EP1193310A1 - Teilchenförmiges waschmitteladditiv - Google Patents
Teilchenförmiges waschmitteladditiv Download PDFInfo
- Publication number
- EP1193310A1 EP1193310A1 EP00939055A EP00939055A EP1193310A1 EP 1193310 A1 EP1193310 A1 EP 1193310A1 EP 00939055 A EP00939055 A EP 00939055A EP 00939055 A EP00939055 A EP 00939055A EP 1193310 A1 EP1193310 A1 EP 1193310A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- particles
- detergent
- detergent additive
- additive particles
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 608
- 239000003599 detergent Substances 0.000 title claims abstract description 396
- 239000000654 additive Substances 0.000 claims abstract description 221
- 230000000996 additive effect Effects 0.000 claims abstract description 221
- 239000000203 mixture Substances 0.000 claims abstract description 118
- 239000000126 substance Substances 0.000 claims abstract description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000004094 surface-active agent Substances 0.000 claims abstract description 56
- 238000004090 dissolution Methods 0.000 claims abstract description 44
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims description 14
- 229920003169 water-soluble polymer Polymers 0.000 claims description 14
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 12
- 229910052753 mercury Inorganic materials 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000008233 hard water Substances 0.000 claims description 4
- 238000002459 porosimetry Methods 0.000 claims description 3
- 239000007900 aqueous suspension Substances 0.000 claims 2
- 238000005406 washing Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 description 45
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 32
- 230000008569 process Effects 0.000 description 31
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 27
- 239000010457 zeolite Substances 0.000 description 25
- 229910021536 Zeolite Inorganic materials 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- -1 alkali metal salts Chemical class 0.000 description 21
- 230000000694 effects Effects 0.000 description 19
- 239000002002 slurry Substances 0.000 description 18
- 238000004867 photoacoustic spectroscopy Methods 0.000 description 17
- 238000001035 drying Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 description 16
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 13
- 150000005215 alkyl ethers Chemical class 0.000 description 13
- 239000002585 base Substances 0.000 description 13
- 230000001747 exhibiting effect Effects 0.000 description 13
- 229910052938 sodium sulfate Inorganic materials 0.000 description 13
- 235000011152 sodium sulphate Nutrition 0.000 description 13
- 229910000323 aluminium silicate Inorganic materials 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 206010001497 Agitation Diseases 0.000 description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
- 238000013019 agitation Methods 0.000 description 11
- 238000009826 distribution Methods 0.000 description 11
- 230000001965 increasing effect Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- 239000011800 void material Substances 0.000 description 7
- 230000003113 alkalizing effect Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 150000004760 silicates Chemical class 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 5
- 229940088598 enzyme Drugs 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000007850 fluorescent dye Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical group OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
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- 229910017053 inorganic salt Inorganic materials 0.000 description 3
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- 239000002243 precursor Substances 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 108010059892 Cellulase Proteins 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- 239000004367 Lipase Substances 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
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- 239000004365 Protease Substances 0.000 description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229940106157 cellulase Drugs 0.000 description 2
- 150000001860 citric acid derivatives Chemical class 0.000 description 2
- 239000004927 clay Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
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- 238000000151 deposition Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
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- 239000004615 ingredient Substances 0.000 description 2
- 235000019421 lipase Nutrition 0.000 description 2
- 108010020132 microbial serine proteinases Proteins 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical class OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- JPGSFSFMINKKJZ-UHFFFAOYSA-N 2-[1,2-dicarboxyethyl(hydroxy)amino]butanedioic acid Chemical class OC(=O)CC(C(O)=O)N(O)C(CC(O)=O)C(O)=O JPGSFSFMINKKJZ-UHFFFAOYSA-N 0.000 description 1
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical class OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 description 1
- UWRBFYBQPCJRRL-UHFFFAOYSA-N 3-[bis(carboxymethyl)amino]propanoic acid Chemical class OC(=O)CCN(CC(O)=O)CC(O)=O UWRBFYBQPCJRRL-UHFFFAOYSA-N 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical class OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- 229910003202 NH4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical group OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical group OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical group OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- 235000011837 pasties Nutrition 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 238000000518 rheometry Methods 0.000 description 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 1
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- 238000010008 shearing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
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- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
-
- 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
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
Definitions
- the present invention relates to detergent additive particles, composite detergent particles and a granular detergent composition.
- granular detergent compositions (compact detergents) have been the main trend.
- the granular detergent composition has been prepared by using various techniques such as mixing, granulation, compression and pulverization, and has brought about great merits in the convenience upon use, reduction of transportation costs, and the like.
- the granular detergent composition tends to have poorer solubility as compared to a low-bulk density detergent.
- Hei 7-509267 discloses a detergent composition
- a detergent composition comprising a base powder comprising particles including a particle having a size of less than 150 ⁇ m in an amount of less than 10% by weight, and a particle having a size of greater than 1700 ⁇ m in an amount of less than 10% by weight, and a fine powder or coarse grain of sodium carbonate, sodium citrate or the like as a filler.
- This art intends to increase the bulk density and the distributivity from the dispenser by reducing a surfactant-containing fine powder, or after-adding a fine powder or coarse grain of rapidly dissoluble non-gelated particle.
- Hei 11-35998 discloses a granular high-density detergent of which 50% mass-base size, the constitution of a mass-base frequency at a particle size of less than 125 ⁇ m, a mass-base frequency at a particle size of 1410 ⁇ m or less, and a mass-base frequency at a specified particle size are limited within specified ranges.
- This art is intended to improve both the dispersibility of the granular detergent composition and the particle dissolubility by controlling the particle size distribution, and it is shown to be suitable for use in a disperser. According to these techniques, the dispersibility from a dispenser is improved, and the frequency of occurrence in the troubles that a pasty high-density detergent composition remains in the dispenser, or the amount remaining is reduced.
- the granular detergent composition may remain in the disperser depending upon a decrease of water pressure upon pouring water, a decrease in the water temperature, the means of water pouring, the form of the dispenser, or the like. Therefore, a further improvement in the distributivity of the granular detergent composition in the dispenser has been desired.
- An object of the present invention is to provide a granular detergent composition having excellent distributivity upon pouring water into a dispenser such as drum-type washing machines and fully automatic washing machines, composite detergent particles contained in the granular detergent composition, and detergent additive particles contained in the composite detergent particles.
- the present invention relates to:
- detergent additive particle refers to a particle which can contain a surfactant in an amount of less than 10% by weight and a builder or the like, and the term “detergent additive particles” refers to an aggregate thereof. Also, the term “detergent particle” refers to a particle comprising a surfactant in an amount of 10 to 50% by weight, and the term “detergent particles” " refers to an aggregate thereof. In addition, the term “composite detergent particles” refers to an aggregate prepared by dry-blending the detergent additive particles and the detergent particles.
- granular detergent composition refers to a completed product of a granular detergent comprising the composite detergent particles prepared by dry-blending the detergent additive particles and the detergent particles, which encompasses those comprising particles comprising separately added detergent components (for instance, builder particles, fluorescent dyes, enzymes, perfumes, defoaming agents, bleaching agents, bleaching activators, and the like) as desired, other than the above-mentioned detergent additive particles and detergent particles.
- detergent additive particles for instance, builder particles, fluorescent dyes, enzymes, perfumes, defoaming agents, bleaching agents, bleaching activators, and the like
- the detergent additive particles of the present invention which exhibit excellent dispenser distributivity of the granular detergent composition by formulating the detergent additive particles as a component of the granular detergent composition contain no surfactant or have a very low surfactant content of less than 10% by weight.
- the detergent additive particles have the following characteristics.
- the present invention is characterized in that detergent additive particles having a specified composition and specified powder properties are mixed with a granular detergent composition, and further that the detergent additive particles have the fast dissolubility described below.
- the formed paste layer comprising a high-concentration surfactant is rapidly made discontinuous upon pouring water, and at the same time there is an action of dissolving the detergent additive particles in the poured water at a fast rate, whereby the granular detergent composition can be rapidly and efficiently distributed from the dispenser.
- the formed paste is rather hardened in the dispenser upon pouring water, so that the reduction in the distributivity from the dispenser is observed. Therefore, it is extremely important that the detergent additive particles have fast dissolubility.
- the fast dissolubility owned by the detergent additive particles can be confirmed by showing a remarkably high dissolution rate in a case where individual constituent particles are dispersed in water.
- the fast dissolubility owned by the detergent additive particles of the present invention is such that a dissolution rate as calculated by the equation (1) is 90% or more in a case where the detergent additive particles are stirred for 60 seconds in accordance with the method described below, and filtered with a standard sieve having a sieve-opening of 74 ⁇ m as defined by JIS Z 8801.
- the dissolution rate is preferably 92% or more, more preferably 94% or more, still more preferably 96% or more, still more preferably 97% or more, still more preferably 98% or more, most preferably 99% or more, from the viewpoint of further increasing the distributivity from the dispenser.
- a 1-L beaker (a cylindrical form having an inner diameter of 105 mm and a height of 150 mm, for instance, a 1-L glass beaker manufactured by Iwaki Glass Co., Ltd.) is charged with 1 L of hard water cooled to 5°C and having a water hardness corresponding to 71.2 mg CaCO 3 /L (a molar ratio of Ca/Mg: 7/3).
- a liquid dispersion of the particles in the beaker is filtered with a standard sieve (100 mm in diameter) and a sieve-opening of 74 ⁇ m as defined by JIS Z 8801 of a known weight. Thereafter, water-containing particles remaining on the sieve are collected in an open vessel of a known weight together with the sieve.
- the operation time from the start of filtration to collection with the sieve is set at 10 sec ⁇ 2 sec: The insoluble remnants of the collected particles are dried for one hour in an electric dryer heated to 105°C. Thereafter, the dried insolubles are cooled by keeping in a desiccator with a silica gel at 25°C for 30 minutes.
- Dissolution Rate (%) ⁇ 1 - (T/S) ⁇ ⁇ 100 wherein S is a weight (g) of the detergent additive particles supplied; and T is a dry weight (g) of insoluble remnants of the detergent additive particles remaining on the sieve when an aqueous solution prepared under the above stirring conditions is filtered with the sieve.
- the adjustment of the particle size distribution of the detergent additive particles in consideration of the relationship between the size of the particles constituting the detergent additive particles and the dissolution rate is an effective means.
- a dissolution rate per unit time period is determined for the detergent additive particles which are classified in a plural steps by the sizes of the particle size.
- the fast dissolubility can be exhibited by reconstituting the particles so as to have a particle size distribution having a high dissolution rate by using the detergent additive particles which are classified with sieves.
- the fast dissolubility can be attained by further increasing the dissolution rate of the particle constituting the detergent additive particles (detergent additive particle).
- the fast dissolubility can be exhibited by constructing the detergent additive particles with a particle having a fine void in the inner portion of the particle.
- the detergent additive particle having a fine void in the inner portion not only the detergent additive particle gradually dissolves from the surface but also water is allowed to enter into the fine void in the inner portion of the particle after the surface is dissolved, so that the particle is dissolved from the inner portion and the particle is disintegrated by the entered water, whereby the dissolution rate per unit time period can be increased.
- the fine void of the inner portion of the particle can be determined as a microporous capacity at 0.01 to 4 ⁇ m by mercury porosimetry. It is preferable that the microporous capacity is 0.2 mL/g or more. In addition, the microporous capacity is more preferably a larger amount of 0.25 mL/g or more, still more preferably 0.3 mL/g or more, most preferably 0.35 mL/g or more, from the viewpoint of exhibiting an even more excellent fast dissolubility by allowing a greater amount of water to enter in the inner portion of the particle.
- the microporous capacity is preferably 1.2 mL/g or less, more preferably 1.0 mL/g or less, still more preferably 0.8 mL/g or less, from the viewpoints of securing appropriate particle density and particle strength.
- a mercury porosimeter for instance, one manufactured by SHIMADZU CORPORATION, "SHIMADZU Poresizer 9320.”
- the microporous capacity is a value obtained for a microporous capacity at 0.01 to 4 ⁇ m as determined for a sample-reduced detergent by a mercury porosimeter.
- the fast dissolubility can be exhibited by constructing the detergent additive particles with a detergent additive particle capable of releasing a bubble of 1/10 or more of the particle size in a process in which the detergent additive particle is dissolved in water (hereinafter referred to as "bubble-releasing detergent additive particle").
- a detergent additive particle capable of releasing a bubble of 1/10 or more of the particle size in a process in which the detergent additive particle is dissolved in water
- bubble-releasing detergent additive particle a detergent additive particle capable of releasing a bubble of 1/10 or more of the particle size in a process in which the detergent additive particle is dissolved in water
- the detergent additive particle not only the dissolution takes place from the surface, but also water is allowed to enter into the inner portion of the particle along with the release of the bubble from the inner portion of the particle, so that the dissolution from the inner portion and the disintegration of the particle are caused by the entered water, whereby the dissolution ratio per unit time is increased.
- the dissolution behavior described above can be confirmed by a digital microscope or optical microscope as a phenomenon in which a bubble of 1/10 or more, preferably 1/5 or more, more preferably 1/4 or more, still more preferably 1/3 or more, especially preferably 1/2 or more of the particle size of the particle (hereinafter referred to as "bubble having a given size") is released in the case where the bubble-releasing detergent additive particle is dissolved in water.
- bubble having a given size is generated preferably within 120 seconds, more preferably within 60 seconds, still more preferably within 45 seconds, still more preferably within 30 seconds, still more preferably within 20 seconds, most preferably within 10 seconds.
- the bubble-releasing detergent additive particle may have a single or a plurality of pores capable of releasing a bubble having a given size, and the bubble-releasing detergent particle is not particularly limited in the form and structure of the particle.
- the bubble-releasing detergent additive particle may be a detergent additive particle capable of releasing a single bubble, or it may be a detergent additive particle capable of releasing a plural bubbles in which the detergent additive particles are aggregated.
- the bubble-releasing detergent additive particle constitutes preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, still more preferably 80% by weight or more, most preferably 90% by weight or more, of the detergent additive particles.
- the distributivity can be improved also by the effect of the release of bubbles from the granular detergent composition upon pouring water in the dispenser and the effect of water entry caused by the release, in addition to the effect by the fast dissolubility.
- the size of the bubble is measured as follows.
- a double-sided adhesive tape is attached to a bottom center of a glass petri dish (inner diameter: 50 mm).
- the detergent additive particles are adhered to the double-sided adhesive tape.
- a projected area diameter ( ⁇ ⁇ m) for each of the particles is determined from an image obtained by a digital microscope.
- a digital microscope for example, "VH-6300" manufactured by KEYENCE CORPORATION can be used.
- ⁇ ⁇ m the projected area diameter ( ⁇ ⁇ m) of the bubble is measured from an image of an instant at which the bubble leaves from the particle.
- ⁇ ⁇ m is referred to a maximum value of the projected area diameter measured for each of the bubbles.
- the ratio of the bubble diameter to the particle size ( ⁇ / ⁇ ) for each of the particles is calculated.
- a pore having a size of 1/10 to 4/5, preferably 1/5 to 4/5, more preferably 1/4 to 4/5, still more preferably 1/3 to 4/5, especially preferably 1/2 to 4/5, of the particle size is present in the inner portion of the particle.
- the pore size can be determined as follows.
- the selected detergent additive particle is split at a cross section so as to include the maximum particle size without disintegrating the particle with a surgical knife, or the like.
- the split cross section is observed by a scanning electron microscope (SEM).
- SEM scanning electron microscope
- a projected area diameter (particle size) [ ⁇ ⁇ m] of a split cross section of the split particle and in the case where the presence of a pore in the inner portion of the particle is confirmed, a projected area diameter of the pore (pore size) [ ⁇ ⁇ m] are measured.
- the projected area diameter ⁇ ⁇ m is defined as the largest pore size among them.
- the ratio of the pore size to the particle size ( ⁇ / ⁇ ) is calculated.
- the shape of the preferable bubble-releasing detergent additive particle includes a shape having a structure that there exists a hollow in the inner portion of the particle, and a particle surface is opened and communicated with the hollow in the inner portion (particle surface being caved-in). Since the detergent additive particle having a cave-in hole (cave-in particle) rapidly releases bubbles from the inner portion of the particle, water is allowed to enter into the inner portion of the particle quickly, so that there are advantages that the dissolution from the inner portion and the disintegration of the particle by the entered water are quickened.
- the projected area diameter of the particle can be obtained by photographing a particle using a microscope centering about the opening of the cave-in hole as shown in Figure 1, and calculating the projected area diameter from the equation (2) by using the projected area (S1) of the particle measured from the photographed particle image.
- Projected Area Diameter of Particle 2 ⁇ (S1/ ⁇ ) 1/2
- the projected area diameter of the hole (cave-in hole) can be obtained by the equation (3) by using the projected area (S2) of the hole determined in the same manner as the projected area of the particle mentioned above with an opening.
- Projected Area Diameter of Hole 2 ⁇ (S2/ ⁇ ) 1/2
- the microscope for the above measurement there can be used, for instance, a digital microscope "VH-6300” manufactured by KEYENCE CORPORATION and SEM such as a field emission scanning electron microscope “Model S-4000,” manufactured by Hitachi, Ltd.
- SEM field emission scanning electron microscope
- WinRoof manufactured by Mitsutani, and the like.
- a preferable diameter for the hole which is present in the cave-in particle contained in the detergent additive particles of the present invention is a hole in which: (Projected Area Diameter of Hole) (Projected Area Diameter of Particle) ⁇ 100 is 2% or more.
- the above ratio is more preferably from 2 to 70%, still more preferably from 4 to 60%, still more preferably from 6 to 50%, still more preferably from 8 to 40%, most preferably from 10 to 30%.
- the depth of the hole which is present in the particle contained in the detergent additive particles of the present invention is expressed by the ratio of a distance d between a tangent line X of an open surface of the cave-in hole and a tangent line Y with the bottom of the hole in parallel to the tangent line X as shown in Figure 2 to the projected area diameter of the particle described above, i.e., (Distance d) (Projected Area Diameter of Particle) ⁇ 100
- the depth of the hole can be determined, for instance, by splitting a particle with a surgical knife or the like at a plane perpendicular to the open hole portion of the cave-in hole as shown by the broken line in Figure 1, and photographing the cross section with SEM or the like.
- the depth of the hole which is present in the cave-in particle contained in the detergent additive particles of the present invention is such that the ratio as defined above is 10% or more.
- the ratio is more preferably from 10 to 90%, still more preferably from 15 to 80%, especially preferably from 20 to 70%.
- the cave-in particle is contained in an amount of 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, still more preferably 80% by weight or more, most preferably 90% by weight or more, of the detergent additive particles.
- a fast dissolubility can be exhibited from the surface of the particle.
- the characteristic thereof is such that the particle constituting the particles which is obtained by the drying step and used for the detergent additive particles or for principal constituents of the detergent additive particles has a localized structure in which the composition near the surface of the particle is different from that of the inner portion thereof.
- the particle obtained by the drying step comprises a water-soluble substance and a water-insoluble substance
- the water-soluble substance near the surface more quickly dissolves in water, so that there is exhibited a dissolution behavior of accelerating the disintegration from the surface of the particle, whereby a fast dissolubility can be exhibited.
- water-soluble substance refers to a compound of which solubility is 0.5 g / 100 g or more to water at 25°C, among which the term “water-soluble salt” refers to those having a molecular weight of less than 1000, and the term “water-soluble polymer” refers to an organic polymer having a molecular weight is 1000 or more.
- water-insoluble substance refers to those of which solubility is less than 0.5 g / 100 g of water at 25°C.
- a fast dissolubility can be exhibited by having a localized structure in which the composition near the surface of the particle is different from that in the inner portion thereof.
- the particle comprises a water-soluble polymer and a water-soluble salt
- the particle since the particle has a localized structure in which the water-soluble polymer is present in a larger amount near the surface of the particle than that in the inner portion thereof, there can be exhibited a fast dissolubility by showing a dissolution behavior that the water-soluble polymer near the surface more quickly dissolves in water and that the strength of the particle is lowered, thereby accelerating the disintegration of the particle.
- the most preferable embodiment for exhibiting a fast dissolubility is detergent additive particles which have a localized structure of the composition, and fine voids, more preferably a hollow, in the inner portion of the particle, a particle surface being opened and communicated with the hollow in the inner portion.
- the localized structure is confirmed as follows.
- FT-IR Fourier transform infrared spectroscopy
- PAS photoacoustic spectroscopy
- the measurement method for determining the structure of the detergent additive particle of the present invention will be exemplified below.
- Each cell is charged with the detergent additive particles of two different states to conduct FT-IR/PAS measurement, and the structure of the detergent additive particle can be determined by comparing the measurement values.
- one FT-IR/PAS measurement is taken for the detergent additive particles in a state where the desired structure is retained, and another FT-IR/PAS measurement is taken for the comparative sample in which the detergent additive particles are in a uniform state by sufficiently grinding the detergent additive particles with an agate mortar or the like.
- the FT-IR/PAS is measured, for instance, by using an infrared spectrometer "FTS-60A/896" (manufactured by Bio-Rad Laboratories), and a photoacoustic detector “Model 300" as the PAS cell (manufactured by MTEC Corporation).
- the measurement conditions are resolution of 8 cm -1 , scanning speed of 0.63 cm/s, and 128 scans. In the above measurement conditions, the information up to a depth of about 10 ⁇ m from the particle surface of the detergent additive particles is included.
- each of the characteristic peaks of sodium carbonate, sodium sulfate, zeolite and sodium polyacrylate can be read off at 1434 cm -1 (CO 3 2- degenerate stretching vibration), 1149 cm -1 (SO 4 2- degenerate stretching vibration), 1009 cm -1 (Si-O-Si anti-symmetric stretching vibration), and 1576 cm -1 (CO 2 - anti-symmetric stretching vibration), respectively, and the areal intensity of each peak is measured.
- the resulting relative intensity is then compared with the relative areal intensity of the characteristic peaks of the water-soluble polymer to the characteristic peaks of the zeolite, when measured for each of the above states, and thereby the structural features of the detergent additive particles can be determined.
- the detergent additive particle has a localized structure such that a larger amount of the water-soluble polymer and/or the water-soluble salts is included near the surface of the particle than the inner portion thereof, and that a larger amount of the water-insoluble substance is included in the inner portion of the particle than near the surface thereof.
- the localized structure can be proven by comparing the relative areal intensities of these characteristic peaks.
- ratios of the relative areal intensity based on the characteristic peaks of a given standard substance a substance which is present in a larger amount in the inner portion of the particle than near the surface thereof being selected
- the ratio is 1.1 or more
- the ratio is preferably 1.2 or more, more preferably 1.3 or more, still more preferably 1.4 or more, especially preferably 1.5 or more.
- the detergent additive particle can be said to have a localized structure when the detergent additive particle has these ratios of relative areal intensities.
- EDS energy dispersion-type X-ray spectroscopy
- EPMA electron probe microanalysis
- EMAX 3770 manufactured by Horiba, LTD. which is attached to SEM such as a field emission scanning electron microscope “Model S-4000,” manufactured by Hitachi, Ltd.
- the distribution state of elements measured with respect to C, Na, A1, Si, S, and the like of the split cross section of the detergent additive particle obtained by embedding the detergent additive particle with a resin and splitting the embedded particle with a microtome is such that C, Na and S are present in large amounts in the outer side of the particle cross section, and that A1 and Si are present in large amounts in the central portion. Therefore, there can be confirmed the structure in which large amounts of the water-soluble salts are included near the surface of the detergent additive particle, and a large amount of the water-insoluble substance is included in the central portion.
- the detergent additive particles of the present invention are those comprising 30 to 100% by weight of two or more kinds of water-soluble substances, and further optionally comprising less than 10% by weight of a surfactant and/or 70% by weight or less of a water-insoluble substance.
- water-soluble substance in the present invention refers to a compound of which solubility is 0.1 g or more to 100 g of purified water at 20°C
- water-insoluble substance refers to a compound of which dissolved amount is less than 0.1 g to 100 g of purified water at 20°C.
- the crystalline silicate in the present invention is treated as a water-insoluble substance, and the surfactant is treated so as not to include in both the water-soluble substance and the water-insoluble substance.
- compositional feature of the detergent additive particles of the present invention resides in that the particles contain no surfactant or only have a very little surfactant content.
- the content of the surfactant is less than 10% by weight.
- the preferred content of the surfactant mentioned above is from 0 to 8% by weight, more preferably less than 6% by weight, still more preferably less than 4% by weight, still more preferably less than 2% by weight, still more preferably less than 1% by weight, most preferably containing substantially no surfactant, from the viewpoint of exhibiting a more excellent effect.
- the water-soluble substance in the present invention is formulated in an amount of 30 to 100% by weight.
- the content of the water-insoluble substance is preferably 40% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, still more preferably 70% by weight or more, still more preferably 80% by weight or more, still more preferably 90% by weight or more, most preferably essentially consisting of only the water-soluble substance, from the viewpoints of enhancing the above-mentioned effects by reducing the surfactant content mentioned above and the content of the water-insoluble substance mentioned below.
- the content of the water-insoluble substance in the present invention is 70% by weight or less.
- the content of the water-insoluble substance is preferably 60% by weight or less, more preferably 50% by weight or less, still more preferably 40% by weight or less, still more preferably 30% by weight or less, still more preferably 20% by weight or less, still more preferably 10% by weight or less, most preferably essentially containing no water-insoluble substance, from the viewpoints of suppressing the curing of the granular detergent composition by the water-insoluble substance described above, thereby further increasing the distributivity from the dispenser.
- the water-soluble substance in the present invention includes, for instance, water-soluble inorganic salts such as alkali metal salts, ammonium salts, amine salts, and the like, each having a carbonate group, a hydrogencarbonate group, a sulfate group, a sulfite group, a hydrogensulfate group, a chloride group, a bromate group, an iodate group, a silicate group, a phosphate group, and the like; and water-soluble organic salts having a low molecular weight such as citrates and fumarates (provided that a surfactant is not included herein).
- the carbonate group, the sulfate group and the sulfite group are preferable.
- the water-soluble inorganic salt is preferable because the disintegration of the detergent additive particles in water can be accelerated by generating heat of hydration and heat of dissolution by the reaction with water, and the self-disintegration of the particle can be accelerated by expanding the bubbles in a case where the detergent additive particle is a bubble-releasing particle.
- the water-soluble substance is contained in plural kinds than a single kind.
- the water-soluble substance is a single kind of the water-soluble substance, for instance, sodium carbonate, sodium sulfate, or the like, for forming a hydration crystal at a low temperature, if the temperature of the poured water is high, the distributivity of the granular detergent composition is sufficiently improved by an effect of making discontinuous a paste layer comprising a high-concentration surfactant by mixing with the detergent additive particles.
- a preferable mode of containing the water-soluble substance is a case where a water-soluble substance for forming a hydration crystal in water at a low temperature, and a water-soluble substance for precipitating the crystal by lowering the solubility by a decrease in the water temperature, and the like are contained.
- the growth of the hydration crystals by a single water-soluble substance can be preferably suppressed or delayed. More specifically, on the basis of one kind of the water-soluble substance contained in the detergent additive particles, other one or more kinds of the water-soluble substances are contained in a molar ratio of preferably 9/1 or less, more preferably 8/2 or less, still more preferably 7/3 or less, especially preferably 6/4 or less, most preferably approximate 5/5.
- sodium carbonate is also preferable as an alkalizing agent for showing a suitable pH buffering region in a washing liquid.
- the alkalizing agents other than those mentioned above include amorphous silicates.
- salts having a high degree of dissociation such as sodium sulfate, potassium sulfate, and sodium sulfite enhance an ionic strength of a washing liquid, and favorably act to detergency against sebum stains.
- a sulfite group reduces hypochlorite ions contained in tap water, and has an effect of preventing detergent components such as enzymes and perfumes from oxidation degradation.
- sodium tripolyphosphates which have excellent metal ion capturing ability and the alkalizing ability, can also be suitably used.
- water-soluble organic acid salts having low-molecular weights those base materials having a large pKCa 2+ and/or having a large cationic exchange capacity are preferable in expectation of imparting the metal ion capturing ability.
- citrates there can be also included methyliminodiacetates, iminodisuccinates, ethylenediaminedisuccinates, taurine diacetates, hydroxyethyliminodiacetates, ⁇ -alanine diacetates, hydroxyiminodisuccinates, methylglycine diacetates, glutamine diacetates, asparagine diacetates, serine diacetates, and the like.
- water-soluble polymers are included.
- the water-soluble polymer is preferable, from the viewpoint of having an effect of enhancing the particle strength of the detergent additive particle, when the detergent additive particles of the present invention are obtained by a process including a drying step, together with the viewpoint of having an action of giving a bubble-releasing structure in the particle, a localized structure of the compositions, a fine void in the inner portion of the particle, and further giving a shape having a structure that there exists a hollow in the inner portion of the particle, and a particle surface is opened and communicated with the hollow in the inner portion, in a case where the drying step is a spray-drying step.
- the water-soluble polymer is contained in an amount of from 1 to 40% by weight, more preferably from 2 to 30% by weight, still more preferably from 3 to 20% by weight, still more preferably from 4 to 15% by weight, especially preferably from 5 to 10% by weight, of the detergent additive particles.
- the water-soluble polymer includes, for instance, carboxylic acid-based polymers; carboxymethyl celluloses; water-soluble starches; sugars; and the like.
- carboxylic acid-based polymers are preferable, from the viewpoint of enhancing the detergency of the granular detergent composition.
- salts of acrylic acid-maleic acid copolymers, and polyacrylates Na, K, NH 4 , and the like) are especially excellent.
- the molecular weight of the water-soluble polymers is from 1000 to 100000, more preferably from 2000 to 80000, especially preferably from 5000 to 50000.
- polymers such as polyglyoxylates; cellulose derivatives such as carboxymethyl celluloses; and aminocarboxylic acid-based polymers such as polyaspartates have an ability of capturing metal ions, a dispersibility, and an ability of preventing redeposition.
- polymers include polyvinyl pyrrolidones (PVP), polyethylene glycols (PEG), polypropylene glycols (PPG), and the like.
- PVP polyvinyl pyrrolidones
- PEG polyethylene glycols
- PPG polypropylene glycols
- the PVA is preferable as a dye-transfer inhibitor, and the PEG and the PPG having a molecular weight of from about 100 to about 20000 are preferable, because the viscosity of a paste, which is formed by containing water of aggregates of the granular detergent composition of the present invention, is improved.
- the surfactant in the present invention there can be used one or more kinds selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants.
- the anionic surfactants are exemplified by alkylbenzenesulfonates; alkyl ether or alkenyl ether sulfates; ⁇ -olefinsulfonates; salts of ⁇ -sulfonated fatty acids or esters thereof; alkyl ether or alkenyl ether carboxylates, amino acid-type surfactants; N-acyl amino acid-type surfactants, and the like.
- linear alkylbenzenesulfonates of which alkyl moiety has 10 to 14 carbon atoms; and alkyl sulfates or alkyl ether sulfates, of which each alkyl moiety has 10 to 18 carbon atoms.
- the counter ions are preferably sodium, potassium, monoethanolamine, diethanolamine, and the like.
- a salt of a fatty acid having 12 to 18 carbon atoms can be used in combination therewith.
- the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene-polyoxypropylene alkyl ethers, polyoxyethylene-polyoxypropylene glycols as represented by the trade name "pluronic," polyoxyethylene alkylamines, higher fatty acid alkanolamides, alkyl glucosides, alkyl glucosamides, alkylamine oxides, and the like.
- plural polyoxyethylene alkylamines
- higher fatty acid alkanolamides alkyl glucosides
- alkyl glucosamides alkylamine oxides
- the polyoxyalkylene alkyl ethers are especially preferable.
- EO ethylene oxide
- PO propylene oxide
- the cationic surfactants include quaternary ammonium salts such as alkyl trimethyl ammonium salts.
- amphoteric surfactants are exemplified by carbobetain-type and sulfobetain-type surfactants and the like.
- the water-insoluble inorganic substance which is a water-insoluble substance is preferably those which are fine having a primary particle size of from 0.1 ⁇ m to less than 20 ⁇ m, from the viewpoint of quality.
- the water-insoluble inorganic substance includes, for instance, crystalline or amorphous aluminosilicates, silicon dioxide, hydrated silicate compounds, clay compounds such as perlite and bentonite, and the like, among which crystalline or amorphous aluminosilicates, silicon dioxide and hydrated silicate compounds are favorably used.
- the crystalline aluminosilicates are preferable as a metal ion capturing agent.
- the (average) primary particle size of the crystalline aluminosilicate may be 0.1 ⁇ m to less than 20 ⁇ m. In considerations of the cationic exchange speed and the residuality onto laundered clothes, the smaller the primary particle size the better. The particle size can be confirmed by a scanning electron microscope.
- aggregates of the primary particles. can be used. For instance, A-type zeolites can be used, from the viewpoints of the metal ion capturing ability and the costs.
- a support of a liquid component for instance, a liquid surfactant, by the detergent additive particles is required, a use of a water-insoluble substance having an oil-absorbing ability is effective.
- the value of the oil-absorbing ability of A-type zeolite determined by the method according to JIS K 5101 is preferably from 40 to 50 mL/100 g (for instance, trade name: "TOYOBUILDER,” manufactured by Tosoh Corporation).
- P-type for instance, trade names: "Doucil A24,” “ZSE064" and the like; manufactured by Crosfield B.V.; oil-absorbing ability: 60 to 150 mL/100 g
- X-type zeolite for instance, trade name: "Wessalith XD”; manufactured by Degussa-AG; oil-absorbing ability: 80 to 100 mL/100 g.
- a hybrid zeolite described in WO 98/42622 can be also included as preferable crystalline aluminosilicates.
- amorphous silicas, amorphous aluminosilicates, and the like which have a high oil-absorbing ability but a low metal ion capturing ability, can be used as the water-insoluble substances.
- amorphous aluminosilicates including those described in Japanese Patent Laid-Open No. Sho 62-191417, page 2, lower right column, line 19 to page 5, upper left column, line 17 (especially, the initial temperature being preferably within the range from 15° to 60°C); and those described in Japanese Patent Laid-Open No.
- oil-absorbing carriers for instance, "TOKSIL NR” (manufactured by Tokuyama Soda Co., Ltd.; oil-absorbing ability: 210 to 270 mL/100 g); “FLOWRITE” (the same as above; oil-absorbing ability: 400 to 600 mL/100 g); "TIXOLEX 25” (manufactured by Kofran Chemical; oil-absorbing ability: 220 to 270 mL/100 g); “SILOPURE” (manufactured by Fuji Devison Co., Ltd.; oil-absorbing ability: 240 to 280 mL/100 g), and the like.
- the oil-absorbing carriers favorable are those described in Japanese Patent Laid-Open No. Hei 6-179899, column 12, line 12 to column 13, line 1, and column 17, line 34 to column 19, line 17.
- a crystalline silicate in the water-insoluble substance in the present invention.
- a preferable formulation process includes a process comprising finely pulverizing the crystalline silicate to a size of 1 ⁇ m to less than 20 ⁇ m, preferably to a size of 1 ⁇ m to less than 10 ⁇ m, and thereafter using the pulverized product as a surface-modifying agent.
- the average particle size of the detergent additive particles of the present invention is measured by vibrating a sample with each of standard sieves according to JIS Z 8801 for 5 minutes, and thereafter determining from a weight percentage depending upon the size openings of the sieves.
- the average particle size of the detergent additive particles is adjusted to 150 ⁇ m or more, in order to suppress the powdering when handling the granular detergent composition which is mixed with the particles, and the average particle size is adjusted to 600 ⁇ m or less, in order to secure the fast dissolubility of the detergent additive particles.
- the average particle size is preferably from 170 to 500 ⁇ m, more preferably from 180 to 450 ⁇ m, still more preferably from 190 to 400 ⁇ m, most preferably from 200 to 350 ⁇ m.
- the formed paste layer comprising the surfactant when water is poured to the granular detergent composition, it is preferable that the average particle size approximates the average particle size of the detergent particles (b) described below.
- the preferred difference in the average particle sizes between the detergent additive particles and the detergent particles (b) is preferably within 350 ⁇ m, more preferably within 300 ⁇ m, still more preferably within 250 ⁇ m, still more preferably within 200 ⁇ m, still more preferably within 150 ⁇ m, still more preferably within 100 ⁇ m, most preferably within 50 ⁇ m.
- the bulk density of the detergent additive particles of the present invention is measured by a method according to JIS K 3362.
- the bulk density is from 300 to 1000 g/L, preferably from 320 to 900 g/L, more preferably from 340 to 850 g/L, still more preferably from 360 to 800 g/L, still more preferably from 380 to 750 g/L, still more preferably from 400 to 700 g/L, most preferably from 420 to 650 g/L, in order to impart a more excellent fast dissolubility, and to improve the dispersibility of the granular detergent composition which is mixed with the detergent additive particles in the dispenser, and also to provide a bulk density of the granular detergent composition in a preferable range and to suppress the classification of the detergent additive particles in the granular detergent composition.
- the detergent additive particles of the present invention are prepared by a process comprising the following steps (X) and (Y):
- a step of after-adding a surfactant or a precursor thereof within an amount limited to the compositional range of the detergent additive particles of the present invention; a step of after-adding a water-soluble substance in the form of a paste, a slurry, or a solution; or a step of after-adding a water-insoluble substance having a size of 1 ⁇ m to less than 20 ⁇ m and a water-soluble substance having a size of 1 ⁇ m to less than 20 ⁇ m, thereby depositing the after-added substances to the particle surface.
- a total amount of the after-added substances in the after-addition step is preferably 1/4 or less, more preferably 1/9 or less, still more preferably 1/19 or less, still more preferably 1/49 or less, still more preferably 1/99 or less, most preferably no after-addition, in order to sufficiently exhibit the effect of improving the distributivity in the dispenser owned by the particle obtained in the drying step (Y) mentioned above.
- the slurry or the like may be those which are liquid-conveyable with a pump, and non-curable.
- the addition method of the components and the order can be appropriately varied depending upon the conditions.
- the content of each component such as the water-soluble substance in the slurry or the like is as described above.
- any of drying processes for instance, freeze-drying, drying under reduced pressure and the like, can be employed.
- a structure of the particle after drying takes a structure having a void of a volume of 0.2 mL/g or more in the inner portion of the particle, a structure having a hole capable of releasing a bubble of a size of 1/10 or more of the particle size of the particle, a structure having a cave-in hole and/or a structure having the localizability of the components, it is preferable that the slurry or the like is instantly dried, and an especially preferable drying process is a spray-drying process.
- the detergent particles which are usable for ordinary granular detergent compositions can be used.
- the detergent particles may be prepared by any process, so long as the detergent particles have the composition and powder properties described below.
- the component supplementing the detergency by the surfactant which is deficient in the detergent additive particles (a) mentioned above is detergent particles (b) which contain 10% by weight or more of a surfactant.
- the detergent particles (b) are dry-blended with the detergent additive particles (a), to give composite detergent particles having excellent distributivity in the dispenser.
- the surfactant contained in the detergent particles (b) is a surfactant having a crystal-forming ability, the distributivity improvement effects in the dispenser are more remarkably exhibited by dry-blending the detergent additive particles (a) with the detergent particles, to give composite detergent particles.
- surfactant having a crystal-forming ability refers to a surfactant in which liquid crystals having a water content in the range of 0 to 99%, and being observed in the form of lamella, hexagonal or the like in a temperature range of 5° to 70°C.
- the content of the surfactant in the detergent particles (b) is from 10 to 50% by weight, preferably from 15 to 49% by weight, more preferably from 20 to 48% by weight, still more preferably from 25 to 47% by weight, especially preferably from 30 to 46% by weight, of the detergent particles (b), in order to impart detergency to the composite detergent particles and to give desired powder properties in the detergent particles.
- the detergent particles comprise an anionic surfactant and/or a nonionic surfactant, and may comprise a cationic surfactant and an amphoteric surfactant as occasion demands.
- the detergent particles can contain a water-soluble substance as a component other than the surfactant mentioned above.
- the preferred content of the water-soluble substance is from 20 to 90% by weight.
- the water-soluble substance usable in the detergent particles the same ones as those which are exemplified as the water-soluble substance in the detergent additive particles mentioned above can be exemplified.
- the detergent particles can further comprise a water-insoluble substance as desired.
- the preferred content of the water-insoluble substance is from 0 to 70% by weight.
- the water-insoluble substance usable in the detergent particles the same ones as those which are exemplified in the detergent additive particles mentioned above can be exemplified.
- the average particle size of the detergent particles is adjusted to 150 ⁇ m or more, in order to suppress the powdering when handling the granular detergent composition comprising the detergent particles, and the average particle size is adjusted to 600 ⁇ m or less, in order to secure the dissolubility of the detergent particles in a washtub after being distributed from the dispenser.
- the average particle size is more preferably from 170 to 500 ⁇ m, still more preferably from 180 to 450 ⁇ m, still more preferably from 190 to 400 ⁇ m, most preferably from 200 to 350 ⁇ m.
- the bulk density of the detergent particles is from 500 to 1000 g/L.
- the bulk density is preferably from 550 to 1000 g/L, more preferably from 600 to 1000 g/L, still more preferably from 650 to 1000 g/L or more, especially preferably from 700 to 1000 g/L, in considerations of the improvement in the transportation efficiency of the granular detergent composition comprising the detergent particles, and the convenience of the users.
- the process for preparing detergent particles there can be employed a process comprising obtaining a spray-dried particle from a surfactant and a builder, and increasing the bulk density of the resulting spray-dried particle, and the like.
- This process includes, for instance, a process of increasing the bulk density by granulating the spray-dried particles in a vertical or horizontal mixer with agitation.
- a process comprising granulating a spray-dried particle with agitation as described in Japanese Patent Laid-Open No. Sho 61-69897; a process comprising molding a dried particle and disintegrating and granulating the dried particle as described in Japanese Patent Laid-Open No.
- Sho 62-169900 a process comprising disintegrating a solid detergent obtained by mixing and blending raw detergent materials as described in Japanese Patent Laid-Open No. Sho 62-236897; as a process without using a spray-drying tower from the viewpoint of conservation of energy, a process comprising neutralizing an acid precursor of an anionic surfactant with a granular solid alkalizing agent in a dry state in a high-speed mixer, and granulating the resulting neutralized product by addition of a liquid binder as described in Japanese Patent Laid-Open No. Hei 3-33199; and the like.
- a step of separating with a sieve or the like particles having a particle size equal to or larger than that required (coarse grains) contained in the detergent particles obtained by the above-mentioned operations and the separated coarse grains are disintegrated into a smaller particle size and can be used as the detergent particles.
- the disintegrators of the coarse grains include impact disruptors such as hammer crushers; impact pulverizers such as atomizers and pin-mills; shearing rough pulverizers such as flash mills; and the like. These disintegrators can be carried out in a single-step operation, or in a multi-step operation with the same or different pulverizers.
- a fine powder is added as an agent for suppressing deposition in the device or a treatment agent for modifying a pulverized surface.
- the fine powder is preferable inorganic powders of aluminosilicates, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, and the like, and especially crystalline or amorphous aluminosilicates are preferable.
- fine powders of water-soluble substances such as sodium carbonate, sodium sulfate, and sodium tripolyphosphates can be also used.
- a surface-modifying step for the purposes of fixing and smoothing of a surface-modifying agent in order to improve the flowability of the particles subjected to the disintegration treatment, there can be provided a surface-modifying step.
- this process comprises supplying a composition into a rotary cylindrical mixer or agitator in a batch or continuous process, and treating the composition with tumbling or agitation.
- the composite detergent particles of the present invention are prepared by dry-blending the detergent additive particles (a) and the detergent particles (b) mentioned above.
- the resulting composite detergent particles have excellent distributivity from the dispenser, and by dry-blending the detergent particles (b), the composite detergent particles have excellent detergency.
- a continuous paste layer comprising a high-concentration surfactant formed by the detergent particles (b) can be rapidly made discontinuous by mixing with the detergent additive particles (a) having a specified composition and specified powder properties and fast dissolubility upon pouring water into the dispenser.
- the composite detergent particles can be rapidly and efficiently distributed in the dispenser by the actions of discontinuity together with an action of the fast dissolution of the detergent additive particles (a) upon pouring water.
- the preferred mixing ratio of the detergent additive particles (a) to the detergent particles (b), as expressed by the weight ratio of (a)/(b), is preferably from 1/99 to 70/30, more preferably from 2/98 to 60/40, still more preferably from 3/97 to 55/45, still more preferably from 5/95 to 50/50, still more preferably from 10/90 to 45/55, still more preferably from 15/85 to 40/60, most preferably from 20/80 to 35/65.
- the difference in the surfactant content is preferably within 7%, more preferably within 5%, still more preferably within 3%, most preferably within 1%.
- the granular detergent composition of the present invention comprises 50 to 100% by weight of the composite detergent particles mentioned above, and the granular detergent composition has excellent distributivity from the dispenser.
- the preferred content of the composite detergent particles is 60% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, still more preferably 85% by weight or more, still more preferably 90% by weight or more, most preferably 95% by weight or more, from the viewpoint of further reflecting the excellent distributivity from the dispenser owned by the composite detergent particles to the detergent composition.
- the preferred content of the detergent additive particles (a) in the granular detergent composition is preferably from 1 to 70% by weight, more preferably from 2 to 60% by weight, still more preferably from 3 to 55% by weight, still more preferably from 5 to 50% by weight, still more preferably from 10 to 45% by weight, still more preferably from 15 to 40% by weight, most preferably from 20 to 35% by weight, from the viewpoints of satisfying both the distributivity from the dispenser and the detergency.
- the granular detergent composition of the present invention having improved distributivity from the dispenser by the inclusion of the detergent additive particles (a)
- components such as bleaching agents such as percarbonates and foamable percarbonates; granular crystalline silicates; bleaching activators such as compounds listed in Japanese Patent Laid-Open No. Hei 6-316700 and tetraacetyl ethylenediamine; enzymes such as protease, cellulase, amylase and lipase; biphenyl-type or stilbene-type fluorescent dyes; silicone/silica-based defoaming agents; antioxidants; blueing agents; perfumes, and/or particles including these components, regardless of the fastness of the dissolving rate of the particles.
- Detergent Additive Particles 1 of the present invention were prepared by the process described below.
- This slurry was supplied to a spray-drying tower with a pump, and sprayed with a pressure spray nozzle arranged near the top of the tower at a spraying pressure of 25 kg/cm 2 .
- a high-temperature gas fed to the spray-drying tower was supplied from the lower portion of the tower at a temperature of 220°C and exhausted from the top of the tower at 103°C.
- coarse detergent additive particles obtained from the lower part of the tower were dried with a hot air at 100°C in a fluidized bed until the water content attained to 5% by weight.
- Coarse grains of the resulting particles were removed with a 1410 ⁇ m-sieve, to give Detergent Additive Particles 1.
- the composition and the properties of the resulting Particles 1 are shown in Table 1.
- the microporous capacity at 0.01 to 4 ⁇ m was 0.40 mL/g, as determined by a mercury porosimeter for Detergent Additive Particles 1.
- the dissolution behavior was observed by a digital microscope.
- bubbles having a size of 1/10 or more of the particle size were released from 92% of the particles.
- an average value for size of released bubbles/particle size in the above 92% of the particles was 5.8/10.
- Detergent Additive Particles 1 were analyzed for a cave-in hole.
- the particles were composed of 82% of cave-in particles, in which a hole having a projected area diameter of 2% or more and a depth of 10% or more, of a projected area diameter of the particle was present at one or more points.
- the average of projected area diameter of hole projected area diameter of particle ⁇ 100 of a cave-in hole for the 82% of cave-in particles was 22%.
- the average depth of the cave-in hole was 50% of the projected area diameter of the particle.
- Detergent Additive Particles 2 of the present invention were prepared by the process described below.
- This slurry was supplied to a spray-drying tower with a pump, and sprayed with a pressure spray nozzle arranged near the top of the tower at a spraying pressure of 25 kg/cm 2 .
- a high-temperature gas fed to the spray-drying tower was supplied from the lower portion of the tower at a temperature of 218°C and exhausted from the top of the tower at 101°C.
- coarse detergent additive particles obtained from the lower part of the tower were dried with a hot air at 100°C in a fluidized bed until the water content attained to 5% by weight.
- Coarse grains of the resulting particles were removed with a 1410 ⁇ m-sieve, to give Detergent Additive Particles 2.
- the composition and the properties of the resulting Particles 2 are shown in Table 1.
- the microporous capacity at 0.01 to 4 ⁇ m was 0.44 mL/g, as determined by a mercury porosimeter.
- its dissolution behavior was observed by a digital microscope.
- bubbles having a size of 1/10 or more of the particle size were released from 88% of the particles.
- an average value for size of released bubbles/particle size in the above 88% of the particles was 6.0/10.
- Detergent Additive Particles 2 were analyzed for a cave-in hole.
- the particles were composed of 11% of cave-in particles, in which a hole having a projected area diameter of 2% or more and a depth of 10% or more of a projected area diameter of the particle was present at one or more points.
- the average of projected area diameter of hole projected area diameter of particle ⁇ 100 of a cave-in hole for the 11% of cave-in particles was 14%.
- the average depth of the cave-in hole was 61% of the projected area diameter of the particle.
- Detergent Additive Particles 2 by. FT-IR/PAS and EDS it was confirmed that the particles also had a localized structure, as in Detergent Additive Particles 1.
- Detergent Additive Particles 3 of the present invention were prepared by the process described below.
- This slurry was supplied to a spray-drying tower with a pump, and sprayed with a pressure spray nozzle arranged near the top of the tower at a spraying pressure of 25 kg/cm 2 .
- a high-temperature gas fed to the spray-drying tower was supplied from the lower portion of the tower at a temperature of 228°C and exhausted from the top of the tower at 100°C.
- coarse detergent additive particles obtained from the lower part of the tower were dried with a hot air at 100°C in a fluidized bed until the water content attained to 5% by weight.
- Coarse grains of the resulting particles were removed with a 1410 ⁇ m-sieve, to give Detergent Additive Particles 3.
- the composition and the properties of the resulting Particles 3 are shown in Table 1.
- the microporous capacity at 0.01 to 4 ⁇ m was 0.50 mL/g, as determined by a mercury porosimeter.
- the dissolution behavior was observed by a digital microscope.
- bubbles having a size of 1/10 or more of the particle size were released from 90% of the particles.
- an average value for size of released bubbles/particle size in the above 90% of the particles was 6.3/10.
- Detergent Additive Particles 3 were analyzed for a cave-in hole.
- the particles were composed of 27% of cave-in particles, in which a hole having a projected area diameter of 2% or more and a depth of 10% or more of a projected area diameter of the particle was present at one or more points.
- the average of projected area diameter of hole projected area diameter of particle ⁇ 100 of a cave-in hole for the 27% of cave-in particles was 18%.
- the average depth of the cave-in hole was 68% of the projected area diameter of the particle.
- Detergent Additive Particles 4 of the present invention were prepared by the process described below.
- a 4% by weight polyoxyethylene alkyl ether as listed in Table 1 was heated to 60°C.
- 96% by weight of Detergent Additive Particles 1 were supplied into Lödige Mixer (manufactured by Matsuzaka Giken Co., Ltd.; capacity: 20 L; equipped with a jacket), and agitations of a main shaft (150 rpm) and a chopper (4000 rpm) were initiated.
- the jacket was heated to 60°C.
- the above polyoxyethylene alkyl ether was supplied into the above mixer in 30 seconds, and thereafter the components were agitated for 4 minutes, to give Detergent Additive Particles 4.
- the composition and the properties of the resulting Particles 4 are shown in Table 1.
- the microporous capacity at 0.01 to 4 ⁇ m was 0.38 mL/g, as determined by a mercury porosimeter.
- the dissolution behavior was observed by a digital microscope.
- bubbles having a size of 1/10 or more of the particle size were released from 89% of the particles.
- an average value for size of released bubbles/particle size in the above 89% of the particles was 5.8/10.
- Detergent Additive Particles 4 were analyzed for a cave-in hole.
- the particles were composed of 80% of cave-in particles, in which a hole having a projected area diameter of 2% or more and a depth of 10% or more of a projected area diameter of the particle was present at one or more points.
- the average of projected area diameter of hole projected area diameter of particle ⁇ 100 of a cave-in hole for the 80% of cave-in particles was 21%.
- the average depth of the cave-in hole was 49% of the projected area diameter of the particle.
- Detergent Additive Particles 4 by FT-IR/PAS and EDS it was confirmed that the particles also had a localized structure, as in Detergent Additive Particles 1.
- Detergent Additive Particles 5 of the present invention were prepared by the process described below.
- a batch kneader equipped with a jacket was heated to 50°C, and charged with 24.9 kg water. Thereto were added 8.1 kg of sodium sulfate, 6.9 kg of sodium carbonate, and 6 kg of a 40% by weight-aqueous sodium polyacrylate solution. Further, the resulting mixture was agitated for 15 minutes with temperature-controlled to 50°C, and thereafter 11.1 kg of zeolite was added thereto. The resulting mixture was further agitated for 30 minutes with temperature-controlled to 50°C. Thereafter, the temperature of the jacket was heated to 80°C, and at the same time the pressure inside the mixing vessel of the batch kneader was reduced, thereby drying the components with mixing until the water content attained to 5% by weight. Coarse grains of the resulting particles were removed with a 500 ⁇ m-sieve, to give Detergent Additive Particles 5. The composition and the properties of Particles 5 are shown in Table 1.
- the microporous capacity at 0.01 to 4 ⁇ m was 0.21 mL/g, as determined by a mercury porosimeter.
- the dissolution behavior was observed by a digital microscope.
- bubbles having a size of 1/10 or more of the particle size were released from 9% of the particles.
- an average value for size of released bubbles/particle size in the above 9% of the particles was 1.7/10.
- Detergent Additive Particles 5 were analyzed for a cave-in hole.
- Comparative Particles 1, a comparative example of the present invention were prepared by the process described below.
- a 347.5 kg water was added to a 1 m 3 -mixing vessel having agitation impellers.
- the water temperature was adjusted to 50°C, and 150 kg of a 50% by weight-aqueous sodium alkylbenzenesulfonate solution was added thereto.
- After agitating the resulting mixture for 15 minutes 115 kg of sodium sulfate, 100 kg of sodium carbonate, and 87.5 kg of a 40% by weight-aqueous sodium polyacrylate solution were added thereto.
- the resulting mixture was agitated for additional 15 minutes with temperature-controlled to 50°C, and thereafter 150 kg of zeolite was added thereto.
- the resulting mixture was further agitated for 30 minutes with temperature-controlled to 50°C, to give a homogeneous slurry.
- This slurry was supplied to a spray-drying tower with a pump, and sprayed with a pressure spray nozzle arranged near the top of the tower at a spraying pressure of 25 kg/cm 2 .
- a high-temperature gas fed to the spray-drying tower was supplied from the lower portion of the tower at a temperature of 222°C and exhausted from the top of the tower at 105°C.
- particles obtained from the lower part of the tower was dried with a hot air at 100°C in a fluidized bed until the water content attained to 5% by weight. Coarse grains of the resulting particles were removed with a 1410 ⁇ m-sieve, to give Comparative Particles 1.
- the composition and the properties of Comparative Particles 1 are shown in Table 1.
- the microporous capacity at 0.01 to 4 ⁇ m was 0.43 mL/g, as determined by a mercury porosimeter.
- the dissolution behavior was observed by a digital microscope.
- bubbles having a size of 1/10 or more of the particle size were released from 85% of the particles.
- an average value for size of released bubbles/particle size in the above 85% of the particles was 6.2/10.
- Comparative Particles 1 were analyzed for a cave-in hole.
- the particles were composed of 8% of cave-in particles, in which a hole having a projected area diameter of 2% or more and a depth of 10% or more of a projected area diameter of the particle was present at one or more points.
- the average of projected area diameter of hole projected area diameter of particle ⁇ 100 of a cave-in hole for the 8% of cave-in particles was 10%.
- the average depth of the cave-in hole was 65% of the projected area diameter of the particle.
- Comparative Particles 2 a comparative example of the present invention, were prepared by the process described below.
- a batch kneader equipped with a jacket was heated to 50°C, and charged with 20.85 kg water, and 9 kg of a 50% by weight-aqueous sodium alkylbenzenesulfonate solution was added thereto. After agitating the resulting mixture for 15 minutes, 6.9 kg of sodium sulfate, 6 kg of sodium carbonate, and 5.25 kg of a 40% by weight-aqueous sodium polyacrylate solution were added thereto. The resulting mixture was agitated for additional 15 minutes with temperature-controlled to 50°C, and thereafter 9 kg of zeolite was added thereto. The resulting mixture was further agitated for 30 minutes with temperature-controlled to 50°C.
- Comparative Particles 2 The composition and the properties of Comparative Particles 2 are shown in Table 1.
- the microporous capacity at 0.01 to 4 ⁇ m was 0.19 mL/g, as determined by a mercury porosimeter.
- the dissolution behavior was observed by a digital microscope.
- bubbles having a size of 1/10 or more of the particle size were released from 8% of the particles.
- an average value for size of released bubbles/particle size in the above 8% of the particles was 1.6/10.
- Comparative Particles 2 were analyzed for a cave-in hole.
- Comparative Particles 3 a comparative example of the present invention, sodium carbonate particles (DENSE ASH: manufactured by Central Glass Co., Ltd.) were used. As Comparative Particles 4, sodium percarbonate granular particles (KCPZ: manufactured by Nippon Peroxide K.K.) were used. As Comparative Particles 5, enzyme granular particles (Savinase 18T Type W: manufactured by NOVO Nordisk) were used. The composition and the properties of each group of Comparative Particles 3 to 5 are shown in Table 1.
- Detergent Particles 1 were prepared by the process described below.
- the spray-dried base material was supplied into High-Speed Mixer (manufactured by Fukae Powtec Corp., agitation tumbling granulator, equipped with a jacket), and 20% by weight of the formulated amount of the zeolite, and the entire amount of the crystalline silicate were added thereto.
- the remaining 50% by weight of the formulated amount of the polyoxyethylene alkyl ether heated to 70°C was added by spraying, and the mixture was granulated. Further, the resulting granular product was surface-treated by adding 20% by weight of the formulated amount of the zeolite 60 seconds before the termination of the granulation, to give a granule. Further, the granule was classified with a sieve having a sieve-opening of 1410 ⁇ m, and the remaining 10% by weight of the zeolite was added to coarse grains having a size of 1410 ⁇ m or more.
- the resulting mixture was pulverized by Fitz Mill (pulverizer, manufactured by Hosokawa Micron Corporation) to a size of 1410 ⁇ m or less, and thereafter the pulverized product was mixed with the sieve-passed granule, to give Detergent Particles 1.
- Fitz Mill pulverizer, manufactured by Hosokawa Micron Corporation
- Detergent Particles 2 were prepared by the process described below.
- the spray-dried base material was supplied into High-Speed Mixer (manufactured by Fukae Powtec Corp., agitation tumbling granulator, equipped with a jacket), and 20% by weight of the formulated amount of the zeolite, and the entire amount of the crystalline silicate were added thereto.
- the remaining 50% by weight of the formulated amount of the polyoxyethylene alkyl ether heated to 70°C was added by spraying, and the mixture was granulated. Further, the resulting granular product was surface-treated by adding 20% by weight of the formulated amount of the zeolite 60 seconds before the termination of the granulation, to give a granule. Further, the granule was subjected to the same treatment as in Detergent Particles 1, to give Detergent Particles 2.
- Detergent Particles 3 were prepared by the method described below.
- a slurry having a water content of 50% comprising the entire formulated amount of each of sodium polyacrylate, PEG, sodium sulfate, sodium sulfite, a soap and a fluorescent dye, 50% by weight of the formulated amount of zeolite, and 50% by weight of the formulated amount of sodium carbonate, was spray-dried to give spray-dried base material having a bulk density of 460 g/L.
- the resulting spray-dried base material, the entire formulated amounts of an amorphous aluminosilicate and a crystalline silicate, and the remaining 50% by weight of the formulated amount of sodium carbonate were supplied into Lödige Mixer, and the agitation was initiated. Heated water at 40°C was allowed to flow through the jacket.
- the entire formulated amount of the polyoxyethylene alkyl ether heated to 70°C was added by spraying, and the mixture was granulated. Further, the resulting granular product was surface-treated by adding 30% by weight of the formulated amount of the zeolite at the time 60 seconds before the termination of the granulation, to give a granule. The resulting granule was classified with a sieve having a sieve-opening of 1410 ⁇ m, and 20% by weight of the formulated amount of the zeolite was added to coarse grains having a size of 1410 ⁇ m or more.
- Detergent Particles 1 2 3 Formulating Composition (% by weight) LAS-Na 23 25.6 z AS-Na 7 7.8 Polyoxyethylene Alkyl Ether 2) 4 4.4 20 Soap 3 3.3 5 PEG 2 2.2 2 No.
- each group of Detergent Additive Particles 1 to 5 of the present invention and Comparative Particles 1 to 5 was dry-blended with each group of Detergent Particles 1 to 3 for 5 minutes in a V-blender in a weight ratio of 5/95, 10/90 or 30/70, thereby giving composite detergent particles of the present invention and composite detergent particles of comparative examples.
- the granular detergent compositions obtained as above were evaluated for the distributivity in a dispenser of a drum-type washing machine by the following method.
- each group of the composite detergent particles obtained by dry-blending Detergent Additive Particles 1 and Detergent Particle 1 in a weight ratio of 5/95, 10/90 or 30/70 for 5 minutes in a V-blender was subjected to a classification test by transportation. As a result, the classification of the detergent additive particles was not found.
- the detergent additive particles of the present invention have an effect of enhancing the distributivity of the granular detergent composition in running water prepared by mixing the detergent additive particles with the detergent particle.
- the granular detergent composition is supplied by using a dispenser attached to a washing machine such as a drum-type washing machine, in addition to its excellent distributivity in the washing machine, troubles that the granular detergent composition forms an aggregate and remains in the dispenser are improved.
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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JP17012799 | 1999-06-16 | ||
JP17012799 | 1999-06-16 | ||
PCT/JP2000/003857 WO2000077159A1 (fr) | 1999-06-16 | 2000-06-14 | Particules d'addition a un detergent |
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EP1193310A1 true EP1193310A1 (de) | 2002-04-03 |
EP1193310A4 EP1193310A4 (de) | 2004-07-28 |
EP1193310B1 EP1193310B1 (de) | 2008-10-08 |
EP1193310B2 EP1193310B2 (de) | 2016-06-29 |
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EP00939055.0A Expired - Lifetime EP1193310B2 (de) | 1999-06-16 | 2000-06-14 | Teilchenförmiges waschmitteladditiv |
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EP (1) | EP1193310B2 (de) |
JP (1) | JP3249815B2 (de) |
DE (1) | DE60040462D1 (de) |
WO (1) | WO2000077159A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007020949A1 (en) * | 2005-08-15 | 2007-02-22 | Kao Corporation | Process for washing and powder detergent composition |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4574093B2 (ja) * | 2001-12-21 | 2010-11-04 | 花王株式会社 | 容器入り粉末洗剤 |
JP4591704B2 (ja) * | 2003-02-06 | 2010-12-01 | ライオン株式会社 | 粒状洗剤組成物及びその製造方法 |
JP2006056985A (ja) * | 2004-08-19 | 2006-03-02 | Kao Corp | 洗剤組成物 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4900466A (en) * | 1985-11-01 | 1990-02-13 | Lever Brothers Company | Process for preparing needle-shaped crystal growth modified burkeite detergent additive |
WO1999029829A1 (en) * | 1997-12-10 | 1999-06-17 | Kao Corporation | Detergent particles and method for producing the same |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5835559B2 (ja) * | 1978-09-14 | 1983-08-03 | 水澤化学工業株式会社 | 粒状洗剤ビルダ−組成物 |
AU549000B2 (en) * | 1981-02-26 | 1986-01-09 | Colgate-Palmolive Pty. Ltd. | Base beads for detergent compositions |
DE3424987A1 (de) * | 1984-07-06 | 1986-02-06 | Unilever N.V., Rotterdam | Verfahren zur herstellung eines pulverfoermigen waschmittels mit erhoehtem schuettgewicht |
GB8811447D0 (en) * | 1988-05-13 | 1988-06-15 | Procter & Gamble | Granular laundry compositions |
GB9015504D0 (en) * | 1990-07-13 | 1990-08-29 | Unilever Plc | Detergents composition |
DE4031910A1 (de) * | 1990-10-08 | 1992-04-09 | Henkel Kgaa | Percarbonathaltiges waschmittel |
GB9300311D0 (en) * | 1993-01-08 | 1993-03-03 | Unilever Plc | Detergent powders and process for preparing them |
CN1175099C (zh) * | 1998-10-16 | 2004-11-10 | 花王株式会社 | 洗涤剂颗粒的制备方法 |
-
2000
- 2000-06-14 WO PCT/JP2000/003857 patent/WO2000077159A1/ja active Application Filing
- 2000-06-14 DE DE60040462T patent/DE60040462D1/de not_active Expired - Lifetime
- 2000-06-14 JP JP2001503996A patent/JP3249815B2/ja not_active Expired - Fee Related
- 2000-06-14 EP EP00939055.0A patent/EP1193310B2/de not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4900466A (en) * | 1985-11-01 | 1990-02-13 | Lever Brothers Company | Process for preparing needle-shaped crystal growth modified burkeite detergent additive |
WO1999029829A1 (en) * | 1997-12-10 | 1999-06-17 | Kao Corporation | Detergent particles and method for producing the same |
Non-Patent Citations (1)
Title |
---|
See also references of WO0077159A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007020949A1 (en) * | 2005-08-15 | 2007-02-22 | Kao Corporation | Process for washing and powder detergent composition |
Also Published As
Publication number | Publication date |
---|---|
JP3249815B2 (ja) | 2002-01-21 |
WO2000077159A1 (fr) | 2000-12-21 |
EP1193310B2 (de) | 2016-06-29 |
EP1193310A4 (de) | 2004-07-28 |
DE60040462D1 (de) | 2008-11-20 |
EP1193310B1 (de) | 2008-10-08 |
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