CA2069966A1 - Linear viscoelastic aqueous liquid automatic dishwasher detergent composition - Google Patents
Linear viscoelastic aqueous liquid automatic dishwasher detergent compositionInfo
- Publication number
- CA2069966A1 CA2069966A1 CA 2069966 CA2069966A CA2069966A1 CA 2069966 A1 CA2069966 A1 CA 2069966A1 CA 2069966 CA2069966 CA 2069966 CA 2069966 A CA2069966 A CA 2069966A CA 2069966 A1 CA2069966 A1 CA 2069966A1
- Authority
- CA
- Canada
- Prior art keywords
- ion
- acid
- compo
- detergent composition
- linear
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 239000003599 detergent Substances 0.000 title abstract description 18
- 239000007788 liquid Substances 0.000 title abstract description 18
- 239000011734 sodium Substances 0.000 claims abstract description 22
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 17
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 5
- 239000007844 bleaching agent Substances 0.000 claims description 16
- 239000000460 chlorine Substances 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 7
- 230000008719 thickening Effects 0.000 claims description 7
- 239000005708 Sodium hypochlorite Substances 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 25
- 239000000194 fatty acid Substances 0.000 abstract description 25
- 229930195729 fatty acid Natural products 0.000 abstract description 25
- 150000004665 fatty acids Chemical class 0.000 abstract description 22
- 150000003839 salts Chemical class 0.000 abstract description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002562 thickening agent Substances 0.000 abstract description 10
- 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 abstract description 8
- 229910052700 potassium Inorganic materials 0.000 abstract description 8
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 7
- 239000011591 potassium Substances 0.000 abstract description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 abstract description 4
- 235000021355 Stearic acid Nutrition 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 3
- 230000006870 function Effects 0.000 abstract description 3
- 238000010348 incorporation Methods 0.000 abstract description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000008117 stearic acid Substances 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 62
- 239000002253 acid Substances 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 229910052783 alkali metal Inorganic materials 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 150000001340 alkali metals Chemical class 0.000 description 12
- 239000006260 foam Substances 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- -1 alkali metal cation Chemical class 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- JVTIXNMXDLQEJE-UHFFFAOYSA-N 2-decanoyloxypropyl decanoate 2-octanoyloxypropyl octanoate Chemical compound C(CCCCCCC)(=O)OCC(C)OC(CCCCCCC)=O.C(=O)(CCCCCCCCC)OCC(C)OC(=O)CCCCCCCCC JVTIXNMXDLQEJE-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 6
- 241000212342 Sium Species 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 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 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 244000228957 Ferula foetida Species 0.000 description 3
- 241000283986 Lepus Species 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241001274660 Modulus Species 0.000 description 2
- 241000429017 Pectis Species 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000002844 continuous effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- XILIYVSXLSWUAI-UHFFFAOYSA-N 2-(diethylamino)ethyl n'-phenylcarbamimidothioate;dihydrobromide Chemical compound Br.Br.CCN(CC)CCSC(N)=NC1=CC=CC=C1 XILIYVSXLSWUAI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 101150034533 ATIC gene Proteins 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 101100099490 Alkalihalobacillus halodurans (strain ATCC BAA-125 / DSM 18197 / FERM 7344 / JCM 9153 / C-125) thiY gene Proteins 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 101100087530 Caenorhabditis elegans rom-1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000237074 Centris Species 0.000 description 1
- 241000736839 Chara Species 0.000 description 1
- 241000196359 Dalbergia melanoxylon Species 0.000 description 1
- QFVAWNPSRQWSDU-UHFFFAOYSA-N Dibenzthion Chemical compound C1N(CC=2C=CC=CC=2)C(=S)SCN1CC1=CC=CC=C1 QFVAWNPSRQWSDU-UHFFFAOYSA-N 0.000 description 1
- 101100021869 Drosophila melanogaster Lrch gene Proteins 0.000 description 1
- 101150039033 Eci2 gene Proteins 0.000 description 1
- 206010015137 Eructation Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000152447 Hades Species 0.000 description 1
- 241000243251 Hydra Species 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 101100536883 Legionella pneumophila subsp. pneumophila (strain Philadelphia 1 / ATCC 33152 / DSM 7513) thi5 gene Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 101100059652 Mus musculus Cetn1 gene Proteins 0.000 description 1
- 101100059655 Mus musculus Cetn2 gene Proteins 0.000 description 1
- 101100305983 Mus musculus Rom1 gene Proteins 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ATTZFSUZZUNHBP-UHFFFAOYSA-N Piperonyl sulfoxide Chemical compound CCCCCCCCS(=O)C(C)CC1=CC=C2OCOC2=C1 ATTZFSUZZUNHBP-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 101100313003 Rattus norvegicus Tanc1 gene Proteins 0.000 description 1
- 241000612182 Rexea solandri Species 0.000 description 1
- 101100240664 Schizosaccharomyces pombe (strain 972 / ATCC 24843) nmt1 gene Proteins 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 101100162169 Xenopus laevis adrm1-a gene Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000010936 aqueous wash Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229960001631 carbomer Drugs 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- YZIYKJHYYHPJIB-UUPCJSQJSA-N chlorhexidine gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.C1=CC(Cl)=CC=C1NC(=N)NC(=N)NCCCCCCNC(=N)NC(=N)NC1=CC=C(Cl)C=C1 YZIYKJHYYHPJIB-UUPCJSQJSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- MGKJFRPUFVNFPI-GPHNJDIKSA-N dcid Chemical compound C1=CC=C2[C@@]3(OC(=O)C)[C@]4(OC(C)=O)C5=CC=CC=C5C(=O)[C@@H]4[C@H]3C(=O)C2=C1 MGKJFRPUFVNFPI-GPHNJDIKSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052610 inosilicate Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 244000145841 kine Species 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- ONHFWHCMZAJCFB-UHFFFAOYSA-N myristamine oxide Chemical compound CCCCCCCCCCCCCC[N+](C)(C)[O-] ONHFWHCMZAJCFB-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229940099990 ogen Drugs 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 description 1
- ACXGJHCPFCFILV-UHFFFAOYSA-M sodium;2-(4-chloro-2-methylphenoxy)acetate;3,6-dichloro-2-methoxybenzoic acid Chemical compound [Na+].COC1=C(Cl)C=CC(Cl)=C1C(O)=O.CC1=CC(Cl)=CC=C1OCC([O-])=O ACXGJHCPFCFILV-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
Abstract
LINEAR VISCOELASTIC AQUEOUS LIQUID
AUTOMATIC DISHWASHER DETERGENT COMPOSITION
ABSTRACT OF THE DISCLOSURE
Automatic dishwasher detergent composition is formulated as a linear viscoelastic, pseudoplastic, gel-like aqueous product of exceptionally good physical stability, low bottle residue, low cup leakage, and improved cleaning performance, Linear viscoelasticity and pseudoplastic behavior is attributed by incorporation of cross-linked high molecular weight polyacrylic acid type thickener. Potassium to sodium weight ratios of at least 1/1 minimize amount of undissolved solid particles to further contribute to stability and pourability. Control of incorporated air bubbles functions to provide the product with a bulk density of about 1.35 to 1.40 g/cc which roughly corresponds to the density of the liquid phase. Stearic acid or other fatty acid or salt further improve physical stability.
AUTOMATIC DISHWASHER DETERGENT COMPOSITION
ABSTRACT OF THE DISCLOSURE
Automatic dishwasher detergent composition is formulated as a linear viscoelastic, pseudoplastic, gel-like aqueous product of exceptionally good physical stability, low bottle residue, low cup leakage, and improved cleaning performance, Linear viscoelasticity and pseudoplastic behavior is attributed by incorporation of cross-linked high molecular weight polyacrylic acid type thickener. Potassium to sodium weight ratios of at least 1/1 minimize amount of undissolved solid particles to further contribute to stability and pourability. Control of incorporated air bubbles functions to provide the product with a bulk density of about 1.35 to 1.40 g/cc which roughly corresponds to the density of the liquid phase. Stearic acid or other fatty acid or salt further improve physical stability.
Description
Mf~Y 2~ 3Z ~ P11 C~LI~TE Pf~ l ENl C/EPT . P 1/45 2~69~66 ~P - ~R- 4~81J
l.lN~AR V~SCOEI~ST~C AQUE~OUS
IJIQUID ~UTOMATIC DISHWASH~R
~ET~3RG NT CO~IP :)SITION
Rela~ed Application~
Thi~ appli~tion if2 a Conti~ation~ Par~ of U.~. Serial No. 07~353,71Z filed May 18, 198~.
Fi,çld Q~ II1V~
The pre~ent in~rention relate~ generally to a~ ~utomatic diah~aaher detergen~ compo~i~ion in the Eorm of ~ n aqueou6 linear vi~ccelasti~ liguid.
Liquid automatic diahwa~her deter~ent compo~;i ;ions, bVth aqueou~ and A~onaqueou~ h~ve recerltly received m~A.c.l~ attention~
and the a~ueoll~ product~ have ~chieved con~ercia~ opulari~y.
The ac~e~?tanc~ an~ po~ulari~y of the liquid f 3rmu1ations a~3 compare~ to the more conventiorlal powder produc tc ~t~m~
from the coYlvenience and per~orm~nc~3 of ~he 1i~uicl prod~ct~.
However, ev~n the be3st of th~ rrently availa~ liquid ~ormulation~ sti11 ~uf ~er ~rom two maj or probl~ s, ~rod.uct ~ha~e ir~tability and ~ot~le re~idue, tlncl to ~on~e extell~ c~p lea~caSte f rcm the di~pen~er cup of the a~tomatic d l.~hwa~hing machine .
Rep~e~en~ativ~ o~ the re1~vant pa~ t art i.n thi~ area, m~nt;ion i~ mad~ vf Rek, U.S. Patent a~,5S~5o4i ~3u3h, e~ al., U.S. Patent; 4,~26,736; Ulrich, U.S. Patent 4,43:l.,S59;
Sabatellil U.S. Patent 4,147,650; ~a~lcot, U.S. S~a.cen~
-4,079,015; IJeikh~m, U.S. Patent 4,116,~43; Milol~Gl, U.S. P~tent ~lhY c~ !B J u2~ F~I~I CC~L~HTE PHTEIIT ~:lEPT. p,Z/45 2~69966 4,521,332; Jones, U.5. Pater.Lt 4,597,a8~; Heile, U~S. ~atent 4,512,90a; ~ai~em, ~.5. Patent 4,753,7~8; S~batel-Li, IJ.S, Pa~en~ 3,579,455; ~ynam, U.S. Patent 3,684,722: ot.~er pat~t~
r~lating to thic~ened detergent compooition~ incl~lcl~ U.S.
Patent 3,gP5,668; ~.K. Patent A~plication~ ~ 2,11~ 9A and G~ 240,450A; U.S, Patent 4,511,~87; U.S. Patent 4,'iS2,409 (Drapier, et al.); U.S. ~atent 4,801,395 (Drapi~r, et al.);
U.S. P~ent 4,801,395 ~Drapier, et al.~. Cos~monly a~signed co-pending ~at~r.Lt~ ixLclude, fo~ ex~L~ple, Serial Nb, 204,476 filed June ~, 1988; Serial No. 924,38~, filed o~o:::)er 29, 19B~i S~rial No. 323,138, filed M~Lrch 13, 1989; ',e;sial No.
087,836, filed August 21, 1~87; Serial ~. 328,716, filed Mar~h ~7, 1~8~; Serial No. 323,137, file~ March ~.3, 1~89;
Serial ~o. 323,134, filed ~aLrch 13, 1~89.
The ~resent invention provi~es a solution tc) :he abo~e problems .
Figure3 1-13 ar~ rh~ogxams, plotting ela~tic~ modulec~ G' ~0 and ~iCcou~ modulu~ G" a~ a ~unction o~ a~pl.~ed ~I;rain, ~or the compo~ition~ Oe ~Lmple 1, Form~lations A, ~, D, ~, ~, H, I and ~, E~ample 2, A and ~, ~xam~?le 3, L and M cL:lLd Com~arativ~ ~ample 1, xe~pe~ively.
5Y~
Ac~ording to the pre~ent invention there i~i l?rovided a novel a~ueous liquid autos~L~ic di~hwa~her d~ter~e.~t compo~itiorL. The compo~ition i~ chcaracteriæed by it~ linear Y 29 ~ C~ PM COLG~iTE F'hTEl~T D~F'T . p, 3/45 20B99~
viscoela~tic behavior, Yub~tan~ially in~efinite s~al~ility against ph~ eparation or se~tling of dis olved c,:r ~us~ended particles, low levels of ~ottle re~idue, relativel.y hi~h ~ulk density, and sub~tantial a~ence of unbound or free~ water.
Thi~ unique ,~ombination of pro~ertie~ i9 achieved ~:y vi~tue of the incorpo~atiOn i~to the a~ueous mixture of di~lt,~a~hing de~ergent ~ur~actant, alkali metal de~ergent ~uild~.r 9alt (~) and ~hlorine bleach compound, a ~mall but e~ectivt. amount of high molecular weight cxoss-linke~L polyacrylic acicL type LO thickening agent, a phy~ical stabilizing amoun~ of a long chain fa~ty acid or ~alt thereo~, an~ a ~ource of pota~sium io~ ~o pro~id~ a pota~ium/~odium weight ratio ;.n the range of from ~bout 1:1 to a~o~t 45~ uch that ~ub~tanl,ially all of the detelge~t builder ~alt~ and other normally ~olid deter~en~ additi~es present in the composition ace present di~olved in the a~ueous phase. The compo~ition.~ ~re f~rther characterized by a bulk density o~ at-least about: 1.32 g/cc, ~uch that t'he densit~ o~ the polymeric pha~e and t:he density of the aqueou~ ~continuou~) pha~e are a~proxima~e..y the came.
~.~
~ he compo~ition~ of thi~ inven~iorl are aqueous liquids containing ~arious cleansing active ingr~dients, ,letergent adju~ant~ ruct~ring and ~hickeni~ agent~ ancl 3tabllizing 2S com~onent~, although ~omo ing~edients may serve m~re than one of the~e ~unc~ions.
The a~vantageous characteri~3tic~ o~ the comE~o~ition~3 of this in~ention' inclu~ing physîcal ~tability, lo~l bottl~
MhY 29 ' 9c' ~ 'J8P~1 CSL~:~HTE PHTEI`IT I~EF'T . p, 4/45 2~69966 re~idue, hi~h cleaning pex~ormance, e.g. low spot~ g and ~ilmi~, dirl: re~idue removal, and 90 on, and ~upexior ae~thetics, are believed to be at~ributed to se~ere~l interrelated factor~ ~uch a~ low ~olid~, i.e. und:~~olved i particulate content, product den~i~y and linear v:i~coela~tic rheology. ~hese factor~ a~e, in turn, depandent oll ~e~eral critical compositional compone~t~ o~ the ~or~lat.ic,n9, namely, (1) the inclu~ion of a thickenin~ effec~ive amount of polymexic thickening agen~ havin~ high w~ter absorption capacit~, exemplified ~y hi~h mol~cular weight c~o;~-linked polyacrylic a~id, (2) inclu~ion of a phyYi.~al ~ta~Llizing ~mount of a lon~ chain fa~ty acid or ~alt thereoi', (3) pota~ium ion to sodium ion weight ratio K/Na in tlle range of from ~bout ~:1 to 4S:l, e~pecially ~rom 1;1 to 3:1, and (4l a product bullc den6ity o a~ lea&t a~out 1.32 g/cc, ~uch that the b-llk derl~ity and liguid pha~e density are ab ~lt the ~ame.
The po~ymeric t~ickening agent~ contribute t:c.l ~he linear vi~coela~tic r~eology o~ the inv~Ntion compo~itioI:!.s. ~ used herein, ~llinear ~i~coela~tic "o~" linear vi~coela~!ticity"
mean~ ~hat the ela~tic (~torage) moduli (G') and.~,he vi~cou~
(lo~s) moduli (G") are both ~ubstantlally independent of ~txain, at least in an applied ~train range of fix()m 0-50~, and preferably over a~ applied ~train range of from 0~80~. More ~peci~lcally, a co~po~ition i~ con~ideLed to ~e l-nea~
vi6coela~t~c for pur~o~ej of ~his invention, if c~er the ~train rang~ o~ 0-50~ the ela~ic modul~ ag a minim~m val~e of 100 dyne~/~q.cm., preferahly at least ~ 0 . _", ~,.. .
dy~efi/s~.cm., and varie~ lea~ ~han about 500 ~yn~ q.cm, Mf:~Y 2~ ' 92 la,~: ~i9PI~1 COL~ TE P~TE~ T ~EPT . p . 5/45 2 ~ 6 preferably le~s than 300 dynes/sq.c~., e~pecially E~referably les~ than loO dyne~/cq.~m. Prefera~ly, the miniml~m valu~ of G~ and maximllm varia~ion of G~ applie~ over the ~t~.~in range of 0 ~o 80'~. Typically; tha varia~ion in lo~ mod~ " will be le~s than that of G~. Ac a furth~r characteri~?:ic o~ the preferred lin~ar ~vi~oela~tic ~ompo~itions the ral~io of G"/G
~tan*~) i9 ~ess than 1, prefer~bly les~ than Q.8, ]:,ut more than 0.05, preferably ~ore than 0.2, at lea~t ov~r the ætrain ran~e of 0 to 50~, and ~referably over the strain :range of 0 to 80~. It ~hould be noted in this ~egard tha~ ~ I;train i~
~hear s~raiu xlO0, By way of ~urther ~xplanation, the ela~tic ~ or~ge) moduluæ G' i8 a meaæure of the energy ~tored a~d ~l~trieved when a Rtraln ic applied to ~he compo~,ition while viscous (103~) modulu~ G~ a ~easure to the amou~t of erler~y dis3ipated as heat when ~tr~in i3 applied. rrherefore, a ~alue of tan , 0.05c tan ~1, prefera~ly ao o.~ c tan c 0.8 means that the compo~ition~ will re~airl ~ufflcienl. energy when a ~tre~s ox str~in ig ap~lied, at least over the lixte~t e~pected to be encou~tered for product~ o~ thiY t',~e, Por exa~ple, w~len poured from or ~hake~ in ~he bottle, or stored ~5 in the di~hwa~hor deteryent di~pen~er cup of an alltomatlc di3hwashing machine, ~o return to it~ previous c:o:ldition when the ~,tre~s or ~train i~ removed. The compo~itior,s with tan va1ues in theBe range , ~herefore, will a1so hav~! a hi~h I~IH~ C~ 'iJPI`I l_OLGHTE PHTEI IT ~EPT . P. 6/45 2~69966 cohesive property, ni~mely, whe~l a shear or strain i.3 applied to a portion of the com~o~ition to cause i~ to flow, the ~urro~n~ing portions will follow. As a recult of t;hi~
cohe~i~e~ess of ~he ~ubject linear viecoela~ic cor:lposition~
S the compo~itions will readily ~low uniformly and h~:lmogeneously from a bottle when ~he bottle is tilted, ~here~y c~:ntributing to the physical (phase) stability o~ ~he ~o~mulation and the low bottle re~idue (low prod~ct 10~8 in ~he bot~ ) which characterizes ~he in~ention compo~itions. The li.nl:ar viscq~laj~ic proper~y al~o contfibutes to improved physical ~tability ac~ain~t pha~e cepa of any undi~cl~ed ~iu;~ended particle~ by providing a resi~ance to movement cf the particle~ c.~le to the ~rain exe~te~ by a particlell~n the ~urrounding ~luid medium.
Al~o cont~ibuting to the phy~ical ~ta~ility ancl l~w ~ottle re~idue of the invention co~posi~ions i~ t:he high potassium to ~odium ion ratios i~ t~e range o~ t~ 45:1, pr~ferably 1:1 to 4;1, e~peçially preferiably from 1~05:1 to 3:1, for exi~mple 1.1;1, 1.2:1, 1.5:1, Z:l, or 2.'i:1. At these ratio~ th~ solubility of ~he ~olid salt componen~ uch a~
de~ergent buildex ~alt~, bleach, alkali metal ~ .cate~, ancl the like, i~ cub~tantially increa~ed ~ince the pr!~ence of the potassium ~+) ion~ require~ water of hyd t:him the sodium (~a+) ions, ~uch that more water ic available to ~ solve these ~alt com~ound~. Ther~fore, all or nearly aLl of the no~m~lly ~oli~ com~onent~ are pre~ent dissolved il~ the a~ueou~
pha~e. Since there i~ none or only ~ very low ~ercentage, i.e. le~ han 5~, pre~orably le~ than 3~ by ~ h~, of I`l~Y 2~ ' ~2 ~ 51~PI`1 C~)L~aflTE P~lTEl`lT DEPT . 2 0 ~ 6 8uspend~d ~oLids presen~ in the formula~ion there i.3 rlo or only reduced ~ende~cy for undi~solved particl~ to ~ettle out o~ the compo~ition~ causin~, or example, for~atic~rl of hard masses of particles, which could reault in hiyh but:tle S residues (i.e. los~ o~ pro~uct). Furthexmore, an~r undi~solved 801id~ tend to be ~xe~ent in extremely ~mall ~art:ic:le ~ize~, usuall~ collold~l or ~ub-col~oidal, ~uch as 1 micron or ~e~, ~h~reby further reducing the tendency for the ~ndi,;l~olved particles t~ settl~.
~ ~till further attribute of t~e invention co:l.lposition~
contributinc~ to the overall product ~tabili~y and ow bottle re~idue i8 t;he high water a~orptio~ capacity of tlle cros~-linked ~olyacrylic acid type thickening agent. P.~ a result of thi3 high wa~er ab~orption capaci~y virtu~lly al:L ~f thQ
~5 a~ueous veh:icl~ componen~ i~ held ti~h~ly bound tCI the ~olymer - matrix. Th~3~ore, there i~ no o~ s~bstantially rlo ~r~e wa~ex pre~ent in ~he invention composition~. This ab~eI!ca of f ree water (a~ well as the cohesivenes~ o~ the compo~:Lt:ion) iæ
manifested ~y ~he o~ervation that when ~he compo~!itio~ i~
poured from a bottle onto a ~locc o~ water ab~or~lnt fllter pa~er vi~tually ~o watex i~ ab~orb~d onto the filler pa~er a~d, furthermo~e, the ~as~ of the linear vi~coela.itic material poured onte the filter pa~er will retain its ~ha~ and ~t~uC~ure ~Intil it i~ a~ain ~u~jected to a ~re~ or ~txain.
2~ A~ a re~ul~ of the ab~énce o~ u~ound or free ~I.t~r, ~here i~
virtually I10 pha~ eeparatin between the aqueou~ l?hase and the polymeri~ mAtrix or di~solved ~olid particle~. T~is . ~, ~ .
cha~acteril3tic i~ manifesced hy the fac~ that when the subject ~ht'l' ~9 ' '~ '.lF'M CUL~fl rE ~TE~`11 rlEPT . p, ~3/45 compo~itions ax~e Yubjected eo centri~u~ation, e.~. at 1000 rp~
for 30 minu~lss, there is no ~hase ~epa and the comEI~sition remains homo~eneou~.
However, it has also been di~covered that linea~
viscoelasticity and K/Na ratio~ in ~he a~ove~menti(:ned range do not, by themselve~, assure long term physical ,s~ability (a~
de~ermi~ed by phase ~epa). In order to maxi~i~e ;p~:,y~ical (phase) sta~ility, ~he density of the compo~itio~ hould be controlled ~uch that ~he bulk ~en~ity of the liqui,l ~hase i~
.0 approx~imatel,y ~he ~ame a~ the bulk dengi~y of the entire composition, including the polyme~ic thickening zl~ent. Thi~
con~rol and equalizatio~ of t.he den~itie~ i~ achie~ed, according to the invention, by providing the coml;~c,~iti~n with a bulk den~:Lty o~ at leas~ 1.32 g/cc, prefer~bly a.c lea~t 1.35 g/cc, up to about 1.42 g/cc, preferably up to abo~l~ 1.40 g/cc.
Furt~ermo~e, to ~chievo the~e relatively high bul~: ~en~itie~, it iB impo~ant to minimize the amoun~ of air incc,rporated into the composition (a den~ity o~ about 1.42 g/cc~ is es.~entially e~ui~alen~ to ze~o air Content).
It ha~ previou~ly been found in connec:tion ~ h other ~ypes of thic~ened agueous liguid, autom~ic di~h~,~a~her ~ter~ent compo~itio~ that incorpo of ~inely di.v:~.ded air ~ubble~ in amount~ up to about a to 10% by ~olume can function effectively to stabilize the com~o~ition a~ain~t,~ha3e ~epa, but that to prev~nt a~lomeration of or eccape o~ the air bu~ble~ it wa~ impor~ant to incorporate cer~ain ~ race active ingrediellt~, ~speclally higher fatty acids and ~;.h3 ~alts th~reof, such as Ctearic acid, behenic acid, pa;lmitic acid, I`IH`~ 2~ 'PM COLGQTE P~iTENT LIEPT. 2 Q
sodium ctear~te, aluminum ~tearate, and the like. rhe~
s~race acti~e agents a~paren~ly ~nctioned by fo~ ing ~n int;~rfacial ~ilm at the ~bble ~ur~ace while ~190 I'ol~ing hyd~ogen bond~ or co~tributirlg ~o the electro~ta~:Lc attraction with the 6uæ~ended par~icles, ~uch that ~he air bl~.ble~ and attracted pa~ticle~ ~ormed agglomerates o~ ~pprox.i~l:~tely the ~ame density as ~he den~ity of the conti~uou~ u..d phase.
Therefore, in a preferred embodiment of the p:esent invention, .tabiliza~ion of ai~ ~ubble~ which may l)ecom~
incor~oratrecl i~to the composition~ durln~ ~o~mal proce6~ing, ~uch a~ duri.ng ~arious mixing ~te~, iY avoided ~ po~t-addi~g the surface active ingredient~, including fatty acid or fatty acid 3al~ ~t;a~ilizer, to the remainde~ of ~he co~E~ition, under low shear conditions u~ing mixing device~ de:3igned to lS mini~ize cavit~tion and vortex form~tion.
Ac will be de~cri~ed in gre~er d~tail below ~he ~urface acti~e ingredients pre~ent in the co~lposition wiLl incl~de the main detergent ~urface active cleaning agen~, ~nd will alæo ~referably include anti-foaming ayent and hi~her ;I.atty acid or 20 8alt thereof ~ a phy3ical ~tabilizer.
~ emplar~ o~ ~he cro~-linke~ pol~acrylic a.ci.d-ty~
~hick~nin~ age~6 are the products ~old by B.F. ~ odrich under th~ir Car~c~ol trademark, e~pecially Ca~bopol ~41, which i~
the mo~t ion-in~en~iti~e of thi~ cla~6 of pol~m~r3, and 2S Carbopol ~L0 and Carbo~ol ~3~. The Carbopol resi~, al~o known as I~Carbomer~, are hydro~hilic high molecullr weight, croiss-linked ac~yl~c acid polymers having an avh!rilge ~lh~ c~ ' 9c Cl_: '>8PM CC)L~hTE PhTENT L1EPT . 2 0 6 9 9 6 6 P 10/45 eqlivalent wei~ht of 76, and ~he general structur~: illustrated by the ~ollolwing ~ormula;
H H
I I
C C
H C
~O O n.
Carbopol 941 ha~ a molecular wei~ht of abo~t 1,250,~00;
Carbopol 940 a molecular weight o~ approximately 4 000,000 ~nd Car~o~ol 934 a mol~cular weight o~ approximately 3,000,000.
The C~rbopol. r~sin; are cro~-linked with polyalke;~
polye~her, ~.g. ahout 1~ of a polyallyl ether of ~llcro~e lS havin~ an average o about S.8 allyl ~rou~ $or eal~h molecule of ~ucrose. Further detail~d informa~ion on the C',~rbopol re~ina i~ a~ailable from ~.F. Goodrieh, see, for ~ ampl~, the B.F. Goodrich cataloy GC~67, Car~opol~ Wa~r Sol~le ~e6in~.
While mo~t favorable re~ult~ have been achie~ed with ~0 Carbopol ~41 polyacrylic re~in, o~her lightly cro~s-linked polyacrylic acid-type thickeni~g ~g~nt~ can also ~:e used in the compo~itions oE thi~ in~n~io~. As u~ed hex~:ln llpolyacrylic acid-typell r~f~r~ to water-~oluble :h,~mopolymer~
of acrylic a~id or methacrylic acid or water-di~,p~x6ible or wa~er-~oluk~le ~alt~, e~ter~ or amicles ther~of, or water-~oluble coE)olymer~ o~ the~e acid~ o$ their ~alte;, e~ter~ or ameide~ with oach other or with one or more o~er e~lenically unsaturated monomers, ~uch a~, for e~mple, styrelle, malaic acid, maleic anhydride, 2-hydroxyethylac~ylate, a.~rylonitrile, ~inyl acet;~te, e~hylene, propylene, and the lik~.
r I I l lL ~ I L r ~ I Ll ~ I L LI I .
r-20~9~6 The homopol~ner~ or copolymer~ are characterized by their hig~ molecular weight, in the ran~e o from a~ouc 500,000 to 10,400,000, prefera~ly 500,000 to 5,000,000, e~pecially from about 1,000,000 to ~,000,000, and by their water ~olubility, ~enerally at leaæt to an exten~ of up to about 5~ by wei~ht, or more, in water at 25C.
Theee thi~kening agents are uged in their lightly cro~-linked form wherein ~he cro~s-linking may be accomplished by means known in ~he polymer ar~, a~ by irradiation, or, preferably, by the incorporation into the monomer mixture to be pPlymerized of known chemical CrO8~ - linking monomeric agent~, typically polyunsa~ra~ed (e.g. diethylenlcally un~atura~ed~ monomers, such a~, for example, divinylbenzene, divinyle~her of diethylene ~lycol, ~, N'-methylen~-bi~acrylamide, polyalkenylpolyether~ (~uch a~ de~cribed abo~e), and ~he like. Typicall~, amounts of cro~s-linking agent to be incorporated in the final polymer m~y range fro~
about 0.01 to about 1.5 percent, prefera~ly from about 0.05 to abou~ percent, and especially, preerably from a~out 0.1 to about 0.9 percent, by weighc of cro~s-linking agent to ! weight of total polymer. Generally, thoge ~killed in the art will recognize ~hat the degr~e of cro~-linking should be 6ufficient to impax~ some coillng of the otherwi~e ~enerall~
linear polymeric compound while maintaininy the cross-linked polymer at lea~t water di~ersibl~ and hi~hly water-3wella~1e in an i~nic a~ueous medium. I~ is also uIiderstood ~hat the water-swelling of t~e polymer which provide~ the desired thickeni ~ a ~ vi~cou~ propertieg ~enerally depends on one or I Ir~ n I L I r~ I L ~ ~ I L~L.I I . I . L~
~Ofii~g66 .
two mechanism~, nam~ly, conver~ion o~ ~he ~cid group containing polymers to ~he corre~ponding ~alt~, e.g. ~odium, ge~erating negative charge~ along the polymer backbone, thereby ~au~ing the coiled molecules to expand and thicken the S ayueou~ ~olution; or ~y forma~ion of hydrogen bonds, for : oxample, ~etween the ca~oxyl groups of the polymer ~nd hydroxyl donor. The ~or~er mechanism i~ especially important in ~he ~recent invention, and ~herefore, the pre~erred polyacrylic acid-type thickening ayeIltj will co~ain free car~oxylic acid (COOH) groupx along the polymer backbone.
Also~ it will be understood t~t the degree of cross-linking ~hould not be ~o hlgh as to render ~he cross-linked pol~ner completely insoluble or non-digper6ible in water or inhi~it or prevent the ~ncoiling of the polyme~ molecule~ in the presence of the ionic aqueous By~em.
The amount of the high molecular weight, cro~-linked polyacrylic acid or other high molecular weight, hydrophilic cro~s-linked polyacrylic acid-type thickening agent tO impar~
, the de~i~ed rheological proper~y of line~r ~i~coela~ticity will generally be in the range o~ from about 0.1 ~o 2%, preferably from abou~ 0.2 ~o 1.4~, by w~ight, ~d~ed o~ the weight of the compo~ition, althouyh the amou~ will depend on the partlcular croca-linki~g agent, ionic ~rength of the compo~i~ion, hydroxyl donor~ and the like.
The co~po~itions of thi~ inverl~iorl m~l~t include ~ufficient amo~nt of po~a~sium ion~ and ~odium ion~ to provlde a weight ratio of ~/~a of at lea~t 1:1, prefer~ly from 1;1 to 45:1, especially from about 1:1 to 3:1, more preferably from 2~99~6 1.05:1 ~o 3:1, 6uch a6 1.5:1, or 2;1. When r~he K/Na ratio i~
le99 than 1 ~here i~ insuff icient colubility of the normally ~olid i~gredien~s ~herea~ when the K/Na ratio ic~ more than 45, e~pecially when it i~ greater than a~out 3, the product becomes too liquid and phase ~eparation begin~ ~o occur. W.hen ~he K/~a ratio is more t~lan 45, especially whe~l it i~ greater than a~out 3, the product ~ecome~ too liquid and phase separation be~in~ to occur. When the K/Na ratio~ become muc~
larger ~han ~5, ~uch ~8 in all or mostly potassium formulation, the polymer thlckener lo~e~ it~ a~orptior c~pacity and begin6 to ~alt out o~ ~he aqu~ou~ p~a~e.
The potassium arld ~odium ions can be made present in the compo~i~ion~ a~ the ~lkali metal ca~ion o~ the detergent builder ~alt(~), or alkali metal silica~e or alkali metal hydroxide comporlent~ of the compositions. The alkali metal cation ma~ also be present in the compo ition~ aG a componen~
of an ionic de~ergent, bleach or other ionizable salt compound addi~i~e, e.~. alkall m~tal car~onate. In de~er~ining the K/Na weight ratio~ all of these ~ources should be taken into consideration.
Speci~ic ex~mpl~ of ~c~r~en~ huilder 6al~ inclu~e the polypho~pha~e~, ~uch as alkali metal p~oE)hosphar~e, alkaJ.i me~al tripolypho~phate, alkali m~tal metapho~pha~e, and the like, for example, ~odium or potas~ium txipolypho~phate ~ (hydrated or anhydro~ etra~odi~m or tetrapotassium pyropho~phate, ~odium or pota~siu~ hexa-metapho6pha~e, tri~odium or ~ripotassium orthopho~phate ~nd the ~i~e, ~odium or po~a~3ium carbonate, ~odium or po~a~Yium citrate, ~odium ox 2~99~
potassiuM nitrilocriaceta~e, and th~ like. The pho~phate builder~, where no~ pr~cluded d~e to local re~ula~ion~, are pref~rred and mixcure~ of tetrapota4~ium pyropho~phate (TKPP) and sodium ~ripol.ypho~phate (NaTPP) (especially the hexahydrate) are e~pecially p~eferred. Typical ratios of Na~PP to TKPP ~re from a~out 2:1 to i:8, especially from about 1:1.1 to 1:6. The to~al amou~t of ~etergenc builde~ salts i~
prefera~ly ~rom about 5 to 35~ ~y weight, more prefera~ly from abou~ 15 to ~, especially from about 18 to 30~ by w~ight of the compocition.
In connection with the builder 6alts are optionally u~ed a low molecular wei~ht noncros~linked pol~acrylates havlng a ~olecular weigh~ of abouc 1,000 to about 100,000, more preferably about 2,000 ~o about 80,000. A preferred low molecular ~eigh~ polyacrylace i~ Nora~ol LMW45~ man~factured ~y ~orsoshaas and having a molecular wei~ht of abou~ 4,SOO.
These low molecular wei~ht polyacrylate~ are employed at a concentration of about 0.1 to lS ~t.~, more preferably ~.25 to : 10 wt.~.
Other useful low molecular weight noncro~linked polymer~
axe Acusol~640D provided by ~ohm ~ Ha~ c)rasol QR1014 ~rom Norsohaaq having a GeC molec~lar weight of 10,000.
The linear vi~coela~tic compositions of ~is invention ~ay, and preEerably ~ill, contain a ~mall, but stabilizing ~5 effective amount of a long chain fatty acid or monovalent or po].yvalent calt thereof. Although the manner ~y which the fatcy acid o~ ~alt ~oncribute~ to th~ rheolo~y and stabili~y of ~he compo~i~ion ha~ not been fully elucidated it is I Ir~ .J ~.1 1 1 .. ~ .r~ I rl I L.l I I L'~l I . r~
hypothe~ized that it ~ay function as a hydrogen bonding ~ 9 or cro~s-linking agent for the polymeric thickener.
The preferred lon~ chain fd~ty ~cid~ are the ~ligher aliph~tic fatty acids having ~rom ~cuc ~ ~o 22 c~rbon atom~, more preerably from a~out 10 to ~0 carbon atomq, and e~pecially preferably from about 12 to 18 carbon atoms, and e~pecially preferably from abou~ 1~ to 18 car~on atoms, inclu~i~e of the carbon atom of the carboxyl group o the fatty acid. The aliphatic radical ~ay ~e ~aturated or un4aturated and m~y be ~raight or branched. Straight chain ~aturated fatty acid~ are p~e~exred. Mi~tures of ~atty acids may be used, such a~ Lho~e derived f~om natu;~al Gources, suc~
a6 ~llow fatty acid, coco fatty acid, ~oya fatty acid, mixtures o these acid~, etc. Stea~ic acid and mixed fatty acids, e.~. stearic acid/palmitic acid, are preferred.
; When the ~ree acid form of the fatty acid i~ u~ed directly it will generally ~s~ociate wi~h ~he pota~ium and sodium ion~ in the aqueou~ phase to fo~1n che co~re~ponding alkali metal fatty acid 90~p. However, the fatt~ acid ~alts may ~e directly added ~o t~l~ comr~o~i~i.on a~ ~odium ~alt or pota~ium salt, or as a ~olyvalent met.al ~1L~ althouyh the ~lkali metal salt~ of the ~a~ty acids are preferre~ fa~ty acid ~alts .
The pre~erred polyvalen~ metals are the di- and tri-valent metals of Grou~ IIA, IlB and III~, such ~s sna~n~sium,calcium, ~luminum and zinc, ~lthou~h other polyv~lent metals, incl~ding those of Groups ~ , rvA~ ~rA, IB, I~rB~ ~7B VIB, and VII~: Qf ~e Periodic ~able oI; che Elernent~3 can alqo be 2~699~;
used. ~pecif1c ex~nple~ of ~uc~l other po~yvalent metal6 include Ti, Zr, v, ~ , Fe, Co, ~i, Cd, Sn, Sb, Bi, etc.
Generally, the metal~ may ~e pre~ent in the divalen~ to pentavalent state. Preferably the metal. ~alt~ ar~ used in t~eir higller oxidacion ~tates. Ndtur~lly, for u e in ~tom~tic di~w~her~, as well a~ any o~her ~pplications where the invention compo~i~ion will or may come in corltact with articles u~ed for the handling, ~orage or se~ving of food product~ or which otherwi~e ma~ c~me into concact with or ~e consumed by people or ani~al~, the metal ~alt ~hould be ~elq~ted by ~aking into con~ideration ~he ~oxici~y of the metal. ~or this purpo~e, the ~lkali metal and calcium and magne~iu~ salt~ axe especially higher preferred a~ generally sae food additives.
The amount of the fa~ty acid or fat~y acid ~alt stabilizer to achieve ~he de6ired enhancemerlt of phy~ical stability will depend on ~uch fac~or a~ ~he na~ure of the atty acid or it~ ~alt, the nature and amount of the thickening a~ent, detergeIIt ac~lve co~po~d, inor~ahic salt~, other ingredients, as well aR the anticipate~ sr.orage an~
~hipping condition~.
Generally, ho~e~er, amount~ of the fat~y acid or fatty acid salt s~abilizing agen~ in the r~nge of from about 0.02 to 2~, preferably 0~04 ~o 1~, more pre~erably from abo~t 0.06 to 0.8~, especially preferably fxom about 0.08 to 0.4~, pro~ide a long term stabili~y and absenc2 of pha~e ~eparation upon standing or d~rin~ transport at bo~h low and elevated _. ~ .
u~ r~ t~l l L l~ . r- . L l / -~_ 2~9~6 temperature~ a~ are ret~ired for a c~nunercially acceptable product.
Depending on ~he amounts, proportion~ and types of fatty acid ph~ical s~abillzers and polyacrylic acid-type thickening at3ents, the addition of the fa~ty acid or salt not only increa6e~ phy~ical ~tabilit~ ~u~ al~o provide~ a simul~aneouq incre~e in apparent vi~coqi~y. ~nount~ of fat~y dcid or salt ~o polymeric thickening a~ent in the range of from abou~ 0.08-~ .4 ~Yeight percent fa~ty a~id ~alt and from a~ou~ O .4-1. 5 weigh~ percent polymeric thickenin~ agent are usually s~f~icient to provide ~he4e ~imultaneous benefit~ antl, therefore, ~he use of the~e irlt~redi~nts in these amount~ is m~t preferred.
In order tO achieve the desired benefit fro~ the fa~ty ~cit~ or fatty acid ~al~ 4tabilizer, ~ithout s~abilization of exce~s incorporated air bubbles and con~equent exces~ive lowerirlg of the product bulk den~ity, the fatty acid or salt ~hould be po~-added to the forrllulaciorl, ~referably together with the other surface active i.n~jr~dient~, includ.ing detergent ao active compound and anri- foamint3 a~erll, when pre~erlt. The~q ~urface active int~redierlts are E~refer~bly addt~d a~ an ~mulsior in wa~r wherein the emul~i~ied oily or f~ety ma~erial~ are finely and homogeneously dispersed ~hroughout the a~ueou~
phase, ~o achieve the de~ired fine emulsification of the 2S fatty acid or fatty acid xalt and o~her surface active ingredien~ u~ally nece6~ary ~o heat th~ emulslon (or preheat the water~ to an elevated eemperature near the ~elting temperatUre o~f the fatty acid or itY ~alt. For example, for r I I ~ l L I r~ I Ll ~ ~ LlL-r I . r . ~
stearic acid having a melting poin~ of 68C-69C, a te~perature in the range of between 50~C and 70C. will be used. For lauric acid (m.p.=47~C) an elevated temperature of about 35dC to 50C
can be ~ed. ~pparently, at the~e elevated temperat~res the fatty acid or salt and other surface active ingredients can he more readily and uniformly dispersed (emulsifled) in the form of fine droplet~ throughout the compo~ition.
In contra~t, as will be shown .in the example~ ~hiCh follow, if the fatty acid is ~impiy poY~-added at ambient temperature, the composition i6 ne~ linear ~i~coelastic as deined above and the stabili~y of rhe co~po~ition i~ cle~rly inf erior .
Foam inhibition ic impor~.ant to increase di~hwa~her machine efficiency a~d minimize de~tahilizing effect~ which might occur due ~o the presence of exce~ foam wi.thin the washer duri~ use. Foam may be red~ce b~ jui~able 6election of the type and/or amount of deter~en~ active ma~erial, the main foam-producing ccmponent. The degree of foam is al~o ~ome~hat dependent on the hardne~s ~f the wa~h water in the machine whereby sui~able a~jus~men~ o ~e ~ro~or~ions of the ~uilder salt~ such as NaTL~e which has a w~ter ~o~tening effect, may aid in providing a degree uf foam inhi~ition.
Ho~ever, it is generally preferred to include a chlorine bleach stable foam depressant or i~hibi~or. Par~icularly effective are the alkyl pho~ph~ri~ aci~ e~ter~ of the formul~
~. ~ .
20~66 HV~
OR
and e~pecially the aik~l acid pho~h~e e~ters of the formula HO-P-OR
In the above formulas, one or both R ~roup~ in each type of ester may repre~e~t independently a C~2-C20 alkyl group. The ethoxylated derivative~ of each ty~e of ester, for exa~ple, the conden~a~ion products of one mole of e~er with from 1 to 10 mole~, preerably 2 eo 6 moles, more prefer~bly 3 or 4 mole~, ethylene oxide can al~o be u6ed. Some exa~ples of ~he ~oregoing are commercially av~ilable, ~uch as ~he produc~s SAP
from Hooker and LPK~-158 from Knapsac~. ~ixture~ of ~he ~wo cypes, or an~ other chlorine bleaeh ~table types, or mixt~re~
of mono- a~d di-esters of the same type, may be employed.
Especially pre~erred i~ a mix~ure of mono- and di-C~6-Cl~ alkyl acid pho~phate e~terx ~uch a~ monoYt~aryl./di~te~ryl acid pho~ph~tes 1.2/1, ~nd ~he 3 to 4 mole et;hylene oxide condenaa~es thereof. When ~mployed, proporti.on~ of 0.05 to 1.5 weiyht percent, pre~era~ly 0.1 to 0.5 weight pe~cent, of foam depres~ant in the composition i~ typical, the weight ratio o detergent active component (d) to foam depressant (e) generally ranging from abo~t 10:1 to 1:1 and preferably abou~
5:1 to 1;1. Oth~r defoamer~ which may be u~ed include, for example, ~he known ~ilicone~, such a~ a~a~lable from ~ow Chemical~P ~ a~dition, i~ i~ an advantageo~ feature of ~hi~
~n I ~ L ~rl I L I ~-~ I L I I I ~ Lr I ~
20~9~66 (registered ~rademark) 3~-2 and DOWFAX 2~-1. In addition, ~he surfac~ant 6hould be compa~ible wi~h the other ingredien~ of the compo~ition. Other ~uitable organic anionic, non-~oap s~rfactants include the primary a~kyl~ulphates, alkylsulphonates, alkylaryl~ulphonate~ and sec.-alkylsulphate~. Exampleg in~lude sodi~m Cl0-C,~ alkyl~ulpha~e~
s~ch a~ sodium dodecylsulp~a~e and sodium t~llow alcohol~ulphate; sodium C~O-C~ alkanesulphonate~ such a~ sodiu~
hexadecyl~ ulphonate dnd ~odium Cl2-CI~ -a~k~benzenesulphonate~ ~uch as ~odium dodecylbenzene~ylphonates, ~he corresponding pota~sium salts may also be employed.
~ other ~uitable su~factants or detergen~, the amine oxide surfac~ant~ are typically of the s~ructure R2RINO, in which each R repreeent~ a lower ~l~yl group, for irlstance, methyl, and Rl repxesents a long chain alkyl group having rom 8 to 22 carbon atoms, for in~tance a lauryl, myri~cyl, palmityl or cetyl group. In~tead of an amine oxide, a corre~ponding ~rfactant pho~phine oxide R2R~PO or sulphoxide ~O RRISO can be em~loyed. Betaine ~-lr~.ac~ante are typically ~
the s~ructu~ R2R~NtR"COO-, ln whi~h each i~ repres~nt~ a lower ~lkylene g~oup having from 1 to ~ ca~on a~omY. ~pecific exa~lple~ of theQe surfactant~ incl~1de lauryl-dime~hylamin~
oxide, myristyl-dimethylamine oxide, myri~yl-di~lethyl~mine oxide, t~e corre~ponding ~ho3~hine ox~e~ arld ~ul~hoxide~, and the correeponding betaine~, includin(~ do~ecy]dim~-hylamn~oni-~
aceta~e, tetradecyldiethyl~onium p~ntano~te, hexadecyl~im~4~1a~nonium hex~noa~e and the lL~e. For .
2~
I I r~ L _ I I I _ I ~ L r r 1 I L I ~ I L L I I ~
2G~9966 biodegra~abili~y, ~he alkyl group~ in the~e ~urfac~ant~ should be linear, ~nd ~uch comQc,unds are pre~erred.
Surfactant~ of the foregoing ~ype, all well known in the art, are described, for example, in U.S. Patents 3,985,668 and 5 4,271,030. ~f chloxine bleach 1s not used ~han an~l of the :-well knowrl low-foaming non1onic ~urfactants such as al~oxylated fatty alcohol~r e.s. mixed eShylene oxide-propylene oxide condensa~es of C~-C~2 fatty alcorlols can al~o be used.
The chlorine bleach ~ta~le, ~ater di~Jpe~lble oryanic detergent-active material (suxfac~ant) will noL~ally be presen~ in the composltion 1n minor ~no~nts, ~enerally abou~
1~ hy weight of ~he co~position in ~inor amount~, generally about L~ by weigh~ of the compo4icioII, althou~h smaller or larger a~oun~, such a6 up to about 5~, such as from 0.1 to 5~, preferably fo~m 0.3 or 0.4 to 2~ ~y weight of t~e Composi~ion, may be used.
Alkali ~e~al ~e.g. potas~i~m or ~odium~ si1icace, which provide~ alkalini~y ~nd protectiorl of hard s~rface6, ~uch a~
fine china gl.aze and ~ttern, i~ ~en~rally e~lployed in an amount ranging f~om a~ou~. 5 to 2~ w~i~ht percent, E)refe~ably abouc 5 to 15 weight percen~, more preferably 8 tO 12~ in the composition. The Yodium or po~as~ium Bllicate iY generally add~d in the fox~ of an a~eou~ ~oLu~iorl, p~eferably having Na20:SiO2 or K20:SiO2 ra~io of abo~t 1:1.3 ~o 1:2.8, ~speci~lly preferahly 1:2.0 to 1:2.5. ~ thi~ poin~, it ~hould be mentioned ~hat many of the oth~r componen~s of ~his composit~n,~x~pecially alkali mecal hydroxi~e and bleach, are 2~66 \ -àl~o ofte~ added in ~he ~onm of a preliminaxy prep~red a~ueou~
di~per3ion or solution.
In addition to the de~ergent active surfact~nt, foam inhibitor, alk~li metal silica~e corro6ion inhibitor, and detergent build~r ~alts, whlch all contri.bute to the elean1ng performance, it is also known that t~le efect1ver~e~s of ~he liquid au~omatic di~hwa~her detergenL compositions is related to ~he alkalinity, and par~icularly to moderate to high al~alinity levels. Accordingl~, the compo~i~ion~ of thi~
invention will have p~ value~ of ~t leas~ about 9.5, pref~rably at least about 11 to a~ high as l~, generally up ~o about 13 or mor~, and, when ad~ed ~o ~.he aqueous ~a~h bath a~
a typical concentration level of about 10 gram~ per li~er, will provide a pH in the wa~h bath of a~ lea~t about 9, lS prefera~ly at least about ~C, such as 10.5, ~1, ll.S or 12 or more.
The alkalinity will be achie~ed, in pa~t by the alkali me~al ion~ contributed by the alkali ~etal de~ergen~ b~ilder ~alt~, e.g. sodi~m tripolypho~p~ate, tetrapo~assium pyropho~phate, and alkali metal ~ilic~, however, it i~
u~ually nece~sary to include alkal.i metal hydroxi.de, ~.~. NaOH
or KOH, to achieve ~he deslred high alkalini~y. Amounts of alkali metal hydroxide in the range of (on an active basis) of f~om about 0.5 to 8%, preerably f~om l to ~, mor~ preferably from about 1.2 to 4~, by weight of the composition wil~ be sufficient to achieve ~he de~ired ~H le~el and/o~ to adju~t the X/Na weight racio.
rl I ~ L~ ~ r r~ I . r . ~
2~ii9~66 Other alkali me~al qaltY, ~uch ~ alkali me~al ca~bona~e may also be pre~ent in r.h~ compo~ition~ in minor amounts, for example from O to 4%, preferab~y O ~.o ~-, by weight of the composition.
Other conventional lngredlen~ may be included in theie composition~ in ~mall amoun~s, generally le~ than about 3 weight percen~, 3uch as perfume, hydrotropic a~ents such a~
the sodi~m benzene, ~oluene, xy~ e and cume~e sulphonates, preservatives, dyes~uff~ and pigments and ~he like, all of cour~e bein~ table ~o chlorine bleach compound and hi~h alkalinity. E~ecially preferred for coloring are ~he chlorinated phythalocyanine~ and polysuphides of alu~.inosilicate which provide, re~pectlvely, plea~ing green and blue tint~ Tio2 n~y b~ employed for whi~e~ing or neutrali~ing off~hades. Even more preferred coloranc~ u~ed at a Co~Gentration of about 0,01 to 1.0 ~t. ~ are CI Direct Yellow # 28 and Grapthlol Green pigment both made by Sandoz Chemical Corp.
Al~hough for the rea~ons previou~ly fli~cu~ed e~ces6ive ~ir bub~le~ are nv~ often ~esi.r~le in ~he inverl~ion compo~i~ion~, depending on the amoun~s o~ dl.s~o~ved 30lid~ and liquid phaje densltie4, incorporation of cm~ll amounts of finely divided air ~ubbles, generally up to ~bout 1~% by volume, preferably ~p to about ~ by volume, more ~referably up to about 2~ by volume, can be incorporated ~o adjust ~he bulk de~ity to approximate liquid phaYe den~icy. The inco~porated air bubble~ should be finely divided, such a3 up ~o about 1 ~ micron~ i~ diamet~r, prefer~bly from abou~ 20 to : . ~1, ~ _ 2069966 ~
bleac~ compound ~nd remaining detergen~ additive~, includinc3 any previously unuQed alkali metal hydroxide, if any, of;her tha~ the ~urface-active compounds. ~ll o~ the additional ingredient~ can be added ~lmultaneously or 6equentially.
Preferably, the ingre~ient~ are added ~e~uentially, although i~ ic not necesf~ary to complete the addition of one i~gredient before beginning to add the next ingredie~lt. ~urthermore, one or more c7f ~he~e ingredient~ can be divided into portionY and added at different ti~es. These mixing steps should al60 be performed under moderate ~o high ~hear rate~ co ~chieve complete and unifonm mixin~. The~e mi~ing step~ may be carried o~t at xoom temperat.ure, althou~h the polymer thickener neutr~lization (gelation) i9 usually exo~hermic.
The ~ompo~ition may be allowed to age, if necessa~y, ~o cau~e di~c71ved or disper~ed air to di~sipa~e out of the compo~ition.
The remaining surface ~ctive ingredients, including the ~nti-foaming agen~, organic detergent compound, and fatty acid or fatf y acid ~alt stabilizer i~ ~o~t-added ~o ~he pre~iously formed mixture in th~ form of ~n aqlleo~s em~l~ion (u~iny from ~bout 1 to 10%, pre~erably from abo~t 2 ~o ~% of the tocal water added to ~he compo~ition ot~n~r t.han water added as carrier for other inyredlent~ or water of hydra~ion) which i~
pre-hea~ed to a temperature in ~he range cf from a~70u~ Tm+S to ~-20, preferabl.y from abo~t Tm to TM-10, where ~m is the meltiny point temperat~re of the fat~y a.cid or fatty acid salt. For the preferr~d ~tearic acid ~tabilizer the heating te~peratu~.i~ in the range of 50C to 70C. However, if care . 2~
i6 taken to avoid exce~slve air bu~le i.nc~pora~lon ~urls~y the gela~in gtep or during the mixing of ~he det.ergent builder ~ 6 9 9 salt~ and other addi~ive~, for example, by oper~ting unde~
vacu~m, or u~ing low ~hearing condition~, or special mixing ope~atatus, etc., the order of addition of the surface acti~e in~redients ~hould be less impor~ant.
In accordance with an e~peclally preferred embodime~
the ~hickened linear vi~coelastic aqueous automatic di~hwa~er detergent compo~iti~n of ~his invention includes, on a weight basi~;
(a) 10 ~o 35~, preferably 15 to 30~, of at least one alkali metal detergent ~uilder sal~i (b) 0 to lS, preferably ~ to 12~, alkali ntetal 3ilicate;
(c) 1 to 6%, preferably 1.~ ~o 4~, alkali metal hydroxide;
(d) 0 to 3~, pre~erably 0.1 to 2~, chlorine bleac~
s~able, watex-di~persible, low-~oaming organic detergent acti~e material, preferably non-~oap anionic de~ergent;
(e) 0 ~o ~.S~, preferably 0.1 to 0.~, chlorine bleach stable foam depre~sant;
(f) chlorine bleach co~pound in an amoun~ to providç
about 0.2 to 4~, preferably 0.~ to 1.6~, of available chlorine;
(g) high ~olecular wei~ht ~lydrophilic cro~s-linked polyacrylic acid ~hickening agent in an amount to provide a linear ~iscoelas~icity to the for~ulation, pref~rably fro~
a~out 0.1 to 2.0%, more pre~erably from ~bou~ 0.4 to 1.5~;
(h) a long chain fatty acid or a metal salt of ~ long ch~ln fatty acid in an amount efective to increa~e the phycical ~ability of ~he composi~ion~, prefera~ly from o.oa to 2.0~, m~re prefera~ly frcrn 0.04 to 0.5%; and ; (i) balance water, prefera~ly ~rom abont 30 to 75~, more preferably from a~out 35 co ~5~; and ~herein ln (a) ~he alkali metal polypho~pha~e ~ncludes a mixture of from abo~t 5 ~o 30~, preferably from about 12 to 22~ of tetrapota~iu~
pyrophosphate, and fro~ 0 to a~ouc 20~, preferably from abou~
3 ~o 18% of ~odi~m ~ripolypho~phace, and wherein in the entire compo~ition the ratio, by wei~ht, of potaS~iUm ion~ tO sodium ions i~ fro~ about 1.05/1 ~o 3/1, preferably from 1.1/1 to 2.5tl, the composition~ having an amount of air incorporated therein s~ch that the bulk den~ity of the compo~ition i~ fro~
1~ about 1.32 to 1.42 g/cc, preferably from abou~ 1.35 to 1.40 g/cc.
(j) 0.01 eo i.09~ of a chlorine scable dye or chlorine ~table pigment.
The compocitio~ will ~e supplied ~o ~he con~umex in ~0 suitable di6pen~er cont~inerR preferably formed of molded pl~stic, e~pecially polyolefin pla~tic, an~ mo~ preferably polye~hylene, ~or which ~he inverl~ion composition~ appear to have partic~larly fa~orable 91ip chara~teristic~. In addition to ~heir linear vi~coelastic c~arac~er, the compo~itions of t~i9 inven~ion may also ~e characterized as pseudopla~cic gels (non-thixotropic) which are typi.cally near the ~orderline ~ecween liquid and ~olid ~iscoela~cic gel, depending, for example, on the amount of ~he polymeric thickener. The 2069~66 :
invention composition~ can be readily po~red from their containers without a,ny ghaking or 6queezing, ~lthough ~ueezable con~ainer~ are oten convenient and accepted by the con~uner for gel-like product~.
The liquid aqueou~ line~r vi~coela~tic auton~tic dishwa~her compo~itions oi this invention are readily e~ployed in known manner for waghing diahe~, o~her kitchen utensils and the like in an auto;natic dish~a4her, provided with a suitable detergent di~penser, in an aqueous wash bath containing an effectiYe amount of the compo~ition, generally fiufficient ~o fill,or partially fill the automa~ic dispenser cup of the particular machine being u~ed.
Th~ invention also provides a method for cleanin~
diohware i~ an automatic dishwashin~ machine wi~h an aqueou~
waJh ~ath containing an effecti~e amount of the liquid linear vi~coela~tic automa~ic di8hwasher deter~ent compo6i~ion as described ~bove. The com~osi~ion can be readily poured from ~he polyethylene coneainer with little or ~o ~queezing or shaking ~ n~o the di~pensing cllp of the automatic di~hwa6hing machine and will be ~ufficiently vlscous and cohe~ive ~o remain ~ecurely within r.he di~pen~ing cup until ~hear f orcea are again applied ~hereto, su~h as by che water spray from the dishwa~hing ~achine.
~he invention may be put into pr~ctice in ~ario~s way~
and a n~mber of specifi~ em~odiment~ will he de~cribed to illu~trate the in~en~ion with reference to the accompanying exa~ple~.
n I ~ 1 ~1 1 1 ~ ~n I ~ I r~ I Ll I I L ~l I r All the amount~ ~nd proportion~ referred co herein are by weigh~ of the composi cion unle~;~ otherwi~e indicated . -:
E~311;;~
Tl~e following fonnulatlon~ ~-X were prepared a~ deacri~ed below:
, I ~ ~ ~
1~ ~ ~ 1~ ~ 1~1 `'~
~ ~ 1~
, ?
2~99~6 r ~ ~ ~
L r ~ -- .c _ r u~ F~
~' r~ r~ O O ~r~ ~ V
I 1 ~ a ~
~ ll ~ o ~ ~x~a~
_ r _ _ _ :~
~ . I o ~ .~ aJ a ~ ~ ~ o o o~
_ __ _ O O ~I) O ~
_ o o .~
~D r~ O rd~ O ''~5 :
_ r ~ A A A ~1 0 ~
~ ---- N ~: v-~,.a O
~ .~ o O ,u v ~ ~ ~
_ r~ _- O ~ ho rd al ~ o o j (d _ _ _ _ ~ ~ ~
_ r~ t:) O o h ~ ~ ~ V
_ ~rt r~ o o ~ ,rd SV ~a~ ~
_ r l l ~ , U ~ O r~l U a) h o~
~ r ~ ~ I ~ ~ ~o~ 0~
~ ~; h cn ~ ~ D ~ ~ r~
lil ~ D :~ ~ ~ La o ~ k tn ~ u~
_ _ _ ~
r Form~lation~ A, B, C, ~, E, G, J, and K are prepared by fi~t forming a ~niform dlYper~ion of the Carbopol 941 or 940 thickener in abo~t 9~ of the water (balance). The Carbopol i~ 810wly added to deionized water ~L room temperature using a mixer equipped with a premier blade, wi~h agitation ~et at a medium ~hear rate, ac recon~e~ded by ~he manufact~rer. The disper~ion is then neutralized by addition, u~dex mixi~g, of the ca~stic s~da (50~ ~aOH or ~OH) component to form a thickened product of gel-like consi~tency.
To the res~lting gelled di~persion the ~ilicate, tetrapota~ium pyropho6pha~e (TKPP), ~odium tripolyphosphate TP(TPP, Na) and bleach, axe added ~quentlally, in the ~rder stated, ~ith the mixing continued at medium ghear.
Separacely, an emul~ion o~ the phoephate anci-foaming ~:
agent (LPKN), ~tearic acid/palmi~ic acid mix~ure and detergent (Dowfax 3B2~ i6 prepared by adflin~ thecl~ lngredient~ to the remaining 3~ o water (balance) and hea~ing the res~lting mixture to a ~emperature in the range of 50C to 70C.
Thi~ ~eated emulBion i~ ~hen ~dded ~o the previou~ly prepared gelled di~persion under low ~hear conditions, such that a vortex i8 not formed.
The remaining ~ormulations E~, H and I are prepaLed in e~entially the ~ame manner a6 de~cribed above ~xcept that ~he heated emulsion of LY~N, ~teari~ acid and Dowfax 3B2 i8 dixectly added ~o the neut~ali~ed Carbopol di~pe~ion prior to the addition of ~e remaini~4 ingre~ien~s. A~ a re~ult, formulation~ F, H and I, have hi~her level~ of incorporated air and ~c~ie~ below 1.30 ~/cc.
r~ r~ I L~ ~r I
The rheogrdm~ for the formulations ~, C, D, G and J are shown in figure~ 1-5, re~pectively, and rheogra~ for formulaLions H, I and K are ~hown in figure~ 6, 7 an~ 8 respectlvely.
The~e rheogram~ are o~tained with the Syr~tem 4 Rheometer from Rheometrics equipped wit~ a ~luid Se~o with a 100 gra~s-c~ntime~er ~orque tran3ducer and a 50 millimet~r pa.rallel pla~e geo~etr~ having an 0.8 millimeter gap ~etween plates.
~11 mea~urem~nts are m~de at room tem~era~ure ~25~C~1C) in a humidlty chamber after a 5 m~nute or 10 minute holding period o~ the sample in the gap. The measuremen~ are made by applying a frequency o~ 10 radians per ~econd.
~11 o ~he compogition fonmulation6 A, B, C, ~, G and J
according to the preferred embodiment of the invencion which include Carbopol 941 and ~earic ~cid exhi~it linear viscoela~ticity a~ ~een ~rom the ~heogram4 of figure 1~5.
Formulacion E whlch includes Carbopol 941 but no~ ~teari~ acid showed no p~ase separation at eic~er room ten~perature or 100F
after 3 week~, but exhibi~ed lO'~ phase~ paratlon af~er 8 week~ at room tempera~rc anfl aft~ only ~; w~ks a~ 100P.
Form~l~tion ~, conta1ni.ng C~opol '~0 in plac~ o~
Carbopol 941, a~ ~een from ~he rheo~ram i~\ figure 8, exhibi~
~ub~tantial linearity over ~he ~train range of rom 2~ to 50%
(G' at 1~ ~rain-G' at 50~ s~rain 500 dynes/~q,cm.) ~l~ho~gh 2S tan 1 at a ~r~in above 50~.
J ~
~99~6 This example demonstrates the i~portance o~ the order of ~dition of the surface active eonlponent premix to the rem~inder of the composition on prod~c~ den~i~y and stabili~y.
The following formula~ion~ are prepared by methods A and B:
Inq~di~nt~ ::
Water, deionized Balance Car~opol ~41 0.5 I.
~aOH (50~) 2.4 Na ~ilicate (47.5~) 21 TPP, Na 13 ~Bleach (1~) 7.S
~PKN 0.16 Stea~ic Acid 0.1 Dowfax 3B2 MQ5h~9 ~he Carbopol 341 i~ disperged, under medium ~hear ra~e, ~sing a premier blade mixer, in deiorlized water at ambient ~emp~ra~ure. The NaOH i~ ~dded, ~nder mixing, to neutralize and gel the Carbopol 94~ di~per~ion. To the thickened mixture the following ingredien~ aLe add~d ~equen~ially while the 8tirring is concinu~d: ~odium ~ ate, TKPP, TPP, and bleach.
Separately, an emul~ion i~ prepared by adding the Dow~ax 3B2, stearic aci~ and LeKN ~o wa~er while mlxing at ~oderate ~hear and heating the mixture ~o about 654(' tO ~inely di~per~e the emul~ified ~urf~ce active ingLedien~s in the Wdter pha~e.
Thie emulsion pre~ix is then ~lowly added to ~he Carbopol diiper~ion while mixing under lo~ ~hear ~onditiorls without forming a vortex. Th~ resul~ are ~howrl below.
r I I ' .` 1_`~1~ 1 ~ I n I ~ 'L_r`
2~6996~
et~p~ B~
~ thod ~ i~ repeated except ~hât the heated emulsion premix i9 added to the neu~ra~ized ~arbopc,l ~41 dispersion befoxe the ~odium stearate, TKPP, TPP, and ~leach~ The S resul~s are al~o ~hown below.
Me~hod A Method B
Density (g/cc) ~.38 1.30 Stability (RT-8 week~) 0.00% 7.00~
Rheogram Fig~ 9 Fig.10 From ~he rheograms ~f fiyure~ 9 and 10 lt i~ ~een ~hat both products are linear vi~coela~tic although the elastic and ~i~c~u~ moduli G' and G~ are ~ligher for Method A than for ~ethod B.
From the r~ults it i~ seen ~hat ea.rly addition of the surface active i~gre~ie~ o che Carbopol gel significanrly increases the deyree of aeration and lowers the bulk density of the final product. Since the bulk den~ity i~ lower than the density of the continuou~ liquid pha~e, the liquid phase under~oes i~er~e separation (a ciear li~uid pha~e forms on ~he bot~om of the composicion). T~is proces~ o inver~e ceparation appears to be kine~icall.y ~onr.rolled and will occur a~ter a~ ~he den~ity of the pro~uc~ become~ ~ower.
E~3m~1Y
~hi~ exa~ple ~hows ~e :im~or~.~n~ of the tempera~ure a~
which r,he premixed ~ur~ac~ant ~mu`L~ion 19 prepared.
~wo form~lation~, L and M, ha~ing che sa~e compo~i~ion as in Example 2 e~cept that the amo~m~ of ~tearic aci~ was increase~,r~ 0.1~ to 0.2~ are prepared as ~hown in rqethod A
I lr1 ~ ~r~ I ~ ~ r1 1 1_1 ~ I L~L r I . r~
2~iig96~
for formulation L and by the ~ollo~ g M~thod C ~or form~llation ~.
Met~d_C
The procedure of Me~hod A is repe~ted in all detail~
5 excep~ that emul~i~n premix o~ the surf~c~ acti~e ingredient~
is prepared at room temperat~re a~d i~ not heated beore being po~t-added to the thickened Car~opol dl~persion co~ltai.ning ~ilicate, builders and bleach. ~he fheogram~ for for~ulation~
L and M are jhown in figure~ 11 arld 12, re~pecti~ely. From these rheograms it i~ ~een that formulation L is linear ~i~c~ela3tic i~ bo~h ~' and G" whereas fornlulation M is non-linear vi~coela~tic pa~icularl~ fox elastic modulus G' (G~ at 1~ ~train-G' at 30~ .Qtrain ~ 500 dynes/cmA) and also for G" (G~
at 1~ ~train-G" at 30~ str~in 300 dynes/cm').
Fonmula~ion ~ remai~ cable ate~ storag~ at RT and 100~F
for at le~t 6 weeks whereax formuld~ion M undergoe~ phaRe separa~ion .
m~ C.~0~
The following or~1ation i8 prepared without any pota6~ium salts:
Wei~ht Wa~er ~alance Carbopol 941 0.2 NaOH (50~) 2.~
2S TPP, ~a (50~) 21.0 Na Silicate (47.5~) 17.24 ~ledch (1~) 7,13 Ste~ric Ac~d 0.1.
LPKN (5~) 3.2 Dow~ax 3B2 0.~
Soda Ash 5.0 Acr~ol LMW 45-~ 2.O
~9~
The proced-?re used i~ analogou~ to Method ~ of Example 2 wit~ the oda ash an~ Acrysol L~W 45-N (low molecular weight polyacrylate polymer) bein~ added before and after, re~pecti~ely, the silicate, TPP and ~le~ch, to the thickened Car~opol 941 di~persion, followed by addition to the heated surface active emulsion p~emix. The rheogram is shown in flgure 13 and is non-linear with G~/G' (tan ) ~ 1 over the range of ~rain of from about 5~ to 80~.
Example 4 ,~ormula~ions ~, B, C, P and ~C ~ccording to ~his invention and comparati~e formulations F and a commercial li~uid automatic di~hwa~her detergent product as shown i~ Table l above were subjected to a bo~tle residue test using a standard polyethylene 28 ounce bottle a~ ~e~ for current commercial liquid dighwasher detergent bottle~ :
Six bottles aro filled with th~ re~peetive samplas and the prod~ct is dispensed, with a minimum of force, in 80 gram do~ages, with a ~ minute re~t period between do~ages, until flow stops. At thi~ poi~t, the bottle wa~3 ~i~orou~ly ~haken ~o ~ry ~o expel additional product.
The amount of produc:t -remair~ g in ~.he ~oLt].e. is meafiured a~ a percentage of ~he total product originally f.illed in ~he bottle. The result~ are ~hown below.
~` ~ .
3~
20699~i6 Bottle Re~ldue Formu~i~ a Commercial Product 20 ~T~e jam~le ~eparates upon aging ~xampl e S
The following forrnula, A-I were p-~pared accordin~ to the proc~dure of ~xample 1.
., __ _ __~ _ c~ ~ _ _ ___ __ I
t` O ~ N r~ 0 o u~ o o . . . . ~ . r~ C~ . . U) ~
~ o ~ ~ ~ o o ~\J ~ ~` r~ ~ o o _ _ _ _ _ _ _ _ . . ~_ _ _ _ ~ _ ~ o U~ O ~ (~ r~ 0 O O O 117 U~ O O
td o _ _ _ o o .. ~ __ r o _ _ _ _ _ _ _~ _ _ _ __ o U~ o o o o Lrl o r ~ ~ ~ r~ ~ . . . L~ . o t~ O rl ~i ~ r~l r1 N t~ ~f ) O r1 _ _ _ ~ ~ _ _ ___ ___ ~ _ ~ ~ ' C~ O ~ ' U~ O O O U~ Ll~ ) r u~ ~ ~ ~ a~ ~ u`~ N Ll') r` O ~
1~ O O ~ (~ O O N r1 ~ r~ (' ) O rl _ ___ ~ ~ _ _ __ .____ ,~ _ . __ _ _ ~1) Ln O C~ U~ t'~ C~ ~
r~ O ~ N r~ O r; O In ~n Yr ~ u~
li~ O ~ ~1 ~Y) t~ r~ ~ ~I t-- r_ /'~ r1 ~ ~:
_ _ _ _ _ ~ O --~---- N--~ -- ~D O
t" O ~ ~r~l ~ r;c; O L~J I~ ~ rl O ~ ~I ~) ~ O ~<~I r., t~ ~1) r I ~1 _ _ _ _ ~ , ---- 1 -------- - --~ O ~ ~ rAI a~ O Cl O I~ O r C~
t.) C l rl ~ ~ o O ~ _ ~ ~ ~--1 t~ ~ r~J r~
_ _ _ _ _ _ O O _._.._. _ U~ _ .__ O O ~3 t" Ll~ ~( ~ I_~ ) r; Il~ ~ Ll~ 1~ ~) N L) ~1 O O ~ N O O ~ rl '-I t'` 1' r~ r~
_ . _ ~ _ __ __ ___ L~'l ,~ __ _ O
n ~ ~ r~ a~ o o c, u~ ~ c~ rl :i I¢ C; O ~ O O r U~ r1 r r __ _ _ rl I r _ ` ~
A
O
2~99B6 _ _ _ __ _ _ _ _ _ _~t _ __j . ~;t ~t _ ~ r _ _ _ __ _ ~t L L ~0 O _ _ _ _ _ _ _ _ _ _ __ __ _ ¦ ~
~0 w .p~ , e~ ~ ~ ~r 1- t tl t~ ~ It~
hO Ll'~ ~ O a~ O ~ ~ r ~ ~s) ll C~ C~ r ~ ¦ ~ t O_ r-i _ __ O _~ _ u~ u~ rl t` _ O rt _ ¦ 11~
:) r~) ~ r1 t~ c~ 1~ ~t ~t_ rt _ N O O N O _ rt ~ O O (li ~1 _ _ _ _ _ _ ~ ~ g ~O C~
~ Ll~ a I Irl I ~ L_'~I I I L I 1-1 I L 1 1 1 ~ 1 1 . r -t~ --~_ 20~9966 WXAT IS C.L~IMEP IS;
1. A lin~a~ visGoela~tic aqueous liquid automatic dlshw~cher de~ergen~ composition ~ompri~ing approximately by weight:
(a~ lO ~o 35~ of at lea~t one alkali metal de~ergent builder ~alt, ~aid alkali metal detergent builder : Qalt belng selected from tha group c~onsi~ing essen~ially of al~ali ~ne~al tripolypho~phate, alkali metal pyropho~phate, alkali metal mecapho~ph~te, alkal.i me~al carbonate, al~ali metal citrate and alkali met~l ni~ri.lo~riace~ate an~ mixt~re~
ther~of;
(b) 5 to 15~ alkali me~al silicate;
(c) 1 to 6~ alkali ~etal hydroxide;
~d) 0 to 3.0~ chlorine ~leach sta~l~, ~ater-di~per~ible, organic detergen~ active material;
(e) 0 to 1.5~ chlorir~e bleach stable foam depre~ant;
(f) chlorine ble~ch cornpound in an ~nount to provide 0.2 ~o 4~ o~ a~ailable chlorine;
(g) 0.1 to 2.0~ of a cro~-lixlked pnlya~rylic acid shickening agent having a Molecular weigh~ of from about 1,000,000 to 4,000,000i (h) 0.02 to 2~ of a long chain fat~y aci~ or a metal sal~ o~ a atty aci~;
(i) 0.01 to ~.0 wL. % of ~ ~igment. and/or dye;
(j) water, wherein ~id ~olyacrylic acid thickening agent being ~elected from che ~rou~ c~n~i~tin~ e~entially of acrylic a~ d ~r ~ethacrylic aci~, water-diYper~ible or wa~er-~;~
soluble ~a~.~s, e~ter~, or amldes ~he~o~, and watex-soluble copolymers of these acitls or their s~lt~, e~ter, or amide~
~ith each other or with one or mo~e other ethylenically ~nsaturated monomerj, wherein cha a~ueou~ ph~e include~ both ~odium and pota~6i~n ion~ a~ a K/Na weight xatio of from ~bou~
lJl to abo~t 45/1, wherein subs~arl~ially all of the normally solid component~ of the compo~ition are pre~ent dissolved in ~he aqueou~ pha~e, and sub~tanti.ally all of the wa~er in the compo~ition i~ tightly bound to rhe c-ro3~-linked polyacrylic acid thickening agent, ~aid compo~i~ion having a bulk density of rom 1.32 g/cm3 to 1.~2 tJ/Cm3 an~ ~aid composi~l.o~ doe~ not exhibit phase ~eparation and re~mains homo~enous, when said compo3ition i~ cerltrifugetl at 1000 rpm ~or 30 minu~e~.
2. ~he co~poYi~ion of Clalm 1, wherein ~aid alkali metal builder ~alt i~ a mixture of sodium tripolypho~pha~è and potas~ium tripolypho~phate.
3. The compo~:ition of Claim 1, whercin caid ~lkali metal builder ~alt is a mixLu~e oL ~ot~iu~n ~.rlpol.yphosp~a~e and po~a~sium pyropho4phat~.
l.lN~AR V~SCOEI~ST~C AQUE~OUS
IJIQUID ~UTOMATIC DISHWASH~R
~ET~3RG NT CO~IP :)SITION
Rela~ed Application~
Thi~ appli~tion if2 a Conti~ation~ Par~ of U.~. Serial No. 07~353,71Z filed May 18, 198~.
Fi,çld Q~ II1V~
The pre~ent in~rention relate~ generally to a~ ~utomatic diah~aaher detergen~ compo~i~ion in the Eorm of ~ n aqueou6 linear vi~ccelasti~ liguid.
Liquid automatic diahwa~her deter~ent compo~;i ;ions, bVth aqueou~ and A~onaqueou~ h~ve recerltly received m~A.c.l~ attention~
and the a~ueoll~ product~ have ~chieved con~ercia~ opulari~y.
The ac~e~?tanc~ an~ po~ulari~y of the liquid f 3rmu1ations a~3 compare~ to the more conventiorlal powder produc tc ~t~m~
from the coYlvenience and per~orm~nc~3 of ~he 1i~uicl prod~ct~.
However, ev~n the be3st of th~ rrently availa~ liquid ~ormulation~ sti11 ~uf ~er ~rom two maj or probl~ s, ~rod.uct ~ha~e ir~tability and ~ot~le re~idue, tlncl to ~on~e extell~ c~p lea~caSte f rcm the di~pen~er cup of the a~tomatic d l.~hwa~hing machine .
Rep~e~en~ativ~ o~ the re1~vant pa~ t art i.n thi~ area, m~nt;ion i~ mad~ vf Rek, U.S. Patent a~,5S~5o4i ~3u3h, e~ al., U.S. Patent; 4,~26,736; Ulrich, U.S. Patent 4,43:l.,S59;
Sabatellil U.S. Patent 4,147,650; ~a~lcot, U.S. S~a.cen~
-4,079,015; IJeikh~m, U.S. Patent 4,116,~43; Milol~Gl, U.S. P~tent ~lhY c~ !B J u2~ F~I~I CC~L~HTE PHTEIIT ~:lEPT. p,Z/45 2~69966 4,521,332; Jones, U.5. Pater.Lt 4,597,a8~; Heile, U~S. ~atent 4,512,90a; ~ai~em, ~.5. Patent 4,753,7~8; S~batel-Li, IJ.S, Pa~en~ 3,579,455; ~ynam, U.S. Patent 3,684,722: ot.~er pat~t~
r~lating to thic~ened detergent compooition~ incl~lcl~ U.S.
Patent 3,gP5,668; ~.K. Patent A~plication~ ~ 2,11~ 9A and G~ 240,450A; U.S, Patent 4,511,~87; U.S. Patent 4,'iS2,409 (Drapier, et al.); U.S. ~atent 4,801,395 (Drapi~r, et al.);
U.S. P~ent 4,801,395 ~Drapier, et al.~. Cos~monly a~signed co-pending ~at~r.Lt~ ixLclude, fo~ ex~L~ple, Serial Nb, 204,476 filed June ~, 1988; Serial No. 924,38~, filed o~o:::)er 29, 19B~i S~rial No. 323,138, filed M~Lrch 13, 1989; ',e;sial No.
087,836, filed August 21, 1~87; Serial ~. 328,716, filed Mar~h ~7, 1~8~; Serial No. 323,137, file~ March ~.3, 1~89;
Serial ~o. 323,134, filed ~aLrch 13, 1~89.
The ~resent invention provi~es a solution tc) :he abo~e problems .
Figure3 1-13 ar~ rh~ogxams, plotting ela~tic~ modulec~ G' ~0 and ~iCcou~ modulu~ G" a~ a ~unction o~ a~pl.~ed ~I;rain, ~or the compo~ition~ Oe ~Lmple 1, Form~lations A, ~, D, ~, ~, H, I and ~, E~ample 2, A and ~, ~xam~?le 3, L and M cL:lLd Com~arativ~ ~ample 1, xe~pe~ively.
5Y~
Ac~ording to the pre~ent invention there i~i l?rovided a novel a~ueous liquid autos~L~ic di~hwa~her d~ter~e.~t compo~itiorL. The compo~ition i~ chcaracteriæed by it~ linear Y 29 ~ C~ PM COLG~iTE F'hTEl~T D~F'T . p, 3/45 20B99~
viscoela~tic behavior, Yub~tan~ially in~efinite s~al~ility against ph~ eparation or se~tling of dis olved c,:r ~us~ended particles, low levels of ~ottle re~idue, relativel.y hi~h ~ulk density, and sub~tantial a~ence of unbound or free~ water.
Thi~ unique ,~ombination of pro~ertie~ i9 achieved ~:y vi~tue of the incorpo~atiOn i~to the a~ueous mixture of di~lt,~a~hing de~ergent ~ur~actant, alkali metal de~ergent ~uild~.r 9alt (~) and ~hlorine bleach compound, a ~mall but e~ectivt. amount of high molecular weight cxoss-linke~L polyacrylic acicL type LO thickening agent, a phy~ical stabilizing amoun~ of a long chain fa~ty acid or ~alt thereo~, an~ a ~ource of pota~sium io~ ~o pro~id~ a pota~ium/~odium weight ratio ;.n the range of from ~bout 1:1 to a~o~t 45~ uch that ~ub~tanl,ially all of the detelge~t builder ~alt~ and other normally ~olid deter~en~ additi~es present in the composition ace present di~olved in the a~ueous phase. The compo~ition.~ ~re f~rther characterized by a bulk density o~ at-least about: 1.32 g/cc, ~uch that t'he densit~ o~ the polymeric pha~e and t:he density of the aqueou~ ~continuou~) pha~e are a~proxima~e..y the came.
~.~
~ he compo~ition~ of thi~ inven~iorl are aqueous liquids containing ~arious cleansing active ingr~dients, ,letergent adju~ant~ ruct~ring and ~hickeni~ agent~ ancl 3tabllizing 2S com~onent~, although ~omo ing~edients may serve m~re than one of the~e ~unc~ions.
The a~vantageous characteri~3tic~ o~ the comE~o~ition~3 of this in~ention' inclu~ing physîcal ~tability, lo~l bottl~
MhY 29 ' 9c' ~ 'J8P~1 CSL~:~HTE PHTEI`IT I~EF'T . p, 4/45 2~69966 re~idue, hi~h cleaning pex~ormance, e.g. low spot~ g and ~ilmi~, dirl: re~idue removal, and 90 on, and ~upexior ae~thetics, are believed to be at~ributed to se~ere~l interrelated factor~ ~uch a~ low ~olid~, i.e. und:~~olved i particulate content, product den~i~y and linear v:i~coela~tic rheology. ~hese factor~ a~e, in turn, depandent oll ~e~eral critical compositional compone~t~ o~ the ~or~lat.ic,n9, namely, (1) the inclu~ion of a thickenin~ effec~ive amount of polymexic thickening agen~ havin~ high w~ter absorption capacit~, exemplified ~y hi~h mol~cular weight c~o;~-linked polyacrylic a~id, (2) inclu~ion of a phyYi.~al ~ta~Llizing ~mount of a lon~ chain fa~ty acid or ~alt thereoi', (3) pota~ium ion to sodium ion weight ratio K/Na in tlle range of from ~bout ~:1 to 4S:l, e~pecially ~rom 1;1 to 3:1, and (4l a product bullc den6ity o a~ lea&t a~out 1.32 g/cc, ~uch that the b-llk derl~ity and liguid pha~e density are ab ~lt the ~ame.
The po~ymeric t~ickening agent~ contribute t:c.l ~he linear vi~coela~tic r~eology o~ the inv~Ntion compo~itioI:!.s. ~ used herein, ~llinear ~i~coela~tic "o~" linear vi~coela~!ticity"
mean~ ~hat the ela~tic (~torage) moduli (G') and.~,he vi~cou~
(lo~s) moduli (G") are both ~ubstantlally independent of ~txain, at least in an applied ~train range of fix()m 0-50~, and preferably over a~ applied ~train range of from 0~80~. More ~peci~lcally, a co~po~ition i~ con~ideLed to ~e l-nea~
vi6coela~t~c for pur~o~ej of ~his invention, if c~er the ~train rang~ o~ 0-50~ the ela~ic modul~ ag a minim~m val~e of 100 dyne~/~q.cm., preferahly at least ~ 0 . _", ~,.. .
dy~efi/s~.cm., and varie~ lea~ ~han about 500 ~yn~ q.cm, Mf:~Y 2~ ' 92 la,~: ~i9PI~1 COL~ TE P~TE~ T ~EPT . p . 5/45 2 ~ 6 preferably le~s than 300 dynes/sq.c~., e~pecially E~referably les~ than loO dyne~/cq.~m. Prefera~ly, the miniml~m valu~ of G~ and maximllm varia~ion of G~ applie~ over the ~t~.~in range of 0 ~o 80'~. Typically; tha varia~ion in lo~ mod~ " will be le~s than that of G~. Ac a furth~r characteri~?:ic o~ the preferred lin~ar ~vi~oela~tic ~ompo~itions the ral~io of G"/G
~tan*~) i9 ~ess than 1, prefer~bly les~ than Q.8, ]:,ut more than 0.05, preferably ~ore than 0.2, at lea~t ov~r the ætrain ran~e of 0 to 50~, and ~referably over the strain :range of 0 to 80~. It ~hould be noted in this ~egard tha~ ~ I;train i~
~hear s~raiu xlO0, By way of ~urther ~xplanation, the ela~tic ~ or~ge) moduluæ G' i8 a meaæure of the energy ~tored a~d ~l~trieved when a Rtraln ic applied to ~he compo~,ition while viscous (103~) modulu~ G~ a ~easure to the amou~t of erler~y dis3ipated as heat when ~tr~in i3 applied. rrherefore, a ~alue of tan , 0.05c tan ~1, prefera~ly ao o.~ c tan c 0.8 means that the compo~ition~ will re~airl ~ufflcienl. energy when a ~tre~s ox str~in ig ap~lied, at least over the lixte~t e~pected to be encou~tered for product~ o~ thiY t',~e, Por exa~ple, w~len poured from or ~hake~ in ~he bottle, or stored ~5 in the di~hwa~hor deteryent di~pen~er cup of an alltomatlc di3hwashing machine, ~o return to it~ previous c:o:ldition when the ~,tre~s or ~train i~ removed. The compo~itior,s with tan va1ues in theBe range , ~herefore, will a1so hav~! a hi~h I~IH~ C~ 'iJPI`I l_OLGHTE PHTEI IT ~EPT . P. 6/45 2~69966 cohesive property, ni~mely, whe~l a shear or strain i.3 applied to a portion of the com~o~ition to cause i~ to flow, the ~urro~n~ing portions will follow. As a recult of t;hi~
cohe~i~e~ess of ~he ~ubject linear viecoela~ic cor:lposition~
S the compo~itions will readily ~low uniformly and h~:lmogeneously from a bottle when ~he bottle is tilted, ~here~y c~:ntributing to the physical (phase) stability o~ ~he ~o~mulation and the low bottle re~idue (low prod~ct 10~8 in ~he bot~ ) which characterizes ~he in~ention compo~itions. The li.nl:ar viscq~laj~ic proper~y al~o contfibutes to improved physical ~tability ac~ain~t pha~e cepa of any undi~cl~ed ~iu;~ended particle~ by providing a resi~ance to movement cf the particle~ c.~le to the ~rain exe~te~ by a particlell~n the ~urrounding ~luid medium.
Al~o cont~ibuting to the phy~ical ~ta~ility ancl l~w ~ottle re~idue of the invention co~posi~ions i~ t:he high potassium to ~odium ion ratios i~ t~e range o~ t~ 45:1, pr~ferably 1:1 to 4;1, e~peçially preferiably from 1~05:1 to 3:1, for exi~mple 1.1;1, 1.2:1, 1.5:1, Z:l, or 2.'i:1. At these ratio~ th~ solubility of ~he ~olid salt componen~ uch a~
de~ergent buildex ~alt~, bleach, alkali metal ~ .cate~, ancl the like, i~ cub~tantially increa~ed ~ince the pr!~ence of the potassium ~+) ion~ require~ water of hyd t:him the sodium (~a+) ions, ~uch that more water ic available to ~ solve these ~alt com~ound~. Ther~fore, all or nearly aLl of the no~m~lly ~oli~ com~onent~ are pre~ent dissolved il~ the a~ueou~
pha~e. Since there i~ none or only ~ very low ~ercentage, i.e. le~ han 5~, pre~orably le~ than 3~ by ~ h~, of I`l~Y 2~ ' ~2 ~ 51~PI`1 C~)L~aflTE P~lTEl`lT DEPT . 2 0 ~ 6 8uspend~d ~oLids presen~ in the formula~ion there i.3 rlo or only reduced ~ende~cy for undi~solved particl~ to ~ettle out o~ the compo~ition~ causin~, or example, for~atic~rl of hard masses of particles, which could reault in hiyh but:tle S residues (i.e. los~ o~ pro~uct). Furthexmore, an~r undi~solved 801id~ tend to be ~xe~ent in extremely ~mall ~art:ic:le ~ize~, usuall~ collold~l or ~ub-col~oidal, ~uch as 1 micron or ~e~, ~h~reby further reducing the tendency for the ~ndi,;l~olved particles t~ settl~.
~ ~till further attribute of t~e invention co:l.lposition~
contributinc~ to the overall product ~tabili~y and ow bottle re~idue i8 t;he high water a~orptio~ capacity of tlle cros~-linked ~olyacrylic acid type thickening agent. P.~ a result of thi3 high wa~er ab~orption capaci~y virtu~lly al:L ~f thQ
~5 a~ueous veh:icl~ componen~ i~ held ti~h~ly bound tCI the ~olymer - matrix. Th~3~ore, there i~ no o~ s~bstantially rlo ~r~e wa~ex pre~ent in ~he invention composition~. This ab~eI!ca of f ree water (a~ well as the cohesivenes~ o~ the compo~:Lt:ion) iæ
manifested ~y ~he o~ervation that when ~he compo~!itio~ i~
poured from a bottle onto a ~locc o~ water ab~or~lnt fllter pa~er vi~tually ~o watex i~ ab~orb~d onto the filler pa~er a~d, furthermo~e, the ~as~ of the linear vi~coela.itic material poured onte the filter pa~er will retain its ~ha~ and ~t~uC~ure ~Intil it i~ a~ain ~u~jected to a ~re~ or ~txain.
2~ A~ a re~ul~ of the ab~énce o~ u~ound or free ~I.t~r, ~here i~
virtually I10 pha~ eeparatin between the aqueou~ l?hase and the polymeri~ mAtrix or di~solved ~olid particle~. T~is . ~, ~ .
cha~acteril3tic i~ manifesced hy the fac~ that when the subject ~ht'l' ~9 ' '~ '.lF'M CUL~fl rE ~TE~`11 rlEPT . p, ~3/45 compo~itions ax~e Yubjected eo centri~u~ation, e.~. at 1000 rp~
for 30 minu~lss, there is no ~hase ~epa and the comEI~sition remains homo~eneou~.
However, it has also been di~covered that linea~
viscoelasticity and K/Na ratio~ in ~he a~ove~menti(:ned range do not, by themselve~, assure long term physical ,s~ability (a~
de~ermi~ed by phase ~epa). In order to maxi~i~e ;p~:,y~ical (phase) sta~ility, ~he density of the compo~itio~ hould be controlled ~uch that ~he bulk ~en~ity of the liqui,l ~hase i~
.0 approx~imatel,y ~he ~ame a~ the bulk dengi~y of the entire composition, including the polyme~ic thickening zl~ent. Thi~
con~rol and equalizatio~ of t.he den~itie~ i~ achie~ed, according to the invention, by providing the coml;~c,~iti~n with a bulk den~:Lty o~ at leas~ 1.32 g/cc, prefer~bly a.c lea~t 1.35 g/cc, up to about 1.42 g/cc, preferably up to abo~l~ 1.40 g/cc.
Furt~ermo~e, to ~chievo the~e relatively high bul~: ~en~itie~, it iB impo~ant to minimize the amoun~ of air incc,rporated into the composition (a den~ity o~ about 1.42 g/cc~ is es.~entially e~ui~alen~ to ze~o air Content).
It ha~ previou~ly been found in connec:tion ~ h other ~ypes of thic~ened agueous liguid, autom~ic di~h~,~a~her ~ter~ent compo~itio~ that incorpo of ~inely di.v:~.ded air ~ubble~ in amount~ up to about a to 10% by ~olume can function effectively to stabilize the com~o~ition a~ain~t,~ha3e ~epa, but that to prev~nt a~lomeration of or eccape o~ the air bu~ble~ it wa~ impor~ant to incorporate cer~ain ~ race active ingrediellt~, ~speclally higher fatty acids and ~;.h3 ~alts th~reof, such as Ctearic acid, behenic acid, pa;lmitic acid, I`IH`~ 2~ 'PM COLGQTE P~iTENT LIEPT. 2 Q
sodium ctear~te, aluminum ~tearate, and the like. rhe~
s~race acti~e agents a~paren~ly ~nctioned by fo~ ing ~n int;~rfacial ~ilm at the ~bble ~ur~ace while ~190 I'ol~ing hyd~ogen bond~ or co~tributirlg ~o the electro~ta~:Lc attraction with the 6uæ~ended par~icles, ~uch that ~he air bl~.ble~ and attracted pa~ticle~ ~ormed agglomerates o~ ~pprox.i~l:~tely the ~ame density as ~he den~ity of the conti~uou~ u..d phase.
Therefore, in a preferred embodiment of the p:esent invention, .tabiliza~ion of ai~ ~ubble~ which may l)ecom~
incor~oratrecl i~to the composition~ durln~ ~o~mal proce6~ing, ~uch a~ duri.ng ~arious mixing ~te~, iY avoided ~ po~t-addi~g the surface active ingredient~, including fatty acid or fatty acid 3al~ ~t;a~ilizer, to the remainde~ of ~he co~E~ition, under low shear conditions u~ing mixing device~ de:3igned to lS mini~ize cavit~tion and vortex form~tion.
Ac will be de~cri~ed in gre~er d~tail below ~he ~urface acti~e ingredients pre~ent in the co~lposition wiLl incl~de the main detergent ~urface active cleaning agen~, ~nd will alæo ~referably include anti-foaming ayent and hi~her ;I.atty acid or 20 8alt thereof ~ a phy3ical ~tabilizer.
~ emplar~ o~ ~he cro~-linke~ pol~acrylic a.ci.d-ty~
~hick~nin~ age~6 are the products ~old by B.F. ~ odrich under th~ir Car~c~ol trademark, e~pecially Ca~bopol ~41, which i~
the mo~t ion-in~en~iti~e of thi~ cla~6 of pol~m~r3, and 2S Carbopol ~L0 and Carbo~ol ~3~. The Carbopol resi~, al~o known as I~Carbomer~, are hydro~hilic high molecullr weight, croiss-linked ac~yl~c acid polymers having an avh!rilge ~lh~ c~ ' 9c Cl_: '>8PM CC)L~hTE PhTENT L1EPT . 2 0 6 9 9 6 6 P 10/45 eqlivalent wei~ht of 76, and ~he general structur~: illustrated by the ~ollolwing ~ormula;
H H
I I
C C
H C
~O O n.
Carbopol 941 ha~ a molecular wei~ht of abo~t 1,250,~00;
Carbopol 940 a molecular weight o~ approximately 4 000,000 ~nd Car~o~ol 934 a mol~cular weight o~ approximately 3,000,000.
The C~rbopol. r~sin; are cro~-linked with polyalke;~
polye~her, ~.g. ahout 1~ of a polyallyl ether of ~llcro~e lS havin~ an average o about S.8 allyl ~rou~ $or eal~h molecule of ~ucrose. Further detail~d informa~ion on the C',~rbopol re~ina i~ a~ailable from ~.F. Goodrieh, see, for ~ ampl~, the B.F. Goodrich cataloy GC~67, Car~opol~ Wa~r Sol~le ~e6in~.
While mo~t favorable re~ult~ have been achie~ed with ~0 Carbopol ~41 polyacrylic re~in, o~her lightly cro~s-linked polyacrylic acid-type thickeni~g ~g~nt~ can also ~:e used in the compo~itions oE thi~ in~n~io~. As u~ed hex~:ln llpolyacrylic acid-typell r~f~r~ to water-~oluble :h,~mopolymer~
of acrylic a~id or methacrylic acid or water-di~,p~x6ible or wa~er-~oluk~le ~alt~, e~ter~ or amicles ther~of, or water-~oluble coE)olymer~ o~ the~e acid~ o$ their ~alte;, e~ter~ or ameide~ with oach other or with one or more o~er e~lenically unsaturated monomers, ~uch a~, for e~mple, styrelle, malaic acid, maleic anhydride, 2-hydroxyethylac~ylate, a.~rylonitrile, ~inyl acet;~te, e~hylene, propylene, and the lik~.
r I I l lL ~ I L r ~ I Ll ~ I L LI I .
r-20~9~6 The homopol~ner~ or copolymer~ are characterized by their hig~ molecular weight, in the ran~e o from a~ouc 500,000 to 10,400,000, prefera~ly 500,000 to 5,000,000, e~pecially from about 1,000,000 to ~,000,000, and by their water ~olubility, ~enerally at leaæt to an exten~ of up to about 5~ by wei~ht, or more, in water at 25C.
Theee thi~kening agents are uged in their lightly cro~-linked form wherein ~he cro~s-linking may be accomplished by means known in ~he polymer ar~, a~ by irradiation, or, preferably, by the incorporation into the monomer mixture to be pPlymerized of known chemical CrO8~ - linking monomeric agent~, typically polyunsa~ra~ed (e.g. diethylenlcally un~atura~ed~ monomers, such a~, for example, divinylbenzene, divinyle~her of diethylene ~lycol, ~, N'-methylen~-bi~acrylamide, polyalkenylpolyether~ (~uch a~ de~cribed abo~e), and ~he like. Typicall~, amounts of cro~s-linking agent to be incorporated in the final polymer m~y range fro~
about 0.01 to about 1.5 percent, prefera~ly from about 0.05 to abou~ percent, and especially, preerably from a~out 0.1 to about 0.9 percent, by weighc of cro~s-linking agent to ! weight of total polymer. Generally, thoge ~killed in the art will recognize ~hat the degr~e of cro~-linking should be 6ufficient to impax~ some coillng of the otherwi~e ~enerall~
linear polymeric compound while maintaininy the cross-linked polymer at lea~t water di~ersibl~ and hi~hly water-3wella~1e in an i~nic a~ueous medium. I~ is also uIiderstood ~hat the water-swelling of t~e polymer which provide~ the desired thickeni ~ a ~ vi~cou~ propertieg ~enerally depends on one or I Ir~ n I L I r~ I L ~ ~ I L~L.I I . I . L~
~Ofii~g66 .
two mechanism~, nam~ly, conver~ion o~ ~he ~cid group containing polymers to ~he corre~ponding ~alt~, e.g. ~odium, ge~erating negative charge~ along the polymer backbone, thereby ~au~ing the coiled molecules to expand and thicken the S ayueou~ ~olution; or ~y forma~ion of hydrogen bonds, for : oxample, ~etween the ca~oxyl groups of the polymer ~nd hydroxyl donor. The ~or~er mechanism i~ especially important in ~he ~recent invention, and ~herefore, the pre~erred polyacrylic acid-type thickening ayeIltj will co~ain free car~oxylic acid (COOH) groupx along the polymer backbone.
Also~ it will be understood t~t the degree of cross-linking ~hould not be ~o hlgh as to render ~he cross-linked pol~ner completely insoluble or non-digper6ible in water or inhi~it or prevent the ~ncoiling of the polyme~ molecule~ in the presence of the ionic aqueous By~em.
The amount of the high molecular weight, cro~-linked polyacrylic acid or other high molecular weight, hydrophilic cro~s-linked polyacrylic acid-type thickening agent tO impar~
, the de~i~ed rheological proper~y of line~r ~i~coela~ticity will generally be in the range o~ from about 0.1 ~o 2%, preferably from abou~ 0.2 ~o 1.4~, by w~ight, ~d~ed o~ the weight of the compo~ition, althouyh the amou~ will depend on the partlcular croca-linki~g agent, ionic ~rength of the compo~i~ion, hydroxyl donor~ and the like.
The co~po~itions of thi~ inverl~iorl m~l~t include ~ufficient amo~nt of po~a~sium ion~ and ~odium ion~ to provlde a weight ratio of ~/~a of at lea~t 1:1, prefer~ly from 1;1 to 45:1, especially from about 1:1 to 3:1, more preferably from 2~99~6 1.05:1 ~o 3:1, 6uch a6 1.5:1, or 2;1. When r~he K/Na ratio i~
le99 than 1 ~here i~ insuff icient colubility of the normally ~olid i~gredien~s ~herea~ when the K/Na ratio ic~ more than 45, e~pecially when it i~ greater than a~out 3, the product becomes too liquid and phase ~eparation begin~ ~o occur. W.hen ~he K/~a ratio is more t~lan 45, especially whe~l it i~ greater than a~out 3, the product ~ecome~ too liquid and phase separation be~in~ to occur. When the K/Na ratio~ become muc~
larger ~han ~5, ~uch ~8 in all or mostly potassium formulation, the polymer thlckener lo~e~ it~ a~orptior c~pacity and begin6 to ~alt out o~ ~he aqu~ou~ p~a~e.
The potassium arld ~odium ions can be made present in the compo~i~ion~ a~ the ~lkali metal ca~ion o~ the detergent builder ~alt(~), or alkali metal silica~e or alkali metal hydroxide comporlent~ of the compositions. The alkali metal cation ma~ also be present in the compo ition~ aG a componen~
of an ionic de~ergent, bleach or other ionizable salt compound addi~i~e, e.~. alkall m~tal car~onate. In de~er~ining the K/Na weight ratio~ all of these ~ources should be taken into consideration.
Speci~ic ex~mpl~ of ~c~r~en~ huilder 6al~ inclu~e the polypho~pha~e~, ~uch as alkali metal p~oE)hosphar~e, alkaJ.i me~al tripolypho~phate, alkali m~tal metapho~pha~e, and the like, for example, ~odium or potas~ium txipolypho~phate ~ (hydrated or anhydro~ etra~odi~m or tetrapotassium pyropho~phate, ~odium or pota~siu~ hexa-metapho6pha~e, tri~odium or ~ripotassium orthopho~phate ~nd the ~i~e, ~odium or po~a~3ium carbonate, ~odium or po~a~Yium citrate, ~odium ox 2~99~
potassiuM nitrilocriaceta~e, and th~ like. The pho~phate builder~, where no~ pr~cluded d~e to local re~ula~ion~, are pref~rred and mixcure~ of tetrapota4~ium pyropho~phate (TKPP) and sodium ~ripol.ypho~phate (NaTPP) (especially the hexahydrate) are e~pecially p~eferred. Typical ratios of Na~PP to TKPP ~re from a~out 2:1 to i:8, especially from about 1:1.1 to 1:6. The to~al amou~t of ~etergenc builde~ salts i~
prefera~ly ~rom about 5 to 35~ ~y weight, more prefera~ly from abou~ 15 to ~, especially from about 18 to 30~ by w~ight of the compocition.
In connection with the builder 6alts are optionally u~ed a low molecular wei~ht noncros~linked pol~acrylates havlng a ~olecular weigh~ of abouc 1,000 to about 100,000, more preferably about 2,000 ~o about 80,000. A preferred low molecular ~eigh~ polyacrylace i~ Nora~ol LMW45~ man~factured ~y ~orsoshaas and having a molecular wei~ht of abou~ 4,SOO.
These low molecular wei~ht polyacrylate~ are employed at a concentration of about 0.1 to lS ~t.~, more preferably ~.25 to : 10 wt.~.
Other useful low molecular weight noncro~linked polymer~
axe Acusol~640D provided by ~ohm ~ Ha~ c)rasol QR1014 ~rom Norsohaaq having a GeC molec~lar weight of 10,000.
The linear vi~coela~tic compositions of ~is invention ~ay, and preEerably ~ill, contain a ~mall, but stabilizing ~5 effective amount of a long chain fatty acid or monovalent or po].yvalent calt thereof. Although the manner ~y which the fatcy acid o~ ~alt ~oncribute~ to th~ rheolo~y and stabili~y of ~he compo~i~ion ha~ not been fully elucidated it is I Ir~ .J ~.1 1 1 .. ~ .r~ I rl I L.l I I L'~l I . r~
hypothe~ized that it ~ay function as a hydrogen bonding ~ 9 or cro~s-linking agent for the polymeric thickener.
The preferred lon~ chain fd~ty ~cid~ are the ~ligher aliph~tic fatty acids having ~rom ~cuc ~ ~o 22 c~rbon atom~, more preerably from a~out 10 to ~0 carbon atomq, and e~pecially preferably from about 12 to 18 carbon atoms, and e~pecially preferably from abou~ 1~ to 18 car~on atoms, inclu~i~e of the carbon atom of the carboxyl group o the fatty acid. The aliphatic radical ~ay ~e ~aturated or un4aturated and m~y be ~raight or branched. Straight chain ~aturated fatty acid~ are p~e~exred. Mi~tures of ~atty acids may be used, such a~ Lho~e derived f~om natu;~al Gources, suc~
a6 ~llow fatty acid, coco fatty acid, ~oya fatty acid, mixtures o these acid~, etc. Stea~ic acid and mixed fatty acids, e.~. stearic acid/palmitic acid, are preferred.
; When the ~ree acid form of the fatty acid i~ u~ed directly it will generally ~s~ociate wi~h ~he pota~ium and sodium ion~ in the aqueou~ phase to fo~1n che co~re~ponding alkali metal fatty acid 90~p. However, the fatt~ acid ~alts may ~e directly added ~o t~l~ comr~o~i~i.on a~ ~odium ~alt or pota~ium salt, or as a ~olyvalent met.al ~1L~ althouyh the ~lkali metal salt~ of the ~a~ty acids are preferre~ fa~ty acid ~alts .
The pre~erred polyvalen~ metals are the di- and tri-valent metals of Grou~ IIA, IlB and III~, such ~s sna~n~sium,calcium, ~luminum and zinc, ~lthou~h other polyv~lent metals, incl~ding those of Groups ~ , rvA~ ~rA, IB, I~rB~ ~7B VIB, and VII~: Qf ~e Periodic ~able oI; che Elernent~3 can alqo be 2~699~;
used. ~pecif1c ex~nple~ of ~uc~l other po~yvalent metal6 include Ti, Zr, v, ~ , Fe, Co, ~i, Cd, Sn, Sb, Bi, etc.
Generally, the metal~ may ~e pre~ent in the divalen~ to pentavalent state. Preferably the metal. ~alt~ ar~ used in t~eir higller oxidacion ~tates. Ndtur~lly, for u e in ~tom~tic di~w~her~, as well a~ any o~her ~pplications where the invention compo~i~ion will or may come in corltact with articles u~ed for the handling, ~orage or se~ving of food product~ or which otherwi~e ma~ c~me into concact with or ~e consumed by people or ani~al~, the metal ~alt ~hould be ~elq~ted by ~aking into con~ideration ~he ~oxici~y of the metal. ~or this purpo~e, the ~lkali metal and calcium and magne~iu~ salt~ axe especially higher preferred a~ generally sae food additives.
The amount of the fa~ty acid or fat~y acid ~alt stabilizer to achieve ~he de6ired enhancemerlt of phy~ical stability will depend on ~uch fac~or a~ ~he na~ure of the atty acid or it~ ~alt, the nature and amount of the thickening a~ent, detergeIIt ac~lve co~po~d, inor~ahic salt~, other ingredients, as well aR the anticipate~ sr.orage an~
~hipping condition~.
Generally, ho~e~er, amount~ of the fat~y acid or fatty acid salt s~abilizing agen~ in the r~nge of from about 0.02 to 2~, preferably 0~04 ~o 1~, more pre~erably from abo~t 0.06 to 0.8~, especially preferably fxom about 0.08 to 0.4~, pro~ide a long term stabili~y and absenc2 of pha~e ~eparation upon standing or d~rin~ transport at bo~h low and elevated _. ~ .
u~ r~ t~l l L l~ . r- . L l / -~_ 2~9~6 temperature~ a~ are ret~ired for a c~nunercially acceptable product.
Depending on ~he amounts, proportion~ and types of fatty acid ph~ical s~abillzers and polyacrylic acid-type thickening at3ents, the addition of the fa~ty acid or salt not only increa6e~ phy~ical ~tabilit~ ~u~ al~o provide~ a simul~aneouq incre~e in apparent vi~coqi~y. ~nount~ of fat~y dcid or salt ~o polymeric thickening a~ent in the range of from abou~ 0.08-~ .4 ~Yeight percent fa~ty a~id ~alt and from a~ou~ O .4-1. 5 weigh~ percent polymeric thickenin~ agent are usually s~f~icient to provide ~he4e ~imultaneous benefit~ antl, therefore, ~he use of the~e irlt~redi~nts in these amount~ is m~t preferred.
In order tO achieve the desired benefit fro~ the fa~ty ~cit~ or fatty acid ~al~ 4tabilizer, ~ithout s~abilization of exce~s incorporated air bubbles and con~equent exces~ive lowerirlg of the product bulk den~ity, the fatty acid or salt ~hould be po~-added to the forrllulaciorl, ~referably together with the other surface active i.n~jr~dient~, includ.ing detergent ao active compound and anri- foamint3 a~erll, when pre~erlt. The~q ~urface active int~redierlts are E~refer~bly addt~d a~ an ~mulsior in wa~r wherein the emul~i~ied oily or f~ety ma~erial~ are finely and homogeneously dispersed ~hroughout the a~ueou~
phase, ~o achieve the de~ired fine emulsification of the 2S fatty acid or fatty acid xalt and o~her surface active ingredien~ u~ally nece6~ary ~o heat th~ emulslon (or preheat the water~ to an elevated eemperature near the ~elting temperatUre o~f the fatty acid or itY ~alt. For example, for r I I ~ l L I r~ I Ll ~ ~ LlL-r I . r . ~
stearic acid having a melting poin~ of 68C-69C, a te~perature in the range of between 50~C and 70C. will be used. For lauric acid (m.p.=47~C) an elevated temperature of about 35dC to 50C
can be ~ed. ~pparently, at the~e elevated temperat~res the fatty acid or salt and other surface active ingredients can he more readily and uniformly dispersed (emulsifled) in the form of fine droplet~ throughout the compo~ition.
In contra~t, as will be shown .in the example~ ~hiCh follow, if the fatty acid is ~impiy poY~-added at ambient temperature, the composition i6 ne~ linear ~i~coelastic as deined above and the stabili~y of rhe co~po~ition i~ cle~rly inf erior .
Foam inhibition ic impor~.ant to increase di~hwa~her machine efficiency a~d minimize de~tahilizing effect~ which might occur due ~o the presence of exce~ foam wi.thin the washer duri~ use. Foam may be red~ce b~ jui~able 6election of the type and/or amount of deter~en~ active ma~erial, the main foam-producing ccmponent. The degree of foam is al~o ~ome~hat dependent on the hardne~s ~f the wa~h water in the machine whereby sui~able a~jus~men~ o ~e ~ro~or~ions of the ~uilder salt~ such as NaTL~e which has a w~ter ~o~tening effect, may aid in providing a degree uf foam inhi~ition.
Ho~ever, it is generally preferred to include a chlorine bleach stable foam depressant or i~hibi~or. Par~icularly effective are the alkyl pho~ph~ri~ aci~ e~ter~ of the formul~
~. ~ .
20~66 HV~
OR
and e~pecially the aik~l acid pho~h~e e~ters of the formula HO-P-OR
In the above formulas, one or both R ~roup~ in each type of ester may repre~e~t independently a C~2-C20 alkyl group. The ethoxylated derivative~ of each ty~e of ester, for exa~ple, the conden~a~ion products of one mole of e~er with from 1 to 10 mole~, preerably 2 eo 6 moles, more prefer~bly 3 or 4 mole~, ethylene oxide can al~o be u6ed. Some exa~ples of ~he ~oregoing are commercially av~ilable, ~uch as ~he produc~s SAP
from Hooker and LPK~-158 from Knapsac~. ~ixture~ of ~he ~wo cypes, or an~ other chlorine bleaeh ~table types, or mixt~re~
of mono- a~d di-esters of the same type, may be employed.
Especially pre~erred i~ a mix~ure of mono- and di-C~6-Cl~ alkyl acid pho~phate e~terx ~uch a~ monoYt~aryl./di~te~ryl acid pho~ph~tes 1.2/1, ~nd ~he 3 to 4 mole et;hylene oxide condenaa~es thereof. When ~mployed, proporti.on~ of 0.05 to 1.5 weiyht percent, pre~era~ly 0.1 to 0.5 weight pe~cent, of foam depres~ant in the composition i~ typical, the weight ratio o detergent active component (d) to foam depressant (e) generally ranging from abo~t 10:1 to 1:1 and preferably abou~
5:1 to 1;1. Oth~r defoamer~ which may be u~ed include, for example, ~he known ~ilicone~, such a~ a~a~lable from ~ow Chemical~P ~ a~dition, i~ i~ an advantageo~ feature of ~hi~
~n I ~ L ~rl I L I ~-~ I L I I I ~ Lr I ~
20~9~66 (registered ~rademark) 3~-2 and DOWFAX 2~-1. In addition, ~he surfac~ant 6hould be compa~ible wi~h the other ingredien~ of the compo~ition. Other ~uitable organic anionic, non-~oap s~rfactants include the primary a~kyl~ulphates, alkylsulphonates, alkylaryl~ulphonate~ and sec.-alkylsulphate~. Exampleg in~lude sodi~m Cl0-C,~ alkyl~ulpha~e~
s~ch a~ sodium dodecylsulp~a~e and sodium t~llow alcohol~ulphate; sodium C~O-C~ alkanesulphonate~ such a~ sodiu~
hexadecyl~ ulphonate dnd ~odium Cl2-CI~ -a~k~benzenesulphonate~ ~uch as ~odium dodecylbenzene~ylphonates, ~he corresponding pota~sium salts may also be employed.
~ other ~uitable su~factants or detergen~, the amine oxide surfac~ant~ are typically of the s~ructure R2RINO, in which each R repreeent~ a lower ~l~yl group, for irlstance, methyl, and Rl repxesents a long chain alkyl group having rom 8 to 22 carbon atoms, for in~tance a lauryl, myri~cyl, palmityl or cetyl group. In~tead of an amine oxide, a corre~ponding ~rfactant pho~phine oxide R2R~PO or sulphoxide ~O RRISO can be em~loyed. Betaine ~-lr~.ac~ante are typically ~
the s~ructu~ R2R~NtR"COO-, ln whi~h each i~ repres~nt~ a lower ~lkylene g~oup having from 1 to ~ ca~on a~omY. ~pecific exa~lple~ of theQe surfactant~ incl~1de lauryl-dime~hylamin~
oxide, myristyl-dimethylamine oxide, myri~yl-di~lethyl~mine oxide, t~e corre~ponding ~ho3~hine ox~e~ arld ~ul~hoxide~, and the correeponding betaine~, includin(~ do~ecy]dim~-hylamn~oni-~
aceta~e, tetradecyldiethyl~onium p~ntano~te, hexadecyl~im~4~1a~nonium hex~noa~e and the lL~e. For .
2~
I I r~ L _ I I I _ I ~ L r r 1 I L I ~ I L L I I ~
2G~9966 biodegra~abili~y, ~he alkyl group~ in the~e ~urfac~ant~ should be linear, ~nd ~uch comQc,unds are pre~erred.
Surfactant~ of the foregoing ~ype, all well known in the art, are described, for example, in U.S. Patents 3,985,668 and 5 4,271,030. ~f chloxine bleach 1s not used ~han an~l of the :-well knowrl low-foaming non1onic ~urfactants such as al~oxylated fatty alcohol~r e.s. mixed eShylene oxide-propylene oxide condensa~es of C~-C~2 fatty alcorlols can al~o be used.
The chlorine bleach ~ta~le, ~ater di~Jpe~lble oryanic detergent-active material (suxfac~ant) will noL~ally be presen~ in the composltion 1n minor ~no~nts, ~enerally abou~
1~ hy weight of ~he co~position in ~inor amount~, generally about L~ by weigh~ of the compo4icioII, althou~h smaller or larger a~oun~, such a6 up to about 5~, such as from 0.1 to 5~, preferably fo~m 0.3 or 0.4 to 2~ ~y weight of t~e Composi~ion, may be used.
Alkali ~e~al ~e.g. potas~i~m or ~odium~ si1icace, which provide~ alkalini~y ~nd protectiorl of hard s~rface6, ~uch a~
fine china gl.aze and ~ttern, i~ ~en~rally e~lployed in an amount ranging f~om a~ou~. 5 to 2~ w~i~ht percent, E)refe~ably abouc 5 to 15 weight percen~, more preferably 8 tO 12~ in the composition. The Yodium or po~as~ium Bllicate iY generally add~d in the fox~ of an a~eou~ ~oLu~iorl, p~eferably having Na20:SiO2 or K20:SiO2 ra~io of abo~t 1:1.3 ~o 1:2.8, ~speci~lly preferahly 1:2.0 to 1:2.5. ~ thi~ poin~, it ~hould be mentioned ~hat many of the oth~r componen~s of ~his composit~n,~x~pecially alkali mecal hydroxi~e and bleach, are 2~66 \ -àl~o ofte~ added in ~he ~onm of a preliminaxy prep~red a~ueou~
di~per3ion or solution.
In addition to the de~ergent active surfact~nt, foam inhibitor, alk~li metal silica~e corro6ion inhibitor, and detergent build~r ~alts, whlch all contri.bute to the elean1ng performance, it is also known that t~le efect1ver~e~s of ~he liquid au~omatic di~hwa~her detergenL compositions is related to ~he alkalinity, and par~icularly to moderate to high al~alinity levels. Accordingl~, the compo~i~ion~ of thi~
invention will have p~ value~ of ~t leas~ about 9.5, pref~rably at least about 11 to a~ high as l~, generally up ~o about 13 or mor~, and, when ad~ed ~o ~.he aqueous ~a~h bath a~
a typical concentration level of about 10 gram~ per li~er, will provide a pH in the wa~h bath of a~ lea~t about 9, lS prefera~ly at least about ~C, such as 10.5, ~1, ll.S or 12 or more.
The alkalinity will be achie~ed, in pa~t by the alkali me~al ion~ contributed by the alkali ~etal de~ergen~ b~ilder ~alt~, e.g. sodi~m tripolypho~p~ate, tetrapo~assium pyropho~phate, and alkali metal ~ilic~, however, it i~
u~ually nece~sary to include alkal.i metal hydroxi.de, ~.~. NaOH
or KOH, to achieve ~he deslred high alkalini~y. Amounts of alkali metal hydroxide in the range of (on an active basis) of f~om about 0.5 to 8%, preerably f~om l to ~, mor~ preferably from about 1.2 to 4~, by weight of the composition wil~ be sufficient to achieve ~he de~ired ~H le~el and/o~ to adju~t the X/Na weight racio.
rl I ~ L~ ~ r r~ I . r . ~
2~ii9~66 Other alkali me~al qaltY, ~uch ~ alkali me~al ca~bona~e may also be pre~ent in r.h~ compo~ition~ in minor amounts, for example from O to 4%, preferab~y O ~.o ~-, by weight of the composition.
Other conventional lngredlen~ may be included in theie composition~ in ~mall amoun~s, generally le~ than about 3 weight percen~, 3uch as perfume, hydrotropic a~ents such a~
the sodi~m benzene, ~oluene, xy~ e and cume~e sulphonates, preservatives, dyes~uff~ and pigments and ~he like, all of cour~e bein~ table ~o chlorine bleach compound and hi~h alkalinity. E~ecially preferred for coloring are ~he chlorinated phythalocyanine~ and polysuphides of alu~.inosilicate which provide, re~pectlvely, plea~ing green and blue tint~ Tio2 n~y b~ employed for whi~e~ing or neutrali~ing off~hades. Even more preferred coloranc~ u~ed at a Co~Gentration of about 0,01 to 1.0 ~t. ~ are CI Direct Yellow # 28 and Grapthlol Green pigment both made by Sandoz Chemical Corp.
Al~hough for the rea~ons previou~ly fli~cu~ed e~ces6ive ~ir bub~le~ are nv~ often ~esi.r~le in ~he inverl~ion compo~i~ion~, depending on the amoun~s o~ dl.s~o~ved 30lid~ and liquid phaje densltie4, incorporation of cm~ll amounts of finely divided air ~ubbles, generally up to ~bout 1~% by volume, preferably ~p to about ~ by volume, more ~referably up to about 2~ by volume, can be incorporated ~o adjust ~he bulk de~ity to approximate liquid phaYe den~icy. The inco~porated air bubble~ should be finely divided, such a3 up ~o about 1 ~ micron~ i~ diamet~r, prefer~bly from abou~ 20 to : . ~1, ~ _ 2069966 ~
bleac~ compound ~nd remaining detergen~ additive~, includinc3 any previously unuQed alkali metal hydroxide, if any, of;her tha~ the ~urface-active compounds. ~ll o~ the additional ingredient~ can be added ~lmultaneously or 6equentially.
Preferably, the ingre~ient~ are added ~e~uentially, although i~ ic not necesf~ary to complete the addition of one i~gredient before beginning to add the next ingredie~lt. ~urthermore, one or more c7f ~he~e ingredient~ can be divided into portionY and added at different ti~es. These mixing steps should al60 be performed under moderate ~o high ~hear rate~ co ~chieve complete and unifonm mixin~. The~e mi~ing step~ may be carried o~t at xoom temperat.ure, althou~h the polymer thickener neutr~lization (gelation) i9 usually exo~hermic.
The ~ompo~ition may be allowed to age, if necessa~y, ~o cau~e di~c71ved or disper~ed air to di~sipa~e out of the compo~ition.
The remaining surface ~ctive ingredients, including the ~nti-foaming agen~, organic detergent compound, and fatty acid or fatf y acid ~alt stabilizer i~ ~o~t-added ~o ~he pre~iously formed mixture in th~ form of ~n aqlleo~s em~l~ion (u~iny from ~bout 1 to 10%, pre~erably from abo~t 2 ~o ~% of the tocal water added to ~he compo~ition ot~n~r t.han water added as carrier for other inyredlent~ or water of hydra~ion) which i~
pre-hea~ed to a temperature in ~he range cf from a~70u~ Tm+S to ~-20, preferabl.y from abo~t Tm to TM-10, where ~m is the meltiny point temperat~re of the fat~y a.cid or fatty acid salt. For the preferr~d ~tearic acid ~tabilizer the heating te~peratu~.i~ in the range of 50C to 70C. However, if care . 2~
i6 taken to avoid exce~slve air bu~le i.nc~pora~lon ~urls~y the gela~in gtep or during the mixing of ~he det.ergent builder ~ 6 9 9 salt~ and other addi~ive~, for example, by oper~ting unde~
vacu~m, or u~ing low ~hearing condition~, or special mixing ope~atatus, etc., the order of addition of the surface acti~e in~redients ~hould be less impor~ant.
In accordance with an e~peclally preferred embodime~
the ~hickened linear vi~coelastic aqueous automatic di~hwa~er detergent compo~iti~n of ~his invention includes, on a weight basi~;
(a) 10 ~o 35~, preferably 15 to 30~, of at least one alkali metal detergent ~uilder sal~i (b) 0 to lS, preferably ~ to 12~, alkali ntetal 3ilicate;
(c) 1 to 6%, preferably 1.~ ~o 4~, alkali metal hydroxide;
(d) 0 to 3~, pre~erably 0.1 to 2~, chlorine bleac~
s~able, watex-di~persible, low-~oaming organic detergent acti~e material, preferably non-~oap anionic de~ergent;
(e) 0 ~o ~.S~, preferably 0.1 to 0.~, chlorine bleach stable foam depre~sant;
(f) chlorine bleach co~pound in an amoun~ to providç
about 0.2 to 4~, preferably 0.~ to 1.6~, of available chlorine;
(g) high ~olecular wei~ht ~lydrophilic cro~s-linked polyacrylic acid ~hickening agent in an amount to provide a linear ~iscoelas~icity to the for~ulation, pref~rably fro~
a~out 0.1 to 2.0%, more pre~erably from ~bou~ 0.4 to 1.5~;
(h) a long chain fatty acid or a metal salt of ~ long ch~ln fatty acid in an amount efective to increa~e the phycical ~ability of ~he composi~ion~, prefera~ly from o.oa to 2.0~, m~re prefera~ly frcrn 0.04 to 0.5%; and ; (i) balance water, prefera~ly ~rom abont 30 to 75~, more preferably from a~out 35 co ~5~; and ~herein ln (a) ~he alkali metal polypho~pha~e ~ncludes a mixture of from abo~t 5 ~o 30~, preferably from about 12 to 22~ of tetrapota~iu~
pyrophosphate, and fro~ 0 to a~ouc 20~, preferably from abou~
3 ~o 18% of ~odi~m ~ripolypho~phace, and wherein in the entire compo~ition the ratio, by wei~ht, of potaS~iUm ion~ tO sodium ions i~ fro~ about 1.05/1 ~o 3/1, preferably from 1.1/1 to 2.5tl, the composition~ having an amount of air incorporated therein s~ch that the bulk den~ity of the compo~ition i~ fro~
1~ about 1.32 to 1.42 g/cc, preferably from abou~ 1.35 to 1.40 g/cc.
(j) 0.01 eo i.09~ of a chlorine scable dye or chlorine ~table pigment.
The compocitio~ will ~e supplied ~o ~he con~umex in ~0 suitable di6pen~er cont~inerR preferably formed of molded pl~stic, e~pecially polyolefin pla~tic, an~ mo~ preferably polye~hylene, ~or which ~he inverl~ion composition~ appear to have partic~larly fa~orable 91ip chara~teristic~. In addition to ~heir linear vi~coelastic c~arac~er, the compo~itions of t~i9 inven~ion may also ~e characterized as pseudopla~cic gels (non-thixotropic) which are typi.cally near the ~orderline ~ecween liquid and ~olid ~iscoela~cic gel, depending, for example, on the amount of ~he polymeric thickener. The 2069~66 :
invention composition~ can be readily po~red from their containers without a,ny ghaking or 6queezing, ~lthough ~ueezable con~ainer~ are oten convenient and accepted by the con~uner for gel-like product~.
The liquid aqueou~ line~r vi~coela~tic auton~tic dishwa~her compo~itions oi this invention are readily e~ployed in known manner for waghing diahe~, o~her kitchen utensils and the like in an auto;natic dish~a4her, provided with a suitable detergent di~penser, in an aqueous wash bath containing an effectiYe amount of the compo~ition, generally fiufficient ~o fill,or partially fill the automa~ic dispenser cup of the particular machine being u~ed.
Th~ invention also provides a method for cleanin~
diohware i~ an automatic dishwashin~ machine wi~h an aqueou~
waJh ~ath containing an effecti~e amount of the liquid linear vi~coela~tic automa~ic di8hwasher deter~ent compo6i~ion as described ~bove. The com~osi~ion can be readily poured from ~he polyethylene coneainer with little or ~o ~queezing or shaking ~ n~o the di~pensing cllp of the automatic di~hwa6hing machine and will be ~ufficiently vlscous and cohe~ive ~o remain ~ecurely within r.he di~pen~ing cup until ~hear f orcea are again applied ~hereto, su~h as by che water spray from the dishwa~hing ~achine.
~he invention may be put into pr~ctice in ~ario~s way~
and a n~mber of specifi~ em~odiment~ will he de~cribed to illu~trate the in~en~ion with reference to the accompanying exa~ple~.
n I ~ 1 ~1 1 1 ~ ~n I ~ I r~ I Ll I I L ~l I r All the amount~ ~nd proportion~ referred co herein are by weigh~ of the composi cion unle~;~ otherwi~e indicated . -:
E~311;;~
Tl~e following fonnulatlon~ ~-X were prepared a~ deacri~ed below:
, I ~ ~ ~
1~ ~ ~ 1~ ~ 1~1 `'~
~ ~ 1~
, ?
2~99~6 r ~ ~ ~
L r ~ -- .c _ r u~ F~
~' r~ r~ O O ~r~ ~ V
I 1 ~ a ~
~ ll ~ o ~ ~x~a~
_ r _ _ _ :~
~ . I o ~ .~ aJ a ~ ~ ~ o o o~
_ __ _ O O ~I) O ~
_ o o .~
~D r~ O rd~ O ''~5 :
_ r ~ A A A ~1 0 ~
~ ---- N ~: v-~,.a O
~ .~ o O ,u v ~ ~ ~
_ r~ _- O ~ ho rd al ~ o o j (d _ _ _ _ ~ ~ ~
_ r~ t:) O o h ~ ~ ~ V
_ ~rt r~ o o ~ ,rd SV ~a~ ~
_ r l l ~ , U ~ O r~l U a) h o~
~ r ~ ~ I ~ ~ ~o~ 0~
~ ~; h cn ~ ~ D ~ ~ r~
lil ~ D :~ ~ ~ La o ~ k tn ~ u~
_ _ _ ~
r Form~lation~ A, B, C, ~, E, G, J, and K are prepared by fi~t forming a ~niform dlYper~ion of the Carbopol 941 or 940 thickener in abo~t 9~ of the water (balance). The Carbopol i~ 810wly added to deionized water ~L room temperature using a mixer equipped with a premier blade, wi~h agitation ~et at a medium ~hear rate, ac recon~e~ded by ~he manufact~rer. The disper~ion is then neutralized by addition, u~dex mixi~g, of the ca~stic s~da (50~ ~aOH or ~OH) component to form a thickened product of gel-like consi~tency.
To the res~lting gelled di~persion the ~ilicate, tetrapota~ium pyropho6pha~e (TKPP), ~odium tripolyphosphate TP(TPP, Na) and bleach, axe added ~quentlally, in the ~rder stated, ~ith the mixing continued at medium ghear.
Separacely, an emul~ion o~ the phoephate anci-foaming ~:
agent (LPKN), ~tearic acid/palmi~ic acid mix~ure and detergent (Dowfax 3B2~ i6 prepared by adflin~ thecl~ lngredient~ to the remaining 3~ o water (balance) and hea~ing the res~lting mixture to a ~emperature in the range of 50C to 70C.
Thi~ ~eated emulBion i~ ~hen ~dded ~o the previou~ly prepared gelled di~persion under low ~hear conditions, such that a vortex i8 not formed.
The remaining ~ormulations E~, H and I are prepaLed in e~entially the ~ame manner a6 de~cribed above ~xcept that ~he heated emulsion of LY~N, ~teari~ acid and Dowfax 3B2 i8 dixectly added ~o the neut~ali~ed Carbopol di~pe~ion prior to the addition of ~e remaini~4 ingre~ien~s. A~ a re~ult, formulation~ F, H and I, have hi~her level~ of incorporated air and ~c~ie~ below 1.30 ~/cc.
r~ r~ I L~ ~r I
The rheogrdm~ for the formulations ~, C, D, G and J are shown in figure~ 1-5, re~pectively, and rheogra~ for formulaLions H, I and K are ~hown in figure~ 6, 7 an~ 8 respectlvely.
The~e rheogram~ are o~tained with the Syr~tem 4 Rheometer from Rheometrics equipped wit~ a ~luid Se~o with a 100 gra~s-c~ntime~er ~orque tran3ducer and a 50 millimet~r pa.rallel pla~e geo~etr~ having an 0.8 millimeter gap ~etween plates.
~11 mea~urem~nts are m~de at room tem~era~ure ~25~C~1C) in a humidlty chamber after a 5 m~nute or 10 minute holding period o~ the sample in the gap. The measuremen~ are made by applying a frequency o~ 10 radians per ~econd.
~11 o ~he compogition fonmulation6 A, B, C, ~, G and J
according to the preferred embodiment of the invencion which include Carbopol 941 and ~earic ~cid exhi~it linear viscoela~ticity a~ ~een ~rom the ~heogram4 of figure 1~5.
Formulacion E whlch includes Carbopol 941 but no~ ~teari~ acid showed no p~ase separation at eic~er room ten~perature or 100F
after 3 week~, but exhibi~ed lO'~ phase~ paratlon af~er 8 week~ at room tempera~rc anfl aft~ only ~; w~ks a~ 100P.
Form~l~tion ~, conta1ni.ng C~opol '~0 in plac~ o~
Carbopol 941, a~ ~een from ~he rheo~ram i~\ figure 8, exhibi~
~ub~tantial linearity over ~he ~train range of rom 2~ to 50%
(G' at 1~ ~rain-G' at 50~ s~rain 500 dynes/~q,cm.) ~l~ho~gh 2S tan 1 at a ~r~in above 50~.
J ~
~99~6 This example demonstrates the i~portance o~ the order of ~dition of the surface active eonlponent premix to the rem~inder of the composition on prod~c~ den~i~y and stabili~y.
The following formula~ion~ are prepared by methods A and B:
Inq~di~nt~ ::
Water, deionized Balance Car~opol ~41 0.5 I.
~aOH (50~) 2.4 Na ~ilicate (47.5~) 21 TPP, Na 13 ~Bleach (1~) 7.S
~PKN 0.16 Stea~ic Acid 0.1 Dowfax 3B2 MQ5h~9 ~he Carbopol 341 i~ disperged, under medium ~hear ra~e, ~sing a premier blade mixer, in deiorlized water at ambient ~emp~ra~ure. The NaOH i~ ~dded, ~nder mixing, to neutralize and gel the Carbopol 94~ di~per~ion. To the thickened mixture the following ingredien~ aLe add~d ~equen~ially while the 8tirring is concinu~d: ~odium ~ ate, TKPP, TPP, and bleach.
Separately, an emul~ion i~ prepared by adding the Dow~ax 3B2, stearic aci~ and LeKN ~o wa~er while mlxing at ~oderate ~hear and heating the mixture ~o about 654(' tO ~inely di~per~e the emul~ified ~urf~ce active ingLedien~s in the Wdter pha~e.
Thie emulsion pre~ix is then ~lowly added to ~he Carbopol diiper~ion while mixing under lo~ ~hear ~onditiorls without forming a vortex. Th~ resul~ are ~howrl below.
r I I ' .` 1_`~1~ 1 ~ I n I ~ 'L_r`
2~6996~
et~p~ B~
~ thod ~ i~ repeated except ~hât the heated emulsion premix i9 added to the neu~ra~ized ~arbopc,l ~41 dispersion befoxe the ~odium stearate, TKPP, TPP, and ~leach~ The S resul~s are al~o ~hown below.
Me~hod A Method B
Density (g/cc) ~.38 1.30 Stability (RT-8 week~) 0.00% 7.00~
Rheogram Fig~ 9 Fig.10 From ~he rheograms ~f fiyure~ 9 and 10 lt i~ ~een ~hat both products are linear vi~coela~tic although the elastic and ~i~c~u~ moduli G' and G~ are ~ligher for Method A than for ~ethod B.
From the r~ults it i~ seen ~hat ea.rly addition of the surface active i~gre~ie~ o che Carbopol gel significanrly increases the deyree of aeration and lowers the bulk density of the final product. Since the bulk den~ity i~ lower than the density of the continuou~ liquid pha~e, the liquid phase under~oes i~er~e separation (a ciear li~uid pha~e forms on ~he bot~om of the composicion). T~is proces~ o inver~e ceparation appears to be kine~icall.y ~onr.rolled and will occur a~ter a~ ~he den~ity of the pro~uc~ become~ ~ower.
E~3m~1Y
~hi~ exa~ple ~hows ~e :im~or~.~n~ of the tempera~ure a~
which r,he premixed ~ur~ac~ant ~mu`L~ion 19 prepared.
~wo form~lation~, L and M, ha~ing che sa~e compo~i~ion as in Example 2 e~cept that the amo~m~ of ~tearic aci~ was increase~,r~ 0.1~ to 0.2~ are prepared as ~hown in rqethod A
I lr1 ~ ~r~ I ~ ~ r1 1 1_1 ~ I L~L r I . r~
2~iig96~
for formulation L and by the ~ollo~ g M~thod C ~or form~llation ~.
Met~d_C
The procedure of Me~hod A is repe~ted in all detail~
5 excep~ that emul~i~n premix o~ the surf~c~ acti~e ingredient~
is prepared at room temperat~re a~d i~ not heated beore being po~t-added to the thickened Car~opol dl~persion co~ltai.ning ~ilicate, builders and bleach. ~he fheogram~ for for~ulation~
L and M are jhown in figure~ 11 arld 12, re~pecti~ely. From these rheograms it i~ ~een that formulation L is linear ~i~c~ela3tic i~ bo~h ~' and G" whereas fornlulation M is non-linear vi~coela~tic pa~icularl~ fox elastic modulus G' (G~ at 1~ ~train-G' at 30~ .Qtrain ~ 500 dynes/cmA) and also for G" (G~
at 1~ ~train-G" at 30~ str~in 300 dynes/cm').
Fonmula~ion ~ remai~ cable ate~ storag~ at RT and 100~F
for at le~t 6 weeks whereax formuld~ion M undergoe~ phaRe separa~ion .
m~ C.~0~
The following or~1ation i8 prepared without any pota6~ium salts:
Wei~ht Wa~er ~alance Carbopol 941 0.2 NaOH (50~) 2.~
2S TPP, ~a (50~) 21.0 Na Silicate (47.5~) 17.24 ~ledch (1~) 7,13 Ste~ric Ac~d 0.1.
LPKN (5~) 3.2 Dow~ax 3B2 0.~
Soda Ash 5.0 Acr~ol LMW 45-~ 2.O
~9~
The proced-?re used i~ analogou~ to Method ~ of Example 2 wit~ the oda ash an~ Acrysol L~W 45-N (low molecular weight polyacrylate polymer) bein~ added before and after, re~pecti~ely, the silicate, TPP and ~le~ch, to the thickened Car~opol 941 di~persion, followed by addition to the heated surface active emulsion p~emix. The rheogram is shown in flgure 13 and is non-linear with G~/G' (tan ) ~ 1 over the range of ~rain of from about 5~ to 80~.
Example 4 ,~ormula~ions ~, B, C, P and ~C ~ccording to ~his invention and comparati~e formulations F and a commercial li~uid automatic di~hwa~her detergent product as shown i~ Table l above were subjected to a bo~tle residue test using a standard polyethylene 28 ounce bottle a~ ~e~ for current commercial liquid dighwasher detergent bottle~ :
Six bottles aro filled with th~ re~peetive samplas and the prod~ct is dispensed, with a minimum of force, in 80 gram do~ages, with a ~ minute re~t period between do~ages, until flow stops. At thi~ poi~t, the bottle wa~3 ~i~orou~ly ~haken ~o ~ry ~o expel additional product.
The amount of produc:t -remair~ g in ~.he ~oLt].e. is meafiured a~ a percentage of ~he total product originally f.illed in ~he bottle. The result~ are ~hown below.
~` ~ .
3~
20699~i6 Bottle Re~ldue Formu~i~ a Commercial Product 20 ~T~e jam~le ~eparates upon aging ~xampl e S
The following forrnula, A-I were p-~pared accordin~ to the proc~dure of ~xample 1.
., __ _ __~ _ c~ ~ _ _ ___ __ I
t` O ~ N r~ 0 o u~ o o . . . . ~ . r~ C~ . . U) ~
~ o ~ ~ ~ o o ~\J ~ ~` r~ ~ o o _ _ _ _ _ _ _ _ . . ~_ _ _ _ ~ _ ~ o U~ O ~ (~ r~ 0 O O O 117 U~ O O
td o _ _ _ o o .. ~ __ r o _ _ _ _ _ _ _~ _ _ _ __ o U~ o o o o Lrl o r ~ ~ ~ r~ ~ . . . L~ . o t~ O rl ~i ~ r~l r1 N t~ ~f ) O r1 _ _ _ ~ ~ _ _ ___ ___ ~ _ ~ ~ ' C~ O ~ ' U~ O O O U~ Ll~ ) r u~ ~ ~ ~ a~ ~ u`~ N Ll') r` O ~
1~ O O ~ (~ O O N r1 ~ r~ (' ) O rl _ ___ ~ ~ _ _ __ .____ ,~ _ . __ _ _ ~1) Ln O C~ U~ t'~ C~ ~
r~ O ~ N r~ O r; O In ~n Yr ~ u~
li~ O ~ ~1 ~Y) t~ r~ ~ ~I t-- r_ /'~ r1 ~ ~:
_ _ _ _ _ ~ O --~---- N--~ -- ~D O
t" O ~ ~r~l ~ r;c; O L~J I~ ~ rl O ~ ~I ~) ~ O ~<~I r., t~ ~1) r I ~1 _ _ _ _ ~ , ---- 1 -------- - --~ O ~ ~ rAI a~ O Cl O I~ O r C~
t.) C l rl ~ ~ o O ~ _ ~ ~ ~--1 t~ ~ r~J r~
_ _ _ _ _ _ O O _._.._. _ U~ _ .__ O O ~3 t" Ll~ ~( ~ I_~ ) r; Il~ ~ Ll~ 1~ ~) N L) ~1 O O ~ N O O ~ rl '-I t'` 1' r~ r~
_ . _ ~ _ __ __ ___ L~'l ,~ __ _ O
n ~ ~ r~ a~ o o c, u~ ~ c~ rl :i I¢ C; O ~ O O r U~ r1 r r __ _ _ rl I r _ ` ~
A
O
2~99B6 _ _ _ __ _ _ _ _ _ _~t _ __j . ~;t ~t _ ~ r _ _ _ __ _ ~t L L ~0 O _ _ _ _ _ _ _ _ _ _ __ __ _ ¦ ~
~0 w .p~ , e~ ~ ~ ~r 1- t tl t~ ~ It~
hO Ll'~ ~ O a~ O ~ ~ r ~ ~s) ll C~ C~ r ~ ¦ ~ t O_ r-i _ __ O _~ _ u~ u~ rl t` _ O rt _ ¦ 11~
:) r~) ~ r1 t~ c~ 1~ ~t ~t_ rt _ N O O N O _ rt ~ O O (li ~1 _ _ _ _ _ _ ~ ~ g ~O C~
~ Ll~ a I Irl I ~ L_'~I I I L I 1-1 I L 1 1 1 ~ 1 1 . r -t~ --~_ 20~9966 WXAT IS C.L~IMEP IS;
1. A lin~a~ visGoela~tic aqueous liquid automatic dlshw~cher de~ergen~ composition ~ompri~ing approximately by weight:
(a~ lO ~o 35~ of at lea~t one alkali metal de~ergent builder ~alt, ~aid alkali metal detergent builder : Qalt belng selected from tha group c~onsi~ing essen~ially of al~ali ~ne~al tripolypho~phate, alkali metal pyropho~phate, alkali metal mecapho~ph~te, alkal.i me~al carbonate, al~ali metal citrate and alkali met~l ni~ri.lo~riace~ate an~ mixt~re~
ther~of;
(b) 5 to 15~ alkali me~al silicate;
(c) 1 to 6~ alkali ~etal hydroxide;
~d) 0 to 3.0~ chlorine ~leach sta~l~, ~ater-di~per~ible, organic detergen~ active material;
(e) 0 to 1.5~ chlorir~e bleach stable foam depre~ant;
(f) chlorine ble~ch cornpound in an ~nount to provide 0.2 ~o 4~ o~ a~ailable chlorine;
(g) 0.1 to 2.0~ of a cro~-lixlked pnlya~rylic acid shickening agent having a Molecular weigh~ of from about 1,000,000 to 4,000,000i (h) 0.02 to 2~ of a long chain fat~y aci~ or a metal sal~ o~ a atty aci~;
(i) 0.01 to ~.0 wL. % of ~ ~igment. and/or dye;
(j) water, wherein ~id ~olyacrylic acid thickening agent being ~elected from che ~rou~ c~n~i~tin~ e~entially of acrylic a~ d ~r ~ethacrylic aci~, water-diYper~ible or wa~er-~;~
soluble ~a~.~s, e~ter~, or amldes ~he~o~, and watex-soluble copolymers of these acitls or their s~lt~, e~ter, or amide~
~ith each other or with one or mo~e other ethylenically ~nsaturated monomerj, wherein cha a~ueou~ ph~e include~ both ~odium and pota~6i~n ion~ a~ a K/Na weight xatio of from ~bou~
lJl to abo~t 45/1, wherein subs~arl~ially all of the normally solid component~ of the compo~ition are pre~ent dissolved in ~he aqueou~ pha~e, and sub~tanti.ally all of the wa~er in the compo~ition i~ tightly bound to rhe c-ro3~-linked polyacrylic acid thickening agent, ~aid compo~i~ion having a bulk density of rom 1.32 g/cm3 to 1.~2 tJ/Cm3 an~ ~aid composi~l.o~ doe~ not exhibit phase ~eparation and re~mains homo~enous, when said compo3ition i~ cerltrifugetl at 1000 rpm ~or 30 minu~e~.
2. ~he co~poYi~ion of Clalm 1, wherein ~aid alkali metal builder ~alt i~ a mixture of sodium tripolypho~pha~è and potas~ium tripolypho~phate.
3. The compo~:ition of Claim 1, whercin caid ~lkali metal builder ~alt is a mixLu~e oL ~ot~iu~n ~.rlpol.yphosp~a~e and po~a~sium pyropho4phat~.
4~ T~e compo~it ion of Cl~i.m 1 whereirl Gdid alk~l.i m~tal.
builder ~alt i~ a mixture o~ ~o~lium t~i.poJyE)hosE~hdct~, potassium ~ripolyph~phate, and ~ota~iurn pyropho~phate and mixture thereof.
builder ~alt i~ a mixture o~ ~o~lium t~i.poJyE)hosE~hdct~, potassium ~ripolyph~phate, and ~ota~iurn pyropho~phate and mixture thereof.
5. The compo~ition of C'laim 1, wherein the long chain ~a~ty a~id o~ sal~ ~hereo~ iB pre~e~ in a~ ount of from about 0.06 ~o 0.B~ by weiyht.
Claims
6. The composition of Claim 1 which further comprises up to about 2% by volume, based on the total volume of the composition, of air in the form of finely dispersed bubbles.
7. The composition of Claim 1 wherein the cross-linked polyacrylic acid thickening is present in an amount of from about 0.4 co 1.5% by weight of the composition.
9. The composition of Claim 1 wherein the K/Na ratio is from about 1/1 to about 3/1.
9. The composition of Claim 1 which the chlorine bleach compound is sodium hypochlorite.
10. The composition of Claim 1 further including a fragrance.
7. The composition of Claim 1 wherein the cross-linked polyacrylic acid thickening is present in an amount of from about 0.4 co 1.5% by weight of the composition.
9. The composition of Claim 1 wherein the K/Na ratio is from about 1/1 to about 3/1.
9. The composition of Claim 1 which the chlorine bleach compound is sodium hypochlorite.
10. The composition of Claim 1 further including a fragrance.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US71168891A | 1991-06-07 | 1991-06-07 | |
US71160391A | 1991-06-07 | 1991-06-07 | |
US7/711,603 | 1991-06-07 | ||
US7/711,688 | 1991-06-07 | ||
US7/725,067 | 1991-07-05 | ||
US07/725,067 US5252241A (en) | 1989-05-18 | 1991-07-05 | Linear viscoelastic aqueous liquid automatic dishwasher detergent composition |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2069966A1 true CA2069966A1 (en) | 1992-12-08 |
Family
ID=27418889
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2069966 Abandoned CA2069966A1 (en) | 1991-06-07 | 1992-05-29 | Linear viscoelastic aqueous liquid automatic dishwasher detergent composition |
Country Status (7)
Country | Link |
---|---|
AU (1) | AU1727192A (en) |
CA (1) | CA2069966A1 (en) |
FI (1) | FI922495A (en) |
IE (1) | IE921747A1 (en) |
NO (1) | NO922054L (en) |
NZ (1) | NZ242825A (en) |
PT (1) | PT100549A (en) |
-
1992
- 1992-05-20 NZ NZ24282592A patent/NZ242825A/en unknown
- 1992-05-25 NO NO92922054A patent/NO922054L/en unknown
- 1992-05-28 AU AU17271/92A patent/AU1727192A/en not_active Abandoned
- 1992-05-29 FI FI922495A patent/FI922495A/en not_active Application Discontinuation
- 1992-05-29 PT PT10054992A patent/PT100549A/en not_active Application Discontinuation
- 1992-05-29 CA CA 2069966 patent/CA2069966A1/en not_active Abandoned
- 1992-07-01 IE IE921747A patent/IE921747A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
PT100549A (en) | 1993-09-30 |
NZ242825A (en) | 1994-10-26 |
AU1727192A (en) | 1992-12-10 |
FI922495A (en) | 1992-12-08 |
NO922054L (en) | 1992-12-08 |
FI922495A0 (en) | 1992-05-29 |
IE921747A1 (en) | 1992-12-16 |
NO922054D0 (en) | 1992-05-25 |
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