CA2292966A1 - A multiphase cleaning composition containing end-capped polyalkoxylated alcohol - Google Patents
A multiphase cleaning composition containing end-capped polyalkoxylated alcohol Download PDFInfo
- Publication number
- CA2292966A1 CA2292966A1 CA002292966A CA2292966A CA2292966A1 CA 2292966 A1 CA2292966 A1 CA 2292966A1 CA 002292966 A CA002292966 A CA 002292966A CA 2292966 A CA2292966 A CA 2292966A CA 2292966 A1 CA2292966 A1 CA 2292966A1
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- Canada
- Prior art keywords
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- carbon atoms
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- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 144
- 238000004140 cleaning Methods 0.000 title claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000012071 phase Substances 0.000 claims abstract description 119
- 230000000694 effects Effects 0.000 claims abstract description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 41
- 239000008346 aqueous phase Substances 0.000 claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 30
- 239000000839 emulsion Substances 0.000 claims abstract description 24
- 150000001298 alcohols Chemical class 0.000 claims abstract description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 18
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000001033 ether group Chemical group 0.000 claims abstract description 7
- 125000002015 acyclic group Chemical group 0.000 claims abstract description 6
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 239000002250 absorbent Substances 0.000 claims abstract description 4
- 230000002745 absorbent Effects 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 4
- 238000005507 spraying Methods 0.000 claims abstract description 3
- -1 terpene hydrocarbons Chemical class 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 239000002736 nonionic surfactant Substances 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 16
- 239000003945 anionic surfactant Substances 0.000 claims description 16
- 239000007921 spray Substances 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 229920000151 polyglycol Polymers 0.000 claims description 9
- 239000010695 polyglycol Substances 0.000 claims description 9
- 235000007586 terpenes Nutrition 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 239000002304 perfume Substances 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 229920001522 polyglycol ester Polymers 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 235000019502 Orange oil Nutrition 0.000 claims description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010502 orange oil Substances 0.000 claims description 2
- 239000010665 pine oil Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 125000005233 alkylalcohol group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229920001451 polypropylene glycol Polymers 0.000 claims 1
- 230000000875 corresponding effect Effects 0.000 description 30
- 229920001732 Lignosulfonate Polymers 0.000 description 13
- VPMMJSPGZSFEAH-UHFFFAOYSA-N 2,4-diaminophenol;hydrochloride Chemical compound [Cl-].NC1=CC=C(O)C([NH3+])=C1 VPMMJSPGZSFEAH-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000002689 soil Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000011086 high cleaning Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920005682 EO-PO block copolymer Polymers 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 239000011970 polystyrene sulfonate Substances 0.000 description 2
- 229960002796 polystyrene sulfonate Drugs 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLWCIHPMASUXPI-UHFFFAOYSA-N 1,1'-(propane-1,2-diyl)dibenzene Chemical compound C=1C=CC=CC=1C(C)CC1=CC=CC=C1 XLWCIHPMASUXPI-UHFFFAOYSA-N 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- VEAFKIYNHVBNIP-UHFFFAOYSA-N 1,3-Diphenylpropane Chemical compound C=1C=CC=CC=1CCCC1=CC=CC=C1 VEAFKIYNHVBNIP-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- XJGHNXQUBBXYCH-UHFFFAOYSA-N 1-phenylbutan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(CC)CC1=CC=CC=C1 XJGHNXQUBBXYCH-UHFFFAOYSA-N 0.000 description 1
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 1
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- ZWZGXLKXKAPXMZ-UHFFFAOYSA-N 2,2'-dihydroxy-3,3'-dimethoxy-5,5'-dipropyldiphenylmethane Chemical compound COC1=CC(CCC)=CC(CC=2C(=C(OC)C=C(CCC)C=2)O)=C1O ZWZGXLKXKAPXMZ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- SGQUHMXHLSTYIH-UHFFFAOYSA-N 2-phenylbutan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(CC)C1=CC=CC=C1 SGQUHMXHLSTYIH-UHFFFAOYSA-N 0.000 description 1
- MILSYCKGLDDVLM-UHFFFAOYSA-N 2-phenylpropan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 MILSYCKGLDDVLM-UHFFFAOYSA-N 0.000 description 1
- LTMXQBYDTUQJGE-UHFFFAOYSA-N 3-phenylpentan-3-ylbenzene Chemical compound C=1C=CC=CC=1C(CC)(CC)C1=CC=CC=C1 LTMXQBYDTUQJGE-UHFFFAOYSA-N 0.000 description 1
- GLJFYGFBITUZOE-UHFFFAOYSA-N 4-phenylbutylbenzene Chemical compound C=1C=CC=CC=1CCCCC1=CC=CC=C1 GLJFYGFBITUZOE-UHFFFAOYSA-N 0.000 description 1
- AZZHCIXSZZXEAS-UHFFFAOYSA-N 5-phenylpentylbenzene Chemical compound C=1C=CC=CC=1CCCCCC1=CC=CC=C1 AZZHCIXSZZXEAS-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZCBJDQBSLZREAA-UHFFFAOYSA-N Bisoxatin acetate Chemical compound C1=CC(OC(=O)C)=CC=C1C1(C=2C=CC(OC(C)=O)=CC=2)C(=O)NC2=CC=CC=C2O1 ZCBJDQBSLZREAA-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000019499 Citrus oil Nutrition 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000978776 Senegalia senegal Species 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
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000010500 citrus oil Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 125000003563 glycoside group Chemical group 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000002324 mouth wash Substances 0.000 description 1
- 229940051866 mouthwash Drugs 0.000 description 1
- ONLRKTIYOMZEJM-UHFFFAOYSA-N n-methylmethanamine oxide Chemical compound C[NH+](C)[O-] ONLRKTIYOMZEJM-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked 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
- 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
- C11D17/0017—Multi-phase liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/18—Glass; Plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
End-capped polyalkoxylated alcohols corresponding to formula I:
R1O[CH2CH(CH)3O]p[CH2CH(R2)O]qR3 (I) in which R1 is a linear aliphatic hydrocarbon radical containing 1 to about 22 carbon atoms or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, R3 is a linear or branched, saturated or unsaturated, aliphatic, optionally aryl-substituted, acyclic or cyclic hydrocarbon radical containing 1 to about 78 carbon atoms and optionally one or more hydroxy groups and/or ether groups -O- or a mixture of various such radicals, p is a number of 0 to about 15 and q is a number of 0 to about 50, the sum of p and q being at least 1, may be used (i) in a liquid multiphase cleaning composition with at least two continuous phases which contains at least one aqueous phase I and a non-aqueous liquid phase II immiscible with this aqueous phase and which can be temporarily converted into an emulsion by shaking, (ii) in a composition for cleaning hard surfaces to reduce the rain effect and/or the film effect, (iii) in a process for reducing the rain effect and/or the film effect on a hard surface treated with a liquid cleaning composition, the surface being treated with a liquid cleaning composition in concentrated or diluted form containing at least one end-capped polyalkoxylated alcohol corresponding to formula I and (iv) in a process for cleaning hard surfaces, more particularly glass, in which a cleaning composition according to (i) is temporarily converted into an emulsion by shaking, applied to the surface to be cleaned, preferably by spraying, in quantities of 1.5 to 10 g per m2 and the surface is then optionally cleaned by wiping with a soft absorbent material.
R1O[CH2CH(CH)3O]p[CH2CH(R2)O]qR3 (I) in which R1 is a linear aliphatic hydrocarbon radical containing 1 to about 22 carbon atoms or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, R3 is a linear or branched, saturated or unsaturated, aliphatic, optionally aryl-substituted, acyclic or cyclic hydrocarbon radical containing 1 to about 78 carbon atoms and optionally one or more hydroxy groups and/or ether groups -O- or a mixture of various such radicals, p is a number of 0 to about 15 and q is a number of 0 to about 50, the sum of p and q being at least 1, may be used (i) in a liquid multiphase cleaning composition with at least two continuous phases which contains at least one aqueous phase I and a non-aqueous liquid phase II immiscible with this aqueous phase and which can be temporarily converted into an emulsion by shaking, (ii) in a composition for cleaning hard surfaces to reduce the rain effect and/or the film effect, (iii) in a process for reducing the rain effect and/or the film effect on a hard surface treated with a liquid cleaning composition, the surface being treated with a liquid cleaning composition in concentrated or diluted form containing at least one end-capped polyalkoxylated alcohol corresponding to formula I and (iv) in a process for cleaning hard surfaces, more particularly glass, in which a cleaning composition according to (i) is temporarily converted into an emulsion by shaking, applied to the surface to be cleaned, preferably by spraying, in quantities of 1.5 to 10 g per m2 and the surface is then optionally cleaned by wiping with a soft absorbent material.
Description
A Multiphase Cleaning Composition Containing End-capped Polyalkoxylated Alcohol This invention relates to multiphase, liquid cleaning compositions containing end-capped polyalkoxylated alcohol which can be temporarily emulsified by shaking and which may be used for cleaning hard surfaces, more particularly glass, and to a process for cleaning hard surfaces.
The cleaning compositions typically used nowadays for cleaning hard surfaces are generally aqueous preparations in the form of a stable solution or dispersion which contain surfactants, organic solvents and optionally complexing agents for the hardness constituents of water, abrasives and alkalis with a cleaning effect as their key active ingredients.
Cleaning compositions intended above all for cleaning glass and ceramic surfaces are often formulated as solutions of the active ingredients in a mixture of water and water-miscible organic solvents, primarily lower alcohols and glycol ethers. Examples of such compositions can be found in DE-OS 22 20 540, in US patents 3,389,234 and 3,882,038 and in European patent applications 344 847 and 393 772.
So far as their practical application is concerned, the cleaning compositions are expected to combine high cleaning performance with simple and convenient application. In most cases, the compositions are expected to develop the required effect after a single application, i.e. in the absence of further measures. Difficulties arise here - above all where the compositions are applied to smooth surfaces, particularly to reflective surfaces, such as glass or ceramic surfaces - out of the fact that compositions which have a favorable cleaning performance generally do not dry without leaving streaks while compositions which dry largely without any visible residues have only a limited cleaning effect. In order to combine an adequate cleaning effect, particularly against fatty soils, with acceptable residue behavior, relatively large quantities of more or less volatile alkalis have to be added to the cleaning compositions in addition to organic solvents. Ammonia and alkanolamines in particular have been used for this purpose. Unfortunately, relatively high concentrations of ammonia or amine - apart from the strong odors they emit - produce a corresponding increase in the pH value of the cleaning solution with the result that relatively sensitive surfaces, for example paint surfaces, are clearly attacked by these cleaning compositions.
In addition, smooth surfaces, particularly reflective surfaces, such as glass or ceramic surfaces, present two particular problems which generally do not come to light immediately after cleaning, but only at a later stage.
The first problem is the well-known, but problematical phenomenon of the condensation of water onto the surfaces mentioned, for example in bathrooms during and after showering or bathing, which is referred to hereinafter as the film effect. The second problem is the phenomenon as well-known as it is unwelcome - although unavoidable in the long term -that, after the cleaning of a reflective surface exposed to the weather, such as window glass, a shower of rain destroys the cleaning result through the rain marks it leaves behind, which is referred to hereinafter as the rain effect.
Accordingly, there is still a need for cleaning compositions which have a high cleaning performance without any of the disadvantages mentioned above.
DE-OS 39 10 170 describes mouth-wash compositions for desorbing bacteria from hard surfaces and living tissue which are present in the form of a two-phase preparation and which can be converted by shaking into a temporary oil-in-water emulsion, the aqueous phase making up about 50 to 97% by weight and the water-immiscible oil phase about 3 to 50% by weight. Crucial to the invention is the presence of about 0.003 to 2% by weight of an amphiphilic cationic agent, for example a cationic surfactant, in a quantity which allows the formation of the oil-in-water emulsion, this emulsion collapsing and separating about 10 seconds to 30 minutes after its formation. Anionic surfactants impair the antibacterial action. Other surfactants are not mentioned.
European patent application 0 195 336 describes in two embodiments (1) and (2) compositions emulsifiable by shaking for the care of sensitive surfaces, more particularly (1 ) plastic surfaces and (2) compact discs, which - besides an aqueous phase - contain an organic phase consisting of the chlorofluorocarbon (CFC) 1,1,2-trichloro-1,2,2-trifluoroethane. In addition, the compositions are wax-free and contain in the aqueous phase (1) at least one surfactant and a water-soluble liquid silicone oil and (2) the triethanolamine salt of a C~o_~2 alkyl sulfuric acid semiester. The stability of the emulsion that can be formed by shaking is not discussed. In order to guarantee emulsifiability, the surfactant content is normally between 1 and 10% by weight, preferably between 2 and 8% by weight and, if necessary, even above 10% by weight, anionic surfactants -particularly those containing a sulfate or sulfonate group - being preferred.
However, the use of CFCs should be reduced or, better still, avoided altogether in view of their environmentally harmful properties, particularly in connection with the ozone hole.
DE-OSS 195 01 184, 195 01 187 and 195 01 188 (Henkel KGaA) relate to hair treatment compositions in the form of a two-phase system containing an oil phase and a water phase, the oil phase preferably being based on silicone oil and being mixable in a short time by mechanical action.
WO 96104358 A1 (Procter & Gamble) describes cleaning composi-tions which are capable of cleaning glass without leaving behind any troublesome stains and/or films and which contain an effective quantity of a substantive polymer containing hydrophilic groups which provides the glass with relatively high and long-lasting hydrophilia, so that, the next three times at least the glass is wetted, for example by rain, the water drains from the glass surface and few stains are left behind after drying. Substantive polymers are, in particular, polycarboxylates, such as polyvinyl pyrrolidone-co-acrylic acid), but also polystyrene sulfonate), cationic sugar and starch derivatives and block copolymers of ethylene oxide and propylene oxide, the latter polyethers in particular having relatively little substantivity.
Accordingly, the problem addressed by the present invention was to provide high-performance, storage-stable and easy-to-handle compositions for cleaning hard surfaces which would show separate phases, which could be converted into an emulsion for application, which would remain homogeneous during application and would then revert to separate phases and which, after application to the hard surface, would counteract the rain effect and the film effect, i.e. would develop an anti-rain effect and an anti-~Im effect.
In a first embodiment, the present invention relates to a liquid multiphase cleaning composition with at least two continuous phases which contains at least one aqueous phase I and a non-aqueous liquid phase II
immiscible with this aqueous phase, which can be temporarily converted into an emulsion by shaking and which contains at least one end-capped polyalkoxylated alcohol corresponding to formula I:
R' O[CH2CH(CH)30]P[CH2CH(R2)O]qR3 (I) in which R' is a linear aliphatic hydrocarbon radical containing 1 to about 22 car-bon atoms or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, R3 is a linear or branched, saturated or unsaturated, aliphatic, optionally aryl-substituted, acyclic or cyclic hydrocarbon radical containing 1 to about 78 carbon atoms arid optionally one or more hydroxy groups and/or ether groups -O- or a mixture of various such radicals, p is a number of 0 to about 15 and q is a number of 0 to about 50, the sum of p and q being at least 1.
The cleaning compositions typically used nowadays for cleaning hard surfaces are generally aqueous preparations in the form of a stable solution or dispersion which contain surfactants, organic solvents and optionally complexing agents for the hardness constituents of water, abrasives and alkalis with a cleaning effect as their key active ingredients.
Cleaning compositions intended above all for cleaning glass and ceramic surfaces are often formulated as solutions of the active ingredients in a mixture of water and water-miscible organic solvents, primarily lower alcohols and glycol ethers. Examples of such compositions can be found in DE-OS 22 20 540, in US patents 3,389,234 and 3,882,038 and in European patent applications 344 847 and 393 772.
So far as their practical application is concerned, the cleaning compositions are expected to combine high cleaning performance with simple and convenient application. In most cases, the compositions are expected to develop the required effect after a single application, i.e. in the absence of further measures. Difficulties arise here - above all where the compositions are applied to smooth surfaces, particularly to reflective surfaces, such as glass or ceramic surfaces - out of the fact that compositions which have a favorable cleaning performance generally do not dry without leaving streaks while compositions which dry largely without any visible residues have only a limited cleaning effect. In order to combine an adequate cleaning effect, particularly against fatty soils, with acceptable residue behavior, relatively large quantities of more or less volatile alkalis have to be added to the cleaning compositions in addition to organic solvents. Ammonia and alkanolamines in particular have been used for this purpose. Unfortunately, relatively high concentrations of ammonia or amine - apart from the strong odors they emit - produce a corresponding increase in the pH value of the cleaning solution with the result that relatively sensitive surfaces, for example paint surfaces, are clearly attacked by these cleaning compositions.
In addition, smooth surfaces, particularly reflective surfaces, such as glass or ceramic surfaces, present two particular problems which generally do not come to light immediately after cleaning, but only at a later stage.
The first problem is the well-known, but problematical phenomenon of the condensation of water onto the surfaces mentioned, for example in bathrooms during and after showering or bathing, which is referred to hereinafter as the film effect. The second problem is the phenomenon as well-known as it is unwelcome - although unavoidable in the long term -that, after the cleaning of a reflective surface exposed to the weather, such as window glass, a shower of rain destroys the cleaning result through the rain marks it leaves behind, which is referred to hereinafter as the rain effect.
Accordingly, there is still a need for cleaning compositions which have a high cleaning performance without any of the disadvantages mentioned above.
DE-OS 39 10 170 describes mouth-wash compositions for desorbing bacteria from hard surfaces and living tissue which are present in the form of a two-phase preparation and which can be converted by shaking into a temporary oil-in-water emulsion, the aqueous phase making up about 50 to 97% by weight and the water-immiscible oil phase about 3 to 50% by weight. Crucial to the invention is the presence of about 0.003 to 2% by weight of an amphiphilic cationic agent, for example a cationic surfactant, in a quantity which allows the formation of the oil-in-water emulsion, this emulsion collapsing and separating about 10 seconds to 30 minutes after its formation. Anionic surfactants impair the antibacterial action. Other surfactants are not mentioned.
European patent application 0 195 336 describes in two embodiments (1) and (2) compositions emulsifiable by shaking for the care of sensitive surfaces, more particularly (1 ) plastic surfaces and (2) compact discs, which - besides an aqueous phase - contain an organic phase consisting of the chlorofluorocarbon (CFC) 1,1,2-trichloro-1,2,2-trifluoroethane. In addition, the compositions are wax-free and contain in the aqueous phase (1) at least one surfactant and a water-soluble liquid silicone oil and (2) the triethanolamine salt of a C~o_~2 alkyl sulfuric acid semiester. The stability of the emulsion that can be formed by shaking is not discussed. In order to guarantee emulsifiability, the surfactant content is normally between 1 and 10% by weight, preferably between 2 and 8% by weight and, if necessary, even above 10% by weight, anionic surfactants -particularly those containing a sulfate or sulfonate group - being preferred.
However, the use of CFCs should be reduced or, better still, avoided altogether in view of their environmentally harmful properties, particularly in connection with the ozone hole.
DE-OSS 195 01 184, 195 01 187 and 195 01 188 (Henkel KGaA) relate to hair treatment compositions in the form of a two-phase system containing an oil phase and a water phase, the oil phase preferably being based on silicone oil and being mixable in a short time by mechanical action.
WO 96104358 A1 (Procter & Gamble) describes cleaning composi-tions which are capable of cleaning glass without leaving behind any troublesome stains and/or films and which contain an effective quantity of a substantive polymer containing hydrophilic groups which provides the glass with relatively high and long-lasting hydrophilia, so that, the next three times at least the glass is wetted, for example by rain, the water drains from the glass surface and few stains are left behind after drying. Substantive polymers are, in particular, polycarboxylates, such as polyvinyl pyrrolidone-co-acrylic acid), but also polystyrene sulfonate), cationic sugar and starch derivatives and block copolymers of ethylene oxide and propylene oxide, the latter polyethers in particular having relatively little substantivity.
Accordingly, the problem addressed by the present invention was to provide high-performance, storage-stable and easy-to-handle compositions for cleaning hard surfaces which would show separate phases, which could be converted into an emulsion for application, which would remain homogeneous during application and would then revert to separate phases and which, after application to the hard surface, would counteract the rain effect and the film effect, i.e. would develop an anti-rain effect and an anti-~Im effect.
In a first embodiment, the present invention relates to a liquid multiphase cleaning composition with at least two continuous phases which contains at least one aqueous phase I and a non-aqueous liquid phase II
immiscible with this aqueous phase, which can be temporarily converted into an emulsion by shaking and which contains at least one end-capped polyalkoxylated alcohol corresponding to formula I:
R' O[CH2CH(CH)30]P[CH2CH(R2)O]qR3 (I) in which R' is a linear aliphatic hydrocarbon radical containing 1 to about 22 car-bon atoms or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, R3 is a linear or branched, saturated or unsaturated, aliphatic, optionally aryl-substituted, acyclic or cyclic hydrocarbon radical containing 1 to about 78 carbon atoms arid optionally one or more hydroxy groups and/or ether groups -O- or a mixture of various such radicals, p is a number of 0 to about 15 and q is a number of 0 to about 50, the sum of p and q being at least 1.
5 In the context of the present invention, the expression immiscible non-aqueous phase means a phase not based on water as solvent, although small quantities, based on non-aqueous phase II, of water of up to 10% by weight and normally not more than 5% by weight may be dissolved in the non-aqueous phase II.
In the most simple case, a composition according to the invention comprises a continuous aqueous phase consisting of the entire phase I
and a continuous non-aqueous liquid phase consisting of the entire phase II. However, one or more continuous phases of a composition according to the invention may also contain parts of another phase in emulsified form, so that in a composition such as this part of phase I for example is present as continuous phase I, which represents the continuous aqueous phase of the composition, while another part is emulsified as discontinuous phase I
in the continuous non-aqueous phase II. The same applies to phase II and other continuous phases.
In a second embodiment, the present invention relates to the use of at least one end-capped polyalkoxylated alcohol corresponding to formula I
in a multiphase composition for cleaning hard surfaces to reduce the rain effect and/or the film effect.
In a third embodiment, the present invention relates to a process for reducing the rain effect and/or the film effect on a hard surface treated with a liquid cleaning composition, characterized in that the surface is treated with a liquid cleaning composition in concentrated or diluted form containing at least one end-capped polyalkoxylated alcohol corresponding to formula I.
The present invention also relates to a process for cleaning hard surfaces, more particularly glass, in which a cleaning composition according to the invention is temoporarily converted into an emulsion by shaking, applied to the surface to be cleaned, preferably by spraying, in quantities of 1.5 to 10 g per m2 and the surface is then optionally cleaned by wiping with a soft absorbent material.
A particular advantage of the present invention is that both an anti-rain effect and an anti-film effect are developed through the end-capped polyalkoxylated alcohols according to the invention.
The compositions according to the invention are distinguished not only by their high cleaning performance, but also by their overall high stability in storage. Thus, the individual phases in the composition are stable in storage for long periods, i.e. for example do not form any deposits, and the conversion into a temporary emulsion remains reversible, even after frequent shaking. Also, the physical form of the compositions according to the invention avoids the problem of having to stabilize a composition formulated as an emulsion per se. In addition, the separation of ingredients into separate phases can promote the chemical stability of the composition. Moreover, the compositions according to the invention show excellent residue behavior. Greasy residues are largely avoided so that the surfaces retain their shine without any need for subsequent rinsing.
The content of at least one end-capped polyalkoxylated alcohol corresponding to formula I in the composition according to the invention is normally from 0.001 to 20% by weight, preferably from 0.01 to 10% by weight, more preferably from 0.05 to 5% by weight, most preferably from 0.1 to 1.5% by weight and, in one particularly advantageous embodiment, from 0.15 to 0.5% by weight.
Examples of the end-capped polyalkoxylated alcohols corre-sponding to the invention are those corresponding to formula I in which (a) R' = C~2_~g Or C~v~4 fatty alkyl group, R2 = H, R3 = butyl group, p = 0, q =
10, (b) R' = C~2_~g fatty alkyl group, R2 = H, R3 = butyl group, p = 0, q = 5, (c) R' = CH3, R2 = H, R3 = 02/14 fatty alkyl group, p = 3, q = 5 or (d) R' =
fatty alkyl group, R2 = H, R3 =butyl group, p = 0, q = 5.
Preferred end-capped polyalkoxylated alcohols are those corre-sponding to formula I, in which p and q are both at least 1 and/or R2 is a hydrogen atom and/or R3 represents at least one hydroxy group, more particularly in the a-position, i.e. R3 is a group -CH2CH(OH)-R. End-capped polyalkoxylated alcohols corresponding to formula I, in which R3 is a group -CH2CH(OH)-R, are known for example from DE 37 23 323 A1 (Henkel KGaA).
Particularly preferred end-capped polyalkoxylated alcohols are epoxy-end-capped polyalkoxylated alcohols corresponding to formula I, in which R' is a linear aliphatic hydrocarbon radical containing about 4 to about 18 and preferably about 4 to about 12 carbon atoms, more particularly a butyl, hexyl, octyl or decyl radical or mixtures thereof, or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, preferably a hydrogen atom, R3 is a group [CH2CH(R4)O]~H, where R4 is a linear aliphatic hydrocarbon radical containing about 2 to about 26, preferably about 4 to about 18 and more preferably about 6 to about 14 carbon atoms or a mixture of various such radicals and r is a number of 1 to about 3, preferably 1 to about 2, more preferably 1, p is a number of 1 to about 5, preferably 1 to about 2 and more preferably 1 and q is a number of 1 to about 30, preferably about 4 to about 26 and more preferably about 10 to about 24, for example with R' _ Cs,~o alkyl group, R2 = H, R3 = [CH2CH(R4)O]~H with R4 = C$ alkyl group and r = 1, a = 1 and v = 22.
Corresponding epoxy-end-capped polyalkoxylated alcohols and methods for their preparation are known, for example, from WO 94122800 A1 and WO 96112001 A1.
End-capped alcohols according to the invention are obtainable, for example, under the name of Dehypon~ from Henkel KGaA or under the name of Poly Tergent~ from Olin Corporation, for example Dehypon~ LT
104, Dehypon~ LS 104, Dehypon~ LT 54, Dehypon~ LS 531 or Dehypon~ O 54 and Poly Tergent~ SLF 18 8 48, Poly Tergent~ SLF 18 B
45 or Poly Tergent~ SL 62.
In one particular embodiment of the invention, the composition is substantially CFC-free, i.e. the non-aqueous liquid phase II is not based on CFCs. The compositions according to the invention preferably contain no CFCs at all in view of their adverse effect on the environment, although small quantities, based on the composition as a whole, of up to about 5%
by weight are tolerable.
In one preferred embodiment of the invention, the continuous phases I and II are demarcated from one another by a sharp interface.
In another preferred embodiment of the invention, one or both of the continuous phases I and II contain parts, preferably 0.1 to 35% by volume and more preferably 0.2 to 20% by volume, based on the volume of the particular continuous phase, of the other phase as dispersant. Accordingly, the continuous phase I or II is reduced by that part by volume which is distributed as dispersant in the other phase. Particularly preferred compositions are characterized in that phase I is emulsified in phase II in quantities of 0.1 to 35% by volume and preferably in quantities of 0.2 to 20% by volume, based on the volume of phase II.
Another preferred embodiment of the invention is characterized in that, besides the continuous phases I and II, part of the two phases is present as an emulsion of one of the two phases in the other phase, this emulsion being demarcated by two sharp interfaces, namely an upper interface and a lower interface, from the other parts of phases I and II
which are not involved in the emulsion.
The compositions according to the invention preferably contain 5 to 95% by volume of phase I and 95 to 5% by volume of phase II.
In another preferred embodiment of the invention, the composition contains 35 to 95% by volume of phase I and 5 to 65% by volume of phase II, more preferably 55 to 95% by volume of phase I and 5 to 45% by volume of phase II and most preferably 70 to 95% by volume of phase I
and 5 to 30% by volume of phase II. In addition, the continuous phase 1 preferably represents the lower phase while the continuous phase II
represents the upper phase.
In another preferred embodiment of the invention, the water-immiscible phase II is based on aliphatic gasoline hydrocarbons and/or terpene hydrocarbons. The gasoline hydrocarbons have a boiling point range of preferably 130 to 260°C, more preferably 140 to 240°C
and most preferably 150 to 220°C, such as the C9_~3 isoparaffins with a boiling point range of 184 to 217°C obtainable, for example, as Shellsol~ T from Deutsche Shell Chemie AG (Eschborn). Suitable terpene hydrocarbons are, for example, citrus oils such as the orange oil obtained from the peel of oranges, the orange terpenes - particularly limonene - present therein or pine oil extracted from roots and stubs. Phase II may also consist entirely of aliphatic gasoline hydrocarbons and/or terpene hydrocarbons. In this case, phase II contains gasoline hydrocarbons in quantities of preferably at least 60% by weight, more preferably 90 to 99.99% by weight, most preferably 95 to 99.9% by weight and, in one particularly advantageous embodiment, 97 to 99% by weight.
Suitable surface-active substances for the compositions according to the invention are surfactants, more particularly from the classes of anionic and nonionic surfactants. The compositions preferably contain ani-onic and nonionic surfactants, the anionic surfactants being present in particular in phase I. The quantity of anionic surfactant, based on phase I, is normally not more than 10% by weight, preferably between 0.01 and 5%
by weight, more preferably between 0.01 and 0.5% by weight and most preferably between 0.1 and 0.3% by weight. Where the compositions contain nonionic surfactants, their concentration preferably in phase I, based on phase I, is normally no higher than 3% by weight, preferably between 0.001 and 0.3% by weight and more preferably between 0.001 and 0.1% by weight, and in phase II, based on phase II, normally no higher than 5% by weight, preferably between 0.001 and 0.5% by weight, more 5 preferably between 0.001 and 0.2% by weight, most preferably between 0.005 and 0.1 % by weight and, in one particularly advantageous embodiment, between 0.01 and 0.05% by weight.
Preferred anionic surfactants are Ca_~8 alkyl benzenesulfonates, more particularly containing about 12 carbon atoms in the alkyl moiety, Ca_2o 10 alkane sulfonates, C$_~s monoalkyl sulfates, C$_~8 alkyl polyglycol ether sulfates containing 2 to 6 ethylene oxide units (EO) in the ether moiety and sulfosuccinic acid esters containing 8 to 18 carbon atoms in the alcohol moieties.
The anionic surfactants are preferably used as sodium salts, although they may also be present as other alkali metal or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or amine salts.
Examples of such surfactants are sodium cocoalkyl sulfate, sodium sec.-alkane sulfonate containing about 15 carbon atoms and sodium dioctyl sulfosuccinate. Fatty alkyl sulfates containing 12 to 14 carbon atoms and sodium lauryl ether sulfate containing 2 EO have proved to be particularly suitable.
The nonionic surfactants used include, above all, Ca_~$ alcohol polyglycol ethers, i.e. ethoxylated alcohols containing 8 to 18 carbon atoms in the alkyl moiety and 2 to 15 ethylene oxide units (EO), C8_~$ carboxylic acid polyglycol esters containing 2 to 15 EO, ethoxylated fatty acid amides containing 12 to 18 carbon atoms in the fatty acid moiety and 2 to 8 EO, long-chain amine oxides containing 14 to 20 carbon atoms and long-chain alkyl polyglycosides containing 8 to 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units. Examples of such surfactants are oleyl/cetyl ' CA 02292966 1999-12-17 alcohol containing 5 EO, nonylphenol containing 10 EO, lauric acid di-ethanolamide, cocoalkyl dimethyl amine oxide and cocoalkyl polyglucoside containing on average 1.4 glucose units.
Besides the addition products of ethylene oxide and fatty alcohols containing in particular 4 to 8 ethylene oxide units, preferred nonionic surfactants in the aqueous phase are the alkyl polyglycosides, of which those containing 8 to 10 carbon atoms in the alkyl moiety and up to 2 glucose units are preferred. Particularly preferred nonionic surfactants in the non-aqueous phase II are fatty alcohol polyglycol ethers containing in particular 2 to 8 EO, for example oleyl/cetyl alcohol + 5 EO ether, and/or fatty acid polyglycol esters (FAE) with in particular 2 to 10 EO, for example tallow fatty acid + 6E0 ester. In addition, in the nonionic surfactants, particularly the alcohol polyglycol ethers and carboxylic acid polyglycol esters, for phase II, the degree of ethoxylation is adapted to the C chain length in such a way that shorter C chains are combined with relatively low degrees of ethoxylation and longer C chains with relatively high degrees of ethoxylation.
Particularly preferred compositions contain anionic and nonionic surfactant. Combinations of anionic surfactant in phase I and nonionic surfactant in phase II, for example combinations of fatty alkyl sulfates and/or fatty alcohol polyglycol ether sulfates in phase I with fatty alcohol polyglycol ethers and/or FAE in phase II, are particularly advantageous.
The cleaning compositions according to the invention may additionally contain water-soluble organic solvents in the form of lower alcohols and/or ether alcohols, but preferably mixtures of alcohols and ether alcohols. The quantity of organic solvent is preferably between 0.1 and 15% by weight and more preferably between 1 and 10% by weight, based on aqueous phase I.
The alcohols used are, in particular, ethanol, isopropanol and n-propanol. Suitable ether alcohols are sufficiently water-soluble compounds containing up to 10 carbon atoms in the molecule. Examples of such ether alcohols are ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monotert.-butyl ether and propylene glycol monoethyl ether, of which ethylene glycol monobutyl ether and propylene glycol monobutyl ether are preferred. If alcohol and ether alcohol are used alongside one another, the ratio by weight between them is preferably from 1:2 to 4:1. According to the invention, ethanol is particularly preferred.
The compositions can be converted into the temporary emulsion according to the invention by shaking preferably up to three times, more preferably twice and most preferably once, the temporary emulsion produced by shaking remaining stable (i.e. on the one hand not collapsing immediately after the end of shaking but, on the other hand, not remaining in tact for too long) for a time long enough for convenient application of the composition of about 0.5 to 10 mins., preferably 1 to 5 mins. and most preferably 1.5 to 4 mins. In the present context, stable means that at least 90% by volume of the composition is still present as the temporary emulsion produced by shaking after the particular period of time. Apart from the choice of the basic and active components and the quantities used, another way of establishing the stable property of the composition according to the invention is to control the viscosity of the individual phases.
The aqueous phase I preferably has a Brookfield viscosity (Model DV-II+, spindle 31, rotation frequency 20 m-', 20°C) of 0.1 to 200 mPa~s, more preferably in the range from 0.5 to 100 mPa~s and most preferably in the range from 1 to 60 mPa~s. To this end, the composition or rather its phases may contain viscosity regulators. The quantity of viscosity regulator in phase I, based on phase I, is normally up to 0.5% by weight, preferably between 0.001 and 0.3% by weight, more preferably between 0.01 and 0.2% by weight and most preferably between 0.05 and 0.15% by weight. Suitable viscosity regulators are inter alia synthetic polymers, such as the homopolymers and/or copolymers of acrylic acid and derivatives thereof, for example the products obtainable under the name of Carbopol~
from Goodrich, more particularly the crosslinked acrylic acid copolymer Carbopol-ETD-2623~. International patent application WO 97138076 mentions a number of other polymers derived from acrylic acid which also represent suitable viscosity regulators.
The compositions according to the invention may additionally contain volatile alkali in phase I. Ammonia and/or alkanolamines which may contain up to 9 carbon atoms in the molecule is/are preferably used as the volatile alkali. Preferred alkanolamines are the ethanolamines, preferably monoethanolamine. The ammonia and/or alkanolamine content, based on phase I, is preferably between 0.01 and 3% by weight, more preferably between 0.02 and 1 % by weight and most preferably between 0.05 and 0.5% by weight.
Besides the volatile alkali, the compositions according to the invention may additionally contain carboxylic acid in phase I, the equivalent ratio of amine and/or ammonia to carboxylic acid preferably being between 1:0.9 and 1:0.1. Carboxylic acids containing up to 6 carbon atoms, which may be mono-, di- or polycarboxylic acids, are suitable. Depending on the equivalent weight of amine and carboxylic acid, the carboxylic acid content is preferably between 0.01 and 2.7% by weight and more preferably between 0.01 and 0.9% by weight. Examples of suitable carboxylic acids are acetic acid, glycolic acid, lactic acid, citric acid, succinic acid and adipic acid, of which acetic acid, citric acid and lactic acid are preferably used.
Acetic acid is particularly preferred.
In a preferred embodiment of the composition according to the invention, the use according to the invention and the process according to the invention, at least one end-capped polyalkoxylated alcohol is used together with at least one other additive which also reduces the rain and/or film effect. This other additive may be one or more water-soluble additives and/or one or more additives which for the most part are dissolved in the non-aqueous phase II of a composition according to the invention.
Other additives in the context of this particular embodiment, which are largely dissolved in the aqueous phase I of a composition according to the invention, are in particular (i) the substantive polymers containing hydrophilic groups according to WO 96104358 A1 (Procter & Gamble), more particularly polycarboxylates, such as polyvinyl pyrrolidone-co-acrylic acid), but also polystyrene sulfonate), cationic sugar and starch derivatives and block copolymers of ethylene oxide and propylene oxide, with an average molecular weight of 10,000 to 3,000,000 g/mole, preferably 20,000 to 2,500,000 g/mole, more preferably 300,000 to 2,000,000 g/mole and most preferably 400,000 to 1,500,000 g/mole, (ii) the amine oxide polymers, more particularly poly(4-vinylpyridine-N-oxides), according to WO 97133963 A1 (Procter & Gamble) with an average molecular weight of 2,000 to 100,000 g/mole, preferably 5,000 to 20,000 g/mole and more preferably 8,000 to 12,000 g/mole, (iii) end-capped polyalkoxylated alcohols corresponding to the formula:
RIO[CH2CH(CH)30]p[CH2CH(R2)O]qR3 in which R' is a linear aliphatic hydrocarbon radical containing 1 to about 22 carbon atoms or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, R3 is a linear or branched, saturated or unsaturated, aliphatic, optionally aryl-substituted, acyclic or cyclic hydrocarbon radical containing 1 to about 78 carbon atoms and optionally one or more hydroxy groups and/or ether groups -O- or a mixture of various such radicals, p is a number of 0 to about 15 and q is a number of 0 to about 50, the sum of p and q being at least 1, more particularly epoxy-end-capped polyalkoxylated alcohols corresponding to the above formula, in which R' is a linear aliphatic hydrocarbon radical containing about 4 to about 18 and preferably about 4 to about 12 carbon atoms, more particularly a butyl, hexyl, octyl or decyl radical or mixtures 5 thereof, or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, preferably a hydrogen atom, R3 is a group [CH2CH(R4)O]~H, where R4 is a linear aliphatic hydrocarbon radical containing about 2 to about 26, preferably about 4 to about 18 and more preferably about 6 to about 14 carbon atoms or a 10 mixture of various such radicals and r is a number of 1 to about 3, preferably 1 to about 2, more preferably 1, p is a number of 1 to about 5, preferably 1 to about 2 and more preferably 1 and q is a number of 1 to about 30, preferably about 4 to about 26 and more preferably about 10 to about 24, for example with R' - CB,~o alkyl group, R2 = H, R3 =
15 [CH2CH(R4)O]~H with R4 = C8 alkyl group and r = 1, a = 1 and v = 22, (iv) lignin sulfonates, for example the alkali metal and alkaline earth metal lignin sulfonates and the ammonium lignin sulfonates or mixtures thereof, preferably sodium, magnesium, calcium or ammonium lignin sulfonates and mixtures thereof, more particularly the sodium lignin sulfonates, and/or lignin sulfonic acid optionally neutralized in situ with a corresponding base (suitable lignin sulfonates are commercially obtainable, for example, under the name of Zewa~ from Ligninchemie, for example the sodium lignin sulfonates Zevva~ EF, Zewa~ S, Zewa~ S2, Zewa~ SL and Zewa~ SL 2 and the ammonium lignin sulfonate Zewa~ DIS TR, under the name of Totanin~ from Nike Baeck Industries GmbH, for example the ammonium lignin sulfonate Totanin~ AM 5025-T2 and the calcium lignin sulfonate Totanin~ CA 2032, and under the name of Borresperse~ (about 25% of the molecules have a molecular weight above 20,000 g/mole), Borrewell~, Borrebond~, Ultrazine~, Ufoxane~ (Ultrazine~, Ufoxane~: about 40% of the molecules have a molecular weight above 20,000 g/mole), Marasperse~, Maracell~ and Maratan~ from LignoTech USA, Inc., the Borregard group, for example the calcium lignin sulfonates Borresperse~
CA, Borrebond~ and Ultrazine ~ CA, the sodium lignin sulfonates Borresperse~ NA, Borresperse~ 3A, Ultrazine~ NA, Ultrazine~ NAS, Ufoxane~ 2, Ufoxane~ 3A and Ufoxane~ RG, the ammonium lignin sulfonate Borresperse~ NH and the chromium, ferrochromium and iron lignin sulfonates Borresperse~ C, FC and FE, (v) high molecular weight to low molecular weight, preferably low molecular weight, naphthalene sulfonic acid/formaldehyde condensates and salts thereof, for example the alkali metal and alkaline earth metal salts, preferably the sodium, potassium, magnesium and calcium salts, and the ammonium salts or mixtures thereof, more particularly the sodium salts (suitable naphthalene sulfonic acid/formaldehyde condensates are commercially obtainable, for example, under the name of Lomar~ from Henkel Corp., for example the low molecular weight sodium salts Lomar~ LS, Lomar~ PW, Lomar~
PWFA 40 and Lomar~ PL 4, the high molecular weight sodium salts Lomar~ D and Lomar~ D SOL, the potassium salt Lomar~ HP and the ammonium salt Lomar~ PWA, and under the name of Tamol~ from BASF
AG, for example the low molecular weight condensates Tamol~ NN 2901, Tamol~ NN 7718, Tamol~ NN 8906, Tamol~ NN 9104, Tamol~ NN 9401 (all sodium salts) and Tamol~ NNA 4019 (ammonium salt) with a molecular weight of about 6,500 g/mole, the medium molecular weight condensates Tamol~ NMC 4001 and Tamol~ NN 9401 (both calcium salts) with a molecular weight of about 20,000 g/mole and the high molecular weight condensates Tamol~ NH 3091, Tamol~ NH 7519, Tamol~ NH 9103 (all sodium salts) and Tamol~ NHC 3001 (calcium salt) with a molecular weight of about 35,000 g/mole), (vi) gum arabic, (vii) polyvinyl pyrrolidones and (viii) polyethylene glycols, the polywaxes, solid polyethylene glycols with a molecular weight of ca. 500 to >100,000 g/mole, for example 4,000 g/mole, and a wax-like consistency, being preferred to the liquid polyethylene glycols with a molecular weight of, for example, 200 g/mole.
Other additives in the context of this particular embodiment, which are dissolved largely in the non-aqueous phase II of a composition according to the invention, are in particular alkoxylated aromatic dihydroxy compounds corresponding to formula A:
X
H(OCH(R)CHz],~,0 O[CH2CH(R)O]~H (A) ~Y
in which X is a single bond, a C,_5 alkylene group, a carbonyl group or a group C-R', where R' is a hydrogen atom or a C~_6 alkyl group, Y is a single bond, a C~_5 alkylene group, a carbonyl group, a group C-R2, where R2 is a hydrogen atom or a C» alkyl group, or two hydrogen atoms, the group "-Y-" then corresponding to "-H H=', R is a hydrogen atom, a C~_s alkyl group or mixtures thereof, m is a number of 0 to about 20 and n is a number of 0 to about 20 and the sum of m + n > 0. The quantity of alkoxylated aromatic dihydroxy compound is determined by its solubility in the non-aqueous phase II, alkoxylated aromatic dihydroxy compound preferably being used in no more than the quantity which dissolves homogeneously in the non-aqueous base of phase II. Particularly preferred alkoxylated aromatic dihydroxy compounds have a high solubility in aliphatic gasoline hydrocarbons which, as described hereinafter, represent a preferred base for the non-aqueous phase II. Suitable aromatic parent compounds of the alkoxylated aromatic dihydroxy compounds, i.e. formula A without the groups H[OCH(R)CHZ]m0- and -O[CH2CH(R)]~H, are for example biphenyl, Biphenyl methane, 1,1-diphenylethane, 1,2-diphenylethane, 1,2-diphenylpropane, 1,3-diphenyl-propane, 2,2-diphenylpropane, 1,2-diphenylbutane, 1,4-diphenylbutane, 2,2-diphenylbutane, 1,5-diphenylpentane, 3,3-diphenylpentane, fluorene, fluorenone, anthracene and anthraquinone. Known aromatic dihydroxy compounds, of which the alkoxylates represent compounds of formula A
according to the invention, are for example o,o'-biphenol and the bisphenols bisphenol A (2,2-bis-(4-hydroxyphenyl)-propane), bisphenol 8 (2,2-bis-(4-hydroxyphenyl)-butane) and bisphenol F (2,2'-methylene-diphenol). The alkoxylation of the aromatic dihydroxy compounds to the alkoxylated aromatic dihydroxy compounds of formula A according to the invention can be carried out by known methods of alkoxylation, normally in the presence of an acid or base as catalyst, at elevated temperature and elevated pressure, a normal or narrow homolog distribution being obtained according to the conditions selected. The sum of m + n represents the average total degree of alkoxylation of the alkoxylated aromatic dihydroxy compounds of formula A according to the invention and assumes values in the region of the real numbers of >0 to about 40, m and n at the molecular level standing for corresponding integers of 0 to about 20 according to the particular homolog distribution. The corresponding average degrees of alkoxylation m and n are generally the same whereas, at the molecular level, m and n may be the same or different. Thus, an average total degree of alkoxylation of 13 corresponds to average degrees of alkoxylation m and n of 6.5; in a significant part of the molecules, m = n =
6, m = n= 7 or m = 6 and n = 7. The average total degree of alkoxylation is preferably 0.1 to 30, more preferably 0.5 to 25, most preferably 1 to 20 and, in one particularly advantageous embodiment, 1.5 to 15. According to the invention, the ethoxylated and/or propoxylated aromatic dihydroxy compounds of formula A (R = H and/or CH3) are preferred. These may be mixed alkoxylates containing ethyleneoxy (EO) and propyleneoxy units (PO), but are preferably pure ethoxylates or - more particularly - pure propoxylates. However, aromatic dihydroxy compounds of formula A, in which R is an ethyl, propyl, isopropyl, butyl, sec.butyl, tert.-butyl, pentyl and/or hexyl group, may also be used. Preferred aromatic dihydroxy compounds corresponding to formula A contain two hydrogen atoms "-H
H-" as the group "-Y-" and bear the alkoxylated hydroxy groups in the 4-and 4'-position in particular (relative to X) in accordance with formula B:
H[OCH(R)CH~rt,O O X O O[CH2CH(R)O)~H (B) where -X- is preferably a C~_5 alkylene group -C(R3)(R4)-, where R3 and R4 = H, CH3, CHzCH3 or CH2CH2CH3, more particularly a 2,2-propylene group or 2,2-butylene group. Alkoxylation products of bishenol A, which is also known by the name of Dian, corresponding to formula C:
H[OCH(R)CH~jmO O O O[CHZCH(R)O)~H (C) I
where R is preferably a hydrogen atom and/or a methyl group and m and n are each numbers of 1 to 15 and more particularly 1 to 10, for example R =
H andm+n=2,4,6.5or8.5orR=CH3andm+n=2,4or13and more preferably R = CH3 and m + n = 13, are particularly preferred. Alkoxylated bisphenols A corresponding to formula C are marketed, for example, under the name of Dianol~ by Akzo Nobel, for example DianoK~ 22, Dianol~ 220, Dianol~ 22 D, Dianol~ 240 1, Dianol~ 264, Dianol~ 285, Dianol~ 33, Diano!~ 320, Dianol~ 340, Dianol~ 33 and Dianol~ 3130.
In a preferred variant of this particular embodiment, at least one end-capped polyalkoxylated alcohol corresponding to formula I is used together with at least one alkoxylated aromatic dihydroxy compound corresponding to formula A. In another preferred variant of this particular embodiment, at least one end-capped polyalkoxylated alcohol corresponding to formula I is used together with at least one of the above-mentioned water-soluble additives (i) to (vii). In yet another preferred variant of this particular embodiment, at least one end-capped polyalkoxylated alcohol corresponding to formula I is used together with at 5 least one alkoxylated aromatic dihydroxy compound corresponding to formula A and at least one of the above-mentioned water-soluble additives (i) to (vii).
The content of at least one of these other additives in a composition according to the invention is 0.001 to 20% by weight, preferably 0.01 to 10 10% by weight, more preferably 0.05 to 5% by weight, most preferably 0.1 to 1.5% by weight and, in one particularly advantageous embodiment, 0.15 to 0.5% by weight.
Besides the components mentioned, the compositions according to the invention may contain other auxiliaries and additives of the type 15 typically present in such compositions. These include in particular dyes, perfume oils, pH regulators (for example citric acid, alkanolamines or NaOH), preservatives, complexing agents for alkaline earth metal ions, enzymes, bleaching systems and antistatic agents. The quantity of such additives is normally not more than 2% by weight in the cleaning 20 composition. The lower limit to the quantity used depends on the type of additive and, in the case of dyes for example, may be 0.001 % by weight or lower. The quantity of auxiliaries used is preferably between 0.01 and 1 by weight.
The pH value of the aqueous phase I may be varied over a broad range, although it is preferably in the range from 2.5 to 12, more preferably in the range from 5 to 10.5 and most preferably in the range from 7 to 10.
In one preferred embodiment, the compositions according to the invention contain 70 to 95% by volume of aqueous phase I containing 0.01 to 10% by weight of anionic surfactant, 0 to 3% by weight of nonionic surfactant, 0.1 to 1.5% by weight of at least one end-capped polyalkoxylated alcohol corresponding to formula I, 0 to 1.5% by weight of other water-soluble additive (i) to (vii) for reducing the rain and/or film effect, 0 to 10% by weight of water-soluble organic solvent, 0 to 0.5% by weight of viscosity regulator, 0 to 3% by weight of volatile alkali, 0 to 0.2% by weight of perfume and to 100% by weight water, and 5 to 30% by volume of non-aqueous phase II containing 0 to 100% by weight of aliphatic gasoline hydrocarbons, 0 to 100% by weight of terpene hydrocarbons, 0 to 5% by weight of at least one alkoxylated aromatic dihydroxy compound corresponding to formula A, 0 to 5% by weight of nonionic surfactant and 0 to 1 % by weight of perfume, the % by weight being based on the particular phase, the sum of the gasoline and terpene hydrocarbons completing phase II to 100% by weight and the phases optionally containing small amounts of dye.
The composition according to the invention is sprayable and, accordingly, may be used in a spray dispenser.
Accordingly, the present invention also relates to a product containing a composition according to the invention and a spray dispenser.
The spray dispenser is preferably a hand-operated spray dispenser, more particularly selected from the group consisting of aerosol spray dispensers, self pressure-generating spray dispensers, pump spray dispensers and trigger spray dispensers, more particularly pump spray dispensers and trigger spray dispensers with a container of transparent polyethylene or polyethylene terephthalate. Spray dispensers are described in more detail in WO 96104940 (Procfer & Gamble) and the US
patents cited therein on the subject of spray dispensers, to which reference is made in this connection and of which the disclosure is hereby incorporated in the present application.
The compositions according to the invention are used, for example, by applying the composition temporarily converted into an emulsion by shaking to the surface to be cleaned in quantities of about 1.5 to 10 g per m2 and, more particularly, 3 to 7 g per m2 and immediately wiping the surface with a soft absorbent material and thus cleaning the surface. The compositions are preferably applied by suitable spray applicators, more particularly a spray dispenser or a product according to the invention, in order to obtain uniform distribution. Sponges or cloths in particular are suitable for wiping and may be periodically rinsed out with water in the cleaning of relatively large surfaces.
The compositions according to the invention are prepared by separate mixing of the individual phases directly from their raw materials, subsequent combining and intermixing of the phases and, in a final step, leaving the composition to stand in order to separate the temporary emulsion. They may also be prepared by mixing directly from their raw materials, subsequent intermixing and, in a final step, leaving the composition to stand in order to separate the temporary emulsion. If a component is not completely insoluble in a phase other than the phase to which the particular component was assigned or with which it was introduced into the composition, this other phase may also contain corresponding parts of the particular component in the adjustment of solubility equilibria by diffusion.
Examples Compositions E1 to E3 according to the invention and comparison composition C1 were prepared simply by stirring the components listed in Table 1 together. E1 to E3 contained the end-capped polyalkoxylated alcohol according to the invention corresponding to formula I in which R' _ C8,~o alkyl group, R2 = H, 3= H, R3 = [CH2CH(R4)O]~H where R4 = C8 alkyl group and r = 1, a = 1 and v = 22, in various quantities whereas C1 contained no additive. C9_~3 isoparaffins were used as the aliphatic gasoline hydrocarbon All the compositions ,had a pH value of 10 and contained a clear and transparent aqueous phase 1 as lower phase and a creamy whitish non-aqueous phase II as upper phase in a ratio by volume of phase I to phase II of 80:20, the two phases being separated by a sharp interface. The aqueous phase I was slightly thickened by the polymer so that the temporary emulsions produced by shaking remained stable long enough for convenient application of the composition (about 3 mins.) and then re-separated into their phases.
Table 1 Composition [% by weight] E1 E2 E3 C1 End-capped polyalkoxylated 0.1 0.2 0.4 -alcohol of formula I
Sodium C ~2_~4 fatty alkyl sulfate0.25 0.25 0.25 0.25 Ethanol 5 5 5 5 Crosslinked acrylic acid copolymer0.02 0.02 0.02 0.02 Aliphatic gasoline hydrocarbon 15 15 15 15 Aqueous ammonia solution, 25% by 0.2 0.2 0.2 0.2 wt.
Water to to to 100 to Testing of anti-film and anti-rain effect First, quantities of 2 ml of the particular composition were applied to a mirror measuring 30 cm x 60 cm using a folded nonwoven measuring 20 cm x 20 cm (Chicopee, Duralace 60), after which the mirror was polished in the usual way. After 30 minutes, a second identical treatment was carried out. Another 30 minutes later, the anti-film effect and anti-rain effect were tested as follows.
Anti-film effect. The treated mirror was held for 5 seconds over a bowl (28 cm x 50 cm x 4 cm) containing 1.5 liters of boiling water and was evaluated immediately afterwards to determine whether it was covered with film and, if so, how thick the film was.
Anti-rain effect. Ca. 10 g of test rain prepared from tap water and 8 g/I of wfk-carpet pigment soil (55% by weight kaolin, 43% by weight quartz, 1.5%
by weight lamp black (Flammruf3 101), 0.5% by weight iron oxide black;
wfk-Code wfk-09 1I~ of the wkf Testgewebe GmbH (http://www/wkf.de) were uniformly sprayed onto the pretreated mirror surface over a period of about 4 seconds from a pump spray bottle. Immediately afterwards, evaluations were made of wetting and droplet formation and - after drying -soil distribution and stain formation.
The evaluation was made visually by a panel of five people who were each instructed to award scores of 1 to 4 to the four compositions in order of decreasing effectiveness. The particular average value is shown as a score in Table 2 together with an assessment. The lower the score, the better the particular effect.
Table 2 Effect Score Assessment Composition Anti-film effect E1 3 Little effect E2 2 Good protection against film formation E3 2 Very good protection against film formation 10 C1 3 Little effect Anti-rain effect Overall impression of the wet mirror E1 2.4 Good wetting, few droplets E2 1.8 Very good wetting, hardly any droplets 15 E3 1.6 Very good wetting, no droplets C1 4.0 Good wetting, breaks up quickly Anti-rain effect Overall impression of the dry mirror E1 2.8 Slightly better soil distribution than C1 20 E2 1.8 Soil uniformly distributed, hardly any stains E3 1.6 Soil uniformly distributed, no stains C1 4.0 Some stains and "drainage marks", soil only uniform in the upper part In contrast to C1, compositions E1 to E3 according to the invention show both an anti-rain effect and an anti-film effect.
In the most simple case, a composition according to the invention comprises a continuous aqueous phase consisting of the entire phase I
and a continuous non-aqueous liquid phase consisting of the entire phase II. However, one or more continuous phases of a composition according to the invention may also contain parts of another phase in emulsified form, so that in a composition such as this part of phase I for example is present as continuous phase I, which represents the continuous aqueous phase of the composition, while another part is emulsified as discontinuous phase I
in the continuous non-aqueous phase II. The same applies to phase II and other continuous phases.
In a second embodiment, the present invention relates to the use of at least one end-capped polyalkoxylated alcohol corresponding to formula I
in a multiphase composition for cleaning hard surfaces to reduce the rain effect and/or the film effect.
In a third embodiment, the present invention relates to a process for reducing the rain effect and/or the film effect on a hard surface treated with a liquid cleaning composition, characterized in that the surface is treated with a liquid cleaning composition in concentrated or diluted form containing at least one end-capped polyalkoxylated alcohol corresponding to formula I.
The present invention also relates to a process for cleaning hard surfaces, more particularly glass, in which a cleaning composition according to the invention is temoporarily converted into an emulsion by shaking, applied to the surface to be cleaned, preferably by spraying, in quantities of 1.5 to 10 g per m2 and the surface is then optionally cleaned by wiping with a soft absorbent material.
A particular advantage of the present invention is that both an anti-rain effect and an anti-film effect are developed through the end-capped polyalkoxylated alcohols according to the invention.
The compositions according to the invention are distinguished not only by their high cleaning performance, but also by their overall high stability in storage. Thus, the individual phases in the composition are stable in storage for long periods, i.e. for example do not form any deposits, and the conversion into a temporary emulsion remains reversible, even after frequent shaking. Also, the physical form of the compositions according to the invention avoids the problem of having to stabilize a composition formulated as an emulsion per se. In addition, the separation of ingredients into separate phases can promote the chemical stability of the composition. Moreover, the compositions according to the invention show excellent residue behavior. Greasy residues are largely avoided so that the surfaces retain their shine without any need for subsequent rinsing.
The content of at least one end-capped polyalkoxylated alcohol corresponding to formula I in the composition according to the invention is normally from 0.001 to 20% by weight, preferably from 0.01 to 10% by weight, more preferably from 0.05 to 5% by weight, most preferably from 0.1 to 1.5% by weight and, in one particularly advantageous embodiment, from 0.15 to 0.5% by weight.
Examples of the end-capped polyalkoxylated alcohols corre-sponding to the invention are those corresponding to formula I in which (a) R' = C~2_~g Or C~v~4 fatty alkyl group, R2 = H, R3 = butyl group, p = 0, q =
10, (b) R' = C~2_~g fatty alkyl group, R2 = H, R3 = butyl group, p = 0, q = 5, (c) R' = CH3, R2 = H, R3 = 02/14 fatty alkyl group, p = 3, q = 5 or (d) R' =
fatty alkyl group, R2 = H, R3 =butyl group, p = 0, q = 5.
Preferred end-capped polyalkoxylated alcohols are those corre-sponding to formula I, in which p and q are both at least 1 and/or R2 is a hydrogen atom and/or R3 represents at least one hydroxy group, more particularly in the a-position, i.e. R3 is a group -CH2CH(OH)-R. End-capped polyalkoxylated alcohols corresponding to formula I, in which R3 is a group -CH2CH(OH)-R, are known for example from DE 37 23 323 A1 (Henkel KGaA).
Particularly preferred end-capped polyalkoxylated alcohols are epoxy-end-capped polyalkoxylated alcohols corresponding to formula I, in which R' is a linear aliphatic hydrocarbon radical containing about 4 to about 18 and preferably about 4 to about 12 carbon atoms, more particularly a butyl, hexyl, octyl or decyl radical or mixtures thereof, or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, preferably a hydrogen atom, R3 is a group [CH2CH(R4)O]~H, where R4 is a linear aliphatic hydrocarbon radical containing about 2 to about 26, preferably about 4 to about 18 and more preferably about 6 to about 14 carbon atoms or a mixture of various such radicals and r is a number of 1 to about 3, preferably 1 to about 2, more preferably 1, p is a number of 1 to about 5, preferably 1 to about 2 and more preferably 1 and q is a number of 1 to about 30, preferably about 4 to about 26 and more preferably about 10 to about 24, for example with R' _ Cs,~o alkyl group, R2 = H, R3 = [CH2CH(R4)O]~H with R4 = C$ alkyl group and r = 1, a = 1 and v = 22.
Corresponding epoxy-end-capped polyalkoxylated alcohols and methods for their preparation are known, for example, from WO 94122800 A1 and WO 96112001 A1.
End-capped alcohols according to the invention are obtainable, for example, under the name of Dehypon~ from Henkel KGaA or under the name of Poly Tergent~ from Olin Corporation, for example Dehypon~ LT
104, Dehypon~ LS 104, Dehypon~ LT 54, Dehypon~ LS 531 or Dehypon~ O 54 and Poly Tergent~ SLF 18 8 48, Poly Tergent~ SLF 18 B
45 or Poly Tergent~ SL 62.
In one particular embodiment of the invention, the composition is substantially CFC-free, i.e. the non-aqueous liquid phase II is not based on CFCs. The compositions according to the invention preferably contain no CFCs at all in view of their adverse effect on the environment, although small quantities, based on the composition as a whole, of up to about 5%
by weight are tolerable.
In one preferred embodiment of the invention, the continuous phases I and II are demarcated from one another by a sharp interface.
In another preferred embodiment of the invention, one or both of the continuous phases I and II contain parts, preferably 0.1 to 35% by volume and more preferably 0.2 to 20% by volume, based on the volume of the particular continuous phase, of the other phase as dispersant. Accordingly, the continuous phase I or II is reduced by that part by volume which is distributed as dispersant in the other phase. Particularly preferred compositions are characterized in that phase I is emulsified in phase II in quantities of 0.1 to 35% by volume and preferably in quantities of 0.2 to 20% by volume, based on the volume of phase II.
Another preferred embodiment of the invention is characterized in that, besides the continuous phases I and II, part of the two phases is present as an emulsion of one of the two phases in the other phase, this emulsion being demarcated by two sharp interfaces, namely an upper interface and a lower interface, from the other parts of phases I and II
which are not involved in the emulsion.
The compositions according to the invention preferably contain 5 to 95% by volume of phase I and 95 to 5% by volume of phase II.
In another preferred embodiment of the invention, the composition contains 35 to 95% by volume of phase I and 5 to 65% by volume of phase II, more preferably 55 to 95% by volume of phase I and 5 to 45% by volume of phase II and most preferably 70 to 95% by volume of phase I
and 5 to 30% by volume of phase II. In addition, the continuous phase 1 preferably represents the lower phase while the continuous phase II
represents the upper phase.
In another preferred embodiment of the invention, the water-immiscible phase II is based on aliphatic gasoline hydrocarbons and/or terpene hydrocarbons. The gasoline hydrocarbons have a boiling point range of preferably 130 to 260°C, more preferably 140 to 240°C
and most preferably 150 to 220°C, such as the C9_~3 isoparaffins with a boiling point range of 184 to 217°C obtainable, for example, as Shellsol~ T from Deutsche Shell Chemie AG (Eschborn). Suitable terpene hydrocarbons are, for example, citrus oils such as the orange oil obtained from the peel of oranges, the orange terpenes - particularly limonene - present therein or pine oil extracted from roots and stubs. Phase II may also consist entirely of aliphatic gasoline hydrocarbons and/or terpene hydrocarbons. In this case, phase II contains gasoline hydrocarbons in quantities of preferably at least 60% by weight, more preferably 90 to 99.99% by weight, most preferably 95 to 99.9% by weight and, in one particularly advantageous embodiment, 97 to 99% by weight.
Suitable surface-active substances for the compositions according to the invention are surfactants, more particularly from the classes of anionic and nonionic surfactants. The compositions preferably contain ani-onic and nonionic surfactants, the anionic surfactants being present in particular in phase I. The quantity of anionic surfactant, based on phase I, is normally not more than 10% by weight, preferably between 0.01 and 5%
by weight, more preferably between 0.01 and 0.5% by weight and most preferably between 0.1 and 0.3% by weight. Where the compositions contain nonionic surfactants, their concentration preferably in phase I, based on phase I, is normally no higher than 3% by weight, preferably between 0.001 and 0.3% by weight and more preferably between 0.001 and 0.1% by weight, and in phase II, based on phase II, normally no higher than 5% by weight, preferably between 0.001 and 0.5% by weight, more 5 preferably between 0.001 and 0.2% by weight, most preferably between 0.005 and 0.1 % by weight and, in one particularly advantageous embodiment, between 0.01 and 0.05% by weight.
Preferred anionic surfactants are Ca_~8 alkyl benzenesulfonates, more particularly containing about 12 carbon atoms in the alkyl moiety, Ca_2o 10 alkane sulfonates, C$_~s monoalkyl sulfates, C$_~8 alkyl polyglycol ether sulfates containing 2 to 6 ethylene oxide units (EO) in the ether moiety and sulfosuccinic acid esters containing 8 to 18 carbon atoms in the alcohol moieties.
The anionic surfactants are preferably used as sodium salts, although they may also be present as other alkali metal or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or amine salts.
Examples of such surfactants are sodium cocoalkyl sulfate, sodium sec.-alkane sulfonate containing about 15 carbon atoms and sodium dioctyl sulfosuccinate. Fatty alkyl sulfates containing 12 to 14 carbon atoms and sodium lauryl ether sulfate containing 2 EO have proved to be particularly suitable.
The nonionic surfactants used include, above all, Ca_~$ alcohol polyglycol ethers, i.e. ethoxylated alcohols containing 8 to 18 carbon atoms in the alkyl moiety and 2 to 15 ethylene oxide units (EO), C8_~$ carboxylic acid polyglycol esters containing 2 to 15 EO, ethoxylated fatty acid amides containing 12 to 18 carbon atoms in the fatty acid moiety and 2 to 8 EO, long-chain amine oxides containing 14 to 20 carbon atoms and long-chain alkyl polyglycosides containing 8 to 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units. Examples of such surfactants are oleyl/cetyl ' CA 02292966 1999-12-17 alcohol containing 5 EO, nonylphenol containing 10 EO, lauric acid di-ethanolamide, cocoalkyl dimethyl amine oxide and cocoalkyl polyglucoside containing on average 1.4 glucose units.
Besides the addition products of ethylene oxide and fatty alcohols containing in particular 4 to 8 ethylene oxide units, preferred nonionic surfactants in the aqueous phase are the alkyl polyglycosides, of which those containing 8 to 10 carbon atoms in the alkyl moiety and up to 2 glucose units are preferred. Particularly preferred nonionic surfactants in the non-aqueous phase II are fatty alcohol polyglycol ethers containing in particular 2 to 8 EO, for example oleyl/cetyl alcohol + 5 EO ether, and/or fatty acid polyglycol esters (FAE) with in particular 2 to 10 EO, for example tallow fatty acid + 6E0 ester. In addition, in the nonionic surfactants, particularly the alcohol polyglycol ethers and carboxylic acid polyglycol esters, for phase II, the degree of ethoxylation is adapted to the C chain length in such a way that shorter C chains are combined with relatively low degrees of ethoxylation and longer C chains with relatively high degrees of ethoxylation.
Particularly preferred compositions contain anionic and nonionic surfactant. Combinations of anionic surfactant in phase I and nonionic surfactant in phase II, for example combinations of fatty alkyl sulfates and/or fatty alcohol polyglycol ether sulfates in phase I with fatty alcohol polyglycol ethers and/or FAE in phase II, are particularly advantageous.
The cleaning compositions according to the invention may additionally contain water-soluble organic solvents in the form of lower alcohols and/or ether alcohols, but preferably mixtures of alcohols and ether alcohols. The quantity of organic solvent is preferably between 0.1 and 15% by weight and more preferably between 1 and 10% by weight, based on aqueous phase I.
The alcohols used are, in particular, ethanol, isopropanol and n-propanol. Suitable ether alcohols are sufficiently water-soluble compounds containing up to 10 carbon atoms in the molecule. Examples of such ether alcohols are ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monotert.-butyl ether and propylene glycol monoethyl ether, of which ethylene glycol monobutyl ether and propylene glycol monobutyl ether are preferred. If alcohol and ether alcohol are used alongside one another, the ratio by weight between them is preferably from 1:2 to 4:1. According to the invention, ethanol is particularly preferred.
The compositions can be converted into the temporary emulsion according to the invention by shaking preferably up to three times, more preferably twice and most preferably once, the temporary emulsion produced by shaking remaining stable (i.e. on the one hand not collapsing immediately after the end of shaking but, on the other hand, not remaining in tact for too long) for a time long enough for convenient application of the composition of about 0.5 to 10 mins., preferably 1 to 5 mins. and most preferably 1.5 to 4 mins. In the present context, stable means that at least 90% by volume of the composition is still present as the temporary emulsion produced by shaking after the particular period of time. Apart from the choice of the basic and active components and the quantities used, another way of establishing the stable property of the composition according to the invention is to control the viscosity of the individual phases.
The aqueous phase I preferably has a Brookfield viscosity (Model DV-II+, spindle 31, rotation frequency 20 m-', 20°C) of 0.1 to 200 mPa~s, more preferably in the range from 0.5 to 100 mPa~s and most preferably in the range from 1 to 60 mPa~s. To this end, the composition or rather its phases may contain viscosity regulators. The quantity of viscosity regulator in phase I, based on phase I, is normally up to 0.5% by weight, preferably between 0.001 and 0.3% by weight, more preferably between 0.01 and 0.2% by weight and most preferably between 0.05 and 0.15% by weight. Suitable viscosity regulators are inter alia synthetic polymers, such as the homopolymers and/or copolymers of acrylic acid and derivatives thereof, for example the products obtainable under the name of Carbopol~
from Goodrich, more particularly the crosslinked acrylic acid copolymer Carbopol-ETD-2623~. International patent application WO 97138076 mentions a number of other polymers derived from acrylic acid which also represent suitable viscosity regulators.
The compositions according to the invention may additionally contain volatile alkali in phase I. Ammonia and/or alkanolamines which may contain up to 9 carbon atoms in the molecule is/are preferably used as the volatile alkali. Preferred alkanolamines are the ethanolamines, preferably monoethanolamine. The ammonia and/or alkanolamine content, based on phase I, is preferably between 0.01 and 3% by weight, more preferably between 0.02 and 1 % by weight and most preferably between 0.05 and 0.5% by weight.
Besides the volatile alkali, the compositions according to the invention may additionally contain carboxylic acid in phase I, the equivalent ratio of amine and/or ammonia to carboxylic acid preferably being between 1:0.9 and 1:0.1. Carboxylic acids containing up to 6 carbon atoms, which may be mono-, di- or polycarboxylic acids, are suitable. Depending on the equivalent weight of amine and carboxylic acid, the carboxylic acid content is preferably between 0.01 and 2.7% by weight and more preferably between 0.01 and 0.9% by weight. Examples of suitable carboxylic acids are acetic acid, glycolic acid, lactic acid, citric acid, succinic acid and adipic acid, of which acetic acid, citric acid and lactic acid are preferably used.
Acetic acid is particularly preferred.
In a preferred embodiment of the composition according to the invention, the use according to the invention and the process according to the invention, at least one end-capped polyalkoxylated alcohol is used together with at least one other additive which also reduces the rain and/or film effect. This other additive may be one or more water-soluble additives and/or one or more additives which for the most part are dissolved in the non-aqueous phase II of a composition according to the invention.
Other additives in the context of this particular embodiment, which are largely dissolved in the aqueous phase I of a composition according to the invention, are in particular (i) the substantive polymers containing hydrophilic groups according to WO 96104358 A1 (Procter & Gamble), more particularly polycarboxylates, such as polyvinyl pyrrolidone-co-acrylic acid), but also polystyrene sulfonate), cationic sugar and starch derivatives and block copolymers of ethylene oxide and propylene oxide, with an average molecular weight of 10,000 to 3,000,000 g/mole, preferably 20,000 to 2,500,000 g/mole, more preferably 300,000 to 2,000,000 g/mole and most preferably 400,000 to 1,500,000 g/mole, (ii) the amine oxide polymers, more particularly poly(4-vinylpyridine-N-oxides), according to WO 97133963 A1 (Procter & Gamble) with an average molecular weight of 2,000 to 100,000 g/mole, preferably 5,000 to 20,000 g/mole and more preferably 8,000 to 12,000 g/mole, (iii) end-capped polyalkoxylated alcohols corresponding to the formula:
RIO[CH2CH(CH)30]p[CH2CH(R2)O]qR3 in which R' is a linear aliphatic hydrocarbon radical containing 1 to about 22 carbon atoms or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, R3 is a linear or branched, saturated or unsaturated, aliphatic, optionally aryl-substituted, acyclic or cyclic hydrocarbon radical containing 1 to about 78 carbon atoms and optionally one or more hydroxy groups and/or ether groups -O- or a mixture of various such radicals, p is a number of 0 to about 15 and q is a number of 0 to about 50, the sum of p and q being at least 1, more particularly epoxy-end-capped polyalkoxylated alcohols corresponding to the above formula, in which R' is a linear aliphatic hydrocarbon radical containing about 4 to about 18 and preferably about 4 to about 12 carbon atoms, more particularly a butyl, hexyl, octyl or decyl radical or mixtures 5 thereof, or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, preferably a hydrogen atom, R3 is a group [CH2CH(R4)O]~H, where R4 is a linear aliphatic hydrocarbon radical containing about 2 to about 26, preferably about 4 to about 18 and more preferably about 6 to about 14 carbon atoms or a 10 mixture of various such radicals and r is a number of 1 to about 3, preferably 1 to about 2, more preferably 1, p is a number of 1 to about 5, preferably 1 to about 2 and more preferably 1 and q is a number of 1 to about 30, preferably about 4 to about 26 and more preferably about 10 to about 24, for example with R' - CB,~o alkyl group, R2 = H, R3 =
15 [CH2CH(R4)O]~H with R4 = C8 alkyl group and r = 1, a = 1 and v = 22, (iv) lignin sulfonates, for example the alkali metal and alkaline earth metal lignin sulfonates and the ammonium lignin sulfonates or mixtures thereof, preferably sodium, magnesium, calcium or ammonium lignin sulfonates and mixtures thereof, more particularly the sodium lignin sulfonates, and/or lignin sulfonic acid optionally neutralized in situ with a corresponding base (suitable lignin sulfonates are commercially obtainable, for example, under the name of Zewa~ from Ligninchemie, for example the sodium lignin sulfonates Zevva~ EF, Zewa~ S, Zewa~ S2, Zewa~ SL and Zewa~ SL 2 and the ammonium lignin sulfonate Zewa~ DIS TR, under the name of Totanin~ from Nike Baeck Industries GmbH, for example the ammonium lignin sulfonate Totanin~ AM 5025-T2 and the calcium lignin sulfonate Totanin~ CA 2032, and under the name of Borresperse~ (about 25% of the molecules have a molecular weight above 20,000 g/mole), Borrewell~, Borrebond~, Ultrazine~, Ufoxane~ (Ultrazine~, Ufoxane~: about 40% of the molecules have a molecular weight above 20,000 g/mole), Marasperse~, Maracell~ and Maratan~ from LignoTech USA, Inc., the Borregard group, for example the calcium lignin sulfonates Borresperse~
CA, Borrebond~ and Ultrazine ~ CA, the sodium lignin sulfonates Borresperse~ NA, Borresperse~ 3A, Ultrazine~ NA, Ultrazine~ NAS, Ufoxane~ 2, Ufoxane~ 3A and Ufoxane~ RG, the ammonium lignin sulfonate Borresperse~ NH and the chromium, ferrochromium and iron lignin sulfonates Borresperse~ C, FC and FE, (v) high molecular weight to low molecular weight, preferably low molecular weight, naphthalene sulfonic acid/formaldehyde condensates and salts thereof, for example the alkali metal and alkaline earth metal salts, preferably the sodium, potassium, magnesium and calcium salts, and the ammonium salts or mixtures thereof, more particularly the sodium salts (suitable naphthalene sulfonic acid/formaldehyde condensates are commercially obtainable, for example, under the name of Lomar~ from Henkel Corp., for example the low molecular weight sodium salts Lomar~ LS, Lomar~ PW, Lomar~
PWFA 40 and Lomar~ PL 4, the high molecular weight sodium salts Lomar~ D and Lomar~ D SOL, the potassium salt Lomar~ HP and the ammonium salt Lomar~ PWA, and under the name of Tamol~ from BASF
AG, for example the low molecular weight condensates Tamol~ NN 2901, Tamol~ NN 7718, Tamol~ NN 8906, Tamol~ NN 9104, Tamol~ NN 9401 (all sodium salts) and Tamol~ NNA 4019 (ammonium salt) with a molecular weight of about 6,500 g/mole, the medium molecular weight condensates Tamol~ NMC 4001 and Tamol~ NN 9401 (both calcium salts) with a molecular weight of about 20,000 g/mole and the high molecular weight condensates Tamol~ NH 3091, Tamol~ NH 7519, Tamol~ NH 9103 (all sodium salts) and Tamol~ NHC 3001 (calcium salt) with a molecular weight of about 35,000 g/mole), (vi) gum arabic, (vii) polyvinyl pyrrolidones and (viii) polyethylene glycols, the polywaxes, solid polyethylene glycols with a molecular weight of ca. 500 to >100,000 g/mole, for example 4,000 g/mole, and a wax-like consistency, being preferred to the liquid polyethylene glycols with a molecular weight of, for example, 200 g/mole.
Other additives in the context of this particular embodiment, which are dissolved largely in the non-aqueous phase II of a composition according to the invention, are in particular alkoxylated aromatic dihydroxy compounds corresponding to formula A:
X
H(OCH(R)CHz],~,0 O[CH2CH(R)O]~H (A) ~Y
in which X is a single bond, a C,_5 alkylene group, a carbonyl group or a group C-R', where R' is a hydrogen atom or a C~_6 alkyl group, Y is a single bond, a C~_5 alkylene group, a carbonyl group, a group C-R2, where R2 is a hydrogen atom or a C» alkyl group, or two hydrogen atoms, the group "-Y-" then corresponding to "-H H=', R is a hydrogen atom, a C~_s alkyl group or mixtures thereof, m is a number of 0 to about 20 and n is a number of 0 to about 20 and the sum of m + n > 0. The quantity of alkoxylated aromatic dihydroxy compound is determined by its solubility in the non-aqueous phase II, alkoxylated aromatic dihydroxy compound preferably being used in no more than the quantity which dissolves homogeneously in the non-aqueous base of phase II. Particularly preferred alkoxylated aromatic dihydroxy compounds have a high solubility in aliphatic gasoline hydrocarbons which, as described hereinafter, represent a preferred base for the non-aqueous phase II. Suitable aromatic parent compounds of the alkoxylated aromatic dihydroxy compounds, i.e. formula A without the groups H[OCH(R)CHZ]m0- and -O[CH2CH(R)]~H, are for example biphenyl, Biphenyl methane, 1,1-diphenylethane, 1,2-diphenylethane, 1,2-diphenylpropane, 1,3-diphenyl-propane, 2,2-diphenylpropane, 1,2-diphenylbutane, 1,4-diphenylbutane, 2,2-diphenylbutane, 1,5-diphenylpentane, 3,3-diphenylpentane, fluorene, fluorenone, anthracene and anthraquinone. Known aromatic dihydroxy compounds, of which the alkoxylates represent compounds of formula A
according to the invention, are for example o,o'-biphenol and the bisphenols bisphenol A (2,2-bis-(4-hydroxyphenyl)-propane), bisphenol 8 (2,2-bis-(4-hydroxyphenyl)-butane) and bisphenol F (2,2'-methylene-diphenol). The alkoxylation of the aromatic dihydroxy compounds to the alkoxylated aromatic dihydroxy compounds of formula A according to the invention can be carried out by known methods of alkoxylation, normally in the presence of an acid or base as catalyst, at elevated temperature and elevated pressure, a normal or narrow homolog distribution being obtained according to the conditions selected. The sum of m + n represents the average total degree of alkoxylation of the alkoxylated aromatic dihydroxy compounds of formula A according to the invention and assumes values in the region of the real numbers of >0 to about 40, m and n at the molecular level standing for corresponding integers of 0 to about 20 according to the particular homolog distribution. The corresponding average degrees of alkoxylation m and n are generally the same whereas, at the molecular level, m and n may be the same or different. Thus, an average total degree of alkoxylation of 13 corresponds to average degrees of alkoxylation m and n of 6.5; in a significant part of the molecules, m = n =
6, m = n= 7 or m = 6 and n = 7. The average total degree of alkoxylation is preferably 0.1 to 30, more preferably 0.5 to 25, most preferably 1 to 20 and, in one particularly advantageous embodiment, 1.5 to 15. According to the invention, the ethoxylated and/or propoxylated aromatic dihydroxy compounds of formula A (R = H and/or CH3) are preferred. These may be mixed alkoxylates containing ethyleneoxy (EO) and propyleneoxy units (PO), but are preferably pure ethoxylates or - more particularly - pure propoxylates. However, aromatic dihydroxy compounds of formula A, in which R is an ethyl, propyl, isopropyl, butyl, sec.butyl, tert.-butyl, pentyl and/or hexyl group, may also be used. Preferred aromatic dihydroxy compounds corresponding to formula A contain two hydrogen atoms "-H
H-" as the group "-Y-" and bear the alkoxylated hydroxy groups in the 4-and 4'-position in particular (relative to X) in accordance with formula B:
H[OCH(R)CH~rt,O O X O O[CH2CH(R)O)~H (B) where -X- is preferably a C~_5 alkylene group -C(R3)(R4)-, where R3 and R4 = H, CH3, CHzCH3 or CH2CH2CH3, more particularly a 2,2-propylene group or 2,2-butylene group. Alkoxylation products of bishenol A, which is also known by the name of Dian, corresponding to formula C:
H[OCH(R)CH~jmO O O O[CHZCH(R)O)~H (C) I
where R is preferably a hydrogen atom and/or a methyl group and m and n are each numbers of 1 to 15 and more particularly 1 to 10, for example R =
H andm+n=2,4,6.5or8.5orR=CH3andm+n=2,4or13and more preferably R = CH3 and m + n = 13, are particularly preferred. Alkoxylated bisphenols A corresponding to formula C are marketed, for example, under the name of Dianol~ by Akzo Nobel, for example DianoK~ 22, Dianol~ 220, Dianol~ 22 D, Dianol~ 240 1, Dianol~ 264, Dianol~ 285, Dianol~ 33, Diano!~ 320, Dianol~ 340, Dianol~ 33 and Dianol~ 3130.
In a preferred variant of this particular embodiment, at least one end-capped polyalkoxylated alcohol corresponding to formula I is used together with at least one alkoxylated aromatic dihydroxy compound corresponding to formula A. In another preferred variant of this particular embodiment, at least one end-capped polyalkoxylated alcohol corresponding to formula I is used together with at least one of the above-mentioned water-soluble additives (i) to (vii). In yet another preferred variant of this particular embodiment, at least one end-capped polyalkoxylated alcohol corresponding to formula I is used together with at 5 least one alkoxylated aromatic dihydroxy compound corresponding to formula A and at least one of the above-mentioned water-soluble additives (i) to (vii).
The content of at least one of these other additives in a composition according to the invention is 0.001 to 20% by weight, preferably 0.01 to 10 10% by weight, more preferably 0.05 to 5% by weight, most preferably 0.1 to 1.5% by weight and, in one particularly advantageous embodiment, 0.15 to 0.5% by weight.
Besides the components mentioned, the compositions according to the invention may contain other auxiliaries and additives of the type 15 typically present in such compositions. These include in particular dyes, perfume oils, pH regulators (for example citric acid, alkanolamines or NaOH), preservatives, complexing agents for alkaline earth metal ions, enzymes, bleaching systems and antistatic agents. The quantity of such additives is normally not more than 2% by weight in the cleaning 20 composition. The lower limit to the quantity used depends on the type of additive and, in the case of dyes for example, may be 0.001 % by weight or lower. The quantity of auxiliaries used is preferably between 0.01 and 1 by weight.
The pH value of the aqueous phase I may be varied over a broad range, although it is preferably in the range from 2.5 to 12, more preferably in the range from 5 to 10.5 and most preferably in the range from 7 to 10.
In one preferred embodiment, the compositions according to the invention contain 70 to 95% by volume of aqueous phase I containing 0.01 to 10% by weight of anionic surfactant, 0 to 3% by weight of nonionic surfactant, 0.1 to 1.5% by weight of at least one end-capped polyalkoxylated alcohol corresponding to formula I, 0 to 1.5% by weight of other water-soluble additive (i) to (vii) for reducing the rain and/or film effect, 0 to 10% by weight of water-soluble organic solvent, 0 to 0.5% by weight of viscosity regulator, 0 to 3% by weight of volatile alkali, 0 to 0.2% by weight of perfume and to 100% by weight water, and 5 to 30% by volume of non-aqueous phase II containing 0 to 100% by weight of aliphatic gasoline hydrocarbons, 0 to 100% by weight of terpene hydrocarbons, 0 to 5% by weight of at least one alkoxylated aromatic dihydroxy compound corresponding to formula A, 0 to 5% by weight of nonionic surfactant and 0 to 1 % by weight of perfume, the % by weight being based on the particular phase, the sum of the gasoline and terpene hydrocarbons completing phase II to 100% by weight and the phases optionally containing small amounts of dye.
The composition according to the invention is sprayable and, accordingly, may be used in a spray dispenser.
Accordingly, the present invention also relates to a product containing a composition according to the invention and a spray dispenser.
The spray dispenser is preferably a hand-operated spray dispenser, more particularly selected from the group consisting of aerosol spray dispensers, self pressure-generating spray dispensers, pump spray dispensers and trigger spray dispensers, more particularly pump spray dispensers and trigger spray dispensers with a container of transparent polyethylene or polyethylene terephthalate. Spray dispensers are described in more detail in WO 96104940 (Procfer & Gamble) and the US
patents cited therein on the subject of spray dispensers, to which reference is made in this connection and of which the disclosure is hereby incorporated in the present application.
The compositions according to the invention are used, for example, by applying the composition temporarily converted into an emulsion by shaking to the surface to be cleaned in quantities of about 1.5 to 10 g per m2 and, more particularly, 3 to 7 g per m2 and immediately wiping the surface with a soft absorbent material and thus cleaning the surface. The compositions are preferably applied by suitable spray applicators, more particularly a spray dispenser or a product according to the invention, in order to obtain uniform distribution. Sponges or cloths in particular are suitable for wiping and may be periodically rinsed out with water in the cleaning of relatively large surfaces.
The compositions according to the invention are prepared by separate mixing of the individual phases directly from their raw materials, subsequent combining and intermixing of the phases and, in a final step, leaving the composition to stand in order to separate the temporary emulsion. They may also be prepared by mixing directly from their raw materials, subsequent intermixing and, in a final step, leaving the composition to stand in order to separate the temporary emulsion. If a component is not completely insoluble in a phase other than the phase to which the particular component was assigned or with which it was introduced into the composition, this other phase may also contain corresponding parts of the particular component in the adjustment of solubility equilibria by diffusion.
Examples Compositions E1 to E3 according to the invention and comparison composition C1 were prepared simply by stirring the components listed in Table 1 together. E1 to E3 contained the end-capped polyalkoxylated alcohol according to the invention corresponding to formula I in which R' _ C8,~o alkyl group, R2 = H, 3= H, R3 = [CH2CH(R4)O]~H where R4 = C8 alkyl group and r = 1, a = 1 and v = 22, in various quantities whereas C1 contained no additive. C9_~3 isoparaffins were used as the aliphatic gasoline hydrocarbon All the compositions ,had a pH value of 10 and contained a clear and transparent aqueous phase 1 as lower phase and a creamy whitish non-aqueous phase II as upper phase in a ratio by volume of phase I to phase II of 80:20, the two phases being separated by a sharp interface. The aqueous phase I was slightly thickened by the polymer so that the temporary emulsions produced by shaking remained stable long enough for convenient application of the composition (about 3 mins.) and then re-separated into their phases.
Table 1 Composition [% by weight] E1 E2 E3 C1 End-capped polyalkoxylated 0.1 0.2 0.4 -alcohol of formula I
Sodium C ~2_~4 fatty alkyl sulfate0.25 0.25 0.25 0.25 Ethanol 5 5 5 5 Crosslinked acrylic acid copolymer0.02 0.02 0.02 0.02 Aliphatic gasoline hydrocarbon 15 15 15 15 Aqueous ammonia solution, 25% by 0.2 0.2 0.2 0.2 wt.
Water to to to 100 to Testing of anti-film and anti-rain effect First, quantities of 2 ml of the particular composition were applied to a mirror measuring 30 cm x 60 cm using a folded nonwoven measuring 20 cm x 20 cm (Chicopee, Duralace 60), after which the mirror was polished in the usual way. After 30 minutes, a second identical treatment was carried out. Another 30 minutes later, the anti-film effect and anti-rain effect were tested as follows.
Anti-film effect. The treated mirror was held for 5 seconds over a bowl (28 cm x 50 cm x 4 cm) containing 1.5 liters of boiling water and was evaluated immediately afterwards to determine whether it was covered with film and, if so, how thick the film was.
Anti-rain effect. Ca. 10 g of test rain prepared from tap water and 8 g/I of wfk-carpet pigment soil (55% by weight kaolin, 43% by weight quartz, 1.5%
by weight lamp black (Flammruf3 101), 0.5% by weight iron oxide black;
wfk-Code wfk-09 1I~ of the wkf Testgewebe GmbH (http://www/wkf.de) were uniformly sprayed onto the pretreated mirror surface over a period of about 4 seconds from a pump spray bottle. Immediately afterwards, evaluations were made of wetting and droplet formation and - after drying -soil distribution and stain formation.
The evaluation was made visually by a panel of five people who were each instructed to award scores of 1 to 4 to the four compositions in order of decreasing effectiveness. The particular average value is shown as a score in Table 2 together with an assessment. The lower the score, the better the particular effect.
Table 2 Effect Score Assessment Composition Anti-film effect E1 3 Little effect E2 2 Good protection against film formation E3 2 Very good protection against film formation 10 C1 3 Little effect Anti-rain effect Overall impression of the wet mirror E1 2.4 Good wetting, few droplets E2 1.8 Very good wetting, hardly any droplets 15 E3 1.6 Very good wetting, no droplets C1 4.0 Good wetting, breaks up quickly Anti-rain effect Overall impression of the dry mirror E1 2.8 Slightly better soil distribution than C1 20 E2 1.8 Soil uniformly distributed, hardly any stains E3 1.6 Soil uniformly distributed, no stains C1 4.0 Some stains and "drainage marks", soil only uniform in the upper part In contrast to C1, compositions E1 to E3 according to the invention show both an anti-rain effect and an anti-film effect.
Claims (27)
1. A liquid multiphase cleaning composition with at least two continuous phases which contains at least one aqueous phase I and a non-aqueous liquid phase II immiscible with this aqueous phase and which can be temporarily converted into an emulsion by shaking, characterized in that it contains at least one end-capped polyalkoxylated alcohol corresponding to formula I:
R1O[CH2CH(CH)3O]p[CH2CH(R2)O]qR3 (I) in which R1 is a linear aliphatic hydrocarbon radical containing 1 to about 22 carbon atoms or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, R3 is a linear or branched, saturated or unsaturated, aliphatic, optionally aryl-substituted, acyclic or cyclic hydrocarbon radical containing 1 to about 78 carbon atoms and optionally one or more hydroxy groups and/or ether groups -O- or a mixture of various such radicals, p is a number of 0 to about 15 and q is a number of 0 to about 50, the sum of p and q being at least 1.
R1O[CH2CH(CH)3O]p[CH2CH(R2)O]qR3 (I) in which R1 is a linear aliphatic hydrocarbon radical containing 1 to about 22 carbon atoms or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, R3 is a linear or branched, saturated or unsaturated, aliphatic, optionally aryl-substituted, acyclic or cyclic hydrocarbon radical containing 1 to about 78 carbon atoms and optionally one or more hydroxy groups and/or ether groups -O- or a mixture of various such radicals, p is a number of 0 to about 15 and q is a number of 0 to about 50, the sum of p and q being at least 1.
2. A composition as claimed in claim 1, characterized in that it contains at least one end-capped polyalkoxylated alcohol corresponding to formula I
in a quantity of 0.001 to 20% by weight, preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, most preferably 0.1 to 1.5% by weight and, in one particularly advantageous embodiment, 0.15 to 0.5% by weight.
in a quantity of 0.001 to 20% by weight, preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, most preferably 0.1 to 1.5% by weight and, in one particularly advantageous embodiment, 0.15 to 0.5% by weight.
3. A composition as claimed in claim 1 or 2, characterized in that the end-capped polyalkoxylated alcohol is an epoxy-end-capped poly-alkoxylated alcohol corresponding to formula I, in which R1 is a linear aliphatic hydrocarbon radical containing about 4 to about 18 carbon atoms or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, R3 is a group [CH2CH(R4)O]r H, where R4 is a linear aliphatic hydrocarbon radical containing about 2 to about 26 carbon atoms or a mixture of various such radicals and r is a number of 1 to about 3, p is a number of 1 to about 5 and q is a number of 1 to about 30.
4. A composition as claimed in any of claims 1 to 3, characterized in that the continuous phases I and II are demarcated from one another by a sharp interface.
5. A composition as claimed in any of the preceding claims, characterized in that one or both of the continuous phases I and II contain parts, preferably 0.1 to 35% by volume and more preferably 0.2 to 20% by volume, based on the volume of the particular continuous phase, of the other phase as dispersant.
6. A composition as claimed in any of the preceding claims, characterized in that phase I is emulsified into phase II in quantities of 0.1 to 35% by volume and preferably in quantities of 0.2 to 20% by volume, based on the volume of phase II.
7. A composition as claimed in any of the preceding claims, characterized in that besides the continuous phases I and II, part of the two phases is present as an emulsion of one of the two phases in the other phase, this emulsion being demarcated by two sharp interfaces, namely an upper and a lower interface, from those parts of phases I and II which are not involved in the emulsion.
8. A composition as claimed in any of the preceding claims, characterized in that it contains 35 to 95% by volume of phase I and 5 to 65% by volume of phase II, more preferably 55 to 95% by volume of phase I and 5 to 45% by volume of phase II and most preferably 70 to 95% by volume of phase I and 5 to 30% by volume of phase II.
9. A composition as claimed in any of the preceding claims, characterized in that it contains a phase II based on or consisting of aliphatic gasoline hydrocarbons, preferably with a boiling range of 130 to 260°C, and/or terpene hydrocarbons, preferably orange oil and/or pine oil.
10. A composition as claimed in any of the preceding claims, characterized in that it contains in phase II aliphatic gasoline hydrocarbons with a boiling range of 140 to 220°C, preferably 150 to 200°C, in quantities - based on phase II - of 60 to 99.99% by weight, preferably 90 to 99.99%
by weight, more preferably 95 to 99.9% by weight and, in one particularly advantageous embodiment, 97 to 99% by weight.
by weight, more preferably 95 to 99.9% by weight and, in one particularly advantageous embodiment, 97 to 99% by weight.
11. A composition as claimed in any of the preceding claims, characterized in that it contains anionic and/or nonionic surfactant.
12. A composition as claimed in any of the preceding claims, characterized in that it contains anionic surfactant from the group consisting of C8-18 alkyl benzenesulfonates, C8-20 alkane sulfonates, C8-18 monoalkyl sulfates, C8-18 alkyl polyglycol ether sulfates containing 2 to 6 ethylene oxide units and C8-18 alkyl alcohol/sulfosuccinic acid esters and mixtures thereof.
13. A composition as claimed in any of the preceding claims, characterized in that it contains nonionic surfactant from the group of ethoxylates of relatively long-chain alcohols, alkyl polyglycosides and mixtures thereof in phase I and/or II.
14. A composition as claimed in any of the preceding claims, characterized in that it contains anionic and nonionic surfactant.
15. A composition as claimed in any of the preceding claims, characterized in that it contains anionic surfactant, more particularly C12-14 fatty alcohol sulfates and/or C12-14 fatty alcohol polyglycol ether sulfates preferably containing 2 ethylene oxide units (EO), in phase I and nonionic surfactant, more particularly C16-18 fatty alcohol polyglycol ethers preferably containing 2 to 8 EO and/or C14-18 fatty acid polyglycol esters preferably containing 2 to 10 EO, in phase II.
16. A composition as claimed in any of the preceding claims, characterized in that it contains water-soluble organic solvents from the group of lower alcohols and/or ether alcohols containing 2 or 3 carbon atoms, the glycol ethers ethylene glycol monobutyl ether or polypropylene glycol monobutyl ether and mixtures thereof.
17. A composition as claimed in any of the preceding claims, characterized in that it contains - based on phase I - 0.1 to 15% by weight and preferably 1 to 10% by weight of solvent in phase I.
18. A composition as claimed in any of the preceding claims, characterized in that it contains viscosity regulators, more particularly homopolymers and/or copolymers of acrylic acid or salts thereof, in phase I
in quantities - based on phase I - of up to 0.5% by weight, preferably 0.001 to 0.3% by weight, more preferably 0.01 to 0.2% by weight and most preferably 0.05 to 0.15% by weight.
in quantities - based on phase I - of up to 0.5% by weight, preferably 0.001 to 0.3% by weight, more preferably 0.01 to 0.2% by weight and most preferably 0.05 to 0.15% by weight.
19. A composition as claimed in any of the preceding claims, characterized in that it contains a phase I with a viscosity of 0.1 to 200 mPa~s, preferably 0.5 to 100 mPa~s and more preferably 1 to 60 mPa~s.
20. A composition as claimed in any of the preceding claims, characterized in that it contains volatile alkali, more particularly ammonia and/or alkanolamine containing up to 9 carbon atoms, in phase I in quantities - based on phase 1 - of 0.01 to 3% by weight, preferably 0.02 to 1 % by weight and more preferably 0.05 to 0.5% by weight.
21. A composition as claimed in any of the preceding claims, characterized in that it contains at least one other additive which also reduces the rain and/or film effect, preferably at least one alkoxylated aromatic dihydroxy compound.
22. A composition as claimed in any of the preceding claims, characterized in that it contains 70 to 95% by volume of aqueous phase I containing 0.01 to 10% by weight of anionic surfactant, 0 to 3% by weight of nonionic surfactant, 0.1 to 1.5% by weight of at least one end-capped polyalkoxylated alcohol corresponding to formula I, 0 to 1.5% by weight of other water-soluble additive for reducing the rain and/or film effect, 0 to 10% by weight of water-soluble organic solvent, 0 to 0.5% by weight of viscosity regulator, 0 to 3% by weight of volatile alkali, 0 to 0.2% by weight of perfume and to 100% by weight water, and 5 to 30% by volume of non-aqueous phase II containing 0 to 100% by weight of aliphatic gasoline hydrocarbons, 0 to 100% by weight of terpene hydrocarbons, 0 to 5% by weight of at least one alkoxylated aromatic dihydroxy compound corresponding to formula A, 0 to 5% by weight of nonionic surfactant and 0 to 1% by weight of perfume, the % by weight being based on the particular phase, the sum of the aliphatic gasoline and terpene hydrocarbons completing phase II to 100%
by weight and the phases optionally containing small amounts of dye.
by weight and the phases optionally containing small amounts of dye.
23. A composition as claimed in any of the preceding claims, characterized in that it contains the anionic surfactants in quantities of 0.01 to 5% by weight, preferably 0.01 to 0.5% by weight and more preferably 0.1 to 0.3% by weight and the nonionic surfactants in quantities of 0.001 to 0.5% by weight, preferably 0.005 to 0.1 % by weight and more preferably 0.01 to 0.05% by weight.
24. A process for cleaning hard surfaces, more particularly glass, in which a cleaning composition according to any of the preceding claims is temporarily converted into an emulsion by shaking, applied to the surface to be cleaned, preferably by spraying, in quantities of 1.5 to 10 g per m2 and the surface is then optionally cleaned by wiping with a soft absorbent material.
25. A process for reducing the rain effect and/or the film effect on a hard surface treated with a liquid cleaning composition, characterized in that the surface is treated with a liquid cleaning composition in concentrated or diluted form containing at least one end-capped polyalkoxylated alcohol corresponding to formula I:
R1O[CH2CH(CH)3O]p[CH2CH(R2)O]q R3 ~(I) in which R1 is a linear aliphatic hydrocarbon radical containing 1 to about 22 carbon atoms or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, R3 is a linear or branched, saturated or unsaturated, aliphatic, optionally aryl-substituted, acyclic or cyclic hydrocarbon radical containing 1 to about 78 carbon atoms and optionally one or more hydroxy groups and/or ether groups -O- or a mixture of various such radicals, p is a number of 0 to about 15 and q is a number of 0 to about 50, the sum of p and q being at least 1.
R1O[CH2CH(CH)3O]p[CH2CH(R2)O]q R3 ~(I) in which R1 is a linear aliphatic hydrocarbon radical containing 1 to about 22 carbon atoms or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, R3 is a linear or branched, saturated or unsaturated, aliphatic, optionally aryl-substituted, acyclic or cyclic hydrocarbon radical containing 1 to about 78 carbon atoms and optionally one or more hydroxy groups and/or ether groups -O- or a mixture of various such radicals, p is a number of 0 to about 15 and q is a number of 0 to about 50, the sum of p and q being at least 1.
26. The use of at least one end-capped polyalkoxylated alcohol corresponding to formula I:
R1O[CH2CH(CH)3O)p[CH2CH(R2)O]q R3~(I) in which R1 is a linear aliphatic hydrocarbon radical containing 1 to about 22 carbon atoms or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, R3 is a linear or branched, saturated or unsaturated, aliphatic, optionally aryl-substituted, acyclic or cyclic hydrocarbon radical containing 1 to about 78 carbon atoms and optionally one or more hydroxy groups and/or ether groups -O- or a mixture of various such radicals, p is a number of 0 to about 15 and q is a number of 0 to about 50, the sum of p and q being at least 1, in a multiphase composition for cleaning hard surfaces to reduce the rain effect and/or the film effect.
R1O[CH2CH(CH)3O)p[CH2CH(R2)O]q R3~(I) in which R1 is a linear aliphatic hydrocarbon radical containing 1 to about 22 carbon atoms or a mixture of various such radicals, R2 is a hydrogen atom or a lower alkyl group containing 1 to 6 carbon atoms, R3 is a linear or branched, saturated or unsaturated, aliphatic, optionally aryl-substituted, acyclic or cyclic hydrocarbon radical containing 1 to about 78 carbon atoms and optionally one or more hydroxy groups and/or ether groups -O- or a mixture of various such radicals, p is a number of 0 to about 15 and q is a number of 0 to about 50, the sum of p and q being at least 1, in a multiphase composition for cleaning hard surfaces to reduce the rain effect and/or the film effect.
27. A product containing a composition as claimed in any of the preceding composition claims and a spray dispenser.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19859799.1 | 1998-12-23 | ||
DE19859799A DE19859799A1 (en) | 1998-12-23 | 1998-12-23 | Multi-phase cleaning agent with end-capped polyalkoxylated alcohol |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2292966A1 true CA2292966A1 (en) | 2000-06-23 |
Family
ID=7892493
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002292966A Abandoned CA2292966A1 (en) | 1998-12-23 | 1999-12-17 | A multiphase cleaning composition containing end-capped polyalkoxylated alcohol |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP1141224B1 (en) |
AT (1) | ATE250122T1 (en) |
AU (1) | AU1978400A (en) |
CA (1) | CA2292966A1 (en) |
DE (2) | DE19859799A1 (en) |
ES (1) | ES2207978T3 (en) |
WO (1) | WO2000039268A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7448556B2 (en) | 2002-08-16 | 2008-11-11 | Henkel Kgaa | Dispenser bottle for at least two active fluids |
US7592301B2 (en) * | 2002-11-27 | 2009-09-22 | Ecolab Inc. | Cleaning composition for handling water hardness and methods for manufacturing and using |
US7879785B2 (en) | 2002-11-27 | 2011-02-01 | Ecolab Inc. | Method for foaming a cleaning composition |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1064349B1 (en) * | 1998-03-16 | 2003-05-14 | Henkel Kommanditgesellschaft auf Aktien | Aqueous multiphase detergents |
US7964544B2 (en) | 2005-10-31 | 2011-06-21 | Ecolab Usa Inc. | Cleaning composition and method for preparing a cleaning composition |
MX2011006788A (en) | 2008-12-22 | 2012-09-28 | Henkel Ag & Co Kgaa | Water-based cleaner for cleaning solvent-based paints. |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2921791B2 (en) * | 1988-08-22 | 1999-07-19 | 新高化学工業株式会社 | Detergent for automatic dishwasher comprising two or more kinds of separated detergent components and supply device thereof |
JP2736365B2 (en) * | 1994-10-13 | 1998-04-02 | 花王株式会社 | Cleaning method and cleaning agent |
EP0723005A1 (en) * | 1995-01-19 | 1996-07-24 | Kiwi Brands Inc | Dusting and cleaning composition |
DE19811386A1 (en) * | 1998-03-16 | 1999-09-23 | Henkel Kgaa | Aqueous multiphase detergent forming temporary emulsion on shaking and used on hard surfaces |
-
1998
- 1998-12-23 DE DE19859799A patent/DE19859799A1/en not_active Withdrawn
-
1999
- 1999-12-14 AT AT99963521T patent/ATE250122T1/en not_active IP Right Cessation
- 1999-12-14 DE DE59907059T patent/DE59907059D1/en not_active Expired - Lifetime
- 1999-12-14 ES ES99963521T patent/ES2207978T3/en not_active Expired - Lifetime
- 1999-12-14 WO PCT/EP1999/009890 patent/WO2000039268A1/en active IP Right Grant
- 1999-12-14 EP EP99963521A patent/EP1141224B1/en not_active Expired - Lifetime
- 1999-12-14 AU AU19784/00A patent/AU1978400A/en not_active Abandoned
- 1999-12-17 CA CA002292966A patent/CA2292966A1/en not_active Abandoned
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7448556B2 (en) | 2002-08-16 | 2008-11-11 | Henkel Kgaa | Dispenser bottle for at least two active fluids |
US7592301B2 (en) * | 2002-11-27 | 2009-09-22 | Ecolab Inc. | Cleaning composition for handling water hardness and methods for manufacturing and using |
US7696142B2 (en) | 2002-11-27 | 2010-04-13 | Ecolab Inc. | Methods for manufacturing and using a cleaning composition for handling water hardness |
US7879785B2 (en) | 2002-11-27 | 2011-02-01 | Ecolab Inc. | Method for foaming a cleaning composition |
Also Published As
Publication number | Publication date |
---|---|
ES2207978T3 (en) | 2004-06-01 |
AU1978400A (en) | 2000-07-31 |
ATE250122T1 (en) | 2003-10-15 |
EP1141224A1 (en) | 2001-10-10 |
WO2000039268A1 (en) | 2000-07-06 |
DE19859799A1 (en) | 2000-06-29 |
EP1141224B1 (en) | 2003-09-17 |
DE59907059D1 (en) | 2003-10-23 |
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