CA2205404A1 - Microemulsion all purpose liquid cleaning compositions - Google Patents
Microemulsion all purpose liquid cleaning compositionsInfo
- Publication number
- CA2205404A1 CA2205404A1 CA002205404A CA2205404A CA2205404A1 CA 2205404 A1 CA2205404 A1 CA 2205404A1 CA 002205404 A CA002205404 A CA 002205404A CA 2205404 A CA2205404 A CA 2205404A CA 2205404 A1 CA2205404 A1 CA 2205404A1
- Authority
- CA
- Canada
- Prior art keywords
- composition
- group
- microemulsion
- water
- acid
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 263
- 239000004530 micro-emulsion Substances 0.000 title claims abstract description 121
- 238000004140 cleaning Methods 0.000 title claims description 57
- 239000007788 liquid Substances 0.000 title description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000002304 perfume Substances 0.000 claims abstract description 67
- 239000004064 cosurfactant Substances 0.000 claims abstract description 54
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 41
- 239000003599 detergent Substances 0.000 claims abstract description 39
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 30
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 30
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 30
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims description 37
- -1 alkane sulfonate Chemical class 0.000 claims description 35
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 30
- 239000000194 fatty acid Substances 0.000 claims description 30
- 229930195729 fatty acid Natural products 0.000 claims description 30
- 150000004665 fatty acids Chemical class 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 9
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 8
- 150000005690 diesters Chemical class 0.000 claims description 8
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 claims description 8
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000005691 triesters Chemical class 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 244000005700 microbiome Species 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical group CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 231100000584 environmental toxicity Toxicity 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 claims 3
- 239000004743 Polypropylene Substances 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 claims 1
- 239000002689 soil Substances 0.000 abstract description 38
- 239000004519 grease Substances 0.000 abstract description 37
- 150000002314 glycerols Chemical class 0.000 abstract description 30
- 239000004615 ingredient Substances 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 9
- 230000006872 improvement Effects 0.000 abstract description 7
- 150000005846 sugar alcohols Polymers 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 29
- 239000002904 solvent Substances 0.000 description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- 239000003921 oil Substances 0.000 description 19
- 235000019198 oils Nutrition 0.000 description 16
- 239000012188 paraffin wax Substances 0.000 description 15
- 239000003760 tallow Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 239000004094 surface-active agent Substances 0.000 description 13
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 12
- 150000003505 terpenes Chemical class 0.000 description 12
- 235000007586 terpenes Nutrition 0.000 description 12
- 229910052783 alkali metal Inorganic materials 0.000 description 11
- 125000000129 anionic group Chemical group 0.000 description 11
- 238000009472 formulation Methods 0.000 description 11
- 239000000344 soap Substances 0.000 description 11
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 11
- 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 10
- 239000002736 nonionic surfactant Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 9
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000006260 foam Substances 0.000 description 8
- 159000000003 magnesium salts Chemical class 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 7
- 229920000388 Polyphosphate Polymers 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000001205 polyphosphate Substances 0.000 description 6
- 235000011176 polyphosphates Nutrition 0.000 description 6
- 150000003871 sulfonates Chemical class 0.000 description 6
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 150000005215 alkyl ethers Chemical class 0.000 description 5
- 239000003752 hydrotrope Substances 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000001180 sulfating effect Effects 0.000 description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000005456 glyceride group Chemical group 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 235000011044 succinic acid Nutrition 0.000 description 3
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 101000800807 Homo sapiens Tumor necrosis factor alpha-induced protein 8 Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 102100033649 Tumor necrosis factor alpha-induced protein 8 Human genes 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 125000006294 amino alkylene group Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 2
- 239000012669 liquid formulation Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000008053 sultones Chemical class 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 125000000204 (C2-C4) acyl group Chemical group 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- GQCZPFJGIXHZMB-UHFFFAOYSA-N 1-tert-Butoxy-2-propanol Chemical compound CC(O)COC(C)(C)C GQCZPFJGIXHZMB-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- REMWXNDENMKZDS-UHFFFAOYSA-N 2-(2-hydroxypropoxy)propan-1-ol;propanoic acid Chemical compound CCC(O)=O.CC(O)COC(C)CO REMWXNDENMKZDS-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- MXVMODFDROLTFD-UHFFFAOYSA-N 2-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethanol Chemical compound CCCCOCCOCCOCCOCCO MXVMODFDROLTFD-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 101100277337 Arabidopsis thaliana DDM1 gene Proteins 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
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- 235000015278 beef Nutrition 0.000 description 1
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
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- 101150113676 chr1 gene Proteins 0.000 description 1
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- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
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- 230000000774 hypoallergenic effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 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
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- CQQJGTPWCKCEOQ-UHFFFAOYSA-L magnesium dipropionate Chemical compound [Mg+2].CCC([O-])=O.CCC([O-])=O CQQJGTPWCKCEOQ-UHFFFAOYSA-L 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- 239000003002 pH adjusting agent Substances 0.000 description 1
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
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- 229930004725 sesquiterpene Natural products 0.000 description 1
- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 1
- 229940079842 sodium cumenesulfonate Drugs 0.000 description 1
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003444 succinic acids Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- DXRFOGXSSDRZFP-UHFFFAOYSA-N tripentyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCOC(=O)CC(O)(C(=O)OCCCCC)CC(=O)OCCCCC DXRFOGXSSDRZFP-UHFFFAOYSA-N 0.000 description 1
- FQAZRHVERGEKOS-UHFFFAOYSA-N tripropan-2-yl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CC(C)OC(=O)CC(O)(C(=O)OC(C)C)CC(=O)OC(C)C FQAZRHVERGEKOS-UHFFFAOYSA-N 0.000 description 1
- ODHUFJLMXDXVRC-UHFFFAOYSA-N tripropyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCOC(=O)CC(O)(C(=O)OCCC)CC(=O)OCCC ODHUFJLMXDXVRC-UHFFFAOYSA-N 0.000 description 1
- AGBVGLJAIGBYAD-UHFFFAOYSA-N tris(2-methylpropyl) 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CC(C)COC(=O)CC(O)(C(=O)OCC(C)C)CC(=O)OCC(C)C AGBVGLJAIGBYAD-UHFFFAOYSA-N 0.000 description 1
- ZGJMYWFCNCIEFN-UHFFFAOYSA-N tris(3-methylbutyl) 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CC(C)CCOC(=O)CC(O)(C(=O)OCCC(C)C)CC(=O)OCCC(C)C ZGJMYWFCNCIEFN-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
-
- 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
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0017—Multi-phase liquid compositions
- C11D17/0021—Aqueous microemulsions
-
- 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
- C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
-
- 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
- C11D3/162—Organic compounds containing Si
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2072—Aldehydes-ketones
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
-
- 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
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
-
- 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
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
- Lubricants (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
An improvement is described in the liquid crystal composition or the microemulsion compositions more environmentally friendly, which is especially effective in the removal of oily and greasy soil and having an evidenced grease release effect, contains an anionic detergent, an ethoxylated glycerol type compound, a hydrocarbon ingredient, and water which comprises the use of a water-insoluble odoriferous perfume as the essential hydrocarbon ingredient in a proportion sufficient to form either a dilute o/w microemulsion composition containing, by weight, 1 % to 20 % of an anionic surfactant, 0.1 % to 50 % of a cosurfactant, 0.1 % to 20 % of an ethoxylated glycerol type compound, 0.4 % to 10 % of perfume and the balance being water.
Description
CA 02205404 1997-0~-14 W O 96/15217 PCTrUS95/14583 MICROEMULSION ALL PURPOSE LIQUID CLEANING COMPOSITIONS
Field of the Invention This invention relates to an improved all-purpose liquid cleaner in the form of a 5 liquid crystal or a microemulsion designed in particular for cleaning hard surfaces and which is effective in removing grease soil and/or bath soil and in leaving unrinsed surfaces with a shiny appearance.
B~k~round of the Invention In recent years all-purpose liquid detergents have become widely accepted for 10 cleaning hard surfaces, e.g., painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or tile floors, washable wall paper, etc.. Such all-purpose liquids comprise clear and opaque aqueous mixtures of water-soluble synthetic organic detergents and water-soluble detergent builder salts. In order to achieve comparable cleaning efficiency with granular or powdered all-purpose cleaning compositions, use of 15 water-soluble inorganic phosphate builder salts was favored in the prior art all-purpose liquids. For example, such early phosphate-containing compositions are described in U.S. Patent Nos. 2,560,839; 3,234,138; 3,350,319; and British Patent No. 1,223,739.
In view of the environmentalist~s efforts to reduce phosphate levels in ground water, improved all-purpose liquids containing reduced concentrations of inorganic 20 phosphate builder salts or non-phosphate builder salts have appeared. A particularly useful self-opacified liquid of the latter type is described in U.S. Patent No. 4,244,840.
However, these prior art all-purpose liquid detergents containing detergent builder salts or other equivalent tend to leave films, spots or streaks on cleaned unrinsed surfaces, particularly shiny surfaces. Thus, such liquids require thorough 25 rinsing of the cleaned surfaces which is a time-consuming chore for the user.In order to overcome the foregoing disadvantage of the prior art all-purpose llquid, U.S. Patent No. 4,017,409 teaches that a mixture of paraffin sulfonate and a reduced concentration of inorganic phosphate builder salt should be employed.
However, such compositions are not completely acceptable from an environmental CA 0220~404 1997-0~-14 point of view based upon the phosphate content. On the other hand, another alternative to achieving phosphate-free all-purpose liquids has been to use a major proportion of a mixture of anionic and nonionic detergents with minor amounts of glycol ether solvent and organic amine as shown in U.S. Patent NO. 3,935,130. Again, this approach has not been completely satisfactory and the high levels of organic detergents necessary to achieve cleaning cause foaming which, in turn, leads to the need for thorough rinsing which has been found to be undesirable to today's consumers.
Another approach to formulating hard surfaced or all-purpose liquid detergent composition where product homogeneity and clarity are important considerations involves the formation of oil-in-water (o/w) microemulsions which contain one or more surface-active detergent compounds, a water-immiscible solvent (typically a hydrocarbon solvent), water and a "cosurfactant" compound which provides productstability. By definition, an o/w microemulsion is a spontaneously forming colloidal dispersion of "oil" phase particles having a particle size in the range of 25 A to 800 A in a continuous aqueous phase.
In view of the extremely fine particle size of the dispersed oil phase particles, microemulsions are transparent to light and are clear and usually highly stable against phase separation.
Patent disclosures relating to use of grease-removal solvents in o/w microemulsions include, for example, European Patent Applications EP 0137615 andEP 0137616 - Herbots et al; European Patent Application EP 0160762 - Johnston et al;
and U.S. Patent No. 4,561,991 - Herbots et al. Each of these patent disclosures also teaches using at least 5% by weight of grease-removal solvent.
It also is known from British Patent Application GB 2144763A to Herbots et al, published March 13,1985, that magnesium salts enhance grease-removal performanceof organic grease-removal solvents, such as the terpenes, in o/w microemulsion liquid detergent compositions. The compositions of this invention described by Herbots et al.
require at least 5% of the mixture of grease-removal solvent and magnesium salt and WO 96/1',217 PCT/US95/14583 preferably at least 5% of solvent (which may be a mixture of water-immiscible non-polar solvent with a sparingly soluble slightly polar solvent) and at least 0.1% magnesium salt.
However, since the amount of water immiscible and sparingly soluble 5 components which can be present in an o/w microemulsion, with low total activeingredients without impairing the stability of the microemulsion is rather limited (for example, up to 18% by weight of the aqueous phase), the presence of such high quantities of grease-removal solvent tend to reduce the total amount of greasy or oily soils which can be taken up by and into the microemulsion without causing phase 10 separation.
The following representative prior art patents also relate to liquid detergent cleaning compositions in the form of o/w microemulsions: U.S. Patents Nos.. 4,472,291 - Rosario; 4,540,448 - Gauteer et al; 3,723,330 - Sheflin; etc.
Liquid detergent compositions which include terpenes, such as d-limonene, or other grease-removal solvent, although not disclosed to be in the form of o/w microemulsions, are the subject matter of the following representative patent documents: European Patent Application 0080749; British Patent Specification 1,603,047; 4,414,128; and 4,540,505. For example, U.S. Patent No. 4,414,128 broadly discloses an aqueous liquid detergent composition characterized by, by weight:
(a) from 1% to 20% of a synthetic anionic, nonionic, amphoteric or zwitterionic surfactant or mixture thereof;
(b) from 0.5% to 10% of a mono- or sesquiterpene or mixture thereof, at a weight ratio of (a):(b) Iying in the range of 5:1 to 1:3; and (c ) from 0.5% 10% of a polar solvent having a solubility in water at 1 5C in the range of from 0.2% to 10%. Other ingredients present in the formulations disclosed in this patent include from 0.05% to 2% by weight of an alkali metal, ammonium or alkanolammonium soap of a C1 3-C24 fatty acid; a calcium sequestrant from 0.5% to 13% by weight; non-aqueous solvent, e.g., alcohols and glycol ethers, up to 10% by weight; and hydrotropes, e.g., urea, ethanolamines, salts of lower alkylaryl sulfonates, CA 0220~404 1997-0~-14 up to 10% by weight. All of the formulations shown in the Examplas of this patent include relatively large amounts of detergent builder salts which are detrimental to surface shine.
Furthermore, the present inventors have observed that in formulations containing5 grease-removal assisting magnesium compounds, the addition of minor amounts ofbuilder salts, such as alkali metal polyphosphates, alkali metal carbonates, nitrilotriacetic acid salts, and so on, tends to make it more difficult to form stable microemulsion systems.
U.S. Patent 5,082,584 discloses a microemulsion composition having an anionic 10 surfactant, a cosurfactant, nonionic surfactant, perfume and water; however, these compositions do not possess the low ecotoxicity profile and the improved interfacial tension properties as exhibited by the compositions of the instant invention.
British Patent No 1,453,385 discloses polyesterified nonionic surfactants similar to the polyesterified nonionic surfactants of the instant invention. However, these nonionic surfactants of British Patent 1,453,385 do not disclose the formula (Il) portion of the instant composition. Additionally, the formulated compositions of British Patent 1,453,385 fail to disclose the critical limitations of the instant invention.
A number of patents teach esterified ethoxylated glycerol compounds for various applications. These patents are Great Britian 1,453,385; Japan 59-1600 and Japan 58-206693 and European Patent Application 0586,323A1. These publications fail to appreciate that a mixture of esterified ethoxylated glycerol and nonesterified ethoxylated glycerol, when used in a hard surface cleaning composition, functions as a grease release agent.
Summary of the Invention The present invention provides an improved, clear, liquid cleaning composition having improved interfacial tension which improves cleaning hard surface in the form of a liquid crystal or a microemulsion which is suitable for cleaning hard surfaces such as plastic, vitreous and metal surfaces having a shiny finish. More particularly, the improved cleaning compositions exhibit good grease soil removal properties due to the CA 0220~7404 1997-0~7-14 improved interfacial tensions, when used in undiluted (neat) form and leave the cleaned surfaces shiny without the need of or requiring only minimal additional rinsing or wiping.
The latter characteristic is evidenced by little or no visible residues on the unrinsed cleaned surfaces and, accordingly, overcomes one of the disadvantages of prior art products. The instant compositions exhibit a grease release effect in that the instant compositions impede or decrease the anchoring of greasy soil on surfaces that have been cleaned with the instant compositions as compared to surfaces cleaned with a liquid crystal composition or a commercial microemulsion composition which meansthat the grease soiled surface is easier to clean upon subsequent cleanings.
Surprisingly, these desirable results are accomplished even in the absence of polyphosphate or other inorganic or organic detergent builder salts and also in the complete absence or substantially complete absence of grease-removal solvent.
The instant compositions are more friendly for the environment due to the low ecotoxicity of the ethoxylated glycerol type compounds used in the instant 1 5 compositions.
The compositions of the instant invention have an ecotoxocity value as measured by the LC 50 test as deferred by The Organization for Economic Cooperation and Development (OECD)(of which the United States is a member) in OECD Test No.
202 of at least 0.18 ml/L measured on Daphniae microorganisms.
In one aspect, the invention generally provides a stable, clear all-purpose, hard surface cleaning composition especially effective in the removal of oily and greasy oil, which is in the form of a substantially dilute oil-in-water microemulsion having an aqueous phase and an oil phase. The dilute o/w microemulsion comprises on a weight basis:
from 0.1% to 20% of an anionic surfactant;
from 0.1% to 50% of a water-mixable cosurfactant having either limited ability or substantially no ability to dissolve oily or greasy soil;
0.1% to 20% of a compound which is a mixture of a partially esterified ethoxylated polyhydric alcohol, a fully esterified ethoxylated polyhydric alcohol and a AM~NDED SI~EET
CA 0220~404 1997-0~-14 nonesterified ethoxylated polyhydric alcohol, said mixture being (herein after referred to as an ethoxylated glycerol type compound);
0 to 15% of magnesium sulfate heptahydrate;
0.1 to 10.0% of a perfume or water insoluble hydrocarbon; and 10 to 85% of water, said proportions being based upon the total weight of the composition.
In another aspect, the invention generally provides a stable, clear all-purpose,hard surface cleaning composition especially effective in the removal of oily and greasy oil, which is in the form of a substantially dilute oil-in-water microemulsion having an aqueous phase and an oil phase. The aqueous phase of the dilute o/w microemulsion comprises on a weight basis:
from 0.1% to 20% of an anionic surfactant;
from 0.1% to 50% of a water-mixable cosurfactant having either limited ability or substantially no ability to dissolve oily or greasy soil;
0.4% to 1.0% of a trialkyl ester of citric acid;
0.1% to 10% of a mixture of a partially esterified ethoxylated polyhydric alcohol, a fully esterified ethoxylated polyhydric alcohol and a nonesterified polyhydric alcohol, (said mixture being herein after referred to as an ethoxylated glycerol type compound);
0 to 15% of magnesium sulfate heptahydrate;
Field of the Invention This invention relates to an improved all-purpose liquid cleaner in the form of a 5 liquid crystal or a microemulsion designed in particular for cleaning hard surfaces and which is effective in removing grease soil and/or bath soil and in leaving unrinsed surfaces with a shiny appearance.
B~k~round of the Invention In recent years all-purpose liquid detergents have become widely accepted for 10 cleaning hard surfaces, e.g., painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or tile floors, washable wall paper, etc.. Such all-purpose liquids comprise clear and opaque aqueous mixtures of water-soluble synthetic organic detergents and water-soluble detergent builder salts. In order to achieve comparable cleaning efficiency with granular or powdered all-purpose cleaning compositions, use of 15 water-soluble inorganic phosphate builder salts was favored in the prior art all-purpose liquids. For example, such early phosphate-containing compositions are described in U.S. Patent Nos. 2,560,839; 3,234,138; 3,350,319; and British Patent No. 1,223,739.
In view of the environmentalist~s efforts to reduce phosphate levels in ground water, improved all-purpose liquids containing reduced concentrations of inorganic 20 phosphate builder salts or non-phosphate builder salts have appeared. A particularly useful self-opacified liquid of the latter type is described in U.S. Patent No. 4,244,840.
However, these prior art all-purpose liquid detergents containing detergent builder salts or other equivalent tend to leave films, spots or streaks on cleaned unrinsed surfaces, particularly shiny surfaces. Thus, such liquids require thorough 25 rinsing of the cleaned surfaces which is a time-consuming chore for the user.In order to overcome the foregoing disadvantage of the prior art all-purpose llquid, U.S. Patent No. 4,017,409 teaches that a mixture of paraffin sulfonate and a reduced concentration of inorganic phosphate builder salt should be employed.
However, such compositions are not completely acceptable from an environmental CA 0220~404 1997-0~-14 point of view based upon the phosphate content. On the other hand, another alternative to achieving phosphate-free all-purpose liquids has been to use a major proportion of a mixture of anionic and nonionic detergents with minor amounts of glycol ether solvent and organic amine as shown in U.S. Patent NO. 3,935,130. Again, this approach has not been completely satisfactory and the high levels of organic detergents necessary to achieve cleaning cause foaming which, in turn, leads to the need for thorough rinsing which has been found to be undesirable to today's consumers.
Another approach to formulating hard surfaced or all-purpose liquid detergent composition where product homogeneity and clarity are important considerations involves the formation of oil-in-water (o/w) microemulsions which contain one or more surface-active detergent compounds, a water-immiscible solvent (typically a hydrocarbon solvent), water and a "cosurfactant" compound which provides productstability. By definition, an o/w microemulsion is a spontaneously forming colloidal dispersion of "oil" phase particles having a particle size in the range of 25 A to 800 A in a continuous aqueous phase.
In view of the extremely fine particle size of the dispersed oil phase particles, microemulsions are transparent to light and are clear and usually highly stable against phase separation.
Patent disclosures relating to use of grease-removal solvents in o/w microemulsions include, for example, European Patent Applications EP 0137615 andEP 0137616 - Herbots et al; European Patent Application EP 0160762 - Johnston et al;
and U.S. Patent No. 4,561,991 - Herbots et al. Each of these patent disclosures also teaches using at least 5% by weight of grease-removal solvent.
It also is known from British Patent Application GB 2144763A to Herbots et al, published March 13,1985, that magnesium salts enhance grease-removal performanceof organic grease-removal solvents, such as the terpenes, in o/w microemulsion liquid detergent compositions. The compositions of this invention described by Herbots et al.
require at least 5% of the mixture of grease-removal solvent and magnesium salt and WO 96/1',217 PCT/US95/14583 preferably at least 5% of solvent (which may be a mixture of water-immiscible non-polar solvent with a sparingly soluble slightly polar solvent) and at least 0.1% magnesium salt.
However, since the amount of water immiscible and sparingly soluble 5 components which can be present in an o/w microemulsion, with low total activeingredients without impairing the stability of the microemulsion is rather limited (for example, up to 18% by weight of the aqueous phase), the presence of such high quantities of grease-removal solvent tend to reduce the total amount of greasy or oily soils which can be taken up by and into the microemulsion without causing phase 10 separation.
The following representative prior art patents also relate to liquid detergent cleaning compositions in the form of o/w microemulsions: U.S. Patents Nos.. 4,472,291 - Rosario; 4,540,448 - Gauteer et al; 3,723,330 - Sheflin; etc.
Liquid detergent compositions which include terpenes, such as d-limonene, or other grease-removal solvent, although not disclosed to be in the form of o/w microemulsions, are the subject matter of the following representative patent documents: European Patent Application 0080749; British Patent Specification 1,603,047; 4,414,128; and 4,540,505. For example, U.S. Patent No. 4,414,128 broadly discloses an aqueous liquid detergent composition characterized by, by weight:
(a) from 1% to 20% of a synthetic anionic, nonionic, amphoteric or zwitterionic surfactant or mixture thereof;
(b) from 0.5% to 10% of a mono- or sesquiterpene or mixture thereof, at a weight ratio of (a):(b) Iying in the range of 5:1 to 1:3; and (c ) from 0.5% 10% of a polar solvent having a solubility in water at 1 5C in the range of from 0.2% to 10%. Other ingredients present in the formulations disclosed in this patent include from 0.05% to 2% by weight of an alkali metal, ammonium or alkanolammonium soap of a C1 3-C24 fatty acid; a calcium sequestrant from 0.5% to 13% by weight; non-aqueous solvent, e.g., alcohols and glycol ethers, up to 10% by weight; and hydrotropes, e.g., urea, ethanolamines, salts of lower alkylaryl sulfonates, CA 0220~404 1997-0~-14 up to 10% by weight. All of the formulations shown in the Examplas of this patent include relatively large amounts of detergent builder salts which are detrimental to surface shine.
Furthermore, the present inventors have observed that in formulations containing5 grease-removal assisting magnesium compounds, the addition of minor amounts ofbuilder salts, such as alkali metal polyphosphates, alkali metal carbonates, nitrilotriacetic acid salts, and so on, tends to make it more difficult to form stable microemulsion systems.
U.S. Patent 5,082,584 discloses a microemulsion composition having an anionic 10 surfactant, a cosurfactant, nonionic surfactant, perfume and water; however, these compositions do not possess the low ecotoxicity profile and the improved interfacial tension properties as exhibited by the compositions of the instant invention.
British Patent No 1,453,385 discloses polyesterified nonionic surfactants similar to the polyesterified nonionic surfactants of the instant invention. However, these nonionic surfactants of British Patent 1,453,385 do not disclose the formula (Il) portion of the instant composition. Additionally, the formulated compositions of British Patent 1,453,385 fail to disclose the critical limitations of the instant invention.
A number of patents teach esterified ethoxylated glycerol compounds for various applications. These patents are Great Britian 1,453,385; Japan 59-1600 and Japan 58-206693 and European Patent Application 0586,323A1. These publications fail to appreciate that a mixture of esterified ethoxylated glycerol and nonesterified ethoxylated glycerol, when used in a hard surface cleaning composition, functions as a grease release agent.
Summary of the Invention The present invention provides an improved, clear, liquid cleaning composition having improved interfacial tension which improves cleaning hard surface in the form of a liquid crystal or a microemulsion which is suitable for cleaning hard surfaces such as plastic, vitreous and metal surfaces having a shiny finish. More particularly, the improved cleaning compositions exhibit good grease soil removal properties due to the CA 0220~7404 1997-0~7-14 improved interfacial tensions, when used in undiluted (neat) form and leave the cleaned surfaces shiny without the need of or requiring only minimal additional rinsing or wiping.
The latter characteristic is evidenced by little or no visible residues on the unrinsed cleaned surfaces and, accordingly, overcomes one of the disadvantages of prior art products. The instant compositions exhibit a grease release effect in that the instant compositions impede or decrease the anchoring of greasy soil on surfaces that have been cleaned with the instant compositions as compared to surfaces cleaned with a liquid crystal composition or a commercial microemulsion composition which meansthat the grease soiled surface is easier to clean upon subsequent cleanings.
Surprisingly, these desirable results are accomplished even in the absence of polyphosphate or other inorganic or organic detergent builder salts and also in the complete absence or substantially complete absence of grease-removal solvent.
The instant compositions are more friendly for the environment due to the low ecotoxicity of the ethoxylated glycerol type compounds used in the instant 1 5 compositions.
The compositions of the instant invention have an ecotoxocity value as measured by the LC 50 test as deferred by The Organization for Economic Cooperation and Development (OECD)(of which the United States is a member) in OECD Test No.
202 of at least 0.18 ml/L measured on Daphniae microorganisms.
In one aspect, the invention generally provides a stable, clear all-purpose, hard surface cleaning composition especially effective in the removal of oily and greasy oil, which is in the form of a substantially dilute oil-in-water microemulsion having an aqueous phase and an oil phase. The dilute o/w microemulsion comprises on a weight basis:
from 0.1% to 20% of an anionic surfactant;
from 0.1% to 50% of a water-mixable cosurfactant having either limited ability or substantially no ability to dissolve oily or greasy soil;
0.1% to 20% of a compound which is a mixture of a partially esterified ethoxylated polyhydric alcohol, a fully esterified ethoxylated polyhydric alcohol and a AM~NDED SI~EET
CA 0220~404 1997-0~-14 nonesterified ethoxylated polyhydric alcohol, said mixture being (herein after referred to as an ethoxylated glycerol type compound);
0 to 15% of magnesium sulfate heptahydrate;
0.1 to 10.0% of a perfume or water insoluble hydrocarbon; and 10 to 85% of water, said proportions being based upon the total weight of the composition.
In another aspect, the invention generally provides a stable, clear all-purpose,hard surface cleaning composition especially effective in the removal of oily and greasy oil, which is in the form of a substantially dilute oil-in-water microemulsion having an aqueous phase and an oil phase. The aqueous phase of the dilute o/w microemulsion comprises on a weight basis:
from 0.1% to 20% of an anionic surfactant;
from 0.1% to 50% of a water-mixable cosurfactant having either limited ability or substantially no ability to dissolve oily or greasy soil;
0.4% to 1.0% of a trialkyl ester of citric acid;
0.1% to 10% of a mixture of a partially esterified ethoxylated polyhydric alcohol, a fully esterified ethoxylated polyhydric alcohol and a nonesterified polyhydric alcohol, (said mixture being herein after referred to as an ethoxylated glycerol type compound);
0 to 15% of magnesium sulfate heptahydrate;
2(~ 0.4 to 10.0% of a perfume or water insoluble hydrocarbon; and 10 to 85% of water, said proportions being based upon the total weight of the composition.
In another aspect, the invention generally provides a stable, clear all-purpose,hard surface cleaning composition especially effective in the removal of particle soil, which is in the form of a substantially dilute oil-in-water microemulsion having an aqueous phase and an oil phase. The dilute o/w microemulsion comprises on a weight basis:
from 0.1% to 20% of an anionic surfactant;
AM~ND~ SHE~T
CA 0220~404 1997-0~-14 from 0.1% to 50% of a water-mixable cosurfactant having either limited ability or substantially no ability to dissolve oily or greasy soil;
0.1% to 20% of an ethoxylated polyhydric alcohol;
0 to 15% of magnesium sulfate heptahydrate;
0.1 to 10.0% of a perfume or water insoluble hydrocarbon; and l O to 85% of water, said proportions being based upon the total weight of the composition. This composition can also contain 0 to 10 wt. % of a monoester of an ethoxylated polyhydric alcohol depicted by the formula:
R' CH2 O (cH2cH O )x B
R' [ CH O (CH2CH O )y Blw R' CH2 O (CH2CH O )z B) 15 wherein w equals one to four. Two of the B's are hydrogen and one B is selected from the group consisting of a group represented by:
o C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon 20 atoms, more preferably 11 to 15 carbon atoms and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals about 2 to about 100. This composition can also contain 0 to 2 wt. %, of a diester of an ethoxylated polyhydric alcohol depicted by the formula A~NGE~ Sn~ET
CA 0220~404 1997-0~-14 R' CH2 O (cH2cH O )x B
[CH O (CH2CH O )yB]w R' CH2 O (CH2CH O )z B
wherein w equals one to four. One of the B's is hydrogen and two B's are selected from the group consisting of a group represented by:
o wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100. This composition can also contain 0 to 15 1.0 wt. %, of a triester of an ethoxylated polyhydric alcohol depicted by the formula R' CH2 O (CH2CH O )x B
R' [ CH O (CH2CH O )y B]w 20 R' CH2 O (CH2CH O )z B
wherein w equals one to four. The three B's are selected from the group consisting of a group represented by:
O
25; C R
wherein R is selected from the group consisti-ng of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals about 2 to about 100.
4;-~N~ ET
The dispersed oil phase of the o/w microemulsion is composed essentially of the water-immiscible or hardly water-soluble perfume.
Quite surprisingly although the perfume is not, per se, a solvent for greasy or oily soil, -- even though some perfumes may, in fact, contain as much as 80% of terpenes which are known as good grease solvents -- the inventive compositions in dilute form have the capacity to solubilize up to 10 times or more of the weight of the perfume of oily and greasy soil, which is removed or loosened from the hard surface by virtue of the action of the anionic and nonionic surfactants, said soil being taken up into the oil phase of the o/w microemulsion.
In another aspect, the invention generally provides highly concentration microemulsion compositions in the form of either an oil-in-water (o/w) microemulsion or a water-in-oil (w/o) microemulsion which when diluted with additional water before use can form dilute o/w microemulsion compositions. The concentrated microemulsion compositions comprise, by weight, 0.1% to 20% of an anionic surfactant, 0.1% to 20%
15 of an ethoxylated glycerol type compound, 0% to 2.5% of a fatty acid, 0.1% to 10% of perfume or water insoluble hydrocarbon having 6 to 18 carbon atoms, 0.1% to 50% of a cosurfactant, and 20% to 97% of water.
In another aspect of the invention, liquid crystal compositions are provided which comprise by weight 0.1% to 20% of an anionic surfactant, 0.1% to 20% of an 20 ethoxylated glycerol type compound, 0 to 2.5% of a fatty acid, 0.1% to 10% of a perfume, more preferably 1% to 10%, 1% to 50% of cosurfactant selected from the group consisting of propylene glycol monobutylether, dipropylene glycol monobutylether and tripropyleneglycol monobutyl ether and mixtures thereof and the balance being water.
In another aspect, the invention provides highly concentration microemulsion compositions in the form of either an oil-in-water (o/w) microemulsion or a water-in-oil (w/o) microemulsion which when diluted with additional water before use can form dilute o/w microemulsion compositions. The concentrated microemulsion compositions comprise, by weight, 0.1% to 20% of an anionic surfactant, 0.1% to 20% of an CA 0220~404 1997-0~-14 ethoxylated glycerol type compound, 0% to 2.5% of a fatty acid, 0.1% to 10% of perfume or water insoluble hydrocarbon having 6 to 18 carbon atoms, 0.1% to 50% of a cosurfactant, and 20% to 97% of water.
In another aspect, the invention generally provides highly concentration 5 microemulsion compositions in the form of either an oil-in-water (o/w) microemulsion or a water-in-oil (w/o) microemulsion which when diluted with additional water before use can form dilute o/w microemulsion compositions. The concentrated microemulsion compositions comprise, by weight, 0.1% to 20% of an anionic surfactant, 0.1% to 20%
of an ethoxylated polyhydric alcohol, 0.1% to 10% of perfume or water insoluble hydrocarbon having 6 to 18 carbon atoms, 0.1% to 50% of a cosurfactant, and 20% to 97% of water.
In another aspect of the invention, liquid crystal compositions are provided which comprise by weight 0.1% to 20% of an anionic surfactant, 0.1% to 20% of an ethoxylated polyhydric alcohol, 0.1% to 10% of a perfume, 1% to 50% of cosurfactant 15 and the balance being water.
Detailed Description of the Invention The present invention relates to a stable liquid crystal or microemulsion composition comprising by weight: 0.1% to 20% of an anionic suRactant, 0.1% to 50%
of a cosurfactant, 0.1% to 20% of an ethoxylated glycerol type compound, 0.1% to 10%
20 of a water insoluble hydrocarbon or a perfume and the balance being water, said composition having an ecotoxocity value as measured by the LC50 test of at least 0.18 ml/L measured on Daphniae microorganisms.
The present invention relates to a stable liquid crystal or microemulsion composition comprising by weight: 0.1% to 20% of an anionic surfactant, 0.1% to 50%
25 of a cosurfactant, 0.4 to 1.0 wt. % of a trialkyl ester of citric aicd such as tri-n butyl citrate, 0.1% to 20% of an ethoxylated glycerol type compound, 0.1% to 10% of a water insoluble hydrocarbon or a perfume and the balance being water, said compositionhaving an ecotoxocity value as measured by the LC50 test of at least 0.18 ml/L
measured on Daphniae microorganisms.
CA 0220~404 1997-0~-14 The present invention relates to a stable liquid crystal or microemulsion composition comprising by weight: 0.1% to 20% of an anionic surfactant, 0.1% to 50%
of a cosurfactant, 0.1% to 20% of an ethoxylated polyhydric alcohol, 0.1% to 10% of a water insoluble hydrocarbon or a perfume and the balance being water. This composition can also contain 0 to 10 wt. % of a monoester of an ethoxylated polyhydric alcohol depicted by the formula R' CH2 O (CH2CH O )x B
R' [CH O (CH2CH Q )y B]w R' CH2 O (CH2CH O )z B
wherein w equals one to four. Two of the B's are hydrogen and one B is selected from the group consisting of a group represented by:
O
C R
wherein R is selected from the group consisting of alkyl group having about 6 to 22 carbon atoms, and alkenyl groups having about 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have 20 a value between 0 and 60, provided that (x+y+z) equals about 2 to about 100. This composition can also contain 0 to 2 wt. % of a diester of an ethoxylated polyhydric alcohol depicted by the formula R' CH2 O (CH2CH O )x B
R' [CH O (CH2CH O )y B]w R' CH2 O (CH2CH O )z B
CA 0220~404 1997-0~-14 wherein w equals one to four. One of the B's is hydrogen and two B's are selected from the group consisting of a group represented by:
o C R
S wherein R is selected from the group consisting of alkyl group having about 6 to 22 carbon atoms, and alkenyl groups having about 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals about 2 to about 100. This composition can also contain 0 to about 1.0 wt. % of a triester of an ethoxylated 10 polyhydric alcohol depicted by the formula R' CH2 O (CH2CH O )x B
R' [ CH O (CH2CH O )y B]w R' CH2 O (CH2CH O )z B
wherein w equals one to four. The three B's are selected from the group consisting of a group represented by:
o C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100.
According to the present invention, the role of the hydrocarbon is provided by anon-water-soluble perfume Typically, in aqueous based compositions the presence of a solubilizers, such as alkali metal lower alkyl aryl sulfonate hydrotrope, triethanolamine, urea, etc., is required for perfume dissolution, especially at perfume levels of 1% and higher, since perfumes are generally a mixture of fragrant essential p~N~D ~
CA 0220~404 1997-0~-14 oils and aromatic compounds which are generally not water-soluble. Therefore, byincorporating the perfume into the aqueous cleaning composition as the oil (hydrocarbon) phase of the ultimate o/w microemulsion composition, several different important advantages are achieved.
First, the cosmetic properties of the ultimate cleaning composition are improved:
the compositions are both clear (as a consequence of the formation of a microemulsion) and highly fragranced (as a consequence of the perfume level).
Second, the need for use of solubilizers, which do not contribute to cleaning performance, is eliminated.
Third, an improved grease release effect and an improved grease removal capacity in neat (undiluted) usage of the dilute aspect or after dilution of the concentrate can be obtained without detergent builders or buffers or conventional grease removal solvents at neutral or acidic pH and at low levels of active ingredients while improved cleaning performance can also be achieved in diluted usage.
As used herein and in the appended claims the term "perfume" is used in its ordinary sense to refer to and include any non-water soluble fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flower, herb, blossom or plant), artificial (i.e., mixture of natural oils or oil constituents) and synthetically produced substance) odoriferous substances. Typically, perfumes are 20 complex mixtures of blends of various organic compounds such as alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils (e.g., terpenes) such as from 0% to 80%, by weight, the essential oils themselves being volatile odoriferous compounds and also serving to dissolve the other components of the perfume.
In the present invention the precise composition of the perfume is of no particular 25 consequence to cleaning performance so long as it meets the criteria of waterimmiscibility and having a pleasing odor. Naturally, of course, especially for cleaning compositions intended for use in the home, the perfume, as well as all other ingredients, should be cosmetically acceptable, i.e., non-toxic, hypoallergenic, etc.. The ~MENDE~ SI~Er~T
CA 0220~404 1997-0~-14 instant compositions show a marked improvement in ecotoxocity as compared to existing commercial products.
The hydrocarbon such as a perfume is present in the dilute o/w microemulsion in an amount of from 0.1% to l O% by weight. If the amount of hydrocarbon (perfume) is 5 less than 0.4% by weight it becomes more difficult to form the o/w microemulsion In the case of the liquid crystal one need at least 0.5 weight % of perfume. If thehydrocarbon (perfume) is added in amounts more than 10% by weight, the cost is increased without any additional cleaning benefit and, in fact, with some diminishing of cleaning performance insofar as the total amount of greasy or oily soil which can be 10 taken up in the oil phase of the microemulsion will decrease proportionately.Furthermore, although superior grease removal performance will be achieved for perfume compositions not containing any terpene solvents, it is apparently difficult for perfumers to formulate sufficiently inexpensive perfume compositions for products of this type (i.e., very cost sensitive consumer-type products) which includes less than 15 20%, usually less than 30%, of such terpene solvents.
Thus, merely as a practical matter, based on economic consideration, the dilute o/w microemulsion detergent cleaning compositions of the present invention may often include as much as 0.2% to 7% by weight, based on the total composition, of terpene solvents introduced thereunto via the perfume component. However, even when the 20 amount of terpene solvent in the cleaning formulation is less than 1.5% by weight, such as up to 0.6% by weight or 0.4% by weight or less, satisfactory grease removal and oil removal capacity is provided by the inventive diluted o/w microemulsions.
Thus, for a typical formulation of a diluted o/w microemulsion according to thisinvention a 20 milliliter sample of o/w microemulsion containing 1% by weight of25 perfume will be able to solubilize, for example, up to 2 to 3 ml of greasy and/or oily soil, while retaining its form as a microemulsion, regardless of whether the perfume contains 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% or 0.8% by weight of terpene solvent.
In other words, it is an essential feature of the compositions of this invention that grease A~4EI~DED SHE~, CA 0220~404 1997-0~-14 removal is a function of the result of the microemulsion, per se, and not of the presence or absence in the microemulsion of a "greasy soil removal" type of solvent.
In place of the perfume one can employ a water insoluble paraffin or isoparaffinhaving 6 to 18 carbon at a concentration of 0.4 to 8.0 wt. percent.
The water-soluble organic detergent materials which are used in forming the ultimate o/w microemulsion compositions of this invention may be selected from the group consisting of water-soluble, non-soap, anionic surfactants mixed with a fatty acid and the solubilizing agent which is a partially esterified ethoxylated polyhydric alcohol such as a partially esterified ethoxylated glycerol.
Although conventional nonionic surfactants can be used in the instant compositions, the employment of such conventional nonionic in the instant composition will decrease the environmental profile of the composition as well as having an adverse effect on the grease release and grease + particulate soil removal properties of the composition.
Regarding the anionic surfactant present in the o/w microemulsions any of the conventionally used water-soluble anionic surfactants or mixtures of said anionic detergents and anionic detergents can be used in this invention. As used herein the term "anionic surfactant" is intended to refer to the class of anionic and mixed anionic-nonionic surfactants providing detersive action.
Suitable water-soluble non-soap, anionic suRactants include those surface-activeor detergent compounds which contain an organic hydrophobic group containing generally 8 to 26 carbon atoms in their molecular structure and at least one water-solubilizing group selected from the group of sulfonate, sulfate and carboxylate so as to form a water-soluble surfactant. Usually, the hydrophobic group will include or comprise a Cg-C22 alkyl, alkyl or acyl group. Such surfactants are employed in the form of water-soluble salts and the salt-forming cation usually is selected from the group consisting of sodium, potassium, ammonium, magnesium and mono-, di- or tri-C2-C3 alkanolammonium, with the sodium, magnesium and ammonium cations again being preferred.
~EN~E~
CA 0220~404 1997-0~-14 r ~
Examples of suitable sulfonated anionic surfactants are the well known higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the higher alkyl group in a straight orbranched chain, Cg-c1s alkyl toluene sulfonates and C8-c1s alkyl phenol sulfonates.
A preferred sulfonate is iinear alkyl benzene suifonate having a high content of 3-(or higher) phenyl isomers and a correspondingly low content (well below 50%) of 2- (or lower) phenyl isomers, that is, wherein the benzene ring is preferably attached in large part at the 3 or higher (for example, 4, 5, 6 or 7) position of the alkyl group and the content of the isomers in which the benzene ring is attached in the 2 or 1 position is 10 correspondingly low. Particularly preferred materials are set forth in U.S. Patent 3,320,174.
Other suitable anionic surfactants are the olefin sulfonates, including long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. These olefin sulfonate detergents may be 15 prepared in a known manner by the reaction of sulfur trioxide (SO3) with long-chain olefins containing 8 to 25, and having the formula RCH=CHR1 where R is a higher alkyl group of 6 to 23 carbons and R1 is an alkyl group of 1 to 17 carbons or hydrogen to form a mixture of sultones and alkene sulfonic acids which is then treated to convert the sultones to sulfonates. Olefin sulfonates contain from 14 to 16 carl~on atoms in the R
20 alkyl group and are obtained by sulfonating an a-olefin.
Other examples of suitable anionic sulfonate surfactants are the paraffin sulfonates containing 10 to 20. Primary paraffin sulfonates are made by reacting long-chain alpha olefins and bisulfites and paraffin sulfonates having the sulfonate group distributed along the paraffin chain are shown in U.S. Patents Nos2,503,280;
25 2,507,088; 3,260,744; 3,372,188; and Gerrnan Patent 735,096.
Examples of satisfactory anionic sulfate surfactants are the Cg C1 g alkyl sulfate salts and the Cg-C1 g alkyl sulfate salts and the Cg-C1 g alkyl ether polyethenoxy sulfate salts having the formula R(OC2H4)n OSO3M wherein n is 1 to 12, and M is a solubilizing cation selected from the group consisting of sodium, potassium, ammonium, NDED S~
CA 0220~404 1997-0~-14 17 .~
magnesium and mono-, di- and triethanol ammonium ions. The alkyl sulfates may beobtained by sulfating the alcohols obtained by reducing glycerides of coconut oil or tallow or mixtures thereof and neutralizing the resultant product. On the other hand, the alkyl ether polyethenoxy sulfates are obtained by sulfating the condensation product of 5 ethylene oxide with a C8-cl8 alkanol and neutralizing the resultant product. The alkyl sulfates may be obtained by sulfating the alcohols obtained by reducing glycerides of coconut oil or tallow or mixtures thereof and neutralizing the resultant product. On the other hand, the alkyl ether polyethenoxy sulfates are obtained by sulfating the condensation product of ethylene oxide with a Cg-C1g alkanol and neutralizing the 10 resultant product. The alkyl ether polyethenoxy sulfates differ from one another in the number of moles of ethylene oxide reacted with one mole of alkanol. Preferred alkyl sulfates and preferred alkyl ether polyethenoxy sulfates contain 10 to 16 carbon atoms in the alkyl group.
The Cg-C12 alkylphenyl ether polyethenoxy sulfates containing from 2 to 6 15 moles of ethylene oxide in the molecule also are suitable for use in the inventive compositions. These detergents can be prepared by reacting an alkyl phenol with 2 to 6 moles of ethylene oxide and sulfating and neutralizing the resultant ethoxylated alkylphenol.
Obviously, these anionic surfactants will be present either in acid form or salt20 form depending upon the pH of the final composition, with salt forming cation being the same as for the other anionic detergents.
Of the foregoing non-soap anionic surfactants, the preferred surfactants are theCg-C1s linear alkylbenzene sulfonates and the C13-C17 paraffin or alkane sulfonates.
Particularly, preferred compounds are sodium C10-c13 alkylbenzene sulfonate and 25 sodium C13-C17 alkane sulfonate.
Generally, the proportion of the nonsoap-anionic surfactant will be in the range of 0.1% to 20.0%, by weight of the dilute o/w microemulsion composition.
The instant composition contains a composition (herein after referred to as ethoxylated glycerol type compound) which is a mixture of a fully esterified ethoxylated AMENDED S~EEr CA 0220~404 1997-0~-14 18 `' ;~
polyhydric alcohol, a partially esterified ethoxylated polyhydric alcohol and a nonesterified ethoxylated polyhydric alcohol, wherein the preferred polyhydric alcohol is glycerol, and the compound is:
R' 5CH2 O (CH2CH O )x B
R' 1CH O (CH2CH O )yB]w Formula R' (I) CH2 O (CH2CH O )z B
10and R' CH2 O (CH2CH O )X H
R' [CH O (CH2CH O )Y H]W Formula 15 R' (Il) CH2 O (CH2CH O )z H
wherein w equals one to four. B is selected from the group consisting of hydrogen or a group represented by:
o C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, wherein at least one of the B groups is represented by said O
C R, and R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100, wherein in Formula (I) the ratio of monoester / diester / triester is 45 to 90 / 5 to 40 / 1 to 20, AMENO~ E~T
CA 0220~404 1997-0~-14 19 ~ . , .
wherein the ratio of Formula (I) to Formula (Il) is a value between 3 to 0.02, wherein it is most preferred that there is more of Formula (Il) than Formula (I) in the mixture that forms the compound.
The ethoxylated glycerol type compound used in the instant composition is 5 manufactured by the Kao Corporation and sold under the trade name LEVENOL suchas Levenol F-200 which has an average EO of 6 and a molar ratio of coco fatty acid to glycerol of 0.55 or LEVENOL V501/2 which has an average EO of.17 and a molar ratio of tallow fatty acid to glycerol of 1Ø It is preferred that the molar ratio of the fatty acid to glycerol is less than 1.7, more preferably less than 1.5 and most preferably less than 1Ø The ethoxylated glycerol type compound has a molecular weight of 400 to 1600, and a pH (50 grams / liter of water) of 5-7. The LEVENOL compounds are substantially non irritant to human skin and have a primary biodegradabillity higher than 90% as measured by the Wickbold method Bias-7d.
Two examples of the LEVENOL compounds are LEVENOL V-501/2 which has 15 17 ethoxylated groups and is derived from tallow fatty acid with a fatty acid to glycerol ratio of 1.0 and a molecular weight of 1465 and LEVENOL F-200 has 6 ethoxylated groups and is derived from coco fatty acid with a fatty acid to glycerol ratio of 0.55.
Both LEVENOL F-200 and Levenol V-501/2 are composed of a mixture of Formula (I) and Formula (Il). The LEVENOL compounds has ecoxicity values of algae growth 2u inhibition > 100 mg/iiter; acute toxiciiy for Daphniae > i û0 mg/iiter and acute fish toxicity > 100 mg/liter. The LEVENOL compounds have a ready biodegradability higher than 60% which is the minimum required value according to OECD 301 B measurement to be acceptably biodegradable.
Polyesterified nonionic compounds also useful in the instant compositions are 25 CROV`OL PK-40 and CROVOL PK-70 manufactured by Croda GMBH of the Netherlands. CROVOL PK-40 is a polyoxyethylene (12) Palm Kernel Glyceride which has 12 EO groups. CROVOL PK-70 which is prefered is a polyoxyethyiene (45) Palm Kernel Glyceride have 45 EO groups.
~N~
CA 0220~404 1997-0~-14 20 " ;'`;
In the dilute o/w microemulsion compositions or liquid crystal compositions the ethoxylated glycerol type compounds or the polyesterified nonionic compounds will be present in admixture with the anionic detergent. The proportion of the ethoxylated glycerol type compound or the polyesterified nonionic solubilizing agent based upon the weight of the liquid crystal composition or the final dilute o/w microemulsion composition will be 0.1% to 20%, by weight.
Furthermore, in the more preferred compositions the weight ratio of nonsoap anionic detergent to the ethoxylated glycerol type compound will be in the range of 3:1 to 1:3 with especially good results being obtained at a weight ratio of 2:1.
The ethoxylated polyhydric alcohol such as an ethoxylated glycerol of the instant invention is depicted by the following formula R' CH2 O (CH2CH O )x H
R' [CH O (CH2CH O )y Hlw R' CH2 O (CH2CH O )z H
wherein w equals one to four, x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100.
In the dilute o/w microemulsion compositions or liquid crystal compositions the ethoxylated alcohol will be present in admixture with the anionic surfactant. The proportion of the ethoxylated glycerol type based upon the weight of the liquid crystal composition or the final dilute o/w microemulsion composition will be 0.1% to 20% by weight.
Furthermore, in the more preferred compositions the weight ratio of nonsoap anionic surfactant to the ethoxylated polyhydric alcohol will be in the range of 3:1 to 1:3 with especially good results being obtained at a weight ratio of 2:1.
The instant composition can also contain 0 to 10 wt. %, of a monoester of an ethoxylated polyhydric alcohol depicted by the formula ~ 3 ~tiEE~
CA 0220~404 1997-0~-14 21 ` `
R' CH2 O (CH2CH O )X B
R' 1CH O (CH2CH 0 )Y B]W
R' CH2 O (CH2CH O )Z B
wherein w equals one to four. Two of the BS are hydrogen and one B jS selected from the group consisting of a group represented by:
o C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tailow alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100 The instant composition can also contain 0 to 2 wt %, of a diester of an ethoxylated polyhydric alcohol depicted by the formula R' CH2 O (CH2CH O )X B
R' [ CH O (CH2CH O )Y B]W
R' CH2 O (CH2CH O )Z B
wherein w equals one to foun One of the BS jS hydrogen and two BS are selected from the group consisting of a group represented by:
O
C R
wherein R jS selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow ~3,~ ?~ r, !
. CA 0220~404 1997-0~-14 22 `` ~
alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals about 2 to 100.
The instant composition can also contain 0 to 1.0 wt. %, of a triester of an ethoxylated polyhydric alcohol depicted by the formula R' CH2 O (CH2CH O )x B
R' [CH O (CH2CH O )y B]w R' CH2 O (CH2CH O )z B
wherein w equals one to four. The three Bs are selected from the group consisting of a group represented by:
o C R
15 wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100.
The instant compositions contain 0 to 1.0 wt. % of a tri-alkyl citrate such as tri-n-20 butyl citrate, tri-n-propyl citrate, tri-isopropyl citrate, tri-isobutyl citrate, tri-n-pentyl citrate, tri-isopentyl citrate and tri-n-hexyl, wherein tri-n-butyl citrate is preferred. The tri-n-butyl citrate functions in the formula as a foam control agent in that the foam is more readily collapsed such that the article can be rinsed more effectively.
The cosurfactant may play an essential role in the formation of the the liquid 25 crystal composition or dilute o/w microemulsion and the concentrated microèmulsion compositions. Three major classes of compounds have been found to provide highly suitable cosurfactants for the microemulsion over temperature ranges extending from 5 C to 43 C for instance; (1 ) water-soluble C3-C4 alkanols, polypropylene glycol of the formula HO(CH3CHCH2O)nH wherein n is a number from 2 to 18 and monoalkyl ethers p~,4F~ SH~
CA 0220~404 1997-0~-14 23 .:.
and esters of ethylene glycol and propylene glycol having the structural formulas R(X)nOH and R1 (x)noH wherein R is C1-c6 alkyl, R1 is C2-C4 acyl group, X is (OCH2CH2) or (ocH2(cH3)cH) and n is a number from 1 to 4; (2) aliphatic mono- and di-carboxylic acids containing 2 to 10 carbon atoms, preferably 3 to 6 carbons in the molecule; and (3) triethyl phosphate. Additionally, mixtures of two or more of the four classes of cosurfactant compounds may be employed where specific pH's are desired.
When the mono- and di-carboxylic acid (Class 2) cosurfactants are employed in the instant microemulsion compositions at a concentration of 2 to 10 wt. %, the microemulsion compositions can be used as a cleaners for bathtubs and other hardsurfaced items, which are acid resistant thereby removing lime scale, soap scum and greasy soil from the surfaces of such items damaging such surfaces. If these surfaces are of zirconium white enamel, they can be damaged by these compositions.
An aminoalkylene phophonic acid at a concentration of 0.01 to 0.2 wt. % can be optionally used in conjunction with the mono- and di-carboxylic acids, wherein the aminoalkylene phophonic acid helps prevent damage to zirconium white enamel surfaces. Additionally, 0.05 to 1% of phosphoric acid can be used in the composition.
Methanol and ethanol are explicitly excluded from the instant composition because of their low flash point.
Representative members of the polypropylene glycol include dipropylene glycol and polypropylene glycol having a molecular weight of 200 to 1000, e.g., polypropylene glycol 400. Other satisfactory glycol ethers are ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monobutyl ether, mono, di, tri propylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol tertiary butyl ether, ethylene glycol monoacetate and dipropylene glycol propionate. When these glycol type cosurfactants are at a concentartion of at least 1.0 weight %, in combination with a perfume at a concentration of at least 0.5 weight %, one can form a liquid crystal composition Representative members of the aliphatic carboxylic acids include C3-C6 alkyl and alkenyl monobasic acids and dibasic acids such as glutaric acid and mixtures of N~ED Sl i~
CA 0220~404 1997-0~-14 24 ~ ~ .
glutaric acid with adipic acid and succinic acid, as well as mixtures of the foregoing acids as well as acrylic acid or propionic acid.
While all of the aforementioned glycol ether compounds and acid compounds provide the described stability, the most preferred cosurfactant compounds of each type, on the basis of cost and cosmetic appearance (particularly odor), are diethylene glycol monobutyl ether and a mixture of adipic, glutaric and succinic acids? respectively.
The ratio of acids in the foregoing mixture is not particularly critical and can be modified to provide the desired odor. Generally, to maximize water solubility of the acid mixture glutaric acid, the most water-soluble of these three saturated aliphatic dibasic acids, will 10 be used as the major component.
Generally, weight ratios of adipic acid: glutaric acid:succinic acid is 1-3:1-8:1-5, can be used with equally good results.
Still other classes of cosurfactant compounds providing stable microemulsion compositions at low and elevated temperatures are the mono-, di- and triethyl esters of 15 phosphoric acid such as triethyl phosphate.
The amount of cosurfactant required to stabilize the liquid crystal compositionsor the microemulsion compositions will, of course, depend on such factors as thesurface tension characteristics of the cosurfactant, the type and amounts of the primary surfactants and perfumes, and the type and amounts of any other additional ingredients 20 which may be present in the composition and which have an influence on the thermodynamic factors enumerated above. The amounts of cosurfactant in the rangeof from 0.5% to 15%, by weight provide stable dilute o/w microemulsions for the above-described levels of primary surfactants and perfume and any other additional ingredients as described below.
As will be appreciated by the practitioner, the pH of the final microemulsion will be dependent upon the identity of the cosurfactant compound, with the choice of the cosurfactant being effected by cost and cosmetic properties, particularly odor. For example, microemulsion compositions which have a pH in the range of 1 to 10 may employ either the class 1 or the class 4 cosurfactant as the sole cosurfactant, but the ~ ?~ S~
CA 0220~404 1997-0~-14 pH range is reduced to 1 to 8.5 when the polyvalent metal salt is present. On the other hand, the class 2 cosurfactant can only be used as the sole cosurfactant where the product pH is below 3.2. However, where the acidic cosurfactants are employed inadmixture with a glycol ether cosurfactant, compositions can be formulated at a 5 substantially neutral pH (e.g., pH 7+1.5).
The ability to formulate neutral and acidic products without builders which havegrease removal capacities is a feature of the present invention because the prior art o/w microemulsion formulations most usually are highly alkaline or highly built or both.
In addition to their excellent capacity for cleaning greasy and oily soils, the low 10 pH o/w microemulsion formulations also exhibit excellent cleaning performance and removal of soap scum and lime scale in neat (undiluted) as well as in diluted usage.
The final essential ingredient in the inventive microemulsion compositions having improved interfacial tension properties is water. The proportion of water in themicroemulsion compositions generally is in the range of 20% to 97%, by weight of the 15 usual diluted o/w microemulsion composition.
As believed to have been made clear from the foregoing description, the dilute o/w microemulsion liquid all-purpose cleaning compositions of this invention areespecially effective when used as is, that is, without further dilution in water, since the properties of the composition as an o/w microemulsion are best manifested in the neat 20 (undiluted) form. However, at the same time it should be understood that depending on the levels of surfactants, cosurfactants, perfume and other ingredients, some degree of dilution without disrupting the microemulsion, per se, is possible. For example, at the preferred low levels of active surfactant compounds (i.e., primary anionic and nonionic surfactants) dilutions up to 50% will generally be well tolerated without causing phase 25 separation, that is, the microemulsion state will be maintained.
However, even when diluted to a great extent, such as a 2- to 1 0-fold or more dilution, for example, the resulting compositions are still effective in cleaning greasy, oily and other types of soil. Furthermore, the presence of magnesium ions or other N~3~SH~FT
CA 0220~404 1997-0~-14 26 ` ;; ~
polyvalent ions, e.g., aluminum, as will be described in greater detail below further serves to boost cleaning performance of the primary detergents in dilute usage.
On the other hand, it is also within the scope of this invention to formulate highly concentrated microemulsions which will be diluted with additional water before use.
The present invention also relates to a stable concentrated microemulsion or acidic microemulsion composition comprising by weight:
(a) 1 to 30% of an anionic surfactant;
(b) 0.5 to 15% of an ethoxylated glycerol type compound;
(c) 2 to 30% of a cosurfactant; ~
(d) 0.4 to 10% of a water insoluble hydrocarbon or perfume;
(e) 0 to 18% of at least one dicarboxylic acid;
(f) 0 to 1% of phosphoric acid;
(g) 0 to 0.2% of an aminoalkylene phosphonic acid;
(h) 0 to 15% of magnesium sulfate heptahydrate;
(i) 0 to 1.0% of a tri-alkyl citrate; and (h) balance being water, wherein the composition has an ecotoxocity as measured by the LC 50 test of at least 0.18 ml/L measured on Daphniae microorganisms.
The present invention also relates to a stable liquid crystal microemulsion or 20 acidic microemulsion composition comprising by weight:
(a) 1 to 30% of an anionic surfactant;
(b) 0.5 to 15% of an ethoxylated glycerol type compound;
(c) 0 to 2.5% of a fatty acid;
(d) 2 to 30% of a cosurfactant;
(e) 0.5 to 10% of a water insoluble hydrocarbon or perfume;
(f) 0 to 15% of magnesium sulfate heptahydrate;
(9) 0 to 1.0% of a tri-alkyl citrate; and ~ENDED S~E
CA 0220~404 1997-0~-14 27 ;, ;
(h) balance being water, wherein the composition has an ecotoxocity as measured by the LC 50 test of at least 0.18 ml/L measured on Daphniae mlcroorganlsms.
The present invention also relates to a stable concentrated microemulsion or 5 acidic microemulsion composition comprising approximately by weight:
(a) 1 to 30% of an anionic surfactant;
(b) 0.5 to 15% of an ethoxylated polyhydric alcohol such as an ethoxylated glycerol;
(c) 2 to 30% of a cosurfactant;
(d) 0.4 to 10% of a water insoluble hydrocarbon or perfume;
(e) 0 to 18% of at least one dicarboxylic acid;
(f) 0 to 1% of phosphoric acid;
(g) 0 to 0.2% of an aminoalkylene phosphonic acid;
(h) 0 to 15% of magnesium sulfate heptahydrate; and (i) the balance being water.
The present invention also relates to a stable liquid crystal microemulsion or acidic microemulsion composition comprising approximately by weight:
(a) 1 to 30% of an anionic surfactant;
(b) 0.5 to 15% of an ethoxylated polyhydric alcohol such as an ethoxylated 20 glycerol;
(c) 2 to 30% of a cosurfactant;
(d) 0.5 to 10% of a water insoluble hydrocarbon or perfume;
(e) 0 to 15% of magnesium sulfate heptahydrate; and (f) the balance being water.
Such concentrated microemuisions can be diiuted by mixing with up to 20 times or more, their weight of water to form o/w microemulsions similar to the dilutedmicroemulsion compositions described above. While the degree of dilution is suitably chosen to yield an o/w microemulsion composition after dilution, it should be recognized p~~ 3 S~~
CA 0220~404 1997-0~-14 28 ` '~ ' that during the course of dilution both microemulsion and non-microemulsions may be successively encountered.
In addition to the above-described essential ingredients required for the formation of the liquid crystal composition or the microemulsion composition, the 5 compositions of this invention may often and preferably do contain one or moreadditional ingredients which serve to improve overall product performance.
One such ingredient is an inorganic or organic salt of oxide of a multivalent metal cation, particularly Mg++. The metal salt or oxide provides several benefits including improved cleaning performance in dilute usage, particularly in soft water areas, and 10 minimized amounts of perfume required to obtain the microemulsion state. Magnesium sulfate, either anhydrous or hydrated (e.g., heptahydrate), is especially preferred as the magnesium salt. Good results also have been obtained with magnesium oxide, magnesium chloride, magnesium acetate, magnesium propionate and magnesium hydroxide. These magnesium salts can be used with formulations at neutral or acidic 15 pH since magnesium hydroxide will not precipitate at these pH levels.
Although magnesium is the preferred multivalent metal from which the salts (inclusive of the oxide and hydroxide) are formed, other polyvalent metal ions also can be used provided that their salts are nontoxic and are soluble in the aqueous phase of the system at the desired pH level. Thus, depending on such factors as the pH of the 20 system, the nature of the primary surfactants and cosurfactant, and so on, as well as the availability and cost factors, other suitable polyvalent metal ions include aluminum, copper, nickel, iron, calcium, etc. It should be noted, for example, that with the preferred paraffin sulfonate anionic detergent calcium salts will precipitate and should not be used. It has also been found that the aluminum salts work best at pH below 5 or 25 when a low level, for example 1 weight percent, of citric acid is added to the composition which is designed to have a neutral pH. Alternatively, the aluminum salt can be directly added as the citrate in such case. As the salt, the same general classes of anions as mentioned for the magnesium salts can be used, such as halide (e.g., bromide, chloride), sulfate, nitrate, hydroxide, oxide, acetate, propionate, etc.
p~~ S~
CA 0220~404 1997-0~-14 In the dilute compositions the metal compound is added to the composition in an amount sufficient to provide at least a stoichiometric equivalence between the anionic surfactant and the multivalent metal cation. For example, for each gram-ion of Mg++
there will be 2 gram moles of paraffin sulfonate, alkylbenzene sulfonate, etc., while for S each gram-ion of A13+ there will be 3 gram moles of anionic surfactant. Thus, the proportion of the multivalent salt generally will be selected so that one equivalent of compound will neutralize from 0.1 to 1.5 equivalents, of the acid form of the anionic surfactant.
At higher concentrations of anionic surfactant, the amount of multivalent salt will 10 be in range of 0.5 to 1 equivalents per equivalent of anionic surfactant.
The liquid crystal composition or the o/w microemulsion compositions comprises from 0% to 2.5%, by weight of the composition of a C8-C22 fatty acid or fatty acid soap as a foam suppressant. The addition of fatty acid or fatty acid soap provides animprovement in the rinseability of the composition whether applied in neat or diluted 15 form. Generally, however, it is necessary to increase the level of cosurfactant to maintain product stability when the fatty acid or soap is present. If more than 2.5wt %
of the fatty acid is used in the instant compositions, the composition will become unstable at low temperatures as well as having an objectionable smell.
As example of the fatty acids which can be used as such or in the form of soap, 20 mention can be made of distilled coconut oil fatty acids, "mixed vegetable" type fatty acids (e.g. high percent of saturated, mono-and/or polyunsaturated C18 chains); oleic acid, stearic acid, palmitic acid, eiocosanoic acid, and the like, generally those fatty acids having from 8 to 22 carbon atoms being acceptable.
The all-purpose liquid cleaning composition of this invention may, if desired, also 25 contain other components either to provide additional effect or to make the product more attractive to the consumer. The following are mentioned by way of example:
Colors or dyes in amounts up to 0.5% by weight; bactericides in amounts up to 1% by weight; preservatives or antioxidizing agents, such as formalin, 5-bromo-5-nitro-dioxan-1,3; 5-chloro-2-methyl-4-isothaliazolin-3-one, 2,6-di-tert.butyl-p-cresol, etc., in amounts ~ C~ S~E~
CA 0220~404 1997-0~-14 up to 2% by weight; and pH adjusting agents, such as sulfuric acid or sodium hydroxide, as needed. Furthermore, if opaque compositions are desired, up to 4% by weight of an opacifier may be added.
The instant compositions of the instant invention explicitly exclude zwitterionic 5 surfactant such as betaines because these zwetterionic surfactants are extremely high foaming which, if used in the instant composition, would cause the instant compositions to have to high a foam profile and that too much foam would leave residue on thesurface being cleaned.
In final form, the all-purpose liquids are clear oil-in-water microemulsions or liquid 10 crystal compositions and exhibit stability at reduced and increased temperatures. More specifically, such compositions remain clear and stable in the range of 5 C to 50 C.
Such compositions exhibit a pH in the acid or neutral range depending on intended end use. The liquid microemulsion compositions are readily pourable and exhibit a viscosity in the range of 6 to 60 milliPascal . second (mPas.) as measured at 25 C. with a15 Brookfield RVT Viscometer using a #1 spindle rotating at 20 RPM.
The compositions are directly ready for use or can be diluted as desired and in either case no or only minimal rinsing is required and substantially no residue or streaks are left behind. Furthermore, because the compositions are free of detergent builders such as alkali metal polyphosphates they are environmentally acceptable and provide a 20 better "shine" on cleaned hard surfaces.
When intended for use in the neat form, the liquid compositions can be packaged under pressure in an aerosol container or in a pump-type sprayer for the so-called spray-and-wipe type of application.
Because the compositions as prepared are aqueous liquid formulations and 25 sincè- no particular mixing is required to form the o/w microemulsion, the compositions are easily prepared simply by combining all the ingredients in a suitable vessel or container. The order of mixing the ingredients is not particularly important andgenerally the various ingredients can be added sequentially or all at once or in the form of aqueous solutions of each or all of the primary detergents and cosurfactants can be CA 0220~404 1997-0~-14 31 , . .
separately prepared and combined with each other and with the perfume. The magnesium salt, or other multivalent metal compound, when present, can be added as an aqueous solution thereof or can be added directly. It is not necessary to useelevated temperatures in the formation step and room temperature is sufficient.
The instant microemulsion formulas explicitly exclude alkali metal silicates andalkali meta builders such as alkali metal polyphosphates, alkali metal carbonates, alkali metal phosphonates and alkali metal citrates because these materials, if used in the instant composition, would cause the composition to have a high pH as well as leaving residue on the surface being cleaned.
It is contemplated within the scope of the instant invention that the ethoxylated glycerol type compound can be employed in hard surface cleaning compositions such as wood cleaners, window cleaners and light duty liquid cleaners, wherein improvements in a grease release effect in desirable.
The following examples illustrate liquid cleaning compositions of the described 15 invention. Unless otherwise specified, all percentages are by weight. The exemplified compositions are illustrative only and do not limit the scope of the invention. Unless otherwise specified, the proportions in the examples and elsewhere in the specification are by weight.
CA 0220.,404 1997 - 0., - 14 such as alkali metal polyphosphates they are environmentally acceptable and provide a better "shine" on cleaned hard surfaces.
When intended for use in the neat form, the liquid compositions can be packaged under pressure in an aerosol container or in a pump-type sprayer for the so-called spray-and-wipe type of application.
Because the compositions as prepared are aqueous liquid formulations and since no particular mixing is required to form the o/w microemulsion, the compositions are easily prepared simply by combining all the ingredients in a suitable vessel or container. The order of mixing the ingredients is not particularly important and10 generally the various ingredients can be added sequentially or all at once or in the form of aqueous solutions of each or all of the primary detergents and cosurfactants can be separately prepared and combined with each other and with the perfume. The magnesium salt, or other multivalent metal compound, when present, can be added as an aqueous solution thereof or can be added directly. It is not necessary to use15 elevated temperatures in the formation step and room temperature is sufficient.
The instant microemulsion formulas explicitly exclude alkali metal silicates andalkali meta builders such as alkali metal polyphosphates, alkali metal carbonates, alkali metal phosphonates and alkali metal citrates because these materials, if used in the instant composition, would cause the composition to have a high pH as well as leaving 20 residue on the surface being cleaned.
It is contemplated within the scope of the instant invention that the ethoxylated glycerol type compound can be employed in hard surface cleaning compositions such as wood cleaners. window cleaners and light duty liquid cleaners, wherein improvements in a grease release effect in desirable.
The following examples illustrate liquid cleaning compositions of the described invention. Unless otherwise specified, all percentages are by weight. The exemplified compositions are illustrative only and do not limit the scope of the invention. Unless otherwise specified, the proportions in the examples and elsewhere in the specification are by weight.
- - - -CA 0220~404 1997-05-14 W O 96/15217 PCTrUS95/14583 Exam~le 1 The following compositions in wt. % were prepared:
A B C D EF Mr. Proper St Marc Lemon Sodium C1~ -C17 4.7 4.3 4 4.314.1 7.05 2.9 Paraffin sul onate EO/PO nor onic - - - - - - - 3.2 Levenol F-200 2.3 2.2 2 2.2 6.3 345 C13-C15 EO 14 - - - - - - 3.3 nonionic DEGMBE 4 4 . 4 12 6 4.4 3 Fatty acid C 7 0.5 ~.~ C 72.25 1.125 0.65 0.3 M~SO4 7 H20 . 2 . . 6.3 3.15 Per'ume(a) ~ . 0.75 0.~ . 2.4 1.2 presentpresent Soc ium Citrate - - - - - - 3.2 Wa-er Bal Bal Bal Bal Bal Bal Bal Bal pH 7 7 7 7 7 7 9.5 7 Degreasing test Neat (b) 30 35 35 35 30 30 70 >100 Dilute (b) 45 60 60 60 45 45 ~90 90 Residue Equal Equal Equal Equal Equal Equal WorseEqualto ref.
to ref. to ref. to ref. to ref. to ref. to ref.
Foam in hard Water Equal Equal Equal Equal Equal Equal Equal to Equal to ref.
to ref. to ref. to ref. to ref. to ref. to ref. ref.
LC50-Ecotoxicityon 0.18 - - - - - 0.1 mVI0.033 mVI
Daphniae (c) mVI
G H
Linear alkyl benzene sulfonic 4.7 4.5 5 r-cjd ~laOH to reach pH 7 ~. 0.57 0.64 evenol F-200 . 2.5 2 DEGMBE . 6 .2 Fattyacid C.7 ~.75 0 75 M~SO4 7 H20 .1 .~6 Perfume(a) ~.8 ~. .
Water Bal Ba Ba pH 7 7 7 (a) contains 25% by weight of terpenes.
(b) the lower the number of strokes, the better the degreasing performance.
(c) the higher the results, the lower the ecotoxicity.
Furthermore, "dissolution power" of the o/w microemulsion of this example is 10 compared to the "dissolution power" of an identical composition except that an equal amount (5 weight percent) of sodium cumene sulfonate hydrotrope is used in place of the diethylene glycol monobutyl ether cosurfactant in a test wherein equal concentrations of heptane are added to both compositions. The o/w microemulsion of CA 0220~404 1997-0~-14 this invention solubilizes 12 grams of the water immiscible substance as compared to 1.4 grams in the hydrotrope containing liquid composition.
In a further comparative test using blue colored cooking oil--a fatty triglyceride soil --, the composition of Example 1 is clear after the addition of 0.2 grams of cooking 5 oil whereas the cooking oil floats on the top of the composition containing the sulfonate hydrotrope.
When the concentration of perfume is reduced to 0.4% in the composition of Example 1, a stable o/w microemulsion composition is obtained. Similarly, a stable o/w microemulsion is obtained when the concentration of perfume is increased to 2% by 10 weight and the concentration of cosurfactant is increased to 6% by weight in Example 1.
The present invention also relates to an aqueous solution of a grease release system which comprises:
(a) 0.1 to 20.0 wt. % of a mixture of:
R' CH2 O (CH2CH O )x B
R' [ CH O (CH2CH O )y B]w R' (I) CH2 O (CH2CH O )z B
and R' CH2 O (CH2CH O )x H
R' [ CH O (CH2CH O )y H]w R' (I 1) CH2 O (CH2CH O )z H
wherein w equals one to four. B is selected from the group consisting of hydrogen or a group represented by:
:
CA 0220~404 1997-05-14 W O 96tl5217 PCTAUS95/14583 o C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein at least one of the B
5 groups is represented by said o C R, R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100, wherein in Formula (I) the ratio of monoester / diester / triester is 40 to 90 / 5 to 35 / 1 to 20, wherein the ratio of Formula (I) to Formula (Il) is a value between 3 to 0.02, more preferably 3 to 0.1, and most preferably 1.5 to 0.2, wherein it is most preferred that there is more of Formu!a (!!) than Formula (I) in the mixture; and (b) the balance being water.
The aqueous solution of the grease release agent can be coated onto a hard surface. The treated hard surface will prevent the adhering of grease to the hard surface thereby providing easier cleaning of the hard surface with a conventional hard surface cleaning composition.
Exam~le 2 The example illustrates a typical formulation of a ~'concentrated" o/w microemulsion based on the present invention:
% by wei~ht Coco fatty acid 4 Sodium C13-C17 Paraffin Sulfonate 20.75 Levenol F-200 12 Diethylene glycol monobutyl ether 20 Perfume (a) 12.5 Water Bal to 100 pH: 7.0 + 0.2 This concentrated formulation can be easily diluted, for example, five times with tap water, to yield a diluted o/w microemulsion composition. Thus, by using microemulsion technology it becomes possible to provide a product having high levels CA 0220~404 1997-0~-14 WO 96/lS217 PCT/US95/14583 of active detergent ingredients and perfume, which has high consumer appeal in terms of clarity, odor and stability, and which is easily diluted at the usual usage concentration for similar all-purpose hard surface liquid cleaning compositions, while retaining its cosmetically attractive attributes.
Naturally, these formulations can be used, where desired, without further dilution and can also be used at full or diluted strength to clean soiled fabrics by hand or in an automatic laundry washing machine.
Example 3 This example illustrates a diluted o/w microemulsion composition according to 10 the invention having an acidic pH and which also provides improved cleaning performance on soap scum and lime scale removal as well as for cleaning greasy soil.
% by wei~ht Sodium C13-C17 paraffin sulfonate 4.7 Levenol F-200 2.3 Mg SO4 7H20 2.2 Mixture of succinic acid/glutaric acid/adipic acid (1:1:1 ) 5 Perfume (d) 1.0 Water, minors (dye) balance to 100 Phosphonic acid 0.2 Amino tris - (methylene-phosphonic acid) 0.03 pH=3 iO.2 (d) contains 40% by weight of terpene Example 4 Formula A of Example I was tested for the removal of a combination of grease and particulate soil as well as for a grease release effect and compared to commercial AjaxtmNME
1. Grease + particulate soil removal;
Test Method A) Soil composition:
70 9 of mineral oil 35 9 of particulate soil (vacuum cleaner dust + 1% of carbon black) -CA 0220~404 1997-0~-14 B) Soil Dreparation:
- Weigh cleaned/dried glass tiles - Soil the tiles with the grease + particulate soil - Bake the tiles 1 hour at 80C
- Weigh the soiled tiles which aged 2 hours at RT.
C) Soil removal:
The soiled tiles are soaked for 15 minutes at RT in the test products, then they are delicately rinsed with tap water.
After drying 45 minutes at 50C, the tiles are weighed again.
Results Grease + particulate soil % of removal me -n of 6 tiles Commercial Ajaxtm NME I 60 Formula A of Example I ¦ 95 Formula A exhibits improved grease + particulate soil removal over the Commercial Ajaxtm NME
Il. Grease release effect Test Method A) Soil composition:
20% hardened tallow 80% beef tallow fat blue dye B) Soil preparation:
The fat mixture is heated and sprayed with an automatic spraying device on cleaned and dried ceramic tiles.
C) Soil removal:
Product used neat: 2.5 9 on sponge Product used dilute: 1.2% sol in tap water- 10 ml of the solution on the sponge The cleaning procedure is done with the gardner device for both product concentrations.
CA 0220~404 l997-0~-l4 W O 96/lS217 PCTAUS95/14583 Results A) On treated ceramic tiles (treated with the product before spraying the soil) Neat ¦ Dilute Number of Strokes First grease layer deposHionmean of 4mean of 6 tiles tiles Commercial Current Ajaxtm NME27 19 19 5~
Second grease layer deposHion on the mean of 4 mean of 6 same tile tiles tiles Commercial Ajaxtm NME 25 48 1 8*
B) On untreated ceramic tiles In addition to the previous test, the 3 following procedures were used to verify that Formula A remains on the surface a~ter rinsing or wiping. After the first cleaning procedure and before the second spraying:
1) the tiles were allowed to dry in open air 2) the surface was wiped with paper towel 3) the surface was rinsed with wet sponge 1) dry in open air Neat ¦ Dilute Number of Strokes First grease layer deposHionmean of 4mean of 6 tiles tiles Commercial Ajaxtm NME 29 30 Formula A 27 32 Second grease layer cleposHion on themean of 4 mean of 6 same tile tiles tiles Commercial Ajaxtm NME 33 21 FormulaA 30 6 2) wipe dry the surface Neat ¦ Dilute Number cf Strokes First grease layer depositionmean of 4mean of 6 tiles tiles Commercial Ajaxtm NME 29 30 FormulaA 27 32 Second grease layer deposition on themean of 4 mean of 6 same tile tiles tiles Commercial Ajaxtm NME 35 46 FormulaA 30 48.5 CA 0220~404 1997-0~-14 3) wet wiping the surface Neat ¦ Dilute Number Gf Strokes First grease layer depos~ n mean of 4 mean of 6 tiles tiles Commercial Ajaxtm NME 29 30 Formula A 27 32 Second grease layer del~os;li~n on the mean of 4 mean of 6 same tile . tiles tiles Commercial Ajaxtm NME 34 58 Formula A 27 41 * highly significant difference ** after 5 strokes, 65% of the grease is already removed These results clearly demonstrate the important grease release effect obtained with Formula A especially when the product is used dilute.
Example ~
The following liquid crystal compositions were prepared by simple mixing procedure B
Sodium C13-C17 Paraffin sulfonate~.~ 4.3 ~.3 Levenol F-200 ~ . 2.2 .. 2 Propylene glycol monbutyl eth;r Dipropyl ne glycol monbutyl e ler - 3.5 ripropy ne ~Iycol monbutyl e-her attyac ~ 0 5 ~ -ulgS04 H20 1.6 .6 .6 P ~rfume (a) 1 . : .
~ater Bal Ba Ba p~ 7 7 7 0 ExamDle 6 The following optically clear microemulsion compositions were made by forming first a solution by mixing at 25C water, magnesium lauryl ether sulfate, Levenol V-510/2 and 1-Pentanol. To this solution with mixing at 25C was added the dodecane to form the optically clear microemulsion. The formula are expressed in weight percent.
A B C D E F G H
Magnesium 7 2.04 3.04 4.99 3.01 6.38 5.01 4.02 2.99 Lauryl suHate LevenolV-501/2 3.2 .1 7. . 7. 3.9 .~ 6. ~ 7.2 1-Pentanol .1 .0 4. ~.0 . 5.67 . . 1.13 Dodecane .2 ~C.717.' 6 1 .22 ~.: 7 15.2 2. ' . 2.9 water Ba Ba Bal Bal Bal Bal Ba Ba Bal CA 0220~404 1997-0~-14 Fxample 7 The following composition was prepared by simple mixing procedure:
Sodium C 1 3-C17 4.0 Paraffin Sulfonate Levenol F-200 2.0 DEGMBE 4.5 Fatty Acid 0.5 MgSO4 7H2O 1.8 Perfume (a) 0.8 tri-n-butyl citrate 0.5 Water Balance pH 7 Degreasing test Neat (6) Dilute (6) Residue Foam in hand Water (a) contains 25% by weight of terpenes (b) the lower the number of strokes, the better the degreasing performance.
The addition of the tri-n-butyl citrate improves the rinsability of the surface being rinsed in that the collapse of the foam is improved as compared to a composition not containing the tri-n-butyl citrate.
In summary, the described invention broadly relates to an improvement in microemulsion compositions containing an anionic surfactant, an ethoxylated glycerol type compound, a fatty acid, one of the specified cosurfactants, a hydrocarbon ingredient and water which comprise the use of a water-insoluble, odoriferous perfume as the essential hydrocarbon ingredient in a proportion sufficient to form either a dilute o/w microemulsion composition or liquid crystal composition containing, by weight, 0.1% to 20.0% of an anionic detergent, 0.1% to 10% of an ethoxylated glycerol type compound, 0% to 50% of cosurfactant, 0 to 1.0% of a tri-alkyl citrate, 0.4% to 10% of perfume and the balance being water.
CA 0220~404 1997-0~-14 WO 96/15217 PCT/US9!j/14583 Fxample 8 The following compositions in wt. % were prepared:
A B C D E F
Na C13-17 paraffin 4.7 4.7 4.7 4.7 4.7 4.7 sul~onate DEGtv BE 4 4 4 4 4 4 Coco attyacidt.'5 C 7 C.75 C 7 ~.75 C 7 MgSO4 . . ~ .2 ~.
Perfume ~ .. .8 Compounc a) . j , 7 I , - ..
Compounc b) . ~~
~~ompounc c). ,~ . ~ .~
~,ompounc d) . 5 . 1. 78 . 2.3 --~ eodol 91- -- -- -- -- -- 2.3 Water Bal. Bal.Bal. Bal. Bal. Bal.
PhasebehaviorOne One One One One One phase phasephasephase phase phase Particulate soil 71.079.8 84.0 86.0 88.7 51.0 (Kaolin removal Compound (a) is CH2 - 0 (cH2cH2o)2 R 1 CH - 0 (cH2cH2o)2 R2 CH2 - 0 (cH2cH2o)2 R3 wherein R1, R2 and R3 are coco alkyl chains 10 Compound (b) is CH2 - 0 (CH2CH20)2 R4 CH - 0 (CH2CH20)2 Rs CH2 - 0 (CH2CH20)2 H
wherein R4 and Rs are coco alkyl chains 15 Compound (c) is CH2 - 0 (CH2CH20)2 R6 CH - 0 (CH2CH20)2 H
CH2 - 0 (CH2CH20)2 H
wherein R6 is a coco alkyl chains CA 0220.,404 1997 - OF7 - 14 Compound (d) is CH2 - O (CH2CH2O)2 H
CH - O (CH2CH2O)2 H
CH2 - O (CH2CHzO)2 H
In summary, the described invention broadly relates to an improvement in microemulsion compositions for the removal of particulate soil containing an anionic surfactant, an ethoxylated polyhydric alcohol a cosurfactantl a hydrocarbon ingredient and water which comprise the use of a water-insoluble, odoriferous perfume as the essential hydrocarbon ingredient in a proportion sufficient to form either a dilute o/w microemulsion composition or liquid crystal composition containing, by weight, 0.1% to 20% of an anionic detergent, 0.1% to 20.0% of an ethoxylated polyhydric alcohol, 0% to 50% of cosurfactant, 0.4% to 10% of perfume and the balance being water In summary, the described invention broadly relates to an improvement in microemulsion compositions containing an anionic surfactant, an esterified polyethoxyether nonionic surfactant, a fatty acid, one of the specified cosurfactants, a hydrocarbon ingredient and water which comprise the use of a water-insoluble, odoriferous perfume as the essential hydrocarbon ingredient in a proportion sufficient to form either a dilute o/w microemulsion composition or liquid crystal compositioncontaining, by weight, 0.1% to 20% of an anionic detergent, 0.1% to 20.0% of a solubilizing agent which is an ethoxylated glycerol type compound, 0% to 50% of cosurfactant, 0.4% to 10% of perfume and the balance being water.
In another aspect, the invention generally provides a stable, clear all-purpose,hard surface cleaning composition especially effective in the removal of particle soil, which is in the form of a substantially dilute oil-in-water microemulsion having an aqueous phase and an oil phase. The dilute o/w microemulsion comprises on a weight basis:
from 0.1% to 20% of an anionic surfactant;
AM~ND~ SHE~T
CA 0220~404 1997-0~-14 from 0.1% to 50% of a water-mixable cosurfactant having either limited ability or substantially no ability to dissolve oily or greasy soil;
0.1% to 20% of an ethoxylated polyhydric alcohol;
0 to 15% of magnesium sulfate heptahydrate;
0.1 to 10.0% of a perfume or water insoluble hydrocarbon; and l O to 85% of water, said proportions being based upon the total weight of the composition. This composition can also contain 0 to 10 wt. % of a monoester of an ethoxylated polyhydric alcohol depicted by the formula:
R' CH2 O (cH2cH O )x B
R' [ CH O (CH2CH O )y Blw R' CH2 O (CH2CH O )z B) 15 wherein w equals one to four. Two of the B's are hydrogen and one B is selected from the group consisting of a group represented by:
o C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon 20 atoms, more preferably 11 to 15 carbon atoms and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals about 2 to about 100. This composition can also contain 0 to 2 wt. %, of a diester of an ethoxylated polyhydric alcohol depicted by the formula A~NGE~ Sn~ET
CA 0220~404 1997-0~-14 R' CH2 O (cH2cH O )x B
[CH O (CH2CH O )yB]w R' CH2 O (CH2CH O )z B
wherein w equals one to four. One of the B's is hydrogen and two B's are selected from the group consisting of a group represented by:
o wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100. This composition can also contain 0 to 15 1.0 wt. %, of a triester of an ethoxylated polyhydric alcohol depicted by the formula R' CH2 O (CH2CH O )x B
R' [ CH O (CH2CH O )y B]w 20 R' CH2 O (CH2CH O )z B
wherein w equals one to four. The three B's are selected from the group consisting of a group represented by:
O
25; C R
wherein R is selected from the group consisti-ng of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals about 2 to about 100.
4;-~N~ ET
The dispersed oil phase of the o/w microemulsion is composed essentially of the water-immiscible or hardly water-soluble perfume.
Quite surprisingly although the perfume is not, per se, a solvent for greasy or oily soil, -- even though some perfumes may, in fact, contain as much as 80% of terpenes which are known as good grease solvents -- the inventive compositions in dilute form have the capacity to solubilize up to 10 times or more of the weight of the perfume of oily and greasy soil, which is removed or loosened from the hard surface by virtue of the action of the anionic and nonionic surfactants, said soil being taken up into the oil phase of the o/w microemulsion.
In another aspect, the invention generally provides highly concentration microemulsion compositions in the form of either an oil-in-water (o/w) microemulsion or a water-in-oil (w/o) microemulsion which when diluted with additional water before use can form dilute o/w microemulsion compositions. The concentrated microemulsion compositions comprise, by weight, 0.1% to 20% of an anionic surfactant, 0.1% to 20%
15 of an ethoxylated glycerol type compound, 0% to 2.5% of a fatty acid, 0.1% to 10% of perfume or water insoluble hydrocarbon having 6 to 18 carbon atoms, 0.1% to 50% of a cosurfactant, and 20% to 97% of water.
In another aspect of the invention, liquid crystal compositions are provided which comprise by weight 0.1% to 20% of an anionic surfactant, 0.1% to 20% of an 20 ethoxylated glycerol type compound, 0 to 2.5% of a fatty acid, 0.1% to 10% of a perfume, more preferably 1% to 10%, 1% to 50% of cosurfactant selected from the group consisting of propylene glycol monobutylether, dipropylene glycol monobutylether and tripropyleneglycol monobutyl ether and mixtures thereof and the balance being water.
In another aspect, the invention provides highly concentration microemulsion compositions in the form of either an oil-in-water (o/w) microemulsion or a water-in-oil (w/o) microemulsion which when diluted with additional water before use can form dilute o/w microemulsion compositions. The concentrated microemulsion compositions comprise, by weight, 0.1% to 20% of an anionic surfactant, 0.1% to 20% of an CA 0220~404 1997-0~-14 ethoxylated glycerol type compound, 0% to 2.5% of a fatty acid, 0.1% to 10% of perfume or water insoluble hydrocarbon having 6 to 18 carbon atoms, 0.1% to 50% of a cosurfactant, and 20% to 97% of water.
In another aspect, the invention generally provides highly concentration 5 microemulsion compositions in the form of either an oil-in-water (o/w) microemulsion or a water-in-oil (w/o) microemulsion which when diluted with additional water before use can form dilute o/w microemulsion compositions. The concentrated microemulsion compositions comprise, by weight, 0.1% to 20% of an anionic surfactant, 0.1% to 20%
of an ethoxylated polyhydric alcohol, 0.1% to 10% of perfume or water insoluble hydrocarbon having 6 to 18 carbon atoms, 0.1% to 50% of a cosurfactant, and 20% to 97% of water.
In another aspect of the invention, liquid crystal compositions are provided which comprise by weight 0.1% to 20% of an anionic surfactant, 0.1% to 20% of an ethoxylated polyhydric alcohol, 0.1% to 10% of a perfume, 1% to 50% of cosurfactant 15 and the balance being water.
Detailed Description of the Invention The present invention relates to a stable liquid crystal or microemulsion composition comprising by weight: 0.1% to 20% of an anionic suRactant, 0.1% to 50%
of a cosurfactant, 0.1% to 20% of an ethoxylated glycerol type compound, 0.1% to 10%
20 of a water insoluble hydrocarbon or a perfume and the balance being water, said composition having an ecotoxocity value as measured by the LC50 test of at least 0.18 ml/L measured on Daphniae microorganisms.
The present invention relates to a stable liquid crystal or microemulsion composition comprising by weight: 0.1% to 20% of an anionic surfactant, 0.1% to 50%
25 of a cosurfactant, 0.4 to 1.0 wt. % of a trialkyl ester of citric aicd such as tri-n butyl citrate, 0.1% to 20% of an ethoxylated glycerol type compound, 0.1% to 10% of a water insoluble hydrocarbon or a perfume and the balance being water, said compositionhaving an ecotoxocity value as measured by the LC50 test of at least 0.18 ml/L
measured on Daphniae microorganisms.
CA 0220~404 1997-0~-14 The present invention relates to a stable liquid crystal or microemulsion composition comprising by weight: 0.1% to 20% of an anionic surfactant, 0.1% to 50%
of a cosurfactant, 0.1% to 20% of an ethoxylated polyhydric alcohol, 0.1% to 10% of a water insoluble hydrocarbon or a perfume and the balance being water. This composition can also contain 0 to 10 wt. % of a monoester of an ethoxylated polyhydric alcohol depicted by the formula R' CH2 O (CH2CH O )x B
R' [CH O (CH2CH Q )y B]w R' CH2 O (CH2CH O )z B
wherein w equals one to four. Two of the B's are hydrogen and one B is selected from the group consisting of a group represented by:
O
C R
wherein R is selected from the group consisting of alkyl group having about 6 to 22 carbon atoms, and alkenyl groups having about 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have 20 a value between 0 and 60, provided that (x+y+z) equals about 2 to about 100. This composition can also contain 0 to 2 wt. % of a diester of an ethoxylated polyhydric alcohol depicted by the formula R' CH2 O (CH2CH O )x B
R' [CH O (CH2CH O )y B]w R' CH2 O (CH2CH O )z B
CA 0220~404 1997-0~-14 wherein w equals one to four. One of the B's is hydrogen and two B's are selected from the group consisting of a group represented by:
o C R
S wherein R is selected from the group consisting of alkyl group having about 6 to 22 carbon atoms, and alkenyl groups having about 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals about 2 to about 100. This composition can also contain 0 to about 1.0 wt. % of a triester of an ethoxylated 10 polyhydric alcohol depicted by the formula R' CH2 O (CH2CH O )x B
R' [ CH O (CH2CH O )y B]w R' CH2 O (CH2CH O )z B
wherein w equals one to four. The three B's are selected from the group consisting of a group represented by:
o C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100.
According to the present invention, the role of the hydrocarbon is provided by anon-water-soluble perfume Typically, in aqueous based compositions the presence of a solubilizers, such as alkali metal lower alkyl aryl sulfonate hydrotrope, triethanolamine, urea, etc., is required for perfume dissolution, especially at perfume levels of 1% and higher, since perfumes are generally a mixture of fragrant essential p~N~D ~
CA 0220~404 1997-0~-14 oils and aromatic compounds which are generally not water-soluble. Therefore, byincorporating the perfume into the aqueous cleaning composition as the oil (hydrocarbon) phase of the ultimate o/w microemulsion composition, several different important advantages are achieved.
First, the cosmetic properties of the ultimate cleaning composition are improved:
the compositions are both clear (as a consequence of the formation of a microemulsion) and highly fragranced (as a consequence of the perfume level).
Second, the need for use of solubilizers, which do not contribute to cleaning performance, is eliminated.
Third, an improved grease release effect and an improved grease removal capacity in neat (undiluted) usage of the dilute aspect or after dilution of the concentrate can be obtained without detergent builders or buffers or conventional grease removal solvents at neutral or acidic pH and at low levels of active ingredients while improved cleaning performance can also be achieved in diluted usage.
As used herein and in the appended claims the term "perfume" is used in its ordinary sense to refer to and include any non-water soluble fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flower, herb, blossom or plant), artificial (i.e., mixture of natural oils or oil constituents) and synthetically produced substance) odoriferous substances. Typically, perfumes are 20 complex mixtures of blends of various organic compounds such as alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils (e.g., terpenes) such as from 0% to 80%, by weight, the essential oils themselves being volatile odoriferous compounds and also serving to dissolve the other components of the perfume.
In the present invention the precise composition of the perfume is of no particular 25 consequence to cleaning performance so long as it meets the criteria of waterimmiscibility and having a pleasing odor. Naturally, of course, especially for cleaning compositions intended for use in the home, the perfume, as well as all other ingredients, should be cosmetically acceptable, i.e., non-toxic, hypoallergenic, etc.. The ~MENDE~ SI~Er~T
CA 0220~404 1997-0~-14 instant compositions show a marked improvement in ecotoxocity as compared to existing commercial products.
The hydrocarbon such as a perfume is present in the dilute o/w microemulsion in an amount of from 0.1% to l O% by weight. If the amount of hydrocarbon (perfume) is 5 less than 0.4% by weight it becomes more difficult to form the o/w microemulsion In the case of the liquid crystal one need at least 0.5 weight % of perfume. If thehydrocarbon (perfume) is added in amounts more than 10% by weight, the cost is increased without any additional cleaning benefit and, in fact, with some diminishing of cleaning performance insofar as the total amount of greasy or oily soil which can be 10 taken up in the oil phase of the microemulsion will decrease proportionately.Furthermore, although superior grease removal performance will be achieved for perfume compositions not containing any terpene solvents, it is apparently difficult for perfumers to formulate sufficiently inexpensive perfume compositions for products of this type (i.e., very cost sensitive consumer-type products) which includes less than 15 20%, usually less than 30%, of such terpene solvents.
Thus, merely as a practical matter, based on economic consideration, the dilute o/w microemulsion detergent cleaning compositions of the present invention may often include as much as 0.2% to 7% by weight, based on the total composition, of terpene solvents introduced thereunto via the perfume component. However, even when the 20 amount of terpene solvent in the cleaning formulation is less than 1.5% by weight, such as up to 0.6% by weight or 0.4% by weight or less, satisfactory grease removal and oil removal capacity is provided by the inventive diluted o/w microemulsions.
Thus, for a typical formulation of a diluted o/w microemulsion according to thisinvention a 20 milliliter sample of o/w microemulsion containing 1% by weight of25 perfume will be able to solubilize, for example, up to 2 to 3 ml of greasy and/or oily soil, while retaining its form as a microemulsion, regardless of whether the perfume contains 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% or 0.8% by weight of terpene solvent.
In other words, it is an essential feature of the compositions of this invention that grease A~4EI~DED SHE~, CA 0220~404 1997-0~-14 removal is a function of the result of the microemulsion, per se, and not of the presence or absence in the microemulsion of a "greasy soil removal" type of solvent.
In place of the perfume one can employ a water insoluble paraffin or isoparaffinhaving 6 to 18 carbon at a concentration of 0.4 to 8.0 wt. percent.
The water-soluble organic detergent materials which are used in forming the ultimate o/w microemulsion compositions of this invention may be selected from the group consisting of water-soluble, non-soap, anionic surfactants mixed with a fatty acid and the solubilizing agent which is a partially esterified ethoxylated polyhydric alcohol such as a partially esterified ethoxylated glycerol.
Although conventional nonionic surfactants can be used in the instant compositions, the employment of such conventional nonionic in the instant composition will decrease the environmental profile of the composition as well as having an adverse effect on the grease release and grease + particulate soil removal properties of the composition.
Regarding the anionic surfactant present in the o/w microemulsions any of the conventionally used water-soluble anionic surfactants or mixtures of said anionic detergents and anionic detergents can be used in this invention. As used herein the term "anionic surfactant" is intended to refer to the class of anionic and mixed anionic-nonionic surfactants providing detersive action.
Suitable water-soluble non-soap, anionic suRactants include those surface-activeor detergent compounds which contain an organic hydrophobic group containing generally 8 to 26 carbon atoms in their molecular structure and at least one water-solubilizing group selected from the group of sulfonate, sulfate and carboxylate so as to form a water-soluble surfactant. Usually, the hydrophobic group will include or comprise a Cg-C22 alkyl, alkyl or acyl group. Such surfactants are employed in the form of water-soluble salts and the salt-forming cation usually is selected from the group consisting of sodium, potassium, ammonium, magnesium and mono-, di- or tri-C2-C3 alkanolammonium, with the sodium, magnesium and ammonium cations again being preferred.
~EN~E~
CA 0220~404 1997-0~-14 r ~
Examples of suitable sulfonated anionic surfactants are the well known higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the higher alkyl group in a straight orbranched chain, Cg-c1s alkyl toluene sulfonates and C8-c1s alkyl phenol sulfonates.
A preferred sulfonate is iinear alkyl benzene suifonate having a high content of 3-(or higher) phenyl isomers and a correspondingly low content (well below 50%) of 2- (or lower) phenyl isomers, that is, wherein the benzene ring is preferably attached in large part at the 3 or higher (for example, 4, 5, 6 or 7) position of the alkyl group and the content of the isomers in which the benzene ring is attached in the 2 or 1 position is 10 correspondingly low. Particularly preferred materials are set forth in U.S. Patent 3,320,174.
Other suitable anionic surfactants are the olefin sulfonates, including long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. These olefin sulfonate detergents may be 15 prepared in a known manner by the reaction of sulfur trioxide (SO3) with long-chain olefins containing 8 to 25, and having the formula RCH=CHR1 where R is a higher alkyl group of 6 to 23 carbons and R1 is an alkyl group of 1 to 17 carbons or hydrogen to form a mixture of sultones and alkene sulfonic acids which is then treated to convert the sultones to sulfonates. Olefin sulfonates contain from 14 to 16 carl~on atoms in the R
20 alkyl group and are obtained by sulfonating an a-olefin.
Other examples of suitable anionic sulfonate surfactants are the paraffin sulfonates containing 10 to 20. Primary paraffin sulfonates are made by reacting long-chain alpha olefins and bisulfites and paraffin sulfonates having the sulfonate group distributed along the paraffin chain are shown in U.S. Patents Nos2,503,280;
25 2,507,088; 3,260,744; 3,372,188; and Gerrnan Patent 735,096.
Examples of satisfactory anionic sulfate surfactants are the Cg C1 g alkyl sulfate salts and the Cg-C1 g alkyl sulfate salts and the Cg-C1 g alkyl ether polyethenoxy sulfate salts having the formula R(OC2H4)n OSO3M wherein n is 1 to 12, and M is a solubilizing cation selected from the group consisting of sodium, potassium, ammonium, NDED S~
CA 0220~404 1997-0~-14 17 .~
magnesium and mono-, di- and triethanol ammonium ions. The alkyl sulfates may beobtained by sulfating the alcohols obtained by reducing glycerides of coconut oil or tallow or mixtures thereof and neutralizing the resultant product. On the other hand, the alkyl ether polyethenoxy sulfates are obtained by sulfating the condensation product of 5 ethylene oxide with a C8-cl8 alkanol and neutralizing the resultant product. The alkyl sulfates may be obtained by sulfating the alcohols obtained by reducing glycerides of coconut oil or tallow or mixtures thereof and neutralizing the resultant product. On the other hand, the alkyl ether polyethenoxy sulfates are obtained by sulfating the condensation product of ethylene oxide with a Cg-C1g alkanol and neutralizing the 10 resultant product. The alkyl ether polyethenoxy sulfates differ from one another in the number of moles of ethylene oxide reacted with one mole of alkanol. Preferred alkyl sulfates and preferred alkyl ether polyethenoxy sulfates contain 10 to 16 carbon atoms in the alkyl group.
The Cg-C12 alkylphenyl ether polyethenoxy sulfates containing from 2 to 6 15 moles of ethylene oxide in the molecule also are suitable for use in the inventive compositions. These detergents can be prepared by reacting an alkyl phenol with 2 to 6 moles of ethylene oxide and sulfating and neutralizing the resultant ethoxylated alkylphenol.
Obviously, these anionic surfactants will be present either in acid form or salt20 form depending upon the pH of the final composition, with salt forming cation being the same as for the other anionic detergents.
Of the foregoing non-soap anionic surfactants, the preferred surfactants are theCg-C1s linear alkylbenzene sulfonates and the C13-C17 paraffin or alkane sulfonates.
Particularly, preferred compounds are sodium C10-c13 alkylbenzene sulfonate and 25 sodium C13-C17 alkane sulfonate.
Generally, the proportion of the nonsoap-anionic surfactant will be in the range of 0.1% to 20.0%, by weight of the dilute o/w microemulsion composition.
The instant composition contains a composition (herein after referred to as ethoxylated glycerol type compound) which is a mixture of a fully esterified ethoxylated AMENDED S~EEr CA 0220~404 1997-0~-14 18 `' ;~
polyhydric alcohol, a partially esterified ethoxylated polyhydric alcohol and a nonesterified ethoxylated polyhydric alcohol, wherein the preferred polyhydric alcohol is glycerol, and the compound is:
R' 5CH2 O (CH2CH O )x B
R' 1CH O (CH2CH O )yB]w Formula R' (I) CH2 O (CH2CH O )z B
10and R' CH2 O (CH2CH O )X H
R' [CH O (CH2CH O )Y H]W Formula 15 R' (Il) CH2 O (CH2CH O )z H
wherein w equals one to four. B is selected from the group consisting of hydrogen or a group represented by:
o C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, wherein at least one of the B groups is represented by said O
C R, and R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100, wherein in Formula (I) the ratio of monoester / diester / triester is 45 to 90 / 5 to 40 / 1 to 20, AMENO~ E~T
CA 0220~404 1997-0~-14 19 ~ . , .
wherein the ratio of Formula (I) to Formula (Il) is a value between 3 to 0.02, wherein it is most preferred that there is more of Formula (Il) than Formula (I) in the mixture that forms the compound.
The ethoxylated glycerol type compound used in the instant composition is 5 manufactured by the Kao Corporation and sold under the trade name LEVENOL suchas Levenol F-200 which has an average EO of 6 and a molar ratio of coco fatty acid to glycerol of 0.55 or LEVENOL V501/2 which has an average EO of.17 and a molar ratio of tallow fatty acid to glycerol of 1Ø It is preferred that the molar ratio of the fatty acid to glycerol is less than 1.7, more preferably less than 1.5 and most preferably less than 1Ø The ethoxylated glycerol type compound has a molecular weight of 400 to 1600, and a pH (50 grams / liter of water) of 5-7. The LEVENOL compounds are substantially non irritant to human skin and have a primary biodegradabillity higher than 90% as measured by the Wickbold method Bias-7d.
Two examples of the LEVENOL compounds are LEVENOL V-501/2 which has 15 17 ethoxylated groups and is derived from tallow fatty acid with a fatty acid to glycerol ratio of 1.0 and a molecular weight of 1465 and LEVENOL F-200 has 6 ethoxylated groups and is derived from coco fatty acid with a fatty acid to glycerol ratio of 0.55.
Both LEVENOL F-200 and Levenol V-501/2 are composed of a mixture of Formula (I) and Formula (Il). The LEVENOL compounds has ecoxicity values of algae growth 2u inhibition > 100 mg/iiter; acute toxiciiy for Daphniae > i û0 mg/iiter and acute fish toxicity > 100 mg/liter. The LEVENOL compounds have a ready biodegradability higher than 60% which is the minimum required value according to OECD 301 B measurement to be acceptably biodegradable.
Polyesterified nonionic compounds also useful in the instant compositions are 25 CROV`OL PK-40 and CROVOL PK-70 manufactured by Croda GMBH of the Netherlands. CROVOL PK-40 is a polyoxyethylene (12) Palm Kernel Glyceride which has 12 EO groups. CROVOL PK-70 which is prefered is a polyoxyethyiene (45) Palm Kernel Glyceride have 45 EO groups.
~N~
CA 0220~404 1997-0~-14 20 " ;'`;
In the dilute o/w microemulsion compositions or liquid crystal compositions the ethoxylated glycerol type compounds or the polyesterified nonionic compounds will be present in admixture with the anionic detergent. The proportion of the ethoxylated glycerol type compound or the polyesterified nonionic solubilizing agent based upon the weight of the liquid crystal composition or the final dilute o/w microemulsion composition will be 0.1% to 20%, by weight.
Furthermore, in the more preferred compositions the weight ratio of nonsoap anionic detergent to the ethoxylated glycerol type compound will be in the range of 3:1 to 1:3 with especially good results being obtained at a weight ratio of 2:1.
The ethoxylated polyhydric alcohol such as an ethoxylated glycerol of the instant invention is depicted by the following formula R' CH2 O (CH2CH O )x H
R' [CH O (CH2CH O )y Hlw R' CH2 O (CH2CH O )z H
wherein w equals one to four, x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100.
In the dilute o/w microemulsion compositions or liquid crystal compositions the ethoxylated alcohol will be present in admixture with the anionic surfactant. The proportion of the ethoxylated glycerol type based upon the weight of the liquid crystal composition or the final dilute o/w microemulsion composition will be 0.1% to 20% by weight.
Furthermore, in the more preferred compositions the weight ratio of nonsoap anionic surfactant to the ethoxylated polyhydric alcohol will be in the range of 3:1 to 1:3 with especially good results being obtained at a weight ratio of 2:1.
The instant composition can also contain 0 to 10 wt. %, of a monoester of an ethoxylated polyhydric alcohol depicted by the formula ~ 3 ~tiEE~
CA 0220~404 1997-0~-14 21 ` `
R' CH2 O (CH2CH O )X B
R' 1CH O (CH2CH 0 )Y B]W
R' CH2 O (CH2CH O )Z B
wherein w equals one to four. Two of the BS are hydrogen and one B jS selected from the group consisting of a group represented by:
o C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tailow alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100 The instant composition can also contain 0 to 2 wt %, of a diester of an ethoxylated polyhydric alcohol depicted by the formula R' CH2 O (CH2CH O )X B
R' [ CH O (CH2CH O )Y B]W
R' CH2 O (CH2CH O )Z B
wherein w equals one to foun One of the BS jS hydrogen and two BS are selected from the group consisting of a group represented by:
O
C R
wherein R jS selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow ~3,~ ?~ r, !
. CA 0220~404 1997-0~-14 22 `` ~
alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals about 2 to 100.
The instant composition can also contain 0 to 1.0 wt. %, of a triester of an ethoxylated polyhydric alcohol depicted by the formula R' CH2 O (CH2CH O )x B
R' [CH O (CH2CH O )y B]w R' CH2 O (CH2CH O )z B
wherein w equals one to four. The three Bs are selected from the group consisting of a group represented by:
o C R
15 wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100.
The instant compositions contain 0 to 1.0 wt. % of a tri-alkyl citrate such as tri-n-20 butyl citrate, tri-n-propyl citrate, tri-isopropyl citrate, tri-isobutyl citrate, tri-n-pentyl citrate, tri-isopentyl citrate and tri-n-hexyl, wherein tri-n-butyl citrate is preferred. The tri-n-butyl citrate functions in the formula as a foam control agent in that the foam is more readily collapsed such that the article can be rinsed more effectively.
The cosurfactant may play an essential role in the formation of the the liquid 25 crystal composition or dilute o/w microemulsion and the concentrated microèmulsion compositions. Three major classes of compounds have been found to provide highly suitable cosurfactants for the microemulsion over temperature ranges extending from 5 C to 43 C for instance; (1 ) water-soluble C3-C4 alkanols, polypropylene glycol of the formula HO(CH3CHCH2O)nH wherein n is a number from 2 to 18 and monoalkyl ethers p~,4F~ SH~
CA 0220~404 1997-0~-14 23 .:.
and esters of ethylene glycol and propylene glycol having the structural formulas R(X)nOH and R1 (x)noH wherein R is C1-c6 alkyl, R1 is C2-C4 acyl group, X is (OCH2CH2) or (ocH2(cH3)cH) and n is a number from 1 to 4; (2) aliphatic mono- and di-carboxylic acids containing 2 to 10 carbon atoms, preferably 3 to 6 carbons in the molecule; and (3) triethyl phosphate. Additionally, mixtures of two or more of the four classes of cosurfactant compounds may be employed where specific pH's are desired.
When the mono- and di-carboxylic acid (Class 2) cosurfactants are employed in the instant microemulsion compositions at a concentration of 2 to 10 wt. %, the microemulsion compositions can be used as a cleaners for bathtubs and other hardsurfaced items, which are acid resistant thereby removing lime scale, soap scum and greasy soil from the surfaces of such items damaging such surfaces. If these surfaces are of zirconium white enamel, they can be damaged by these compositions.
An aminoalkylene phophonic acid at a concentration of 0.01 to 0.2 wt. % can be optionally used in conjunction with the mono- and di-carboxylic acids, wherein the aminoalkylene phophonic acid helps prevent damage to zirconium white enamel surfaces. Additionally, 0.05 to 1% of phosphoric acid can be used in the composition.
Methanol and ethanol are explicitly excluded from the instant composition because of their low flash point.
Representative members of the polypropylene glycol include dipropylene glycol and polypropylene glycol having a molecular weight of 200 to 1000, e.g., polypropylene glycol 400. Other satisfactory glycol ethers are ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monobutyl ether, mono, di, tri propylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol tertiary butyl ether, ethylene glycol monoacetate and dipropylene glycol propionate. When these glycol type cosurfactants are at a concentartion of at least 1.0 weight %, in combination with a perfume at a concentration of at least 0.5 weight %, one can form a liquid crystal composition Representative members of the aliphatic carboxylic acids include C3-C6 alkyl and alkenyl monobasic acids and dibasic acids such as glutaric acid and mixtures of N~ED Sl i~
CA 0220~404 1997-0~-14 24 ~ ~ .
glutaric acid with adipic acid and succinic acid, as well as mixtures of the foregoing acids as well as acrylic acid or propionic acid.
While all of the aforementioned glycol ether compounds and acid compounds provide the described stability, the most preferred cosurfactant compounds of each type, on the basis of cost and cosmetic appearance (particularly odor), are diethylene glycol monobutyl ether and a mixture of adipic, glutaric and succinic acids? respectively.
The ratio of acids in the foregoing mixture is not particularly critical and can be modified to provide the desired odor. Generally, to maximize water solubility of the acid mixture glutaric acid, the most water-soluble of these three saturated aliphatic dibasic acids, will 10 be used as the major component.
Generally, weight ratios of adipic acid: glutaric acid:succinic acid is 1-3:1-8:1-5, can be used with equally good results.
Still other classes of cosurfactant compounds providing stable microemulsion compositions at low and elevated temperatures are the mono-, di- and triethyl esters of 15 phosphoric acid such as triethyl phosphate.
The amount of cosurfactant required to stabilize the liquid crystal compositionsor the microemulsion compositions will, of course, depend on such factors as thesurface tension characteristics of the cosurfactant, the type and amounts of the primary surfactants and perfumes, and the type and amounts of any other additional ingredients 20 which may be present in the composition and which have an influence on the thermodynamic factors enumerated above. The amounts of cosurfactant in the rangeof from 0.5% to 15%, by weight provide stable dilute o/w microemulsions for the above-described levels of primary surfactants and perfume and any other additional ingredients as described below.
As will be appreciated by the practitioner, the pH of the final microemulsion will be dependent upon the identity of the cosurfactant compound, with the choice of the cosurfactant being effected by cost and cosmetic properties, particularly odor. For example, microemulsion compositions which have a pH in the range of 1 to 10 may employ either the class 1 or the class 4 cosurfactant as the sole cosurfactant, but the ~ ?~ S~
CA 0220~404 1997-0~-14 pH range is reduced to 1 to 8.5 when the polyvalent metal salt is present. On the other hand, the class 2 cosurfactant can only be used as the sole cosurfactant where the product pH is below 3.2. However, where the acidic cosurfactants are employed inadmixture with a glycol ether cosurfactant, compositions can be formulated at a 5 substantially neutral pH (e.g., pH 7+1.5).
The ability to formulate neutral and acidic products without builders which havegrease removal capacities is a feature of the present invention because the prior art o/w microemulsion formulations most usually are highly alkaline or highly built or both.
In addition to their excellent capacity for cleaning greasy and oily soils, the low 10 pH o/w microemulsion formulations also exhibit excellent cleaning performance and removal of soap scum and lime scale in neat (undiluted) as well as in diluted usage.
The final essential ingredient in the inventive microemulsion compositions having improved interfacial tension properties is water. The proportion of water in themicroemulsion compositions generally is in the range of 20% to 97%, by weight of the 15 usual diluted o/w microemulsion composition.
As believed to have been made clear from the foregoing description, the dilute o/w microemulsion liquid all-purpose cleaning compositions of this invention areespecially effective when used as is, that is, without further dilution in water, since the properties of the composition as an o/w microemulsion are best manifested in the neat 20 (undiluted) form. However, at the same time it should be understood that depending on the levels of surfactants, cosurfactants, perfume and other ingredients, some degree of dilution without disrupting the microemulsion, per se, is possible. For example, at the preferred low levels of active surfactant compounds (i.e., primary anionic and nonionic surfactants) dilutions up to 50% will generally be well tolerated without causing phase 25 separation, that is, the microemulsion state will be maintained.
However, even when diluted to a great extent, such as a 2- to 1 0-fold or more dilution, for example, the resulting compositions are still effective in cleaning greasy, oily and other types of soil. Furthermore, the presence of magnesium ions or other N~3~SH~FT
CA 0220~404 1997-0~-14 26 ` ;; ~
polyvalent ions, e.g., aluminum, as will be described in greater detail below further serves to boost cleaning performance of the primary detergents in dilute usage.
On the other hand, it is also within the scope of this invention to formulate highly concentrated microemulsions which will be diluted with additional water before use.
The present invention also relates to a stable concentrated microemulsion or acidic microemulsion composition comprising by weight:
(a) 1 to 30% of an anionic surfactant;
(b) 0.5 to 15% of an ethoxylated glycerol type compound;
(c) 2 to 30% of a cosurfactant; ~
(d) 0.4 to 10% of a water insoluble hydrocarbon or perfume;
(e) 0 to 18% of at least one dicarboxylic acid;
(f) 0 to 1% of phosphoric acid;
(g) 0 to 0.2% of an aminoalkylene phosphonic acid;
(h) 0 to 15% of magnesium sulfate heptahydrate;
(i) 0 to 1.0% of a tri-alkyl citrate; and (h) balance being water, wherein the composition has an ecotoxocity as measured by the LC 50 test of at least 0.18 ml/L measured on Daphniae microorganisms.
The present invention also relates to a stable liquid crystal microemulsion or 20 acidic microemulsion composition comprising by weight:
(a) 1 to 30% of an anionic surfactant;
(b) 0.5 to 15% of an ethoxylated glycerol type compound;
(c) 0 to 2.5% of a fatty acid;
(d) 2 to 30% of a cosurfactant;
(e) 0.5 to 10% of a water insoluble hydrocarbon or perfume;
(f) 0 to 15% of magnesium sulfate heptahydrate;
(9) 0 to 1.0% of a tri-alkyl citrate; and ~ENDED S~E
CA 0220~404 1997-0~-14 27 ;, ;
(h) balance being water, wherein the composition has an ecotoxocity as measured by the LC 50 test of at least 0.18 ml/L measured on Daphniae mlcroorganlsms.
The present invention also relates to a stable concentrated microemulsion or 5 acidic microemulsion composition comprising approximately by weight:
(a) 1 to 30% of an anionic surfactant;
(b) 0.5 to 15% of an ethoxylated polyhydric alcohol such as an ethoxylated glycerol;
(c) 2 to 30% of a cosurfactant;
(d) 0.4 to 10% of a water insoluble hydrocarbon or perfume;
(e) 0 to 18% of at least one dicarboxylic acid;
(f) 0 to 1% of phosphoric acid;
(g) 0 to 0.2% of an aminoalkylene phosphonic acid;
(h) 0 to 15% of magnesium sulfate heptahydrate; and (i) the balance being water.
The present invention also relates to a stable liquid crystal microemulsion or acidic microemulsion composition comprising approximately by weight:
(a) 1 to 30% of an anionic surfactant;
(b) 0.5 to 15% of an ethoxylated polyhydric alcohol such as an ethoxylated 20 glycerol;
(c) 2 to 30% of a cosurfactant;
(d) 0.5 to 10% of a water insoluble hydrocarbon or perfume;
(e) 0 to 15% of magnesium sulfate heptahydrate; and (f) the balance being water.
Such concentrated microemuisions can be diiuted by mixing with up to 20 times or more, their weight of water to form o/w microemulsions similar to the dilutedmicroemulsion compositions described above. While the degree of dilution is suitably chosen to yield an o/w microemulsion composition after dilution, it should be recognized p~~ 3 S~~
CA 0220~404 1997-0~-14 28 ` '~ ' that during the course of dilution both microemulsion and non-microemulsions may be successively encountered.
In addition to the above-described essential ingredients required for the formation of the liquid crystal composition or the microemulsion composition, the 5 compositions of this invention may often and preferably do contain one or moreadditional ingredients which serve to improve overall product performance.
One such ingredient is an inorganic or organic salt of oxide of a multivalent metal cation, particularly Mg++. The metal salt or oxide provides several benefits including improved cleaning performance in dilute usage, particularly in soft water areas, and 10 minimized amounts of perfume required to obtain the microemulsion state. Magnesium sulfate, either anhydrous or hydrated (e.g., heptahydrate), is especially preferred as the magnesium salt. Good results also have been obtained with magnesium oxide, magnesium chloride, magnesium acetate, magnesium propionate and magnesium hydroxide. These magnesium salts can be used with formulations at neutral or acidic 15 pH since magnesium hydroxide will not precipitate at these pH levels.
Although magnesium is the preferred multivalent metal from which the salts (inclusive of the oxide and hydroxide) are formed, other polyvalent metal ions also can be used provided that their salts are nontoxic and are soluble in the aqueous phase of the system at the desired pH level. Thus, depending on such factors as the pH of the 20 system, the nature of the primary surfactants and cosurfactant, and so on, as well as the availability and cost factors, other suitable polyvalent metal ions include aluminum, copper, nickel, iron, calcium, etc. It should be noted, for example, that with the preferred paraffin sulfonate anionic detergent calcium salts will precipitate and should not be used. It has also been found that the aluminum salts work best at pH below 5 or 25 when a low level, for example 1 weight percent, of citric acid is added to the composition which is designed to have a neutral pH. Alternatively, the aluminum salt can be directly added as the citrate in such case. As the salt, the same general classes of anions as mentioned for the magnesium salts can be used, such as halide (e.g., bromide, chloride), sulfate, nitrate, hydroxide, oxide, acetate, propionate, etc.
p~~ S~
CA 0220~404 1997-0~-14 In the dilute compositions the metal compound is added to the composition in an amount sufficient to provide at least a stoichiometric equivalence between the anionic surfactant and the multivalent metal cation. For example, for each gram-ion of Mg++
there will be 2 gram moles of paraffin sulfonate, alkylbenzene sulfonate, etc., while for S each gram-ion of A13+ there will be 3 gram moles of anionic surfactant. Thus, the proportion of the multivalent salt generally will be selected so that one equivalent of compound will neutralize from 0.1 to 1.5 equivalents, of the acid form of the anionic surfactant.
At higher concentrations of anionic surfactant, the amount of multivalent salt will 10 be in range of 0.5 to 1 equivalents per equivalent of anionic surfactant.
The liquid crystal composition or the o/w microemulsion compositions comprises from 0% to 2.5%, by weight of the composition of a C8-C22 fatty acid or fatty acid soap as a foam suppressant. The addition of fatty acid or fatty acid soap provides animprovement in the rinseability of the composition whether applied in neat or diluted 15 form. Generally, however, it is necessary to increase the level of cosurfactant to maintain product stability when the fatty acid or soap is present. If more than 2.5wt %
of the fatty acid is used in the instant compositions, the composition will become unstable at low temperatures as well as having an objectionable smell.
As example of the fatty acids which can be used as such or in the form of soap, 20 mention can be made of distilled coconut oil fatty acids, "mixed vegetable" type fatty acids (e.g. high percent of saturated, mono-and/or polyunsaturated C18 chains); oleic acid, stearic acid, palmitic acid, eiocosanoic acid, and the like, generally those fatty acids having from 8 to 22 carbon atoms being acceptable.
The all-purpose liquid cleaning composition of this invention may, if desired, also 25 contain other components either to provide additional effect or to make the product more attractive to the consumer. The following are mentioned by way of example:
Colors or dyes in amounts up to 0.5% by weight; bactericides in amounts up to 1% by weight; preservatives or antioxidizing agents, such as formalin, 5-bromo-5-nitro-dioxan-1,3; 5-chloro-2-methyl-4-isothaliazolin-3-one, 2,6-di-tert.butyl-p-cresol, etc., in amounts ~ C~ S~E~
CA 0220~404 1997-0~-14 up to 2% by weight; and pH adjusting agents, such as sulfuric acid or sodium hydroxide, as needed. Furthermore, if opaque compositions are desired, up to 4% by weight of an opacifier may be added.
The instant compositions of the instant invention explicitly exclude zwitterionic 5 surfactant such as betaines because these zwetterionic surfactants are extremely high foaming which, if used in the instant composition, would cause the instant compositions to have to high a foam profile and that too much foam would leave residue on thesurface being cleaned.
In final form, the all-purpose liquids are clear oil-in-water microemulsions or liquid 10 crystal compositions and exhibit stability at reduced and increased temperatures. More specifically, such compositions remain clear and stable in the range of 5 C to 50 C.
Such compositions exhibit a pH in the acid or neutral range depending on intended end use. The liquid microemulsion compositions are readily pourable and exhibit a viscosity in the range of 6 to 60 milliPascal . second (mPas.) as measured at 25 C. with a15 Brookfield RVT Viscometer using a #1 spindle rotating at 20 RPM.
The compositions are directly ready for use or can be diluted as desired and in either case no or only minimal rinsing is required and substantially no residue or streaks are left behind. Furthermore, because the compositions are free of detergent builders such as alkali metal polyphosphates they are environmentally acceptable and provide a 20 better "shine" on cleaned hard surfaces.
When intended for use in the neat form, the liquid compositions can be packaged under pressure in an aerosol container or in a pump-type sprayer for the so-called spray-and-wipe type of application.
Because the compositions as prepared are aqueous liquid formulations and 25 sincè- no particular mixing is required to form the o/w microemulsion, the compositions are easily prepared simply by combining all the ingredients in a suitable vessel or container. The order of mixing the ingredients is not particularly important andgenerally the various ingredients can be added sequentially or all at once or in the form of aqueous solutions of each or all of the primary detergents and cosurfactants can be CA 0220~404 1997-0~-14 31 , . .
separately prepared and combined with each other and with the perfume. The magnesium salt, or other multivalent metal compound, when present, can be added as an aqueous solution thereof or can be added directly. It is not necessary to useelevated temperatures in the formation step and room temperature is sufficient.
The instant microemulsion formulas explicitly exclude alkali metal silicates andalkali meta builders such as alkali metal polyphosphates, alkali metal carbonates, alkali metal phosphonates and alkali metal citrates because these materials, if used in the instant composition, would cause the composition to have a high pH as well as leaving residue on the surface being cleaned.
It is contemplated within the scope of the instant invention that the ethoxylated glycerol type compound can be employed in hard surface cleaning compositions such as wood cleaners, window cleaners and light duty liquid cleaners, wherein improvements in a grease release effect in desirable.
The following examples illustrate liquid cleaning compositions of the described 15 invention. Unless otherwise specified, all percentages are by weight. The exemplified compositions are illustrative only and do not limit the scope of the invention. Unless otherwise specified, the proportions in the examples and elsewhere in the specification are by weight.
CA 0220.,404 1997 - 0., - 14 such as alkali metal polyphosphates they are environmentally acceptable and provide a better "shine" on cleaned hard surfaces.
When intended for use in the neat form, the liquid compositions can be packaged under pressure in an aerosol container or in a pump-type sprayer for the so-called spray-and-wipe type of application.
Because the compositions as prepared are aqueous liquid formulations and since no particular mixing is required to form the o/w microemulsion, the compositions are easily prepared simply by combining all the ingredients in a suitable vessel or container. The order of mixing the ingredients is not particularly important and10 generally the various ingredients can be added sequentially or all at once or in the form of aqueous solutions of each or all of the primary detergents and cosurfactants can be separately prepared and combined with each other and with the perfume. The magnesium salt, or other multivalent metal compound, when present, can be added as an aqueous solution thereof or can be added directly. It is not necessary to use15 elevated temperatures in the formation step and room temperature is sufficient.
The instant microemulsion formulas explicitly exclude alkali metal silicates andalkali meta builders such as alkali metal polyphosphates, alkali metal carbonates, alkali metal phosphonates and alkali metal citrates because these materials, if used in the instant composition, would cause the composition to have a high pH as well as leaving 20 residue on the surface being cleaned.
It is contemplated within the scope of the instant invention that the ethoxylated glycerol type compound can be employed in hard surface cleaning compositions such as wood cleaners. window cleaners and light duty liquid cleaners, wherein improvements in a grease release effect in desirable.
The following examples illustrate liquid cleaning compositions of the described invention. Unless otherwise specified, all percentages are by weight. The exemplified compositions are illustrative only and do not limit the scope of the invention. Unless otherwise specified, the proportions in the examples and elsewhere in the specification are by weight.
- - - -CA 0220~404 1997-05-14 W O 96/15217 PCTrUS95/14583 Exam~le 1 The following compositions in wt. % were prepared:
A B C D EF Mr. Proper St Marc Lemon Sodium C1~ -C17 4.7 4.3 4 4.314.1 7.05 2.9 Paraffin sul onate EO/PO nor onic - - - - - - - 3.2 Levenol F-200 2.3 2.2 2 2.2 6.3 345 C13-C15 EO 14 - - - - - - 3.3 nonionic DEGMBE 4 4 . 4 12 6 4.4 3 Fatty acid C 7 0.5 ~.~ C 72.25 1.125 0.65 0.3 M~SO4 7 H20 . 2 . . 6.3 3.15 Per'ume(a) ~ . 0.75 0.~ . 2.4 1.2 presentpresent Soc ium Citrate - - - - - - 3.2 Wa-er Bal Bal Bal Bal Bal Bal Bal Bal pH 7 7 7 7 7 7 9.5 7 Degreasing test Neat (b) 30 35 35 35 30 30 70 >100 Dilute (b) 45 60 60 60 45 45 ~90 90 Residue Equal Equal Equal Equal Equal Equal WorseEqualto ref.
to ref. to ref. to ref. to ref. to ref. to ref.
Foam in hard Water Equal Equal Equal Equal Equal Equal Equal to Equal to ref.
to ref. to ref. to ref. to ref. to ref. to ref. ref.
LC50-Ecotoxicityon 0.18 - - - - - 0.1 mVI0.033 mVI
Daphniae (c) mVI
G H
Linear alkyl benzene sulfonic 4.7 4.5 5 r-cjd ~laOH to reach pH 7 ~. 0.57 0.64 evenol F-200 . 2.5 2 DEGMBE . 6 .2 Fattyacid C.7 ~.75 0 75 M~SO4 7 H20 .1 .~6 Perfume(a) ~.8 ~. .
Water Bal Ba Ba pH 7 7 7 (a) contains 25% by weight of terpenes.
(b) the lower the number of strokes, the better the degreasing performance.
(c) the higher the results, the lower the ecotoxicity.
Furthermore, "dissolution power" of the o/w microemulsion of this example is 10 compared to the "dissolution power" of an identical composition except that an equal amount (5 weight percent) of sodium cumene sulfonate hydrotrope is used in place of the diethylene glycol monobutyl ether cosurfactant in a test wherein equal concentrations of heptane are added to both compositions. The o/w microemulsion of CA 0220~404 1997-0~-14 this invention solubilizes 12 grams of the water immiscible substance as compared to 1.4 grams in the hydrotrope containing liquid composition.
In a further comparative test using blue colored cooking oil--a fatty triglyceride soil --, the composition of Example 1 is clear after the addition of 0.2 grams of cooking 5 oil whereas the cooking oil floats on the top of the composition containing the sulfonate hydrotrope.
When the concentration of perfume is reduced to 0.4% in the composition of Example 1, a stable o/w microemulsion composition is obtained. Similarly, a stable o/w microemulsion is obtained when the concentration of perfume is increased to 2% by 10 weight and the concentration of cosurfactant is increased to 6% by weight in Example 1.
The present invention also relates to an aqueous solution of a grease release system which comprises:
(a) 0.1 to 20.0 wt. % of a mixture of:
R' CH2 O (CH2CH O )x B
R' [ CH O (CH2CH O )y B]w R' (I) CH2 O (CH2CH O )z B
and R' CH2 O (CH2CH O )x H
R' [ CH O (CH2CH O )y H]w R' (I 1) CH2 O (CH2CH O )z H
wherein w equals one to four. B is selected from the group consisting of hydrogen or a group represented by:
:
CA 0220~404 1997-05-14 W O 96tl5217 PCTAUS95/14583 o C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein at least one of the B
5 groups is represented by said o C R, R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100, wherein in Formula (I) the ratio of monoester / diester / triester is 40 to 90 / 5 to 35 / 1 to 20, wherein the ratio of Formula (I) to Formula (Il) is a value between 3 to 0.02, more preferably 3 to 0.1, and most preferably 1.5 to 0.2, wherein it is most preferred that there is more of Formu!a (!!) than Formula (I) in the mixture; and (b) the balance being water.
The aqueous solution of the grease release agent can be coated onto a hard surface. The treated hard surface will prevent the adhering of grease to the hard surface thereby providing easier cleaning of the hard surface with a conventional hard surface cleaning composition.
Exam~le 2 The example illustrates a typical formulation of a ~'concentrated" o/w microemulsion based on the present invention:
% by wei~ht Coco fatty acid 4 Sodium C13-C17 Paraffin Sulfonate 20.75 Levenol F-200 12 Diethylene glycol monobutyl ether 20 Perfume (a) 12.5 Water Bal to 100 pH: 7.0 + 0.2 This concentrated formulation can be easily diluted, for example, five times with tap water, to yield a diluted o/w microemulsion composition. Thus, by using microemulsion technology it becomes possible to provide a product having high levels CA 0220~404 1997-0~-14 WO 96/lS217 PCT/US95/14583 of active detergent ingredients and perfume, which has high consumer appeal in terms of clarity, odor and stability, and which is easily diluted at the usual usage concentration for similar all-purpose hard surface liquid cleaning compositions, while retaining its cosmetically attractive attributes.
Naturally, these formulations can be used, where desired, without further dilution and can also be used at full or diluted strength to clean soiled fabrics by hand or in an automatic laundry washing machine.
Example 3 This example illustrates a diluted o/w microemulsion composition according to 10 the invention having an acidic pH and which also provides improved cleaning performance on soap scum and lime scale removal as well as for cleaning greasy soil.
% by wei~ht Sodium C13-C17 paraffin sulfonate 4.7 Levenol F-200 2.3 Mg SO4 7H20 2.2 Mixture of succinic acid/glutaric acid/adipic acid (1:1:1 ) 5 Perfume (d) 1.0 Water, minors (dye) balance to 100 Phosphonic acid 0.2 Amino tris - (methylene-phosphonic acid) 0.03 pH=3 iO.2 (d) contains 40% by weight of terpene Example 4 Formula A of Example I was tested for the removal of a combination of grease and particulate soil as well as for a grease release effect and compared to commercial AjaxtmNME
1. Grease + particulate soil removal;
Test Method A) Soil composition:
70 9 of mineral oil 35 9 of particulate soil (vacuum cleaner dust + 1% of carbon black) -CA 0220~404 1997-0~-14 B) Soil Dreparation:
- Weigh cleaned/dried glass tiles - Soil the tiles with the grease + particulate soil - Bake the tiles 1 hour at 80C
- Weigh the soiled tiles which aged 2 hours at RT.
C) Soil removal:
The soiled tiles are soaked for 15 minutes at RT in the test products, then they are delicately rinsed with tap water.
After drying 45 minutes at 50C, the tiles are weighed again.
Results Grease + particulate soil % of removal me -n of 6 tiles Commercial Ajaxtm NME I 60 Formula A of Example I ¦ 95 Formula A exhibits improved grease + particulate soil removal over the Commercial Ajaxtm NME
Il. Grease release effect Test Method A) Soil composition:
20% hardened tallow 80% beef tallow fat blue dye B) Soil preparation:
The fat mixture is heated and sprayed with an automatic spraying device on cleaned and dried ceramic tiles.
C) Soil removal:
Product used neat: 2.5 9 on sponge Product used dilute: 1.2% sol in tap water- 10 ml of the solution on the sponge The cleaning procedure is done with the gardner device for both product concentrations.
CA 0220~404 l997-0~-l4 W O 96/lS217 PCTAUS95/14583 Results A) On treated ceramic tiles (treated with the product before spraying the soil) Neat ¦ Dilute Number of Strokes First grease layer deposHionmean of 4mean of 6 tiles tiles Commercial Current Ajaxtm NME27 19 19 5~
Second grease layer deposHion on the mean of 4 mean of 6 same tile tiles tiles Commercial Ajaxtm NME 25 48 1 8*
B) On untreated ceramic tiles In addition to the previous test, the 3 following procedures were used to verify that Formula A remains on the surface a~ter rinsing or wiping. After the first cleaning procedure and before the second spraying:
1) the tiles were allowed to dry in open air 2) the surface was wiped with paper towel 3) the surface was rinsed with wet sponge 1) dry in open air Neat ¦ Dilute Number of Strokes First grease layer deposHionmean of 4mean of 6 tiles tiles Commercial Ajaxtm NME 29 30 Formula A 27 32 Second grease layer cleposHion on themean of 4 mean of 6 same tile tiles tiles Commercial Ajaxtm NME 33 21 FormulaA 30 6 2) wipe dry the surface Neat ¦ Dilute Number cf Strokes First grease layer depositionmean of 4mean of 6 tiles tiles Commercial Ajaxtm NME 29 30 FormulaA 27 32 Second grease layer deposition on themean of 4 mean of 6 same tile tiles tiles Commercial Ajaxtm NME 35 46 FormulaA 30 48.5 CA 0220~404 1997-0~-14 3) wet wiping the surface Neat ¦ Dilute Number Gf Strokes First grease layer depos~ n mean of 4 mean of 6 tiles tiles Commercial Ajaxtm NME 29 30 Formula A 27 32 Second grease layer del~os;li~n on the mean of 4 mean of 6 same tile . tiles tiles Commercial Ajaxtm NME 34 58 Formula A 27 41 * highly significant difference ** after 5 strokes, 65% of the grease is already removed These results clearly demonstrate the important grease release effect obtained with Formula A especially when the product is used dilute.
Example ~
The following liquid crystal compositions were prepared by simple mixing procedure B
Sodium C13-C17 Paraffin sulfonate~.~ 4.3 ~.3 Levenol F-200 ~ . 2.2 .. 2 Propylene glycol monbutyl eth;r Dipropyl ne glycol monbutyl e ler - 3.5 ripropy ne ~Iycol monbutyl e-her attyac ~ 0 5 ~ -ulgS04 H20 1.6 .6 .6 P ~rfume (a) 1 . : .
~ater Bal Ba Ba p~ 7 7 7 0 ExamDle 6 The following optically clear microemulsion compositions were made by forming first a solution by mixing at 25C water, magnesium lauryl ether sulfate, Levenol V-510/2 and 1-Pentanol. To this solution with mixing at 25C was added the dodecane to form the optically clear microemulsion. The formula are expressed in weight percent.
A B C D E F G H
Magnesium 7 2.04 3.04 4.99 3.01 6.38 5.01 4.02 2.99 Lauryl suHate LevenolV-501/2 3.2 .1 7. . 7. 3.9 .~ 6. ~ 7.2 1-Pentanol .1 .0 4. ~.0 . 5.67 . . 1.13 Dodecane .2 ~C.717.' 6 1 .22 ~.: 7 15.2 2. ' . 2.9 water Ba Ba Bal Bal Bal Bal Ba Ba Bal CA 0220~404 1997-0~-14 Fxample 7 The following composition was prepared by simple mixing procedure:
Sodium C 1 3-C17 4.0 Paraffin Sulfonate Levenol F-200 2.0 DEGMBE 4.5 Fatty Acid 0.5 MgSO4 7H2O 1.8 Perfume (a) 0.8 tri-n-butyl citrate 0.5 Water Balance pH 7 Degreasing test Neat (6) Dilute (6) Residue Foam in hand Water (a) contains 25% by weight of terpenes (b) the lower the number of strokes, the better the degreasing performance.
The addition of the tri-n-butyl citrate improves the rinsability of the surface being rinsed in that the collapse of the foam is improved as compared to a composition not containing the tri-n-butyl citrate.
In summary, the described invention broadly relates to an improvement in microemulsion compositions containing an anionic surfactant, an ethoxylated glycerol type compound, a fatty acid, one of the specified cosurfactants, a hydrocarbon ingredient and water which comprise the use of a water-insoluble, odoriferous perfume as the essential hydrocarbon ingredient in a proportion sufficient to form either a dilute o/w microemulsion composition or liquid crystal composition containing, by weight, 0.1% to 20.0% of an anionic detergent, 0.1% to 10% of an ethoxylated glycerol type compound, 0% to 50% of cosurfactant, 0 to 1.0% of a tri-alkyl citrate, 0.4% to 10% of perfume and the balance being water.
CA 0220~404 1997-0~-14 WO 96/15217 PCT/US9!j/14583 Fxample 8 The following compositions in wt. % were prepared:
A B C D E F
Na C13-17 paraffin 4.7 4.7 4.7 4.7 4.7 4.7 sul~onate DEGtv BE 4 4 4 4 4 4 Coco attyacidt.'5 C 7 C.75 C 7 ~.75 C 7 MgSO4 . . ~ .2 ~.
Perfume ~ .. .8 Compounc a) . j , 7 I , - ..
Compounc b) . ~~
~~ompounc c). ,~ . ~ .~
~,ompounc d) . 5 . 1. 78 . 2.3 --~ eodol 91- -- -- -- -- -- 2.3 Water Bal. Bal.Bal. Bal. Bal. Bal.
PhasebehaviorOne One One One One One phase phasephasephase phase phase Particulate soil 71.079.8 84.0 86.0 88.7 51.0 (Kaolin removal Compound (a) is CH2 - 0 (cH2cH2o)2 R 1 CH - 0 (cH2cH2o)2 R2 CH2 - 0 (cH2cH2o)2 R3 wherein R1, R2 and R3 are coco alkyl chains 10 Compound (b) is CH2 - 0 (CH2CH20)2 R4 CH - 0 (CH2CH20)2 Rs CH2 - 0 (CH2CH20)2 H
wherein R4 and Rs are coco alkyl chains 15 Compound (c) is CH2 - 0 (CH2CH20)2 R6 CH - 0 (CH2CH20)2 H
CH2 - 0 (CH2CH20)2 H
wherein R6 is a coco alkyl chains CA 0220.,404 1997 - OF7 - 14 Compound (d) is CH2 - O (CH2CH2O)2 H
CH - O (CH2CH2O)2 H
CH2 - O (CH2CHzO)2 H
In summary, the described invention broadly relates to an improvement in microemulsion compositions for the removal of particulate soil containing an anionic surfactant, an ethoxylated polyhydric alcohol a cosurfactantl a hydrocarbon ingredient and water which comprise the use of a water-insoluble, odoriferous perfume as the essential hydrocarbon ingredient in a proportion sufficient to form either a dilute o/w microemulsion composition or liquid crystal composition containing, by weight, 0.1% to 20% of an anionic detergent, 0.1% to 20.0% of an ethoxylated polyhydric alcohol, 0% to 50% of cosurfactant, 0.4% to 10% of perfume and the balance being water In summary, the described invention broadly relates to an improvement in microemulsion compositions containing an anionic surfactant, an esterified polyethoxyether nonionic surfactant, a fatty acid, one of the specified cosurfactants, a hydrocarbon ingredient and water which comprise the use of a water-insoluble, odoriferous perfume as the essential hydrocarbon ingredient in a proportion sufficient to form either a dilute o/w microemulsion composition or liquid crystal compositioncontaining, by weight, 0.1% to 20% of an anionic detergent, 0.1% to 20.0% of a solubilizing agent which is an ethoxylated glycerol type compound, 0% to 50% of cosurfactant, 0.4% to 10% of perfume and the balance being water.
Claims (15)
1. A microemulsion composition having a viscosity at 25°C of 6 to 60 milli Pascals and comprising:
(a) 0.1 wt. % to 20 wt. % of a mixture of (I) and (II) wherein w equals one to four. B is selected from the group consisting of hydrogen or a group represented by:
O
C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein at least one of the B
groups is represented by said O
C R, R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100, wherein in Formula (I) the ratio of monoester/diester/triester is 40 to 90/5 to 35/1 to 20, wherein the ratio of Formula (I) to Formula (II) is a value between 3 to 0.02;
(b) 0.1 wt. % to 20 wt. % of an anionic surfactant;
(c) 0.1 wt. % to 50 wt. % of a cosurfactant;
(d) 0.1 wt. % to 10 wt. % of a water insoluble hydrocarbon or a perfume;
(e) 0 to 1.0 wt. % of a tri-alkyl citrate; and (f) the balance being water, said composition not containing a zwitterionic surfactant or methanol.
(a) 0.1 wt. % to 20 wt. % of a mixture of (I) and (II) wherein w equals one to four. B is selected from the group consisting of hydrogen or a group represented by:
O
C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein at least one of the B
groups is represented by said O
C R, R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100, wherein in Formula (I) the ratio of monoester/diester/triester is 40 to 90/5 to 35/1 to 20, wherein the ratio of Formula (I) to Formula (II) is a value between 3 to 0.02;
(b) 0.1 wt. % to 20 wt. % of an anionic surfactant;
(c) 0.1 wt. % to 50 wt. % of a cosurfactant;
(d) 0.1 wt. % to 10 wt. % of a water insoluble hydrocarbon or a perfume;
(e) 0 to 1.0 wt. % of a tri-alkyl citrate; and (f) the balance being water, said composition not containing a zwitterionic surfactant or methanol.
2. The cleaning composition of Claim 1 which further contains a salt of a multivalent metal cation in an amount sufficient to provide from 0.5 to 1.5 equivalents of said cation per equivalent of said anionic detergent.
3. The cleaning composition of Claim 2 wherein the multivalent metal cation is magnesium or aluminium.
4. The cleaning composition of Claim 2, wherein said composition contains 0.9 to 1.4 equivalents of said cation per equivalent of anionic detergent.
5. The cleaning composition of Claim 3 wherein said multivalent salt is magnesium oxide, magnesium chloride or magnesium sulfate.
6. The cleaning composition of Claim 1 further comprises fatty acid has 8 to 22 carbon atoms.
7. The cleaning composition of Claim 1 which contains from 0.5-15% to 7%
by weight of said cosurfactant and from 0.4% to 3.0% by weight of said hydrocarbon.
by weight of said cosurfactant and from 0.4% to 3.0% by weight of said hydrocarbon.
8. The cleaning composition of Claim 1 wherein the cosurfactant is a water soluble glycol ether.
9. The cleaning composition of Claim 8 wherein the glycol ether is selected from the group consisting of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, poly-propylene glycol having an average molecular weight of from 200 to 1,000 and propylene glycol tert.butyl ether, mono, di, tri propylene glycol monobutyl ether.
10. The cleaning composition of Claim 9 wherein the glycol ether is ethylene glycol monobutyl ether or diethylene glycol monobutyl ether.
11. The cleaning composition of Claim 1 wherein the cosurfactant is a C3-C6 aliphatic carboxylic acid selected from the group consisting of acrylic acid, propionic acid, glutaric acid, mixtures of glutaric acid and succinic acid and adipic acid and mixtures of any of the foregoing.
12. The cleaning composition of Claim 11 wherein the aliphatic carboxylic acid is a mixture of adipic acid, glutaric acid and succinic acid.
13. The cleaning composition of Claim 1 wherein the anionic surfactant is a C9-C15 alkyl benzene sulfonate or a C10-C20 alkane sulfonate.
14. A stable concentrated microemulsion composition having a viscosity at 25°C of 6 to 60 milli Pascals and comprising by weight:
(a) 1 to 30% of an anionic surfactant;
(b) 0.5 to 15% of a mixture of (I) and (II) wherein w equals one to four. B is selected from the group consisting of hydrogen or a group represented by:
O
C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein at least one of the B
groups is represented by said O
C R, R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100, wherein in Formula (I) the ratio of monoester / diester / triester is 40 to 90/5 to 35/1 to 20, wherein the ratio of Formula (I) to Formula (II) is a value between 3 to 0.02;
(c) 2 to 30% of a cosurfactant;
(d) 0.4 to 10% of a water insoluble hydrocarbon or perfume;
(e) 0 to 18% of at least one dicarboxylic acid;
(f) 0 to 0.2% of an aminoalkylene phosphonic acid;
(g) 0 to 1.0% of phosphoric acid;
(h) 0 to 15% of magnesium sulfate heptahydrate;
(i) 0 to 1.0 wt. % of a tri-alkyl citrate; and (h) the balance being water, wherein the composition has an ecotoxicity value as measured by the LC50 test of at least 0.18 ml/L measured on Daphniae microorganisms and said composition does not contain methanol or a zwitterionic surfactant.
(a) 1 to 30% of an anionic surfactant;
(b) 0.5 to 15% of a mixture of (I) and (II) wherein w equals one to four. B is selected from the group consisting of hydrogen or a group represented by:
O
C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein at least one of the B
groups is represented by said O
C R, R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100, wherein in Formula (I) the ratio of monoester / diester / triester is 40 to 90/5 to 35/1 to 20, wherein the ratio of Formula (I) to Formula (II) is a value between 3 to 0.02;
(c) 2 to 30% of a cosurfactant;
(d) 0.4 to 10% of a water insoluble hydrocarbon or perfume;
(e) 0 to 18% of at least one dicarboxylic acid;
(f) 0 to 0.2% of an aminoalkylene phosphonic acid;
(g) 0 to 1.0% of phosphoric acid;
(h) 0 to 15% of magnesium sulfate heptahydrate;
(i) 0 to 1.0 wt. % of a tri-alkyl citrate; and (h) the balance being water, wherein the composition has an ecotoxicity value as measured by the LC50 test of at least 0.18 ml/L measured on Daphniae microorganisms and said composition does not contain methanol or a zwitterionic surfactant.
15. A liquid crystal composition having a viscosity at 25°C of 6 to 60 milli Pascals and comprising approximately by weight: 0.1% to 20% of an anionic surfactant;
2% to 50% of a cosurfactant; 0% to 2.5% of a fatty acid; 0.1% to 20% of a mixture of (I) and (II) wherein w equals one to four. B is selected from the group consisting of hydrogen or a group represented by:
O
C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein at least one of the B
groups is represented by said O
C R, R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100, wherein in Formula (I) the ratio of monoester / diester / triester is 40 to 90/5 to 35/1 to 20, wherein the ratio of Formula (I) to Formula (II) is a value between 3 to 0.02; 0.5% to 10% of a water insoluble hydrocarbon or a perfume and the balance being water, wherein said composition does not contain a zwitterionic surfactant or methanol.
2% to 50% of a cosurfactant; 0% to 2.5% of a fatty acid; 0.1% to 20% of a mixture of (I) and (II) wherein w equals one to four. B is selected from the group consisting of hydrogen or a group represented by:
O
C R
wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, and alkenyl groups having 6 to 22 carbon atoms, wherein at least one of the B
groups is represented by said O
C R, R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, provided that (x+y+z) equals 2 to 100, wherein in Formula (I) the ratio of monoester / diester / triester is 40 to 90/5 to 35/1 to 20, wherein the ratio of Formula (I) to Formula (II) is a value between 3 to 0.02; 0.5% to 10% of a water insoluble hydrocarbon or a perfume and the balance being water, wherein said composition does not contain a zwitterionic surfactant or methanol.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/336,932 | 1994-11-15 | ||
US08/336,932 US5599785A (en) | 1993-08-04 | 1994-11-15 | Cleaning composition in microemulsion or liquid crystal form comprising mixture of partially esterified, fully esterified and non-esterified polyhydric alchohols |
US08/336,936 US5549840A (en) | 1993-08-04 | 1994-11-15 | Cleaning composition in microemulsion, liquid crystal or aqueous solution form comprising mixture of partially esterified, full esterified and non-esterified ethoxylated polyhydric alcohols |
US08/336,936 | 1994-11-15 | ||
US08/385,212 | 1995-02-05 | ||
US08/385,212 US5593958A (en) | 1995-02-06 | 1995-02-06 | Cleaning composition in microemulsion, crystal or aqueous solution form based on ethoxylated polyhydric alcohols and option esters's thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2205404A1 true CA2205404A1 (en) | 1996-05-23 |
Family
ID=27407167
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002205404A Abandoned CA2205404A1 (en) | 1994-11-15 | 1995-11-09 | Microemulsion all purpose liquid cleaning compositions |
Country Status (17)
Country | Link |
---|---|
EP (2) | EP0994180A1 (en) |
CN (1) | CN1170433A (en) |
AT (1) | ATE207110T1 (en) |
AU (1) | AU696196B2 (en) |
BR (1) | BR9509682A (en) |
CA (1) | CA2205404A1 (en) |
CZ (1) | CZ294825B6 (en) |
DE (1) | DE69523330T2 (en) |
DK (1) | DK0791049T3 (en) |
ES (1) | ES2165926T3 (en) |
HU (1) | HUT77481A (en) |
MY (1) | MY118429A (en) |
PL (1) | PL320224A1 (en) |
PT (1) | PT791049E (en) |
RO (1) | RO115540B1 (en) |
RU (1) | RU2147312C1 (en) |
WO (1) | WO1996015217A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10100270B1 (en) | 2017-01-04 | 2018-10-16 | Gail R. Moser | Procedure to acquire cleaning agent |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5741760A (en) * | 1993-08-04 | 1998-04-21 | Colgate-Palmolive Company | Aqueous cleaning composition which may be in microemulsion form comprising polyalkylene oxide-polydimethyl siloxane |
US5759983A (en) * | 1993-08-04 | 1998-06-02 | Colgate-Palmolive Co. | Aqueous cleaning composition which may be in microemulsion form comprising polyalkylene oxide -polydimethyl siloxane and ethoxylated secondary alcohol |
US5719114A (en) * | 1996-06-28 | 1998-02-17 | Colgate Palmolive Company | Cleaning composition in various liquid forms comprising acaricidal agents |
US5665689A (en) * | 1996-09-04 | 1997-09-09 | Colgate-Palmolive Co. | Cleaning compositions comprising mixtures of partially esterified full esterified and non-esterfied ethoxylated polyhydric alcohols and N-alkyl aldonamides |
US6322778B1 (en) | 1998-02-10 | 2001-11-27 | Johnson & Johnson Consumer Companies, Inc. | Hair conditioning compositions comprising a quaternary ammonium compound |
DE19958398A1 (en) * | 1999-12-03 | 2001-06-13 | Cognis Deutschland Gmbh | Use of partial glyceride polyglycol ethers |
JP3543813B2 (en) | 2002-07-31 | 2004-07-21 | セイコーエプソン株式会社 | Droplet discharging method and droplet discharging apparatus, liquid crystal device manufacturing method and liquid crystal device, and electronic equipment |
ES2293825B1 (en) * | 2006-06-07 | 2008-12-16 | Kao Corporation, S.A. | COMPOSITION CONTAINING A MONO-DI MIXTURE, AND TRIGLICERIDS AND GLYCERINE. |
WO2007144555A1 (en) * | 2006-06-16 | 2007-12-21 | Reckitt Benckiser Inc. | Foaming hard surface cleaning compositions |
BRPI0913009A2 (en) * | 2008-05-02 | 2015-08-04 | Ethicon Inc | Microemulsion germicidal composition |
EP2285946B1 (en) * | 2008-05-09 | 2017-06-21 | Rhodia Opérations | Cleaning compositions incorporating green solvents and methods for use |
AR071894A1 (en) * | 2008-05-23 | 2010-07-21 | Colgate Palmolive Co | MULTI PURPOSE CLEANING COMPOSITIONS |
AU2010292056B9 (en) | 2009-09-11 | 2014-07-10 | Stepan Company | Liquid cleaning compositions containing sulfonated estolides and alkyl ester sulfonates |
WO2013178990A2 (en) * | 2012-05-30 | 2013-12-05 | Reckitt Benckiser N.V. | Composition |
CN108130227B (en) * | 2017-12-29 | 2020-08-28 | 深圳市华星光电技术有限公司 | Auxiliary cleaning agent suitable for self-oriented liquid crystal material and application thereof |
WO2021099095A1 (en) | 2019-11-20 | 2021-05-27 | Unilever Ip Holdings B.V. | Composition |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5438603B2 (en) * | 1973-12-11 | 1979-11-22 | ||
GB2144763B (en) * | 1983-08-11 | 1987-10-28 | Procter & Gamble | Liquid detergent compositions with magnesium salts |
US5075026A (en) * | 1986-05-21 | 1991-12-24 | Colgate-Palmolive Company | Microemulsion all purpose liquid cleaning composition |
US5035826A (en) * | 1989-09-22 | 1991-07-30 | Colgate-Palmolive Company | Liquid crystal detergent composition |
NZ264113A (en) * | 1993-08-04 | 1996-06-25 | Colgate Palmolive Co | Liquid crystal or microemulsion liquid cleaners containing esterified polyethoxyether nonionic surfactant, anionic surfactant, cosurfactant, optionally a fatty acid, and water-insoluble hydrocarbon or perfume |
AU680087B2 (en) * | 1993-11-22 | 1997-07-17 | Colgate-Palmolive Company, The | Microemulsion all purpose liquid cleaning compositions |
US5571459A (en) * | 1994-02-07 | 1996-11-05 | Colgate-Palmolive Co. | Microemulsion all purpose liquid cleaning compositions |
AU1355995A (en) * | 1994-03-14 | 1995-09-21 | Colgate-Palmolive Company, The | Microemulsion all purpose liquid cleaning compositions |
AU681487B2 (en) * | 1994-04-15 | 1997-08-28 | Colgate-Palmolive Company, The | Microemulsion all purpose liquid cleaning compositions with insect repellent |
-
1995
- 1995-11-09 PT PT95939106T patent/PT791049E/en unknown
- 1995-11-09 EP EP99204486A patent/EP0994180A1/en not_active Ceased
- 1995-11-09 AT AT95939106T patent/ATE207110T1/en not_active IP Right Cessation
- 1995-11-09 WO PCT/US1995/014583 patent/WO1996015217A1/en active IP Right Grant
- 1995-11-09 HU HU9702416A patent/HUT77481A/en unknown
- 1995-11-09 RO RO97-00907A patent/RO115540B1/en unknown
- 1995-11-09 PL PL95320224A patent/PL320224A1/en unknown
- 1995-11-09 CN CN95196880A patent/CN1170433A/en active Pending
- 1995-11-09 DE DE69523330T patent/DE69523330T2/en not_active Expired - Fee Related
- 1995-11-09 RU RU97110079A patent/RU2147312C1/en active
- 1995-11-09 CA CA002205404A patent/CA2205404A1/en not_active Abandoned
- 1995-11-09 ES ES95939106T patent/ES2165926T3/en not_active Expired - Lifetime
- 1995-11-09 DK DK95939106T patent/DK0791049T3/en active
- 1995-11-09 EP EP95939106A patent/EP0791049B1/en not_active Expired - Lifetime
- 1995-11-09 AU AU41059/96A patent/AU696196B2/en not_active Ceased
- 1995-11-09 CZ CZ19971502A patent/CZ294825B6/en not_active IP Right Cessation
- 1995-11-09 BR BR9509682A patent/BR9509682A/en not_active Application Discontinuation
- 1995-11-10 MY MYPI95003421A patent/MY118429A/en unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10100270B1 (en) | 2017-01-04 | 2018-10-16 | Gail R. Moser | Procedure to acquire cleaning agent |
Also Published As
Publication number | Publication date |
---|---|
RU2147312C1 (en) | 2000-04-10 |
CZ294825B6 (en) | 2005-03-16 |
AU4105996A (en) | 1996-06-06 |
BR9509682A (en) | 1997-09-30 |
EP0994180A1 (en) | 2000-04-19 |
ES2165926T3 (en) | 2002-04-01 |
PL320224A1 (en) | 1997-09-15 |
DE69523330T2 (en) | 2002-07-11 |
DE69523330D1 (en) | 2001-11-22 |
MY118429A (en) | 2004-11-30 |
RO115540B1 (en) | 2000-03-30 |
EP0791049A1 (en) | 1997-08-27 |
WO1996015217A1 (en) | 1996-05-23 |
HUT77481A (en) | 1998-05-28 |
AU696196B2 (en) | 1998-09-03 |
EP0791049B1 (en) | 2001-10-17 |
PT791049E (en) | 2002-04-29 |
CZ150297A3 (en) | 1998-10-14 |
DK0791049T3 (en) | 2002-02-11 |
ATE207110T1 (en) | 2001-11-15 |
CN1170433A (en) | 1998-01-14 |
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Legal Events
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FZDE | Discontinued |