EP0015887A1 - Improved laundering method - Google Patents
Improved laundering method Download PDFInfo
- Publication number
- EP0015887A1 EP0015887A1 EP80870013A EP80870013A EP0015887A1 EP 0015887 A1 EP0015887 A1 EP 0015887A1 EP 80870013 A EP80870013 A EP 80870013A EP 80870013 A EP80870013 A EP 80870013A EP 0015887 A1 EP0015887 A1 EP 0015887A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- surfactant
- temperature
- washing
- sodium
- cloud point
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000004900 laundering Methods 0.000 title claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 139
- 239000000203 mixture Substances 0.000 claims abstract description 104
- 238000004581 coalescence Methods 0.000 claims abstract description 59
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 48
- 239000002689 soil Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007785 strong electrolyte Substances 0.000 claims abstract description 26
- 239000004744 fabric Substances 0.000 claims abstract description 21
- 230000014759 maintenance of location Effects 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims description 211
- 239000000243 solution Substances 0.000 claims description 32
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 30
- 150000002191 fatty alcohols Chemical class 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- -1 nitrilo trimethylene Chemical group 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 18
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- 239000003945 anionic surfactant Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims 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 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 235000011180 diphosphates Nutrition 0.000 claims description 6
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 6
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 150000003138 primary alcohols Chemical class 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 4
- BPSYZMLXRKCSJY-UHFFFAOYSA-N 1,3,2-dioxaphosphepan-2-ium 2-oxide Chemical compound O=[P+]1OCCCCO1 BPSYZMLXRKCSJY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 125000006539 C12 alkyl 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 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims description 2
- 229920005682 EO-PO block copolymer Polymers 0.000 claims 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims 1
- 229940048084 pyrophosphate Drugs 0.000 claims 1
- 229940048086 sodium pyrophosphate Drugs 0.000 claims 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 34
- 239000004615 ingredient Substances 0.000 abstract description 12
- 239000002671 adjuvant Substances 0.000 abstract description 3
- 230000003467 diminishing effect Effects 0.000 abstract 1
- 239000000693 micelle Substances 0.000 description 20
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 19
- 125000004432 carbon atom Chemical group C* 0.000 description 19
- 239000003599 detergent Substances 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 125000003158 alcohol group Chemical group 0.000 description 8
- 238000007046 ethoxylation reaction Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 230000014509 gene expression Effects 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 229920001983 poloxamer Polymers 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- ATBQNLZREVOGBO-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-(4-nonylphenoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCO)C=C1 ATBQNLZREVOGBO-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 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
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UZABCLFSICXBCM-UHFFFAOYSA-N ethoxy hydrogen sulfate Chemical compound CCOOS(O)(=O)=O UZABCLFSICXBCM-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- DUUPDCPVCHSTFF-UHFFFAOYSA-N nonane Chemical compound [CH2]CCCCCCCC DUUPDCPVCHSTFF-UHFFFAOYSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical class [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/364—Organic compounds containing phosphorus containing nitrogen
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- 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
- C11D3/08—Silicates
-
- 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
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic 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
- 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
- C11D2111/12—Soft surfaces, e.g. textile
-
- 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
- C11D2111/40—Specific cleaning or washing processes
- C11D2111/44—Multi-step processes
Definitions
- the area of technology pertaining to this invention is that of laundering fabrics, particularly in the context of commercial or industrial-laundries which handle very heavy soil loads.
- the field of compositions useful for laundering fabrics to remove oily soil is also dealt with herein.
- the nonionic surfactant used to practice the invention is preferably selected from alkyl phenol ethoxylates, ethylene oxide/propylene oxide block copolymers, and aliphatic ethoxylated alcohols.
- the condensation products of fatty alcohols having 12 to 15 carton atoms with an average of 5 to 8 ethoxylate moieties per molecule of surfactant are especially preferred, and most preferred is the condensate of a primary fatty alcohol having 14 to 15 carbon atoms with an average of about 7 ethoxylate moieties per molecule of surfactant.
- composition aspect of the invention there is provided by weight of the composition
- composition comprises
- compositions contain preferred proportions of specific'ingredients. They may be diluted in the proportions noted above to form washing liquors which may be used to practice the method disclosed herein:
- compositions are specifically formulated for optimal washing when a wash temperature of about 140°F (60 0 Celsius) is selected:
- composition incorporating a mixed surfactant system comprises
- Figure 1 is a graph showing the relation of the cleaning performance of a washing liquor of the present invention to washing temperature, for a surfactant system with a cloud point temperature of 36°C and a phase coalescence temperature of 71°C.
- Figure 2 is a graph showing the cloud point temperature (C) and phase coalescence temperature (B) of a 3000 ppm solution of the. condensate of a primary fatty alcohol having 14 to 15 carbon atoms with an average of about 7 ethylene oxide moieties per molecule of surfactant-as a function of electrolyte (sodium sulfate) concentration. Superimposed is a plot (A) of cleaning performance at 60°C of the solution as a function of electrolyte concentration.
- Figure 4 is a graph of soil removal versus wash time for three nonionic surfactants (A, B, and C) with different hydrophilic/lipophilic balance indices but similar characteristics in other respects.
- Figure 5 is a graph of cleaning performance versus time under prior art washing conditions for a surfactant having a high critical micelle concentration (B) versus a surfactant having a low critical micelle concentration (A).
- cloud point temperature is meant the minimum temperature at which the first traces of cloudiness are observed in an aqueous surfactant solution as it is heated.
- the existence of a cloud point is one of the indicia of nonionic surfactants which are useful to practice the present invention.
- phase coalescence temperature is meant the minimum temperature at which a solution comprising a nonionic surfactant and water separates into two bulk phases, as distinguished from the cloud point temperature at which a single, colloidal bulk phase is observed.
- the two bulk phases above the phase coalescence temperature are a largely dehydrated surfactant phase and a phase which is largely water.
- the presence of a specific phase coalescence temperature in aqueous solution is another characteristic of nonionic surfactants which is a key to the practice of the present invention.
- strong electrolyte is meant a compound which completely ionizes in aqueous solution at moderate concentrations (such as a concentration of 700 ppm to 20,000 ppm).
- Sequestering builder is meant a detergent additive which sequesters.water hardness to assist a surfactant in performing its intended function.
- Sequestering builders are electrolytes, but typically are not strong electrolytes as defined herein.
- adjuvant is meant a detergent ingredient which provides a function, such.as brightening, bleaching, or the like, other than the functions performed by surface active agents and sequestering builders.
- Molecules of a surface active agent consist of a lipophilic portion, commonly referred to as a "tail,” and a hydrophilic portion, commonly known as a "head.”
- the head being hydrophilic, prefers an orientation of the surfactant molecule which allows it to be in contact with the water of an aqueous solution.
- the tail of the surfactant molecule being lipophilic, prefers an orientation of the surfactant molecule which allows it to be in contact with oily species or. tails of other surfactant molecules.
- the contrasting properties of the head and tail portions of the surfactant molecule particularly in the case of nonionic surfactants useful in the present invention, dictate the orientation of the surfactant in aqueous solution.
- the orientation of surfactant molecules in an aqueous system is not constant, but varies in relation to solution temperature, surfactant identity and concentration, the presence of other species in. solution, and so forth.
- surfactant molecules in aqueous solution exist in the form of monomers.
- the individual molecules are largely independent of each other, and each surfactant molecule is surrounded by water molecules.
- CMC critical micelle concentration
- the micelles will each become sufficiently large that the solution will scatter light, rendering it cloudy in appearance.
- the surfactant species begin to dehydrate. This means that the surfactant species progressively lose their solution- like attraction to water molecules.
- the inventors have found that by using low CMC surfactants in a washing-liquor maintained at a temperature substantially exceeding its cloud point temperature, so that the surfactant species coexist in a single bulk phase with water but are largely dehydrated, the rate of cleaning of low CMC surfactants is sufficiently increased that they clean better than high CMC surfactants. This surprising result is explained as follows.
- the micelles which predominate in solutions of low CMC surfactants migrate to sites of oily soil very slowly and/or do not quickly reorient themselves from their water-stable form, in which their hydrophilic heads are presented outward, to a'form in which their lipophilic tails are able to contact droplets of oily soils and solubilize or emulsify them.
- a high CMC surfactant can clean more quickly because its high concentration of monomers travels quickly through solution to sites of oily soil. These monomers also do not need to reorient themselves into a less stable state to attach themselves to soils, for their lipophilic tails are constantly exposed.
- this surfactant species is believed to be transported by bulk transport to the sites of oily soils more rapidly than ordinary micelles, in contrast to prior art conditions which allow only monomeric species to participate in rapid cleaning, thus limiting the concentration of species available for cleaning to CMC, which is low for the preferred (low CMC) surfactants.
- the inventors have also ascertained an upper limit to washing temperatures which may be used if the benefits of the present invention are to be obtained. It has been found that the present invention should be practiced at a washing temperature which does not exceed the phase coalescence temperature of the washing liquor. (Or, to put it another way, the phase coalescence temperature must not be lowered to below the washing temperature selected.) This upper limit is probably observed because, while the surfactant will be delivered and mixed with oily soils more rapidly, it will not be removed at all because it is dehydrated and too hydrophobic to be a good solubilizing or emulsifying agent under these conditions. Methods not forming a part of the present invention must be employed to effectively clean fabrics with the two-phase surfactant/water system which exists when the washing temperature exceeds the phase coalescence temperature of the surfactant system in a washing liquor.
- washing is conducted at a temperature within a range given by the following expression: wherein A is the cloud point temperature of the.washing liquor, B is the phase coalescence temperature of the washing liquor and T is the washing temperature.
- A is the cloud point temperature of the.washing liquor
- B is the phase coalescence temperature of the washing liquor
- T is the washing temperature.
- washing temperatures for washing liquors having particular cloud point and phase coalescence temperatures.
- A cloud point temperature
- B phase coalescence temperature
- the especially preferred temperature for use of the indicated washing liquor is calculated as follows: Using the above calculations for the hypothetical washing liquor, the broad, preferred, and especially preferred washing temperatures for this washing liquor are found to be 52°C to just less than 80°C, 60°C to just less than 80°C, and 68°C.to just less than 80°C.
- Figures 1 and 2 illustrate the importance of choosing a washing liquor with certain cloud point and phase coalescence temperatures in relation to the washing temperature in order to produce an optimum cleaning result.
- Figure I is a plot of cleaning performance (Hunter whiteness) versus temperature for a washing liquor with a cloud point of 36°C and a phase coalescence temperature of 71°C. As the graph illustrates, cleaning performance - continues to increase as the wash temperature is increased above the cloud point until the general area of the phase coalescence temperature is reached. Beyond this point, higher temperatures produce poorer performance.
- plot A shows the washing performance at 60 Q Celsius (measured as Hunter whiteness of fabrics washed by a standard method) of Neodol 45-7 (a surfactant comprising a primary fatty alcohol containing 14 to 15 carbon atoms condensed.with an average of 7 ethylene oxide moieties per molecule of surfactant commercially available from Shell Chemical Co., Industrial Chemicals Division) as a function of concentration of sodium sulfate -- an electrolyte which has no substantial function except to lower the phase coalescence and, cloud point temperatures of the system.
- the area between the dotted lines represents an unstable area because the phase coalescence temperature is near the washing temperature. Accurate experimental data in this area is impossible to obtain.
- the washing liquors of the present invention are aqueous dispersions of a nonionic surfactant.
- the surfactant may be present in concentrations of from about 1400 ppm to about 20,000 ppm. If it is desirable to raise the cloud point and phase coalescence temperatures of the washing liquor in accordance with the teachings of the present invention, the washing liquor may include up to about 10% of an anionic surfactant.
- one or more nonionic surfactants having a high cloud point temperature may be added to the washing liquor to raise the net cloud point and phase coalescence temperatures of the system.
- 700 to 10,000 ppm of a strong electrolyte are also added to the washing liquor and serve to lower the-cloud point and phase coalescence temperatures of the washing liquor.
- the cloud point and phase coalescence temperatures of the washing liquor may alternatively be lowered by adding a surfactant with a low cloud point temperature to the washing liquor to lower the net cloud point and phase coalescence temperatures of the system.
- Washing liquors of the present invention also include 500 to 10,000 ppm of a sequestering builder in order to improve their cleaning ability.
- many detergency adjuvants and other optional ingredients may be added to compositions within the scope of the present invention. In the text which follows, the selection of each of these ingredients is described in greater detail.
- the major essential ingredient of an aqueous washing liquor designed to practice the present invention is a surfactant. ⁇ or mixtures of surfactants) which has certain properties.
- the desired concentration of the- surfactant in the washing liquor is from about 1400 ppm to about 20,000 ppm. It will be noted that this concentration is at least 28 times the critical micelle concentration of the surfactant, which should be less than 50 ppm.
- the present invention teaches a very high concentration of surfactant compared to.its critical micelle concentration, in contrast to the prior art teaching that washing with surfactant concentrations substantially in excess of the critical micelle concentration of the system does not improve surfactant performance because the concentration of the surfactant in excess of its CMC is tied up in the form of micelle's..
- the first consideration in choosing a surfactant or mixture of surfactants for use in the present invention is that the primary surfactant should be a nonionic surfactant.
- nonionic surfactants the main category of surfactants which have HLB's within the range which is useful in the present invention, but in addition only a surfactant system consisting entirely or mostly of nonionic surfactants will exhibit a cloud point temperature and a phase coalescence temperature. Since the existence of these particular phase attributes of the washing liquor is essential to the definition of the present invention, it is important that the surfactant system primarily comprise nonionic surfactants.
- the second consideration in choosing a surfactant is its HLB.
- the choice of a surfactant with an optimized HLB is demonstrated in the plots of Figure 4, in which three washing systems are compared which differ only in the choice of a surfactant HLB.
- three nonionic surfactants were chosen, each of which is a condensate of a fatty alcohol and a chain of ethylene oxide moieties.
- the surfactant chosen for the HLB 8.2 plot (plot C) was an ethoxylation 'product of a primary fatty alcohol having 12 to 13 carbon atoms with an average of 3 ethylene oxide moieties per molecule of surfactant.
- the HLB 15.0 plot depicts the performance of a nonionic surfactant comprising a condensate of primary fatty alcohols having 14 to 15 carbon atoms with an average of 7 ethylene oxide moieties per molecule of surfactant.
- the critical micelle concentrations of the nonionic surfactants were 10 ppm, 5 ppm, and 12 ppm, respectively.
- the performance of each of these surfactants was optimized for the washing temperature used (60° Celsius) by the addition of electrolytes as will be described hereinafter.
- total surfactant hydrophilic/ lipophilic balance index is used to denote that net HLB .of all surfactants in a system.
- the- total surfactants hydrophilic/lipophilic balance index lies in the range 9.75-12.5, most preferably in the range 10-12.
- the third consideration in choosing a surfactant or mixture of surfactants for use in the present invention is that the. surfactant should have a CMC which is below about 50 ppm. As is explained above, selection of a surfactant with a CMC which is must less than its in-use concentration, using the. particular washing temperatures of the present invention, improves the cleaning action of the surfactant.
- Example 2 below below also demonstrates that a low CMC surfactant displays superior cleaning when used in accordance with the teachings of the present invention.
- cloud point temperature and phase coalescence temperature values specified herein refer to properties of the washing liquor.
- the HLB and CMC of the surfactant system are essentially independent of the other components in the wash liquor. Consequently, HLB values for specific surfactants can be determined by methods known to those skilled in the art and CMC values can be measured in distilled water. The values of these parameters for a mixture of surfactants are determined as follows.
- the CMC of a mixture of surfactants is determined using the following equation: wherein the numerators are the mole fractions of the respective components (compared to total moles of surfactants) and the denominators are the CMC's of the respective surfactants.
- anionic surfactant In the event that an anionic surfactant is to be included in the nonionic surfactant system to raise its cloud point and phase coalescence temperatures, an additional problem in formulation is raised because anionic detergents do not typically have a cloud point or phase coalescence temperature in aqueous solutions. This is the case because the temperature at which such a surfactant dispersion would exhibit these properties is greater than the boiling point of the aqueous dispersion at atmospheric pressure.
- a person skilled in the art of formulating detergents can resolve this difficulty by obtaining cloud point and phase coalescence temperatures of aqueous surfactant solutions which are subjected to a pressure exceeding their vapor pressure. This will then aid the formulator's initial estimate of the amount of the anionic surfactant which must be added in order to obtain the desired adjustment in the phase properties of the system.
- nonionic surfactants which may be used to formulate surfactant systems when practicing the present invention.
- a first category of nonionic surfactants which are useful in the practice of the present invention are most broadly defined as ethoxylated aliphatic alcohols. These surfactants are the condensation products of a fatty alcohol with an ethoxylate chain comprising at least one ethoxylate moiety per molecule of surfactant, especially between about 1 and about 12 moles of ethoxylate moieties per molecule of surfactant for purposes of the present invention.
- Commercially available ethoxylated fatty alcohols generally contain between about 8 and about 22 carbon atoms in.their alcohol moiety, preferably 12 to 15 carbon atoms for the purpose of the, present invention..
- Typical surfactants of this type have a.
- ethoxylated alcohol surfactants for use in the present invention have an average of 5 to 8 moieties of ethylene oxide per molecule of surfactant, preferably an average of 7 moieties.
- a degree of ethoxylation is specified hereinafter, it will be understood that this refers to the average number of ethoxylate moieties per molecule of surfactant.
- Neodol series of surfactants which are available from Shell Chemical Company, Industrial Chemicals 'Division.
- the Neodol surfactants are characterized by a low degree of branching in the alcohol chain; typically less than about 20% of the surfactant molecules are branched.
- Neodols are primary alcohol ethoxylates which each have a narrow and precisely indicated range of alcohol chain lengths, but a large variation in the degree of ethoxylation in a given molecule; the average number of ethoxylate groups per molecule is provided for the surfactants.
- Neodol 45-7 is a condensate of a 14 to 15 carbon fatty alcohol with an average of 7 ethylene oxide moieties per molecule of surfactant.
- Neodol 91-6 which comprises the condensate of a 9 to 11 carbon fatty alcohol with an average of 6-ethylene oxide moieties per molecule of surfactant.
- Neodol surfactants which are useful in practicing the present invention are as follows: Neodol 45-7, 45-15, 23-6.5, or 25-7; a mixture of 75% Neodol 25-5 and 25% Neodol 45-7; a mixture of 50% Neodol 25-7 and 50% Neodol 45-7; a mixture of 50% Neodol 91-6 and 50% Neodol 45-7; and so forth. (Some of these surfactants are useful only in conjunction with other ingredients. Formulation of such mixtures is explained elsewhere in this specification.).
- Tergitols are alcohol ethoxylates, and may be divided into S Tergitols and L Tergitols. The former are relatively unbranched secondary alcohols, while the latter are primary alcohols having a high numerical percentage of branched species. (About 40% of the alcohol moieties of L Tergitols are branched, while a lower percentage of the alcohol moieties of S Tergitols are branched.) In commercially supplied Tergitols, the range of ethoxylation for a given surfactant is somewhat narrower than is observed in the Neodols.
- the Tergitols are named in a manner analogous to the naming of Neodols, except that the name contains an upper case "S" or "L” interposed between the numerals indicating alcohol chain length and the numeral indicating degree of ethoxylation.
- Specific examples of Tergitol surfactants which are useful in the practice of the pre-sent invention are Tergitols 15-S-3, 15-S-5, 15-S-7, 15-S-9, 25-L-3, 25-L-5, 25-L-7, or 25-L-9. (Again, some of these surfactants must be combined with other ingredients as disclosed herein in order to be useful in the practice of the present invention.)
- a second major category of nonionic surfactants which are useful in the practice of the present invention is that of the alkyl phenol ethoxylates.
- the structure of these surfactants is that of benzene with two substituents in para relationship.
- the first substituent is an alkyl moiety with a chain length of 7 to 12 carbon atoms, preferably 8 to 9 carbon atoms for purposes of the present invention.
- the second substituent is an ethoxylation chain.
- the alkyl phenol ethoxylates have an ethylene oxide substitution level which varies widely for a given surfactant.
- the degree of ethoxylation in such surfactants is essentially from 1 to 12 ethylene oxide moieties per molecule of surfactant; an average of 7 ethylene oxide moieties per molecule of surfactant is preferred for use in this invention.
- Igepal surfactants manufactured by General Aniline and Film Corporation.
- the Igepal surfactants are designated by two upper case letters followed by a numeral or series of numerals; the lettered prefix "CA” indicates an octyl radical as the alkyl moiety of the surfactant, while the lettered prefix "CO” indicates a nonyl radical as the alkyl moiety.
- CA octyl radical
- CO indicates a nonyl radical as the alkyl moiety.
- the inventors are not aware of any connection between the numerals designating species of this class of surfactants-and the structures thereof.
- a specific example of an Igepal surfactant useful in the practice of the present invention is Igepal CO-610.
- a third broad class of nonionic surfactants which are useful in the practice of the present invention are the condensation products of a chain of ethylene oxide moieties with a hydrophobic base formed by the condensation of a chain of propylene oxide moieties with propylene glycol, known hereinafter as ethylene oxide/propylene oxide block copolymers.
- Pluronic L-43 is a liquid composition with a hydrophobic portion molecular weight of 1200 and 30% by composition weight of ethylene oxide.
- nonionic surfactants are polyoxyethylene adducts of alkyl amines, such as the Ethoduomeen and Ethomeen surfactants marketed by. A rmak Company. Polyoxyethylene alkyl amides may also be used in the practice of this invention. Another category of nonionic surfactants is the sorbitan esters, such as sorbitan monolaurate. Finally, the Surfonic surfactants manufactured by Jefferson Chemical Company, Inc., such as Surfonic N-95, which is an alcohol phenol ethoxylate, may be used in the practice of the present invention. This list of nonionic surfactants is not exhaustive, and it is contemplated that routine experimentation will result in the location of other surfactants which may be used to practice the present method invention.
- Table II below contains HLB, CMC, cloud point, and phase coalescence temperature data for a variety of aqueous solutions of pure commercial surfactants. With the aid of this table, a person skilled in the art may formulate a wide variety of washing liquors which are useful for laundering fabrics.
- TAE 11 is a primary fatty alcohol ethoxylate surfactant having a predominance of alcohol chain lengths of about 14 to 18 carbon atoms and an average of 11 ethoxylate moieties per molecule of surfactant
- TAE 9 is a similar surfactant, but is substituted with an average of 9 ethoxylate moieties per molecule of surfactant
- STP is sodium tripolyphosphate
- LAS is a linear alkylate sulfonate surfactant comprising benzene, substituted by a sulfonate group and a C 12 alkylate group in para orientation
- Na 2 C0 3 is sodium carbonate.
- the cloud point temperatures and phase coalescence temperatures of Table II were measured on a photo gonio diffusometer made by SOFICA (Model 42.000).
- the index vat of the above apparatus contained Dow Corning 702 Silicone fluid and the temperature range of the instrument was 30°C. to 100°C.
- the photo detection unit of the instrument was positioned at an angle of 90° with respect to the incoming light beam.
- Samples of each surfactant were prepared at a concentration of 3,000 ppm using laboratory distilled water. No other special treatment was used to reduce interfering impurity particles.
- a green instrument filter and'no polarizing filter were used, and the instrument's variable slit was adjusted for appropriate base intensity starting light scattering measurements.
- the samples were heated at the rate of approximately 1/2° Celsius per minute using a variable voltage transformer.
- the cloud point temperature was determined as the initial temperature at which the light scatter reading deviated from the base light scatter, indicating a sharp increase in light scattering due to the formation of nuclei of sufficient size to scatter light.
- the phase coalescence temperature was interpreted to be the temperature at which the light scattering returned to the base line scatter after having increased to the maximum. This represents a temperature at which the solution separates into two bulk phases, each of which is much less cloudy than the mixture before separation of aqueous and surfactant phases.
- the CMC's of Table II were. determined in distilled water at 25°C.
- a nonionic surfactant has relatively low cloud point and phase coalescence temperatures, so that the temperature for washing in accordance with the teaching of the invention is lower than the- desired washing temperature for given fabric and soil - conditions
- small amounts of an anionic detergent may be incorporated into a surfactant system which contains a major amount of the nonionic surfactant in order to substantially raise the cloud point and phase coalescence temperatures of the system.
- the percentage of total surfactant content supplied by an anionic surfactant should not exceed about 10% of the surfactant system to avoid creating a surfactant system which does not have a cloud point or phase coale- scene temperature.
- the anionic surfactant preferably comprises 0.5% to 5% of the composition.
- One typical anionic surfactant which may be used to raise the cloud point and phase coalescence temperatures of the washing liquors is a linear alkylate sulfonate (LAS), which is benzene substituted with an alkylate moiety and a sulfonate moiety in para relation.
- LAS linear alkylate sulfonate
- An especially preferred LAS has a dodecanate group as its alkylate moiety and is typically referred to in the art as C 12 LAS.
- Another type of anionic surfactant which may be used for this purpose is an alkylate ethoxylate sulfate (AES) comprising an alkyl moiety, to which is attached an ethoxylate chain, to which in turn is attached a sulfate moiety.
- AES alkylate ethoxylate sulfate
- AES surfactant has a dodecyl.group as its alkyl moiety and a six-unit ethoxylate chain.
- a third type of anionic surfactant which may be used to raise the cloud point and phase coalescence temperatures of a nonionic surfactant system is a tallow alkyl sulfate (TAS) surfactant.
- TAS tallow alkyl sulfate
- This surfactant contains alkyl moieties having a range of carbon chain lengths, predominantly alkyl moieties having from about 14 to about 18 carbon atoms.
- electrolytes are those which supply some alkalinity to the washing medium, although a high degree of alkalinity is not.necessary to the practice of the present invention.
- the sodium salts are highly preferred as strong electrolytes because they are highly soluble and inexpensive, and of those sodium salts sodium carbonate and sodium metasilicate are the most pre- - ferred strong electrolytes in the practice of the present invention.
- the amount of a strong electrolyte which must be added to the washing liquor to optimize the cloud point and micelle inversion temperatures will lie between about 700 ppm and 20,000 ppm...
- Figure 3 is a plot of cleaning performance (Hunter whiteness) versus wash time-for two washing liquors.
- Plot "A” is for a washing liquor containing Neodol 45-7 and a strong electrolyte (sodium sulfate) to optimize its performance at the washing temperature used.
- Plot B is for the same washing liquor and washing temperature, but excluding the electrolyte. As indicated in Figure 3, for any of the wash times tested the washing liquor containing an electrolyte produces superior washing results.
- washing liquors containing a nonionic surfactant and having particular cloud point and phase coalescence temperatures are useful in themselves for laundering fabrics, their effect is improved by adding thereto about 500 ppm to 10,000 ppm of a sequestering builder.
- sequestering detergency builders A wide variety of sequestering detergency builders is known in the art. A number of these are conveniently described as compounds of a cation selected from sodium, potassium, lithium, or hydrogen, and an anion selected from tripolyphosphate, pyrophosphate, orthophosphate, nitrilotriacetate, ethylene diamine tetraacetate, nitrilotrimethylenephosphonate, and ethylene diamine tetra- methylenephosphonate. It will also be noted that some ingredients. which act as strong electrolytes may also. be useful, as. sequestering detergency builders, for example, orthophosphates. However, the best sequestering builders are only modestly electrolytic at the concentration typically used in a detergent.
- Especially preferred sequestering builder salts for incorporation in washing liquors of the present invention are any of the polyphosphate builders known to the art, particularly alkali metal tripolyphosphates and pyrophosphates such as sodium tripolyphosphate or tetrasodium pyrophosphate.
- sequestering builders are widely recognized in the art as important additives for laundry detergents. These builders have traditionally been thought to be primarily useful to prevent water hardness cations from interacting with soaps or anionic detergents to form an insoluble precipitate or soap scum. However, such sequestering builders are also known to provide cleaning benefits to washing liquors containing only nonionic surfactants,-which do not interact with water hardness ions.
- the sequestering builders prevent water hardness ions such as calcium and magnesium from interacting with fatty soils to form insoluble precipitates.
- the sequestering builders also sequester other metal ions such as copper and iron ions which can interfere with the action of the bleaching agents which are frequently used in conjunction with laundry detergents.
- Several of the sequestering builders also peptize clay soils by replacing various cations in the insoluble clays with sodium cations or the like, rendering the clays somewhat soluble in the washing liquor. Finally, these builders have utility as soil suspending agents.
- washing compositions for laundering fabrics are typically sold as concentrated formulas which are diluted in water by the user in order to produce the desired aqueous washing liquor. What follows is a specific description of washing compositions which may be diluted in water to form washing liquors within the definition of the present method invention.
- compositions which may be diluted in water to produce washing compositions useful to practice the present invention:
- compositions may be dissolved in water to form a solution which contains from about 1000 to 40,000 ppm (0.10% to 4.0%) of the composition.
- compositions contain preferred proportions of specific ingredients. They may be diluted in the proportions noted above to form washing liquors:
- composition designed to employ a mixed surfactant system comprises:
- Typical washing liquors used in industrial laundries arts are highly alkaline, having an pH substantially in excess of 11.5. Such pH's are essential in conventional industrial laundry detergents in order to saponify oily soils and thus increase their solubility in the washing liquor.
- compositions of the present invention are desirably formulated to have a pH of 11 or less, particularly from about 7 to about 11. This is possible because the cleaning ability of the compositions disclosed herein has been found to be relatively insensitive to pH. While a high pH cleaning composition may easily be formulated in accordance with the present invention (for example, a composition which provides a washing liquor pH greater than 11.5), no substantial cleaning benefit is found to result from the selection of a high pH.
- the compositions of the present invention are able to solubilize or emulsify oil quite effectively without relying on saponification.
- compositions may be assembled in any of the ways known to the art to form commercial preparations which are suitable for sale.
- Neodol surfactants are certain primary fatty alcohol ethoxylates, as characterized above, and “TAE 9 " is a primary fatty alcohol ethoxylate having apredominance of alcohol chain lengths in the range of from 14 to 18 carbon atoms and an average of 9 ethoxylate moieties per molecule of surfactant. Where dextrin is present it functions as a binder and does I not substantially affect the performance of compositions containing it.
- a series of 65% polyester/35% cotton swatches with a permanent press finish were soiled with used motor oil obtained from automobile crankcases. These swatches were washed for 20 minutes in a Tergotometer, Model 7243, at 60°C in soft.water with the compositions listed below. Octadecane at a level of 300 ppm was added to the wash solutiow to simulate extra soil in the system. The temperature of each washing liquor was within the range of the present invention. The washed swatches were rinsed for 10 seconds in cold water and dried, and Hunter whiteness measurements were made using a Hunter Laboratories Color/Difference Meter (Model D25D2). (This instrument provides a direct readout of Hunter whiteness.)
- a series of stains were cut from discarded, naturally soiled industrial uniforms: These stains were split into equally soiled parts; each part was washed with one of the compositions listed below. The stains were washed in a 35 lb. Milnor washer/extractor with 18.5 lbs. of industrial uniform shirts soiled with 1.5 1b. of used motor oil. A wash temperature of 60°C was used. After washing, the stained parts were placed back together and graded visually. in a paired comparison manner by a panel of 3 judges using a 0-4 scale.
- a grade of "0" indicated no difference between the paired swatches; a grade of "1” indicated a perceived difference between the swatches; a grade of "2” indicated a clear difference between the swatches; a grade of "3” indicated a large difference between the swatches; and a grade of "4" indicated a very large difference between the swatches.
- These grades were statistically combined to produce Paired Comparison Grades, which represent_the difference in cleaning performance for a given composition (positive for an improvement) with respect to the inferior composition.
- the CMC of Composition B was outside the range required by the present invention.
- the process used with Composition A was within the scope of the present invention and demonstrated superior performance.
- composition B is outside the claims of this invention because the wash temperature used was below the cloud point temperature of Composition B.
- the process used with Composition A was within the claims of this invention and produced superior performance, even though Composition A was substantially more dilute and had a much lower pH than Composition B.
- Example 2 The procedure of Example 2 was used. The compositions were added to the wash water to produce washing liquors having the indicated concentrations.
- Composition B is outside the more preferred composition range claimed in this invention due to its high Na 2 CO 3 level.
- Composition A is near the center of the range and produces superior performance.
- the 60°C wash temperature was within the temperature range of the present invention for each composition.
- Composition B is outside the more preferred composition range claimed in this invention due to its low Na 2 CO 3 level.
- Composition A is near the center of the range and produces superior performance. Again, the 60°C washing temperature for each composition was within the temperature range of the present invention.
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Abstract
Description
- The area of technology pertaining to this invention is that of laundering fabrics, particularly in the context of commercial or industrial-laundries which handle very heavy soil loads. The field of compositions useful for laundering fabrics to remove oily soil is also dealt with herein.
- The prior art teaches that laundering processes may be conducted at a washing temperature roughly equal to the cloud point temperature of the washing liquor, but does not appear to suggest that washing should be carried out substantially above the cloud point temperature, yet below the phase coalescence temperature. For example, U.S. Patent No. 3,707,506, issued to Lozo on December 26, 1972, suggests at Col. 1, lines 44-54, that there is some error in the prior art belief that maximum efficiency in removing dirt with a nonionic washing liquor is obtained at temperatures below the detergent cloud point. The Lozo reference does not provide any positive teaching, however, as to what washing temperature may be selected to improve washing results. An article by Cook entitled "Versatility of Nonionic Detergents" published by Soap and Chemical Specialities, May 1975, pages 47-49, indicates that a nonionic deter- 'gent works best if its surface active agent is not completely dissolved, but rather is partially.in a colloidal state which promotes micelle formation. U.S. Patent No. 3,925,224, issued to Winston on December 9, 1975, similarly teaches that a cloudy solution of a surfactant is optimal for laundering fabrics. It is believed that the Cook and Winston references'essentially describe washing at the cloud point temperature of the washing liquor rather than at a temperature substantially above the cloud point temperature.
- Two references have been found which provide teachings contrary to the present development, indicating that it is undesirable to wash at or above the cloud point temperature. These references are: U.S.. Patent No. 3,890,238, issued to Boehmer on June 17, 1975; and Colwell et al., "Considerations in the Use of Nonionic Surface Active Agents," American Dye Stuff Reporter, Vol. 39, Sept. 4, '1961, page 679.
- British Patent Specification No. 1,518,676, naming Mould et al. as inventors and published July 19, 1978, teaches washing substantially above the phase coalescence temperature of the washing liquor, but not within-the temperature range between the cloud point and phase coalescence temperatures.
- The prior art teaches that it is known to add a strong electrolyte to an aqueous solution containing a nonionic surfactant in order to lower the cloud point of the solution. For example, see Schick, Nonionic Surfactants, Marcel Dekker, Inc. (NY, 1966), Library of Congress Cat. Card No. 66-22492, especially pages 572-573.
- Numerous prior art references can be found which generally indicate-that a nonionic detergent may be combined with a builder, a strong electrolyte, or mixtures thereof to form washing compositions. However, no such disclosures are known which reveal compositions having the relatively narrow ranges of proportions of strong electrolytes and builders which are necessary to realize the present improvement at specific temperatures which are typical in the field of commercial laundering.
- According to the invention there is provided a process for laundering oily soil from a fabric by contacting the fabric with an aqueous washing liquor containing a nonionic surfactant characterised in that it comprises
- a) treating said fabric with a wash liquor having a total surfactant hydrophilic-lipophilic balance (HLB) index of from 9.5 to 13; said liquor containing 1400-20,000 ppm of a nonionic surfactant component having a CMC of 50 ppm at 25°C in distilled water, 500-10,000 ppm of a sequestering builder selected from sodium potassium and lithium tripolyphosphate, pyrophosphate, orthophosphate, nitrilo triacetate, ethylene diamine tetra acetate nitrilo trimethylene phosphonate ethylene diamine tetra methylene phosphonate and mixtures thereof and 700-20,000 ppm of a strong electrolyte; and
- b) maintaining said washing liquor at a temperature in the range 0.30 (B-A)+A ≤ T < B wherein T is the wash liquor temperature, B is the phase coalescence temperature of the wash liquor and A is the cloud point temperature of the wash liquor.
- The nonionic surfactant used to practice the invention is preferably selected from alkyl phenol ethoxylates, ethylene oxide/propylene oxide block copolymers, and aliphatic ethoxylated alcohols. The condensation products of fatty alcohols having 12 to 15 carton atoms with an average of 5 to 8 ethoxylate moieties per molecule of surfactant are especially preferred, and most preferred is the condensate of a primary fatty alcohol having 14 to 15 carbon atoms with an average of about 7 ethoxylate moieties per molecule of surfactant.
- A preferred temperature range for practice of the present invention is given by the expression:
- .50 (B-A) + A < T < B
- .70 (B-A) + A ≤ T < B.
- In a composition aspect of the invention there is provided by weight of the composition
- (a) from 10% to 78% of a nonionic component, the total surfactant having an HLB index of from 9. 5-13 and a CMC < 50 ppm;
- (b) from 4% to 70% of a strong electrolyte; and
- (c) from 3% to 55% of a sequestering builder.
- Preferably the composition comprises
- (a) 20%-51% by weight of a C12-C15 fatty alcohol condensed with 5-8 moles ethylene oxide per mole alcohol, preferably 29%-35% of a C14-C15 fatty alcohol condensed with an average of seven moles ethylene oxide per mole alcohol;
- (b) 20%-40% preferably 34%-35% of an alkali metal carbonate and
- (c) 20%-51% preferably 30%-36% of an alkali metal . pyrophosphate or tripolyphosphate.
- The following compositions contain preferred proportions of specific'ingredients. They may be diluted in the proportions noted above to form washing liquors which may be used to practice the method disclosed herein:
- (a) 20% to 51% of an alkali metal tripolyphosphate;
- (b) 24% to 40% of an alkali metal carbonate; and
- (c) 20% to 51% of the condensate of a fatty alcohol having 12 to 15 carbon atoms with an average of about 5 to about 8 ethoxylate moieties per molecule of surfactant.
- Additionally, the following compositions are specifically formulated for optimal washing when a wash temperature of about 140°F (600 Celsius) is selected:
- (a) about 36% sodium tripolyphosphate;
- (b) about 35% sodium carbonate; and
- (c) about 29% of the condensate of a primary fatty alcohol having 14 to 15 carbon atoms with an average of about 7 ethylene oxide moieties per molecule of surfactant; or
- (a) about 31% tetrasodium pyrophosphate;
- (b) about 34.6% sodium carbonate; and
- (c) about 34.4% of the condensate of a primary fatty alcohol having 14 to 15 carbon atoms with an average of about 7 ethylene oxide moieties per molecule of surfactant.
- Finally a composition incorporating a mixed surfactant system comprises
- (a) 10%-40% preferably 15%-35% of a mixture of a C12-C15 fatty alcohol condensed with an average of 6-7 moles of ethylene oxide per mole of alcohol and a G12-C15 primary alcohol condensed with an average of three moles of ethylene oxide per mole of alcohol.
- (b) 50%-70% preferably 55% to 65% of a strong electrolyte selected from sodium carbonate, sodium metasilicate and mixtures thereof.
- (c) 10%-25% preferably 12%-15% of sodium tripolyphosphate and
- (d) from 0.5% to 5% of an anionic surfactant selected from sodium C12 alkyl benzene sulphonate, sodium dodecyl hexa ethoxy sulphate, sodium tallow alkyl sulphate and mixtures thereof.
- The washing liquors and compositions of the present invention-provide optimal cleaning performance for a particular washing temperature. Certain embodiments of the invention are.also useful.for effective washing at a pH of less than 11, ie. from 7 to 11 preferably from 9 to 11, with essentially undiminished cleaning performance. These lower pH compositions and washing liquors are gentler to fabrics than the typical compositions used in industrial laundries, which provide a pH in the wash liquor greater than 11.5.
- Figure 1 is a graph showing the relation of the cleaning performance of a washing liquor of the present invention to washing temperature, for a surfactant system with a cloud point temperature of 36°C and a phase coalescence temperature of 71°C.
- Figure 2 is a graph showing the cloud point temperature (C) and phase coalescence temperature (B) of a 3000 ppm solution of the. condensate of a primary fatty alcohol having 14 to 15 carbon atoms with an average of about 7 ethylene oxide moieties per molecule of surfactant-as a function of electrolyte (sodium sulfate) concentration. Superimposed is a plot (A) of cleaning performance at 60°C of the solution as a function of electrolyte concentration.
- Figure 3 is a graph of cleaning performance versus time for a washing liquor (A) which contains a strong electrolyte, as opposed to a washing liquor (B) which does not.
- Figure 4 is a graph of soil removal versus wash time for three nonionic surfactants (A, B, and C) with different hydrophilic/lipophilic balance indices but similar characteristics in other respects.
- Figure 5 is a graph of cleaning performance versus time under prior art washing conditions for a surfactant having a high critical micelle concentration (B) versus a surfactant having a low critical micelle concentration (A).
- In the course of describing this invention it will be useful to define the following terms:
- By "nonionic surfactant" is meant a surfactant comprising a lipophilic moiety and a hydrophilic moiety, which does not ionize in aqueous solution.
- By "hydrophilic/lipophilic balance index," or "HLB," is meant a numerical index for a given surfactant structure, indicating its balance of hydrophilic and lipophilic properties. A surfactant with a high HLB is more hydrophilic and less lipophilic in character than a surfactant with a low HLB.
- By "critical micelle concentration," or "CMC," is meant the concentration of a surfactant in aqueous solution at which the. concentration of monomeric. surfactant molecules (as opposed to micelles) is maximized. At concentrations of a surfactant exceeding its CMC, monomer concentration remains essentially constant.
- By "cloud point temperature" is meant the minimum temperature at which the first traces of cloudiness are observed in an aqueous surfactant solution as it is heated. The existence of a cloud point is one of the indicia of nonionic surfactants which are useful to practice the present invention.
- By "phase coalescence temperature" is meant the minimum temperature at which a solution comprising a nonionic surfactant and water separates into two bulk phases, as distinguished from the cloud point temperature at which a single, colloidal bulk phase is observed. (The two bulk phases above the phase coalescence temperature are a largely dehydrated surfactant phase and a phase which is largely water.) The presence of a specific phase coalescence temperature in aqueous solution is another characteristic of nonionic surfactants which is a key to the practice of the present invention.
- By "strong electrolyte" is meant a compound which completely ionizes in aqueous solution at moderate concentrations (such as a concentration of 700 ppm to 20,000 ppm).
- By "sequestering builder" is meant a detergent additive which sequesters.water hardness to assist a surfactant in performing its intended function. Sequestering builders are electrolytes, but typically are not strong electrolytes as defined herein.
- By "adjuvant" is meant a detergent ingredient which provides a function, such.as brightening, bleaching, or the like, other than the functions performed by surface active agents and sequestering builders.
- While no limit on the scope of the invention is intended by setting forth the theory of its operation which 'follows, it is believed that the following theory of operation explains the present invention and distinguishes it from the prior art.
- Molecules of a surface active agent, in particular nonionic surfactants, consist of a lipophilic portion, commonly referred to as a "tail," and a hydrophilic portion, commonly known as a "head." The head, being hydrophilic, prefers an orientation of the surfactant molecule which allows it to be in contact with the water of an aqueous solution. The tail of the surfactant molecule, being lipophilic, prefers an orientation of the surfactant molecule which allows it to be in contact with oily species or. tails of other surfactant molecules. The contrasting properties of the head and tail portions of the surfactant molecule, particularly in the case of nonionic surfactants useful in the present invention, dictate the orientation of the surfactant in aqueous solution. The orientation of surfactant molecules in an aqueous system is not constant, but varies in relation to solution temperature, surfactant identity and concentration, the presence of other species in. solution, and so forth.
- At a temperature below its cloud point temperature and at a concentration below its critical micelle'concentration, surfactant molecules in aqueous solution exist in the form of monomers. In effect, the individual molecules are largely independent of each other, and each surfactant molecule is surrounded by water molecules.
- If the concentration of surfactant in the foregoing solution of monomers is allowed to exceed the-critical micelle concentration (CMC) of the surfactant, individual molecules of surfactant begin to orient themselves into micelles, which are structures wherein several surfactant molecules arrange themselves with their oleophilic tails together and their hydrophilic heads presented outward, so that water molecules are isolated from the surfactant tails by an exterior surface of surfactant heads. At surfactant concentrations exceeding the CMC, the concentration of monomers remains more or less equal to the critical micelle concentration, so that the surfactant species present in excess of the CMC exist as micelles.
- If the temperature of the surfactant solution is now increased to exceed the cloud point temperature of the aqueous solution (or if agents are added to the solution to lower its cloud point temperature to below the solution temperature, as further explained hereinafter), the micelles will each become sufficiently large that the solution will scatter light, rendering it cloudy in appearance.
- If the solution temperature is further raised (or its cloud point temperature is further lowered) so that the solution is somewhat warmer than its cloud point temperature, the surfactant species begin to dehydrate. This means that the surfactant species progressively lose their solution- like attraction to water molecules.
- Ultimately, if the temperature of the solution is raised to its phase coalescence temperature (or if the solution's phase coalescence temperature is lowered below its actual temperature by adding agents similar to those added to lower the cloud point temperature), the surfactant species will dehydrate to such an extent that much of the surfactant will separate as a second, surfactant rich, bulk phase.
- Now consider the effects-of these potential conditions of a surfactant solution on its ability to function as a washing liquor, particularly in the context of laundering oily soils from fabrics in a washing machine. In this context, cleaning must be both thorough and rapid if a product is to be effective.
- Solutions containing a large proportion of monomeric surfactant species have long been selected by workers in the art for use in washing because they act much faster (under prior art conditions) than highly micellized solutions. This is graphically illustrated in Figure 5, in which plot A illustrates the performance of a surfactant with a CMC of 5 ppm (Neodol 45-7, which is described more fully below), and in which plot B illustrates the performance of a surfactant with a CMC of 200 ppm (Neodol 91-6, as further defined below). The concentration of each surfactant is equal, each surfactant has an HLB of about 11.5, and in each case the surfactant concentration is many times greater than the surfactant CMC. The test is conducted below the cloud point temperature of each washing liquor., Under these conditions each salution has a monomer concentration which is roughly the same as its CMC. As will be noted from Figure 5, the high CMC surfactant, with its high concentration of monomers, outperforms the low CMC surfactant for more than 15 minutes, which is a typical maximum length for the washing. cycle of a commercial laundering machine. Thus, the need for efficient. laundering has led the prior art to the choice of high CMC surfactants.
- It is known in the art that a .low CMC surfactant should exhibit better ultimate cleaning than a high CMC surfactant because the former surfactants are superior to the latter ones for reducing the interfacial tension between oil and water in a two-phase system. This means that low CMC surfactants should more efficiently solubilize or emulsify fatty soils. And as Figure 5 suggests, a low CMC surfactant does clean to a better end result, even under prior art conditions, if given enough time. Thus, what has been needed is a way to improve the rate of cleaning of'low CMC surfactants while retaining their thoroughness of cleaning.
- The inventors have found that by using low CMC surfactants in a washing-liquor maintained at a temperature substantially exceeding its cloud point temperature, so that the surfactant species coexist in a single bulk phase with water but are largely dehydrated, the rate of cleaning of low CMC surfactants is sufficiently increased that they clean better than high CMC surfactants. This surprising result is explained as follows.
- Under prior art conditions the micelles which predominate in solutions of low CMC surfactants migrate to sites of oily soil very slowly and/or do not quickly reorient themselves from their water-stable form, in which their hydrophilic heads are presented outward, to a'form in which their lipophilic tails are able to contact droplets of oily soils and solubilize or emulsify them. Under these prior art conditions a high CMC surfactant can clean more quickly because its high concentration of monomers travels quickly through solution to sites of oily soil. These monomers also do not need to reorient themselves into a less stable state to attach themselves to soils, for their lipophilic tails are constantly exposed.
- However, when washing is conducted at a temperature substantially in excess of the cloud point temperature (or, conversely, if the cloud point temperature of the solution is made lower than the washing temperature selected), the disadvantages of micelles as cleaning species are largely eliminated. This effect is believed to result because at a temperature somewhat above the cloud point temperature the surfactant species have just enough affinity for water to remain in a single bulk phase, and this largely .dehydrated surfactant species has little difficulty in solubilizing or emulsifying oily soils since the surfactant molecules apparently are more randomly oriented. Moreover, this surfactant species is believed to be transported by bulk transport to the sites of oily soils more rapidly than ordinary micelles, in contrast to prior art conditions which allow only monomeric species to participate in rapid cleaning, thus limiting the concentration of species available for cleaning to CMC, which is low for the preferred (low CMC) surfactants.
- The inventors have also ascertained an upper limit to washing temperatures which may be used if the benefits of the present invention are to be obtained. It has been found that the present invention should be practiced at a washing temperature which does not exceed the phase coalescence temperature of the washing liquor. (Or, to put it another way, the phase coalescence temperature must not be lowered to below the washing temperature selected.) This upper limit is probably observed because, while the surfactant will be delivered and mixed with oily soils more rapidly, it will not be removed at all because it is dehydrated and too hydrophobic to be a good solubilizing or emulsifying agent under these conditions. Methods not forming a part of the present invention must be employed to effectively clean fabrics with the two-phase surfactant/water system which exists when the washing temperature exceeds the phase coalescence temperature of the surfactant system in a washing liquor.
- In practicing the present invention washing is conducted at a temperature within a range given by the following expression:
- The following hypothetical example will illustrate the use of the above expressions to select washing temperatures for washing liquors having particular cloud point and phase coalescence temperatures.. Consider a washing liquor of the present invention with a cloud point temperature (A) of 40°C and a phase coalescence temperature (B) of 80°C. (These values would be determined for an actual washing liquor according to the procedure taught below, using a photo gonio diffusometer.) The broadest range of washing temperatures is calculated thus:
-
- In like fashion, the especially preferred temperature for use of the indicated washing liquor is calculated as follows:
- Figures 1 and 2 illustrate the importance of choosing a washing liquor with certain cloud point and phase coalescence temperatures in relation to the washing temperature in order to produce an optimum cleaning result.
- Figure I is a plot of cleaning performance (Hunter whiteness) versus temperature for a washing liquor with a cloud point of 36°C and a phase coalescence temperature of 71°C. As the graph illustrates, cleaning performance - continues to increase as the wash temperature is increased above the cloud point until the general area of the phase coalescence temperature is reached. Beyond this point, higher temperatures produce poorer performance.
- In Figure 2, plot A shows the washing performance at 60Q Celsius (measured as Hunter whiteness of fabrics washed by a standard method) of Neodol 45-7 (a surfactant comprising a primary fatty alcohol containing 14 to 15 carbon atoms condensed.with an average of 7 ethylene oxide moieties per molecule of surfactant commercially available from Shell Chemical Co., Industrial Chemicals Division) as a function of concentration of sodium sulfate -- an electrolyte which has no substantial function except to lower the phase coalescence and, cloud point temperatures of the system. The area between the dotted lines represents an unstable area because the phase coalescence temperature is near the washing temperature. Accurate experimental data in this area is impossible to obtain. On the same graph are plotted the cloud point and phase coalescence temperatures of the washing liquor (C and B, respectively) versus percentage sodium sulfate in the washing liquor, thus defining a series of systems which have the same surfactant and washing temperature but differing phase coalescence and cloud point temperatures. The cleaning test was run at a single temperature in order to eliminate the difference in cleaning which would be expected due to the choice of differing washing temperatures. Figure 2 is an example of altering the cloud point and phase coalescence temperature of a washing system by electrolyte addition. The maximum performance of the system occurs when the phase coalescence temperature is maintained slightly above the wash temperature (60°C).
- The washing liquors of the present invention are aqueous dispersions of a nonionic surfactant. The surfactant may be present in concentrations of from about 1400 ppm to about 20,000 ppm. If it is desirable to raise the cloud point and phase coalescence temperatures of the washing liquor in accordance with the teachings of the present invention, the washing liquor may include up to about 10% of an anionic surfactant. Alternatively, one or more nonionic surfactants having a high cloud point temperature may be added to the washing liquor to raise the net cloud point and phase coalescence temperatures of the system. In accordance with the teachings of the present invention, 700 to 10,000 ppm of a strong electrolyte are also added to the washing liquor and serve to lower the-cloud point and phase coalescence temperatures of the washing liquor. The cloud point and phase coalescence temperatures of the washing liquor may alternatively be lowered by adding a surfactant with a low cloud point temperature to the washing liquor to lower the net cloud point and phase coalescence temperatures of the system. Washing liquors of the present invention also include 500 to 10,000 ppm of a sequestering builder in order to improve their cleaning ability. Finally, many detergency adjuvants and other optional ingredients may be added to compositions within the scope of the present invention. In the text which follows, the selection of each of these ingredients is described in greater detail.
- The major essential ingredient of an aqueous washing liquor designed to practice the present invention is a surfactant.{or mixtures of surfactants) which has certain properties. The desired concentration of the- surfactant in the washing liquor is from about 1400 ppm to about 20,000 ppm. It will be noted that this concentration is at least 28 times the critical micelle concentration of the surfactant, which should be less than 50 ppm. Thus it will be apparent that the present invention teaches a very high concentration of surfactant compared to.its critical micelle concentration, in contrast to the prior art teaching that washing with surfactant concentrations substantially in excess of the critical micelle concentration of the system does not improve surfactant performance because the concentration of the surfactant in excess of its CMC is tied up in the form of micelle's..
- The first consideration in choosing a surfactant or mixture of surfactants for use in the present invention is that the primary surfactant should be a nonionic surfactant. Not only are nonionic surfactants the main category of surfactants which have HLB's within the range which is useful in the present invention, but in addition only a surfactant system consisting entirely or mostly of nonionic surfactants will exhibit a cloud point temperature and a phase coalescence temperature. Since the existence of these particular phase attributes of the washing liquor is essential to the definition of the present invention, it is important that the surfactant system primarily comprise nonionic surfactants.
- The second consideration in choosing a surfactant is its HLB. The choice of a surfactant with an optimized HLB is demonstrated in the plots of Figure 4, in which three washing systems are compared which differ only in the choice of a surfactant HLB. In this test, three nonionic surfactants were chosen, each of which is a condensate of a fatty alcohol and a chain of ethylene oxide moieties. The surfactant chosen for the HLB 8.2 plot (plot C) was an ethoxylation 'product of a primary fatty alcohol having 12 to 13 carbon atoms with an average of 3 ethylene oxide moieties per molecule of surfactant. The HLB 15.0 plot (plot B) depicts the performance of a nonionic surfactant comprising a condensate of primary fatty alcohols having 14 to 15 carbon atoms with an average of 7 ethylene oxide moieties per molecule of surfactant. The critical micelle concentrations of the nonionic surfactants were 10 ppm, 5 ppm, and 12 ppm, respectively. The performance of each of these surfactants was optimized for the washing temperature used (60° Celsius) by the addition of electrolytes as will be described hereinafter. As shown in Figure 4, which plots cleaning performance (measured as Hunter whiteness of fabrics washed with the respective solutions, which is determined as shown in Example 1 below) versus time in minutes, the surfactant with an HLB of 11.6 demonstrated better cleaning performance for all tested washing times than did the surfactant with an HLB of about 15 or the. surfactant with an HLB of about 8.2. This illustrates that optimum cleaning performance is obtained using a surfactant system with an HLB between 9.5 and 13. It will be noted that individual surfactants which have HLB's outside this range may be combined to form a surfactant system which has an HLB within the indicated range without departing from- the present-invention. Hereinafter the phrase "total surfactant hydrophilic/ lipophilic balance index" is used to denote that net HLB .of all surfactants in a system. Preferably the- total surfactants hydrophilic/lipophilic balance index lies in the range 9.75-12.5, most preferably in the range 10-12.
- The third consideration in choosing a surfactant or mixture of surfactants for use in the present invention is that the. surfactant should have a CMC which is below about 50 ppm. As is explained above, selection of a surfactant with a CMC which is must less than its in-use concentration, using the. particular washing temperatures of the present invention, improves the cleaning action of the surfactant. Example 2 below below also demonstrates that a low CMC surfactant displays superior cleaning when used in accordance with the teachings of the present invention.
- When a mixture of surfactants is selected as the surfactant component of a washing liquor which is to be used to practice the present invention, cloud point temperature and phase coalescence temperature values specified herein refer to properties of the washing liquor. The HLB and CMC of the surfactant system are essentially independent of the other components in the wash liquor. Consequently, HLB values for specific surfactants can be determined by methods known to those skilled in the art and CMC values can be measured in distilled water. The values of these parameters for a mixture of surfactants are determined as follows.
-
-
- . There is no simple relationship between the cloud point and phase coalescence temperatures of individual surfactants and of mixtures of surfactants. However, addition of a high cloud point surfactant to a surfactant solution with a lower cloud point will raise the cloud point of the solution, while addition of a low cloud point surfactant to a similar solution will lower its'cloud point. An analogous relation also holds true when the phase coalescence temperature of the system is to be adjusted. Thus, it will be a simple matter for a person skilled in the art to formulate a mixture of surfactants with the desired cloud point and phase coalescence temperatures.
- In the event that an anionic surfactant is to be included in the nonionic surfactant system to raise its cloud point and phase coalescence temperatures, an additional problem in formulation is raised because anionic detergents do not typically have a cloud point or phase coalescence temperature in aqueous solutions. This is the case because the temperature at which such a surfactant dispersion would exhibit these properties is greater than the boiling point of the aqueous dispersion at atmospheric pressure. A person skilled in the art of formulating detergents can resolve this difficulty by obtaining cloud point and phase coalescence temperatures of aqueous surfactant solutions which are subjected to a pressure exceeding their vapor pressure. This will then aid the formulator's initial estimate of the amount of the anionic surfactant which must be added in order to obtain the desired adjustment in the phase properties of the system.
- Following is a detailed description of specific nonionic surfactants which may be used to formulate surfactant systems when practicing the present invention.
- A first category of nonionic surfactants which are useful in the practice of the present invention are most broadly defined as ethoxylated aliphatic alcohols. These surfactants are the condensation products of a fatty alcohol with an ethoxylate chain comprising at least one ethoxylate moiety per molecule of surfactant, especially between about 1 and about 12 moles of ethoxylate moieties per molecule of surfactant for purposes of the present invention. Commercially available ethoxylated fatty alcohols generally contain between about 8 and about 22 carbon atoms in.their alcohol moiety, preferably 12 to 15 carbon atoms for the purpose of the, present invention.. Typical surfactants of this type have a. broad distribution of degrees of ethoxylation, since species having various ethoxylate chain lengths are difficult to separate, or even to identify, in the commercially available materials. Preferred ethoxylated alcohol surfactants for use in the present invention have an average of 5 to 8 moieties of ethylene oxide per molecule of surfactant, preferably an average of 7 moieties. When a degree of ethoxylation is specified hereinafter, it will be understood that this refers to the average number of ethoxylate moieties per molecule of surfactant.
- One commercial source of alcohol ethoxylates useful in the practice of the present invention is the Neodol series of surfactants, which are available from Shell Chemical Company, Industrial Chemicals 'Division. The Neodol surfactants are characterized by a low degree of branching in the alcohol chain; typically less than about 20% of the surfactant molecules are branched. Neodols are primary alcohol ethoxylates which each have a narrow and precisely indicated range of alcohol chain lengths, but a large variation in the degree of ethoxylation in a given molecule; the average number of ethoxylate groups per molecule is provided for the surfactants. An example of how Neodols are named is Neodol 45-7, which is a condensate of a 14 to 15 carbon fatty alcohol with an average of 7 ethylene oxide moieties per molecule of surfactant. Another example is Neodol 91-6, which comprises the condensate of a 9 to 11 carbon fatty alcohol with an average of 6-ethylene oxide moieties per molecule of surfactant.
- Specific examples of Neodol surfactants which are useful in practicing the present invention are as follows: Neodol 45-7, 45-15, 23-6.5, or 25-7; a mixture of 75% Neodol 25-5 and 25% Neodol 45-7; a mixture of 50% Neodol 25-7 and 50% Neodol 45-7; a mixture of 50% Neodol 91-6 and 50% Neodol 45-7; and so forth. (Some of these surfactants are useful only in conjunction with other ingredients. Formulation of such mixtures is explained elsewhere in this specification.).
- Another commercial source of ethoxylated fatty alcohols is the Tergitol series of surfactants which are commercially available from Union Carbide Corporation. Tergitols are alcohol ethoxylates, and may be divided into S Tergitols and L Tergitols. The former are relatively unbranched secondary alcohols, while the latter are primary alcohols having a high numerical percentage of branched species. (About 40% of the alcohol moieties of L Tergitols are branched, while a lower percentage of the alcohol moieties of S Tergitols are branched.) In commercially supplied Tergitols, the range of ethoxylation for a given surfactant is somewhat narrower than is observed in the Neodols. The Tergitols are named in a manner analogous to the naming of Neodols, except that the name contains an upper case "S" or "L" interposed between the numerals indicating alcohol chain length and the numeral indicating degree of ethoxylation. Specific examples of Tergitol surfactants which are useful in the practice of the pre-sent invention are Tergitols 15-S-3, 15-S-5, 15-S-7, 15-S-9, 25-L-3, 25-L-5, 25-L-7, or 25-L-9. (Again, some of these surfactants must be combined with other ingredients as disclosed herein in order to be useful in the practice of the present invention.)
- A second major category of nonionic surfactants which are useful in the practice of the present invention is that of the alkyl phenol ethoxylates. The structure of these surfactants is that of benzene with two substituents in para relationship. The first substituent is an alkyl moiety with a chain length of 7 to 12 carbon atoms, preferably 8 to 9 carbon atoms for purposes of the present invention. The second substituent is an ethoxylation chain. The alkyl phenol ethoxylates have an ethylene oxide substitution level which varies widely for a given surfactant. The degree of ethoxylation in such surfactants is essentially from 1 to 12 ethylene oxide moieties per molecule of surfactant; an average of 7 ethylene oxide moieties per molecule of surfactant is preferred for use in this invention.
- Specific alkylphenol ethoxylates which are useful in the practice of the present invention are the Igepal surfactants manufactured by General Aniline and Film Corporation. The Igepal surfactants are designated by two upper case letters followed by a numeral or series of numerals; the lettered prefix "CA" indicates an octyl radical as the alkyl moiety of the surfactant, while the lettered prefix "CO" indicates a nonyl radical as the alkyl moiety. The inventors are not aware of any connection between the numerals designating species of this class of surfactants-and the structures thereof. A specific example of an Igepal surfactant useful in the practice of the present invention is Igepal CO-610.
- A third broad class of nonionic surfactants which are useful in the practice of the present invention are the condensation products of a chain of ethylene oxide moieties with a hydrophobic base formed by the condensation of a chain of propylene oxide moieties with propylene glycol, known hereinafter as ethylene oxide/propylene oxide block copolymers.
- One commercially available series of ethylcne oxidc/propylenc oxide block capolymers is the PLURONIC (trademark) Series marketed by BASF Wyandotte Corporation. The Pluronics are named using a letter prefix (L for a liquid, P for a paste, and F for a flaked or solid composition) and a two to three digit suffix, .the first digit or two defining a molecular weight range and the final digit defining the percent of ethylene oxide in the surfactant, divided by 10. The molecular weight corresponding to the first digits in the surfactant name is indicated in Table I which follows:
- A specific example of a Pluronic surfactant which is useful in the present invention is Pluronic L-43, which is a liquid composition with a hydrophobic portion molecular weight of 1200 and 30% by composition weight of ethylene oxide.
- While certain nonionic surfactants have been indicated as preferred,.the invention may be practiced using any of a broad selection of nonionic surfactants, several additional examples of which follow. One additional example of such a surfactant is a polyoxyethylene ester of a fatty acid, such as Stearox CD, which is marketed by the Monsanto Company. Another example is the Triton series of nonionic alkyl phenol surfactants, marketed by Rohm and haas Company. Other nonionics which are useful in the present invention are the polyoxyethylene mercaptan analogs of the alcohol ethoxylates, such as Nonic 218 and Stearox SK which are manufactured by the Monsanto Company. Other examples of nonionic surfactants are polyoxyethylene adducts of alkyl amines, such as the Ethoduomeen and Ethomeen surfactants marketed by.Armak Company. Polyoxyethylene alkyl amides may also be used in the practice of this invention. Another category of nonionic surfactants is the sorbitan esters, such as sorbitan monolaurate. Finally, the Surfonic surfactants manufactured by Jefferson Chemical Company, Inc., such as Surfonic N-95, which is an alcohol phenol ethoxylate, may be used in the practice of the present invention. This list of nonionic surfactants is not exhaustive, and it is contemplated that routine experimentation will result in the location of other surfactants which may be used to practice the present method invention.
- Table II below contains HLB, CMC, cloud point, and phase coalescence temperature data for a variety of aqueous solutions of pure commercial surfactants. With the aid of this table, a person skilled in the art may formulate a wide variety of washing liquors which are useful for laundering fabrics. (In the table which follows, TAE11 is a primary fatty alcohol ethoxylate surfactant having a predominance of alcohol chain lengths of about 14 to 18 carbon atoms and an average of 11 ethoxylate moieties per molecule of surfactant; TAE9 is a similar surfactant, but is substituted with an average of 9 ethoxylate moieties per molecule of surfactant; STP is sodium tripolyphosphate; LAS is a linear alkylate sulfonate surfactant comprising benzene, substituted by a sulfonate group and a C12 alkylate group in para orientation; and Na2C03 is sodium carbonate.)
- The cloud point temperatures and phase coalescence temperatures of Table II were measured on a photo gonio diffusometer made by SOFICA (Model 42.000). The index vat of the above apparatus contained Dow Corning 702 Silicone fluid and the temperature range of the instrument was 30°C. to 100°C. The photo detection unit of the instrument was positioned at an angle of 90° with respect to the incoming light beam. Samples of each surfactant were prepared at a concentration of 3,000 ppm using laboratory distilled water. No other special treatment was used to reduce interfering impurity particles. A green instrument filter and'no polarizing filter were used, and the instrument's variable slit was adjusted for appropriate base intensity starting light scattering measurements. To obtain the cloud point and phase coalescence temperatures, the samples were heated at the rate of approximately 1/2° Celsius per minute using a variable voltage transformer. The cloud point temperature was determined as the initial temperature at which the light scatter reading deviated from the base light scatter, indicating a sharp increase in light scattering due to the formation of nuclei of sufficient size to scatter light. The phase coalescence temperature was interpreted to be the temperature at which the light scattering returned to the base line scatter after having increased to the maximum. This represents a temperature at which the solution separates into two bulk phases, each of which is much less cloudy than the mixture before separation of aqueous and surfactant phases. The CMC's of Table II were. determined in distilled water at 25°C.
Cloud Point/Phase Coalescence Temperature Adjustment - Given that the optimum washing conditions for a given surfactant are confined to a narrow temperature range, it is highly desirable to enable the practitioner to vary the cloud point and phase coalescence temperatures of a given surfactant system in order to formulate a composition containing a desired nonionic surfactant to be used at a selected washing temperature. This is highly desirable because certain washing temperatures are highly preferred in the art for washing certain types of fabrics and for removing particular soils.
- In the.event that a nonionic surfactant has relatively low cloud point and phase coalescence temperatures, so that the temperature for washing in accordance with the teaching of the invention is lower than the- desired washing temperature for given fabric and soil - conditions, small amounts of an anionic detergent may be incorporated into a surfactant system which contains a major amount of the nonionic surfactant in order to substantially raise the cloud point and phase coalescence temperatures of the system. It will be noted, however, that the percentage of total surfactant content supplied by an anionic surfactant should not exceed about 10% of the surfactant system to avoid creating a surfactant system which does not have a cloud point or phase coale- scene temperature. In such systems the anionic surfactant preferably comprises 0.5% to 5% of the composition.
- One typical anionic surfactant which may be used to raise the cloud point and phase coalescence temperatures of the washing liquors is a linear alkylate sulfonate (LAS), which is benzene substituted with an alkylate moiety and a sulfonate moiety in para relation. An especially preferred LAS has a dodecanate group as its alkylate moiety and is typically referred to in the art as C12 LAS. Another type of anionic surfactant which may be used for this purpose-is an alkylate ethoxylate sulfate (AES) comprising an alkyl moiety, to which is attached an ethoxylate chain, to which in turn is attached a sulfate moiety. One typical AES surfactant has a dodecyl.group as its alkyl moiety and a six-unit ethoxylate chain. A third type of anionic surfactant which may be used to raise the cloud point and phase coalescence temperatures of a nonionic surfactant system is a tallow alkyl sulfate (TAS) surfactant. This surfactant contains alkyl moieties having a range of carbon chain lengths, predominantly alkyl moieties having from about 14 to about 18 carbon atoms.
- 'For the nonionic surfactants described above which have been found to be most useful for washing, it is typically necessary to lower the phase coalescence temperature and cloud point temperature of the surfactant system in order to produce a composition which is useful for washing at temperatures which are preferred in the art. This is especially true given the recent tendency in the art to prefer lower washing temperatures in order to save energy in the laundering process. A highly preferred way to lower the optimum washing temperature of a washing liquor to a preferred value is to add to the surfactant system any of a wide variety of strong electrolytes.
- It will be appreciate by those skilled in the art of formulating nonionic surfactant compositions that the addition of nearly any strong electrolyte to a system containing a nonionic surfactant will lower the cloud point of the surfactant system, as well as the phase coalescence temperature. Just a very few examples of appropriate electrolytes are the water-soluble chemical compounds of an anion selected from chloride, bromide, silicate, orthosilicate, metasilicate, orthophosphate, sulfate, carbonate, nitrate, fluoride, acetate, hydroxide, citrate, and others, and a cation selected from sodium, potassium, lithium, calcium, magnesium and hydrogen. This list is by no means exhaustive, and those skilled in the art will easily select any of a wide variety of strong electrolytes, depending on the availability of particular salts and other factors. Preferred electrolytes are those which supply some alkalinity to the washing medium, although a high degree of alkalinity is not.necessary to the practice of the present invention. Of the electrolytes noted above, the sodium salts are highly preferred as strong electrolytes because they are highly soluble and inexpensive, and of those sodium salts sodium carbonate and sodium metasilicate are the most pre- - ferred strong electrolytes in the practice of the present invention. Typically the amount of a strong electrolyte which must be added to the washing liquor to optimize the cloud point and micelle inversion temperatures will lie between about 700 ppm and 20,000 ppm...
- Figure 3 is a plot of cleaning performance (Hunter whiteness) versus wash time-for two washing liquors. Plot "A" is for a washing liquor containing Neodol 45-7 and a strong electrolyte (sodium sulfate) to optimize its performance at the washing temperature used. Plot B is for the same washing liquor and washing temperature, but excluding the electrolyte. As indicated in Figure 3, for any of the wash times tested the washing liquor containing an electrolyte produces superior washing results. This result is obtained because the washing liquor which did not contain a strong electrolyte had cloud point and phase coalescence temperatures which placed the washing composition and conditions outside the scope of the present invention, while the washing liquor containing a strong electrolyte had lowered phase coalescence and cloud point temperatures which placed the identical washing composition and conditions within the scope of the present invention.
- While washing liquors containing a nonionic surfactant and having particular cloud point and phase coalescence temperatures are useful in themselves for laundering fabrics, their effect is improved by adding thereto about 500 ppm to 10,000 ppm of a sequestering builder.
- A wide variety of sequestering detergency builders is known in the art. A number of these are conveniently described as compounds of a cation selected from sodium, potassium, lithium, or hydrogen, and an anion selected from tripolyphosphate, pyrophosphate, orthophosphate, nitrilotriacetate, ethylene diamine tetraacetate, nitrilotrimethylenephosphonate, and ethylene diamine tetra- methylenephosphonate. It will also be noted that some ingredients. which act as strong electrolytes may also. be useful, as. sequestering detergency builders, for example, orthophosphates. However, the best sequestering builders are only modestly electrolytic at the concentration typically used in a detergent. Especially preferred sequestering builder salts for incorporation in washing liquors of the present invention are any of the polyphosphate builders known to the art, particularly alkali metal tripolyphosphates and pyrophosphates such as sodium tripolyphosphate or tetrasodium pyrophosphate.
- These sequestering builders are widely recognized in the art as important additives for laundry detergents. These builders have traditionally been thought to be primarily useful to prevent water hardness cations from interacting with soaps or anionic detergents to form an insoluble precipitate or soap scum. However, such sequestering builders are also known to provide cleaning benefits to washing liquors containing only nonionic surfactants,-which do not interact with water hardness ions. The sequestering builders prevent water hardness ions such as calcium and magnesium from interacting with fatty soils to form insoluble precipitates. The sequestering builders also sequester other metal ions such as copper and iron ions which can interfere with the action of the bleaching agents which are frequently used in conjunction with laundry detergents. Several of the sequestering builders also peptize clay soils by replacing various cations in the insoluble clays with sodium cations or the like, rendering the clays somewhat soluble in the washing liquor. Finally, these builders have utility as soil suspending agents.
- Commercially useful detergent compositions for laundering fabrics are typically sold as concentrated formulas which are diluted in water by the user in order to produce the desired aqueous washing liquor. What follows is a specific description of washing compositions which may be diluted in water to form washing liquors within the definition of the present method invention.
- The following ingredients may be combined in the indicated proportions to produce compositions which may be diluted in water to produce washing compositions useful to practice the present invention:
- (a) from 10% to 78% of a nonionic surfactant;
- (b) from 4% to 70% of an electrolyte; and
- (c) from 3% to 55% of a detergency builder salt.
- Such compositions may be dissolved in water to form a solution which contains from about 1000 to 40,000 ppm (0.10% to 4.0%) of the composition.
- The following compositions contain preferred proportions of specific ingredients. They may be diluted in the proportions noted above to form washing liquors:
- (a) 20% to 51% of an alkali metal tripolyphosphate;
- (b) 24% to 40% of an alkali metal carbonate; and
- (c) 20% to 51% of the condensate of a fatty alcohol having 12 to 15 carbon atoms with an average of about 5 to about 8 ethoxylate moieties per molecule of surfactant; or;
- (a) 20% to 40% of an alkali metal pyrophosphate;
- (b) 25% to 40% of an alkali metal carbonate; and
- (c) 20% to 55%· of the condensate of a fatty alcohol having 12 to 15 carbon atoms with an average of about 5 to about 8 ethoxylate moieties per molecule of surfactant.
- In addition, the following compositions are specifically formulated for optimal washing in the concentrations specified above at a temperature of about 140°F (60° Celsius):
- (a) about 36% sodium tripolyphosphate;
- (b) about 35% sodium carbonate; and
- (c) about 29% of the condensate of a primary fatty alcohol having 14 to 15 carbon atoms with an average of about 7 ethylene oxide moieties per molecule (Neodol 45-7).; or
- (a) about 31% tetrasodium pyrophosphate;
- (b) about 34 sodium carbonate; and
- (c) about 34.4% of the condensate of a primary fatty alcohol having 14 to 15 carbon atoms with an average of about 7 ethylene oxide moieties per molecule of surfactant (Neodol 45-7).
- Finally a composition designed to employ a mixed surfactant system comprises:
- (a) 10%-40% preferably 15%-35% of a mixture of a C12 -C15 fatty alcohol condensed with an average of 6-7 moles of ethylene oxide per mole of alcohol and a C12-C15 primary alcohol condensed with an average of three moles of ethylene oxide per mole of alcohol.
- (b) 50%-70% preferably 55% to 65% of a strong electrolyte selected from sodium carbonate sodium metasilicate and.mixtures thereof.
- (c) 10%-25% preferably 12%-15% of sodium tripolyphosphate and
- - (d) from 0.5% to 5% of an anionic surfactant selected from sodium C12 alkyl benzene sulphonate sodium dodecyl hexaethoxy sulphate, sodium tallowalkyl sulphate and mixtures thereof.
- In addition to the cleaning benefits of formulations which may be used to practice the present invention, they may be used to wash effectively at a relatively low pH. Typical washing liquors used in industrial laundries arts are highly alkaline, having an pH substantially in excess of 11.5. Such pH's are essential in conventional industrial laundry detergents in order to saponify oily soils and thus increase their solubility in the washing liquor.
- A number of preferred compositions of the present invention are desirably formulated to have a pH of 11 or less, particularly from about 7 to about 11. This is possible because the cleaning ability of the compositions disclosed herein has been found to be relatively insensitive to pH. While a high pH cleaning composition may easily be formulated in accordance with the present invention (for example, a composition which provides a washing liquor pH greater than 11.5), no substantial cleaning benefit is found to result from the selection of a high pH. The compositions of the present invention are able to solubilize or emulsify oil quite effectively without relying on saponification.
- The compositions may be assembled in any of the ways known to the art to form commercial preparations which are suitable for sale.
- The following examples do not limit the scope of the present invention, which is defined by the claims concluding this specification. Rather, these examples illustrate the practice of the invention under con- trolled cbnditions. In these examples "Na2C03" is sodium carbonate, "Na2SO4" is sodium sulfate, "STP" is sodium tripolyphosphate, "TSPP" is tetrasodium pyrophosphate, the Neodol surfactants are certain primary fatty alcohol ethoxylates, as characterized above, and "TAE9" is a primary fatty alcohol ethoxylate having apredominance of alcohol chain lengths in the range of from 14 to 18 carbon atoms and an average of 9 ethoxylate moieties per molecule of surfactant. Where dextrin is present it functions as a binder and does I not substantially affect the performance of compositions containing it.
- A series of 65% polyester/35% cotton swatches with a permanent press finish were soiled with used motor oil obtained from automobile crankcases. These swatches were washed for 20 minutes in a Tergotometer, Model 7243, at 60°C in soft.water with the compositions listed below. Octadecane at a level of 300 ppm was added to the wash solutiow to simulate extra soil in the system. The temperature of each washing liquor was within the range of the present invention. The washed swatches were rinsed for 10 seconds in cold water and dried, and Hunter whiteness measurements were made using a Hunter Laboratories Color/Difference Meter (Model D25D2). (This instrument provides a direct readout of Hunter whiteness.)
- The HLB ranges of Compositions B and C were outside the temperature range required for the present invention, while Composition A had an HLB range within the invention and demonstrated superior performance.
- A series of stains were cut from discarded, naturally soiled industrial uniforms: These stains were split into equally soiled parts; each part was washed with one of the compositions listed below. The stains were washed in a 35 lb. Milnor washer/extractor with 18.5 lbs. of industrial uniform shirts soiled with 1.5 1b. of used motor oil. A wash temperature of 60°C was used. After washing, the stained parts were placed back together and graded visually. in a paired comparison manner by a panel of 3 judges using a 0-4 scale. A grade of "0" indicated no difference between the paired swatches; a grade of "1" indicated a perceived difference between the swatches; a grade of "2" indicated a clear difference between the swatches; a grade of "3" indicated a large difference between the swatches; and a grade of "4" indicated a very large difference between the swatches. These grades were statistically combined to produce Paired Comparison Grades, which represent_the difference in cleaning performance for a given composition (positive for an improvement) with respect to the inferior composition.
- The CMC of Composition B was outside the range required by the present invention. The process used with Composition A was within the scope of the present invention and demonstrated superior performance.
-
- The process using Composition B was outside the claims of this invention, for the wash temperature (60°C) exceeded the phase coalescence temperature of the washing liquor. The process used with Composition A is within the claims and produces superior performance.
-
- The process using Composition B is outside the claims of this invention because the wash temperature used was below the cloud point temperature of Composition B. The process used with Composition A was within the claims of this invention and produced superior performance, even though Composition A was substantially more dilute and had a much lower pH than Composition B.
-
- Composition B is outside the more preferred composition range claimed in this invention due to its high Na2CO3 level. Composition A is near the center of the range and produces superior performance. The 60°C wash temperature was within the temperature range of the present invention for each composition.
-
- Composition B is outside the more preferred composition range claimed in this invention due to its low Na2CO3 level. Composition A is near the center of the range and produces superior performance. Again, the 60°C washing temperature for each composition was within the temperature range of the present invention.
and an especially.preferred temperature for practice of the present invention is given by the expression:
Such compositions may be dissolved in water to. form a solution which contains from about 1000 ppm to 40,000 ppm (0.10% to 4.0%) of the composition.
Claims (10)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US1604879A | 1979-02-28 | 1979-02-28 | |
US16048 | 1993-02-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0015887A1 true EP0015887A1 (en) | 1980-09-17 |
EP0015887B1 EP0015887B1 (en) | 1985-05-08 |
Family
ID=21775101
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80870013A Expired EP0015887B1 (en) | 1979-02-28 | 1980-02-27 | Improved laundering method |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0015887B1 (en) |
JP (1) | JPS55152862A (en) |
CA (1) | CA1140832A (en) |
DE (1) | DE3070609D1 (en) |
ES (1) | ES8103218A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2309226A (en) * | 1996-01-22 | 1997-07-23 | Procter & Gamble | Phase separated detergent composition |
CN1037912C (en) * | 1993-03-01 | 1998-04-01 | 上海锦华科技开发公司 | Emulsive dirt detergent and its prepn. |
EP2625256B1 (en) * | 2010-10-08 | 2017-11-22 | Ecolab USA Inc. | Laundry detergent composition for low temperature washing and disinfection |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2878286T3 (en) | 2016-10-31 | 2021-11-18 | Sabic Global Technologies Bv | Formula for superior detergency and anti-redeposition benefit |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB716641A (en) * | 1951-04-06 | 1954-10-13 | Salkin Nicolas | Method of scouring suint wool |
GB1489694A (en) * | 1974-01-28 | 1977-10-26 | Procter & Gamble | Nonionic detergent composition |
GB1495145A (en) * | 1974-04-11 | 1977-12-14 | Procter & Gamble | Controlled sudsing detergent compositions |
GB1495146A (en) * | 1974-04-11 | 1977-12-14 | Procter & Gamble | Controlled sudsing detergent compositions |
-
1980
- 1980-02-26 CA CA000346491A patent/CA1140832A/en not_active Expired
- 1980-02-27 EP EP80870013A patent/EP0015887B1/en not_active Expired
- 1980-02-27 DE DE8080870013T patent/DE3070609D1/en not_active Expired
- 1980-02-28 JP JP2461980A patent/JPS55152862A/en active Pending
- 1980-02-28 ES ES489015A patent/ES8103218A1/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB716641A (en) * | 1951-04-06 | 1954-10-13 | Salkin Nicolas | Method of scouring suint wool |
GB1489694A (en) * | 1974-01-28 | 1977-10-26 | Procter & Gamble | Nonionic detergent composition |
GB1495145A (en) * | 1974-04-11 | 1977-12-14 | Procter & Gamble | Controlled sudsing detergent compositions |
GB1495146A (en) * | 1974-04-11 | 1977-12-14 | Procter & Gamble | Controlled sudsing detergent compositions |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1037912C (en) * | 1993-03-01 | 1998-04-01 | 上海锦华科技开发公司 | Emulsive dirt detergent and its prepn. |
GB2309226A (en) * | 1996-01-22 | 1997-07-23 | Procter & Gamble | Phase separated detergent composition |
US5883065A (en) * | 1996-01-22 | 1999-03-16 | The Procter & Gamble Company | Phase separated detergent composition |
EP2625256B1 (en) * | 2010-10-08 | 2017-11-22 | Ecolab USA Inc. | Laundry detergent composition for low temperature washing and disinfection |
Also Published As
Publication number | Publication date |
---|---|
ES489015A0 (en) | 1981-02-16 |
EP0015887B1 (en) | 1985-05-08 |
CA1140832A (en) | 1983-02-08 |
JPS55152862A (en) | 1980-11-28 |
ES8103218A1 (en) | 1981-02-16 |
DE3070609D1 (en) | 1985-06-13 |
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