EP0110731B1 - Solidification non-évaporative de pâtes de détergents - Google Patents
Solidification non-évaporative de pâtes de détergents Download PDFInfo
- Publication number
- EP0110731B1 EP0110731B1 EP83307439A EP83307439A EP0110731B1 EP 0110731 B1 EP0110731 B1 EP 0110731B1 EP 83307439 A EP83307439 A EP 83307439A EP 83307439 A EP83307439 A EP 83307439A EP 0110731 B1 EP0110731 B1 EP 0110731B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- foregoing
- surfactant
- phase
- alkyl
- solid
- 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.)
- Expired
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 21
- 238000007711 solidification Methods 0.000 title claims abstract description 17
- 230000008023 solidification Effects 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 60
- -1 alkyl sulphates Chemical class 0.000 claims abstract description 53
- 239000007787 solid Substances 0.000 claims abstract description 26
- 239000004615 ingredient Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000013042 solid detergent Substances 0.000 claims abstract description 4
- 239000004094 surface-active agent Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000002736 nonionic surfactant Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 239000008247 solid mixture Substances 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 150000002194 fatty esters Chemical class 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000000344 soap Substances 0.000 abstract description 9
- 239000012071 phase Substances 0.000 description 51
- 238000001704 evaporation Methods 0.000 description 12
- 235000002639 sodium chloride Nutrition 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- 239000012530 fluid Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 150000004996 alkyl benzenes Chemical class 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002280 amphoteric surfactant Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 159000000000 sodium salts Chemical group 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003752 hydrotrope Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007944 soluble tablet Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000003826 tablet Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- QSUHIERZZQYNPA-UHFFFAOYSA-N 1-dodecyl-2,3-dimethylbenzene;sodium Chemical compound [Na].CCCCCCCCCCCCC1=CC=CC(C)=C1C QSUHIERZZQYNPA-UHFFFAOYSA-N 0.000 description 1
- LANDRZNMJOEVQO-UHFFFAOYSA-N 3-ethenoxypropane-1,2-diol Chemical group OCC(O)COC=C LANDRZNMJOEVQO-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- QZXSMBBFBXPQHI-UHFFFAOYSA-N N-(dodecanoyl)ethanolamine Chemical compound CCCCCCCCCCCC(=O)NCCO QZXSMBBFBXPQHI-UHFFFAOYSA-N 0.000 description 1
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical class O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-H [oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O YDHWWBZFRZWVHO-UHFFFAOYSA-H 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical class OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000001683 neutron diffraction Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- SVMNBAVEQLDZNO-UHFFFAOYSA-M potassium;2-hexadecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O SVMNBAVEQLDZNO-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical class OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 150000003626 triacylglycerols Chemical class 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
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920003170 water-soluble synthetic polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D13/00—Making of soap or soap solutions in general; Apparatus therefor
- C11D13/14—Shaping
- C11D13/20—Shaping in the form of small particles, e.g. powder or flakes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0069—Laundry bars
Definitions
- the present invention relates to the preparation of solid compositions containing non-soap detergents, especially in bar, tablet or powder form, by non-evaporative solidification of aqueous detergent pastes.
- NSD non-soap laundry detergents
- the term includes the sulphated and sulphonated anionic surfactants, non-ionic, Zwitterionic, amphoteric and semi-polar surfactants and mixtures thereof, including mixtures with minor proportions of soap.
- the term excludes soap and active mixtures containing major proportions of soap.
- the term includes those cationic surfactants, which are effective as laundry cleaning agents or fabric softeners generally used in admixture with non-ionic or amphoteric surfactants.
- soap was the only laundry surfactant of industrial significance. It was used mainly in the form of moulded bars, or sometimes as a powder. It suffers, however, from the major disadvantages that it forms an insoluble curd with alkaline earth metals, which commonly occur in water especially in "hard” water areas.
- NSD which, apart from a small proportion sold as liquid detergents, is invariably supplied as a powder formed by the evaporation of a slurry of NSD, with builders and other auxiliary detergent ingredients, in water. Evaporation is normally effected in a spray drier.
- the conventional dried NSD powder has certain disadvantages.
- the energy cost of evaporating substantial quantities of water is high, and the capital cost and relative sophistication of spray driers is prohibitive for many developing countries seeking to establish an indigenous detergent industry.
- a market persists, even in industrialised countries, for laundry surfactants in the form of bars for repeated use, or of rapidly soluble tablets which can be used as a convenient means of adding measured amounts of surfactant to the wash liquor.
- Spray drying technology is not well adapted to satisfy this demand.
- a method for the manufacture of solid detergent compositions which comprises mixing an aqueous surfactant, which surfactant comprises at least a major proportion of a water-soluble salt of an acid selected from alkyl sulphuric acids, sulphonated fatty acids, sulphonated fatty esters and mixtures thereof, at a concentration and temperature such that said surfactant is present, at least predominantly, in the "G" phase with at least one builder and, optionally, other ingredients of said detergent compositions, and forming the mixture into a solid composition at least primarily by (A) cooling said "G" phase below its solidification temperature and/or (B) adding sufficient electrolyte to elevate said solidification temperature above ambient and/or (C) removing sufficient water, as water of hydration of at least one hydratable compound, to convert said "G" phase into a solid.
- aqueous surfactant which surfactant comprises at least a major proportion of a water-soluble salt of an acid selected from alkyl sulphuric acids, s
- the first of the foregoing phenomena (A) requires a "G" phase which exists only at a substantially elevated temperature and which is converted to the hydrated solid phase on cooling to ambient temperature.
- Suitable higher temperature "G” phase surfactants include sodium, potassium and tris (hydroxyethyl) ammonium alkyl sulphates, olefin sulphonates and alkyl benzene sulphonates.
- the second phenomenon (B) depends on the effects of electrolyte in raising the temperature of the "G" phase/solid phase transition boundary, and hence, effectively increasing the temperature at which the "G” phase solidifies, enabling a normally liquid crystalline surfactant composition to be obtained as the hydrated solid at ambient temperature.
- Suitable electrolytes to be used in raising the transition temperature include, for example, sodium silicate, sodium sulphate, sodium chloride, or sodium carbonate.
- the surfactant is anionic a common cation is employed to maximise the effect, thus where, as will normally be the case, the surfactant is a sodium salt, the preferred electrolyte will be a water soluble, strongly dissociable sodium salt.
- the amount of electrolyte required will depend upon the particular NSD and the extent to which the other non-evaporative solidication effects such as cooling or hydration of hydratable salts is relied upon.
- the third of the aforesaid phenomena (C) involves the abstraction of water from the "G” phase by a hydratable compound, in an amount sufficient to convert the "G" phase into a hydrated solid.
- a hydratable compound any anhydrous hydratable salts capable of exerting a dessicant action on a "G” phase surfactant may be used, the most convenient is anhydrous tetrasodium pyrophosphate or sodium tripolyphosphate, which are commonly included in NSD formulations as builders.
- the hydratable compound may be a partially hydrated compound.
- non-evaporative solidification does not exclude the possibiltiy that some evaporation of moisture occurs during the process. Incidental evaporation of moisture is inevitable when aqueous materials are handled, especially at elevated temperatures. The term merely indicates that techniques and employed which do not rely on evaporation to effect solidification. It is possible within the scope of our invention to use evaporation in conjunction with the non-evporative techniqes. However, if the evaporation requires expensive drying equipment or removes a sufficiently large proportion of the moisture to increase, substantially, the energy costs, then a part of the economic benefit of the invention will have been forfeited.
- the NSD feed in the process of our invention is essentially present as a "G" phase, although it may be possible in certain circumstances to add minor proportions of the NSD in other forms, e.g. as a dilute aqueous solution, or as an anhydrous or partially hydrated solid product. In the latter case the addition of the anhydrous surfactant may contribute to the non-evaporative solidification by raising the active concentration, and may in fact constitue some or all of the hydratable compound.
- the “G” phase is a pumpable fluid which is formed over a narrow range of concentrations which range usually lies somewhere between 45% and 80% by weight of active ingredient and is characterised by a lamellar structure in which the surfactant molecules are associated to form plates of indefinite size separated by planes of water molecules.
- concentration of a surfactant in the "M 1 " phase is progressively increased a phase change occurs to give either a hydrated solid phase, or, if the temperature is sufficiently elevated, to convert the M 1 phase progressively to a fluid "G” phase until a viscosity minimum is reached. Further increase in the concentration of the "G” phase causes the viscosity to rise until a further phase change occurs, leading to the formation of a hydrated solid phase.
- hydrated solid phase has been used broadly to include those systems which comprise suspensions of solid or immobile gel phases in one or more viscous or gel phase to provide a more or less rigid material.
- any "G” phase can be located very rapidly and easily, using standard laboratory equipment by making a test composition having an active concentration of say 75% (or, where appropriate, whatever concentration has been estimated on the basis of the foregoing formula) and placing a sample on a slide on the block of a heated stage microscope. Examination between crossed polarisers will reveal in which phase the sample is present.
- the various phases each have a characteristic appearance which is easily identified by comparison for example with the photographs of typical liquid crystal phases in the classic paper by Rosevear, JAOCS Vol. 31 P. 628 (1954) or in J. Colloid and Interfacial Science, Vol. 30 No. 4. P. 500. They may also be identified by X-ray or neutron diffraction.
- the mixture is in an M 1 phase, water may be allowed to evaporate from the edges of the sample under the cover disc and any phase changes observed. If any M 2 phase or hydrated solid is present, water may be added around the edge of the cover disc and allowed to diffuse into the composition. If no "G" phase is located in this way samples may be heated progressively on the block and the operations repeated.
- the composition is pumpable at concentrations within a range of ⁇ 10%, preferably ⁇ 5%, e.g. ⁇ 2.5% of the minimum viscosity concentration. This range tends to be broader at more elevated temperatures. Compositions may be obtained, at the limits of the range in which one or more solid or gel phase is suspended in a continuous "G" phase. Such compositions may be useful according to the invention.
- the "G” phase may generally be prepared by converting a suitable precursor to the NSD in the presence of the appropriate quantity of water (e.g. an alkyl sulphuric or fatty ester sulphonic acid may be neutralised with aqueous alkali of the appropriate strength).
- Mixed NSD may be prepared either by mixing the separately prepared components, each preferably in the "G" phase, or where this is impractical, by preparing one component from its precursor in the presence of the other component as described in our British Patent 2,022,125.
- alkyl sulphates avaialble for NSD solid formulations have been either substantially anhydrous solids and therefore difficult to mix with other ingredients, or more usually dilute solutions containing more than 60% water, which cannot be solidified at ambient temperatures except by evaporation of a major proportion of the water content.
- Non-evaporative solidification has not therefore been contemplated.
- Our invention takes advantage of a property of the more concentrated fluid "G" phase alkyl sulphates, namely their sensitivity to small changes in active or electrolyte concentration or of temperature, which enables them to be much more easily converted into hydrated solids than the more conventional detergent solutions.
- the alkyl sulphate for use according to our invention may be potassium, ammonium or lower alkyl ammonium or alkylolammonium alkyl sulphate. Particularly preferred are sodium alkyl sulphates. Sodium alkyl sulphates do not form "G" phases at ambient temperatures and are normally only available as dilute solutions less than 30% active concentration. Solid anhydrous or hydrated sodium alkyl sulphate cannot normally be melted, but tends to decompose on heating. The instability of alkyl sulphuric acids has prevented the adoption of dry neutralisation for making sodium alkyl sulphate based solid NSD formulations.
- alkyl sulphates would be attractive alternatives to alkyl benzene sulphonate for many developing countries who could prepare the former by sulphation of locally produced vegetable based feedstocks rather than imported petrochemical feedstocks required for the latter.
- sodium alkyl sulphates are prepared at temperatures of, e.g. 70°C, or even lower where mixed alkyl feedstocks were used, and the water used in the neutralisation is controlled within narrow limits to form the "G" phase, a pumpable and stable hot fluid can be obtained which is mixable with other detergent ingredients and which can be solidified by cooling to form a solid composition.
- the solid composition will normally be formed by extrusion.
- the hot alkyl sulphate mixture may be injected into a mould and cooled to form cast bars. Also, depending upon the consistency and physical form of the mixture, it may be milled to a powder and sold as such, or compacted into rapidly soluble tablets.
- the alkyl sulphate for use according to preferred embodiments of our invention is typically sodium C I - 20 linear alkyl sulphates, preferably a mixed C 10 - 18 alkyl sulphate. Particularly preferred is lauryl alkyl sulphate.
- Other alkyl sulphates which may be used include potassium, lithium, ammonium, monoethanolamine, diethanolamine, triethanolamine and mono-, di- tri- and tetra-alkylammonium salts having up to 6 carbon atoms, preferably 1 to 4 carbon atoms per cation. Salts of mixtures of the aforesaid cations and branched chain alkyl sulphates are also useful.
- alkyl sulphate may be used in admixture with any other "G" phase forming anionic NSD, or nonionic, Zwitterionic, amphoteric or semi-polar NSD or mixtures thereof.
- Cationic surfactants preferably in conjunction with non-ionic or amphoteric surfactants, may also be used.
- the alkyl sulphate constitutes at least 30% more preferably at least 50%, e.g. at least 75% of the total surfactant.
- the alkyl sulphate constitute at least 80% and preferably substantially all of the anionic surfactant.
- the non-ionic surfactant is preferably present in a proportion of from 1 to 49%, especially 2 to 20%, e.g. 3 to 10% of the total weight of surfactant.
- the alkyl sulphate may be used in conjunction with, or be replaced by, water soluble salts of a sulphonated fatty acid or ester such as the methyl ester of coconut fatty acid.
- the surfactant may contain an at least sparingly water-soluble, alkali metal, ammonium, alkylolamine or amine, alkylbenzene sulphonate, alkyl ether sulphate, olefin sulphonate, alkane sulphonate, alkyl phenol sulphate, alkyl phenol ether sulphate, alkylethanolamide sulphate, or alkylethanolamide ether sulphate, each having at least one alkyl or alkenyl group with from 10 to 20 aliphatic carbon atoms.
- Said alkyl or alkenyl groups are preferably straight chain primary groups but may optionally be secondary, or branched chain groups.
- ether refers to polyoxyethylene, polyoxypropylene, glyceryl and mixed polyoxyethylene-oxy propylene or mixed glyceryl-oxyethylene or glyceryl-oxy propylene groups, typically containing from 1 to 20 oxyalkylene groups.
- the sulphonated or sulphated surfactant may be sodium dodecyl benzene sulphonate, potassium hexadecyl benzene sulphonate, sodium dodecyl dimethyl benzene sulphonate, ammonium lauryl monethoxy sulphate, or monoethanolamine cetyl 10 mole ethoxylate sulphate.
- anionic surfactants useful according to the present invention include fatty alkyl sulphosuccinates, fatty alkyl ether sulphosuccinates, fatty alkyl sulphosuccinamates, fatty alkyl ether sulphosuccinamates, acyl sarcosinates, acyl taurides, isethionates, and alkyl ether carboxylates.
- Anionic phosphate fatty esters may also be used.
- Preferred anionic surfactants are sodium salts.
- Other salts of commercial interest include those of potassium, lithium, ammonium, monoethanolamine, diethanolamine, triethanolamine, and alkyl amines containing up to six aliphatic carbon atoms.
- the surfactants may optionally but preferably contain nonionic surfactants.
- the nonionic surfactant may preferably be, e.g. a C 10 - 22 ethanolamide such as coconut monoethanolamide.
- Other nonionic surfactants which may optionally be present include ethoxylated alcohols, ethoxylated carboxylic acids, ethoxylated amines, ethoxylated alkylolamides, ethoxylated alkylphenols, ethoxylated glyceryl esters, ethoxylated sorbitan esters, ethoxylated phosphate esters, and the propoxylated, or ethoxylated and propoxylated, analogues of all the aforesaid ethoxylated nonionics, all having a C s - 22 alkyl or alkenyl group, or any other nonionic surfactant which has hitherto been incorporated in powder compositions, e.
- the preferred nonionics for our invention are the less water soluble compounds, for example those ethoxylates having an HLB range of 7-18, e.g 12-15. However, more water soluble ones may sometimes be present, usually in minor amounts. In particular, fatty alkanolamides may be useful, in minor proportions, as internal lubricants to assist in the mixing and plodding of the alkyl sulphates.
- compositions of our invention may also contain amphoteric surfactant, usually as a minor component of the active material.
- Amphoteric surfactants include betaines and sulphobetaines formed by substituting a suitable tertiary nitrogen compound having a long chain alkyl or alkenyl group with a (3-acid-forming substituting agent such as chloroacetic acid.
- suitable tertiary nitrogen containing compounds include: tertiary amines having one or two long chain alkyl or alkenyl groups, optionally a benzyl group and any other substituent a short chain alkyl group; imidazoline having one or two long chain alkyl or alkenyl groups and amidoamines having one or two long chain alkyl or alkenyl groups.
- the surfactant is mixed with builders and other auxiliary detergent ingredients.
- builder is sometimes used loosely in the detergent art to include any non-surfactant whose presence in a detergent formulation enhances the cleaning effect of the surfactant. More usually, however, the term is restricted to those typical "builders”, which are primarily useful as means of preventing or ameliorating the adverse effects on washing of calcium ions, e.g. by chelation, sequestering, precipitation or absorption of the ions, and secondarily as a source of alkalinity and buffering.
- builder refers to additives which produce the foregoing effects to a substantial extent.
- phosphate and condensed phosphate salts such as sodium or potassium orthophophates, pyrophosphates, metaphosphates or tetraphosphate, as well as phosphonates such as acetodiphosphonates and amino tris methylene phosphonates. It also includes alkali metal carbonates, zeolites and other "molecular sieves" and such organic sequestrants as salts nitrilotriacetic acid, citric acid and ethylene diamine tetracetic acid.
- compositions of our invention may contain fillers which help to provide a suitable physical form of bar.
- auxiliary detergent ingredients may comprise anti redeposition agents such as sodium carboxy methyl cellulose, perfumes, dyes, optical brightening agents, hydrotropes, buffers, bleach activators, alkalis and the like.
- auxiliairies are present in proportions of less than 10% and more usually less than 5% wt. each and less than 25%, e.g., less than 15% total.
- an NSD bar according to our invention will have the following composition:
- the filler may comprise any inert solid having suitable physical properties, e.g. sodium sulphate or talc.
- the other auxiliaries may include any or all of:- sodium carboxymethyl cellulose or other soil suspending agent; enzymes; dyestuffs; perfumes; optical brighteners; oxidising bleaches such as peroxides, perborates, percarbonates or hypochlorites; gums; starches; water soluble synthetic polymers; organic polyelectrolytes such as polyacrylic acid; and hydrotropes. Tablets for addition to washing machines may contain minor proportions of soap as foam depressants, and/or silicone anti foams.
- the properties of the "G" phase surfactant may further be modified by the inclusion of mono- di- or tri-glycerides, fatty alcohols, glycerol, glycols, polyethylene glycol or polypropylene glycol, which may help to lubricate the mixture in cases where difficulties are encountered with mixing or extrusion.
- the sodium lauryl sulphate paste had the following composition:-
- composition of the fatty alcohol was:-
- the resulting phase was then allowed to age for a minimum period of 1/2 hour to allow it to harden off.
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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- Detergent Compositions (AREA)
Claims (26)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT83307439T ATE33994T1 (de) | 1982-12-07 | 1983-12-07 | Verfestigung von reinigungsmittelpasten ohne loesungsmittelabdampfung. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8234861 | 1982-12-07 | ||
GB8234861 | 1982-12-07 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0110731A2 EP0110731A2 (fr) | 1984-06-13 |
EP0110731A3 EP0110731A3 (en) | 1986-07-09 |
EP0110731B1 true EP0110731B1 (fr) | 1988-05-04 |
Family
ID=10534799
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83307439A Expired EP0110731B1 (fr) | 1982-12-07 | 1983-12-07 | Solidification non-évaporative de pâtes de détergents |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0110731B1 (fr) |
JP (1) | JPS59115400A (fr) |
KR (1) | KR900004559B1 (fr) |
AT (1) | ATE33994T1 (fr) |
AU (1) | AU560525B2 (fr) |
BR (1) | BR8306706A (fr) |
DE (1) | DE3376487D1 (fr) |
GB (1) | GB2131447B (fr) |
IN (1) | IN160448B (fr) |
MY (1) | MY8700135A (fr) |
PH (1) | PH20175A (fr) |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4595520A (en) * | 1984-10-18 | 1986-06-17 | Economics Laboratory, Inc. | Method for forming solid detergent compositions |
US5096608A (en) * | 1985-05-13 | 1992-03-17 | The Procter & Gamble Company | Ultra mild skin cleansing composition |
DE3612701A1 (de) * | 1986-04-15 | 1987-10-22 | Degussa | Waschmittel in stueckiger form |
US5000652A (en) * | 1986-09-22 | 1991-03-19 | International Business Machines Corporation | Wafer transfer apparatus |
GB8800763D0 (en) * | 1988-01-14 | 1988-02-17 | Unilever Plc | Detergent compositions |
JP2526831B2 (ja) * | 1988-06-13 | 1996-08-21 | 井関農機株式会社 | 歩行型農作業機 |
US4925585A (en) * | 1988-06-29 | 1990-05-15 | The Procter & Gamble Company | Detergent granules from cold dough using fine dispersion granulation |
ES2076963T3 (es) * | 1988-06-29 | 1995-11-16 | Procter & Gamble | Procedimiento para la fabricacion de granulos de tensioactivo concentrado. |
JP2820257B2 (ja) * | 1988-12-02 | 1998-11-05 | 井関農機株式会社 | 田植機の植付深さ制御装置 |
US5152932A (en) * | 1989-06-09 | 1992-10-06 | The Procter & Gamble Company | Formation of high active detergent granules using a continuous neutralization system |
US5045238A (en) * | 1989-06-09 | 1991-09-03 | The Procter & Gamble Company | High active detergent particles which are dispersible in cold water |
DE4038476A1 (de) * | 1990-12-03 | 1992-06-04 | Henkel Kgaa | Feste waschmittel |
WO1996025482A1 (fr) * | 1995-02-13 | 1996-08-22 | The Procter & Gamble Company | Procede pour produire des agglomerats detergents a classe granulometrique controlee |
US5574005A (en) * | 1995-03-07 | 1996-11-12 | The Procter & Gamble Company | Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties |
DE69812403T2 (de) * | 1997-11-10 | 2004-01-29 | Procter & Gamble | Verfahren zur herstellung einer waschmitteltablette |
DE69816112T2 (de) | 1997-11-10 | 2004-04-22 | The Procter & Gamble Company, Cincinnati | Verfahren zur herstellung einer waschmitteltablette |
BR9815064A (pt) | 1997-11-26 | 2001-11-20 | Procter & Gamble | Tablete detergente |
JP2001509837A (ja) | 1997-11-26 | 2001-07-24 | ザ、プロクター、エンド、ギャンブル、カンパニー | 圧縮部分および非圧縮部分の双方を有する多層洗剤タブレット |
WO1999037746A1 (fr) | 1998-01-26 | 1999-07-29 | The Procter & Gamble Company | Pastille detergente multicouches |
DE19831707A1 (de) * | 1998-07-15 | 2000-01-20 | Henkel Kgaa | Verfahren zur Herstellung fettalkoholsulfathaltiger Wasch- und Reinigungsmittelformkörper |
DE10046363A1 (de) * | 2000-09-20 | 2002-03-28 | Cognis Deutschland Gmbh | Fließfähige wässrige Fettalkoholsulfatpasten |
WO2009125335A2 (fr) * | 2008-04-07 | 2009-10-15 | Ecolab Inc. | Composition de dégraissage liquide ultra-concentrée |
US10851331B2 (en) | 2017-04-27 | 2020-12-01 | Ecolab Usa Inc. | Solid controlled release carbonate detergent compositions |
JP7091454B2 (ja) | 2017-11-14 | 2022-06-27 | エコラボ ユーエスエー インコーポレイティド | 固形制御放出苛性洗剤組成物 |
EP3743494A1 (fr) | 2018-01-26 | 2020-12-02 | Ecolab Usa Inc. | Solidification de tensioactifs d'oxyde d'amine, de bétaïne et/ou de sultaïne liquide à l'aide d'un liant et d'un éventuel un vecteur |
WO2019148090A1 (fr) | 2018-01-26 | 2019-08-01 | Ecolab Usa Inc. | Solidification de tensioactifs liquides d'oxyde d'amine, de bétaïne et/ou de sultaïne ayant un véhicule |
JP7485606B2 (ja) | 2018-01-26 | 2024-05-16 | エコラボ ユーエスエー インコーポレイティド | 液体アニオン性界面活性剤の固化 |
EP4007803A1 (fr) | 2019-09-27 | 2022-06-08 | Ecolab USA Inc. | Détergent et produit de rinçage concentré 2-en-1 pour lave-vaisselle |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH281137A (fr) * | 1945-07-10 | 1952-02-29 | Brunel Henri | Procédé de fabrication d'un produit détersif. |
US3639286A (en) * | 1968-05-28 | 1972-02-01 | Mario Ballestra | Synthetic detergent in bar or cake form and the method to manufacture same |
AU461648B2 (en) * | 1971-01-14 | 1975-06-05 | Bell Chemicals Pty. Ltd | Improvements inthe manufacture of detergent-powders |
DE2907029A1 (de) * | 1979-02-23 | 1980-09-04 | Henkel Kgaa | Verfahren zur herstellung von abspuelbloecken fuer die toilettenhygiene |
-
1983
- 1983-11-28 IN IN791/DEL/83A patent/IN160448B/en unknown
- 1983-12-05 PH PH29924A patent/PH20175A/en unknown
- 1983-12-06 BR BR8306706A patent/BR8306706A/pt unknown
- 1983-12-06 AU AU22103/83A patent/AU560525B2/en not_active Ceased
- 1983-12-07 DE DE8383307439T patent/DE3376487D1/de not_active Expired
- 1983-12-07 JP JP58229974A patent/JPS59115400A/ja active Pending
- 1983-12-07 KR KR1019830005793A patent/KR900004559B1/ko not_active IP Right Cessation
- 1983-12-07 AT AT83307439T patent/ATE33994T1/de not_active IP Right Cessation
- 1983-12-07 EP EP83307439A patent/EP0110731B1/fr not_active Expired
- 1983-12-07 GB GB08332607A patent/GB2131447B/en not_active Expired
-
1987
- 1987-12-30 MY MY135/87A patent/MY8700135A/xx unknown
Also Published As
Publication number | Publication date |
---|---|
JPS59115400A (ja) | 1984-07-03 |
KR840007102A (ko) | 1984-12-05 |
GB2131447A (en) | 1984-06-20 |
DE3376487D1 (en) | 1988-06-09 |
MY8700135A (en) | 1987-12-31 |
AU560525B2 (en) | 1987-04-09 |
GB2131447B (en) | 1986-04-30 |
AU2210383A (en) | 1984-06-14 |
PH20175A (en) | 1986-10-14 |
ATE33994T1 (de) | 1988-05-15 |
BR8306706A (pt) | 1984-07-17 |
EP0110731A3 (en) | 1986-07-09 |
GB8332607D0 (en) | 1984-01-11 |
KR900004559B1 (ko) | 1990-06-29 |
EP0110731A2 (fr) | 1984-06-13 |
IN160448B (fr) | 1987-07-11 |
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