JPWO2006016700A1 - Nonionic surfactant-containing particles and method for producing the same - Google Patents
Nonionic surfactant-containing particles and method for producing the same Download PDFInfo
- Publication number
- JPWO2006016700A1 JPWO2006016700A1 JP2006531782A JP2006531782A JPWO2006016700A1 JP WO2006016700 A1 JPWO2006016700 A1 JP WO2006016700A1 JP 2006531782 A JP2006531782 A JP 2006531782A JP 2006531782 A JP2006531782 A JP 2006531782A JP WO2006016700 A1 JPWO2006016700 A1 JP WO2006016700A1
- Authority
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- Prior art keywords
- nonionic surfactant
- water
- inorganic powder
- containing particles
- less
- 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 144
- 239000002736 nonionic surfactant Substances 0.000 title claims abstract description 120
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000000843 powder Substances 0.000 claims abstract description 98
- 238000010521 absorption reaction Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005243 fluidization Methods 0.000 claims description 5
- 239000003599 detergent Substances 0.000 abstract description 42
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000005469 granulation Methods 0.000 description 29
- 230000003179 granulation Effects 0.000 description 29
- 238000000034 method Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- -1 fatty acid salt Chemical class 0.000 description 15
- 239000003921 oil Substances 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000013042 solid detergent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000004067 bulking agent Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000004665 fatty acids Chemical group 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- MQDBGHZVYLTFMG-UHFFFAOYSA-N 2-phenyl-1-[4-[4-(2-phenyl-1-sulfoethenyl)phenyl]phenyl]ethenesulfonic acid Chemical group C=1C=C(C=2C=CC(=CC=2)C(=CC=2C=CC=CC=2)S(O)(=O)=O)C=CC=1C(S(=O)(=O)O)=CC1=CC=CC=C1 MQDBGHZVYLTFMG-UHFFFAOYSA-N 0.000 description 1
- ZTGKHKPZSMMHNM-UHFFFAOYSA-N 3-(2-phenylethenyl)benzene-1,2-disulfonic acid Chemical class OS(=O)(=O)C1=CC=CC(C=CC=2C=CC=CC=2)=C1S(O)(=O)=O ZTGKHKPZSMMHNM-UHFFFAOYSA-N 0.000 description 1
- QJRVOJKLQNSNDB-UHFFFAOYSA-N 4-dodecan-3-ylbenzenesulfonic acid Chemical compound CCCCCCCCCC(CC)C1=CC=C(S(O)(=O)=O)C=C1 QJRVOJKLQNSNDB-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
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 102100025840 Coiled-coil domain-containing protein 86 Human genes 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 101000932708 Homo sapiens Coiled-coil domain-containing protein 86 Proteins 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- NWBJYWHLCVSVIJ-UHFFFAOYSA-N N-benzyladenine Chemical compound N=1C=NC=2NC=NC=2C=1NCC1=CC=CC=C1 NWBJYWHLCVSVIJ-UHFFFAOYSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 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
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- OTNVGWMVOULBFZ-UHFFFAOYSA-N sodium;hydrochloride Chemical compound [Na].Cl OTNVGWMVOULBFZ-UHFFFAOYSA-N 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/40—Specific cleaning or washing processes
- C11D2111/44—Multi-step processes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Glanulating (AREA)
Abstract
本発明により、適当な粒子強度を有し、他の洗剤含有粒子と併用しても非イオン性界面活性剤含有粒子単独のときと同様の溶解性を発揮する非イオン性界面活性剤含有粒子を提供する。詳細には、（Ａ）吸油能が１５ｍＬ／１００ｇ以上であり、かつ８０ｍＬ／１００ｇ未満である水不溶性無機粉体、（Ｂ）吸油能が３０ｍＬ／１００ｇ以下である水溶性無機粉体、及び（Ｃ）非イオン性界面活性剤を含有してなる非イオン性界面活性剤含有粒子を提供する。According to the present invention, nonionic surfactant-containing particles having appropriate particle strength and exhibiting the same solubility as that of nonionic surfactant-containing particles alone even when used in combination with other detergent-containing particles provide. Specifically, (A) a water-insoluble inorganic powder having an oil absorption capacity of 15 mL / 100 g or more and less than 80 mL / 100 g, (B) a water-soluble inorganic powder having an oil absorption capacity of 30 mL / 100 g or less, and ( C) Provided is a nonionic surfactant-containing particle containing a nonionic surfactant.
Description
本発明は、衣料等に用いることのできる非イオン性界面活性剤含有粒子およびその製造方法に関する。詳しくは、崩れの小さい粒子強度を有し、本発明の非イオン性界面活性剤含有粒子以外の洗剤含有粒子（以降、「他の洗剤含有粒子」と称することもある）と併用したときでも、溶解性が良好な非イオン性界面活性剤含有粒子に関する。本発明はまた、撹拌造粒法を用いてこの組成物を製造する際に、造粒装置内部への非イオン性界面活性剤含有粒子等の付着を一定に保ち、稼働率の低下を抑制できる非イオン性界面活性剤含有粒子の製造方法に関する。 The present invention relates to nonionic surfactant-containing particles that can be used in clothing and the like, and a method for producing the same. Specifically, it has a particle strength with a small collapse, and even when used in combination with detergent-containing particles other than the nonionic surfactant-containing particles of the present invention (hereinafter sometimes referred to as “other detergent-containing particles”), The present invention relates to nonionic surfactant-containing particles having good solubility. The present invention can also keep the adhesion of nonionic surfactant-containing particles and the like inside the granulating apparatus constant when producing this composition by using the stirring granulation method, and can suppress the decrease in operating rate. The present invention relates to a method for producing nonionic surfactant-containing particles.
衣料用洗剤組成物は、一般に、洗浄基剤と洗剤ビルダーとを含有する粒子から製造されている。洗浄基剤としては、合成アニオン界面活性剤及び脂肪酸塩を主体としたものと非イオン性界面活性剤が多く使用されている。このうち非イオン性界面活性剤は、一般に低泡性であり、洗浄力が水の硬度の影響を受けにくく、特に泥汚れや低温での汚れ分散性にも優れ、生分解性が良好で環境負荷が低く、低毒性で安全性にも問題がないなどの特性を持つことから特にその活用が望まれている。洗剤ビルダーは、基本的な役割である洗浄助剤に加えて洗剤粒子を形成する上で重要である構造化剤の役目を果している。
ところが、洗剤ビルダーを含有しても、洗浄基剤として多割合の非イオン性界面活性剤を含有する粒子の粒子強度が、多割合のアニオン性界面活性剤を含有する粒子に比べ劣ることがあり、その結果、洗剤粒子壊れに伴う分級、洗浄性低下が問題となっている。
これまでに、粒子強度を向上する方法として、攪拌造粒装置内に平均粒子径５０μｍ以下の微粉を５％以上含む粉体原料を流動化させ発塵ゾーンを形成させ非イオン性界面活性剤のバインダー力を増強する方法が提案されている（例えば特許文献１参照）。
しかし、この方法では、粒子強度を増大せるために非イオン界面活性剤の粒子径を特定する必要があり、微粒化が難しい液体に対しては応用しづらいという問題点がある。Garment detergent compositions are generally made from particles containing a cleaning base and a detergent builder. As the cleaning base, a synthetic anionic surfactant and a fatty acid salt as a main component and a nonionic surfactant are often used. Among these, nonionic surfactants generally have low foaming properties, and their detergency is not easily affected by the hardness of water. Especially, they are excellent in mud stains and dirt dispersibility at low temperatures, and have good biodegradability and environmental friendliness. Utilization is particularly desired because of its low load, low toxicity and safety. Detergent builders serve as structuring agents that are important in forming detergent particles in addition to the basic role of cleaning aids.
However, even if it contains a detergent builder, the particle strength of particles containing a large proportion of nonionic surfactant as a cleaning base may be inferior to particles containing a large proportion of anionic surfactant. As a result, classification due to breakage of the detergent particles and deterioration of cleaning properties are problematic.
Up to now, as a method for improving the particle strength, a powder raw material containing 5% or more of fine powder having an average particle diameter of 50 μm or less is fluidized in a stirring granulator to form a dust generation zone and a nonionic surfactant. A method for enhancing the binder force has been proposed (see, for example, Patent Document 1).
However, in this method, it is necessary to specify the particle size of the nonionic surfactant in order to increase the particle strength, and there is a problem that it is difficult to apply to a liquid that is difficult to atomize.
また、近年、衣料用洗剤組成物に要求される性能が高くなるのに伴って、洗剤粒子には従来配合されなかった原料・素材を、これまでとは別の粒子形態で配合するなどの工夫が必要となってきている。
ところが、このような原料・素材を含有する粒子や他の洗剤含有粒子と、非イオン性界面活性剤含有粒子とを混合した場合、何れかの粒子が選択的に溶け残ってしまう現象が見出され単一組成粒子に比べ溶解性が劣ることがわかった。
これまでに、洗剤組成物の溶解性を改善するための手段として、特定の結晶性層状珪酸塩と吸油能が80ｍＬ/100ｇ以上の多孔性吸油担体とを特定量併用すること（特許文献２参照）、非イオン性界面活性剤と粘土鉱物とを併用すること（特許文献３参照）、特定量の油ゲル化剤、アルミノ珪酸塩、多孔質酸化物粉体、炭酸ナトリウムと共に非イオン性界面活性とを併用すること（例えば、特許文献４）等が提案されている。
しかしながら、上記の特許文献に記載の非イオン性界面活性剤主体粒子と他の洗剤含有粒子とを後混合すると、非イオン界面活性剤粒子単独の物性とは異なり、特に溶解性の悪化が認められた。In recent years, as the performance required for detergent compositions for clothing has increased, it has been devised to incorporate raw materials and materials that were not previously blended into detergent particles in a different particle form. Is becoming necessary.
However, when particles containing such raw materials / materials or other detergent-containing particles are mixed with non-ionic surfactant-containing particles, a phenomenon has been found in which any of the particles remains selectively undissolved. It was found that the solubility was inferior to that of single composition particles.
So far, as a means for improving the solubility of the detergent composition, a specific crystalline layered silicate and a porous oil-absorbing carrier having an oil absorption capacity of 80 mL / 100 g or more are used in combination (see Patent Document 2). ), Using nonionic surfactant and clay mineral together (see Patent Document 3), specific amount of oil gelling agent, aluminosilicate, porous oxide powder, sodium carbonate and nonionic surfactant (For example, patent document 4) etc. are proposed.
However, when the nonionic surfactant-based particles described in the above-mentioned patent document and other detergent-containing particles are post-mixed, the solubility is particularly deteriorated, unlike the physical properties of the nonionic surfactant particles alone. It was.
他方、非イオン性界面活性剤含有粒子を撹拌造粒により製造する時の問題点として、非イオン界面活性剤と洗浄ビルダーその他の粉体材料との緻密混合性が悪いため、装置内部への生成物等の付着が発生しやすく、造粒物の流動性や耐ケーキング性の低下等を引き起こし、安定な連続生産が難しいという欠点があげられる。また、造粒開始から終了までの嵩密度の変化が大きいため、造粒装置の容量の２０〜３０ｖｏｌ％程度しか製造することができず、更に前述の付着物の影響でバッチ当たりの生産量が安定しないという問題点がある。
これまでに、このような問題点を解決するため、攪拌造粒装置内壁に洗剤原料混合物の付着層を形成させつつ造粒を行った後、表面改質剤でコーティングを行うことが提案されている（例えば、特許文献５、特許文献６参照）。
しかし、これら方法により繰り返し造粒作業を行うと、装置クリアランスにできる粉体層の構造が密度の高い付着層へと変化し、造粒装置の負荷が大きくなり連続的な生産に支障をきたすという問題点を有することが判った。On the other hand, as a problem when producing nonionic surfactant-containing particles by agitation granulation, the intimate mixing of the nonionic surfactant with the cleaning builder and other powder materials is poor, so it is generated inside the device. There are disadvantages in that it is difficult for stable continuous production to occur, which tends to cause adhesion of substances and the like, causing a decrease in fluidity and caking resistance of the granulated material. Moreover, since the change of the bulk density from the start to the end of granulation is large, only about 20 to 30 vol% of the capacity of the granulation apparatus can be produced, and the production amount per batch is further influenced by the above-mentioned deposits. There is a problem that it is not stable.
Until now, in order to solve such problems, it has been proposed to perform granulation while forming an adhesion layer of the detergent raw material mixture on the inner wall of the agitation granulator and then coating with a surface modifier. (For example, see Patent Document 5 and Patent Document 6).
However, if repeated granulation operations are performed by these methods, the structure of the powder layer that can be used as the device clearance changes to a dense adherent layer, which increases the load on the granulation device and hinders continuous production. It turned out to have problems.
従って、本発明の目的は、適当な粒子強度を有し、他の洗剤含有粒子と併用しても非イオン性界面活性剤含有粒子単独のときと同等の溶解性を維持する非イオン性界面活性剤含有粒子を提供することである。
本発明の目的はまた、撹拌造粒により非イオン性界面活性剤含有粒子を製造する上で、造粒装置内部における非イオン界面活性剤含有物又は未造粒物の付着を一定に保ち、稼働率の低下を抑制させ、撹拌造粒装置を洗浄する際に短時間で且つ効率良く作業が行える製造方法を提供することにある。Accordingly, an object of the present invention is to provide a nonionic surfactant having an appropriate particle strength and maintaining the same solubility as that of a nonionic surfactant-containing particle alone even when used in combination with other detergent-containing particles. It is to provide agent-containing particles.
The object of the present invention is also to produce nonionic surfactant-containing particles by agitation granulation, and keep the adhesion of nonionic surfactant-containing or non-granulated material inside the granulating device in a constant operation. It is an object of the present invention to provide a manufacturing method capable of suppressing the reduction of the rate and performing the work efficiently in a short time when washing the agitation granulator.
本発明者らは、鋭意研究を重ねた結果、非イオン界面活性剤と混合・造粒する粉体を特定の組成にすることで、上記目的が達成されることを見出し本発明に至った。
すなわち、本発明は、（Ａ）吸油能が１５ｍＬ／１００ｇ以上であり、かつ８０ｍＬ／１００ｇ未満である水不溶性無機粉体、（Ｂ）吸油能が３０ｍＬ／１００ｇ以下である水溶性無機粉体、及び（Ｃ）非イオン性界面活性剤を含有してなる非イオン性界面活性剤含有粒子を提供する。
本発明者らはまた、攪拌造粒において、非イオン界面活性剤添加前に特定の水不溶性無機粉体で造粒装置内壁に粉体層を形成させた後、造粒を行うと、上記製造上の目的が達成されることを見出し本発明に至った。
すなわち本発明はまた、非イオン性界面活性剤含有粒子の製造方法であって、
（i）吸油能が１５ｍＬ／１００ｇ以上であり、かつ８０ｍＬ／１００ｇ未満である水不溶性無機粉体を、攪拌機能を備えた造粒装置に投入する工程、
（ii）前記造粒装置を作動させ、前記造粒装置に入っている水不溶性無機粉体を攪拌させることにより、少なくともその一部を該装置の内壁に付着させる工程、
（iii）さらに、吸油能が３０ｍＬ／１００ｇ以下の水溶性無機粉体、及び非イオン性界面活性剤を前記造粒装置に投入する工程、及び
（iv）前記造粒装置を作動させ、前記水不溶性無機粉体、前記水溶性無機粉体及び前記非イオン性界面活性剤を混合することにより、非イオン性界面活性剤含有粒子を造粒する工程、
を含む、前記製造方法を提供する。As a result of intensive studies, the present inventors have found that the above object can be achieved by making the powder mixed and granulated with a nonionic surfactant into a specific composition, and have reached the present invention.
That is, the present invention includes (A) a water-insoluble inorganic powder having an oil absorption capacity of 15 mL / 100 g or more and less than 80 mL / 100 g, (B) a water-soluble inorganic powder having an oil absorption capacity of 30 mL / 100 g or less, And (C) a nonionic surfactant-containing particle comprising a nonionic surfactant.
In addition, in the stirring granulation, when the granulation is performed after the powder layer is formed on the inner wall of the granulating apparatus with the specific water-insoluble inorganic powder before the addition of the nonionic surfactant, the above production is performed. The inventors have found that the above object can be achieved and have reached the present invention.
That is, the present invention is also a method for producing nonionic surfactant-containing particles,
(I) a step of introducing a water-insoluble inorganic powder having an oil absorption capacity of 15 mL / 100 g or more and less than 80 mL / 100 g into a granulator equipped with a stirring function;
(Ii) actuating the granulator and stirring the water-insoluble inorganic powder contained in the granulator to attach at least a part thereof to the inner wall of the apparatus;
(Iii) a step of adding a water-soluble inorganic powder having an oil absorption capacity of 30 mL / 100 g or less and a nonionic surfactant to the granulator; and (iv) actuating the granulator, and A step of granulating nonionic surfactant-containing particles by mixing the insoluble inorganic powder, the water-soluble inorganic powder and the nonionic surfactant;
The manufacturing method is provided.
本発明によれば、適当な粒子強度を有し、他の洗剤含有粒子と併用しても非イオン性界面活性剤含有粒子単独のときと同様の溶解性を発揮する非イオン性界面活性剤含有粒子を提供することができる。本発明によればまた、稼働率の低下を抑制し、短時間で効率よく非イオン性界面活性剤含有粒子を得ることができる。本発明によればまた、高嵩密度で、染み出し少ない非イオン性界面活性剤含有粒子を得ることが出来る。 According to the present invention, it contains a nonionic surfactant that has appropriate particle strength and exhibits the same solubility as that of a nonionic surfactant-containing particle alone even when used in combination with other detergent-containing particles. Particles can be provided. According to the present invention, it is also possible to obtain nonionic surfactant-containing particles efficiently in a short time while suppressing a decrease in operating rate. According to the present invention, it is also possible to obtain nonionic surfactant-containing particles having a high bulk density and little oozing.
（Ａ）水不溶性無機粉体
本発明において使用できる水不溶性無機粉体とは、吸油能が１５ｍＬ／１００ｇ以上、８０ｍＬ／１００ｇ未満、好ましくは１８〜７８ｍＬ／１００ｇ、更に好ましくは、２０〜７７ｍＬ／１００ｇの水不溶性無機粉体をいう。吸油能が１５ｍＬ／１００ｇ以上であると、造粒装置内の付着を抑制できる。また、非イオン性界面活性剤の染み出しも抑制できるので好ましい。吸油能が８０ｍＬ／１００ｇ未満のとき、他の洗剤粒子と併用しても、洗剤組成物の品質が低下することなく、特に、良好な溶解性を発揮できる。なお、本明細書において、吸油能はＪＩＳ−Ｋ６２２０に規定される試験方法により測定できる。
本発明において使用できる水不溶性無機粉体は、２０℃における水への溶解度が好ましくは０．１ｇ／１００ｇ以下、より好ましくは０．０５ｇ／１００ｇ以下、さらに好ましくは０．０１ｇ／１００ｇ以下である。水への溶解度がこのような範囲にあると、冷水溶解時のゲル化、イオン性物質の過度の水和を抑制して、溶解性の劣化を抑えるので好ましい。
このような水不溶性無機粉体であれば特に限定されず、１種単独で又は２種以上を適宜組み合わせて用いることができる。具体的には、アルミノケイ酸塩、結晶性ケイ酸塩、水難溶性の炭酸塩、硫酸塩、塩化物等が挙げられる。このうち、アルミノケイ酸塩、炭酸塩が好ましく、特に、アルミノケイ酸ナトリウム、アルミノケイ酸マグネシウム、炭酸カルシウムが好ましい。このような水不溶性無機粉体は商業的に入手することが出来る。例えば、Ａ型ゼオライト（シルトンＢ，水沢化学（株）製）、Ｐ型ゼオライト（クロスフィールド社製）、炭酸カルシウム（白石工業製）などがあげられる。
水不溶性無機粉体は、本発明の非イオン性界面活性剤含有粒子中に、好ましくは２０重量％以上、より好ましくは２５重量％以上、更に好ましくは３０重量％以上、好ましくは８０重量％以下、より好ましくは６５重量％以下、更に好ましくは６０重量％以下配合される。２０重量％以上であると、非イオン界面活性剤等の装置内壁への付着が抑制され、造粒物の流動性が低下することが少ないので好ましい。８０重量％超過では発塵性が悪化するので好ましくない。(A) Water-insoluble inorganic powder The water-insoluble inorganic powder that can be used in the present invention has an oil absorption capacity of 15 mL / 100 g or more and less than 80 mL / 100 g, preferably 18 to 78 mL / 100 g, more preferably 20 to 77 mL / 100 g of water-insoluble inorganic powder. When the oil absorption capacity is 15 mL / 100 g or more, adhesion in the granulating apparatus can be suppressed. Moreover, since the exudation of a nonionic surfactant can also be suppressed, it is preferable. When the oil absorption capacity is less than 80 mL / 100 g, even when used in combination with other detergent particles, the quality of the detergent composition is not deteriorated, and particularly good solubility can be exhibited. In addition, in this specification, oil absorption ability can be measured by the test method prescribed | regulated to JIS-K6220.
The water-insoluble inorganic powder that can be used in the present invention has a solubility in water at 20 ° C. of preferably 0.1 g / 100 g or less, more preferably 0.05 g / 100 g or less, and still more preferably 0.01 g / 100 g or less. . When the solubility in water is in such a range, it is preferable because gelation at the time of dissolution in cold water and excessive hydration of the ionic substance are suppressed, and deterioration of solubility is suppressed.
If it is such a water-insoluble inorganic powder, it will not specifically limit, 1 type can be used individually or in combination of 2 or more types. Specific examples include aluminosilicates, crystalline silicates, poorly water-soluble carbonates, sulfates, and chlorides. Of these, aluminosilicate and carbonate are preferable, and sodium aluminosilicate, magnesium aluminosilicate, and calcium carbonate are particularly preferable. Such a water-insoluble inorganic powder can be obtained commercially. Examples include A-type zeolite (Silton B, manufactured by Mizusawa Chemical Co., Ltd.), P-type zeolite (manufactured by Crossfield), calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd.), and the like.
The water-insoluble inorganic powder is preferably 20% by weight or more, more preferably 25% by weight or more, still more preferably 30% by weight or more, preferably 80% by weight or less in the nonionic surfactant-containing particles of the present invention. More preferably, it is 65 wt% or less, and still more preferably 60 wt% or less. When the content is 20% by weight or more, adhesion of nonionic surfactant or the like to the inner wall of the apparatus is suppressed, and the fluidity of the granulated product is less likely to deteriorate, which is preferable. Exceeding 80% by weight is not preferable because dust generation deteriorates.
（Ｂ）水溶性無機粉体
本発明において使用できる水溶性無機粉体とは、吸油能が３０ｍＬ／１００ｇ以下、好ましくは、２５ｍＬ／１００ｇ以下である。吸油能が３０ｍＬ／１００ｇ以下であると、界面活性剤によるものと思われるゲル状物が発生するのを抑制することができ、特に冬場の衣類への洗剤の溶け残りが改善するので好ましい。
本発明において使用できる水溶性無機粉体は、２０℃における水への溶解度が好ましくは１ｇ／１００ｇ以上、より好ましくは２ｇ／１００ｇ以上、さらに好ましくは５ｇ／１００ｇ以上である。水への溶解度がこのような範囲にあると、洗濯時に洗剤が溶け、すすぎ時に溶け残りがなくなるので好ましい。
このような水溶性無機粉体であれば特に限定されず、１種単独で又は２種以上を適宜組み合わせて用いることができる。具体的には、水溶性の炭酸塩、硫酸塩、塩化物、珪酸塩、リン酸塩等が挙げられる。このような水溶性無機粉体は商業的に入手することが出来る。例えば、炭酸ナトリウム（粒灰、旭硝子（株）製）、硫酸ナトリウム（中性無水茫硝、日本化学工業（株））、亜硫酸ナトリウム（無水亜硫酸曹達、神州化学（株））などがあげられる。
水溶性無機粉体の平均粒子径は、好ましくは１５０μｍ以上、４５０μｍ未満、より好ましくは２００〜４３０μｍである。平均粒子径がこのような範囲にあると、最終的に得られる非イオン性界面活性剤含有粒子の強度が高く、流動性が維持できるため好ましい。
なかでも、吸油能が２５ｍＬ／１００ｇ以下であって、平均粒子径が２００μｍ以上４５０μｍ未満、特に、吸油能が２５ｍＬ／１００ｇ以下であって、平均粒子径が２３０μｍ以上４３０μｍの水溶性無機粉体が好ましい。吸油能が高く、平均粒子径が小さいと、他の洗剤含有粒子と混合したときの品質、特に、溶解性の劣化に加え、非イオン界面活性剤含有粒子の強度が低下し粉体の流動性・固化性が非イオン界面活性剤の染み出し以外の効果で低下することがある。
水溶性無機粉体は、非イオン性界面活性剤含有粒子中に、好ましくは０．５重量％以上、より好ましくは２重量％以上、さらに好ましくは４重量％以上、好ましくは３５重量％以下、より好ましくは３０重量％以下、さらに好ましくは２５重量％以下配合される。配合量が０．５重量％以上であると粒子強度の高い非イオン性界面活性剤含有粒子が得られるので好ましい。３５重量％を越えると製造時に過造粒となり粗大粒子が多量に生成し実生産に支障をきたすので好ましくない。(B) Water-soluble inorganic powder The water-soluble inorganic powder that can be used in the present invention has an oil absorption capacity of 30 mL / 100 g or less, preferably 25 mL / 100 g or less. When the oil absorption capacity is 30 mL / 100 g or less, it is possible to suppress the generation of a gel-like material that is thought to be caused by the surfactant, and this is particularly preferable because the undissolved residue of the detergent in winter clothes is improved.
The water-soluble inorganic powder that can be used in the present invention has a solubility in water at 20 ° C. of preferably 1 g / 100 g or more, more preferably 2 g / 100 g or more, and even more preferably 5 g / 100 g or more. When the solubility in water is within such a range, the detergent dissolves during washing, and the undissolved residue disappears during rinsing.
If it is such a water-soluble inorganic powder, it will not specifically limit, 1 type can be used individually or in combination of 2 or more types. Specific examples include water-soluble carbonates, sulfates, chlorides, silicates, and phosphates. Such water-soluble inorganic powder can be obtained commercially. Examples thereof include sodium carbonate (granular ash, manufactured by Asahi Glass Co., Ltd.), sodium sulfate (neutral anhydrous sodium sulfate, Nippon Chemical Industry Co., Ltd.), sodium sulfite (anhydrous sulfite, Shinshu Chemical Co., Ltd.), and the like.
The average particle size of the water-soluble inorganic powder is preferably 150 μm or more and less than 450 μm, more preferably 200 to 430 μm. When the average particle diameter is in such a range, the nonionic surfactant-containing particles finally obtained are preferable because the strength is high and fluidity can be maintained.
Among these, a water-soluble inorganic powder having an oil absorption capacity of 25 mL / 100 g or less and an average particle diameter of 200 μm or more and less than 450 μm, particularly an oil absorption capacity of 25 mL / 100 g or less and an average particle diameter of 230 μm or more and 430 μm. preferable. If the oil absorption capacity is high and the average particle size is small, the quality when mixed with other detergent-containing particles, in particular, the deterioration of solubility, the strength of nonionic surfactant-containing particles decreases, and the fluidity of the powder -Solidification property may decrease due to effects other than exudation of nonionic surfactant.
The water-soluble inorganic powder is preferably 0.5% by weight or more, more preferably 2% by weight or more, further preferably 4% by weight or more, preferably 35% by weight or less in the nonionic surfactant-containing particles. More preferably, it is 30 wt% or less, and further preferably 25 wt% or less. A blending amount of 0.5% by weight or more is preferable because nonionic surfactant-containing particles having high particle strength can be obtained. If it exceeds 35% by weight, excessive granulation occurs during production, and a large amount of coarse particles are produced, which hinders actual production.
（Ｃ）非イオン性界面活性剤
本発明において、非イオン界面活性剤としては特に制限なく各種の非イオン界面活性剤を使用することができる。好ましい非イオン界面活性剤としては、例えば、以下のものを挙げることができる。
（１）炭素数６〜２２、好ましくは８〜１８の脂肪族アルコールに炭素数２〜４のアルキレンオキシドを平均３〜３０モル、好ましくは５〜２５モル付加したポリオキシアルキレンアルキル（又はアルケニル）エーテル。この中でも、ポリオキシエチレンアルキル（又はアルケニル）エーテル、ポリオキシエチレンポリオキシプロピレンアルキル（又はアルケニル）エーテルが好適である。
（２）ポリオキシエチルアルキル（又はアルケニル）フェニルエーテル。
（３）長鎖脂肪酸アルキルエステルのエステル結合間にアルキレンオキシドが付加した以下の式（I）で示される脂肪酸アルキルエステルアルコキシレート。
Ｒ１ＣＯ（ＯＡ）n ＯＲ２ （I）
（Ｒ１ＣＯは、炭素数６〜２２、好ましくは８〜１８の脂肪酸残基を表わす。ＯＡは、エチレンオキシド、プロピレンオキシド等の炭素数２〜４、好ましくは２〜３のアルキレンオキシドの付加単位を表わす。ｎは、アルキレンオキシドの平均付加モル数を示し、一般に３〜３０、好ましくは５〜２５の数である。Ｒ２は、炭素数１〜３の置換基を有してもよい低級アルキル基を表す。）
（４）ポリオキシエチレンソルビタン脂肪酸エステル。
（５）ポリオキシエチレンソルビット脂肪酸エステル。
（６）ポリオキシエチレン脂肪酸エステル。
（７）ポリオキシエチレン硬化ヒマシ油。
（８）グリセリン脂肪酸エステル。(C) Nonionic surfactant In the present invention, various nonionic surfactants can be used without any particular limitation as the nonionic surfactant. Examples of preferable nonionic surfactants include the following.
(1) Polyoxyalkylene alkyl (or alkenyl) obtained by adding an average of 3 to 30 moles, preferably 5 to 25 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms ether. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable.
(2) Polyoxyethyl alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate represented by the following formula (I) in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.
R1CO (OA) n OR2 (I)
(R1CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. OA represents an addition unit of alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms such as ethylene oxide and propylene oxide. N represents the average number of added moles of alkylene oxide, and is generally a number of 3 to 30, preferably 5 to 25. R2 represents a lower alkyl group which may have a substituent of 1 to 3 carbon atoms. To express.)
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbite fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene hydrogenated castor oil.
(8) Glycerin fatty acid ester.
このうち、流動化点が６５℃以下のものが好ましい。Ｇｒｉｆｆｉｎの式により算出されるＨＬＢ値が９〜１６のものもまた好ましい。特に、上記の非イオン界面活性剤の中でも、流動化点が６５℃以下でＨＬＢが９〜１６のポリオキシエチレンアルキル（又はアルケニル）エーテル、脂肪酸メチルエステルにエチレンオキシドが付加した脂肪酸メチルエステルエトキシレートが特に好適に用いられる。特に、炭素数８−１８の脂肪族アルコールにエチレンオキシドを５−２５モル付加したポリオキシエチレンアルキルエーテルが好ましい。上記式（I）において、Ｒ１の炭素数が８−１８であり、Ｒ２の炭素数が１であり、ＯＡがエチレンオキシドであり、ｎが５−２５である脂肪酸アルキルエステルアルコキシレートもまた好ましい。また、これらのノニオン界面活性剤は混合物として使用してもよい。なお、本明細書において、流動化点は、ＤＳＣによる吸熱（発熱）ピークの最大値（温度）として測定することができる。
非イオン界面活性剤は、本発明の非イオン性界面活性剤含有粒子中に、好ましくは１０重量％以上、更に好ましくは１２重量％以上、特に好ましくは１５重量％以上、好ましくは６０重量％以下、更に好ましくは５５重量％以下、特に好ましくは４８重量％以下含有される。１０重量％以上配合することにより、他の洗剤含有粒子と併用した場合でも、本発明の非イオン性界面活性剤含有粒子の品質、特に溶解性、固化性が良好であるので好ましい。６０重量％以下であると、得られる非イオン性界面活性剤含有粒子の溶解性、流動性などが良好であり、また、製造時、造粒装置内壁への造粒物の付着が抑制され、稼働率が低下することないので好ましい。Of these, those having a fluidization point of 65 ° C. or lower are preferred. Those having an HLB value calculated by the Griffin equation of 9 to 16 are also preferable. In particular, among the above nonionic surfactants, polyoxyethylene alkyl (or alkenyl) ethers having a fluidization point of 65 ° C. or less and an HLB of 9 to 16 and fatty acid methyl ester ethoxylates obtained by adding ethylene oxide to fatty acid methyl esters are included. Particularly preferably used. In particular, polyoxyethylene alkyl ether obtained by adding 5 to 25 mol of ethylene oxide to an aliphatic alcohol having 8 to 18 carbon atoms is preferable. In the above formula (I), a fatty acid alkyl ester alkoxylate in which R1 has 8 to 18 carbon atoms, R2 has 1 carbon atom, OA is ethylene oxide, and n is 5 to 25 is also preferable. These nonionic surfactants may be used as a mixture. In this specification, the fluidization point can be measured as the maximum value (temperature) of the endothermic (exothermic) peak by DSC.
The nonionic surfactant is preferably 10% by weight or more, more preferably 12% by weight or more, particularly preferably 15% by weight or more, preferably 60% by weight or less in the nonionic surfactant-containing particles of the present invention. More preferably, it is 55% by weight or less, particularly preferably 48% by weight or less. By blending 10% by weight or more, even when used in combination with other detergent-containing particles, the quality, particularly solubility and solidification properties of the nonionic surfactant-containing particles of the present invention are preferable. When it is 60% by weight or less, the resulting nonionic surfactant-containing particles have good solubility, fluidity, and the like, and during production, adhesion of the granulated material to the inner wall of the granulator is suppressed, It is preferable because the operating rate does not decrease.
＜任意成分＞
本発明の非イオン性界面活性剤含有粒子は、上記（Ａ）〜（Ｃ）成分の他、任意成分を含有することができる。具体的には、通常洗剤に配合される粘土鉱物や少量成分、例えば蛍光剤、酵素、漂白剤、帯電防止剤、表面改質剤、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、再汚染防止剤、増量剤、香料、還元剤等を含有することができる。これらの任意成分は、例えば、水溶性無機粉体と共に造粒装置に投入して混合することにより、本発明の非イオン性界面活性剤含有粒子中に配合することが出来る。
このような任意成分としては、具体的には以下のものがあげられる：
（１）粘土鉱物：モンモリロナイト、ノントロナイト、バイデライト、パイロフィライト、サポナイト、ヘクトライト、スチーブンサイト、タルク等。
（２）蛍光剤：ビス（トリアジニルアミノ）スチルベンジスルホン酸誘導体、ビス（スルホスチリル）ビフェニル塩［チノパールＣＢＳ］等。
（３）酵素：リパーゼ、プロテアーゼ、セルラーゼ、アミラーゼ等。
（４）漂白剤：過炭酸塩、過硼酸塩等。
（５）帯電防止剤：ジアルキル型４級アンモニウム塩などのカチオン界面活性剤等。
（６）表面改質剤：微粉炭酸カルシウム、微粉ゼオライト、ポリエチレングリコール等。
（７）アニオン界面活性剤：α−スルホ脂肪酸メチルエステル塩、直鎖アルキルベンゼンスルホン酸塩、α−オレフィンスルホン酸塩、アルキル硫酸エステル塩、脂肪酸石鹸等。
（８）カチオン界面活性剤：第３級アミンおよび／または四級アンモニウム化合物
（９）両性界面活性剤：アルキルカルボベタイン、アルキルスルホベタイン、アルキルヒドロキシスルホベタイン、アルキルアミドヒドロキシスルホベタイン、アルキルアミドアミン型ベタイン、アルキルイミダゾリン型ベタイン等
（10）再汚染防止剤：カルボキシメチルセルロースなどのセルロース誘導体等。
（11）増量剤：硫酸ナトリウム、硫酸カリウム、塩酸ナトリウム、尿素等。
（12）香料：
（13）還元剤：亜硫酸ナトリウム、亜硫酸カリウム等。
（14）繊維表面処理剤：セルロース類等。
本発明の非イオン性界面活性剤含有粒子が、（Ｃ）非イオン性界面活性剤に加え、（７）アニオン界面活性剤、（８）カチオン界面活性剤及び（９）両性界面活性剤からなる群から選ばれる少なくとも１種の界面活性剤を含有する場合、粒子中の界面活性剤全量に占める（Ｃ）非イオン性界面活性剤の量は、好ましくは７０重量％以上、より好ましくは８０重量％以上である。７０重量％以上であると、本発明の非イオン性界面活性剤含有粒子自体の水への溶解性が良好であるので好ましい。<Optional component>
The nonionic surfactant-containing particles of the present invention can contain optional components in addition to the components (A) to (C). Specifically, clay minerals and minor components that are usually blended in detergents, such as fluorescent agents, enzymes, bleaching agents, antistatic agents, surface modifiers, anionic surfactants, cationic surfactants, amphoteric surfactants, A recontamination inhibitor, a bulking agent, a fragrance, a reducing agent, and the like can be contained. These optional components can be blended in the nonionic surfactant-containing particles of the present invention by, for example, putting them in a granulator together with water-soluble inorganic powder and mixing them.
Specific examples of such optional components include the following:
(1) Clay minerals: Montmorillonite, nontronite, beidellite, pyrophyllite, saponite, hectorite, stevensite, talc, etc.
(2) Fluorescent agent: bis (triazinylamino) stilbene disulfonic acid derivative, bis (sulfostyryl) biphenyl salt [Tinopearl CBS] and the like.
(3) Enzyme: lipase, protease, cellulase, amylase, etc.
(4) Bleaching agent: percarbonate, perborate and the like.
(5) Antistatic agents: cationic surfactants such as dialkyl quaternary ammonium salts.
(6) Surface modifier: fine powder calcium carbonate, fine powder zeolite, polyethylene glycol and the like.
(7) Anionic surfactant: α-sulfo fatty acid methyl ester salt, linear alkylbenzene sulfonate, α-olefin sulfonate, alkyl sulfate ester salt, fatty acid soap and the like.
(8) Cationic surfactant: tertiary amine and / or quaternary ammonium compound (9) Amphoteric surfactant: alkylcarbobetaine, alkylsulfobetaine, alkylhydroxysulfobetaine, alkylamidohydroxysulfobetaine, alkylamidoamine type betaine , Alkyl imidazoline type betaines, etc. (10) Anti-contamination agents: cellulose derivatives such as carboxymethyl cellulose.
(11) Bulking agent: sodium sulfate, potassium sulfate, sodium hydrochloride, urea and the like.
(12) Fragrance:
(13) Reducing agent: sodium sulfite, potassium sulfite and the like.
(14) Fiber surface treatment agent: celluloses and the like.
The nonionic surfactant-containing particles of the present invention comprise (7) an anionic surfactant, (8) a cationic surfactant, and (9) an amphoteric surfactant in addition to (C) the nonionic surfactant. When containing at least one surfactant selected from the group, the amount of (C) nonionic surfactant in the total amount of surfactant in the particles is preferably 70% by weight or more, more preferably 80% by weight. % Or more. When it is 70% by weight or more, the solubility of the nonionic surfactant-containing particles of the present invention per se in water is favorable.
＜他の洗剤含有粒子＞
本発明の非イオン性界面活性剤含有粒子はまた、他の洗剤含有粒子と併用して洗剤組成物を製造することができる。他の洗剤含有粒子中に配合できる成分としては、上記（１）〜（14）及び非イオン性界面活性剤を使用することができる。なお、非イオン性界面活性剤を含有する場合、粒子中の界面活性剤全量に占める非イオン性界面活性剤の量は、好ましくは３０重量％以下、より好ましくは２８重量％以下である。他の洗剤含有粒子は、本発明の非イオン性界面活性剤含有粒子と同様の方法で製造することができる。<Other detergent-containing particles>
The nonionic surfactant-containing particles of the present invention can also be used in combination with other detergent-containing particles to produce a detergent composition. As a component which can be mix | blended with other detergent-containing particle | grains, said (1)-(14) and a nonionic surfactant can be used. In addition, when a nonionic surfactant is contained, the amount of the nonionic surfactant in the total amount of the surfactant in the particles is preferably 30% by weight or less, more preferably 28% by weight or less. Other detergent-containing particles can be produced in the same manner as the nonionic surfactant-containing particles of the present invention.
＜本発明の非イオン性界面活性剤含有粒子の製造方法＞
工程（i）
本発明において使用できる造粒装置としては、攪拌混合機能と剪断機能とを備えた造粒機を使用するのが好ましい。例えば、内部に撹拌軸を有し、全体混合用の撹拌翼と解砕用の撹拌翼を装着したものや、内部に攪拌翼を有さずに、装置全体が回転することにより、装置内に充填された内容物を攪拌・混合することができるものがあげられる。撹拌翼と造粒装置内部壁面との間に、１〜３０ｍｍ、より好ましくは３〜１０ｍｍのクリアランスを有する撹拌式造粒装置が好ましい。クリアランスが１ｍｍ未満では付着層により混合機が過動力となり易い。３０ｍｍを超えると圧密化の効率が低下するため粒度分布がブロードに、また、造粒時間が長くなり生産性が低下する場合がある。この様な構造の装置としては、ハイスピードミキサー［深江工業（株）製］、バーチカルグラニュレーター［（株）パウレック製］等が挙げられ、更に横型の混合槽を有するミキサーで鋤歯若しくは鋸歯状撹拌翼を装着したもの、例えばレーディゲミキサー〔（株）マツボー製〕、プローシェアーミキサー〔大平洋機工（株）製〕等が特に好ましい。
本工程において、水不溶性無機粉体を投入する前に攪拌翼を作動させ、攪拌翼を回転させながら水不溶性無機粉体を投入しても良いし、水不溶性無機粉体を全て投入した後に攪拌し始めても良い。
攪拌は、攪拌軸の回転数を５０〜３００ｒｐｍで行うのが好ましい。また、攪拌翼を周速度（ｕ）１．５〜７．０ｍ／ｓｅｃの範囲で回転させることにより行うのが好ましい。
より好ましくは２．１〜６．２ｍ／ｓｅｃ．、更に好ましくは２．３〜６．０ｍ／ｓｅｃ．である。このような範囲内で攪拌混合を行うことにより、溶解性に優れた非イオン性界面活性剤含有粒子を得ることができる。<Method for Producing Nonionic Surfactant-Containing Particles of the Present Invention>
Process (i)
As a granulator which can be used in the present invention, it is preferable to use a granulator having a stirring and mixing function and a shearing function. For example, the inside of the device has a stirring shaft inside and is equipped with a stirring blade for mixing and a stirring blade for crushing, or the entire device rotates without having a stirring blade inside. What can stir and mix the filled content is mention | raise | lifted. A stirring granulator having a clearance of 1 to 30 mm, more preferably 3 to 10 mm, between the stirring blade and the inner wall surface of the granulating device is preferable. If the clearance is less than 1 mm, the mixer tends to be overpowered by the adhesion layer. If it exceeds 30 mm, the consolidation efficiency is lowered, so the particle size distribution is broad, and the granulation time is lengthened, which may reduce the productivity. Examples of such an apparatus include a high-speed mixer [Fukae Kogyo Co., Ltd.], a vertical granulator [Powrec Co., Ltd.], etc., and a mixer having a horizontal mixing tank with a toothed or serrated shape. Particularly preferred are those equipped with a stirring blade, such as a Laedige mixer (manufactured by Matsubo Co., Ltd.), a pro-shear mixer (manufactured by Taihei Koki Co., Ltd.), and the like.
In this step, the stirring blade may be operated before the water-insoluble inorganic powder is charged, and the water-insoluble inorganic powder may be charged while the stirring blade is rotated. You may start doing.
Stirring is preferably performed at a rotation speed of the stirring shaft of 50 to 300 rpm. Moreover, it is preferable to carry out by rotating a stirring blade in the range of peripheral speed (u) 1.5-7.0 m / sec.
More preferably, 2.1 to 6.2 m / sec. More preferably, it is 2.3-6.0 m / sec. It is. By carrying out stirring and mixing within such a range, nonionic surfactant-containing particles having excellent solubility can be obtained.
工程（ii）
本発明において、非イオン性界面活性剤を造粒装置に投入する前に、水不溶性無機粉体の少なくとも一部を造粒装置内壁に付着させる。この結果、造粒装置内壁に造粒物等が付着して、稼働率が低下するのを抑制することが出来る。水不溶性無機粉体を造粒装置内壁に付着させるためには、水不溶性無機粉体そのものが有する付着力と装置内壁との親和力が重要である。例えば、装置内壁の材料がステンレスなどの金属である場合、水不溶性無機粉体を該内壁に付着させるには、水不溶性無機粉体の平均粒子径を１０μｍ以下にし、主軸を回転させることで摩擦を起こさせることにより達成することができる。
攪拌は、工程（i）の回転数、周速度と同じでも異なっていても良い。このような範囲内で攪拌混合を行うことにより、水不溶性無機粉体を造粒装置内壁に付着させることができる。
なお、本工程において水溶性無機粉体を投入することは好ましくない。その理由としては、メカニズムは解明できていないが水溶性無機粉体が、既に装置内壁に付着している造粒物粉体層と水分を介在した複合物を形成し、水不溶性無機粉体の付着層形成を妨げるため、と推定されるが、如何なる理論にも拘束されるものではない。Step (ii)
In the present invention, before introducing the nonionic surfactant into the granulator, at least a part of the water-insoluble inorganic powder is adhered to the inner wall of the granulator. As a result, it is possible to prevent the operation rate from being reduced due to adhesion of the granulated material or the like to the inner wall of the granulator. In order for the water-insoluble inorganic powder to adhere to the inner wall of the granulator, the adhesion between the water-insoluble inorganic powder itself and the inner wall of the device is important. For example, when the material of the inner wall of the apparatus is a metal such as stainless steel, in order to adhere the water-insoluble inorganic powder to the inner wall, the average particle diameter of the water-insoluble inorganic powder is set to 10 μm or less, and the main shaft is rotated to cause friction. This can be achieved by causing
Stirring may be the same as or different from the rotational speed and peripheral speed in step (i). By performing stirring and mixing within such a range, the water-insoluble inorganic powder can be adhered to the inner wall of the granulator.
In addition, it is not preferable to introduce water-soluble inorganic powder in this step. The reason for this is that the water-insoluble inorganic powder forms a composite with the granulated powder layer already adhering to the inner wall of the device and moisture, but the mechanism has not been elucidated. This is presumed to prevent adhesion layer formation, but is not bound by any theory.
工程（iii）
水溶性無機粉体と非イオン性界面活性剤を造粒装置に添加する工程としては、例えば次の1)〜4)の方法のうちいずれの方法を採用する事ができる。
1) 粉体層を形成させた後、造粒装置に水溶性無機粉体を投入し速やかに非イオン界面活性剤を添加する。
2) 粉体層を形成させた後、造粒装置に水溶性無機粉体と非イオン界面活性剤を同時に添加する。
3) 粉体層を形成させた後、造粒装置に少量の非イオン界面活性剤を添加し、更に残りの非イオン界面活性剤と水溶性無機粉体を添加する。
4) 粉体層を形成させた後、造粒装置に水溶性無機粉体と非イオン界面活性剤の混合物を添加する。
これらの中で、造粒装置に水溶性無機粉体を投入し速やかに非イオン界面活性剤を添加する方法が特に好ましい。また、水不溶性無機粉体の一部を水溶性無機粉体若しくは、非イオン界面活性剤と共に添加することも可能である。その量については、非イオン界面活性剤含有粒子中の粉体層形成時に添加する水不溶性無機粉体量が２０重量％を下回らないのが好ましい。Step (iii)
As a step of adding the water-soluble inorganic powder and the nonionic surfactant to the granulator, any of the following methods 1) to 4) can be employed.
1) After forming the powder layer, the water-soluble inorganic powder is put into the granulator and the nonionic surfactant is quickly added.
2) After forming the powder layer, the water-soluble inorganic powder and the nonionic surfactant are simultaneously added to the granulator.
3) After forming the powder layer, a small amount of nonionic surfactant is added to the granulator, and the remaining nonionic surfactant and water-soluble inorganic powder are added.
4) After forming the powder layer, add a mixture of water-soluble inorganic powder and nonionic surfactant to the granulator.
Among these, a method in which water-soluble inorganic powder is introduced into a granulator and a nonionic surfactant is quickly added is particularly preferable. It is also possible to add a part of the water-insoluble inorganic powder together with the water-soluble inorganic powder or the nonionic surfactant. Regarding the amount thereof, it is preferable that the amount of water-insoluble inorganic powder added at the time of forming the powder layer in the nonionic surfactant-containing particles does not fall below 20% by weight.
工程（iv）
本工程において、水不溶性無機粉体、水溶性無機粉体及び非イオン性界面活性剤、及び必要により任意成分を共に剪断・圧密化することにより造粒する。
任意成分を配合する場合は、水溶性無機粉体と同時に造粒装置に投入するか、又は造粒装置に投入する前に水溶性無機粉体と混合してから該装置に投入することが好ましい。
更に、得られた非イオン性界面活性剤含有粒子に対して、例えば、転動ドラム中でコーティング剤を添加してコーティング処理してもよい。これにより、流動特性を改良することができる。コーティング剤としては、ＪＩＳ２００メッシュふるい通過分が５０％以上の無機質粉末が好適であり、素材的には例えば、炭酸ナトリウム、炭酸カルシウム等の炭酸塩や、非晶質シリカ、ケイ酸カルシウム、ケイ酸マグネシウム等のケイ酸塩、ゼオライト等のアルミノケイ酸塩等を使用することができる。コーティング剤は、本発明の非イオン性界面活性剤含有粒子中に、一般に０．５〜１５重量％、好ましくは１〜１０重量％の量で使用できる。Step (iv)
In this step, granulation is performed by shearing and compacting together the water-insoluble inorganic powder, the water-soluble inorganic powder, the nonionic surfactant, and optionally the optional components.
When blending optional components, it is preferable to put into the granulator at the same time as the water-soluble inorganic powder, or to mix with the water-soluble inorganic powder before feeding into the granulator and then into the device. .
Further, the obtained nonionic surfactant-containing particles may be coated, for example, by adding a coating agent in a rolling drum. Thereby, a flow characteristic can be improved. As the coating agent, an inorganic powder having a JIS 200 mesh sieve passing rate of 50% or more is suitable. Examples of the material include carbonates such as sodium carbonate and calcium carbonate, amorphous silica, calcium silicate, and silicic acid. Silicates such as magnesium and aluminosilicates such as zeolite can be used. The coating agent can be generally used in the nonionic surfactant-containing particles of the present invention in an amount of 0.5 to 15% by weight, preferably 1 to 10% by weight.
＜製造条件＞
（１）フルード数（Ｆｒ）
撹拌造粒法においては、下記式で定義されるフルード数は１〜１６であるのが好ましく、２〜９がより好ましい。前記フルード数が１未満であると、流動化が不十分であるため高分子によるコーティングも不十分となる場合がある。一方、１６を超えると粒子に対するせん断力が強くなり過ぎコーティング膜に壊れが発生する場合がある。
Ｆｒ＝Ｖ2／（Ｒ×ｇ）
Ｖ：撹拌羽根の先端の周速（ｍ／ｓ）
Ｒ：撹拌羽根の回転半径（ｍ）
ｇ：重力加速度（ｍ／ｓ2）
（２）チョッパー回転数
撹拌造粒法において、使用される撹拌造粒装置には、造粒物の圧密化促進及び粗粉解砕促進の為に高速で回転するチョッパーが装備されている。チョッパーの回転速度としてはコーティング膜の壊れが発生しない程度の回転数が好ましい。チョッパー先端速度（周速）で０〜４０ｍ／ｓが好ましく、５〜３０ｍ／ｓがより好ましい。<Production conditions>
(1) Fluid number (Fr)
In the stirring granulation method, the fluid number defined by the following formula is preferably 1 to 16, and more preferably 2 to 9. When the Froude number is less than 1, fluidization is insufficient, so that coating with a polymer may be insufficient. On the other hand, if it exceeds 16, the shearing force on the particles becomes too strong, and the coating film may be broken.
Fr = V2 / (R × g)
V: peripheral speed at the tip of the stirring blade (m / s)
R: Rotating radius of stirring blade (m)
g: Gravity acceleration (m / s 2 )
(2) Chopper rotation speed In the stirring granulation method, the stirring granulator used is equipped with a chopper that rotates at a high speed for promoting compaction and coarse powder crushing of the granulated product. The rotation speed of the chopper is preferably such that the coating film is not broken. The chopper tip speed (circumferential speed) is preferably 0 to 40 m / s, and more preferably 5 to 30 m / s.
（３）造粒時間
撹拌造粒法において、好適な造粒物を得るための回分式の造粒における造粒時間及び連続式の造粒における平均滞留時間は、０．５〜３０分が好ましく、３〜２０分がより好ましい。造粒時間（平均滞留時間）が０．５分未満であると、時間が短過ぎて好適な平均粒子径及び嵩密度を得るための造粒制御が困難となり、粒度分布がブロードになる場合がある一方、３０分を超えると時間が長過ぎて生産性が低下する場合がある。
（４）非イオン界面活性剤含有粒子製造時の充填率
撹拌造粒法において、非イオン性界面活性剤の造粒装置への充填率（仕込み量）としては、混合機の全内容積の７０容量％以下が好ましく、１５〜５５容量％がより好ましい。充填率（仕込み量）が、７０容量％を超えると混合機内での混合効率が低下し、好適に造粒を行うことができない場合がある。
（５）造粒温度
撹拌造粒の温度は、一般に２０〜６０℃、好ましくは３０〜５０℃、更に好ましくは３５〜５０℃である。温度が２０℃よりも低い場合には、造粒が進みにくく、好ましくない。一方、温度が６０℃よりも高くなると、逆に、造粒装置への付着が生じやすくなるので好ましくない。(3) Granulation time In the stirring granulation method, the granulation time in batch granulation and the average residence time in continuous granulation for obtaining a suitable granulated product are preferably 0.5 to 30 minutes. 3 to 20 minutes are more preferable. If the granulation time (average residence time) is less than 0.5 minutes, the time is too short and it becomes difficult to control granulation to obtain a suitable average particle size and bulk density, and the particle size distribution may become broad. On the other hand, if it exceeds 30 minutes, the time may be too long and the productivity may decrease.
(4) Filling rate during production of nonionic surfactant-containing particles In the stirring granulation method, the filling rate (charge amount) of the nonionic surfactant into the granulator is 70 of the total internal volume of the mixer. The volume% or less is preferable, and 15 to 55 volume% is more preferable. If the filling rate (preparation amount) exceeds 70% by volume, the mixing efficiency in the mixer may be lowered, and granulation may not be performed appropriately.
(5) Granulation temperature The temperature of stirring granulation is generally 20 to 60 ° C, preferably 30 to 50 ° C, more preferably 35 to 50 ° C. When the temperature is lower than 20 ° C., granulation is difficult to proceed, which is not preferable. On the other hand, when the temperature is higher than 60 ° C., it is not preferable because adhesion to the granulator tends to occur.
＜非イオン性界面活性剤含有粒子の物性＞
本発明の非イオン界面活性剤含有粒子の粒子強度は、粒子圧縮試験法により測定することができ、通常、５５ｇ以上、好ましくは７５ｇ以上である。
嵩密度は、ＪＩＳ Ｋ３３６２の方法により測定することができ、通常、０．３ｇ／ｍＬ以上、好ましくは０．５〜１．３ｇ／ｍＬ、より好ましくは０．５〜１．２／ｍＬである。嵩密度が小さ過ぎても大きすぎても他の粒子と混合して使用する際に分級しやすくなる。
平均粒子径は、ロータップ式篩振とう機により測定することができ、好ましくは１５０〜１５００μｍ、より好ましくは２００〜１０００μｍである。平均粒子径が１５０μｍ未満になると、比表面積が大き過ぎ、発塵が多くなる可能性があり、一方、１５００μｍを超えると被覆粒子そのものの溶解性が劣化する場合がある。
安息角は、ＪＩＳ Ｋ２５０２の方法により測定することができ、通常、３０〜６０°、好ましくは３０〜５０°である。
圧壊値とは、粉体の自重によってその粉体が流動性を維持できるかの指標で、後述する（物性測定）（４）に示す方法により測定することができる。通常、３ｋｇ以下、好ましくは２ｋｇ以下である。<Physical properties of nonionic surfactant-containing particles>
The particle strength of the nonionic surfactant-containing particles of the present invention can be measured by a particle compression test method, and is usually 55 g or more, preferably 75 g or more.
The bulk density can be measured by the method of JIS K3362, and is usually 0.3 g / mL or more, preferably 0.5 to 1.3 g / mL, more preferably 0.5 to 1.2 / mL. . When the bulk density is too small or too large, it becomes easy to classify when used by mixing with other particles.
The average particle diameter can be measured with a low-tap sieve shaker, and is preferably 150 to 1500 μm, more preferably 200 to 1000 μm. When the average particle diameter is less than 150 μm, the specific surface area is too large and dust generation may increase. On the other hand, when the average particle diameter exceeds 1500 μm, the solubility of the coated particles themselves may be deteriorated.
The angle of repose can be measured by the method of JIS K2502, and is usually 30 to 60 °, preferably 30 to 50 °.
The crushing value is an index of whether the powder can maintain fluidity by its own weight, and can be measured by the method shown in (Physical property measurement) (4) described later. Usually, it is 3 kg or less, preferably 2 kg or less.
以下、本発明について、実施例及び比較例により更に詳細に説明する。
（他の洗剤含有粒子）
ＬＡＳ−Ｈ：直鎖アルキルベンゼンスルホン酸（ライオン（株）製、ライポンＬＨ−２００）
α−ＳＦ−Ｈ：α−スルホ脂肪酸アルキルエステル（メチルエステル（パステルＭ−１４、パステルＭ−１６（ライオンオレオケミカル（株）製）を２：８で混合したもの）を特開２００１−６４２４８号公報の実施例１で開示されている方法に準拠してスルホン化し、エステル化工程後に抜き出しα−スルホ脂肪酸アルキルエステルとしたもの）
石鹸：ライオン（株）製
ノニオン：ライオン（株）製
ポリアクリル酸Ｎａ：アクアリックＤＬ−４０（日本触媒（株）製）（純分４０％水溶液）
アクリル酸／マレイン酸コポリマー：アクアリックＴＬ−４００（日本触媒（株）製） Ａ型ゼオライト：シクロンＢ（水沢化学（株）製）
炭酸カリウム：炭酸カリウム（粉末）（旭硝子（株）製）(Other detergent-containing particles)
LAS-H: linear alkylbenzene sulfonic acid (Lypon LH-200, manufactured by Lion Corporation)
α-SF-H: α-sulfo fatty acid alkyl ester (methyl ester (Pastel M-14, Pastel M-16 (manufactured by Lion Oleochemical Co., Ltd.) mixed at 2: 8)) is disclosed in JP-A No. 2001-64248. Sulfonated according to the method disclosed in Example 1 of the publication, extracted after the esterification step and made into α-sulfo fatty acid alkyl ester)
Soap: manufactured by Lion Co., Ltd. Nonion: manufactured by Lion Co., Ltd. Polyacrylic acid Na: Aqualic DL-40 (manufactured by Nippon Shokubai Co., Ltd.) (pure 40% aqueous solution)
Acrylic acid / maleic acid copolymer: Aqualic TL-400 (manufactured by Nippon Shokubai Co., Ltd.) A-type zeolite: Cyclon B (manufactured by Mizusawa Chemical Co., Ltd.)
Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd.)
＜非イオン性界面活性剤含有粒子の製造）＞
上記原料を用い、実施例１〜６については表１、比較例１〜５については表２に示す比率、添加順序で各種原料をレーデイゲミキサー〔（株）マツボー製Ｍ−２０型、内容積２０Ｌ、撹拌翼直径０．３ｍ〕にて非イオン性界面活性剤含有粒子を得た。
具体的には、実施例１においては、Ａ−１及びＡ−２の水不溶性無機粉体を装置に添加し、主軸２００ｒｐｍ、チョッパー５８００ｒｐｍの条件でＡｉｒを混入させつつ攪拌、粉体層を形成した後に非イオン性界面活性剤Ｃ−１と水溶性無機粉体Ｂ−２をそれぞれ別の添加口より添加した。
実施例２においては、添加する非イオン性界面活性剤及び水溶性無機粉体の種類を変えたこと以外は実施例１と同様の操作を行った。
実施例３においては、Ａ−１及びＡ−３の水不溶性無機粉体を装置に添加し、主軸２００ｒｐｍ、チョッパー５８００ｒｐｍの条件でＡｉｒを混入させつつ攪拌、粉体層を形成した後に非イオン性界面活性剤Ｃ−３と水溶性無機粉体Ｂ−１を予め混合した後に添加した。
実施例４においては、添加する非イオン性界面活性剤及び水溶性無機粉体の種類を変えたこと以外は実施例３と同様の操作を行った。
実施例５及び６は、添加する非イオン性界面活性剤及び水溶性無機粉体の種類を変え、実施例１と同様の操作を行った。
比較例１は、主軸２００ｒｐｍ、チョッパー５８００μｍの条件で攪拌しているレーデイゲミキサーに非イオン性界面活性剤Ｃ−２、水不溶性無機粉体Ａ−１、Ａ−５、水溶性無機粉体Ｂ−４を同時に添加した。
比較例２は、主軸２００ｒｐｍ、チョッパー５８００μｍの条件で攪拌しているレーデイゲミキサーに非イオン性界面活性剤Ｃ−１を添加した後、水不溶性無機粉体、水溶性無機粉体を添加した。
比較例３は、非イオン性界面活性剤、水溶性無機粉体を予め混合した後にレーデイゲミキサーに添加し、その後、水不溶性無機粉体を添加した。
ここで、充填率は投入する全ての粉体容積が内容積の５０vol％となるようにし、一方、添加する非イオン界面活性剤の供給速度は１L/minで添加した。最後に３０秒間混合し、非イオン性界面活性剤含有粒子を得た。<Production of nonionic surfactant-containing particles>
Using the above raw materials, various raw materials were mixed in the ratio and addition order shown in Table 1 for Examples 1 to 6 and Table 2 for Comparative Examples 1 to 5 [M-20, made by Matsubo Co., Ltd., contents Nonionic surfactant-containing particles were obtained at a product volume of 20 L and a stirring blade diameter of 0.3 m].
Specifically, in Example 1, water-insoluble inorganic powders A-1 and A-2 were added to the apparatus, and stirring and powder layer formation were performed while mixing Air under the conditions of the main shaft 200 rpm and the chopper 5800 rpm. After that, nonionic surfactant C-1 and water-soluble inorganic powder B-2 were added through separate addition ports.
In Example 2, the same operation as in Example 1 was performed except that the types of the nonionic surfactant and the water-soluble inorganic powder to be added were changed.
In Example 3, the water-insoluble inorganic powders A-1 and A-3 were added to the apparatus, and the mixture was stirred while air was mixed under the conditions of the main shaft 200 rpm and the chopper 5800 rpm. Surfactant C-3 and water-soluble inorganic powder B-1 were added after mixing in advance.
In Example 4, the same operation as in Example 3 was performed except that the types of the nonionic surfactant and the water-soluble inorganic powder to be added were changed.
In Examples 5 and 6, the same operations as in Example 1 were performed by changing the types of the nonionic surfactant and the water-soluble inorganic powder to be added.
In Comparative Example 1, a non-ionic surfactant C-2, water-insoluble inorganic powders A-1 and A-5, water-soluble inorganic powders were added to a Reidege mixer that was stirred under conditions of a main shaft of 200 rpm and a chopper of 5800 μm. B-4 was added simultaneously.
In Comparative Example 2, after adding the nonionic surfactant C-1 to the Reidege mixer stirred under the conditions of the main shaft 200 rpm and the chopper 5800 μm, the water-insoluble inorganic powder and the water-soluble inorganic powder were added. .
In Comparative Example 3, a nonionic surfactant and a water-soluble inorganic powder were mixed in advance and then added to a Reedige mixer, and then a water-insoluble inorganic powder was added.
Here, the filling rate was such that the total powder volume to be charged was 50 vol% of the internal volume, while the supply rate of the nonionic surfactant to be added was 1 L / min. Finally, mixing was performed for 30 seconds to obtain nonionic surfactant-containing particles.
＜他の洗剤含有粒子の製造方法＞
表−３記載の他の洗剤含有粒子の組成のうち、非イオン性界面活性剤、３．０％相当量の粉砕助剤用及び０．５％相当量の表面被覆用のA型ゼオライト、酵素、色素及び香料を除く成分を水に溶解若しくは分散させた水分３８％のスラリーを調製した後、向流式噴霧乾燥塔を用いて熱風温度３００℃の条件で噴霧乾燥し、水分３％の噴霧乾燥粒子を得た。この乾燥粒子と共に、非イオン性界面活性剤及び水を連続ニーダー（（株）栗本鐵工所製、ＫＲＣ−Ｓ４型）に投入し、捏和能力１２０kg/h、温度６０℃の条件で捏和し、不定形固形洗剤を得た。この不定形固形洗剤を穴径１０ｍｍのダイスを装備したペレッターダブル（不二パウダル(株)製、ＥＸＤＦＪＳ−１００型）を用いて押し出しつつ、カッターで切断し（カッター周速は５ｍ／ｓ）長さ５〜３０ｍｍ程度のペレット状固形洗剤を得た。
次いで、得られた固形洗剤に粉砕助剤としての粒子状A型ゼオライト（平均粒子径１８０μｍ）を４．２％添加し、冷風（１０℃、１５m/s）共存下で直列３段に配置したフィッツミル（ホソカワミクロン（株）製、ＤＫＡ−３）を用いて粉砕した（スクリーン穴径：１段目／２段目／３段目＝１２mm／６mm／２mm、回転数：全段４７００rpm）。最後に水平円筒型転動混合機（円筒直径５８５ｍｍ、円筒長さ４９０ｍｍ、容器１３１．７Ｌのドラム内部壁面に内部壁面とのクリアランス２０ｍｍ、高さ４５ｍｍの邪魔板を２枚有するもの）で、充填率３０％、回転数２２ｒｐｍ、２５℃の条件で０．５％の微粉A型ゼオライト加え、１分間転動し表面改質して、洗剤粒子を得た。
次いで、水平円筒型転動混合機（円筒直径５８５ｍｍ、円筒長さ４９０ｍｍ、容器１３１．７Ｌのドラム内部壁面に内部壁面とのクリアランス２０ｍｍ、高さ４５ｍｍの邪魔板を２枚有するもの）で、充填率３０％、回転数２２ｒｐｍ、２５℃の条件で得られた洗剤粒子を混合しつつ、０．１％相当量の香料を噴霧して洗剤粒子に賦香した。
次いで、得られた洗剤粒子の一部を着色するために、洗剤粒子をベルトコンベアで０．５ｍ／ｓの速度で移送しつつ（ベルトコンベア上の洗剤粒子層高３０ｍｍ、層幅３００ｍｍ）その表面に青色色素溶液を噴霧し、洗剤粒子（平均粒径５５０μｍ、嵩密度０．８５ｇ／ｃｍ3）を得た。<Method for producing other detergent-containing particles>
Among the compositions of other detergent-containing particles described in Table 3, non-ionic surfactants, A-type zeolite for 3.0% equivalent amount of grinding aid and 0.5% equivalent amount of surface coating, enzyme After preparing a slurry with a water content of 38% in which components other than pigments and fragrances are dissolved or dispersed in water, the slurry is spray-dried at a hot air temperature of 300 ° C. using a countercurrent spray drying tower, and sprayed with a water content of 3%. Dry particles were obtained. Along with these dry particles, a nonionic surfactant and water were added to a continuous kneader (Kurimoto Steel Works, KRC-S4 type), and kneaded under conditions of a kneading capacity of 120 kg / h and a temperature of 60 ° C. Thus, an amorphous solid detergent was obtained. This unshaped solid detergent is extruded with a pelleter double equipped with a die with a hole diameter of 10 mm (EXDFJS-100 type, manufactured by Fuji Powder Co., Ltd.) and cut with a cutter (cutter peripheral speed is 5 m / s) A pellet-shaped solid detergent having a length of about 5 to 30 mm was obtained.
Next, 4.2% of particulate A-type zeolite (average particle size: 180 μm) as a grinding aid was added to the obtained solid detergent, and arranged in three stages in series in the presence of cold air (10 ° C., 15 m / s). The resultant was pulverized using a Fitzmill (manufactured by Hosokawa Micron Corporation, DKA-3) (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 2 mm, rotation speed: 4700 rpm in all stages). Finally, filled with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, the inner wall surface of the drum of the container 131.7L has two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm) 0.5% fine powder A-type zeolite was added under the conditions of a rate of 30%, a rotation speed of 22 rpm, and 25 ° C., and rolled for 1 minute to surface-modify to obtain detergent particles.
Next, filling with a horizontal cylindrical rolling mixer (cylinder diameter: 585 mm, cylinder length: 490 mm, inner wall surface of drum of container 131.7L having two baffle plates with clearance of 20 mm from inner wall surface and height of 45 mm) While mixing the detergent particles obtained under the conditions of a rate of 30%, a rotation speed of 22 rpm, and 25 ° C., a perfume equivalent to 0.1% was sprayed to perfume the detergent particles.
Next, in order to color a part of the obtained detergent particles, the detergent particles are transferred on the belt conveyor at a speed of 0.5 m / s (the detergent particle layer height on the belt conveyor is 30 mm, the layer width is 300 mm). The blue pigment solution was sprayed onto the resulting product to obtain detergent particles (average particle size 550 μm, bulk density 0.85 g / cm 3 ).
（物性の測定）
下記方法に基づいて非イオン性界面活性剤含有粒子の平均粒子径、嵩密度、安息角、圧壊値、及び他の洗剤含有粒子と混合したときの非イオン性界面活性剤含有粒子の布付着を評価した。
（１）平均粒子径の測定
目開き１６８０μｍ、１４１０μｍ、１１９０μｍ、１０００μｍ、７１０μｍ、５００μｍ、３５０μｍ、２５０μｍ、１４９μｍ、の９段の篩と受け皿を用いて分級操作を行なった。分級操作は、受け皿に目開きの小さな篩から目開きの大きな篩の順に積み重ね、最上部の１６８０μｍの篩の上から１００ｇ／回の非イオン性界面活性剤含有粒子を入れ、蓋をしてロータップ型ふるい振盪機（（株）飯田製作所製、タッピング：１５６回／分、ローリング：２９０回／分）に取り付け、１０分間振動させた後、それぞれの篩及び受け皿上に残留したサンプルを篩目ごとに回収する操作を行った。(Measurement of physical properties)
Based on the following method, the average particle size, bulk density, angle of repose, crush value of nonionic surfactant-containing particles, and cloth adhesion of nonionic surfactant-containing particles when mixed with other detergent-containing particles evaluated.
(1) Measurement of average particle diameter Classification operation was performed using a 9-stage sieve and a saucer having openings of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm. In the classification operation, a sieve with a small opening is stacked on a tray in the order of a sieve with a large opening, and 100 g / times of nonionic surfactant-containing particles are put on the top of the top 1680 μm sieve. Attached to a type sieve shaker (manufactured by Iida Seisakusho Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute), after shaking for 10 minutes, each sample remaining on each sieve and tray is sieved The operation to collect was performed.
この操作を繰すことによって１４１０〜１６８０μｍ（１４１０μｍ．ｏｎ）、１１９０〜１４１０μｍ（１１９０μｍ．ｏｎ）、１０００〜１１９０μｍ（１０００μｍ．ｏｎ）、１０００〜７１０μｍ（７１０μｍ．ｏｎ）５００〜７１０μｍ（５００μｍ．ｏｎ）、３５０〜５００μｍ（３５０μｍ．ｏｎ）、２５０〜３５０μｍ（２５０μｍ．ｏｎ）、１４９〜２５０μｍ（１４９μｍ．ｏｎ）、皿〜１４９μｍ（１４９μｍ．ｐａｓｓ）の各粒子径の分級サンプルを得、重量頻度（％）を算出した。
次に、算出した重量頻度が５０％以上となる最初の篩の目開きをａμｍとし、またａμｍよりも一段大きい篩の目開きをｂμｍとし、受け皿からａμｍの篩までの重量頻度の積算をｃ％、またａμｍの篩上の重量頻度をｄ％として、次式によって平均粒子径（重量５０％）を求めた。By repeating this operation, 1410 to 1680 μm (1410 μm.on), 1190 to 1410 μm (1190 μm.on), 1000 to 1190 μm (1000 μm.on), 1000 to 710 μm (710 μm.on) 500 to 710 μm (500 μm.on) , 350 to 500 μm (350 μm.on), 250 to 350 μm (250 μm.on), 149 to 250 μm (149 μm.on), dish to 149 μm (149 μm.pass), and classification samples with respective particle diameters were obtained. ) Was calculated.
Next, the opening of the first sieve with a calculated weight frequency of 50% or more is set to a μm, the opening of the sieve that is one step larger than a μm is set to b μm, and the cumulative weight frequency from the tray to the sieve of a μm is calculated as c %, And the weight frequency on a μm sieve was d%, and the average particle diameter (weight 50%) was determined by the following formula.
平均粒子径（重量５０％径）＝
１０(50-(c-d/(log b-log a) x log b))/(d/(log b-log a))Average particle diameter (weight 50% diameter) =
10 (50- (cd / (log b-log a) x log b)) / (d / (log b-log a))
（２）嵩密度の測定
嵩密度はＪＩＳ Ｋ３３６２に準じて測定した。
（３）安息角
ＪＩＳ Ｚ２５０２に準じて測定した。
（４）圧壊値
非イオン性界面活性剤含有粒子を直径５ｃｍ、高さ５ｃｍの円筒形の筒に均一になるように入れ、４５℃恒温槽中で３Ｋｇの荷重を３分加えて成形した後、得られた成形体をメトラーの上に静置し、３ｃｍ／分の条件で荷重を加え、成形体が崩壊するまでにかかった最大荷重（Ｋｇ）を測定した。
◎…最大加重が１ｋｇｆ未満
○…最大加重が１〜３ｋｇｆ
△…最大加重が３〜５ｋｇｆ
×…最大加重が５ｋｇｆ以上
製造上のハンドリング性を考慮すると〇以上の評価が好ましい。(2) Measurement of bulk density The bulk density was measured according to JIS K3362.
(3) Angle of repose Measured according to JIS Z2502.
(4) Crushing value After putting nonionic surfactant-containing particles uniformly into a cylindrical cylinder having a diameter of 5 cm and a height of 5 cm, and molding by applying a load of 3 kg for 3 minutes in a 45 ° C. constant temperature bath Then, the obtained molded body was allowed to stand on a Mettler, a load was applied under the condition of 3 cm / min, and the maximum load (Kg) applied until the molded body collapsed was measured.
◎… Maximum load is less than 1 kgf ○… Maximum load is 1 to 3 kgf
Δ: Maximum load is 3-5kgf
X: The maximum load is 5 kgf or more. Considering the handleability in production, an evaluation of ◯ or more is preferable.
（５）粒子強度の測定
ＪＩＳ１４メッシュ篩を通過し、ＪＩＳ１６メッシュ篩を通過しない非イオン界面活性剤粒子１０サンプルを、(株)フロンテックス製圧縮試験機Ｓ４７９−００４−＃を用いて圧縮速度０．１０ｍｍ／ｓの条件で粒子強度を測定した。この値の平均値をとり評価した。
◎…最大強度が７５ｇ以上
○…最大強度が５５〜７５ｇ
△…最大強度が４０〜５５ｇ
×…最大強度が４０ｇ以下
使用上の利便性を考慮すると〇以上の評価が好ましい。(5) Measurement of particle strength 10 samples of nonionic surfactant particles that pass through a JIS14 mesh sieve but do not pass through a JIS16 mesh sieve are compressed using a compression tester S479-004- # manufactured by Frontex Co., Ltd. The particle strength was measured under the condition of 10 mm / s. Evaluation was made by taking the average of these values.
◎… Maximum strength is 75g or more ○… Maximum strength is 55 to 75g
Δ: Maximum strength is 40 to 55 g
X: Maximum strength is 40 g or less Considering convenience in use, an evaluation of ◯ or more is preferable.
（６）布付着
二槽式洗濯機（三菱電機（株）製、ＣＷ−Ｃ３０Ａ１−Ｈ）に、５℃の水道水３０Ｌを張り、綿肌シャツ７枚、ポリエステルシャツ２枚、アクリルシャツ２枚で浴比２０倍に調整し、それらを折り畳んで水面に浮かべた。その中心に非イオン界面活性剤含有粒子と表３に示す他の洗剤含有粒子とを20/80の比率で混合した粉体30ｇを溶解性試験用サンプルとし、布ごと２分間浸漬後、弱水流で５分間撹拌した。排水後、布を１分間脱水し、布上と洗濯機中にある溶け残りを拾い出し、目視にて溶け残り量を下記評価基準に基づいて評価した。
◎：溶け残りがほとんどない
○：溶け残りがやや見られるが問題ないレベル
△：溶け残りが目立つ
×：溶け残りが著しく見られる
家庭における使用性を考慮すると、洗剤組成物としては○以上の評価が好ましい。(6) Cloth adhesion Two tank type washing machine (Mitsubishi Electric Co., Ltd., CW-C30A1-H) is filled with 30L of tap water at 5 ° C, 7 cotton shirts, 2 polyester shirts, 2 acrylic shirts The bath ratio was adjusted to 20 times, and they were folded and floated on the water surface. At the center, 30 g of powder containing nonionic surfactant-containing particles and other detergent-containing particles shown in Table 3 mixed at a ratio of 20/80 is used as a sample for solubility test. For 5 minutes. After draining, the cloth was dehydrated for 1 minute, the undissolved residue on the cloth and in the washing machine was picked up, and the undissolved amount was visually evaluated based on the following evaluation criteria.
◎: There is almost no undissolved residue ○: Undissolved residue is slightly seen but there is no problem △: Undissolved residue is conspicuous ×: Undissolved residue is noticeable Considering the usability at home, the detergent composition is rated as better than ○ Is preferred.
（７）造粒装置付着性の評価
レーデイゲミキサー〔（株）マツボー製Ｍ−２０型、内容積２０Ｌ、撹拌翼直径０．３ｍ〕における造粒時の攪拌翼(主軸)負荷により評価した。
◎…最大負荷が４．３Ａ以内
○…最大負荷が４．４〜４．５Ａ
△…最大負荷が４．６〜５．０Ａ
×…最大負荷が５．０Ａ以上で造粒装置が振動する。
製造上の安定性を考慮すると〇以上の評価が好ましい。(7) Evaluation of adhesion of granulator Evaluated by load on stirring blade (main shaft) during granulation in Ladige mixer [M-20 type manufactured by Matsubo, internal volume 20L, stirring blade diameter 0.3m] .
◎… Maximum load is within 4.3A ○… Maximum load is 4.4 to 4.5A
Δ: Maximum load is 4.6 to 5.0 A
X: The granulator vibrates when the maximum load is 5.0 A or more.
Considering stability in production, an evaluation of ◯ or more is preferable.
（８）造粒装置洗浄性の評価
実施例および比較例に示した組成を10Bt繰り返し造粒し、その後の造粒内付着物を50℃温水で洗浄した場合の状況を以下の尺度で評価した。評価にはレーデイゲミキサー〔（株）マツボー製Ｍ−２０型、内容積２０Ｌ、撹拌翼直径０．３ｍ〕を用いた。
◎…1〜2回でほぼ付着物が無くなった。
○…1〜2回で付着物が若干残ったが、3〜4回で付着物がほぼ無くなった。
△…3〜4回で付着物が若干残った。
×…3〜4回で付着物が残り、次回の生産時に撹拌翼の負荷が高いままとなり再度
洗浄を要した。
製造上の安定性を考慮すると〇以上の評価が好ましい。(8) Evaluation of granulator cleanability The composition shown in Examples and Comparative Examples was repeatedly granulated 10Bt, and the situation when the adhered material in the granulation was washed with warm water at 50 ° C was evaluated according to the following scale. . For evaluation, a Reidege mixer (M-20 type, manufactured by Matsubo Co., Ltd., internal volume 20 L, stirring blade diameter 0.3 m) was used.
◎… There was almost no deposit in 1 to 2 times.
○: Some deposits remained after 1 to 2 times, but almost 3 to 4 times.
Δ: Some deposits remained after 3-4 times.
X: Deposits remained 3 to 4 times, and the load on the stirring blade remained high during the next production, requiring cleaning again.
Considering stability in production, an evaluation of ◯ or more is preferable.
Claims (8)
（Ｂ）吸油能が３０ｍＬ／１００ｇ以下である水溶性無機粉体、及び
（Ｃ）非イオン性界面活性剤
を含有してなる非イオン性界面活性剤含有粒子。(A) a water-insoluble inorganic powder having an oil absorption capacity of 15 mL / 100 g or more and less than 80 mL / 100 g;
(B) Water-soluble inorganic powder having an oil absorption capacity of 30 mL / 100 g or less, and (C) Nonionic surfactant-containing particles comprising a nonionic surfactant.
（Ｂ）水溶性無機粉体の平均粒子径が１５０μｍ以上４５０μｍ未満であり、及び
（Ｃ）の流動化点が６５℃以下である、
請求項１記載の非イオン性界面活性剤含有粒子。(A) The average particle size of the water-insoluble inorganic powder is 25 μm or less,
(B) The average particle diameter of the water-soluble inorganic powder is 150 μm or more and less than 450 μm, and the fluidization point of (C) is 65 ° C. or less.
The nonionic surfactant-containing particle according to claim 1.
（i）吸油能が１５ｍＬ／１００ｇ以上であり、かつ８０ｍＬ／１００ｇ未満である水不溶性無機粉体を、攪拌機能を備えた造粒装置に投入する工程、
（ii）前記造粒装置を作動させ、前記造粒装置に入っている水不溶性無機粉体を攪拌させることにより、少なくともその一部を該装置の内壁に付着させる工程、
（iii）さらに、吸油能が３０ｍＬ／１００ｇ以下の水溶性無機粉体、及び非イオン性界面活性剤を前記造粒装置に投入する工程、及び
（iv）前記造粒装置を作動させ、前記水不溶性無機粉体、前記水溶性無機粉体及び前記非イオン性界面活性剤を混合することにより、非イオン性界面活性剤含有粒子を造粒する工程、
を含む、前記製造方法。A method for producing nonionic surfactant-containing particles,
(I) a step of introducing a water-insoluble inorganic powder having an oil absorption capacity of 15 mL / 100 g or more and less than 80 mL / 100 g into a granulator equipped with a stirring function;
(Ii) actuating the granulator and stirring the water-insoluble inorganic powder contained in the granulator to attach at least a part thereof to the inner wall of the apparatus;
(Iii) a step of adding a water-soluble inorganic powder having an oil absorption capacity of 30 mL / 100 g or less and a nonionic surfactant to the granulator; and (iv) actuating the granulator, and A step of granulating nonionic surfactant-containing particles by mixing the insoluble inorganic powder, the water-soluble inorganic powder and the nonionic surfactant;
The said manufacturing method including.
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| JP2003221599A (en) * | 2002-01-30 | 2003-08-08 | Kao Corp | Granular fuller for powdery detergent |
-
2005
- 2005-08-15 JP JP2006531782A patent/JP4970036B2/en not_active Expired - Fee Related
- 2005-08-15 WO PCT/JP2005/014894 patent/WO2006016700A1/en active Application Filing
- 2005-08-15 KR KR1020077002199A patent/KR100841514B1/en active IP Right Grant
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0667117A (en) * | 1992-05-22 | 1994-03-11 | Kaiser Aerospace & Electron Corp | Field-sequence-type color headup display system |
| JP2000073096A (en) * | 1998-09-01 | 2000-03-07 | Lion Corp | Granular nonionic detergent composition and its production |
| JP2000109899A (en) * | 1998-10-01 | 2000-04-18 | Lion Corp | Atomization of nonionic surface active agent composition and preparation of granular detergent composition using the same |
| JP2000186300A (en) * | 1998-10-16 | 2000-07-04 | Kao Corp | Preparation of mononuclear detergent particle group |
| JP2000192098A (en) * | 1998-12-25 | 2000-07-11 | Lion Corp | Tablet detergent composition |
| JP2001081499A (en) * | 1999-09-17 | 2001-03-27 | Lion Corp | Manufacture of granulated detergent composition |
| JP2002255540A (en) * | 2000-12-28 | 2002-09-11 | Kao Corp | Microparticle zeolite |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20070029827A (en) | 2007-03-14 |
| KR100841514B1 (en) | 2008-06-25 |
| JP4970036B2 (en) | 2012-07-04 |
| WO2006016700A1 (en) | 2006-02-16 |
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