EP0170091A1 - Compositions détergentes liquides - Google Patents
Compositions détergentes liquides Download PDFInfo
- Publication number
- EP0170091A1 EP0170091A1 EP85108260A EP85108260A EP0170091A1 EP 0170091 A1 EP0170091 A1 EP 0170091A1 EP 85108260 A EP85108260 A EP 85108260A EP 85108260 A EP85108260 A EP 85108260A EP 0170091 A1 EP0170091 A1 EP 0170091A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- weight
- composition according
- builder
- sodium
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 406
- 239000003599 detergent Substances 0.000 title claims abstract description 83
- 239000007788 liquid Substances 0.000 title claims description 47
- 239000004094 surface-active agent Substances 0.000 claims abstract description 111
- 239000012071 phase Substances 0.000 claims abstract description 73
- 239000007787 solid Substances 0.000 claims abstract description 72
- 239000003792 electrolyte Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000004615 ingredient Substances 0.000 claims abstract description 42
- 239000012530 fluid Substances 0.000 claims abstract description 22
- 238000009472 formulation Methods 0.000 claims description 111
- -1 ions alkali metal Chemical class 0.000 claims description 84
- 239000004480 active ingredient Substances 0.000 claims description 58
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 33
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 30
- 239000003945 anionic surfactant Substances 0.000 claims description 28
- 239000011734 sodium Substances 0.000 claims description 27
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 26
- 229910052708 sodium Inorganic materials 0.000 claims description 26
- 239000002736 nonionic surfactant Substances 0.000 claims description 25
- 239000000344 soap Substances 0.000 claims description 25
- 125000000129 anionic group Chemical group 0.000 claims description 21
- 229910019142 PO4 Inorganic materials 0.000 claims description 20
- 239000008346 aqueous phase Substances 0.000 claims description 20
- 235000021317 phosphate Nutrition 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000004115 Sodium Silicate Substances 0.000 claims description 17
- 230000003287 optical effect Effects 0.000 claims description 17
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- 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 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 13
- 239000010452 phosphate Substances 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 239000004665 cationic fabric softener Substances 0.000 claims description 12
- 238000004062 sedimentation Methods 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 102000004190 Enzymes Human genes 0.000 claims description 8
- 108090000790 Enzymes Proteins 0.000 claims description 8
- 238000005282 brightening Methods 0.000 claims description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 8
- 150000004760 silicates Chemical class 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 5
- 239000000975 dye Substances 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- YHGREDQDBYVEOS-UHFFFAOYSA-N [acetyloxy-[2-(diacetyloxyamino)ethyl]amino] acetate Chemical class CC(=O)ON(OC(C)=O)CCN(OC(C)=O)OC(C)=O YHGREDQDBYVEOS-UHFFFAOYSA-N 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021647 smectite Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 2
- 238000010936 aqueous wash Methods 0.000 claims description 2
- UZABCLFSICXBCM-UHFFFAOYSA-N ethoxy hydrogen sulfate Chemical compound CCOOS(O)(=O)=O UZABCLFSICXBCM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 4
- YNDGLMYLSGEDHX-UHFFFAOYSA-N 1,2,4,3-trioxathiane 3,3-dioxide Chemical compound O=S1(=O)OCCOO1 YNDGLMYLSGEDHX-UHFFFAOYSA-N 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 1
- 150000005215 alkyl ethers Chemical class 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 31
- 239000007791 liquid phase Substances 0.000 abstract description 11
- 230000005484 gravity Effects 0.000 abstract description 2
- 239000006260 foam Substances 0.000 description 43
- 239000000843 powder Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 239000003381 stabilizer Substances 0.000 description 18
- 239000000725 suspension Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000003966 growth inhibitor Substances 0.000 description 14
- 125000003342 alkenyl group Chemical group 0.000 description 13
- 230000000994 depressogenic effect Effects 0.000 description 12
- 239000003112 inhibitor Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 238000005054 agglomeration Methods 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000005187 foaming Methods 0.000 description 10
- 239000003752 hydrotrope Substances 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 9
- 239000000499 gel Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 8
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 8
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 8
- QZXSMBBFBXPQHI-UHFFFAOYSA-N N-(dodecanoyl)ethanolamine Chemical compound CCCCCCCCCCCC(=O)NCCO QZXSMBBFBXPQHI-UHFFFAOYSA-N 0.000 description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- 238000013459 approach Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000013049 sediment Substances 0.000 description 7
- 159000000000 sodium salts Chemical class 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000003019 stabilising effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 6
- 125000002252 acyl group Chemical group 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 5
- 239000000872 buffer Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- GBFLZEXEOZUWRN-VKHMYHEASA-N S-carboxymethyl-L-cysteine Chemical compound OC(=O)[C@@H](N)CSCC(O)=O GBFLZEXEOZUWRN-VKHMYHEASA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000002304 perfume Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001493 electron microscopy Methods 0.000 description 3
- 239000002979 fabric softener Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001683 neutron diffraction Methods 0.000 description 3
- 238000001956 neutron scattering Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000009974 thixotropic effect Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- 239000004117 Lignosulphonate Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229920002323 Silicone foam Polymers 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229940105329 carboxymethylcellulose Drugs 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000004851 dishwashing Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 150000002462 imidazolines Chemical class 0.000 description 2
- 235000019357 lignosulphonate Nutrition 0.000 description 2
- 239000012669 liquid formulation Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 125000005341 metaphosphate group Chemical group 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000013514 silicone foam Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 230000007704 transition Effects 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
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- QSUHIERZZQYNPA-UHFFFAOYSA-N 1-dodecyl-2,3-dimethylbenzene;sodium Chemical compound [Na].CCCCCCCCCCCCC1=CC=CC(C)=C1C QSUHIERZZQYNPA-UHFFFAOYSA-N 0.000 description 1
- QSBUNJDGFZLSTQ-UHFFFAOYSA-N 2-(4-phenyltriazol-2-yl)-6-[2-(2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=CC(N2N=C(C=N2)C=2C=CC=CC=2)=C1S(O)(=O)=O QSBUNJDGFZLSTQ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- YRPYTFXEHXXYQW-UHFFFAOYSA-N 2-ethenyl-1h-benzimidazole Chemical group C1=CC=C2NC(C=C)=NC2=C1 YRPYTFXEHXXYQW-UHFFFAOYSA-N 0.000 description 1
- LANDRZNMJOEVQO-UHFFFAOYSA-N 3-ethenoxypropane-1,2-diol Chemical group OCC(O)COC=C LANDRZNMJOEVQO-UHFFFAOYSA-N 0.000 description 1
- BCFOOQRXUXKJCL-UHFFFAOYSA-N 4-amino-4-oxo-2-sulfobutanoic acid Chemical class NC(=O)CC(C(O)=O)S(O)(=O)=O BCFOOQRXUXKJCL-UHFFFAOYSA-N 0.000 description 1
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 1
- VKRZNAWSCAUDRQ-UHFFFAOYSA-N 5-methyl-2-[2-(5-methyl-1,3-benzoxazol-2-yl)ethenyl]-1,3-benzoxazole Chemical group CC1=CC=C2OC(C=CC=3OC4=CC=C(C=C4N=3)C)=NC2=C1 VKRZNAWSCAUDRQ-UHFFFAOYSA-N 0.000 description 1
- GZEYLLPOQRZUDF-UHFFFAOYSA-N 7-(dimethylamino)-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(N(C)C)=CC=C21 GZEYLLPOQRZUDF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 244000291564 Allium cepa Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 241000282994 Cervidae Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 241001527806 Iti Species 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- CBSOFSBFHDQRLV-UHFFFAOYSA-N N-methylbenzylamine hydrochloride Chemical compound [Cl-].C[NH2+]CC1=CC=CC=C1 CBSOFSBFHDQRLV-UHFFFAOYSA-N 0.000 description 1
- RONMCPWSECSNGE-UHFFFAOYSA-N N.CCCCCCCCCCCCOS(=O)(=O)OOCC Chemical compound N.CCCCCCCCCCCCOS(=O)(=O)OOCC RONMCPWSECSNGE-UHFFFAOYSA-N 0.000 description 1
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical class O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- WFRXSOIFNFJAFL-UHFFFAOYSA-N P1(OCCCCO1)=O.C(CN)N Chemical class P1(OCCCCO1)=O.C(CN)N WFRXSOIFNFJAFL-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-H [oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O YDHWWBZFRZWVHO-UHFFFAOYSA-H 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- VJHCJDRQFCCTHL-UHFFFAOYSA-N acetic acid 2,3,4,5,6-pentahydroxyhexanal Chemical compound CC(O)=O.OCC(O)C(O)C(O)C(O)C=O VJHCJDRQFCCTHL-UHFFFAOYSA-N 0.000 description 1
- LBZXFVVTQURNLY-UHFFFAOYSA-N acetic acid nitrous acid Chemical class C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.N(=O)O LBZXFVVTQURNLY-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005501 benzalkonium group Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- PMPJQLCPEQFEJW-HPKCLRQXSA-L disodium;2-[(e)-2-[4-[4-[(e)-2-(2-sulfonatophenyl)ethenyl]phenyl]phenyl]ethenyl]benzenesulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC=C1\C=C\C1=CC=C(C=2C=CC(\C=C\C=3C(=CC=CC=3)S([O-])(=O)=O)=CC=2)C=C1 PMPJQLCPEQFEJW-HPKCLRQXSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical class CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 150000002190 fatty acyls Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical class OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- QUFIXTQDTDCCLJ-UHFFFAOYSA-N methyl naphthalene-1-sulfonate Chemical class C1=CC=C2C(S(=O)(=O)OC)=CC=CC2=C1 QUFIXTQDTDCCLJ-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002942 palmitic acid derivatives Chemical class 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- NIXKBAZVOQAHGC-UHFFFAOYSA-N phenylmethanesulfonic acid Chemical class OS(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- SVMNBAVEQLDZNO-UHFFFAOYSA-M potassium;2-hexadecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O SVMNBAVEQLDZNO-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002797 proteolythic effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Chemical class 0.000 description 1
- 229920005989 resin Chemical class 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001998 small-angle neutron scattering Methods 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical class OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical class [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0017—Multi-phase liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
Definitions
- builder is sometimes used loosely in the detergent art to include any non-surfactant whose presence in a detergent formulation enhances the cleaning effect of the formulation. More usually, however, the term is restricted to those typical "builders”, which are primarily useful as a means of preventing or ameliorating the adverse effects on washing of calcium and magnesium ions e.g. by chelation, sequestering, precipitation or absorption of the ions, and secondarily as a source of alkalinity and buffering.
- the term “Buil der” is used herein in the latter sense, and refers to additives which ameliorate the aforesaid adverse effects to a substantial extent.
- It includes sodium or potassium tripolyphosphate and other phosphate and condensed phosphate salts such as sodium or potassium orthophosphates, pyrophosphates, metaphosphates or tetraphosphate, as well as phosphonates such as acetodiphosphonates, amino tris methylene phosphonates and ethylenediamine tetramethylene phosphonates. It also includes alkali metal carbonates, zeolites and such organic sequestrants as salts of nitrilotriacetic acid, citric acid and ethylene diamine tetracetic acid, polymeric polycarboxylic acids such as polyacrylates and maleic anhydride based copolymers.
- phosphate and condensed phosphate salts such as sodium or potassium orthophosphates, pyrophosphates, metaphosphates or tetraphosphate, as well as phosphonates such as acetodiphosphonates, amino tris methylene phosphonates and ethylenediamine t
- Builder is used herein to include water soluble alkali metal silicates such as sodium silicate, but excludes additives such as carboxymethyl cellulose, or polyvinyl pyrrolidone whose function is primarily that of soil suspending or anti-redeposition agent.
- Electrode is used herein to denote those water soluble ionic compounds which dissociate at least partially in aqueous solution to provide ions, and which tend to lower the solubility or micellar concentration of surfactants in such solutions by a “salting out” effect. It includes water soluble dissociable, inorganic salts such as, for example alkali metal or ammonium, chlorides, nitrates, phosphates, carbonates, silicates, perborates and polyphosphates, and also certain water soluble organic salts which desolubilise or "salt out” surfactants. It does not include salts of cations which form water insoluble precipitates with the surfactants present.
- Hydrotrope denotes any water soluble compound which tends to increase the solubility of surfactants in aqueous solution.
- Typical Hydrotropes include urea and the alkali metal or ammonium salts of the lower alkyl benzene sulphonic acids such as sodium toluene sulphonate . and sodium xylene sulphonate.
- Soap means an at least sparingly water soluble salt of a natural or synthetic aliphatic monocarboxylic acid, which salt has surfactant properties.
- the term includes sodium, potassium, lithium, ammonium and alkanolamine salts of C 8-22 natural and synthetic fatty acids, including stearic, palmitic, oleic, li-noleic, ricinoleic, behenic and dodecanoic acids, resin acids and branched chain monocarboxylic acids.
- the "Usual Minor Ingredients” includes those ingredients other than Water, Active Ingredients, Builders and Electrolytes which may be included in laundry detergent compositions, typically in proportions up to 5%, and which are compatible in the relevant Formulation with a pourable, chemically stable Non-sedimenting composition.
- the term includes antiredeposition agents, perfumes, dyes, optical brightening agents, Hydrotropes, solvents, buffers, bleaches, corrosion inhibitors, antioxidants, preservatives, scale inhibitors, humectants, enzymes and their stabilizers, bleach activators, and the like.
- “Functional Ingredients” means ingredients which are required to provide a beneficial effect in the wash liquor and includes ingredients which contribute to the washing effectiveness of the composition e.g. surfactants, Builders, bleaches, optical brighteners, buffers, enzymes and anti- redeposition agents, and also anti-corrosives but excludes water, solvents, dyes, perfume, Hydrotropes, sodium chloride, sodium sulphate, solubilisers and stabilisers whose sole function is to impart stability, fluidity or other desirable characteristics to a concentrated formulation.
- “Payload” means the percentage of Functional Ingredients based on the total weight of the composition.
- Active Ingredients means surface active materials.
- Separable Phase is used herein to denote phases which are each separable from the mixture to form a distinct layer upon Centrifuging. Unless the context requires otherwise all references to the composition of Separable Phases are references to the compositions of the centrifugally separated phases and references to the structure of a composition relate to the uncentrifuged composition.
- a single Separable Phase may comprise two or more thermodynamically distinct phases, which are not separable from each other on Centrifuging as in, for example, a stable emulsion.
- Dispersed is used herein to describe a phase which is discontinuously distributed as discrete particles or droplets in at least one other phase.
- Co-continuous describes two or more interpenetrating phases each of which extends continuously through a common volume, or else is formed of discreet elements which interact to form a continuous matrix tending to maintain the position and orientation of each element in relation to the matrix when the system is at rest.
- Interspersed describes two or more phases which are either Co-continuous or of which one or more is Dispersed in the other or others.
- Solid phases are to substances actually present in the composition in the solid state at ambient temperature, and including any water of crystallization or hydration unless the context requires otherwise.
- a “Solid Layer” is a solid, pasty or non-pourable gelatinous layer formed on Centrifuging.
- Total Water refers to water present as liquid water in a predominantly aqueous phase, together with any other water in the composition, e.g. water of crystallisation or hydration or water dissolved or otherwise present in any predominantly non-aqueous phase.
- Total Weight refers to residual weight after removal of Total Water and also of any solvent which has a boiling point below 110°C.
- Formulation is used to describe the combination of ingredients which make up the Dry Weight of a composition.
- formulation may be exemplified by a number of compositions, differing in their Percentage Dry Weight.
- Pulsable as used herein means having a viscosity of less than 11.5 Pascal Seconds.
- L1 phase denotes a fluid, isotropic, micellar solution of surfactant in water, which occurs at concentrations between the critical micellar concentration and the first lyotropic mesophase, wherein the surfactant molecules aggregate to form spherical or rod shaped micelles.
- G phase refers to a liquid crystal phase of the type, also known in the literature as “neat phase” or “lamellar phase” in which the surfactant molecules are arranged in parallel layers of indefinite extent separated by layers of water or an aqueous solution. The layers may be bilayers or interdigited layers of surfactant.
- the "G” phase for any given surfactant or surfactant mixture normally exists in a narrow range of concentrations. Pure “G” phases can normally be identified by examination of a sample under a polarising microscope, between crossed polarisers. Characteristic textures are observed in accordance with the classic paper by Rosevear, JAOCS Vol. 31 P628 (1954) or in J. Colloid and Interfacial Science, Vol. 30 No. 4, P.500 (1969).
- Yield Points whenever referred to herein are as measured on an RML Series II “DEER” (R.T.M.) Rheometer at 25 0 C.
- references herein to “sedimentation” include references to upward as well as downward separation of solid particles.
- “Non-sedimenting” means non-sedimentary under normal conditions of storage unless otherwise stated. Typically “Non-sedimenting” implies no significant sedimentation after three months at room temperature under normal earth gravity. The term does not exclude compositions which show a degree of syneresis, whereby a part of the aqueous phase separates to form a clear layer external to a homogeneous gel or dispersion. Such partly separated systems can usually be Dispersed by shaking. This is in contrast to sedimented systems wherein a solid sediment separates from the dispersion, which generally presents substantially greater problems in Dispersing and dispensing the product.
- Liquid detergents have hitherto been used mainly for light duty applications such as dish washing.
- the market for heavy duty detergents e.g. laundry detergents
- Such liquids should in theory be cheaper than powder detergents since they would avoid the need to dry and would in many instances replace the sulphate filler conventionally used in powder detergents with water. They also offer the possibilities of greater convenience and more rapid dissolution in wash water than powder.
- Attempts to provide solutions of the Functional Ingredients have been relatively unsuccessful commercially. One reason for this lack of success has been that the most commonly used and cost effective Functional Ingredients, e.g.
- sodium tripolyphosphate and sodium dodecyl benzene sulphonate are insufficiently soluble in aqueous compositions.
- Potassium pyrophosphate and amine salts of the Active Ingredients which are more soluble, have been tried as alternatives but have not been found cost effective.
- the Payload has been undesirably low.
- the proportion of Builder to Active Ingredient has generally been less than is preferred for optimum washing, and expensive ingredients, not usually required in powder Formulations, have often been needed to increase the amount of Functional Ingredient in solution, and to inhibit sedimentation of the suspended solid.
- Non-sedimenting, Pourable, fluid, aqueous based detergent compositions which have novel structural features and which can employ as surfactant virtually any surfactant or surfactant combination which is useful in laundry applications, in desired optimum proportions with any of the commonly used detergent Builders.
- compositions of our invention can be obtained, which contain substantially higher Payloads at effective Builder to surfactant ratio than have hitherto been attainable.
- Preferred embodiments of our invention exhibit at least some of the following advantages compared with products marketed hitherto: Higher Payload; increased Builder to surfactant ratio; improved stability; lower cost due to use of cheaper ingredients and ease of production; satisfactory mobility; improved washing performance; "non-drip" characteristics, permitting the compositions to be added to the compartments of washing machines designed to operate with powders, without premature release; a consistency suitable for automatic dispensing; and the flexibility to select optimum surfactant combinations for the requirements of any particular market.
- surfactants can be constrained to form an open three dimensional structure conferring stability on aqueous suspensions, by the presence of Electrolytes and by controlling the conditions of mixing.
- thixotropic gels which may contain suspended particles of solid Builder, which have particular advantages over conventional detergent suspensions.
- Powder detergents are normally prepared by spray drying aqueous slurries, which may superficially resemble liquid detergent formulations, but which are not required to be stable to storage, and which, are prepared and handled at elevated tempertures. Such slurries are generally not Pourable at ambient temperature. Patents describing the preparation and spray drying of such slurry intermediates include U.S.P.3639288 and W. German OLS 1567656.
- the invention provides a Non-sedimenting, Pourable, fluid, built, detergent composition, containing Active Ingredients which comprise a substantially linear alkyl benzene sulphonate, said composition having a Payload of at least 25% by weight, and comprising at least one, predominantly aqueous, liquid Separable Phase containing dissolved Electrolyte and one or more other Separable Phases, Interspersed therewith, which contain suspended solid particulate Builder, said Electrolyte comprising at least 4.7% and preferably at least 5.6% by weight of the composition of sodium carbonate and being present in at least sufficient amount to maintain at least a substantial proportion of the total Active Ingredients of the composition in at least one of said other phases, and thereby inhibiting sedimentation of said Builder.
- Active Ingredients which comprise a substantially linear alkyl benzene sulphonate, said composition having a Payload of at least 25% by weight, and comprising at least one, predominantly aqueous, liquid Separable Phase containing dissolved Electrolyte and one or more other Se
- the invention provides a Non-sedimenting, Pourable, fluid detergent composition
- a Non-sedimenting, Pourable, fluid detergent composition comprising at least one predominantly aqueous liquid Separable Phase, containing sufficient dissolved Electrolyte selected from alkali metal chlorides, phosphates, condensed phosphates, phosphonates, citrates, nitrilotriacetates, ethylene diamine tetracetates, carbonates, silicates, and mixtures thereof to provide from 2 to 4.5 gram ions per litre of said phase total of akali metal cations; at'least one other Separable Phase containing Active Ingredients; and suspended solid Builder; said composition having a Payload between the minimum concentration to provide a Non-sedimenting composition and the maximum concentration to provide a Pourable composition.
- our invention provides a Non-sedimenting, Pourable, fluid detergent composition having a Payload of greater than 25% which, on Centrifuging, is separable into a single liquid layer containing sufficient dissolved Electrolyte consisting essentially of sodium chloride, sodium phosphate, sodium carbonate, sodium silicate, sodium tripolyphosphate or mixtures thereof to provide from 2 to 4.5 gram ions sodium per litre of said layer and a Solid Layer containing surfactant and Builder.
- our invention comprises a Non-sedimentary, Pourable, fluid, detergent composition containing Active Ingredients which comprise a substantially linear alkylbenzene sulphonate, said composition having a Payload of at least 25% by weight which separates on Centrifuging into a predominantly aqueous liquid layer containing sufficient dissolved Electrolyte to provide from 2 to 4.5 gm ions per litre of alkali metal and at least one other layer, said at least one other layer comprising solid Builder and at least part of said Active Ingredient.
- Active Ingredients which comprise a substantially linear alkylbenzene sulphonate, said composition having a Payload of at least 25% by weight which separates on Centrifuging into a predominantly aqueous liquid layer containing sufficient dissolved Electrolyte to provide from 2 to 4.5 gm ions per litre of alkali metal and at least one other layer, said at least one other layer comprising solid Builder and at least part of said Active Ingredient.
- our invention comprises a Non-sedimenting, Pourable, fluid detergent composition having a Payload of at least 35% and comprising Active Ingredient, dissolved Electrolyte and suspended solid Builder, which separates on Centrifuging into a predominantly aqueous layer containing sufficient of said dissolved Electrolyte to provide from 2 to 4.5 gm ions alkali metal per litre of said aqueous layer, and at least one other layer containing solid Builder and at least part of said Active Ingredients, the weight ratio of the total Builder to the total Active Ingredients being greater than 1.2:1.
- compositions comprising Active Ingredients and Dispersed solid Builder said compositions comprising at least one predominantly aqueous liquid phase and one or more other phases separable from said predominantly aqueous liquid phase by Centrifuging and containing Active Ingredient present in at least one of said one or more other phases, and a Builder, present in at least one of said one or more other phases, said one or more other phases being Interspersed with the predominantly aqueous phase, all of which compositions exhibit at least some, but not necessarily all, of the following characteristics: They are thixotropic; they are gels; they comprise a continuous, at least predominantly aqueous Separable Phase, containing dissolved Electrolyte, a Separable Phase containing a substantial proportion of the Active Ingredient as spheroids or vesicles Interspersed with said at least predominantly aqueous phase, and a Dispersed solid phase consisting at least predominantly of Builder; said one or more other phases are
- the predominantly aqueous phase contains a concentration of less than 15%, preferably less than 8%, e.g. less than 2%, typically, in the case of nonionic surfactant or alkyl benzene sulphonates, less than 0.5% by weight dissolved Active Ingredients; the proportion by weight of Active Ingredient in the predominantly aqueous phase to total Active Ingredient in the composition is less than 1:1.5 preferably less than 1:2 e.g.
- the at least one predominantly aqueous liquid phase contains sufficient Electrolyte to provide a concentration of at least 0.8, typically at least 1.2, preferably 2.0 to 4.5 gram ions per litre of total alkali metal and/or ammonium cations; the compositions contain at least 15% by weight, preferably more than 20% by weight of Builder; the Builder is at least predominantly sodium tripolyphosphate; the Builder comprises a minor proportion of alkali metal silicate, preferably sodium silicate; the bulk viscosity of the composition is between 0.1 and 10 pascal seconds, preferably between 0.5 and 5 pascal seconds; the composition has a Yield Point preferably of at least 2 e.g. at least 5, preferably less than 200 e.g.
- a phase containing Builder comprises solid particles having a maximum particle size below the limit at which the particles tend to sediment; the particles have, adsorbed on their surfaces at least one crystal growth inhibitor sufficient to maintain the solid particles below the limit at which the particles tend to sediment; the composition contains an agglomeration inhibitor sufficient to prevent flocculation or coagulation of the solid particles.
- Aqueous based liquid laundry detergents containing suspended solid builder can, in general, conveniently be classified by Centrifuging as hereinbefore defined.
- Group I Three principal types of laundry liquid having a continuous aqueous phase and dispersed solid are distinguishable, which will be hereinafter referred to as Group I, Group II and Group III suspensions.
- the first Group of laundry suspensions is characteristic of the prior art discussed above which relates to suspensions of solid Builder in aqueous solutions or emulsions of surfactant.
- Group I compositions separate into a Solid Layer consisting essentially of Builder, and a viscous liquid layer comprising water and surfactant.
- Formulation factors tending to form Group 1 compositions include the use of the more water soluble surfactants, such as alkyl ether sulphates, the presence of solubilising agents such as Hydrotropes and water miscible organic solvents, relatively low levels of Electrolyte and relatively low Payloads.
- Group 1 compositions normally display at least some of the following typical properties.
- the bulk viscosity of the composition is determined by, and is similar to, the viscosity of the aqueous liquid layer.
- the aqueous layer typically has a viscosity of from 0.1-1.0 pascal seconds. Viscosities of the compositions are generally also under 1 pascal second, e.g. 0.3 to 0.6 pascal seconds.
- the compositions usually have yield points of less than 4, often less than 1, dyne cm . This implies a relatively unstructured composition. This is confirmed by neutron scattering and x-ray diffraction studies and by electron microscopy. Subjection to high shear rate renders many Group I compositions unstable.
- Group II is essentially distinguished from Group I in that at least the major proportion of the surfactant is present in a Separable Phase, which is distinct from the predominantly aqueous liquid phase containing the Electrolyte.
- This Group is distinguished from Group III in that at least the major portion of the surfactant separates on centrifuging as a liquid or liquid crystal layer.
- Group II compositions typically show a three layer separation on Centrifuging, giving a non-viscous liquid aqueous layer (e.g. less than 0.1 pascal seconds, usually less than 0.02 pascal seconds), which contains Electrolyte but little or no surfactant, a viscous liquid layer which contains a major proportion of the Active Ingredients and a Solid Layer consisting predominantly of Builder.
- a non-viscous liquid aqueous layer e.g. less than 0.1 pascal seconds, usually less than 0.02 pascal seconds
- a viscous liquid layer which contains a major proportion of the Active Ingredients and a Solid Layer consisting predominantly of Builder.
- Group II compositions have, typically, a very low yield point on being first prepared but become more gel like on ageing.
- the viscosity of the composition is usually between 1 and 1.5 pascal seconds.
- the compositions of this type show evidence of lamellar structure in X-ray and neutron diffraction experiments and by electron microscopy.
- Centrifuged Group II compositions have the liquid or liquid crystal surfactant layer uppermost, but we do not exclude compositions in which the aqueous Electrolyte layer is uppermost or in which there are two or more Solid Layers distinguishable from each other, at least one of which may sediment upwardly, in relation to either or both liquid layers on Centrifuging.
- Group III The essential distinction of Group III from the other Groups is that at least a substantial proportion of the surfactant Centrifuges into a Solid Layer.
- Group III compositions may Centrifuge into more than one Solid Layer. Normally both surfactant and Builder sediment downwardly on Centrifuging and the two phases are intermixed. However some Group III compositions may provide an upwardly sedimentary surfactant phase or more than one surfactant phase at least one of which may sediment upwardly. It is also possible for some or all of the Builder to sediment upwardly.
- the third Group of laundry liquids is typical of those compositions of the present invention prepared from those surfactants which are more sparingly soluble in the aqueous phase, especially anionic surfactants such as sodium alkyl benzene sulphonates, as well as mixtures of such surfactants with minor proportions of non-ionic surfactant.
- Group III compositions typically separate on Centrifuging into two layers. The first of which is an aqueous layer containing dissolved Electrolyte and the second is a Solid Layer comprising Builder and surfactant.
- the rheological properties of Group III typically, show the strongest evidence for structure.
- the Viscosity of the suspension is substantially greater than that of the aqueous layer, e.g. typically 1.2 to 2 Pascal seconds
- the compositions generally have a fairly high Yield Point, e.g. greater than 10 dynes cm and a very short recovery time after subjection to shear stresses in excess of the Yield Point, e.g. usually 20 to 100 minutes. On recovery after subjection to very high shear stresses many Group III compositions exhibit increased Viscosity and greater stability.
- compositions of our invention may show, in addition to a liquid layer and a Solid Layer, a small amount of a third layer which is liquid on Centrifuging, but have rheological properties characteristic of Group III.
- Compositions at the borderline of Groups I and II are sometimes unstable but maybe converted into stable Group II compositions of the invention by addition of sufficient Electrolyte and/or by increasing Pay Load. Most Group I compositions may be converted into Group II if sufficient Electrolyte is added. Similarly, addition of more Electrolyte tends to convert Group II compositions into Group III. Conversely, Group III can generally be converted to Group II, and Group II to Group I, by addition of Hydrotrope. Some Group III compositions may be converted directly to Group I and vice versa by addition of Hydrotrope or Electrolyte respectively.
- compositions of our invention and of the prior art have been examined by x-ray and neutron diffraction and by electron microscopy.
- Samples for neutron diffraction studies were prepared using deuterium oxide in place of water. Water was kept to a minimum, although some ingredients, normally added as aqueous solutions (e.g. sodium silicate), or as hydrates, were not available in a deuterated form.
- aqueous solutions e.g. sodium silicate
- Deuterium oxide based compositions were examined on the Harwell small angle Neutron Scattering Spectrometer. Both deuterium oxide based and aqueous samples were also examined using a small angle x-ray diffractometer. Aqueous samples were freeze fracture etched, coated with gold or gold/paladium and studied under the Lancaster University Low Temperature Scanning Electron Microscope. Competitive commercial compositions, which are not, of course, available in a deuterated form, could not be examined by neutron scattering.
- compositions belonging typically to Group I were characterised under both neutron and x-ray analysis by high levels of small angle scattering and an absence of discrete peaks, corresponding to regular, repeating, structural features. Some compositions showed broad indistinct shoulders or humps, others a smooth continuum.
- Small angle scattering is scattering very close to the line of the incident beam and is usually dominated by scattering from dilute dispersions of inhomogeneities in the composition.
- the shoulders or humps observed with some Group I compositions additionally show a form and angular displacement typical of concentrated micellar solutions of surfactant (L l phase).
- Typical Group III compositions gave relatively narrow and intense small angle scattering, together with distinct peaks indicative of a lamellar structure.
- the peaks were broader than in the case of typical Group II compositions, and second and third order peaks were not always separately distinguishable.
- the displacement of the peaks indicated a lamellar structure with the lamellae more closely spaced than in the case of typical Group II compositions (e.g. 26-36 Angstrom).
- Lamellar structures were clearly visible under the electron microscope. In some instances spheroidal structures could also be observed e.g. of approximately 1 micron diameter.
- Group III compositions are believed to comprise pourable gel systems in which there may be two or more Co-continuous or Interspersed phases.
- the properties of the Group III compositions can be explained on the basis that they are thixotropic gels comprising a relatively weak three dimensional network of solid surfactant hydrate Interspersed with a relatively non viscous aqueous phase which contains dissolved Electrolyte, but little or no surfactant.
- the network prevents sedimentation of the network- forming solids, and any suspended discrete particles.
- the network forming solids may be present as platelets, sheets of indefinite extent, or fibres or alternatively, as asymetric particles joined into or interacting to provide, a random mesh, which is Interspersed with the liquid.
- the structure is sufficiently stable to inhibit or prevent precipitation on storage and will also limit the extent of spreading of the gel on a horizontal surface, however the structure is weak enough to permit the compositions to be poured or pumped.
- the solid structure is composed at least predominantly of surfactant hydrate e.g. sodium alkyl benzene sulphonate or alkyl sulphate. Thus no other stabilising agent is required over that required in the end-use of the composition.
- Such gels may, in particular, exhibit a clay-like structure, sometimes referred to as a "house of cards” structure, with a matrix of plate shaped crystals orientated at random and enclosing substantial interstices, which accomodate the particles of builder.
- the solid surfactant may, in some instances be associated with, or at least partially replaced by "G" phase surfactant.
- the phases detected by diffraction comprise a lamellar phase, which is probably a "G” phase, but possibly in some instances surfactant hydrate or a mixture thereof with “G” phase, and predominantly aqueous "L l " micellar solution, together with the solid Builder.
- the Builder is suspended in a system which may comprise a network of "G” phase and/or spheroids or vesicles, which may have an onion like structure, or outer shell, formed from successive layers of surfactant e.g. as "G” phase, and which may contain at least one of the predominantly aqueous phases, e.g. the electrolyte solution, or more probably the "L 1 " micellar solution. At least one of the predominantly aqueous phases is the continuous phase.
- Evidence for the presence of vesicles is provided by microscopy in the case of the compositions containing olefin and paraffin sulphonates.
- compositions of our invention preferably contain at least 5% by weight of surfactants.
- surfactant constitutes from 7 to 35% by weight of the composition, e.g. 10 to 20% by weight.
- the surfactant may for example consist substantially of an at least sparingly water-soluble, salt of sulphonic or mono esterified sulphuric acids e.g. an alkylbenzene sulphonate, alkyl sulphate, alkyl ether sulphate, olefin sulphonate, alkane sulphonate, alkylphenol sulphate, alkylphenol ether sulphate, alkylethanolamide sulphate, alkylethanolamide ether sulphate, or alpha sulpho fatty acid or its esters each having at least one alkyl or alkenyl group with from 8 to 22, more usually 10 to 20, aliphatic carbon atoms.
- sulphonic or mono esterified sulphuric acids e.g. an alkylbenzene sulphonate, alkyl sulphate, alkyl ether sulphate, olefin sulphonate, alkane sulphonate
- alkyl or alkenyl groups are preferably straight chain primary groups but may optionally be secondary, or branched chain groups.
- ether hereinbefore refers to polyoxyethylene, polyoxypropylene, glyceryl and mixed polyoxyethylene-oxy propylene or mixed glyceryl-oxyethylene or glyceryl-oxy propylene groups, typically containing from 1 to 20 oxyalkylene groups.
- the sulphonated or sulphated surfactant may be sodium dodecyl benzene sulphonate, potassium hexadecyl benzene sulphonate, sodium dodecyl dimethyl benzene sulphonate, sodium lauryl sulphate, sodium tallow sulphate, potassium oleyl sulphate, ammonium lauryl monoethoxy sulphate, or monoethanolamine cetyl 10 mole ethoxylate sulphate.
- anionic surfactants useful according to the present invention include fatty alkyl sulphosuccinates, fatty alkyl ether sulphosuccinates, fatty alkyl sulphosuccinamates, fatty alkyl ether sulphosuccinamates, acyl sarcosinates, acyl taurides, isethionates, Soaps such as stearates, palmitates, resinates, oleates, linoleates, and alkyl ether carboxylates.
- Anionic phosphate esters may also be used.
- the anionic surfactant typically contains at least one aliphatic hydrocarbon chain having from 8 to 22 preferably 10 to 20 carbon atoms, and, in the case of ethers one or more glyceryl and/or from 1 to 20 ethyleneoxy and or propyleneoxy groups.
- anionic surfactants such as olefin sulphonates and paraffin sulphonates are commercially available only in a form which contains some disulphonates formed as by-products of the normal methods of industrial manufacture. The latter tend to solubilise the surfactant in the manner of a Hydrotope.
- the olefin and paraffin sulphonates readily form stable compositions which, on Centrifuging, contain a minor portion of the total surfactant in the aqueous phase, and which show evidence of spheroidal structures.
- These compositions are valuable, novel, laundry detergents and which accordingly constitute a particular aspect of the present invention.
- Preferred anionic surfactants are sodium salts.
- Other salts of commercial interest include those of potassium, lithium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, triethanolamine and alkyl amines containing up to seven aliphatic carbon atoms.
- the surfactant may optionally contain or consist of nonionic surfactants.
- the nonionic surfactant may be e.g. a C 10 - 22 alkanolamide of a mono or di- lower alkanolamine, such as coconut monoethanolamide.
- nonionic surfactants which may optionally be present, include ethoxylated alcohols, ethoxylated carboxylic acids, ethoxylated amines, ethoxylated alkylolamides, ethoxylated alkylphenols, ethoxylated glyceryl esters, ethoxylated sorbitan esters, ethoxylated phosphate esters, and the propoxylated or ethoxylated and propoxylated analogues of all the aforesaid ethoxylated nonionics, all having a C S - 22 alkyl or alkenyl group and up to 20 ethyleneoxy and/or propyleneoxy groups, or any other nonionic surfactant which has hitherto been incorporated in powder or liquid detergent compositions e.g. amine oxides.
- the latter typically have at least one C 8 - 22 , preferably C 10-20 alkyl or alkenyl group and up to two lower
- the preferred nonionics for our invention are for example those having an HLB range of 7-18 e.g. 12-15.
- Cationic fabric softeners of value in the invention include quaternary amines having two long chain (e.g. C 12-22 typically C 16-20 ) alkyl or alkenyl groups and either two short chain (e.g. C 1-4 ) alkyl groups, or one short chain and one benzyl group. They also include imidazoline and quaternised imidazolines having two long chain alkyl or alkenyl groups, and amido amines and quaternised amido amines having two long chain alkyl or alkenyl groups.
- the quaternised softeners are all usually salts of anions which impart a measure of water solubility such as formate, acetate, lactate, tartrate, chloride, methosulphate, ethosulphate, sulphate or nitrate.
- Compositions of our invention having fabric softener character may contain smectite clays.
- compositions of our invention may also contain amphoteric surfactant, which may be included typically in surfactants having cationic fabric softener, but may also be included, usually as a minor component of the Active Ingredients, in any of the other detergent types discussed above.
- amphoteric surfactant may be included typically in surfactants having cationic fabric softener, but may also be included, usually as a minor component of the Active Ingredients, in any of the other detergent types discussed above.
- Amphoteric surfactants include betaines, sulphobetaines and phosphobetains formed by reacting a suitable tertiary nitrogen compound having a long chain alkyl or alkenyl group with the appropriate reagent,such as chloroacetic acid or propane sultone.
- suitable tertiary nitrogen containing compounds include:
- the Builder in preferred compositions of our invention is believed to be normally present, at least partially, as discrete solid crystallites suspended in the composition.
- the crystallites typically have a size of up to 60 eg 5 to 50 microns.
- Formulations containing sodium tripolyphosphate as Builder exhibit stability and mobility over a wider range of Dry Weight than corresponding Formulations with other Builders. Such Formulations are therefore preferred.
- Our invention also provides compositions comprising other Builders such as potassium tripolyphosphate, carbonates, zeolites, nitrite triacetates, citrates, metaphosphates, pyrophosphates, phosphonates, EDTA and/or polycarboxylates, optionally but preferably, in admixture with tripolyphosphate.
- Orthophosphates may be present, preferably as minor components in admixture with tripolyphosphate, as may alkali metal silicates.
- compositions of our invention should contain at least 1% and up to 12.3% by weight of the composition preferably at least 2% and up to 10%, most preferably more than 3% and up to 6.5% e.g. 3.5 to 5% of alkali metal silicate, preferably sodium silicate measured as SiO 2 based on the total weight of * composition.
- the silicate used to prepare the above compositions has an Na 2 O: SiO 2 ratio of from 1:1 to 1:2 or 1:1.5 to 1:1.8. It will however be appreciated that any ratio of Na 2 0 (or other base) to Si0 2 , or even silicic acid could be used to provide the silicate in the composition, and any necessary additional alkalinity provided by addition of another base such as sodium carbonate or hydroxide. Formulations not intended for use in washing machines do not require silicates provided that there is an alternative source of alkalinity.
- the Builder normally constitutes at least 15% by weight of the compositions, preferably at least 20%.
- the ratio of Builder to surfactant is greater than 1:1 preferably 1.2:1 to 5:1.
- the concentration of dissolved organic material and more particularly of Active Ingredients in the predominantly aqueous, liquid phase is preferably maintained at a low level. This may be achieved by selecting, so far as possible, surfactants which are sparingly soluble in the predominantly .aqueous phase, and keeping to a minimum the amount of any more soluble surfactant which is desired for the particular end use. For a given surfactant system and Payload, we have found that it is generally possible to stabilise the system in accordance with an embodiment of our invention by including in the at least one predominantly aqueous phase a sufficient quantity of Electrolyte.
- An effect of the Electrolyte is to limit the solubility of Active Ingredient in the at least one predominantly aqueous phase, thereby increasing the proportion of surfactant available to provide a solid, or liquid crystal, matrix which stabilises the compositions of our invention.
- a further effect of the Electrolyte is to raise the transition temperature of the "G" phase to solid for the surfactant.
- One consequence of raising the phase transition temperature is to raise the minimum temperature above which the surfactant forms a liquid or liquid crystal phase.
- surfactants which in the presence of water are normally liquid crystals or aqueous micellar solutions at ambient temperature may be constrained by the presence of Electrolyte to form solid matrices or "G" phases.
- the proportion of Electrolyte dissolved in the at least one predominantly aqueous phase is sufficient to provide a concentration of at least 0.8 preferably at least 1.2 e.g 2.0 to 4.5 gram moles per litre of alkali metal, alkaline earth metal and/or ammonium cations.
- the stability of the system may be further improved by ensuring so far as possible that the anions required in the composition are provided by salts which have a common cation, preferably sodium.
- the preferred Builder is sodium tripolyphosphate
- the preferred anionic surfactants are sodium salts of sulphated or sulphonated anionic surfactants and any anti-redeposition agent, e.g.
- carboxymethyl cellulose, or alkali, e.g. silicate or carbonate are also preferably present as the sodium salts.
- Sodium chloride, or other soluble inorganic sodium salts may be added to increase the Electrolyte concentration and minimise the concentration of Active Ingredients in the predominantly aqueous liquid phase.
- the preferred electrolyte is sodium silicate.
- Alkaline earth metals are only normally present when the Active Ingredients comprise surfactants, such as olefin sulphonates or non-ionics which are tolerant of their presence.
- the particle size of any solid phase should be less than that which would give rise to sedimentation.
- the critical maximum limit to particle size will vary according to the density of the particles and the density of the continuous phase and the yield point of the composition.
- Compositions of our invention preferably contain a particle growth inhibitor.
- the particle growth inhibitor is believed to function by adsorption onto the faces of suspended crystallites of sparingly soluble solids preventing deposition of further solid thereon from the saturated solution in the predominantly aqueous liquid phase.
- Typical particle growth inhibitors include sulphonated aromatic compounds.
- a sodium alkyl benzene sulphonate such as sodium dodecyl benzene sulphonate when present as a surfactant is itself a particle growth inhibitor and may be sufficient to maintain particles of; for example, builder in the desired size range without additional stabilisers.
- lower alkyl benzene sulphonate salts such as sodium xylene sulphonate or sodium toluene sulphonate have stabilising activity, as well as being conventionally added to liquid detergents as Hydrotropes.
- the presence of the lower alkyl benzene sulphonates is less preferred.
- Sulphonated naphthalenes especially methyl naphthalene sulphonates are effective crystal growth inhibitors. They are not, however, normal ingredients of detergent compositions and therefore on cost grounds they are not preferred.
- Other particle growth inhibitors include water soluble polysaccharide derivatives such as sodium carboxymethyl cellulose, which is frequently included in detergent compositions as a soil anti-redeposition agent.
- compositions according to our invention should be present in minor amounts in compositions according to our invention, sufficient to perform its normal functions in detergent compositions and to assist in stabilising the suspension, but preferably not sufficient to increase so substantially the viscosity of the predominantly aqueous liquid phase as to impair the pourability of the composition.
- compositions according to our invention are the sulphonated aromatic dyes, especially the sulphonated aromatic optical brightening agents, which are sometimes included in powder formulations.
- Typical examples include 4,4'-bis (4-phenyl-1,2,3-triazol-2-yl-2,2'-stilbene disulphonate salts and 4,4'-diphenylvinylene-2,2'-biphenyl disulphonate salts.
- Such particle growth inhibitors may be included instead of, or more usually in addition to,for example, a sulphonated surfactant.
- effective particle growth inhibitors include lignosulphonates and C 6-18 alkane sulphonate surfactants, which latter compounds may also be present as part of the surfactant content of the composition.
- the presence of an agglomeration inhibitor is also preferred.
- the agglomeration inhibitor for use according to our invention may also conveniently be sodium carboxymethyl cellulose. It is preferred that the composition should include an effective agglomeration inhibitor which is chemically distinct from the particle growth inhibitor, despite the fact that, for example, sodium carboxymethyl cellulose, is capable of performing either function. It is sometimes preferred, when preparing the detergent I composition to add the crystal growth inhibitor to the composition prior to the agglomeration inhibitor, and to add the agglomeration inhibitor subsequent to the solid phase, so that the crystal growth inhibitor is first adsorbed onto the solid particles to inhibit growth thereof and the agglomeration inhibitor is subsequently introduced to inhibit agglomeration of the coated particles.
- agglomeration inhibitors which may less preferably be used include polyacrylates and other polycarboxylates, polyvinyl pyrrolidone, carboxy methyl starch and lignosulphonates.
- the concentration of the crystal growth inhibitor and agglomeration inhibitor can be widely varied according to the proportion of solid particles and the nature of the dispersed solid as well as the nature of the compound used as the inhibitor and whether that compound is fulfilling an additional function in the composition.
- the preferred proportions of alkyl benzene sulphonate are as set out hereinbefore in considering the proportion of surfactant.
- the preferred proportions of sodium carboxy methyl cellulose are up to 2.5% by weight of the composition preferably 0.5 to 2% by weight e.g. 1 to 2a although substantially higher proportions up to 3 or even 5% are not excluded provided they are consistent in the particular formulation with a pourable composition.
- the sulphonated optical brighteners may typically be present in proportions of 0.05 to 1% by weight e.g. 0.1 to 0.3% although higher proportions e.g. up to 5% may less preferably be present in suitable compositions.
- compositions of our invention are preferably alkaline, being desirably buffered with an alkaline buffer adapted to provide a pH above 8 eg above 9 most preferably above 10 in a wash liquor containing the composition diluted to 0.5% Dry Weight. They preferably have sufficient free alkalinity to require from 0,4 to 12 mls. preferably 3 to 10 mls of N/10 HC1 to reduce the pH.of 100 mls. . of a dilute solution of the composition, containing 0.5% Dry Weight, to 9, although compositions having higher alkalinity may also be commercially acceptable. In general lower alkalin.ities are less acceptable in commercial practice, although not excluded from the scope of our invention.
- the alkaline buffer is preferably sodium tripolyphosphate and the alkalinity preferably provided at least in part by sodium silicate.
- Other less preferred alkaline buffers include sodium carbonate.
- liquid detergent compositions have commonly contained substantial concentrations of Hydrotropes and/or organic water miscible hydroxylic solvents such as methanol, ethanol, isopropanol, glycol, glycerol, polyethylene glycol and polypropylene glycol.
- Hydrotropes and/or organic water miscible hydroxylic solvents such as methanol, ethanol, isopropanol, glycol, glycerol, polyethylene glycol and polypropylene glycol.
- Such additives are often necessary to stabilise Group I formulations.
- they may have a destabilising effect which often requires the addition of extra amounts of Electrolyte to maintain stability.
- They are, moreover, costly and not Functional Ingredients. They may, however, in certain circumstances, promote Pourability. We do not therefore totally exclude them from all compositions of our invention, but we prefer that their presence be limited to the minimum required to ensure adequate Pourability. If not so required we prefer that they be absent.
- Optimum Payload may vary considerably from one type of Formulation to another. Generally speaking it has not been found possible to guarantee Non-sedimenting compositions below about 35% by weight Payload, although some types of Formulation can be obtained in a Non-sedimenting form below 30% Payload, and sometimes as low as 25% Payload. In particular we have obtained Soap based Formulations at concentrations below 25% Pay Load eg 24%. We do not exclude the possibility of making such Formulations at Payloads down to 20%.
- a range of Payloads can be identified within which the composition is both stable and pourable. Generally below this range, sedimentation occurs and above the range the Formulation is too viscous.
- the acceptable range may be routinely determined for any given Formulation by preparing the suspension using the minimum water required to maintain a stirrable composition, diluting a number of samples to progressively higher dilutions, and observing the samples for signs of sedimentation over a suitable period.
- the acceptable range of Payloads may extend from 30%, or 35% to 60, or 70%, or even 75% by weight for others it may be much narrower, e.g. 40 to 45% by weight.
- Group III Formulations show an increase in Yield Point with increasing Payload.
- the minimum stable Payload for such typical Group III Formulations usually corresponds to a Yield Point of about 10-12 dynes/cm 2 .
- compositions of our invention can, in many instances be readily prepared by normal stirring together of the ingredients. However, some Formulations according to the invention are not fully stable unless the composition is subjected to more prolonged or vigorous mixing. In some extreme cases the solid content of product may require comminution in the presence of the liquid phase. The use of a colloid mill for the latter is not excluded, but is not generally necessary. In some instances mixing under high shear rate provides products of high viscosity.
- a method of preparation that we have found generally suitable for preparing stable mixtures from those Formulations which are capable of providing them, is to mix the Active Ingredients or their hydrates, in a concentrated form, with concentrated (e.g. 30 to 60%, preferably 45-50%) aqueous silicate solution, or alternatively, a concentrated solution of any other non-surfactant Electrolyte required in the Formulation. Other ingredients are then added including any anti-redeposition agents, optical brightening agents and foaming agents.
- the Builder when not required to provide the initial Electrolyte solution, may be added last. During mixing, just sufficient water is added at each addition to maintain the composition fluid and homogeneous. When all the Functional Ingredients are present, the mixture is diluted to provide the required Pay Load.
- mixing is carried out at ambient temperature where consistent with adequate dispersion.
- Certain ingredients e.g. non-ionic surfactants such as coconut monoethanolamide require gentle warming e.g. 40° for adequate dispersion. This degree of warming may generally be achieved by the heat of hydration of sodium tripolyphosphate.
- To ensure sufficient warming we prefer to add the tripolyphosphate in the anhydrous form containing a sufficiently high proportion of the high temperature rise modification commonly called "Phase I".
- Phase I the high temperature rise modification
- our Formulations may most conveniently be an anionic type (Type "A") in which the Active Ingredient preferably consists at least predominantly of sulphated or sulphonated anionic surfactant, optionally with a minor proportion of non-ionic surfactant.
- Type "A" the Active Ingredient preferably consists at least predominantly of sulphated or sulphonated anionic surfactant, optionally with a minor proportion of non-ionic surfactant.
- High foaming Formulations may typically be based on sodium C 10-14 straight or branched chain alkyl benzene sulphonate, alone or in admixture with a C 10-18 alkyl sulphate and/or C alkyl 1-10 mole ether sulphate. Small amounts (e.g. up to 1% of the weight of the compositions) of Soap may be present to aid rinsing of the fabric.
- Nonionic foam boosters and stabilisers such as C 12-18 acyl (e.g.
- coconut) monoethanolamide or diethanolamide or their ethoxylates, ethoxylated alkyl phenol, fatty alcohols or their ethoxylates may optionally be present as foam boosters or stabilisers, usually in proportions up to about 6% of the Dry Weight of the composition.
- the sodium alkyl benzene sulphonate may be totally or partially replaced, in the above Formulations by other sulphonated surfactants including fatty alkyl xylene or toluene sulphonates, or by e.g. alkyl ether sulphates (preferably) or alkyl sulphates, paraffin sulphonates and olefin sulphonates, sulphocarboxylates, and their esters and amides, including sulphosuccinates and sulphosuccinamates, alkyl phenyl ether sulphates, fatty acyl monoethanolamide ether sulphates or mixtures thereof.
- alkyl ether sulphates preferably
- alkyl sulphates preferably
- paraffin sulphonates and olefin sulphonates sulphocarboxylates
- esters and amides including sulphosuccinates and sulphosucc
- the sulphated or sulphonated anionic surfactant consists substantially of alkyl benzene sulphonate preferably sodium alkyl benzene sulphonate, e.g. C 10-14 alkyl benzene sulphonate.
- the proportion of alkyl benzene sulphonate in the absence of foam boosters is preferably from 20 to 60% e.g. 30 to 55% of the Dry Weight of the composition.
- the anionic surfactant may comprise a mixture of alkyl benzene sulphonate, and alkyl sulphate and/or alkyl ether sulphate and/or alkyl phenol ether sulphate in weight proportions of e.g. from 1:5 to 5:1 typically 1:2 to 2:1 preferably 1:1.5 to 1.5:1 e..g. 1:1.
- the total anionic surfactant is preferably from 15 to 50% e.g. 20 to 40% of the Dry Weight of the compositions, in the absence of foam booster.
- the alkyl sulphate, and/or alkyl ether sulphate for use in admixture with the alkyl benzene sulphonate typically has an average of from 0 to 5 ethyleneoxy groups per sulphate group e.g. 1 to 2 groups.
- our invention provides a Pourable, Non-sedimenting, fluid detergent composition consisting essentially of water and: (A) from 10 to 20% based on the weight of the composition of Active Ingredients comprising a substantially linear sodium alkyl benzene sulphonate having from 10 to 20 aliphatic carbon atoms and optionally an alkyl ethoxy sulphate having an alkyl group with from 10 to 20 carbon atoms, and/or a minor proporition of a non-ionic surfactant and/or of a soap; (B) at least 15% of Builder partly present as solid and selected from condensed phosphates, zeolites, citrates, nitrilotriacetates, ethylenediamine tetracetates, orthophosphates and silicates, wherein at least 50% by weight of said Builder is sodium tripolyphosphate and said Builder further comprises at least 4.7%, based on the total weight of the composition, of sodium carbonate; (C) optionally up to
- our invention provides a Pourable, Non-Sedimenting, fluid, liquid detergent composition consisting essentially of water and (A)from 10 to 20% based on the weight of the composition of a mixture of a substantially linear C 10-18 alkyl benzene sulphonate and C 10 - 20 alkyl 1-10 mole ethoxy sulphate; (B) at least 15% by weight of the composition of total Builder partly present as suspended solid, selected from sodium tripolyphosphate, zeolite, sodium carbonate, sodium silicate and mixtures thereof; (C) an aqueous Separable Phase containing sufficient dissolved Electrolyte selected from sodium
- the anionic surfactant consists substantially of alkyl sulphate and/or, alkyl ether sulphate.
- the total concentration of Active Ingredients in the absence of foam booster is preferably from 15 to 50% of the Dry Weight of the composition.
- the Active Ingredients comprise an average of from 0 to 5 e.g. 0.5 to 3 ethyleneoxy groups per molecule of sulphated surfactant.
- the fatty alkyl chain length is preferably from 10 to 20C, higher chain lengths being preferred with higher ethylene-oxy content.
- Soap may be added to any of the foregoing detergent Formulations as an aid to rinsing the fabric. Soap is preferably present for this purpose in concentrations of from 0 to 6% preferably 0.1 to 4% e.g. 0.5 to 2% by Dry Weight of the composition. The amount of Soap is preferably less than 25% of the total sulphated and sulphonated surfactant, to avoid foam suppression; typically less than 10%.
- Foam boosters and/or stabilisers may be incorporated in any of the foregoing types of high foam anionic detergent.
- the foam boosters or stabilisers are typically C 10-18 alkyl nonionic surfactants such as coconut monoethanolamide or diethanolamide or their ethoxylates, alkyl phenol ethoxylates, fatty alcohols or their ethoxylates or fatty acid ethoxylates.
- the foam booster and/or stabiliser is added typically in proportions up to 20% of the Dry Weight of the composition e.g. 0.1 to 6% preferably 0.5 to 4%.
- the presence of foam booster and/or stabiliser may permit a reduction of total concentration of Active Ingredients in a high foam product.
- compositions comprising alkyl benzene sulphonate with a foam booster and/or stabiliser will contain from 15 to 40% of alkyl benzene sulphate based on the weight of the composition preferably 20 to 36% e.g. 25% with from 2 to 6% e.g. 4% of nonionic surfactant, the lower proportions of anionic surfactant being preferred with higher proportions of nonionic surfactant and vice versa.
- the other sulphated or sulphonated anionic surfactant Formulations discussed above may be similarly reduced in active concentration by inclusion of foam boosters and/or stabilisers.
- the Builder is preferably sodium tripolyphosphate, optionally but preferably with a minor proportion of soluble silicate although the alternative Builders hereinbefore described may be employed instead, as may mixed Builders.
- the proportion of Builder in type "A" Formulations is usually at least 30% of the Dry Weight of the composition, preferably from 35% to 85% e.g. 40 to 80%. Builder proportions in the range 50 to 70% of Dry Weight are particularly preferred.
- the Builder to Active Ingredients ratio should desirably be greater than 1:1 preferably from 1.2:1 to 4:1 e.g. from 1.5:1 to 3:1.
- Low foaming Formulations are generally dependent upon the presence of lower proportions of sulphated or sulphonated anionic surfactant than in the high foam types together with higher, but still minor, proportions of Soap, and/or the addition of non-ionic, silicone, or phosphate ester foam depressants.
- a Non-sedimenting Pourable fluid, aqueous based detergent composition comprising an at least predominantly aqueous phase containing Electrolyte in solution, and suspended particles of Builder, said composition comprising from 15 to 50% based on Dry Weight of Active Ingredient , at least 30% of Builder based on Dry Weight, a ratio of Builder to Active Ingredient greater than 1:1, and optionally the Usual Minor Ingredients, wherein the surfactant comprises from 15 to 50% based on the Dry weight of the composition of sulphated and/or sulphonated anionic surfactant and an effective amount of at least one foam depressant.
- the foam depressant is selected from Soap, in a proportion of from 20 to 60% based on the weight of sulphated or sulphonated anionic surfactant, C 16-20 alkyl nonionic foam depressant in a proportion of up to 10% of the Dry Weight of the composition, C 16-20 alkyl phosphate ester in a proportion of up to 10% of the Dry Weight of the composition and silicone antifoams.
- Soap as a foam depressant is dependant on the proportion of Soap to sulphated or sulphonated anionic surfactant. Proportions of 10% or less are not effective as foam depressants but are useful as rinse aids in high foaming detergent compositions. Foam depressant action requires a minimum proportion of about 20% of soap based on the sulphated and/or sulphonated surfactant. If the proportion of soap to sulphated/sulphonated surfactant in a type "A" detergent is above about 60% by weight, the foam depressant action is reduced. Preferably, the proportion of Soap is from 25 to 50% e.g. 30 to 45% of the weight of sulphated/sulphonated surfactant.
- Low foaming detergents may contain, in addition to, or instead of soap, a nonionic foam depressant.
- a nonionic foam depressant may, for example, be a C 16-22 acyl monoethanolamide e.g. rape monoethanolamide, a C 16-22 alkyl phenol ethoxylate, C 16-22 alcohol ethoxylate or C 16-22 fatty acid ethoxylate.
- the composition may contain an alkali metal mono and/or di C 16-22 alkyl phosphate ester.
- the nonionic or phosphate ester foam depressant is typically present in the Formulation in a proportion of up to 10%, preferably 2 to 8% e.g. 3 to 4% based on Dry Weight.
- Silicone antifoams may also be used, as or as part of, the foam depressant.
- the effective concentration of these last in the formulation is generally substantially lower than in the case of the other foam depressants discussed above. Typically, it is less than 2%, preferably less than 0.1%, usually 0.01 to 0.05% e.g. 0.02% of the Dry Weight of the formulation.
- Our Formulations preferably contain the Usual Minor Ingredients.
- Certain fabric softeners, such as clays, may be included, however cationic fabric softeners are not normally effective in anionic based Formulations, but may sometimes be included in specially formulated systems.
- the type "B" Formulations of our invention comprise Soap as the principal active component. They may additionally contain minor amounts of nonionic or other anionic surfactants.
- the typical percentage Dry Weight of type "B" Formulations may be rather lower than type "A", e.g. 20 to 60%, preferably 29 to 45%.
- the total proportion of Active Ingredients is usually between 10 and 55%, preferably 15 to 40% e.g. 20 to 30% of the Dry Weight of the composition.
- Builder proportions are typically 20 to 80% of Dry Weight.
- the mobility of type "B" Formulations can be improved by including sufficient water soluble inorganic electrolyte, especially sodium silicate, in the Formulation.
- High foam Soap Formulations may typically contain Active Ingredient consisting substantially of Soap, optionally with a minor proportion of a nonionic foam booster and/or stabilizer as described in relation to type "A" Formulations, and/or with sulphated anionic booster such as alkyl ether sulphate or alkyl ether sulphosuccinate.
- Active Ingredient consisting substantially of Soap, optionally with a minor proportion of a nonionic foam booster and/or stabilizer as described in relation to type "A" Formulations, and/or with sulphated anionic booster such as alkyl ether sulphate or alkyl ether sulphosuccinate.
- Low foam type B Formulations may contain a lower concentration of Soap together with minor proportions of sulphated and or sulphonated anionic surfactant, nonionic or phosphate ester foam depressants and/or silicone antifoams.
- sulphated and/or sulphonated anionic surfactants and Soap in a type "B" low foam formulation is the converse of that in a type "A" low foam formulation.
- the sulphated and/or sulphonated anionic surfactant acts as foam suppressant when present in a proportion of from about 20 to about 60% of the weight of the Socp.
- nonionic, phosphate ester and silicone foam depressants are, conveniently, substantially as described in relation to type "A" detergents.
- Type "B” detergents may contain any of the Usual Minor Ingredients. As in the case of type "A” Formulations, cationic fabric softeners are not normally included, but other fabric softeners may be present.
- Non-ionic based detergents represent a further aspect of the present invention.
- Non- ionics are particularly suitable for cleaning man-made fibres.
- no commercially acceptable, fully built, non-ionic liquid detergent has yet been marketed.
- the surfactant is present as a hydrated solid or liquid crystal Separable Phase.
- the surfactant comprises a C 12-18 alkyl group, usually straight chain, although branched chain and/or unsaturated hydrocarbon groups are not excluded.
- the nonionic surfactants present have an average HLB of 12 to 15.
- the preferred nonionic surfactant in Type C Formulations is fatty alcohol ethoxylate.
- C 12-16 alkyl nonionics having 8 to 20 ethylenoxy groups, alkyl phenol ethoxylate having 6-12 aliphatic carbon atoms and 8 to 20 ethyleneoxy groups together optionally with a minor proportion e.g. 0 to 20% of the Dry Weight of the composition of anionic surfactant preferably sulphated and/or sulphonated anionic e.g.
- the Formulation may however include a nonionic foam booster and/or stabiliser such as C 10-18 acyl monoethanolamide typically in proportions as described above in relation to type "A" Formulations.
- the non-ionic Active Ingredients together have an HLB of 12-15.
- Low foam nonionic compositions are especially preferred. They preferably comprise 10 to 40% based on Dry Weight of the composition of C 12-18 alkyl 5 to 20 mole ethyleneoxy, nonionic surfactants such as fatty alcohol ethoxylates, fatty acid ethoxylates or alkyl phenol ethoxylates, having a preferred HLB of 12 to 15. They optionally contain a minor proportion, e.g.
- any of the anionic sulphated and/or sulphonated surfactants hereinbefore described in relation to type "A" detergents and they contain a foam depressant such as a mono, di- or tr'alkyl phosphate ester or silicone foam depressant, as discussed hereinbefore in the context of low foaming type "A" detergents.
- Type "C” Formulations may contain any of the Usual Minor Ingredients.
- nonionic based detergents of our invention may incorporate cationic fabric softeners.
- the cationic fabric softeners may be added to type "C" Formulations, in a weight proportion based on the nonionic surfactant of from 1:1.5 to 1:4 preferably 1:2 to -1:3.
- the cationic fabric softeners are cationic surfactants having two long chain alkyl or alkenyl groups, typically two C 16-20 alkyl or alkenyl groups, preferably two tallowyl groups. Examples include di C 12-20 alkyl di (lower, e.g. C 1- 3 , alkyl) ammonium salts, e.g.
- di tallowyl dimethyl ammonium chloride di(C 16-20 alkyl) benzalkonium salts e.g. ditallowyl methyl benzyl ammonium chloride, di C 16-20 alkyl amido imidazolines and di C 16-20 acyl amido amines or quaternised amino amines, e.g. bis (tallow amido ethyl) ammonium salts.
- Formulations containing cationic fabric softeners preferably do not contain sulphated or sulphonated anionic surfactants or soaps. They may however contain minor proportions of anionic phosphate ester surfactants e.g. up to 3% by weight of the composition preferably up to 2%. They may additionally or alternatively contain minor proportions (e.g. up to 3%, preferably 1 to 2% by weight of amphoteric surfactants such as betaines and sulphobetaines. They may also contain smectite clays, and the Usual Minor Ingredients.
- Compositions of the invention may contain the Usual Minor Ingredients. Principal of these are antiredeposition agents, optical brightening agents and bleaches.
- the most commonly used antiredeposition agent in making detergents is sodium carboxymethyl cellulose (SMC), and we prefer that this be present in compositions of this invention, e.g. in conventional amounts, e.g. greater than 0.1 but less than 5%, and more usually between 0.2 and 4%, especially 0.5 to 2% preferably 0.7 to 1.5%.
- SCMC is effective at concentrations suitable for use in powder detergents.
- the OBA may be present in conventional amounts. However we have found that OBA's in some liquid detergent (e.g. type "C" formulations) tend to be slightly less efficient than in powder detergents and therefore may prefer to add them in slightly higher concentrations relative to the Formulation than is normal with powders.
- concentrations of OBA between 0.05 and 0.5% are sufficient e.g. 0.075 to 0.3% typically 0.1 to 0.2%. Lower concentrations could be used but are unlikely to be effective, while higher concentrations, while we do not exclude them, are unlikely to prove cost effective and may, in some instances give rise to problems of compatibility.
- OBA's which may be used in the present invention include : ethoxylated 1, 2-(benzimidazolyl) ethylene; 2- styrylnaphth[1,2d-]oxazole; 1,2-bis(5' methyl-2-benzoxazolyl) ethylene; disodium-4,4'-bis(6-methylethanolamine-3-anilino-1,3,5-triazin-2"-yl)-2,2'-stilbene sulphonate; N-(2-hydroxyethyl-4,4'-bis (benzimidazolyl)stilbene; tetrasodium 4,4'-bis [4"-bis(2"- hydroxymthyl)-amino-6"(3"-sulphophenyl) amino-1", 3", 5"-triazin-2"- y1 amino]-2,2 1- stilbenedisulphonate; disodium-4-(6"- sulphonaphtho[1',2'-d
- Bleaches may optionally be incorporated in liquid detergent compositions of our invention subject to chemical stability and compatibility. Encapsulated bleaches may form part of the suspended solid.
- peroxy bleaches in compositions of our invention may be enhanced by the presence of bleach activators such as tetra acetyl ethylenediamine, in effective amounts.
- Photoactive bleaches such as zinc or aluminium sulphonated phthalocyanin, may be present
- Perfumes and colourings are conventionally present in laundry detergents in amounts up to 1 or 2%, and may similarly he present in compositions of our invention. Provided normal care is used in selecting additives which are compatible with the Formulation, they do not affect the performance of the present invention.
- Proteolytic and amylolitic enzymes may optionally be present in conventional amounts, together optionally with enzyme stabilizers and carriers. Encapsulated enzymes may be suspended.
- Minor Ingredients include germicides such as formaldehyde , opacifiers such as vinyl latex emulsion and anticorrosives such as benzotriazole.
- compositions of our invention are, in general, suitable for laundry use and our invention provides a method of washing clothes or other soiled fabric by contacting and, preferably, agitating them in an aqueous wash liquor containing any composition of the invention as described herein.
- Low foam compositions herein described are in particular of use in automatic washing machines.
- the compositions may also be used in the washing of dishes, or the cleaning of hard surfaces, the low foam products being particularly suitable for use in dishwashing machines. These uses constitute a further aspect of the invention.
- compositions of our invention may, generally, be used for washing clothes in boiling water, or for washing at medium or cool temperatures, e.g. 50 to 80°C, especially 55 to 68 0 C, or 20 to 50 0 C especially 30 to 40°C, respectively.
- the compositions may be added to the washwater at concentrations of between 0.05 and 3% Dry Weight based on the wash water preferably 0.1 to 2%, more usually 0.3 to 1% e.g. 0.4 to 0.8%.
- compositions of the Various Feedstocks Materials
- alkyl benzene sulphonate used was the sodium salt of the largely para-sulphonated "Dobane" JN material. (Dobane is a Registered Trade Mark).
- composition is as follows:-
- This composition refers only to the alkyl chain length.
- This material is the sodium salt of sulphonated C 16 /C 18 olefin having the following approximate composition.
- This material is an average 8 mole ethylene oxide condensate of an alcohol of the following composition:-
- This material was prepared by neutralising sulphonated C 14 -C 17 normal paraffins with sodium hydroxide and contained 10% disulphonates based on total Active Ingredients.
- This material was added as anhydrous Na 5 P 3 0 10 containing 30% Phase I.
- This material is added to Formulations as a viscous aqueous solution containing 47% solids with a Na 2 0:Si0 2 ratio of 1:1.6.
- optical brightening agent for Examples 51 to 66 was the disodium salt of 4;4'- [di(styryl-2-sulphonic acid)] biphenyl which is marketed under the trademark "TINOPAL CBS-X ".
- the optical brightener for Examples 1 to 50 was a mixture of the aforesaid Optical brightener with the disodium salt of 4;4'- [di(4-chlorostyryl-3-sulphonic acid)] biphenyl which mixture is marketed under the trademark "TINOPAL ATS-X".
- 1 and 2 represent a basic type A Formulation
- 3 and 4 a type A formulation with SCMC and optical brightener
- 5(a), (b) and (c) represent a type A Formulation at three different Pay '-oads
- 6 and 7 demonstrate that neither SCMC nor optical brightener is essential to obtain a Non-sedimenting Formulation
- 8 contains anticorrosive and perfume
- 9 (a) and (b) illustrate a high Builder to Active ratio Formulation (3:1) at two Pay Loads
- 10(a) and (b) illustrate a relatively low Builder to Active Formulation at two Pay Loads
- 11 corresponds to a Non-sedimenting Formulation obtained by centrifuging the Formulation of Example 9 at low Payload for only three hours and decanting the supernatent liquor
- 12 illustrates the effect of relatively high SCMC levels
- 13 to 19 illustrate Type A Formulations with various anionic surfactants
- 20 to 24 illustrate various Electrolytes
- 25 is a Formulation in which sodium trip
- the comparative example represents a commercial Formulation currently being marketed in Australia corresponding to Australian Patent 522983.
- the comparative example was the material as purchased, except for the neutron scattering results which were carried out on a sample prepared in accordance with the example of the patent to match the commercial Formulation as analysed and using deuterium oxide instead of water.
- the composition, by analysis was; were
- Effective Wash Solids refers to the sum of the Active Ingredient and Builder.
- the powder standard was used at 6gm/1 and the Examples adjusted to give the same % Effective Wash Solids in the wash Liquor.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Detergent Compositions (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT85108260T ATE42113T1 (de) | 1982-02-05 | 1983-02-07 | Fluessige detergenszusammensetzungen. |
Applications Claiming Priority (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8203398 | 1982-02-05 | ||
GB8203398 | 1982-02-05 | ||
GB8210670 | 1982-04-13 | ||
GB8210670 | 1982-04-13 | ||
GB8219227 | 1982-07-02 | ||
GB8219227 | 1982-07-02 | ||
GB8236664 | 1982-12-23 | ||
GB8236664 | 1982-12-23 | ||
EP83300605A EP0086614B2 (fr) | 1982-02-05 | 1983-02-07 | Compositions détergentes liquides |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83300605.9 Division | 1983-02-07 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0170091A1 true EP0170091A1 (fr) | 1986-02-05 |
EP0170091B1 EP0170091B1 (fr) | 1989-04-12 |
EP0170091B2 EP0170091B2 (fr) | 1997-11-19 |
Family
ID=27513261
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP85108260A Expired - Lifetime EP0170091B2 (fr) | 1982-02-05 | 1983-02-07 | Compositions détergentes liquides |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0170091B2 (fr) |
AT (1) | ATE47424T1 (fr) |
DE (1) | DE3379590D1 (fr) |
MY (1) | MY102009A (fr) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0301882A1 (fr) * | 1987-07-31 | 1989-02-01 | Unilever Plc | Compositions détergentes liquides |
EP0354010A2 (fr) * | 1988-08-05 | 1990-02-07 | Albright & Wilson Limited | Compositions de nettoyage liquides |
EP0530708A2 (fr) * | 1991-08-30 | 1993-03-10 | ALBRIGHT & WILSON UK LIMITED | Détergent liquide pour le linge |
DE19849247A1 (de) * | 1998-10-26 | 2000-04-27 | Benckiser Nv | Flüssige Reinigungs- oder Waschmittelzusammensetzung |
DE10060095A1 (de) * | 2000-12-02 | 2002-06-20 | Henkel Kgaa | Verfahren zur Herstellung wäßriger mehrphasiger Reinigungsmittel |
EP1445301A1 (fr) | 2003-01-28 | 2004-08-11 | Clariant GmbH | Dispersions aqueuses liquides détergentes |
US7271141B2 (en) | 2000-08-25 | 2007-09-18 | Reckitt Benckiser N.V. & Reckitt Benckiser (Uk) Limited | Water soluble packages containing liquid compositions |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3075922A (en) * | 1957-08-01 | 1963-01-29 | Colgate Palmolive Co | Prepartion of liquid detergent compositions |
GB930394A (en) * | 1959-12-22 | 1963-07-03 | Colgate Palmolive Co | Liquid detergent compositions |
US3346503A (en) * | 1963-10-11 | 1967-10-10 | Monsanto Co | Heavy-duty liquid detergent emulsion compositions and processes for preparing the same |
US3574122A (en) * | 1967-08-18 | 1971-04-06 | Lever Brothers Ltd | Liquid detergent compositions |
US4018720A (en) * | 1975-07-14 | 1977-04-19 | The Procter & Gamble Company | Laundry detergent compositions in emulsion/suspension |
DE2921366A1 (de) * | 1978-05-26 | 1979-12-06 | Albright & Wilson | Konzentrierte waessrige oberflaechenaktive zubereitung |
GB2031941A (en) * | 1978-02-07 | 1980-04-30 | Albright & Wilson | Concentrated aqueous surfactant compositions |
-
1983
- 1983-02-07 EP EP85108260A patent/EP0170091B2/fr not_active Expired - Lifetime
- 1983-02-07 AT AT83300605T patent/ATE47424T1/de not_active IP Right Cessation
- 1983-02-07 DE DE8585108260T patent/DE3379590D1/de not_active Expired
-
1987
- 1987-09-15 MY MYPI87001676A patent/MY102009A/en unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3075922A (en) * | 1957-08-01 | 1963-01-29 | Colgate Palmolive Co | Prepartion of liquid detergent compositions |
GB930394A (en) * | 1959-12-22 | 1963-07-03 | Colgate Palmolive Co | Liquid detergent compositions |
US3346503A (en) * | 1963-10-11 | 1967-10-10 | Monsanto Co | Heavy-duty liquid detergent emulsion compositions and processes for preparing the same |
US3574122A (en) * | 1967-08-18 | 1971-04-06 | Lever Brothers Ltd | Liquid detergent compositions |
US4018720A (en) * | 1975-07-14 | 1977-04-19 | The Procter & Gamble Company | Laundry detergent compositions in emulsion/suspension |
GB2031941A (en) * | 1978-02-07 | 1980-04-30 | Albright & Wilson | Concentrated aqueous surfactant compositions |
DE2921366A1 (de) * | 1978-05-26 | 1979-12-06 | Albright & Wilson | Konzentrierte waessrige oberflaechenaktive zubereitung |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0301882A1 (fr) * | 1987-07-31 | 1989-02-01 | Unilever Plc | Compositions détergentes liquides |
EP0354010A2 (fr) * | 1988-08-05 | 1990-02-07 | Albright & Wilson Limited | Compositions de nettoyage liquides |
EP0354010A3 (fr) * | 1988-08-05 | 1990-04-04 | Albright & Wilson Limited | Compositions de nettoyage liquides |
EP0530708A2 (fr) * | 1991-08-30 | 1993-03-10 | ALBRIGHT & WILSON UK LIMITED | Détergent liquide pour le linge |
EP0530708A3 (en) * | 1991-08-30 | 1993-06-09 | Albright & Wilson Limited | Liquid laundry detergent compositions |
TR27553A (tr) * | 1991-08-30 | 1995-06-08 | Albright & Wilson Uk Ltd | Konsantre sulu sürfaktan bilesimleri. |
DE19849247A1 (de) * | 1998-10-26 | 2000-04-27 | Benckiser Nv | Flüssige Reinigungs- oder Waschmittelzusammensetzung |
US7271141B2 (en) | 2000-08-25 | 2007-09-18 | Reckitt Benckiser N.V. & Reckitt Benckiser (Uk) Limited | Water soluble packages containing liquid compositions |
DE10060095A1 (de) * | 2000-12-02 | 2002-06-20 | Henkel Kgaa | Verfahren zur Herstellung wäßriger mehrphasiger Reinigungsmittel |
EP1445301A1 (fr) | 2003-01-28 | 2004-08-11 | Clariant GmbH | Dispersions aqueuses liquides détergentes |
Also Published As
Publication number | Publication date |
---|---|
DE3379590D1 (en) | 1989-05-18 |
EP0170091B2 (fr) | 1997-11-19 |
ATE47424T1 (de) | 1989-11-15 |
EP0170091B1 (fr) | 1989-04-12 |
MY102009A (en) | 1992-02-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0086614B1 (fr) | Compositions détergentes liquides | |
CA1325946C (fr) | Detergent liquide | |
US4793943A (en) | Liquid detergent compositions | |
US4618446A (en) | Spherulitic liquid detergent composition | |
EP0623670B1 (fr) | Compositions tensioactives à base aqueuse | |
EP0452106B2 (fr) | Composition aqueuse d'un tensio-actif | |
US6090762A (en) | Aqueous based surfactant compositions | |
JP2003503587A (ja) | 構造的界面活性剤系 | |
JPS6169895A (ja) | 液体洗剤組成物 | |
EP0170091B1 (fr) | Compositions détergentes liquides | |
EP0808359A1 (fr) | Compositions liquides | |
JP2693827B2 (ja) | 液体洗剤組成物 | |
KR880001859B1 (ko) | 액체 세정제 조성물 | |
CA1227719A (fr) | Detergents liquides | |
CA1234733A (fr) | Detergent fluide | |
IE55457B1 (en) | Liquid detergent compositions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19850704 |
|
AC | Divisional application: reference to earlier application |
Ref document number: 86614 Country of ref document: EP |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
17Q | First examination report despatched |
Effective date: 19861128 |
|
D17Q | First examination report despatched (deleted) | ||
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AC | Divisional application: reference to earlier application |
Ref document number: 86614 Country of ref document: EP |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
REF | Corresponds to: |
Ref document number: 42113 Country of ref document: AT Date of ref document: 19890415 Kind code of ref document: T |
|
ITF | It: translation for a ep patent filed | ||
REF | Corresponds to: |
Ref document number: 3379590 Country of ref document: DE Date of ref document: 19890518 |
|
ET | Fr: translation filed | ||
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
26 | Opposition filed |
Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN Effective date: 19891127 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
26 | Opposition filed |
Opponent name: RHONE-POULENC CHIMIE Effective date: 19900110 Opponent name: PROCTER & GAMBLE E.T.C. Effective date: 19900109 Opponent name: COLGATE-PALMOLIVE COMPANY Effective date: 19900108 Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN Effective date: 19891127 |
|
26 | Opposition filed |
Opponent name: UNILEVER N.V. Effective date: 19900112 Opponent name: RHONE-POULENC CHIMIE Effective date: 19900110 Opponent name: PROCTER & GAMBLE E.T.C. Effective date: 19900109 Opponent name: COLGATE-PALMOLIVE COMPANY Effective date: 19900108 Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN Effective date: 19891127 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: HENKEL KGAA. |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: RHONE-POULENC CHIMIE Opponent name: PROCTER & GAMBLE E.T.C. Opponent name: COLGATE-PALMOLIVE COMPANY |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: UNILEVER N.V. |
|
ITTA | It: last paid annual fee | ||
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
R26 | Opposition filed (corrected) |
Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN * 900108 C Effective date: 19891127 |
|
EPTA | Lu: last paid annual fee | ||
EAL | Se: european patent in force in sweden |
Ref document number: 85108260.2 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PFA Free format text: ALBRIGHT & WILSON UK LIMITED |
|
NLT1 | Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1 |
Owner name: ALBRIGHT & WILSON UK LIMITED |
|
APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
PLAW | Interlocutory decision in opposition |
Free format text: ORIGINAL CODE: EPIDOS IDOP |
|
PLAW | Interlocutory decision in opposition |
Free format text: ORIGINAL CODE: EPIDOS IDOP |
|
PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
27A | Patent maintained in amended form |
Effective date: 19971119 |
|
AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
ITF | It: translation for a ep patent filed | ||
REG | Reference to a national code |
Ref country code: CH Ref legal event code: AEN Free format text: AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM |
|
ET3 | Fr: translation filed ** decision concerning opposition | ||
NLR2 | Nl: decision of opposition | ||
NLR3 | Nl: receipt of modified translations in the netherlands language after an opposition procedure | ||
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PUE Owner name: RHODIA CONSUMER SPECIALTIES LIMITED TRANSFER- HUNT Ref country code: CH Ref legal event code: PFA Free format text: ALBRIGHT & WILSON UK LIMITED TRANSFER- RHODIA CONSUMER SPECIALTIES LIMITED |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20011227 Year of fee payment: 20 Ref country code: CH Payment date: 20011227 Year of fee payment: 20 |
|
BECH | Be: change of holder |
Free format text: 20010919 *HUNTSMAN INTERNATIONAL LLC |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP Ref country code: FR Ref legal event code: CD |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20020114 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20020115 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20020129 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20020207 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20020221 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 20020227 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20020328 Year of fee payment: 20 |
|
NLS | Nl: assignments of ep-patents |
Owner name: HUNTSMAN INTERNATIONAL LLC |
|
NLT1 | Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1 |
Owner name: RHODIA CONSUMER SPECIALTIES LIMITED |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20030206 Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20030206 Ref country code: CH Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20030206 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20030207 Ref country code: LU Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20030207 Ref country code: AT Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20030207 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Effective date: 20030206 |
|
BE20 | Be: patent expired |
Owner name: *HUNTSMAN INTERNATIONAL LLC Effective date: 20030207 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
EUG | Se: european patent has lapsed | ||
NLV7 | Nl: ceased due to reaching the maximum lifetime of a patent |
Effective date: 20030207 |
|
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |