rpm and 23 ° C.
Es hat sich gezeigt, daß mit Xanthan-Gum und/oder Guar-Gum in den beschriebenen Kombinationen je nach Wahl der Type mit hohen Parfüm- und APG-Konzentrationen optisch ansprechende transluzente oder klare strukturviskose Gelstrukturen erzielt werden können, die in den dafür geeigneten Behältnissen vergleichbare Haltbarkeiten von festen WC-Blöcken erreichen.It has been shown that with xanthan gum and / or guar gum in the described Combinations depending on the choice of type with high perfume and APG concentrations visually appealing translucent or clear structural viscose Gel structures can be achieved in the appropriate containers achieve comparable durability of fixed toilet blocks.
Andere übliche Gelbildner wie z.B. Polyacrylsäure (Carbopol), tensidverdickte Systeme, MHPC (Natrosol) oder kochsalz- bzw. elektrolytverdickte Tensidsysteme zeigen bei Einsatz der notwendigen hohen Tensid- und Parfümanteile keine ausreichende Gelstabilität. Diese Formulierungen sind häufig nicht ausreichend strukturviskos, verdünnen sich beim Überströmen mit Wasser und tropfen wegen ihres ungenügenden Viskositätsverhalten trotz geeigneter Behältnisse undosiert in die WC-Schüssel. Dagegen sind die erfindungsgemäßen Formulierungen ausgesprochen strukturviskos und widerstehen dabei dem überströmenden Wasser in der Form, daß nur geringe Teilmengen abgegeben werden und die gewünschte Haltbarkeit erzielt wird. Die erhaltenen Mittel dürfen sich nämlich in dem in die dafür vorgesehenen Behältnisse eindringenden Wasser auch nicht zu gut lösen, damit sie nicht nach einer geringen Anzahl von verwendungsgemäßen wässrigen Überströmungen bereits aufgelöst und damit verbraucht sind.Other common gelling agents such as Polyacrylic acid (Carbopol), surfactant thickened Systems, MHPC (Natrosol) or salt or electrolyte thickened When using the necessary high surfactant and Perfume content not sufficient gel stability. These phrases are common not sufficiently viscous, dilute with water when overflowing and drip due to their insufficient viscosity behavior despite more suitable ones Containers dosed into the toilet bowl. In contrast, the invention Formulations that are extremely viscous and resist this overflowing water in the form that only small portions are released and the desired durability is achieved. The funds received may namely penetrate into the containers provided for this purpose Also, do not dissolve water too well, so that it does not flow after a small number of Aqueous overflows according to the use have already been dissolved and thus are used up.
Dabei muß außerdem gewährleistet sein, daß trotz der hohen Parfüm- und Emulgatormenge eine ausreichende Langzeitstabilität der Gele gewährleistet ist, und sich z. B. keine Phasenseparation einstellt, die nicht nur ein für den Verbraucher optisch minder ansprechendes Produkt bedeuten würde, sondern auch Lösekinetik und Dosierfähigkeit beeinträchtigen würde.It must also be ensured that despite the high perfume and Sufficient amount of long-term stability of the gels is guaranteed, and z. B. does not set a phase separation that is not just one for Consumer would mean less visually appealing product, but would also affect the kinetics of dissolution and the ability to dose.
Als Vorteil ist zusätzlich gegeben, daß mit zunehmender Schergeschwindigkeit die Viskosität abnimmt und ein Abfüllen im Produktionsprozeß sowie ein leichtes Handling beim Verbraucher während des Dosierens/Nachfüllung resultiertAnother advantage is that with increasing shear rate the viscosity decreases and a filling in the production process as well as an easy one Handling at the consumer during dosing / refilling results
Überraschenderweise wurde auch gefunden, daß unter bestimmten Bedingungen beim Produktionsprozeß Luftblasen in die Mittel erfindungsgemäßer Zusammensetzung eingebracht werden können, die über einen Zeitraum von mehreren Wochen in Größe und Form stabil sind und damit ein für den Verbraucher optisch noch ansprechenderes Produkt bedeuten.Surprisingly, it was also found that under certain conditions in the production process air bubbles in the agent according to the invention Composition can be introduced over a period of are stable in size and shape for several weeks and therefore one for the Consumers mean optically more appealing product.
Dabei darf die Größe der Luftblasen, die sich z. B. über die Rührgeschwindigkeit im Produktionsprozeß und die Viskosität der Mittel steuern läßt, weder zu groß noch zu klein sein; außerdem sollte die Menge der Luftblasen ebenfalls nur in einem bevorzugten Bereich ausgewählt sein. Sollte also die Anwesenheit von Luftblasen erwünscht sein, so sollte nicht mehr als 30 Vol-% Luft enthalten sein, bevorzugt zwischen 2 und 25 Vol-% Luft und ganz besonders bevorzugt zwischen 5 und 20 Vol.-% Luft. Die ganz besonders bevorzugten Ausführungsformen enthalten Luftblasen zwischen 0,1 mm und 20 mm Durchmesser, äußerst bevorzugt zwischen 1 mm und 15 mm Durchmesser.The size of the air bubbles that z. B. on the stirring speed in the production process and the viscosity of the agents can be controlled, neither too large still be too small; moreover, the amount of air bubbles should also only be in a preferred range. So should the presence of Air bubbles should be desired, so should not contain more than 30 vol% air, preferably between 2 and 25% by volume of air and very particularly preferably between 5 and 20 vol .-% air. The most preferred embodiments contain air bubbles between 0.1 mm and 20 mm in diameter, extremely preferably between 1 mm and 15 mm in diameter.
Die Viskosität der erfindungsgemäßen Mittel erlaubt aber auch, die im Produktionsprozeß bereits eingetragenen Luftblasen durch kurzzeitiges Anlegen eines Unterdrucks, der in einem Bereich knapp unterhalb Raumdruck bis nahe einem Vakuum liegen kann, zuentfernen. Dabei ist die Dauer der Unterdruckbehandlung abhängig von der Stärke des Unterdrucks. Bei stärkerem Unterdruck muß die Behandlung nicht so lange durchgeführt, werden. Der Fachmann weiß aber auch, daß bei zu starkem Unterdruck unerwünschte Nebeneffekte auftreten können, wie z. B. das verstärkte Abdampfen von leichterflüchtigen Parfümkomponenten und u. U. Probleme bei der Rührbarkeit des Systems. Ein Entgasen der erfindungsgemäßen Mittel durch die Behandlung in einer Zentrifuge oder durch ultraschnelles Rühren ist zwar möglich, aber weniger bevorzugt.However, the viscosity of the agents according to the invention also allows the Production process of air bubbles already entered by brief application a negative pressure that is in an area just below room pressure to close vacuum. The duration of the vacuum treatment depending on the strength of the negative pressure. With stronger negative pressure the Treatment should not be carried out for so long. The specialist also knows that undesirable side effects can occur if the vacuum is too strong, such as B. the increased evaporation of volatile perfume components and u. U. Problems with the stirrability of the system. Degassing the agents according to the invention by treatment in a centrifuge or by ultra-fast stirring is possible, but less preferred.
Wenn möglich, vermeidet nämlich der Fachmann gemäß der vorliegenden Erfindung übermäßiges Einwirken von Scherkräften auf die erfindungsgemäßen Mittel während und nach dem Produktionsprozeß, da sonst die erfindungsgemäßen Eigenschaften oft kurz- bis mittelfristig verlorengehen und nur nach längeren Wartezeiten wiedergewonnen werden.If possible, the skilled person avoids according to the present Invention excessive exposure to shear forces on the invention Means during and after the production process, otherwise the properties of the invention are often lost in the short to medium term and can only be recovered after long waiting times.
Bei der Herstellung der erfindungsgemäßen Rezepturen, die in den
unterschiedlichsten Ansatzgrößen bis zum Tonnenmaßstab durchführbar ist,
kann der Fachmann auf unterschiedliche Weise vorgehen.
Üblicherweise wird Wasser in einer handelsüblichen Mischeranlage, wie z. B.
einer Beco-Mix-Anlage, vorgelegt und der Farbstoff eingerührt. Der vorzugsweise
als Polysaccharid verwendete Xanthan-Gum wird mit Lösungsmittel, bevorzugt
Ethanol, und dem gewünschten Parfumöl separat aufgeschlämmt. Die
Suspension wird der Vorlage zugegeben und mit geringen Geschwindigkeiten,
beispielsweise 30 Upm gerührt.
Es zeigt sich bei den Untersuchungen, daß nach Zugabe aller Komponenten eine
Zeit zwischen wenigen Minuten und einigen Stunden zur Erreichung der
erfindungsgemäßen Konsistenz wünschenswert ist. Im vorliegenden Fall wurde
nach 30 min das Tensid (Alkylpolyglycosid) langsam zudosiert. Anschließend
werden die weiteren Komponenten zugesetzt.
Soll ein blasenfreies Gel gewährleistet werden, ist die Mischung, wie oben bereits
beschrieben, in einem geeigneten Behälter in Abhängigkeit von der Viskosität in
der Regel aber für eine kurze Zeit, beispielsweise 15 min, unter reduzierten
Druck oder ein Vakuum zu setzen.The person skilled in the art can proceed in different ways in the preparation of the recipes according to the invention, which can be carried out in a wide variety of batch sizes up to the ton scale.
Usually, water is in a commercial mixer, such as. B. a Beco mix system, submitted and the dye stirred. The xanthan gum, which is preferably used as a polysaccharide, is slurried separately with solvent, preferably ethanol, and the desired perfume oil. The suspension is added to the initial charge and stirred at low speeds, for example 30 rpm.
It turns out in the investigations that a time between a few minutes and a few hours after the addition of all components is desirable to achieve the consistency according to the invention. In the present case, the surfactant (alkyl polyglycoside) was slowly added after 30 minutes. The other components are then added.
If a bubble-free gel is to be ensured, the mixture, as already described above, is generally to be placed in a suitable container, depending on the viscosity, for a short time, for example 15 minutes, under reduced pressure or under a vacuum.
Der Fachmann kann aber auch anders vorgehen. Dies empfiehlt sich z. B. bei der
Einarbeitung von Desinfektionsmitteln. Üblicherweise wird hier Wasser in einer
handelsüblichen Mischeranlage, wie z. B. einer Beco-Mix-Anlage, vorgelegt und
der verwendete Xanthan-Gum eingerührt. Die Suspension wird der Vorlage
zugegeben und mit geringen Geschwindigkeiten, beispielsweise 30 Upm gerührt,
bevor nach 30 min das Tensidgemisch (Alkylpolyglycosid/Fettalkoholethersulfat)
langsam zudosiert wird. Anschließend wird der Farbstoff zugegeben, bevor eine
ethanolische Lösung des Parfüms nachdosiert wurde.
Danach erfolgt die Zugabe des Desinfektionsmittels, bevorzugt ausgewählt aus
der Gruppe der Isothiazoline, der Benzoate oder der Salicylsäure oder Salicylate.
Die Abfüllung kann in diesem Fall z. B. über einen Flaschenrundläufer in eine
handelsübliche Dosierflasche erfolgen.However, the person skilled in the art can also proceed differently. This is recommended for. B. when incorporating disinfectants. Usually water is here in a commercial mixer, such as. B. a Beco mix system, submitted and stirred in the xanthan gum used. The suspension is added to the initial charge and stirred at low speeds, for example 30 rpm, before the surfactant mixture (alkyl polyglycoside / fatty alcohol ether sulfate) is slowly metered in after 30 minutes. The dye is then added before an ethanolic solution of the perfume has been added.
The disinfectant is then added, preferably selected from the group of isothiazolines, benzoates or salicylic acid or salicylates.
The filling can in this case, for. B. done in a commercial dosing bottle over a bottle runner.
Besondere Vorsicht muß man walten lassen, wenn man Substanzen in das vorbereitete und gequollene wässerige Xanthan-Gel zugibt, damit sich die erfindungsgemäße Struktur bilden kann. Bei einer zu schnellen Zugabe kann es zu Phasentrennungsproblemen kommen. Ebenfalls darf bei der Herstellung der Xanthan-Gel-Komponente kein Tensid zugegen sein, da es die Gel-Bildung verhindern könnte. Daher ist es äußerst bevorzugt, die tensidischen Komponenten erst nach der Bildung des Gels zuzugeben.You have to be especially careful when you put substances into it prepared and swollen aqueous xanthan gel admits so that the structure according to the invention can form. If it is added too quickly, it can lead to phase separation problems. Likewise, in the manufacture of the Xanthan gel component will not have any surfactant present as it is gel formation could prevent. Therefore, it is extremely preferred to use the surfactant Only add components after the gel has formed.
Zur Messung der Viskosität können die gängigen Methoden der Viskositätsbestimmung verwendet werden. Im vorliegenden Fall wurde mit Brookfield-Viskosimetern gearbeitet, welche eine für Gele vorgesehene Spindel bereithalten. Mit dieser Helipath-Spindel wurden die erfindungsgemäßen Viskositäten gemessen.To measure the viscosity, the common methods of Viscosity determination can be used. In the present case, with Brookfield viscometers worked, which is a spindle intended for gels ready. With this Helipath spindle, the invention Viscosities measured.
Die erfindungsgemäßen Formulierungen können in einer Rahmenrezeptur
folgende Komponenten enthalten:
Dabei versteht man beispielsweise erfindungsgemäß unter einem Polysaccharid z. B. ein Xanthan-Gum oder ein Guar-Gum oder Gemische desselten Xanthan wird aus einer Kette mit β-1,4-gebundener Glucose (Cellulose) mit Seitenketten gebildet. Die Struktur der Untergruppen besteht aus Glucose, Mannose, Glucuronsäure, Acetat und Pyruvat. Xanthan wird von Xanthomonas campestris unter aeroben Bedingungen mit einem Molekulargewicht von 2-15 X 106 produziert. Xanthan wird u.a. in Batch-Kulturen hergestellt und nach Abtöten der Kultur und Fällen mit Propanol getrocknet und gemahlen. Andere geeignete Verfahren werden in der Literatur ebenfalls beschrieben. Vorzugsweise ist das Polysaccharid, insbesondere Xanthan-Gum, in Mengen zwischen 1 und 4 Gew.-%, insbesondere zwischen1,5 und 3,5 Gew.-% und äußert bevorzugt zwischen 1,8 und 3 Gew.-% in den Mitteln enthalten. According to the invention, this is understood to mean, for example, a polysaccharide e.g. B. a xanthan gum or a guar gum or mixtures of the same xanthan is formed from a chain with β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate. Xanthane is produced by Xanthomonas campestris under aerobic conditions with a molecular weight of 2-15 X 10 6 . Xanthan is produced in batch cultures and dried and ground with propanol after killing the culture and cases. Other suitable methods are also described in the literature. The polysaccharide, in particular xanthan gum, is preferably present in the compositions in amounts of between 1 and 4% by weight, in particular between 1.5 and 3.5% by weight and most preferably between 1.8 and 3% by weight ,
Alkylpolyglycoside sind Tenside, die durch die Reaktion von Zuckern und Alkoholen nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden können, wobei es je nach Art der Herstellung zu einem Gemisch monoalkylierter, oligomerer oder polymerer Zucker kommt. Bevorzugte Alkylpolyglycoside können Alkylpolyglucoside sein, wobei besonders bevorzugt der Alkohol ein langkettiger Fettalkohol ist mit Alkylkettenlängen zwischen C8 und C22, bevorzugt zwischen C8 und C16 und besonders bevorzugt zwischen C8 und C12 liegt oder ein Gemisch langkettiger Fettalkohole ist. Der Oligomerisierungsgrad der Zucker, der eine berechnete und damit in der Regel nicht ganzzahlige Größe ist, liegt zwischen 1 und 10, bevorzugt zwischen 1,1 und 5 und ganz besonders bevorzugt zwischen 1,2 und 3 und äußerst bevorzugt zwischen 1,3 und 2,5. Die Mittel enthalten C8- bis C22-Alkylpolyglycoside vorzugsweise in Mengen von 4 bis 20 Gew.-%, insbesondere von 5 bis 17 Gew.-% und äußerst bevorzugt von 5 bis 15 Gew.-%, wobei auch Mengen bis 12 Gew.-% von Vorteil sein können.Alkyl polyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols according to the relevant methods of preparative organic chemistry, with a mixture of monoalkylated, oligomeric or polymeric sugars depending on the type of preparation. Preferred alkyl polyglycosides can be alkyl polyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol with alkyl chain lengths between C 8 and C 22 , preferably between C 8 and C 16 and particularly preferably between C 8 and C 12 or being a mixture of long-chain fatty alcohols. The degree of oligomerization of the sugars, which is a calculated and therefore generally not an integer size, is between 1 and 10, preferably between 1.1 and 5 and very particularly preferably between 1.2 and 3 and extremely preferably between 1.3 and 2 ; 5. The agents contain C 8 to C 22 alkyl polyglycosides, preferably in amounts of 4 to 20% by weight, in particular 5 to 17% by weight and extremely preferably 5 to 15% by weight, with amounts of up to 12% by weight also .-% can be advantageous.
Anionische Co-Tenside gemäß der vorliegenden Erfindung können aliphatische Sulfate wie Fettalkoholsulfate, Fettalkoholethersulfate, Dialkylethersulfate, Monoglyceridsulfate und aliphatische Sulfonate wie Alkansulfonate, Olefinsulfonate, Ethersulfonate, n-Alkylethersulfonate, Estersulfonate, und Ligninsulfonate sein. Ebenfalls im Rahmen der vorliegenden Erfindung verwendbar, aber nicht bevorzugt sind Fettsäurecyanamide, Sulfobernsteinsäureester, Fettsäureisethionate, Acylaminoalkansulfonate (Fettsäuretauride), Fettsäuresarcosinate, Ethercarbonsäuren und Alkyl(ether)phosphate. Bevorzugt werden Fettalkoholsulfate und Fettalkoholethersulfate verwendet. Weniger gute Ergebnisse wurden bisher mit Alkylbenzolsulfonaten erzielt.Anionic co-surfactants according to the present invention can be aliphatic Sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, Ether sulfonates, n-alkyl ether sulfonates, ester sulfonates, and lignin sulfonates. Also usable in the context of the present invention, but not fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isethionates are preferred, Acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, Ether carboxylic acids and alkyl (ether) phosphates. Fatty alcohol sulfates are preferred and fatty alcohol ether sulfates are used. Less good results were made previously achieved with alkylbenzenesulfonates.
In einer bevorzugten Ausführungsform der Erfindung liegt das Gewichtsverhältnis Alkylpolyglycosid zu Co-Tensiden, insbesondere zu Fettalkoholethersulfat und/oder Fettalkoholsulfat, bei mindestens 1, wobei Verhältnisse zwischen 50:1 und 1:1, besonders bevorzugt zwischen 10:1 und 1,5:1 und ganz besonders bevorzugt zwischen 5:1 und 1,8:1, besonders vorteilhaft sind. Aber auch nichtionische Co-Tenside können Verwendung finden. Nichtionische Tenside im Rahmen der vorliegenden Erfindung können alkoxylierte Alkohole wie Polyglycolether, Fettalkoholpolygycolether, Alkylphenolpolyglycolether, endgruppenverschlossene Polyglycolether, Mischether und Hydroxymischether und Fettsäurepolyglycolester sein. Ebenfalls verwendbar sind Ethylenoxid Propylenoxid, - Blockpolymere, Fettsäurealkanolamide und Fettsäurepolyglycolether.In a preferred embodiment of the invention, the weight ratio is Alkyl polyglycoside to co-surfactants, especially to fatty alcohol ether sulfate and / or fatty alcohol sulfate, at least 1, with ratios between 50: 1 and 1: 1, particularly preferably between 10: 1 and 1.5: 1 and very particularly preferably between 5: 1 and 1.8: 1, are particularly advantageous. Non-ionic co-surfactants can also be used. nonionic Surfactants in the context of the present invention can alkoxylated alcohols such as polyglycol ether, fatty alcohol polyglycol ether, alkylphenol polyglycol ether, End group capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and be fatty acid polyglycol esters. Ethylene oxide can also be used Propylene oxide, block polymers, fatty acid alkanolamides and Fatty acid polyglycol.
Dabei versteht der Fachmann allgemein unter alkoxylierten Alkoholen die Reaktionsprodukte von Alkylenoxid, bevorzugt Ethylenoxid, mit Alkoholen, bevorzugt im Sinne der vorliegenden Erfindung die längerkettigen Alkohole. In der Regel entsteht aus n Molen Ethylenoxid und einem Mol Alkohol, abhängig von den Reaktionsbedingungen ein komplexes Gemisch von Additionsprodukten unterschiedlichen Ethoxylierungsgrades. Eine weitere Ausführungsform besteht im Einsatz von Gemischen der Alkylenoxide, bevorzugt des Gemisches von Ethylenoxid und Propylenoxid. Auch kann man gewünschtenfalls durch eine abschließende Veretherung mit kurzkettigen Alkylgruppen, wie bevorzugt der Butylgruppe, zur Substanzklasse der "verschlossenen" Alkoholethoxylate gelangen, die ebenfalls im Sinne der Erfindung eingesetzt werden kann. Ganz besonders bevorzugt im Sinne der vorliegenden Erfindung sind dabei hochethoxylierte Fettalkohole oder deren Gemische mit endgruppenverschlossenen Fettalkoholethoxylaten.The person skilled in the art generally understands alkoxylated alcohols as Reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferred in the sense of the present invention, the longer-chain alcohols. In usually arises from n moles of ethylene oxide and one mole of alcohol, depending a complex mixture of addition products from the reaction conditions different degrees of ethoxylation. Another embodiment exists when using mixtures of the alkylene oxides, preferably the mixture of Ethylene oxide and propylene oxide. If desired, you can also use a final etherification with short-chain alkyl groups, such as the Butyl group, to the substance class of "closed" alcohol ethoxylates arrive, which can also be used in the sense of the invention. All are particularly preferred for the purposes of the present invention highly ethoxylated fatty alcohols or mixtures thereof end-capped fatty alcohol ethoxylates.
Die beschriebenen Formulierungen können vorzugsweise als kalklösende Mittel anorganische oder organische Säuren wie die Zitronensäure, Essigsäure, Milchsäure oder deren wasserlöslichen Salze in einer Menge von 1 - 12 Gew.-% enthalten. Besonders bevorzugt sind Gehalte von 2 - 5 Gew.-%.The formulations described can preferably be used as descaling agents inorganic or organic acids such as citric acid, acetic acid, Lactic acid or its water-soluble salts in an amount of 1-12% by weight contain. Contents of 2-5% by weight are particularly preferred.
Die erfindungsgemäßen Mittel enthalten vorzugsweise Farbstoff, entweder für die Farbgebung des Produktes oder für die Farbgebung der den Behälter umspielenden Flüssigkeit. Bevorzugt liegt der Gehalt an wasserlöslichen Farbstoffen < 1 Gew.-% und dient zur Verbesserung der Optik des Produktes. The agents according to the invention preferably contain dye, either for the Coloring of the product or for coloring the container playing around liquid. The content of water-soluble is preferably Dyes <1 wt .-% and serves to improve the appearance of the product.
Wenn ein zusätzliches Farbsignal beim Einspülvorgang gewünscht ist, kann der Gehalt an wasserlöslichen Farbstoffen bis 5 Gew.-% betragen. Vorzugsweise liegt der Gehalt bei Mengen bis zu 3 Gew.-%. insbesondere bis zu 2 Gew.-% und äußerst bevorzugt bis zu 1 Gew.-%.If an additional color signal is required during the induction process, the Content of water-soluble dyes up to 5 wt .-%. Preferably the content is up to 3% by weight. in particular up to 2% by weight and most preferably up to 1% by weight.
Obwohl die erfindungsgemäßen Gele bereits ohne diese Komponente eine ausgezeichnete Reinigungswirkung besitzen, kann die hygienische Wirkung durch den Zusatz keimhemmender Mittel verstärkt werden. Die Menge dieser Mittel hängt stark von der Wirksamkeit der jeweiligen Verbindung ab und kann bis zu 5 Gew.-% betragen. Vorzugsweise werden mindestens 0,01 Gew.-% in die Gele eingearbeitet. Besonders bevorzugt ist der Bereich zwischen 0,01 Gew.-% und 3 Gew.-%. Geeignet sind insbesondere lsothiazolingemische, Natriumbenzoat oder Salicylsäure bzw. Salicylate. Weitere bevorzugte Einsatzmengen liegen bei 0,01 bis 2 Gew.-%, insbesondere bei 0,01 bis 1 Gew.-%.Although the gels according to the invention are already without this component can have an excellent cleaning effect, the hygienic effect be reinforced by the addition of germ-inhibiting agents. The amount of this Medium depends heavily on the effectiveness of the particular compound and can last up to amount to 5% by weight. Preferably at least 0.01 wt .-% in the Gels incorporated. The range between 0.01% by weight is particularly preferred. and 3% by weight. Isothiazoline mixtures are particularly suitable, Sodium benzoate or salicylic acid or salicylates. More preferred Amounts used are 0.01 to 2% by weight, in particular 0.01 to 1% by weight.
Als Lösungsvermittler, etwa für Farbstoffe und Parfümöle, können beispielsweise Alkanolamine, Polyole wie Ethylenglycol, Vertreter der niederen Alkohole wie Propylenglycol, Glycerin und andere ein- und mehrwertige Alkohole, sowie Alkylbenzolsulfonate mit 1 bis 3 Kohlenstoffatomen im Alkylrest dienen. Besonders bevorzugt ist dabei die Gruppe der niederen Alkohole, ganz besonders Ethanol. Bevorzugte Einsatzmengen liegen bis zu 5 Gew.-%, insbesondere bei 0,01 bis 4 Gew.-%, vorteilhafterweise bei 0,1 bis 4 Gew.-% und ganz besonders bevorzugt bei 0,5 bis 3 Gew.-%.As solubilizers, for example for dyes and perfume oils, for example Alkanolamines, polyols such as ethylene glycol, representatives of the lower alcohols such as Propylene glycol, glycerin and other mono- and polyhydric alcohols, as well as alkylbenzenesulfonates serve with 1 to 3 carbon atoms in the alkyl radical. Especially the group of lower alcohols is preferred, very particularly ethanol. Preferred amounts are up to 5% by weight, in particular 0.01 to 4 % By weight, advantageously 0.1 to 4% by weight and very particularly preferably at 0.5 to 3% by weight.
Zu den üblichen Verdickungsmitteln, die bei Bedarf zusätzlich ebenfalls einsetzbar wären, zählen Hamstoff, Natriumchlorid, Natriumsulfat, Magnesiumsulfat, Ammoniumchlorid und Magnesiumchlorid sowie die Kombination dieser Verdickungsmittel. Der Einsatz dieser zusätzlichen Verdickungsmittel ist jedoch nicht bevorzugt.In addition to the usual thickeners, which are also available if required could be used include urea, sodium chloride, sodium sulfate, Magnesium sulfate, ammonium chloride and magnesium chloride and the Combination of these thickeners. The use of this additional However, thickener is not preferred.
In den erfindungsgemäßen Reinigungsmitteln können ggf. wasserlösliche und wasserunlösliche Builder enthalten sein. Dabei sind dann wasserlösliche Builder bevorzugt, da sie auf harten Oberflächen in der Regel weniger dazu tendieren, unlösliche Rückstände zu bilden. Übliche Builder oder Komplexbildner, die im Rahmen der Erfindung zugegen sein können, sind die niedermolekularen Polycarbonsäuren und ihre Salze, die homopolymeren und copolymeren Polycarbonsäuren und ihre Salze, die Citronensäure und ihre Salze, die Carbonate, Phosphate und Silikate. Zu wasserunlöslichen Buildern zählen die Zeolithe, die ebenfalls verwendet werden können, ebenso wie Mischungen der vorgenannten Buildersubstanzen. Besonders bevorzugt ist die Gruppe der Citrate. Vorzugsweise enthalten die erfindungsgemäßen Mittel Builder oder Komplexbildner in Mengen bis zu 10 Gew.-% insbesondere 0,1 bis 8 Gew.-%, besonders bevorzugt 1 bis 6 Gew.-% und ganz besonders bevorzugt 2 bis 5 Gew.-%. Water-soluble and water-insoluble builders may be included. Then there are water-soluble builders preferred because they tend to be less prone to to form insoluble residues. Usual builders or complexing agents, which in the The low molecular weight can be present within the scope of the invention Polycarboxylic acids and their salts, the homopolymers and copolymers Polycarboxylic acids and their salts, the citric acid and its salts, the Carbonates, phosphates and silicates. Water-insoluble builders include Zeolites, which can also be used, as well as mixtures of the aforementioned builder substances. The group of is particularly preferred Citrate. The agents according to the invention preferably contain builders or Complexing agents in amounts up to 10% by weight, in particular 0.1 to 8% by weight, particularly preferably 1 to 6% by weight and very particularly preferably 2 to 5 Wt .-%.
Die nachfolgenden Beispiele sollen einige der bevorzugten erfindungsgemäßen Zusammensetzungen beschreiben. Dabei wurde die Leistungsfähigkeit mit folgenden Methoden bestimmt.The following examples are intended to illustrate some of the preferred ones of the invention Describe compositions. The performance was included following methods.
Die Messung der Viskosität in den aufgeführten Beispielen erfolgte mit einem Brookfield Roto Viskosimeter, Rotationsviskosimeter, Typ RVT mit Helipath-Einrichtung und der Spindel TA bei 1 Upm und 23 °C.The viscosity in the examples listed was measured using a Brookfield Roto viscometer, rotary viscometer, type RVT with Helipath device and the spindle TA at 1 rpm and 23 ° C.
0,1 g Gel werden in 500 ml Leitungswasser 17 °d in einem 1000 ml Meßzylinder mit 40 Hüben bei einer Drehgeschwindigkeit von 100 Upm aufgeschäumt. Das Gebilde des Schaumvolumens wird nach 1, 3 und 10 min abgelesen.0.1 g of gel in 500 ml of tap water at 17 ° d in a 1000 ml measuring cylinder foamed with 40 strokes at a rotation speed of 100 rpm. The Formations of the foam volume are read after 1, 3 and 10 min.
Die Messung erfolgt auf einer automatisch gesteuerten WC-Anlage, die in Abständen von 1 Stunde den Inhalt des Wasserkastens abgibt und den Kasten neu mit 9 l Leitungswasser mit 17 °d und einer Wassertemperatur von 15 - 16 °C füllt. Es wird jeweils 1 Füllung eines Gefäßes gemäß der DE 195 201 45 in die Toiletten eingehängt und festgestellt, wieviel Spülungen bis zum vollständigen Verbrauch möglich sind. Die Durchschnittsergebnisse werden aus 5 Parallelversuchen ermittelt.The measurement is carried out on an automatically controlled toilet system that is in Dispenses the contents of the water box and the box every 1 hour new with 9 l tap water with 17 ° d and a water temperature of 15 - 16 ° C crowded. There is 1 filling of a vessel according to DE 195 201 45 in the Toilets hooked in and determined how many flushes to complete Consumption are possible. The average results are from 5 Parallel experiments determined.
Vorgewogene weiße Carrara-Marmorplatten mit der Abmessung 75 x 150 x 5 mm werden in einer Plexiglasküvette vollständig in das Gel eingetaucht. Dies geschieht für eine Zeit von 10 sec. Danach wird die Platte entnommen und senkrecht in ein dafür vorgesehenes Stativ gestellt. Das hat so zu geschehen, daß anhaftendes Produkt ablaufen kann. Die Einwirkzeit des anhaftenden Produktes beträgt weitere 10 min. Danach wird die Platte mit Wasser abgespült und nach Trocknung bei 105 °C der Gewichtsverlust ermittelt.Pre-weighed white Carrara marble slabs measuring 75 x 150 x 5 mm are completely immersed in the gel in a plexiglass cell. This happens for a time of 10 sec. Then the plate is removed and placed vertically in a tripod intended for this purpose. This has to happen that adhering product can run off. The exposure time of the adhesive Product is another 10 min. The plate is then rinsed off with water and after drying at 105 ° C the weight loss is determined.
Die Messung erfolgte elektrochemisch im Konzentrat.The measurement was carried out electrochemically in the concentrate.
Die Lagerung erfolgte in elektrisch gesteuerten Wärmekammern. Die Lagerzeit bei 40 °C beträgt 3 und 4 Wochen, bei 23 °C 12 Wochen. Danach erfolgte eine visuelle Abmusterung der gelagerten Ware.The storage took place in electrically controlled heating chambers. The storage time 3 and 4 weeks at 40 ° C and 12 weeks at 23 ° C. Then there was a visual inspection of the stored goods.
Die Herstellung kann in den unterschiedlichsten Ansatzgrößen bis zum
Tonnenmaßstab durchgeführt werden. Üblicherweise wird Wasser in einer
handelsüblichen Mischeranlage, wie z. B. einer Beco-Mix-Anlage vorgelegt, und
der Farbstoff eingerührt. Der verwendete Xanthan Gum wird mit Lösungsmittel,
bevorzugt Ethanol und dem gewünschten Parfumöl separat aufgeschlämmt. Die
Suspension wird der wässerigen Vorlage zugegeben und mit geringen
Geschwindigkeiten, beispielsweise 30 Upm gerührt.
Es zeigt sich bei den Untersuchungen, daß nach Zugabe aller Komponenten eine
Zeit zwischen wenigen Minuten und einigen Stunden zur Erreichung der
erfindungsgemäßen Konsistenz wünschenswert ist. Im vorliegenden Fall wurde
nach 30 min das Tensid (Alkylpolyglycosid) langsam zudosiert. Anschließend
wurde die Zitronensäure zugesetzt.
Soll ein blasenfreies Gel gewährleistet werden, ist die Mischung in einem
geeigneten Behälter in Abhängigkeit von der Viskosität in der Regel aber für eine
kurze Zeit, beispielsweise 15 min unter reduzierten Druck oder ein Vakuum zu
setzen.
Die Abfüllung in die geeigneten Vorratsbehälter kann dann z. B. über einen
geeigneten handelsüblichen Tubenfüller erfolgen.The production can be carried out in the most varied batch sizes up to the ton scale. Usually water is in a commercial mixer, such as. B. submitted to a Beco mix system, and the dye stirred. The xanthan gum used is slurried separately with solvent, preferably ethanol and the desired perfume oil. The suspension is added to the aqueous receiver and stirred at low speeds, for example 30 rpm.
It turns out in the investigations that, after all components have been added, a time between a few minutes and a few hours is desirable in order to achieve the consistency according to the invention. In the present case, the surfactant (alkyl polyglycoside) was slowly added after 30 minutes. The citric acid was then added.
If a bubble-free gel is to be ensured, the mixture should, as a rule, be placed in a suitable container depending on the viscosity for a short time, for example 15 minutes under reduced pressure or under a vacuum.
The filling in the suitable storage container can then, for. B. via a suitable commercially available tube filler.
12 Wochen bei 23 °C keine Phasentrennung4 weeks at 40 ° C air bubbles in the gel stable
No phase separation for 12 weeks at 23 ° C
Die Herstellung kann auch hier in den unterschiedlichsten Ansatzgrößen bis zum
Tonnenmaßstab durchgeführt werden.
Üblicherweise wird hier Wasser in einer handelsüblichen Mischeranlage, wie z. B.
einer Beco-Mix-Anlage vorgelegt und der verwendete Xanthan Gum eingerührt .
Die Suspension wird der Vorlage zugegeben und mit geringen
Geschwindigkeiten, beispielsweise 30 Upm gerührt, bevor nach 30 min das
Tensid (bzw. das Tensidgemisch; siehe nachfolgende Beispiele) langsam
zudosiert wurde. Anschließend wurde der Farbstoff zugegeben, bevor eine
ethanolische Lösung des Parfums nachdosiert wurde. Danach wurde das
Desinfektionsmittel zugegeben.
Die Abfüllung kann in diesem Fall z. B. über einen Flaschenrundläufer in eine
handelsübliche Dosierflasche erfolgen.Here, too, production can be carried out in a wide variety of batch sizes up to the ton scale.
Usually water is here in a commercial mixer, such as. B. submitted to a Beco mix system and stirred in the xanthan gum used. The suspension is added to the initial charge and stirred at low speeds, for example 30 rpm, before the surfactant (or the surfactant mixture; see examples below) was slowly metered in after 30 minutes. The dye was then added before an ethanolic solution of the perfume was replenished. The disinfectant was then added.
The filling can in this case, for. B. done in a commercial dosing bottle over a bottle runner.
Die Einarbeitung von hohen Parfumgehalten bedarf u. U. kleinerer Dosierschritte, um die Phasenstabilität noch zu gewährleisten. The incorporation of high perfume contents may require U. smaller dosing steps, to still ensure phase stability.
12 Wochen 23 °C keine Phasentrennung3 weeks 40 ° C no phase separation
12 weeks at 23 ° C no phase separation
- A1, A2A1, A2
- Kochsalzverdicktes TensidsystemSaline thickened surfactant system
- B1, B2, B3B1, B2, B3
- Gel auf PolyacrylsäurebasisPolyacrylic acid based gel
- C1C1
- Gel auf Hydroxyethylcellulose-BasisHydroxyethyl cellulose-based gel
Claims (20)
- Stable gelatinous cleaning composition which thins on application of shear forces and comprises polysaccharide, as surfactant system a C8- to C22-alkyl polyglycoside and perfume components, characterized in thata) as polysaccharide xanthan gum and/or guar gum is/are present in amounts between 1 and 5% by weight,b) as a component of the surfactant system, a C8- to C22-alkyl polyglycoside is present in amounts between 3 and 25% by weight andc) the perfume component or the perfume components is/are present in amounts of from 2 to 15% by weightd) and, where appropriate, other ingredients such as co-surfactants, limescale-dissolving agents, dyes, antibacterial agents, pearlizing agents, stabilizers, detergency boosters and odour-absorbers are present, wheree) the compositions have a viscosity of from 30,000 to 150,000 mPas, measured using a Brookfield RVT rotation viscometer with Helipath stand and TA spindle at 1 rpm and 23°C.
- Composition according to Claim 1, characterized in that it comprises xanthan gum and/or guar gum in amounts between 1 and 4% by weight, preferably between 1.5 and 3.5% by weight and in particular between 1.8 and 3% by weight.
- Composition according to Claim 1 or 2, characterized in that it comprises C8- to C22-alkyl polyglycosides in amounts of from 4 to 20% by weight, preferably from 5 to 17% by weight and in particular from 5 to 15% by weight.
- Composition according to one of Claims 1 to 3, characterized in that it comprises the perfume component(s) in amounts of from 2 to 12% by weight and preferably from 3 to 8% by weight.
- Composition according to one of Claims 1 to 4, characterized in that it contains air bubbles, preferably those having diameters of from 0.1 to 20 mm, where, advantageously, not more than 30 vol-% of air are present.
- Composition according to one of Claims 1 to 5, characterized in that the limescale-dissolving agents are inorganic or organic acids or salts thereof or mixtures thereof, preferably citric acid, acetic acid, lactic acid, in amounts of from 1 to 12% by weight, preferably from 2 to 5% by weight.
- Composition according to one of Claims 1 to 6, characterized in that a dye, preferably in watersoluble form, is present in amounts up to 5% by weight, preferably up to 3% by weight, particularly preferably up to 2% by weight and very particularly preferably up to 1% by weight.
- Composition according to one of Claims 1 to 7, characterized in that an antibacterial agent, preferably chosen from the group consisting of isothiazolines, benzoates or salicylic acid or salicylates, is present in amounts up to 5% by weight, preferably from 0.01 to 3% by weight, particularly preferably from 0.01 to 2% by weight and very particularly preferably from 0.01 to 1% by weight.
- Composition according to one of Claims 1 to 8, characterized in that a builder or complexing agent, preferably chosen from the group of citrates, is present in amounts up to 10% by weight, preferably from 0.1 to 8% by weight, particularly preferably from 1 to 6% by weight and very particularly preferably from 2 to 5% by weight.
- Composition according to one of Claims 1 to 9, characterized in that a solvent, preferably chosen from the group of lower alcohols, is present in amounts up to 5% by weight, preferably from 0.01 to 4% by weight, and very particularly preferably from 0.5 to 3% by weight.
- Composition according to one of Claims 1 to 10, characterized in that the additional co-surfactants are fatty alcohol ether sulphates (FAEOS) and/or fatty alcohol sulphates (FAS), the weight ratio of alkyl polyglycoside to co-surfactant preferably being at least 1, advantageously between 50:1 and 1:1, particularly preferably between 10:1 and 1.5 to 1 and very particularly preferably between 5:1 and 1.8:1.
- Process for the preparation of the cleaning compositions according to one of Claims 1 to 11, characterized in that the polysaccharide is slurried separately in a solvent from the group of lower monohydric alcohols, preferably ethanol, with the desired perfume oil, added to an aqueous solution which may contain a dye, and then, optionally after a waiting period of between a few minutes and several hours, the surfactant or the surfactant mixture is slowly metered in and then the other ingredients are added, before, if desired, a reduced pressure is applied for a period of between a few minutes and several hours.
- Use of the cleaning compositions according to one of Claims 1 to 11 as a cleaning composition for flush toilets.
- Process for cleaning a flush toilet wherein flushing water flows over a receptacle filled with a cleaning composition and hung into the toilet, characterized in that the receptacle contains a cleaning composition according to any one of Claims 1 to 11.
- Process according to Claim 14, characterized in that the receptacle is refilled with cleaning composition, preferably from a storage container containing the cleaning composition, especially from a dosing bottle.
- System for cleaning a flush toilet, containing a cleaning composition according to any one of Claims 1 to 11 and a receptacle suitable for the cleaning composition.
- System according to Claim 16, characterized in that the cleaning composition is contained in a storage container or a dosing bottle for refilling the receptacle.
- System according to Claim 16 or 17, characterized in that the receptacle is hung into the toilet.
- System according to any one of Claims 16 to 18, characterized in that the receptacle contains a filling of the cleaning composition.
- Use of a system according to Claim 16 to 19 for cleaning flush toilets.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK98921455T DK0975721T3 (en) | 1997-04-16 | 1998-04-11 | Gel-shaped detergent for flushing toilets |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19715872 | 1997-04-16 | ||
| DE19715872A DE19715872C2 (en) | 1997-04-16 | 1997-04-16 | Gel-shaped detergent for flush toilets |
| PCT/EP1998/002123 WO1998046712A1 (en) | 1997-04-16 | 1998-04-11 | Gelled cleaning agent for flush toilets |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0975721A1 EP0975721A1 (en) | 2000-02-02 |
| EP0975721B1 true EP0975721B1 (en) | 2004-06-16 |
Family
ID=7826682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98921455A Expired - Lifetime EP0975721B1 (en) | 1997-04-16 | 1998-04-11 | Gelled cleaning agent for flush toilets |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0975721B1 (en) |
| JP (1) | JP2001518969A (en) |
| AT (1) | ATE269389T1 (en) |
| BR (1) | BR9811461A (en) |
| CA (1) | CA2287449A1 (en) |
| DE (2) | DE19715872C2 (en) |
| DK (1) | DK0975721T3 (en) |
| ES (1) | ES2224390T3 (en) |
| WO (1) | WO1998046712A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4332207A1 (en) * | 2022-08-29 | 2024-03-06 | Henkel AG & Co. KGaA | Water loss stable gel composition |
Families Citing this family (52)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19826293A1 (en) | 1998-06-12 | 2000-03-23 | Buck Chemie Gmbh | Sanitary ware |
| DE19853110A1 (en) | 1998-11-18 | 2000-05-25 | Cognis Deutschland Gmbh | Gel-shaped detergent for flush toilets |
| DE19906481A1 (en) * | 1999-02-17 | 2000-08-24 | Cognis Deutschland Gmbh | Gel-shaped detergent for flush toilets |
| DE19910788A1 (en) * | 1999-03-11 | 2000-09-14 | Cognis Deutschland Gmbh | Gel-shaped detergent for flush toilets |
| DE19918192A1 (en) * | 1999-04-22 | 2000-10-26 | Cognis Deutschland Gmbh | Cleaning agent for hard surfaces, especially flush toilet pans, comprising a mixture of alk(en)yl oligoglycoside, alk(en)yl (ether)sulfate and/or betaine, and terpene alcohol |
| DE19918189A1 (en) * | 1999-04-22 | 2000-10-26 | Cognis Deutschland Gmbh | Cleaning agent for hard surfaces, especially flush toilet pans, comprising a mixture of alk(en)yl oligoglycoside, alk(en)yl (ether)sulfate and/or betaine, and alkanediol |
| DE19918186A1 (en) * | 1999-04-22 | 2000-10-26 | Cognis Deutschland Gmbh | Cleaning agent, typically in form of viscous gel, includes oligoglycoside derivative, poly(meth)acrylamidoalkyl alkanesulfonic acid and sulfate or betaine component |
| DE19918182A1 (en) * | 1999-04-22 | 2000-10-26 | Cognis Deutschland Gmbh | Cleaning agent for hard surfaces, especially flush toilet pans, comprising a mixture of alk(en)yl oligoglycoside, alk(en)yl (ether)sulfate and/or betaine, and cellulosepolyglycolester |
| DE19918191A1 (en) * | 1999-04-22 | 2000-10-26 | Cognis Deutschland Gmbh | Cleaning agent for hard surfaces, especially flush toilet pans, comprising a mixture of alk(en)yl oligoglycoside, alk(en)yl (ether)sulfate and/or betaine, and ethoxylated glucoside ester |
| DE19918188A1 (en) | 1999-04-22 | 2000-10-26 | Cognis Deutschland Gmbh | Cleaning agent, especially for cleaning toilet bowls, is typically in form of high foaming viscous gel and includes ethoxylated fatty amine as a thickener |
| DE19918184A1 (en) * | 1999-04-22 | 2000-10-26 | Cognis Deutschland Gmbh | Cleaning agent for hard surfaces, especially flush toilet pans, comprising a mixture of alk(en)yl oligoglycoside, alk(en)yl (ether)sulfate and/or betaine, and fatty alcoholpolyglycolether with narrow homologue distribution |
| DE19918185A1 (en) * | 1999-04-22 | 2000-10-26 | Cognis Deutschland Gmbh | Hard surface detergent, typically in form of high foaming viscous gel, includes oligoglycoside derivative, glycerin fatty acid ester and sulfate or betaine component |
| DE19924368A1 (en) * | 1999-05-27 | 2000-11-30 | Henkel Ecolab Gmbh & Co Ohg | Cleaning tablets containing surfactants |
| GB2360293A (en) * | 2000-03-14 | 2001-09-19 | Procter & Gamble | Detergent compositions |
| DE10012949A1 (en) | 2000-03-16 | 2001-09-27 | Henkel Kgaa | Mixtures of cyclic and linear silicic esters of lower alcohols and fragrance and/or biocide alcohols are used as fragrance and/or biocide in liquid or solid laundry and other detergents and in skin and hair cosmetics |
| US7048205B2 (en) | 2000-07-12 | 2006-05-23 | S.C. Johnson & Son, Inc. | Lavatory freshening and/or cleaning system and method |
| GB2364710B (en) * | 2000-07-12 | 2003-01-15 | Johnson & Son Inc S C | Lavatory freshening and/or cleaning system and method |
| GB2364709B (en) * | 2000-07-12 | 2004-12-22 | Johnson & Son Inc S C | Lavatory freshening and/or cleaning system and method |
| DE10048887A1 (en) * | 2000-09-29 | 2002-04-18 | Buck Chemie Gmbh | Adhesive sanitary cleaner and fragrance |
| EP1373449B1 (en) * | 2001-01-11 | 2005-12-07 | Dietrich, René | Agent for removing solid particles |
| JP4541076B2 (en) * | 2004-09-07 | 2010-09-08 | 京都リフレ新薬株式会社 | Urine stone adhesion inhibitor |
| DE102004056554A1 (en) * | 2004-11-23 | 2006-05-24 | Buck-Chemie Gmbh | Adhesive sanitary cleaning and scenting agent |
| JP2005330498A (en) * | 2005-05-09 | 2005-12-02 | Sara Lee De Nv | Freshener-/cleaner-system for lavatory |
| EP1894989A1 (en) * | 2006-09-01 | 2008-03-05 | The Procter and Gamble Company | Pasty Composition for Sanitary Ware |
| EP1894578A1 (en) * | 2006-09-01 | 2008-03-05 | The Procter and Gamble Company | Method of applying a pasty composition for sanitary ware |
| EP1894990A1 (en) * | 2006-09-01 | 2008-03-05 | The Procter and Gamble Company | Unit dose of pasty composition for sanitary ware |
| US7414016B1 (en) * | 2007-11-01 | 2008-08-19 | The Clorox Company | Acidic cleaning compositions |
| US8980813B2 (en) | 2008-02-21 | 2015-03-17 | S. C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion on a vertical hard surface and providing residual benefits |
| US8143206B2 (en) * | 2008-02-21 | 2012-03-27 | S.C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion and providing residual benefits |
| US9481854B2 (en) | 2008-02-21 | 2016-11-01 | S. C. Johnson & Son, Inc. | Cleaning composition that provides residual benefits |
| US8993502B2 (en) | 2008-02-21 | 2015-03-31 | S. C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion to a vertical hard surface and providing residual benefits |
| US9410111B2 (en) | 2008-02-21 | 2016-08-09 | S.C. Johnson & Son, Inc. | Cleaning composition that provides residual benefits |
| JP2011513510A (en) | 2008-02-21 | 2011-04-28 | エス．シー． ジョンソン アンド サン、インコーポレイテッド | Cleaning compositions that have high self-adhesive properties and provide benefits from residue |
| DE102009001841A1 (en) * | 2009-03-25 | 2010-09-30 | Henkel Ag & Co. Kgaa | System of detergent and dispenser |
| JP5579593B2 (en) * | 2010-12-22 | 2014-08-27 | ニュートリー株式会社 | Jelly cleaning composition |
| EP2662435B1 (en) | 2012-05-11 | 2016-12-28 | Eurvest | Sanitary composition |
| BR112015025049B1 (en) | 2013-04-25 | 2021-03-09 | Unilever Ip Holdings B.V. | cleaning fluid composition |
| WO2014180579A1 (en) | 2013-05-10 | 2014-11-13 | Eurvest Sa | New sanitary composition |
| DE102013226098A1 (en) | 2013-12-16 | 2015-06-18 | Henkel Kgaa | Silyl enol ethers of fragrance ketones or aldehydes |
| DE102013226216A1 (en) | 2013-12-17 | 2015-06-18 | Henkel Ag & Co. Kgaa | Michael systems for perfume stabilization |
| DE102013226602A1 (en) | 2013-12-19 | 2015-06-25 | Henkel Ag & Co. Kgaa | Use of CNGA2 agonists to enhance the olfactory effect of a fragrance |
| EP2963103A1 (en) | 2014-07-04 | 2016-01-06 | Henkel AG & Co. KGaA | pH-sensitive nanocapsules |
| DE102017123282A1 (en) | 2017-10-06 | 2019-04-11 | Henkel Ag & Co. Kgaa | Hydrolysis-labile silyl enol ethers of fragrance ketones or aldehydes |
| DE102017124611A1 (en) | 2017-10-20 | 2019-04-25 | Henkel Ag & Co. Kgaa | Thermolabile fragrance storage substances of fragrance ketones |
| DE102017124612A1 (en) | 2017-10-20 | 2019-04-25 | Henkel Ag & Co. Kgaa | Hydrolysis-labile dienol silyl ethers of fragrance ketones or aldehydes |
| DE102017127776A1 (en) | 2017-11-24 | 2019-05-29 | Henkel Ag & Co. Kgaa | Hydrolysis-labile heterocycles of perfume ketones or aldehydes |
| DE102018210801A1 (en) * | 2018-06-29 | 2020-01-02 | Henkel Ag & Co. Kgaa | Self-adhesive foaming sanitary products |
| PL3722401T3 (en) | 2019-04-10 | 2024-05-13 | Henkel Ag & Co. Kgaa | Gel sanitary agent for biofilm inhibition |
| EP4098734A1 (en) | 2021-06-02 | 2022-12-07 | Henkel AG & Co. KGaA | Wc system with multiphase gel composition |
| DE102022121759A1 (en) | 2022-08-29 | 2024-02-29 | Henkel Ag & Co. Kgaa | TEMPERATURE STABLE GEL COMPOSITIONS |
| DE102023202757A1 (en) | 2023-03-27 | 2024-10-02 | Henkel Ag & Co. Kgaa | Process for producing a gel-form cleaning agent |
| DE102023202758A1 (en) * | 2023-03-27 | 2024-10-02 | Henkel Ag & Co. Kgaa | Process for producing a gel-form cleaning agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4668422A (en) * | 1985-05-31 | 1987-05-26 | A. E. Staley Manufacturing Company | Liquid hand-soap or bubble bath composition |
| CA1321115C (en) * | 1987-12-30 | 1993-08-10 | Robert Corring | Gel detergent compositions |
| US5047167A (en) * | 1987-12-30 | 1991-09-10 | Lever Brothers Company, Division Of Conopco, Inc. | Clear viscoelastic detergent gel compositions containing alkyl polyglycosides |
| CA2014220C (en) * | 1989-04-11 | 1995-11-07 | Peter Leonard Dawson | Cleaning composition |
| AU663854B2 (en) * | 1990-09-28 | 1995-10-26 | Procter & Gamble Company, The | Detergent compositions containing polyhydroxy fatty acid amides and suds enhancing agent |
| GB9103090D0 (en) * | 1991-02-14 | 1991-04-03 | Unilever Plc | Hair care compositions |
| GB2288186A (en) * | 1994-02-17 | 1995-10-11 | Kelco Int Ltd | Toilet cleansing gel block |
-
1997
- 1997-04-16 DE DE19715872A patent/DE19715872C2/en not_active Expired - Lifetime
-
1998
- 1998-04-11 CA CA002287449A patent/CA2287449A1/en not_active Abandoned
- 1998-04-11 EP EP98921455A patent/EP0975721B1/en not_active Expired - Lifetime
- 1998-04-11 BR BR9811461-1A patent/BR9811461A/en not_active Application Discontinuation
- 1998-04-11 ES ES98921455T patent/ES2224390T3/en not_active Expired - Lifetime
- 1998-04-11 JP JP54347498A patent/JP2001518969A/en active Pending
- 1998-04-11 WO PCT/EP1998/002123 patent/WO1998046712A1/en active IP Right Grant
- 1998-04-11 DE DE59811584T patent/DE59811584D1/en not_active Expired - Lifetime
- 1998-04-11 DK DK98921455T patent/DK0975721T3/en active
- 1998-04-11 AT AT98921455T patent/ATE269389T1/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4332207A1 (en) * | 2022-08-29 | 2024-03-06 | Henkel AG & Co. KGaA | Water loss stable gel composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2287449A1 (en) | 1998-10-22 |
| ATE269389T1 (en) | 2004-07-15 |
| DK0975721T3 (en) | 2004-10-25 |
| DE19715872A1 (en) | 1998-10-22 |
| EP0975721A1 (en) | 2000-02-02 |
| DE59811584D1 (en) | 2004-07-22 |
| JP2001518969A (en) | 2001-10-16 |
| DE19715872C2 (en) | 1999-04-29 |
| BR9811461A (en) | 2000-09-12 |
| WO1998046712A1 (en) | 1998-10-22 |
| ES2224390T3 (en) | 2005-03-01 |
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