JP5213092B2 - Granular detergent composition for clothing, method for producing the same, and method for using the same - Google Patents
Granular detergent composition for clothing, method for producing the same, and method for using the same Download PDFInfo
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- JP5213092B2 JP5213092B2 JP2006225717A JP2006225717A JP5213092B2 JP 5213092 B2 JP5213092 B2 JP 5213092B2 JP 2006225717 A JP2006225717 A JP 2006225717A JP 2006225717 A JP2006225717 A JP 2006225717A JP 5213092 B2 JP5213092 B2 JP 5213092B2
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- Prior art keywords
- granular
- detergent composition
- component
- composition
- particle size
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 114
- 239000003599 detergent Substances 0.000 title claims description 87
- 238000000034 method Methods 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000002245 particle Substances 0.000 claims description 49
- 238000004140 cleaning Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000008187 granular material Substances 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 26
- 239000007844 bleaching agent Substances 0.000 claims description 25
- 239000003352 sequestering agent Substances 0.000 claims description 25
- 238000005469 granulation Methods 0.000 claims description 24
- 230000003179 granulation Effects 0.000 claims description 24
- 239000004094 surface-active agent Substances 0.000 claims description 23
- 229920001577 copolymer Polymers 0.000 claims description 22
- 239000000460 chlorine Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 17
- 102000004190 Enzymes Human genes 0.000 claims description 16
- 108090000790 Enzymes Proteins 0.000 claims description 16
- 238000010998 test method Methods 0.000 claims description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000271 synthetic detergent Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000009775 high-speed stirring Methods 0.000 claims description 8
- 239000005518 polymer electrolyte Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- DRAJWRKLRBNJRQ-UHFFFAOYSA-N Hydroxycarbamic acid Chemical class ONC(O)=O DRAJWRKLRBNJRQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000881 Modified starch Polymers 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 235000019426 modified starch Nutrition 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229920005615 natural polymer Polymers 0.000 claims description 2
- 238000001139 pH measurement Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims 2
- 239000003085 diluting agent Substances 0.000 claims 1
- -1 polyethylene Polymers 0.000 description 41
- 239000000843 powder Substances 0.000 description 22
- 239000002253 acid Substances 0.000 description 15
- 229940088598 enzyme Drugs 0.000 description 15
- 229910052783 alkali metal Inorganic materials 0.000 description 13
- 238000003860 storage Methods 0.000 description 13
- 239000012459 cleaning agent Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 229920001983 poloxamer Polymers 0.000 description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000004115 Sodium Silicate Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 230000021148 sequestering of metal ion Effects 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 229910052911 sodium silicate Inorganic materials 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 8
- 235000019795 sodium metasilicate Nutrition 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 238000004061 bleaching Methods 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002280 amphoteric surfactant Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- 235000019832 sodium triphosphate Nutrition 0.000 description 4
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007596 consolidation process Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- 239000000176 sodium gluconate Substances 0.000 description 3
- 235000012207 sodium gluconate Nutrition 0.000 description 3
- 229940005574 sodium gluconate Drugs 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000004382 Amylase Substances 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
- 239000004367 Lipase Substances 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- YYXLGGIKSIZHSF-UHFFFAOYSA-N ethene;furan-2,5-dione Chemical group C=C.O=C1OC(=O)C=C1 YYXLGGIKSIZHSF-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003752 hydrotrope Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 235000019421 lipase Nutrition 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 150000004686 pentahydrates Chemical class 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920001444 polymaleic acid Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- ZCQJTYXMYDQDLF-UHFFFAOYSA-M potassium iodide hydroiodide Chemical compound I.I[K] ZCQJTYXMYDQDLF-UHFFFAOYSA-M 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 235000019419 proteases Nutrition 0.000 description 2
- 229940095696 soap product Drugs 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 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 2
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- 229940045872 sodium percarbonate Drugs 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
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- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- XSXSKSKONCDOMZ-UHFFFAOYSA-N sodium;1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound [Na+].ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O XSXSKSKONCDOMZ-UHFFFAOYSA-N 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DTXLBRAVKYTGFE-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)-3-hydroxybutanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)C(O)C(C([O-])=O)NC(C([O-])=O)CC([O-])=O DTXLBRAVKYTGFE-UHFFFAOYSA-J 0.000 description 1
- XFLNVMPCPRLYBE-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XFLNVMPCPRLYBE-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
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- Detergent Compositions (AREA)
Description
本発明は、衣服、タオル、シーツ等の繊維品（以下、本発明では、これらを総称して「衣料」という）の洗浄に適し、特に電気洗濯機を用いた衣料の洗浄に適した衣料用粒状洗浄剤組成物およびその製法、並びにその使用方法に関するものである。 The present invention is suitable for washing textiles such as clothes, towels and sheets (hereinafter collectively referred to as “clothing” in the present invention), and particularly for clothing suitable for washing clothes using an electric washing machine. The present invention relates to a granular detergent composition, a method for producing the same, and a method for using the same.
従来から、全自動洗濯機、二槽式自動洗濯機等の電気洗濯機を用いた衣料の洗浄が広く行なわれている。そして、これらの電気洗濯機を用いた洗浄では、一般に、粉末洗浄剤が用いられており、洗濯開始時に、使用者が自分の手で上記粉末洗浄剤を、洗濯槽もしくは所定の洗剤供給口に投入するようになっている。 Conventionally, washing of clothes using an electric washing machine such as a fully automatic washing machine and a two-tank automatic washing machine has been widely performed. In washing using these electric washing machines, a powder detergent is generally used, and at the start of washing, the user puts the above powder detergent into the washing tub or a predetermined detergent supply port. It is supposed to be thrown in.
しかしながら、上記粉末洗浄剤の投入の際、洗浄剤の粉末が飛散するため、作業者の皮膚に粉末洗浄剤が付着したり肺に吸入されたりするおそれがあり、衛生管理上懸念されている。また、上記粉末洗浄剤は、洗濯槽に注入される水や湯を利用して溶解されるが、粉末洗浄剤の各成分の溶解濃度が均一となるよう溶解することが困難であるという問題もある。 However, since the powder of the cleaning agent is scattered when the powder cleaning agent is added, there is a concern that the powder cleaning agent may adhere to the skin of the worker or may be inhaled into the lungs, which is a concern in terms of hygiene management. In addition, the powder cleaning agent is dissolved using water or hot water poured into the washing tub, but it is difficult to dissolve the powder cleaning agent so that the concentration of each component is uniform. is there.
また、このような粉末の飛散を防止するために、粉末洗浄剤をポリビニルアルコール等の水溶性フィルム等で個装することが提案されているが、コストが高いという問題がある。 Further, in order to prevent such powder scattering, it has been proposed that the powder cleaning agent is individually packaged with a water-soluble film such as polyvinyl alcohol, but there is a problem that the cost is high.
一方、粉末洗浄剤に代えて液体洗浄剤を用いることが提案されている。しかし、上記液体洗浄剤は、粉末のように飛散するおそれがなく衛生的である反面、溶媒の割合が高く有効成分の割合が低いため、比較的多量の洗浄剤が必要になるという問題がある。このため、交換単位が重量物となり、交換作業が容易でないとともに、これを保管するのに多大なスペースを要する。また、液体洗浄剤の収容に汎用される肉厚ポリエチレン容器は、難燃性、難分解性であるため、その廃棄処理が問題となる。 On the other hand, it has been proposed to use a liquid detergent instead of the powder detergent. However, the liquid cleaning agent is hygienic because there is no risk of scattering like powder, but there is a problem that a relatively large amount of cleaning agent is required because the proportion of the solvent is high and the proportion of the active ingredient is low. . For this reason, an exchange unit becomes a heavy article, and exchange work is not easy, and a lot of space is required to store it. Moreover, since the thick polyethylene container generally used for storing the liquid cleaning agent is flame retardant and hardly decomposable, its disposal is a problem.
そこで、粉末洗浄剤を、従来より大きく造粒することで粉立ちを抑えることが検討されており、例えば、界面活性剤、ビルダー、表面改質剤および増量剤等からなる高密度粒状洗剤用の洗剤粉粒物を、特殊な構成の造粒室において、一定の粒度に整粒して取り出すことを連続的に行なう高密度洗剤粒子の連続造粒方法及び装置（特許文献１を参照）が提案されている。
しかしながら、上記特許文献１の高密度洗剤粒子は、比較的細かい粉粒物をバインダーでスプレーしながら粗大化させ、これを整粒して、比較的大きな粒子にして取り出すことを連続的に行なうため、微細な粉末が混入しやすく、充分に粉立ちが防止されるとはいえない。また、平均粒径５４０〜６００μｍという比較的粒の細かいものが実施例として記載されているにすぎず、それ以上大きい粒子に設定した場合、粒子同士の摩擦によって粒子表面から微細な粉末が脱落するおそれもあり、さらに粉立ちが予想される。しかも、優れた分散性、溶解性、貯蔵安定性等が得られるかについては疑問である。 However, since the high-density detergent particles of Patent Document 1 are coarsened while spraying relatively fine powders with a binder, the particles are sized and taken out as relatively large particles continuously. However, it is easy to mix fine powder and it cannot be said that powdering is sufficiently prevented. Moreover, the comparatively fine thing with an average particle diameter of 540-600 micrometers is only described as an Example, and when set to the particle | grain larger than it, a fine powder falls from the particle | grain surface by friction of particle | grains. There is also a risk, and further powdering is expected. Moreover, it is doubtful whether excellent dispersibility, solubility, storage stability and the like can be obtained.
本発明は、このような事情に鑑みなされたもので、（１）洗浄性能、貯蔵安定性に優れ、特に、塩素系漂白剤あるいは酸素系漂白剤を配合したものを高温多湿の条件にて保存した場合でも、上記漂白剤の分解が最小限に抑えられ、所望の漂白性能を有すること、（２）粉立ちが少なく、取扱い時における作業性と安全性に優れていること、（３）造粒しているにもかかわらず所望の溶解性能を有するものであること、これらの性能を兼ね備えた、優れた衣料用粒状洗浄剤組成物を提供することをその目的とする。また、その製法およびその使用方法の提供をも、その目的とする。 The present invention has been made in view of such circumstances. (1) Excellent cleaning performance and storage stability, especially those containing a chlorine bleach or an oxygen bleach are stored under conditions of high temperature and high humidity. Even if it is, the decomposition of the bleaching agent is minimized, it has the desired bleaching performance, (2) it has less dusting and is excellent in workability and safety during handling, (3) It is an object to provide an excellent granular detergent composition for clothing having the desired dissolution performance despite being granulated and having these performances. It is also an object of the present invention to provide a production method and a usage method thereof.
上記の目的を達成するため、本発明は、下記の（Ａ）〜（Ｄ）成分を必須成分として含有するとともに、水を０．１〜９質量％含有する原料組成物が、下記の（Ａ）〜（Ｄ）成分がスラリー状に調製された後に噴霧乾燥されたり加熱溶融されたりしていない状態で、高速攪拌造粒機に供給されバッチ式で造粒されており、ＪＩＳ Ｋ−３３６２：１９９８「合成洗剤試験方法」記載のふるい分け方法によって測定される粒度から求められる平均粒径が０．８〜３．０ｍｍに設定され、かつ下記の式（１）によって算出される真球度が０．７〜１．０に設定された略球状粒状体の集合体からなる衣料用粒状洗浄剤組成物を第１の要旨とする。
（Ａ）アルカリ金属水酸化物、珪酸アルカリ金属塩、炭酸ナトリウムおよび炭酸水素ナトリウムから選ばれる一種または二種以上の化合物
（Ｂ）金属イオン封鎖剤
（Ｃ）界面活性剤
（Ｄ）高分子電解質重合体
〔数１〕
真球度＝Ｒ２／Ｒ１ …（１）
〔Ｒ１：粒状体の長径、Ｒ２：粒状体の短径〕
In order to achieve the above object, the present invention contains the following components (A) to (D) as essential components, and a raw material composition containing 0.1 to 9% by mass of water has the following (A ) To (D) are prepared in the form of a slurry and are not spray-dried or heated and melted, and supplied to a high-speed agitation granulator to be batch-granulated. JIS K-3362: The average particle size obtained from the particle size measured by the screening method described in 1998 “Synthetic detergent test method” is set to 0.8 to 3.0 mm, and the sphericity calculated by the following formula (1) is 0. The first gist of the present invention is a granular detergent composition for clothing comprising an aggregate of substantially spherical granular bodies set to 0.7 to 1.0.
(A) One or more compounds selected from alkali metal hydroxides, alkali metal silicates, sodium carbonate and sodium hydrogen carbonate (B) sequestering agent (C) surfactant (D) polymer electrolyte heavy Combined [Equation 1]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material]
また、本発明は、下記の（Ａ）〜（Ｄ）成分を必須成分として含有するとともに、水は含有せず、これら（Ａ）〜（Ｄ）成分のうち、少なくとも一種類の成分が水化物である原料組成物が、下記の（Ａ）〜（Ｄ）成分がスラリー状に調製された後に噴霧乾燥されたり加熱溶融されたりしていない状態で、高速攪拌造粒機に供給されバッチ式で、上記水化物に由来する水分により各成分粒子同士が隙間を残した状態で結着して造粒されており、ＪＩＳ Ｋ−３３６２：１９９８「合成洗剤試験方法」記載のふるい分け方法によって測定される粒度から求められる平均粒径が０．８〜３．０ｍｍに設定され、かつ下記の式（１）によって算出される真球度が０．７〜１．０に設定された略球状粒状体の集合体からなることを特徴とする衣料用粒状洗浄剤組成物。
（Ａ）アルカリ金属水酸化物、珪酸アルカリ金属塩、炭酸ナトリウムおよび炭酸水素ナトリウムから選ばれる一種または二種以上の化合物
（Ｂ）金属イオン封鎖剤
（Ｃ）界面活性剤
（Ｄ）高分子電解質重合体
〔数２〕
真球度＝Ｒ２／Ｒ１ …（１）
〔Ｒ１：粒状体の長径、Ｒ２：粒状体の短径〕
In addition, the present invention contains the following components (A) to (D) as essential components and does not contain water, and at least one of these components (A) to (D) is a hydrate. In a state where the following components (A) to (D) are prepared in the form of a slurry and are not spray-dried or heated and melted, they are supplied to a high-speed agitation granulator and are batch-type. In addition, each component particle is bound and granulated with moisture derived from the hydrate, and is measured by a screening method described in JIS K-3362: 1998 “Synthetic detergent test method”. The average spherical particle size determined from the particle size is set to 0.8 to 3.0 mm, and the sphericity calculated by the following formula (1) is set to 0.7 to 1.0. Granular wash for clothing characterized by comprising an aggregate Cleaner composition.
(A) One or more compounds selected from alkali metal hydroxides, alkali metal silicates, sodium carbonate and sodium hydrogen carbonate (B) sequestering agent (C) surfactant (D) polymer electrolyte heavy Combine [number 2]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material]
さらに、本発明は、それらのなかでも、特に、上記（Ｂ）成分の金属イオン封鎖剤が、燐酸アルカリ金属塩である衣料用粒状洗浄剤組成物を第３の要旨とし、上記（Ｂ）成分の金属イオン封鎖剤が、無燐系金属イオン封鎖剤である衣料用粒状洗浄剤組成物を第４の要旨とする。 Further, among these, the third aspect of the present invention is a granular detergent composition for clothing in which the sequestering agent of the component (B) is an alkali metal phosphate, and the component (B). The fourth gist of the present invention is a granular detergent composition for clothing in which the sequestering agent is a phosphorus-free sequestering agent.
そして、本発明は、上記第４の要旨である衣料用粒状洗浄剤組成物のなかでも、特に、上記無燐系金属イオン封鎖剤が、アミノカルボン酸およびヒドロキシアミノカルボン酸、並びにその塩から選択される少なくとも一つである衣料用粒状洗浄剤組成物を第５の要旨とする。 And among the granular detergent composition for clothes which is the 4th gist of the present invention, the phosphorus-free sequestering agent is selected from aminocarboxylic acids, hydroxyaminocarboxylic acids, and salts thereof. A granular detergent composition for clothes that is at least one of the above is a fifth aspect .
また、本発明は、それらのなかでも、特に、上記（Ｃ）成分の界面活性剤が、非イオン性界面活性剤である衣料用粒状洗浄剤組成物を第６の要旨とし、上記（Ｄ）成分の高分子電解質重合体が、アクリル酸およびマレイン酸の少なくとも一方を単量体とする重合体、およびその共重合体、並びにその水溶性アルカリ塩から選択される少なくとも一つである衣料用粒状洗浄剤組成物を第７の要旨とし、天然高分子誘導体、デンプン誘導体、セルロース誘導体、アクリル酸誘導体、ポリビニルアルコールおよびポリエチレングリコールから選択される少なくとも一種のバインダーが、造粒時に添加されたものである衣料用粒状洗浄剤組成物を第８の要旨とする。 In addition, among these, the sixth aspect of the present invention is a granular cleaning composition for clothing in which the surfactant of the component (C) is a nonionic surfactant, and the (D) Granules for clothing, wherein the component polyelectrolyte polymer is at least one selected from a polymer comprising at least one of acrylic acid and maleic acid as a monomer, a copolymer thereof, and a water-soluble alkali salt thereof the detergent composition as a seventh gist of, those natural polymer derivatives, starch derivatives, cellulose derivatives, acrylic acid derivatives, at least one binder selected from polyvinyl alcohol and polyethylene glycol were added during granulation A granular detergent composition for clothing is an eighth aspect .
さらに、本発明は、それらのなかでも、特に、上記略球状粒状体の集合体に、下記の（Ｆ）成分および（Ｇ）成分の少なくとも一方が混合されている衣料用粒状洗浄剤組成物を第９の要旨とする。
（Ｆ）平均粒径が０．５〜３．０ｍｍに設定された塩素系漂白剤もしくは酸素系漂白剤。（Ｇ）平均粒径が０．５〜３．０ｍｍに設定された洗剤用酵素。
Furthermore, the present invention includes a granular detergent composition for clothing, in which at least one of the following (F) component and (G) component is mixed with the aggregate of the substantially spherical granular materials. Let it be the 9th summary.
(F) Chlorine bleach or oxygen bleach with an average particle size of 0.5 to 3.0 mm. (G) Detergent enzyme having an average particle size of 0.5 to 3.0 mm.
また、本発明は、上記第１〜第９の要旨のいずれかである衣料用粒状洗浄剤組成物を製造する方法であって、略球状粒状体を調製するための原料組成物を、各原料成分をスラリー状に調製した後に噴霧乾燥したり加熱溶融したりしていない状態で、高速攪拌造粒機に供給し、バッチ式の造粒工程によって、ＪＩＳ Ｋ−３３６２：１９９８「合成洗剤試験方法」記載のふるい分け方法によって測定される粒度から求められる平均粒径が０．８〜３．０ｍｍとなり、下記の式（１）によって算出される真球度が０．７〜１．０となる略球状に造粒するようにした衣料用粒状洗浄剤組成物の製法を第１０の要旨とする。
〔数３〕
真球度＝Ｒ２／Ｒ１ …（１）
〔Ｒ１：粒状体の長径、Ｒ２：粒状体の短径〕
Further, the present invention is a method for producing a granular detergent composition for clothing according to any one of the first to ninth aspects, wherein a raw material composition for preparing a substantially spherical granular material is used as each raw material. the ingredients and do not have or or melted by heating spray-dried after preparing a slurry, and subjected fed to a high-speed stirring granulator, the granulation step of the batch, JIS K-3362: 1998 "synthetic detergent test The average particle size obtained from the particle size measured by the screening method described in “Method” is 0.8 to 3.0 mm, and the sphericity calculated by the following formula (1) is 0.7 to 1.0. A tenth aspect of the present invention is a method for producing a granular detergent composition for clothing that is granulated into a substantially spherical shape.
[Equation 3]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material]
さらに、本発明は、そのなかでも、特に、上記高速攪拌造粒機が、回転攪拌翼および回転解砕翼を有する造粒機である衣料用粒状洗浄剤組成物の製法を第１１の要旨とし、上記高速攪拌造粒機における造粒工程後、減圧乾燥工程を経由するようにした衣料用粒状洗浄剤組成物の製法を第１２の要旨とする。 Furthermore, the present invention has, in particular, the eleventh aspect of the method for producing a granular detergent composition for clothing, in which the high-speed stirring granulator is a granulator having a rotary stirring blade and a rotary crushing blade, A twelfth aspect of the present invention is a method for producing a granular detergent composition for clothing that is subjected to a reduced-pressure drying step after the granulation step in the high-speed stirring granulator.
また、本発明は、それらのなかでも、特に、上記第１〜第９のいずれかの要旨である衣料用粒状洗浄剤組成物を、水で希釈してなる０．１質量％水溶液の、２５℃におけるｐＨ（ＪＩＳ Ｚ−８８０２：１９８４「ｐＨ測定方法」に従う）が、８〜１２の範囲となるよう調製するようにした衣料用粒状洗浄剤組成物の製法を第１３の要旨とする。 In addition, the present invention is 25% of a 0.1% by mass aqueous solution obtained by diluting the granular cleaning composition for clothing according to any of the first to ninth aspects with water. A thirteenth aspect of the present invention is a method for producing a granular detergent composition for clothing that is prepared such that the pH at ℃ (according to JIS Z-8802: 1984 “pH measurement method”) is in the range of 8-12.
そして、本発明は、上記第１〜第９のいずれかの要旨である衣料用粒状洗浄剤組成物を、０．０３〜０．３質量％の洗浄剤希釈液として、電気洗濯機を用いた衣料の洗浄に用いるようにした衣料用粒状洗浄剤組成物の使用方法を第１４の要旨とする。 And this invention used the electric washing machine for the granular cleaning agent composition for clothes which is the summary of any one of the said 1st- 9th as a cleaning agent dilution liquid of 0.03-0.3 mass%. A fourteenth aspect of the present invention is a method for using a granular detergent composition for clothing that is used for washing clothing.
なお、本発明において、「略球状」とは、図１（ａ）に示すように、粒状体（ｎ＝２０個）の長径Ｒ１および短径Ｒ２を測定し、上記の式（１）によって算出される真球度が０．７〜１．０である形状をいい、この値が１．０に近づくほど真球に近い形状である。 In the present invention, the term "substantially spherical", as shown in FIG. 1 (a), the major axis R1 and a minor axis R2 of the granulate (n = 20 cells) was measured, by the equation (1) above The calculated sphericity is 0.7 to 1.0. The closer this value is to 1.0, the closer to the sphere.
また、本発明において、「水化物」とは、分子の形で水を含む化合物をいう。 In the present invention, the “hydrate” refers to a compound containing water in the form of a molecule.
本発明の衣料用粒状洗浄剤組成物は、特定の必須成分を含有する原料組成物が高速攪拌造粒機によりバッチ式で造粒されており、その平均粒径が０．８〜３．０ｍｍという比較的大きな粒であって、しかも真球度が０．７〜１．０という真球に近い特殊な形状の粒状体の集合体であるため、流動性、分散性、溶解性に優れ、優れた洗浄性能を有する。しかも、貯蔵安定性に優れ、特に、塩素系漂白剤や酸素系漂白剤、あるいは洗剤用酵素を配合したものを高温多湿の条件において保存した場合であっても、上記漂白剤や酵素の分解が最小限に抑えられるため、所望の漂白性能、酵素洗浄性能を発揮するという利点を有する。 The granular detergent composition for clothing of the present invention is a batch composition of a raw material composition containing specific essential components, which has a mean particle size of 0.8 to 3.0 mm. a will relatively large grains leave, and since sphericity is an aggregate of granules of a special shape close to a sphere of 0.7 to 1.0, fluidity, dispersibility, solubility Excellent and excellent cleaning performance. In addition, it has excellent storage stability, and in particular, even when a chlorine-based bleach, oxygen-based bleach, or a combination of detergent enzymes is stored under conditions of high temperature and high humidity, the above-mentioned bleaching agents and enzymes are decomposed. Since it can be minimized, it has the advantage of exhibiting desired bleaching performance and enzyme cleaning performance.
また、本発明の衣料用粒状洗浄剤組成物は、平均粒径０．８〜３．０ｍｍ、真球度０．７〜１．０の略球状に造粒されているため、粉立ちが抑えられて（飛散抑制に優れて）おり、取扱い時における作業性と安全性に優れている。そして、比較的大きな粒状に造粒されているにもかかわらず、所望の溶解性能を有している。 Moreover, since the granular detergent composition for clothes of the present invention is granulated into a substantially spherical shape having an average particle diameter of 0.8 to 3.0 mm and a sphericity of 0.7 to 1.0 , it prevents powdering. It has excellent workability and safety during handling. And although it is granulated to a comparatively big granule, it has desired melt | dissolution performance.
そして、本発明の衣料用粒状洗浄剤組成物の製法によれば、上記優れた特性の衣料用粒状洗浄剤組成物を、簡単かつ低コストで製造することができる。 And according to the manufacturing method of the granular cleaning composition for clothes of this invention, the granular cleaning composition for clothes of the said outstanding characteristic can be manufactured simply and at low cost.
また、本発明の衣料用粒状洗浄剤組成物の使用方法によれば、本発明の衣料用粒状洗浄剤組成物の優れた特性を活かし、電気洗濯機を用いて衣料を洗浄することにより、優れた洗浄力を発揮させることができる。 In addition, according to the method for using the granular detergent composition for clothes of the present invention, taking advantage of the excellent characteristics of the granular detergent composition for clothes of the present invention, it is excellent by washing the clothes using an electric washing machine. The cleaning power can be demonstrated.
つぎに、本発明を実施するための最良の形態を詳細に説明する。 Next, the best mode for carrying out the present invention will be described in detail.
まず、本発明の衣料用粒状洗浄剤組成物（以下、「粒状洗浄剤組成物」と略す）は、下記の（Ａ）〜（Ｄ）成分を必須成分として含有するものである。
（Ａ）アルカリ金属水酸化物、珪酸アルカリ金属塩、炭酸ナトリウムおよび炭酸水素ナトリウムから選ばれる一種または二種以上の化合物
（Ｂ）金属イオン封鎖剤
（Ｃ）界面活性剤
（Ｄ）高分子電解質重合体
First, the granular cleaning composition for clothing of the present invention (hereinafter abbreviated as “particulate cleaning composition”) contains the following components (A) to (D) as essential components.
(A) One or more compounds selected from alkali metal hydroxides, alkali metal silicates, sodium carbonate and sodium hydrogen carbonate (B) sequestering agent (C) surfactant (D) polymer electrolyte heavy Coalescence
上記（Ａ）成分において、アルカリ金属水酸化物としては、水酸化ナトリウム、水酸化カリウム等があげられ、これらは、単独もしくは２種以上の併用で用いられる。 In the component (A), the alkali metal hydroxides, sodium water oxidation, potassium hydroxide, and the like. These are used alone or in combination of two or more thereof.
また、上記珪酸アルカリ金属塩としては、下記の化学式（１）で示されるものが好適であり、なかでも、洗浄性能および分散性能の点から、下記のｘ：ｙが１：２〜３：１、特に１：２〜２：１のものが好適である。例えば、無水メタ珪酸ナトリウム、メタ珪酸ナトリウム５水塩、メタ珪酸ナトリウム９水塩、オルソ珪酸ナトリウムが好ましい。また、無水メタ珪酸ナトリウム、ジ珪酸ナトリウム、層状珪酸ナトリウム（ＳＫＳ−６，ヘキスト社製）等を用いることもできる。これらは、単独で用いても２種以上を併用してもよい。 Moreover, as said alkali metal silicate, what is shown by following Chemical formula (1) is suitable, and the following x: y is 1: 2-3: 1 from the point of washing | cleaning performance and dispersion | distribution performance especially. Particularly preferred is 1: 2 to 2: 1. For example, anhydrous sodium metasilicate, sodium metasilicate pentahydrate, sodium metasilicate 9 hydrate, and sodium orthosilicate are preferable. Also, anhydrous sodium metasilicate, sodium disilicate, layered sodium silicate (SKS-6, manufactured by Hoechst) and the like can be used. These may be used alone or in combination of two or more.
上記（Ａ）成分の含有量は、特に限定するものではないが、粒状洗浄剤組成物全体に対し、１〜４０質量％（以下、「％」と略す）に設定することが好ましく、なかでも、５〜２５％が好適である。すなわち、１％未満では、蛋白質、澱粉汚れに対する洗浄力が乏しくなり、逆に、４０％を超えると、全体としてのバランスが悪くなり、貯蔵安定性が低下するとともに、他成分との相乗効果がそれ以上得られず、好ましくない。 Said component (A) content of the content is not particularly limited with respect to the entire granular detergent composition, from 1 to 40 mass% (hereinafter, abbreviated as "%") is preferably set to, cry However, 5 to 25% is preferable. That is, if it is less than 1%, the detergency against protein and starch stains is poor, and conversely, if it exceeds 40%, the balance as a whole is deteriorated, storage stability is lowered, and synergistic effects with other components are exhibited. It cannot be obtained any more and is not preferable.
上記（Ｂ）成分の金属イオン封鎖剤としては、燐系，無燐系のどちらを用いても差し支えはない。これらは、単独で用いても２種以上を併用してもよい。 As the sequestering agent of the component (B), either phosphorus-based or phosphorus-free can be used. These may be used alone or in combination of two or more.
上記燐系の金属イオン封鎖剤としては、燐酸アルカリ金属塩があげられ、用いられる燐酸としては、オルソ燐酸、ポリ燐酸、ピロ燐酸、メタ燐酸、ヘキサメタ燐酸等があげられる。そして、これらの燐酸と化合させるアルカリ金属としては、ナトリウム、カリウム等があげられる。特に、上記燐酸アルカリ金属塩のなかでも、トリポリ燐酸ナトリウムが好適である。 Examples of the phosphorous sequestering agent include alkali metal phosphates, and examples of the phosphoric acid used include orthophosphoric acid, polyphosphoric acid, pyrophosphoric acid, metaphosphoric acid, and hexametaphosphoric acid. And as an alkali metal combined with these phosphoric acids, sodium, potassium, etc. are mention | raise | lifted. Of these alkali metal phosphates, sodium tripolyphosphate is particularly preferred.
また、無燐系のものとしては、アミノポリ酢酸およびこれらのアルカリ金属塩、有機酸またはこれらのアルカリ金属塩、その他の有機ビルダー、アミノ酸またはこれらのアルカリ金属塩等があげられる。 Examples of phosphorus-free compounds include aminopolyacetic acid and alkali metal salts thereof, organic acids or alkali metal salts thereof, other organic builders, amino acids, or alkali metal salts thereof.
上記アミノポリ酢酸およびこれらのアルカリ金属塩としては、エチレンジアミン四酢酸、ニトリロ三酢酸、イミノジ酢酸、ジエチレントリアミン五酢酸、グリコールエーテルジアミン四酢酸、ヒドロキシエチルイミノジ酢酸、トリエチレンテトラミン六酢酸、ポリエチレンイミン酢酸、メチルグリシン二酢酸、ジエンコル酸およびその塩等のアミノポリ酢酸およびこれらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩もしくはアルカノールアミン塩等が用いられる。そして、これらと化合させるアルカリ金属としては、ナトリウム塩、カリウム塩等があげられ、好ましくはナトリウム塩が用いられる。 Examples of the aminopolyacetic acid and alkali metal salts thereof include ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid, polyethyleneimineacetic acid, methyl Aminopolyacetic acid such as glycine diacetic acid, diencoric acid and salts thereof, and alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts thereof are used. And as an alkali metal combined with these, a sodium salt, potassium salt, etc. are mention | raise | lifted, Preferably a sodium salt is used.
上記有機酸またはこれらのアルカリ金属塩としては、クエン酸、グルコン酸、酒石酸、リンゴ酸、コハク酸、乳酸、シュウ酸、ジグリコール酸、オキシジコハク酸、カルボキシメチルオキシコハク酸、カルボキシメチルコハク酸、カルボシキメチル酒石酸、３−ヒドロキシ２，２’−イミノジコハク酸等の有機酸、またはこれらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩もしくはアルカノールアミン塩等を用いることができる。 Examples of the organic acids or alkali metal salts thereof include citric acid, gluconic acid, tartaric acid, malic acid, succinic acid, lactic acid, oxalic acid, diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, carboxymethyl succinic acid, carbohydrate. Organic acids such as shikimethyl tartaric acid and 3-hydroxy 2,2′-iminodisuccinic acid, or alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts thereof can be used.
上記その他の有機ビルダーとしては、エタン−１，１−ジホスホン酸塩、エタン−１，１，２−トリホスホン酸塩、エタン−１−ヒドロキシ−１，１−ジホスホン酸塩およびその誘導体、エタンヒドロキシ−１，１，２−トリホスホン酸、エタン−１，２−ジカルボキシ−１，２−ジホスホン酸、メタンヒドロキシホスホン酸、１−ヒドロキシエチリデン−１，１−ホスホン酸等のホスホン酸化合物、またはこれらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩もしくはアルカノールアミン塩、２−ホスホノブタン−１，２−ジカルボン酸、１−ホスホノブタン−２，３，４−トリカルボン酸、α−メチルホスホノコハク酸等のホスホノカルボン酸またはこれらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩もしくはアルカノールアミン塩を用いることができる。 Examples of the other organic builder include ethane-1,1-diphosphonate, ethane-1,1,2-triphosphonate, ethane-1-hydroxy-1,1-diphosphonate and derivatives thereof, ethanehydroxy- Phosphonic acid compounds such as 1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 1-hydroxyethylidene-1,1-phosphonic acid, or the like Alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, etc. Phosphonocarboxylic acids or their alkali metal salts, alkaline earth metal salts, ammonium salts or amines Kanoruamin salt can be used.
そして、上記アミノ酸またはこれらのアルカリ金属塩としては、アスパラギン酸、グルタミン酸等のアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩もしくはアルカノールアン塩等を用いることができる。 And as said amino acid or these alkali metal salts, alkali metal salts, such as aspartic acid and glutamic acid, alkaline-earth metal salt, ammonium salt, alkanol an salt, etc. can be used.
なかでも、グルコン酸ナトリウム、クエン酸ナトリウム、コハク酸ナトリウム、エチレンジアミン四酢酸ナトリウム、ニトリロ三酢酸ナトリウム、３−ヒドロキシ２，２’−イミノジコハク酸四ナトリウム、メチルグリシン二酢酸三ナトリウム、グルタミン酸−Ｎ，Ｎ’−二酢酸四ナトリウム、ポリエチレンイミン酢酸ナトリウム、トリポリリン酸ナトリウム、１−ヒドロキシエチリデン−１，１−ホスホン酸が好ましく用いられる。 Among them, sodium gluconate, sodium citrate, sodium succinate, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, tetrasodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, glutamic acid-N, N '-Tetrasodium diacetate, sodium polyethylenimine acetate, sodium tripolyphosphate and 1-hydroxyethylidene-1,1-phosphonic acid are preferably used.
上記（Ｂ）成分である金属イオン封鎖剤の含有量も、特に限定するものではないが，本発明の粒状洗浄剤組成物全体に対し、２５〜８０％に設定することが好ましく、なかでも、３０〜６０％が好適である。すなわち、２５％未満では、油、皮脂汚れに対する洗浄力が乏しくなるとともに、スケール生成抑制能が低下し、逆に、８０％を超えると、全体としてのバランスが悪くなり、所望の性能が低下して、好ましくない。 The content of the sequestering agent that is the component (B) is not particularly limited, but is preferably set to 25 to 80% with respect to the entire granular detergent composition of the present invention. 30 to 60% is preferable. That is, if it is less than 25%, the detergency against oil and sebum soil becomes poor, and the ability to suppress scale formation decreases. Conversely, if it exceeds 80%, the balance as a whole deteriorates and the desired performance decreases. It is not preferable.
また、本発明の粒状洗浄剤組成物に用いられる（Ｃ）成分の界面活性剤としては、非イオン界面活性剤、アニオン界面活性剤、カチオン界面活性剤および両性界面活性剤があげられる。 Examples of the component (C) surfactant used in the granular detergent composition of the present invention include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants.
例えば、ポリオキシエチレンポリオキシプロピレン重合物（プルロニック型ブロックポリマー、リバースプルロニック型ブロックポリマー）、燐酸エステル、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビット脂肪酸エステル、ポリエチレングリコール脂肪酸エステル、ポリオキシエチレンひまし油、ポリオキシエチレンアルキルアミン、グリセリン脂肪酸エステル、高級脂肪酸アルカノールアミド、アルキルグルコシド、アルキルアミンオキサイド等の非イオン界面活性剤、アルキル硫酸塩、アルキルエーテル硫酸塩、α−オレフィンスルホン酸塩、直鎖アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩等のアニオン界面活性剤、塩化ベンザルコニウム、ジデシルジメチルアンモニウムクロライド等のカチオン界面活性剤、およびアミノ酸型両性界面活性剤、ベタイン型両性界面活性剤等の両性界面活性剤があげられる。これらは、単独で用いても２種以上を併用してもよい。 For example, polyoxyethylene polyoxypropylene polymer (pluronic block polymer, reverse pluronic block polymer), phosphate ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, poly Nonionic surfactants such as oxyethylene sorbite fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, alkyl glucoside, alkylamine oxide, alkyl sulfate, alkyl Ether sulfate, α-olefin sulfonate, linear alkylbenzene sulfonate, polyoxy Anionic surfactants such as tylene alkyl ether sulfate, cationic surfactants such as benzalkonium chloride and didecyldimethylammonium chloride, and amphoteric surfactants such as amino acid type amphoteric surfactants and betaine type amphoteric surfactants can give. These may be used alone or in combination of two or more.
なかでも、低泡性能や汚れの乳化力の点から、非イオン界面活性剤が好ましく、特に、プルロニック型ブロックポリマー、リバースプルロニック型ブロックポリマー、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、トリメチルプロパンのポリオキシエチレンポリオキシプロピレン付加物、グリセリンのポリオキシエチレンポリオキシプロピレン付加物、ラウリル硫酸ナトリウム、アルキルベンゼンスルホン酸ナトリウムが好ましい。 Among these, nonionic surfactants are preferred from the viewpoint of low foam performance and emulsifying power of dirt, and in particular, pluronic block polymers, reverse pluronic block polymers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxypropylene trimethylpropanes. Ethylene polyoxypropylene adducts, glycerin polyoxyethylene polyoxypropylene adducts, sodium lauryl sulfate and sodium alkylbenzene sulfonate are preferred.
上記（Ｃ）成分である界面活性剤の含有量も、特に限定するものではないが、本発明の粒状洗浄剤組成物全体に対し、５〜４０％に設定することが好ましい。なかでも、１０〜２５％が好適である。すなわち、５％未満では、所望の洗浄性能に乏しく、また、洗浄剤がコンパクトなものとならず経済的に不利になるおそれがある。一方、４０％を超えると、全体としてのバランスが悪くなるとともに、他成分との相乗効果がそれ以上得られず、好ましくない。 The content of the surfactant as the component (C) is not particularly limited, but is preferably set to 5 to 40% with respect to the entire granular detergent composition of the present invention. Among these, 10 to 25% is preferable. That is, if it is less than 5%, the desired cleaning performance is poor, and the cleaning agent may not be compact and may be economically disadvantageous. On the other hand, if it exceeds 40%, the balance as a whole becomes worse, and a synergistic effect with other components cannot be obtained any more, which is not preferable.
また、本発明の粒状洗浄剤組成物に用いられる（Ｄ）成分の高分子電解質重合体としては、ポリアクリル酸、ポリアコニット酸、ポリイタコン酸、ポリシトラコン酸、ポリフマル酸、ポリマレイン酸、ポリメタコン酸、ポリ−α−ヒドロキシアクリル酸、ポリビニルホスホン酸、スルホン化ポリマレイン酸、無水マレイン酸ジイソブチレン共重合体、無水マレイン酸スチレン共重合体、無水マレイン酸メチルビニルエーテル共重合体、無水マレイン酸エチレン共重合体、無水マレイン酸エチレンクロスリンク共重合体、無水マレイン酸酢酸ビニル共重合体、無水マレイン酸アクリロニトリル共重合体、無水マレイン酸アクリル酸エステル共重合体、無水マレイン酸ブタジエン共重合体、無水マレイン酸イソプレン共重合体、無水マレイン酸と一酸化炭素から誘導されるポリ−β−ケトカルボン酸、イタコン酸エチレン共重合体、イタコン酸アコニット酸共重合体、イタコン酸マレイン酸共重合体、イタコン酸アクリル酸共重合体、マロン酸メチレン共重合体、イタコン酸フマール酸共重合体、エチレングリコールエチレンテレフタレート共重合体、ビニルピロリドン酢酸ビニル共重合体等があげられる。これらは、単独で用いても２種以上を併用してもよい。これらのなかでも、ポリアクリル酸ナトリウム、ポリマレイン酸ナトリウム、アクリル酸マレイン酸共重合体、ポリ−α−ヒドロキシアクリル酸ナトリウム、アクリル酸マレイン酸ポリエチレングリコール共重合体、オレフィンマレイン酸共重合体のナトリウム塩、アクリル酸スルホン酸共重合体のナトリウム塩が好ましい。 Further, as the polymer electrolyte polymer of component (D) used in the granular detergent composition of the present invention, polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, Poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride diisobutylene copolymer, maleic anhydride styrene copolymer, maleic anhydride methyl vinyl ether copolymer, maleic anhydride ethylene copolymer , Maleic anhydride ethylene cross-linked copolymer, maleic anhydride vinyl acetate copolymer, maleic anhydride acrylonitrile copolymer, maleic anhydride acrylic ester copolymer, maleic anhydride butadiene copolymer, maleic anhydride isoprene Copolymer, with maleic anhydride Poly-β-ketocarboxylic acid derived from carbon oxide, ethylene itaconate copolymer, itaconic acid aconitic acid copolymer, itaconic acid maleic acid copolymer, itaconic acid acrylic acid copolymer, malonic acid methylene copolymer , Itaconic acid fumaric acid copolymer, ethylene glycol ethylene terephthalate copolymer, vinylpyrrolidone vinyl acetate copolymer and the like. These may be used alone or in combination of two or more. Among these, sodium polyacrylate, sodium polymaleate, maleic acrylate copolymer, sodium poly-α-hydroxy acrylate, maleic acrylate polyethylene glycol copolymer, sodium salt of olefin maleic acid copolymer The sodium salt of acrylic acid sulfonic acid copolymer is preferred.
上記（Ｄ）成分である高分子電解質重合体の含有量も、特に限定するものではないが、本発明の粒状洗浄剤組成物全体に対し、０．１〜２０％に設定することが好ましい。なかでも、０．５〜１５％が好適である。すなわち、０．１％未満では、他の成分とのバランスから充分な洗浄性能が得られにくく、また、２０％を超えると、全体としてのバランスが悪くなり、貯蔵安定性が低下するとともに、他成分との相乗効果がそれ以上得られず、好ましくない。 The content of the polymer electrolyte polymer as the component (D) is not particularly limited, but is preferably set to 0.1 to 20% with respect to the entire granular detergent composition of the present invention. Especially, 0.5 to 15% is suitable. That is, if it is less than 0.1%, sufficient cleaning performance is difficult to obtain from the balance with other components, and if it exceeds 20%, the balance as a whole deteriorates and storage stability decreases. A synergistic effect with the ingredients cannot be obtained any more, which is not preferable.
なお、上記必須成分である（Ａ）〜（Ｄ）成分のうち、少なくとも一種類の成分は、水化物であることが好ましい。すなわち、水化物が組成物中に存在すると、原料組成物を、後述するように、攪拌混合して造粒する際、その水化物に含有されていた水分が、結晶構造から解離して表面にしみ出して、各成分粒子を湿潤させて互いに結着させるため、高温で原料組成物を溶融冷却固化させる必要がなく、非加熱もしくは比較的低い温度で造粒することができる。しかも、各成分粒子の粒子間に微妙な隙間を残した状態で結着させることができるため、得られる粒状洗浄剤組成物が、非常に溶解性に優れたものとなるという利点を有する。また、酵素等の熱に弱い成分を配合しても、その効果を損なうことがないという利点を有する。 In addition, it is preferable that at least 1 type of component is a hydrate among (A)-(D) component which is the said essential component. That is, when a hydrate is present in the composition, the moisture contained in the hydrate is dissociated from the crystal structure on the surface when the raw material composition is agitated and mixed and granulated as described later. Since each component particle is wetted out and bound to each other, it is not necessary to melt and solidify the raw material composition at a high temperature, and granulation can be performed without heating or at a relatively low temperature. And since it can make it bind | conclude in the state which left the fine clearance gap between the particle | grains of each component particle | grain, it has the advantage that the obtained granular cleaning composition becomes a thing excellent in solubility very much. Moreover, even if it mix | blends heat-sensitive components, such as an enzyme, it has the advantage that the effect is not impaired.
本発明の粒状洗浄剤組成物には、上記（Ａ）〜（Ｄ）の必須成分とともに、（Ｅ）成分として、水を配合することができる。上記水としては、例えば、純水、イオン交換水、軟水、蒸留水、水道水等があげられる。これらは、単独で用いても、２種以上を組み合わせて用いてもよい。なかでも、経済性及び貯蔵安定性の点から、水道水、イオン交換水が好ましく用いられる。なお、ここでいう「水」とは、粒状洗浄剤組成物に用いられる他の成分に由来する結晶水や水溶液の形で含まれる水を含まず、単独の成分として外から加えられる水のみをいい、ＪＩＳ Ｋ−３３６２：１９９８「合成洗剤試験方法」記載の加熱減量法によって定量することができる。 In the granular detergent composition of the present invention, water can be blended as the component (E) together with the essential components (A) to (D). Examples of the water include pure water, ion exchange water, soft water, distilled water, and tap water. These may be used alone or in combination of two or more. Of these, tap water and ion-exchanged water are preferably used from the viewpoint of economy and storage stability. Note that “water” as used herein does not include crystal water derived from other components used in the granular detergent composition or water contained in the form of an aqueous solution, but only water added from the outside as a single component. It can be quantified by the heat loss method described in JIS K-3362: 1998 “Synthetic detergent test method”.
上記（Ｅ）成分である水を配合する場合、その含有量は、粒状洗浄剤組成物全体に対し、０．１〜９％である。すなわち、この範囲で水を配合することにより、洗浄剤組成物の造粒性および飛散防止性を高めることができ、好ましい。なお、１５％を超えて配合すると、生産効率が低下し、所望の粒状体を得ることができず、好ましくない。 When mix | blending the water which is the said (E) component, the content is 0.1 to 9 % with respect to the whole granular cleaning composition. That is, it is preferable to add water in this range because the granulation property and scattering prevention property of the cleaning composition can be improved. In addition, when it mix | blends exceeding 15%, production efficiency falls and a desired granule cannot be obtained and it is unpreferable.
また、本発明の粒状洗浄剤組成物には、必要に応じて、無水または水化物の硫酸アルカリ金属塩等の洗浄ビルダー、水溶性溶剤、蛍光増白剤、ハイドロトロープ剤、シリコーン系消泡剤、香料、腐食防止剤、防腐剤等の公知成分を任意に配合することができる。また、後述するように、粒状洗浄剤組成物に漂白剤を配合する場合は、粒状洗浄剤組成物の造粒後、漂白剤とともに、漂白活性剤を配合することができる。 In addition, the granular detergent composition of the present invention includes, if necessary, a cleaning builder such as an anhydrous or hydrated alkali metal sulfate, a water-soluble solvent, a fluorescent brightener, a hydrotrope, a silicone-based antifoaming agent. Well-known components such as fragrances, corrosion inhibitors, and preservatives can be optionally blended. As will be described later, when a bleaching agent is blended in the granular detergent composition, a bleaching activator can be blended together with the bleaching agent after granulation of the granular detergent composition.
上記任意成分のうち、水溶性溶剤としては、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ−メチル−２−ピロリドン、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル、テトラエチレングリコールモノメチルエーテル、テトラエチレングリコールモノエチルエーテル等を用いることができる。 Among the above optional components, the water-soluble solvent includes monoethanolamine, diethanolamine, triethanolamine, N-methyl-2-pyrrolidone, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, Triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether and the like can be used.
また、ハイドロトロープ剤としては、ポリエチレングリコール、プロピレングリコール、グリセリン等を用いることができる。 Further, as the hydrotrope agent, polyethylene glycol, propylene glycol, glycerin and the like can be used.
また、本発明の粒状洗浄剤組成物には、その美観を高めるために、染料または顔料を配合することができる。これらは、上記（Ｅ）成分である水を配合する場合には、この水に溶解して用いたり、後述する造粒工程において、スプレー等によって、造粒された粒状体表面を着色するのに用いられる。このような染料または顔料としては、溶解性および分散性が高く、耐アルカリに優れたものが好ましく、なかでも、食品添加剤グレードのものがより好適に用いられる。このような染料または顔料としては、青色１号、赤色３号、黄色４号、ナフトールグリーン等があげられ、単独もしくは２種以上の併用で用いられる。 In addition, a dye or pigment can be blended with the granular detergent composition of the present invention in order to enhance its aesthetic appearance. These are used when the water component (E) is blended and used by dissolving in this water or coloring the granulated granule surface by spraying or the like in the granulation step described later. Used. As such a dye or pigment, those having high solubility and dispersibility and excellent alkali resistance are preferred, and among them, food additive grades are more preferably used. Examples of such dyes or pigments include Blue No. 1, Red No. 3, Yellow No. 4, and naphthol green, which are used alone or in combination of two or more.
本発明の粒状洗浄剤組成物は、前記必須成分（Ａ）〜（Ｄ）と、上記任意成分等とからなる原料組成物を用い、例えば、つぎのようにして製造することができる。すなわち、まず、上記原料組成物を、高速攪拌造粒機に投入して均一混合した後、所定温度に加熱し、バッチ式の造粒工程を行う。これによって、平均粒径が０．８〜３．０ｍｍの、略球状粒状体の集合体である本発明の粒状洗浄剤組成物を得ることができる。 The granular detergent composition of the present invention can be produced, for example, as follows using a raw material composition composed of the essential components (A) to (D) and the above optional components. That is, first, the raw material composition is charged into a high-speed agitation granulator and uniformly mixed, and then heated to a predetermined temperature to perform a batch granulation step. By this, the granular cleaning composition of this invention which is an aggregate | assembly of a substantially spherical granular material with an average particle diameter of 0.8-3.0 mm can be obtained.
このようにして得られる本発明の粒状洗浄剤組成物は、特定の必須成分を含有し、図１（ｂ）に示すように、その平均粒径が０．８〜３．０ｍｍという、比較的大きな粒であって真球に近い特殊な形状の粒状体の集合体であるため、流動性、分散性、溶解性に優れ、優れた洗浄性能を有する。しかも、貯蔵安定性に優れ、特に、後述する塩素系漂白剤や酸素系漂白剤、あるいは洗剤用酵素を配合したものを高温多湿の条件において保存した場合であっても、上記漂白剤や酵素の分解が最小限に抑えられるため、所望の漂白性能、酵素洗浄性能を発揮するという利点を有する。 The granular detergent composition of the present invention thus obtained contains specific essential components, and as shown in FIG. 1 (b), the average particle size is relatively 0.8 to 3.0 mm. Since it is a large particle and an aggregate of particles having a special shape close to a true sphere, it is excellent in fluidity, dispersibility, and solubility and has excellent cleaning performance. In addition, it is excellent in storage stability, and in particular, even when a chlorine-based bleaching agent, an oxygen-based bleaching agent described later, or a compound containing a detergent enzyme is stored under high temperature and high humidity conditions, Since decomposition is minimized, it has the advantage of exhibiting desired bleaching performance and enzyme cleaning performance.
また、本発明の粒状洗浄剤組成物は、平均粒径０．８〜３．０ｍｍの略球状に造粒されているため、粉立ちが抑えられて（飛散抑制に優れて）おり、取扱い時における作業性と安全性に優れている。そして、比較的大きな粒状に造粒されているにもかかわらず、所望の溶解性能を有している。 In addition, since the granular detergent composition of the present invention is granulated into a substantially spherical shape having an average particle diameter of 0.8 to 3.0 mm, the powdering is suppressed (excellent in suppressing scattering) and is handled. Excellent workability and safety. And although it is granulated to a comparatively big granule, it has desired melt | dissolution performance.
さらに、本発明の粒状洗浄剤組成物において、必須成分（Ａ）〜（Ｄ）の一部に水化物が含有されているものは、すでに述べたように、原料組成物の造粒時に、その水化物に含有されていた水分が各成分粒子を湿潤させて互いに結着させるため、高温で原料組成物を溶融冷却固化させたり、造粒時に水やバインダーを多用する必要がなく、非加熱もしくは比較的低い温度で、粒子間に微妙な隙間を残した状態で造粒されている。したがって、非常に溶解性に優れており、また、酵素等の熱に弱い成分を含有するものであっても、その効果が維持されているという利点を有する。 Furthermore, in the granular detergent composition of the present invention, the hydrated product is contained in some of the essential components (A) to (D), as described above, when granulating the raw material composition, Since the moisture contained in the hydrate wets the component particles and binds them to each other, it is not necessary to melt and solidify the raw material composition at high temperature, or to use a lot of water and binder at the time of granulation. Granulated at a relatively low temperature, leaving a fine gap between the particles. Therefore, it has the advantage that the effect is maintained even if it is very excellent in solubility and contains a heat-sensitive component such as an enzyme.
なお、上記の製法に用いられる高速攪拌造粒機としては、回転攪拌翼と回転解砕翼の両方を有するものが、粒度にばらつきがなく、略球状粒状体を得る上で好ましい。このような造粒機としては、例えば、商品名：ハイスピードミキサー（深江パウテック社製）、商品名：レーディゲミキサー（マツボー社製）、商品名：ヘンシェルミキサー（三井鉱山社製）、商品名：バーチカルグラニュレーター（パウレック社製）、商品名：プロシェアミキサー（太平洋機工社製）等があげられ、なかでも、ハイスピードミキサー、レーディゲミキサーが好適である。 In addition, as a high-speed stirring granulator used for said manufacturing method, what has both a rotation stirring blade and a rotation crushing blade does not have a dispersion | variation in a particle size, and is preferable when obtaining a substantially spherical granular material. Examples of such a granulator include, for example, trade name: High Speed Mixer (Fukae Powtech Co., Ltd.), trade name: Redige Mixer (Matsubo Co., Ltd.), trade name: Henschel Mixer (Mitsui Mining Co., Ltd.), product Name: Vertical granulator (manufactured by POWREC), trade name: Proshare mixer (manufactured by Taiheiyo Kiko Co., Ltd.), etc. Among them, a high speed mixer and a Ladige mixer are preferred.
また、上記高速攪拌造粒機の稼働条件は、得られる粒状洗浄剤組成物の粒度分布が狭く、しかもできるだけ球状に近いものとなるよう、適宜調整される。例えば、回転攪拌翼と回転解砕翼の両方を有するものにおいて、回転攪拌翼の先端周速は３〜１２ｍ／秒に設定することが好ましく、回転解砕翼の回転数は５０〜３０００ｒｐｍに設定することが好ましい。そして、より好適には、回転攪拌翼の先端周速が５〜１０ｍ／秒、回転解砕翼の回転数が１５００〜２５００ｒｐｍである。 The operating conditions of the high-speed agitation granulator are appropriately adjusted so that the granular detergent composition obtained has a narrow particle size distribution and is as close to a sphere as possible. For example, in what has both a rotary stirring blade and a rotary crushing blade, it is preferable to set the tip peripheral speed of a rotary stirring blade to 3-12 m / sec, and it is preferable to set the rotation speed of a rotary crushing blade to 50-3000 rpm. . More preferably, the tip peripheral speed of the rotary stirring blade is 5 to 10 m / second, and the rotational speed of the rotary crushing blade is 1500 to 2500 rpm.
さらに、造粒時の品温は、４０〜８０℃に設定することが好ましく、より好適には、５０〜７０℃である。本発明に用いられる高速攪拌造粒機は、このような品温制御を行なうため、冷水、熱水、スチーム等の冷媒・熱媒を導入するジャケットを備えているものが好ましい。そして、上記ジャケット温度は、１００℃を超えないよう設定することが好ましく、なかでも、原料への熱の影響を考慮して、９０℃以下に設定することがより好ましい。 Furthermore, the product temperature at the time of granulation is preferably set to 40 to 80 ° C., and more preferably 50 to 70 ° C. In order to perform such product temperature control, the high-speed agitation granulator used in the present invention preferably has a jacket for introducing a refrigerant / heat medium such as cold water, hot water, and steam. And it is preferable to set the said jacket temperature so that it may not exceed 100 degreeC, and it is more preferable to set to 90 degrees C or less considering the influence of the heat | fever to a raw material especially.
また、上記の製法において、造粒工程終了後、取り扱い時の微粉飛散を抑制するとともに整粒のために、回転攪拌翼および回転解砕翼の回転速度を適度に調節して、微粉取り込み除去を行なうことが望ましい。 Also, in the above production method, after the granulation process is completed, fine powder uptake and removal should be performed by appropriately adjusting the rotation speed of the rotary stirring blade and the rotary crushing blade in order to suppress fine powder scattering during handling and to regulate the size. Is desirable.
さらに、上記の製法において、造粒工程終了後、ひきつづき乾燥工程を行なうことが好ましいが、粒状洗浄剤組成物の凝集抑制、品質低下の抑制、生産性向上の点から、減圧乾燥を行なうことがより好適である。この減圧乾燥時における高速攪拌造粒機内の圧力は、６〜３２ｋＰａに設定することが好適で、なかでも、真空ポンプへの負荷や気密性の点から、１３．３〜２０ｋＰａに設定することがより好ましい。 Further, in the above production method, after the granulation step is completed, it is preferable to continue the drying step, but from the viewpoints of suppressing aggregation of the granular detergent composition, suppressing deterioration in quality, and improving productivity, drying under reduced pressure may be performed. More preferred. The pressure in the high-speed agitation granulator at the time of drying under reduced pressure is preferably set to 6 to 32 kPa, and in particular, it can be set to 13.3 to 20 kPa in terms of load on the vacuum pump and airtightness. More preferred.
そして、上記乾燥工程において、造粒された粒状体の乾燥を行なうために、本発明に用いられる高速攪拌造粒機には、ガス吹き込み用ノズルが設けられていることが好ましい。乾燥工程において、上記ノズルから吹き込まれるガスとしては、空気、窒素等、適宜のものが用いられ、その温度は、通常、１０〜４０℃に設定することが好ましい。また、ガスの導入量は、１バッチで造粒される粒状洗浄剤組成物の量にもよるが、通常、１〜４０リットル／分に設定することが好ましく、なかでも５〜２０リットル／分に設定することが、より好適である。 And in the said drying process, in order to dry the granulated granule, it is preferable that the nozzle for gas blowing is provided in the high speed stirring granulator used for this invention. In the drying step, an appropriate gas such as air or nitrogen is used as the gas blown from the nozzle, and the temperature is usually preferably set to 10 to 40 ° C. Further, the amount of gas introduced depends on the amount of the granular detergent composition granulated in one batch, but is usually preferably set to 1 to 40 liters / minute, and more preferably 5 to 20 liters / minute. It is more preferable to set to.
なお、本発明の粒状洗浄剤組成物には、本発明が目的とする性能を損なわない範囲で、耐ケーキング性の向上、溶解性の向上、製造性の向上等のために、上記高速攪拌造粒機による造粒時に、原料組成物にバインダーを添加することができる。また、前記（Ｅ）成分である水を、このバインダーとともに、あるいは、バインダーに代えて、添加することができる。 In addition, the granular detergent composition of the present invention has the above-mentioned high-speed agitation for the purpose of improving caking resistance, improving solubility, improving productivity, etc. within the range not impairing the intended performance of the present invention. During granulation by a granulator, a binder can be added to the raw material composition. Moreover, the water which is the said (E) component can be added with this binder instead of a binder.
上記バインダーとしては、所望の粘結性を示すものが好ましく、例えば、アルギン酸ナトリウム、アラビアゴム、グアーガム、ゼラチン、カルボキシメチルスターチナトリウム、デキトスリン、メチルセルロース、カルボキシメチルセルロースナトリウム、ヒドロキシプロピルセルロース、アクリル酸アミド重合物、ポリビニルアルコール、ポリビニルエチルエーテル、ポリエチレングリコール、ポリビニルピロリドン等があげられる。これらは単独で用いても２種以上を併用してもよい。 As the binder, those showing a desired caking property are preferable. For example, sodium alginate, gum arabic, guar gum, gelatin, sodium carboxymethyl starch, dextrose, methyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, acrylic acid amide polymer , Polyvinyl alcohol, polyvinyl ethyl ether, polyethylene glycol, polyvinyl pyrrolidone and the like. These may be used alone or in combination of two or more.
上記バインダーを添加する場合、その添加量は、通常、粒状洗浄剤組成物全体に対し、０．１〜２０％に設定することが好適である。上記範囲を下回ると、バインダーを用いる効果に乏しく、逆に、上記範囲を上回ると、生産効率が低下するだけでなく、所望の粒形状が得られにくいという問題がある。 When adding the said binder, it is suitable that the addition amount is normally set to 0.1 to 20% with respect to the whole granular cleaning composition. If it is below the above range, the effect of using the binder is poor, and conversely, if it exceeds the above range, not only the production efficiency is lowered, but also there is a problem that it is difficult to obtain a desired grain shape.
さらに、本発明において、上記造粒工程（乾燥工程を含む）によって造粒された略球状粒状体の集合体に、（Ｆ）成分として、塩素系漂白剤もしくは酸素系漂白剤を混合することができる。上記塩素系漂白剤としては、ジクロロイソシアヌル酸ナトリウム、トリクロロイソシアヌル酸ナトリウム、次亜塩素酸カルシウム等があげられ、上記酸素系漂白剤としては、過炭酸ナトリウム、過硼酸ナトリウム、過硫酸ナトリウム等があげられる。、これらは単独もしくは２種以上の併用で用いられる。 Further, in the present invention, a chlorine-based bleaching agent or an oxygen-based bleaching agent may be mixed as the component (F) into the aggregate of the substantially spherical particles granulated by the granulation step (including the drying step). it can. Examples of the chlorine bleach include sodium dichloroisocyanurate, sodium trichloroisocyanurate, and calcium hypochlorite. Examples of the oxygen bleach include sodium percarbonate, sodium perborate, and sodium persulfate. It is done. These are used alone or in combination of two or more.
なお、上記（Ｆ）成分の塩素系漂白剤もしくは酸素系漂白剤としては、その平均粒径が０．５〜３．０ｍｍに設定されたものを用いることが望ましい。これは、ベースとなる粒状洗浄剤組成物の平均粒径とのバランスを考慮したもので、（Ｆ）成分の平均粒径が０．５ｍｍ未満では、飛散性抑制効果が損なわれるおそれがあり、一方、平均粒径が３．０ｍｍを超えると、均質な溶解性が得られず、所望の洗浄性能に乏しいものとなり、好ましくない。 In addition, as a chlorine bleach or oxygen bleach of the said (F) component, it is desirable to use that whose average particle diameter was set to 0.5-3.0 mm. This is in consideration of the balance with the average particle size of the granular cleaning composition as a base, and if the average particle size of the component (F) is less than 0.5 mm, the scattering effect may be impaired. On the other hand, if the average particle size exceeds 3.0 mm, homogeneous solubility cannot be obtained, and the desired cleaning performance is poor, which is not preferable.
上記（Ｆ）成分である塩素系漂白剤もしくは酸素系漂白剤を混合する場合、その含有量は、粒状洗浄剤組成物全体に対する有効塩素量もしくは有効酸素量として、０．１〜１０％に設定することが好適で、より好ましくは、０．５〜５％である。すなわち、この範囲で、洗浄力、特にしみになりやすい強固な汚れに対する洗浄力をより高めることができるからである。なお、１０％を超えて配合すると、貯蔵安定性が低下するとともに、他成分との相乗効果がそれ以上得られず、好ましくない。 When the chlorine bleach or oxygen bleach that is the component (F) is mixed, the content is set to 0.1 to 10% as an effective chlorine amount or an effective oxygen amount with respect to the whole granular detergent composition. It is suitable to do, More preferably, it is 0.5 to 5%. That is, in this range, it is possible to further increase the cleaning power, particularly the cleaning power against strong dirt that easily becomes a stain. In addition, when it exceeds 10%, the storage stability is lowered, and a synergistic effect with other components cannot be obtained any more, which is not preferable.
また、本発明において、上記（Ｆ）成分と同様、造粒された略球状粒状体の集合体に、（Ｇ）成分として、洗剤用酵素を混合することができる。上記洗剤用酵素としては、アミラーゼ、プロテアーゼ、リパーゼ、セルラーゼ、プルラナーゼ、ペクチナーゼ等があげられ、これらも単独もしくは２種以上の併用で用いられる。なお、上記洗剤用酵素も、（Ｆ）成分と同様の理由から、その平均粒径が０．５〜３．０ｍｍに設定されたものを用いることが望ましい。 Moreover, in this invention, the enzyme for detergents can be mixed as a (G) component with the aggregate | assembly of the granulated substantially spherical granular material similarly to the said (F) component. Examples of the detergent enzyme include amylase, protease, lipase, cellulase, pullulanase, and pectinase, and these are also used alone or in combination of two or more. In addition, as for the said enzyme for detergents, it is desirable to use what the average particle diameter was set to 0.5-3.0 mm from the reason similar to (F) component.
上記（Ｇ）成分である洗剤用酵素を混合する場合、その含有量は、粒状洗浄剤組成物全体に対し、０．１〜１０％に設定することが好適で、より好ましくは、１〜７％である。すなわち、この範囲で、洗浄力をより高めることができるからである。なお、１０％を超えて配合すると、全体としてのバランスが悪くなるとともに、他成分との相乗効果がそれ以上得られず、経済性の点からも、好ましくない。 When mixing the enzyme for detergents which is the said (G) component, it is suitable to set the content to 0.1 to 10% with respect to the whole granular cleaning composition, More preferably, it is 1-7. %. That is, the cleaning power can be further increased within this range. In addition, when it mixes exceeding 10%, while the balance as a whole worsens, the synergistic effect with another component is not acquired any more, and it is not preferable also from the point of economical efficiency.
そして、このようにして得られる本発明の粒状洗浄剤組成物は、これを水で希釈してなる０．１％水溶液のｐＨが、８〜１２の範囲となるよう調製されていることが、電気洗濯機による衣料の洗浄に用いる上で、好適である。 And the granular detergent composition of the present invention thus obtained is prepared so that the pH of a 0.1% aqueous solution obtained by diluting it with water is in the range of 8-12. It is suitable for use in washing clothes with an electric washing machine.
本発明の粒状洗浄剤組成物は、スタンディングパウチ等の袋体、紙製容器、プラスチック容器等に充填して流通に供することができる。 The granular detergent composition of the present invention can be filled into a bag such as a standing pouch, a paper container, a plastic container or the like for distribution.
そして、本発明の粒状洗浄剤組成物は、家庭用および業務用を問わず、各種の電気洗濯機を用いた衣料の洗浄に用いられる。また、その使用の際の希釈濃度は、０．０３〜０．３％に設定することが好適である。 And the granular cleaning composition of this invention is used for washing | cleaning of the clothing using various electric washing machines regardless of household use and business use. Moreover, it is suitable to set the dilution concentration at the time of use to 0.03 to 0.3%.
つぎに、本発明の実施例について、参考例、比較例と併せて説明する。ただし、本発明は、以下の実施例に限定されるものではない。 Next, examples of the present invention will be described together with reference examples and comparative examples. However, the present invention is not limited to the following examples.
〔実施例１〜１０６、参考例１，２、比較例１〜６〕
後記の表１〜表１６に示す配合組成に従って、全量が５０ｋｇとなるようにハイスピードミキサー（型式：ＦＳ／ＧＳ−１００Ｊ、深江パウテック社製）に原料を順次添加して均一混合した後、加熱して品温が所定の温度に達した時点で造粒を行った。そして、水封式ポンプ（型式：ＳＷ２００Ｓ、神港精密機械社製）による減圧乾燥を行なうことにより、粒状洗浄剤組成物を製造した。
[Examples 1 to 106, Reference Examples 1 and 2 , Comparative Examples 1 to 6]
In accordance with the composition shown in Tables 1 to 16 below, the raw materials are sequentially added to a high speed mixer (model: FS / GS-100J, manufactured by Fukae Powtech Co., Ltd.) so that the total amount becomes 50 kg, and then heated uniformly. Then, granulation was performed when the product temperature reached a predetermined temperature. And the granular cleaning composition was manufactured by performing reduced pressure drying by a water seal pump (model: SW200S, Shinko Seimitsu Co., Ltd.).
得られた粒状洗浄剤組成物について、平均粒径を求めるとともに、前述の式（１）に従って、その真球度を算出した。また、以下の試験方法等に従って、製造性、飛散性、溶解性、ｐＨ、有効塩素もしくは有効酸素の安定性、貯蔵安定性、洗浄性の７項目を評価した。その結果を後記の表１〜表１６に併せて示す。なお、後記の表１〜表１６において、用いた成分とその有効純分（％）の詳細は、下記のとおりであり、表中の数値は、有効純分１００％に換算して示したものである。なお、表中の「水」は、粒状洗浄剤組成物を構成する各成分に由来する結晶水や水溶液の形で含まれる水ではなく、外から加えられる水であり、粒状洗浄剤組成物全体が１００％となるようバランスとして示される。 About the obtained granular cleaning composition, while calculating | requiring an average particle diameter, the sphericity was computed according to above-mentioned Formula (1). In addition, according to the following test methods and the like, seven items of manufacturability, scatterability, solubility, pH, effective chlorine or effective oxygen stability, storage stability, and detergency were evaluated. The results are also shown in Tables 1 to 16 below. In Tables 1 to 16 below, the details of the components used and their effective pure content (%) are as follows, and the values in the table are shown in terms of 100% effective pure content. It is. “Water” in the table is not water contained in the form of crystal water or aqueous solution derived from each component constituting the granular detergent composition, but water added from the outside , and the entire granular detergent composition Is shown as a balance to be 100%.
〔製造性〕
・試験方法
造粒後、原料洗浄剤組成物が粒状成形体となるか否かを目視により観察し、下記の判定基準に従い評価した。
・評価基準
○：造粒後、粒状成形体ができた。
△：造粒後、粒状成形体にならないものが一部混じっていた。
×：造粒後、粒状成形体ができなかった。
〔Manufacturability〕
Test Method After granulation, whether or not the raw material cleaning composition becomes a granular compact was visually observed and evaluated according to the following criteria.
・ Evaluation criteria ○: After granulation, a granular compact was formed.
(Triangle | delta): The thing which does not become a granular molding after granulation was mixed partially.
X: After granulation, a granular molded body could not be formed.
〔飛散性〕
・試験方法
内径５２ｍｍ、高さ１１００ｍｍのアクリル円筒容器を垂直に立て、円筒上部より粒状洗浄剤組成物を２００ｇ自然落下させる。その１秒後に舞い上がった粉塵を吸引し、その時の捕集量から、下記の式（２）にもとづいて飛散率（％）を算出し、下記の判定基準に従って評価した。
[Spattering]
Test Method An acrylic cylindrical container having an inner diameter of 52 mm and a height of 1100 mm is set up vertically, and 200 g of the granular cleaning composition is naturally dropped from the upper part of the cylinder. Dust that soared after 1 second was sucked, and the scattering rate (%) was calculated from the amount collected at that time based on the following formula (2), and evaluated according to the following criteria.
〔数４〕
飛散率（％）＝Ｓ／２００（ｇ）×１００ ……（２）
Ｓ：サンプル捕集量（ｇ）
[Equation 4 ]
Scattering rate (%) = S / 200 (g) × 100 (2)
S: Sample collection amount (g)
・評価基準
◎：飛散率が０．５％未満
○：飛散率が０．５％以上１％未満
△：飛散率が１％以上１．５％未満
×：飛散率が１．５％以上
・ Evaluation criteria ◎: Scatter rate is less than 0.5% ○: Scatter rate is 0.5% or more and less than 1% △: Scatter rate is 1% or more and less than 1.5% ×: Scatter rate is 1.5% or more
〔溶解性〕
・試験方法
マグネティックスターラーに乗せた６０℃のウォーターバスに、６０℃のお湯１リットルと攪拌子の入った１リットルビーカーを浸け、お湯を回転数５００ｒｐｍで回転させた。そこに粒状洗浄剤組成物を１ｇ入れて、溶解するまでの時間を測定し、下記の判定基準に従い評価した。
・評価基準
◎：溶解時間が６０秒未満
○：溶解時間が６０秒以上１２０秒未満
△：溶解時間が１２０秒以上１８０秒未満
×：溶解時間が１８０秒以上
[Solubility]
Test Method A 1 liter beaker containing 1 liter of hot water and a stir bar was immersed in a 60 ° C. water bath placed on a magnetic stirrer, and the hot water was rotated at a rotation speed of 500 rpm. 1 g of the granular detergent composition was put therein, the time until dissolution was measured, and evaluated according to the following criteria.
Evaluation criteria A: Dissolution time less than 60 seconds ○: Dissolution time 60 seconds or more and less than 120 seconds Δ: Dissolution time 120 seconds or more and less than 180 seconds X: Dissolution time 180 seconds or more
〔ｐＨ〕
・試験方法
ＪＩＳ Ｚ−８８０２：１９８４に従い、０．１％に調製された粒状洗浄剤組成物の水溶液の２５℃におけるｐＨを測定し、下記の判定基準に従い評価した。
・評価基準
○：ｐＨが８〜１２である。
×：ｐＨが８未満もしくは１２を超えている。
[PH]
Test Method According to JIS Z-8802: 1984, the pH of an aqueous solution of a granular detergent composition prepared to 0.1% was measured at 25 ° C. and evaluated according to the following criteria.
-Evaluation criteria (circle): pH is 8-12.
X: pH is less than 8 or more than 12.
〔有効塩素、有効酸素の安定性〕
・試験方法
粒状洗浄剤組成物を２５０ｍｌ容量のポリプロピレン製容器に入れ、５０℃にて２ヶ月間保存し、残存する有効塩素もしくは有効酸素を下記の（１）もしくは（２）の方法で測定し、保存前の有効塩素、有効塩素に対する比率を残存率（％）として求め、安定性を下記の判定基準に従い評価した。
（１）有効塩素測定法
試料３ｇを２００ｍｌ容量三角フラスコに取り、それに１０％ヨウ素ヨウ化カリウム溶液１５ｍｌ、（１＋１）硫酸１０ｍｌを添加し、冷暗所に３分間静置してヨウ素を遊離させ、次に０．１Ｎチオ硫酸ナトリウム規定液でヨウ素の黄色が消失するまで滴定し、下記の式（３）から算出する。
[Stability of effective chlorine and effective oxygen]
Test method Put the granular detergent composition in a 250 ml polypropylene container, store it at 50 ° C. for 2 months, and measure the remaining effective chlorine or effective oxygen by the following method (1) or (2). Then, the effective chlorine before storage and the ratio to the effective chlorine were determined as the residual rate (%), and the stability was evaluated according to the following criteria.
(1) Effective chlorine measurement method Take 3 g of sample in a 200 ml Erlenmeyer flask, add 15 ml of 10% potassium iodide iodide solution and 10 ml of (1 + 1) sulfuric acid, and leave it in a cool dark place for 3 minutes to release iodine. The solution is titrated with 0.1N sodium thiosulfate normal solution until the yellow color of iodine disappears and calculated from the following formula (3).
〔数５〕
有効塩素（％：Ｃｌとして）＝０．３５４５×Ａ／Ｓ ……（３）
Ａ：０．１Ｎチオ硫酸ナトリウム規定液の滴定量（ｍｌ）
Ｓ：サンプル採取量（ｇ）
[Equation 5 ]
Effective chlorine (%: as Cl) = 0.545 × A / S (3)
A: Titration volume of 0.1N sodium thiosulfate normal solution (ml)
S: Sample collection amount (g)
（２）有効酸素測定法
試料１ｇを２００ｍｌ容量三角フラスコに取り、それに１７％ヨウ素ヨウ化カリウム溶液１０ｍｌ、（１＋９）硫酸１５ｍｌ、５％モリブデン酸アンモニウム２ｍｌを添加し、冷暗所に３分間静置してヨウ素を遊離させ、次に０．１Ｎチオ硫酸ナトリウム規定液でヨウ素の黄色が消失するまで滴定し、下記の式（４）から算出する。
(2) Effective oxygen measurement method Take 1 g of a sample in a 200 ml Erlenmeyer flask, add 10 ml of 17% potassium iodide iodide solution, 15 ml of (1 + 9) sulfuric acid, 2 ml of 5% ammonium molybdate, and leave it in a cool and dark place for 3 minutes. Then, iodine is liberated, titrated with 0.1N sodium thiosulfate normal solution until the yellow color of iodine disappears, and calculated from the following formula (4).
〔数６〕
有効酸素（％：Ｈ2 Ｏ2 として）＝０．１７×Ａ／Ｓ ……（４）
Ａ：０．１Ｎチオ硫酸ナトリウム規定液の滴定量（ｍｌ）
Ｓ：サンプル採取量（ｇ）
[Equation 6 ]
Effective oxygen (%: H 2 O 2 ) = 0.17 × A / S (4)
A: Titration volume of 0.1N sodium thiosulfate normal solution (ml)
S: Sample collection amount (g)
・評価基準
◎：残存率が７０％以上
○：残存率が７０％未満５０％以上
△：残存率が５０％未満３０％以上
×：残存率が３０％未満
・ Evaluation criteria ◎: Residual rate is 70% or more ○: Residual rate is less than 70% 50% or more △: Residual rate is less than 50% 30% or more ×: Residual rate is less than 30%
〔貯蔵安定性〕
・試験方法
粒状洗浄剤組成物を２５０ｍｌのポリプロピレン製容器に入れ、温度４０℃、湿度７５％の恒温恒湿器（型式：ＩＧ４７Ｍ、ヤマト科学社製）にて３ヶ月間保存した。その外観を目視により観察し、下記の評価基準により貯蔵温安定性を評価した。
・評価基準
○：３ヶ月後、変色・固結等は認められなかった。
△：３ヶ月後、変色・固結等がわずかに認められた。
×：３ヶ月後、変色・固結等が顕著に認められた。
[Storage stability]
Test Method The granular detergent composition was placed in a 250 ml polypropylene container and stored for 3 months in a constant temperature and humidity chamber (model: IG47M, manufactured by Yamato Scientific Co., Ltd.) having a temperature of 40 ° C. and a humidity of 75%. The appearance was visually observed, and storage temperature stability was evaluated according to the following evaluation criteria.
-Evaluation criteria ○: After 3 months, no discoloration or consolidation was observed.
Δ: Slight discoloration or consolidation was observed after 3 months.
X: After 3 months, discoloration, consolidation and the like were remarkably recognized.
〔洗浄性〕
・試験方法
ＪＩＳ Ｋ−３３６２：１９９８に従い、０．１％に調整された粒状洗浄剤組成物の水溶液をかき混ぜ式洗浄力試験機（型式：ＴＭ４ターゴトメーター、大栄科学精器製作所社製）に用意し、被洗浄物（湿式人工汚染布、洗濯科学協会）を投入して、３０℃における洗浄力を、下記の判定基準に従い評価した。洗浄力は被洗浄物を式差計（型式：ＴＣ−１８００ＭＫＩＩ、東京電色社製）で測定し、下記の式（５）から算出する。
[Cleanability]
Test method An aqueous solution of a granular detergent composition adjusted to 0.1% according to JIS K-3362: 1998 is mixed into a stirring type detergency tester (model: TM4 Targotometer, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.). An object to be cleaned (wet artificially contaminated cloth, Association for Laundry Science) was introduced, and the cleaning power at 30 ° C. was evaluated according to the following criteria. The detergency is calculated from the following equation (5) by measuring the object to be cleaned with a differential meter (model: TC-1800MKII, manufactured by Tokyo Denshoku Co., Ltd.).
〔数７〕
洗浄力（％）＝（Ｒｗ−Ｒｓ）／（Ｒ０−Ｒｓ）×１００ ……（５）
Ｒ０：白色布の反射率，
Ｒｓ：洗浄前の湿式人工汚染布の反射率
Ｒｗ：洗浄後の湿式人工汚染布の反射率
[Equation 7 ]
Detergency (%) = (Rw−Rs) / (R0−Rs) × 100 (5)
R0: reflectance of white cloth,
Rs: reflectance of wet artificially contaminated cloth before washing Rw: reflectance of wet artificially contaminated cloth after washing
＊運転条件
洗剤濃度 ：０．１％
洗浄温度 ：３０℃
洗浄 ：回転速度１２０ｒｐｍ、１０分間
すすぎ温度 ：３０℃
すすぎ ：回転速度１２０ｒｐｍ、３分間×２回
水道水の硬度：（ＣａＣＯ3 として）７０〜８０ｐｐｍ
被洗浄物 ：縦５ｃｍ×横５ｃｍの湿式人工汚染布を用いた。
・評価基準
◎：９０％以上の汚れ除去
○：７０％以上９０％未満の汚れ除去
△：５０％以上７０％未満の汚れ除去
×：５０％未満の汚れ除去
* Operating condition Detergent concentration: 0.1%
Washing temperature: 30 ° C
Cleaning: Rotating speed 120 rpm, 10 minutes rinse temperature: 30 ° C
Rinse: Rotating speed 120 rpm, 3 minutes x 2 times Tap water hardness: (as CaCO 3 ) 70-80 ppm
Object to be cleaned: A wet artificial contamination cloth having a length of 5 cm and a width of 5 cm was used.
・ Evaluation criteria ◎: 90% or more dirt removal ○: 70% or more and less than 90% dirt removal △: 50% or more and less than 70% dirt removal ×: Less than 50% dirt removal
なお、後記の表１〜表１６において用いた各種成分とその有効純分（質量％）の詳細は、下記の通りである。 The details of various components used in Tables 1 to 16 below and their effective pure content (% by mass) are as follows.
〔Ａ成分〕
・アルカリ剤１
無水メタ珪酸ナトリウム
商品名：メタ珪酸ソーダ無水粒状（広栄化学工業社製）
・アルカリ剤２
メタ珪酸ナトリウム・五水塩
商品名：メタ珪酸ソーダ・５水塩結晶（広栄化学工業社製）
・アルカリ剤３
メタ珪酸ナトリウム・九水塩
商品名：メタ珪酸ソーダ・９水塩（三宝化学社製）
・アルカリ剤４
オルソ珪酸ナトリウム 純分：６５％
商品名：オルソ６５（東洋珪酸ソーダ社製）
・アルカリ剤５
水酸化ナトリウム
商品名：トーソーパール（東ソー社製）
・アルカリ剤６
水酸化カリウム
商品名：水酸化カリウム特級粧原基劇物（東亞合成社製）
・アルカリ剤７
炭酸ナトリウム
商品名：ライトソーダ灰（徳山曹達社製）
・アルカリ剤８
炭酸水素ナトリウム
商品名：重炭酸ナトリウム（徳山曹達社製）
[Component A]
・ Alkaline agent 1
Anhydrous sodium metasilicate
Product name: Sodium metasilicate anhydrous granule (Guangei Chemical Industry Co., Ltd.)
・ Alkaline agent 2
Sodium metasilicate / pentahydrate Product name: Sodium metasilicate / pentahydrate crystal (Guangei Chemical Industry Co., Ltd.)
・ Alkaline agent 3
Sodium metasilicate / Nine hydrate Product name: Sodium metasilicate / 9 hydrate (manufactured by Sanpo Chemical Co., Ltd.)
・ Alkaline agent 4
Sodium orthosilicate pure content: 65%
Product Name: Ortho 65 (Toyo Silica)
・ Alkaline agent 5
Sodium hydroxide
Product name: Tosoh Pearl (manufactured by Tosoh Corporation)
・ Alkaline agent 6
Potassium hydroxide Product name: Potassium hydroxide special make-up base material (manufactured by Toagosei Co., Ltd.)
・ Alkaline agent 7
sodium carbonate
Product Name: Light Soda Ash (Made by Tokuyama Soda)
・ Alkaline agent 8
sodium hydrogen carbonate
Product name: Sodium bicarbonate (made by Tokuyama Soda Co., Ltd.)
〔Ｂ成分〕
・金属イオン封鎖剤１
グルコン酸ナトリウム
商品名：グルコン酸ソーダ（扶桑化学工業社製）
・金属イオン封鎖剤２
クエン酸ナトリウム
商品名：クエン酸三ナトリウム（磐田化学工業社製）
・金属イオン封鎖剤３
エチレンジアミン四酢酸四ナトリウム
商品名：トリロンＢ（ＢＡＳＦ社製）
・金属イオン封鎖剤４
ニトリロ三酢酸三ナトリウム
商品名：トリロンＡ９２Ｒ（ＢＡＳＦ社製）
・金属イオン封鎖剤５
グルタミン酸−Ｎ，Ｎ′−二酢酸四ナトリウム
純分：３８％
商品名：ディゾルビンＧＬ−３８（アクゾノーベル社製）
・金属イオン封鎖剤６
トリポリリン酸ナトリウム
商品名：トリポリリン酸ソーダ（日本化学工業社製）
・金属イオン封鎖剤７
リン酸三ナトリウム
商品名：第三燐酸ソーダ（日本化学工業社製）
・金属イオン封鎖剤８
１−ヒドロキシエチリデンー１，１−ジホスホン酸
商品名：ディクエスト２０１６Ｄ（ソルーシア社製）
・金属イオン封鎖剤９
ゼオライト
商品名：シルトンＢ粉末（水澤化学工業社製）
[B component]
・ Metal ion sequestering agent 1
Sodium gluconate Product name: Sodium gluconate (manufactured by Fuso Chemical Industries)
・ Metal ion sequestering agent 2
Sodium citrate Product name: Trisodium citrate (manufactured by Iwata Chemical Industries)
・ Metal ion sequestering agent 3
Ethylenediaminetetraacetic acid tetrasodium Product name: Trilon B (manufactured by BASF)
・ Metal ion sequestering agent 4
Nitrilotriacetic acid trisodium Product name: Trilon A92R (BASF)
・ Metal ion sequestering agent 5
Glutamic acid-N, N'-tetrasodium diacetate pure: 38%
Product name: Dissolvin GL-38 (manufactured by Akzo Nobel)
・ Metal ion sequestering agent 6
Sodium tripolyphosphate Product name: Sodium tripolyphosphate (manufactured by Nippon Chemical Industry Co., Ltd.)
・ Metal ion sequestering agent 7
Trisodium phosphate Product name: Trisodium phosphate (manufactured by Nippon Chemical Industry Co., Ltd.)
・ Metal ion sequestering agent 8
1-hydroxyethylidene-1,1-diphosphonic acid Product name: Diquest 2016D (manufactured by Solusia)
・ Metal ion sequestering agent 9
Zeolite trade name: Shilton B powder (manufactured by Mizusawa Chemical Industry Co., Ltd.)
〔Ｃ成分〕
・界面活性剤１
ポリオキシエチレンポリオキシプロピレンブロックポリマー（プルロニック型ブロックポリマー）
ＥＯ／ＰＯ重量比＝０．６７、平均分子量：３，３００
商品名：エパン７４０（第一工業製薬社製）
・界面活性剤２
ポリオキシエチレンポリオキシプロピレンブロックポリマー（リバースプルロニック型ブロックポリマー）
ＥＯ／ＰＯ重量比＝０．６７、平均分子量：２，８００
商品名：プルロニックＲＰＥ１７４０（ＢＡＳＦ社製）
・界面活性剤３
ポリオキシエチレン（Ｐ＝１５）ポリオキシプロピレン（ｑ＝９）直鎖アルキル（Ｃ＝１４、１５）エーテル
ＥＯ／ＰＯ重量比＝１．２６
試作品
・界面活性剤４
ポリオキシエチレン（Ｐ＝８）ポリオキシプロピレン（ｑ＝６）直鎖アルキル（Ｃ＝１２、１３）エーテル
ＥＯ／ＰＯ重量比＝１．０１、曇点＝３１℃
商品名：ペポールＡＳ−０５４Ｃ（東邦化学工業社製）
・界面活性剤５
ポリオキシエチレン（ｍ＝４）ポリオキシプロピレン（ｑ＝３８）直鎖アルキル（Ｃ＝１６〜１８）エーテル
ＥＯ／ＰＯ重量比＝０．０８
商品名：アデカトールＬＧ−２９９（旭電化工業社製）
・界面活性剤６
ポリオキシエチレンポリオキシプロピレンブロックポリマー（プルロニック型ブロックポリマー）
ＥＯ／ＰＯ重量比＝０．１１、平均分子量＝２，０００、曇点２４℃
商品名：プルロニックＰＥ６１００（ＢＡＳＦ社製）
・界面活性剤７
ポリオキシエチレンポリオキシプロピレンブロックポリマー（リバースプルロニック型ブロックポリマー）
ＥＯ／ＰＯ重量比＝０．１１、平均分子量＝２，８００
商品名：プルロニックＲＰＥ２５１０（ＢＡＳＦ社製）
・界面活性剤８
トリメチロールプロパンＥＯ，ＰＯ付加物
ＥＯ／ＰＯ重量比＝０．２１、平均分子量＝４，５００
試作品
・界面活性剤９
グリセリンＥＯ，ＰＯ付加物
ＥＯ／ＰＯ重量比＝０．２２、平均分子量＝４，５００
試作品
・界面活性剤１０
ラウリル硫酸ナトリウム
商品名：モノゲンＹ−１００（第一工業製薬社製）
・界面活性剤１１
アルキルベンゼンスルホン酸ナトリウム
商品名：ネオペレックスＧＳ（花王社製）
・界面活性剤１２
混合脂肪酸石鹸
商品名：ノンサールＰＮ−１７１（日本油脂社製）
・界面活性剤１３
オレイン酸複合石鹸
商品名：ノンサールＯＫ−２（日本油脂社製）
[C component]
・ Surfactant 1
Polyoxyethylene polyoxypropylene block polymer (pluronic block polymer)
EO / PO weight ratio = 0.67, average molecular weight: 3,300
Product name: Epan 740 (Daiichi Kogyo Seiyaku Co., Ltd.)
・ Surfactant 2
Polyoxyethylene polyoxypropylene block polymer (reverse pluronic block polymer)
EO / PO weight ratio = 0.67, average molecular weight: 2,800
Product name: Pluronic RPE 1740 (BASF)
・ Surfactant 3
Polyoxyethylene (P = 15) Polyoxypropylene (q = 9) Linear alkyl (C = 14, 15) ether EO / PO weight ratio = 1.26
Prototype / Surfactant 4
Polyoxyethylene (P = 8) Polyoxypropylene (q = 6) Linear alkyl (C = 12, 13) ether EO / PO weight ratio = 1.01, Cloud point = 31 ° C.
Product name: Pepol AS-054C (manufactured by Toho Chemical Industry Co., Ltd.)
・ Surfactant 5
Polyoxyethylene (m = 4) Polyoxypropylene (q = 38) Linear alkyl (C = 16-18) ether EO / PO weight ratio = 0.08
Product name: Adecatol LG-299 (Asahi Denka Kogyo Co., Ltd.)
・ Surfactant 6
Polyoxyethylene polyoxypropylene block polymer (pluronic block polymer)
EO / PO weight ratio = 0.11, average molecular weight = 2,000, cloud point 24 ° C.
Product name: Pluronic PE6100 (manufactured by BASF)
・ Surfactant 7
Polyoxyethylene polyoxypropylene block polymer (reverse pluronic block polymer)
EO / PO weight ratio = 0.11, average molecular weight = 2,800
Product name: Pluronic RPE2510 (manufactured by BASF)
・ Surfactant 8
Trimethylolpropane EO, PO adduct EO / PO weight ratio = 0.21, average molecular weight = 4,500
Prototype / Surfactant 9
Glycerin EO, PO adduct EO / PO weight ratio = 0.22, average molecular weight = 4,500
Prototype / Surfactant 10
Sodium lauryl sulfate Product name: Monogen Y-100 (Daiichi Kogyo Seiyaku Co., Ltd.)
・ Surfactant 11
Sodium alkylbenzenesulfonate Product name: Neoperex GS (manufactured by Kao Corporation)
・ Surfactant 12
Mixed fatty acid soap Product name: NONSAR PN-171 (manufactured by NOF Corporation)
・ Surfactant 13
Oleic acid complex soap Product name: Nonsal OK-2 (Nippon Yushi Co., Ltd.)
〔Ｄ成分〕
・高分子電解質重合体１
ポリアクリル酸ナトリウム
平均分子量：１５，０００
商品名：ソカランＰＡ−４０Ｐ（ＢＡＳＦ社製）
・高分子電解質重合体２
アクリル酸−マレイン酸共重合体
平均分子量：７０，０００
商品名：ソカランＣＰ−４５Ｇ（ＢＡＳＦ社製）
[D component]
・ Polyelectrolyte polymer 1
Sodium polyacrylate average molecular weight: 15,000
Product name: Socaran PA-40P (BASF)
・ Polyelectrolyte polymer 2
Acrylic acid-maleic acid copolymer Average molecular weight: 70,000
Product name: Socaran CP-45G (BASF)
〔洗浄ビルダー成分〕
・洗浄ビルダー１
無水硫酸ナトリウム
商品名：中性無水芒硝Ａ０（四国化成社製）
・洗浄ビルダー２
硫酸カリウム
商品名：硫酸カリウム（大塚化学社製）
[Cleaning builder ingredients]
・ Cleaning builder 1
Anhydrous sodium sulfate
Product name: Neutral anhydrous sodium sulfate A0 (manufactured by Shikoku Chemicals)
・ Cleaning builder 2
Potassium sulfate
Product name: Potassium sulfate (Otsuka Chemical Co., Ltd.)
〔バインダー成分〕
・バインダー１
アルギン酸ナトリウム
平均分子量：４０，０００
商品名：サンアルギン（三晶社製）
・バインダー２
カルボキシメチルスターチナトリウム
平均分子量：７，５００，０００
商品名：グリコリス−ＬＶ（ロケットジャパン社製）
・バインダー３
カルボキシメチルセルロースナトリウム
平均分子量：１０，０００
商品名：セロゲンＰＲ（第一工業製薬社製）
・バインダー４
アクリル酸アミド重合物
平均分子量：５，０００，０００
商品名：試薬（和光純薬社製）
・バインダー５
ポリビニルアルコール
平均分子量：４４，０００
商品名：ＶＣ−１０（日本酢ビ・ポバール社製）
・バインダー６
ポリエチレングリコール
平均分子量：２０，０００
商品名：ＰＥＧ２００００（三洋化成工業社製）
(Binder component)
・ Binder 1
Sodium alginate Average molecular weight: 40,000
Product name: Sun Argin (Mitsubishi)
・ Binder 2
Sodium carboxymethyl starch Average molecular weight: 7,500,000
Product name: Glicolis-LV (manufactured by Rocket Japan)
・ Binder 3
Sodium carboxymethyl cellulose Average molecular weight: 10,000
Product name: Serogen PR (Daiichi Kogyo Seiyaku Co., Ltd.)
・ Binder 4
Acrylic acid amide polymer average molecular weight: 5,000,000
Product name: Reagent (Wako Pure Chemical Industries, Ltd.)
・ Binder 5
Polyvinyl alcohol Average molecular weight: 44,000
Product name: VC-10 (Nippon Vinegar-Poval)
・ Binder 6
Polyethylene glycol Average molecular weight: 20,000
Product name: PEG 20000 (manufactured by Sanyo Chemical Industries)
〔Ｆ成分〕
・塩素系漂白剤１
ジクロロイソシアヌル酸ナトリウム
純分：６０％
商品名：ネオクロール６０Ｇ（四国化成社製）
・酸素系漂白剤１
過炭酸ナトリウム
商品名：ＰＣ−Ａ（日本パーオキサイド社製）
・酸素系漂白剤２
過ホウ酸ナトリウム
商品名：１５％ぺルボン（第一工業製薬社製）
[F component]
・ Chlorine bleach 1
Sodium dichloroisocyanurate, pure: 60%
Product name: Neocrawl 60G (Shikoku Kasei Co., Ltd.)
・ Oxygen bleach 1
Sodium percarbonate Product name: PC-A (Nippon Peroxide)
・ Oxygen bleach 2
Sodium perborate Brand name: 15% Perbon (Daiichi Kogyo Seiyaku Co., Ltd.)
〔漂白活性剤成分〕
・漂白活性剤１
テトラアセチルエチレンジアミン
商品名：ＴＡＥＤ（クラリアントジャパン社製）
[Bleaching activator component]
・ Bleaching activator 1
Tetraacetylethylenediamine Product name: TAED (manufactured by Clariant Japan)
〔蛍光増白剤成分〕
・蛍光増白剤１
４，４’−ビス［スルホスチリル］ビフェニル２ナトリウム
商品名：チノパールＣＢＳ−Ｘ（チバガイギー社製）
[Fluorescent brightener component]
・ Fluorescent brightener 1
4,4'-bis [sulfostyryl] biphenyl disodium Product name: Tinopearl CBS-X (Ciba Geigy)
〔Ｇ成分〕
・酵素１
アミラーゼ
商品名：ターマミル６０ＴＮＴ（ノボザイム社製）
・酵素２
プロテアーゼ
商品名：エバラーゼ８．０Ｔ（ノボザイム社製）
・酵素３
リパーゼ
商品名：リポラーゼ（ノボザイム社製）
[G component]
・ Enzyme 1
Amylase Product name: Termamyl 60TNT (Novozyme)
・ Enzyme 2
Protease Product name: Everase 8.0T (Novozyme)
・ Enzyme 3
Lipase Product name: Lipolase (Novozyme)
〔消泡剤成分〕
・シリコーン系消泡剤１
シリコーン
商品名：ＫＳ−５３０（信越化学工業社製）
[Antifoaming ingredient]
・ Silicone-based antifoaming agent 1
Silicone Product name: KS-530 (manufactured by Shin-Etsu Chemical Co., Ltd.)
〔比較例７、８〕
本発明の粒状洗浄剤組成物とは形状の異なる比較例７として、図２（ａ）に示すように、ごく微細な粉体からなる洗浄剤組成物（商品名：ちょぴっとくん、ティーポールディバーシー社製）を準備した。また、比較例８として、図２（ｂ）に示すように、ごく微細な粉体と比較的大きな粒状体とが混在する洗浄剤組成物（商品名：ニューホワイトウォッシュ、ティーポールディバーシー社製）を準備した。
[Comparative Examples 7 and 8]
As Comparative Example 7 having a shape different from that of the granular detergent composition of the present invention, as shown in FIG. 2 (a), as shown in FIG. 2 (a), a detergent composition comprising a very fine powder (trade names: Chopittokun, Tea Pole Diversity Prepared). Further, as Comparative Example 8, as shown in FIG. 2 (b), a detergent composition in which very fine powder and relatively large particles are mixed (trade name: New White Wash, manufactured by Tea Pole Diversity) Prepared.
そして、上記２つの比較例品についても、前記と同様の評価項目について評価し、その結果を下記の表１７に示す。なお、各比較例品の特徴を、表１７に併せて示す。 And also about the said 2 comparative example goods, it evaluated about the evaluation item similar to the above, and the result is shown in following Table 17. FIG. The characteristics of each comparative product are shown in Table 17.
表１〜表１７の結果より、実施例品１〜１０６は、組成によっては、一部評価がやや劣る項目もあるが、全般に、真球度、製造性、飛散性、溶解性、ｐＨ、有効塩素もしくは有効酸素の安定性、貯蔵安定性、洗浄性のいずれの評価項目においても、優れた性能を有していることがわかる。これに対し、必須成分が一つでも欠けている比較例品１〜４や、粒子の平均粒径や形状が特許請求の範囲を外れている比較例品５〜８は、悪い評価項目がいくつかあり、実用上問題であることがわかる。 From the results of Tables 1 to 17, although Examples 1 to 106 have some items that are slightly inferior depending on the composition, in general, sphericity, manufacturability, scatterability, solubility, pH, It turns out that it has the outstanding performance in any evaluation item of stability, storage stability, and detergency of effective chlorine or effective oxygen. On the other hand, Comparative Examples 1 to 4 lacking even one essential component and Comparative Examples 5 to 8 whose average particle diameter and shape of the particles are outside the scope of the claims have several bad evaluation items. It turns out that this is a practical problem.
Claims (14)
（Ａ）アルカリ金属水酸化物、珪酸アルカリ金属塩、炭酸ナトリウムおよび炭酸水素ナトリウムから選ばれる一種または二種以上の化合物
（Ｂ）金属イオン封鎖剤
（Ｃ）界面活性剤
（Ｄ）高分子電解質重合体
〔数１〕
真球度＝Ｒ２／Ｒ１ …（１）
〔Ｒ１：粒状体の長径、Ｒ２：粒状体の短径〕 While containing the following (A)-(D) component as an essential component, the raw material composition which contains 0.1-9 mass% of water, the following (A)-(D) component is prepared in the slurry form. In a state that is not spray-dried or heated and melted after that, it is supplied to a high-speed agitation granulator and granulated in a batch system. According to the screening method described in JIS K-3362: 1998 “Synthetic detergent test method” An approximately spherical shape in which the average particle size obtained from the measured particle size is set to 0.8 to 3.0 mm, and the sphericity calculated by the following formula (1) is set to 0.7 to 1.0. A granular detergent composition for clothing, comprising an aggregate of granules.
(A) One or more compounds selected from alkali metal hydroxides, alkali metal silicates, sodium carbonate and sodium hydrogen carbonate (B) sequestering agent (C) surfactant (D) polymer electrolyte heavy Combined [Equation 1]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material]
（Ａ）アルカリ金属水酸化物、珪酸アルカリ金属塩、炭酸ナトリウムおよび炭酸水素ナトリウムから選ばれる一種または二種以上の化合物
（Ｂ）金属イオン封鎖剤
（Ｃ）界面活性剤
（Ｄ）高分子電解質重合体
〔数２〕
真球度＝Ｒ２／Ｒ１ …（１）
〔Ｒ１：粒状体の長径、Ｒ２：粒状体の短径〕 A raw material composition containing the following components (A) to (D) as essential components and not containing water, and at least one of these components (A) to (D) is a hydrate. The following components (A) to (D) are prepared in the form of a slurry and are not spray-dried or heated and melted , supplied to a high-speed agitation granulator, and batch-derived, derived from the hydrated product. The average particle size determined from the particle size measured by the sieving method described in JIS K-3362: 1998 “Synthetic detergent test method”. The diameter is set to 0.8 to 3.0 mm, and the sphericity calculated by the following formula (1) is made of an aggregate of substantially spherical granular materials set to 0.7 to 1.0. A granular cleaning composition for clothing.
(A) One or more compounds selected from alkali metal hydroxides, alkali metal silicates, sodium carbonate and sodium hydrogen carbonate (B) sequestering agent (C) surfactant (D) polymer electrolyte heavy Combine [number 2]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material]
（Ｆ）ＪＩＳ Ｋ−３３６２：１９９８「合成洗剤試験方法」記載のふるい分け方法によ って測定される粒度から求められる平均粒径が０．５〜３．０ｍｍに設定された塩 素系漂白剤もしくは酸素系漂白剤。
（Ｇ）ＪＩＳ Ｋ−３３６２：１９９８「合成洗剤試験方法」記載のふるい分け方法によ って測定される粒度から求められる平均粒径が０．５〜３．０ｍｍに設定された洗 剤用酵素。 The granular detergent composition for clothes according to any one of claims 1 to 8, wherein at least one of the following (F) component and (G) component is mixed in the aggregate of the substantially spherical granular materials.
(F) Chlorine bleaching agent in which the average particle size determined from the particle size measured by the screening method described in JIS K-3362: 1998 “Synthetic detergent test method” is set to 0.5 to 3.0 mm. Or oxygen bleach.
(G) A detergent enzyme having an average particle size determined from the particle size measured by the screening method described in JIS K-3362: 1998 “Synthetic detergent test method” set to 0.5 to 3.0 mm.
〔数３〕
真球度＝Ｒ２／Ｒ１ …（１）
〔Ｒ１：粒状体の長径、Ｒ２：粒状体の短径〕 A method for producing a granular detergent composition for clothing according to any one of claims 1 to 9, wherein a raw material composition for preparing a substantially spherical granular material is prepared, and each raw material component is prepared in a slurry form. the method 1998 "synthetic detergent test method" described sieving: in the state where no or spray-dried or heat-melted after, and subjected fed to a high-speed stirring granulator, the granulation step of the batch, JIS K-3362 The average particle size obtained from the particle size measured by the above is 0.8 to 3.0 mm, and the sphericity calculated by the following formula (1) is granulated into a substantially spherical shape of 0.7 to 1.0. A process for producing a granular detergent composition for clothing, which is characterized in that
[Equation 3]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material]
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| MY159548A (en) * | 2008-06-02 | 2017-01-13 | Lion Corp | Fatty acid alkyl ester sulfonate metal salt flakes and method for producing the same |
| JP5292140B2 (en) * | 2009-03-17 | 2013-09-18 | ディバーシー株式会社 | CIP cleaning composition and cleaning method using the same |
| JP5210243B2 (en) * | 2009-05-19 | 2013-06-12 | 株式会社ニイタカ | Phosphorus-free granular detergent and method for producing phosphorus-free granular detergent |
| US20110021410A1 (en) * | 2009-07-27 | 2011-01-27 | Ecolab Usa Inc. | Novel formulation of a ware washing solid controlling hardness |
| JP6097003B2 (en) | 2010-03-05 | 2017-03-15 | ライオン株式会社 | Granular detergent composition |
| JP5616759B2 (en) * | 2010-11-19 | 2014-10-29 | 株式会社ニイタカ | Granular detergent and method for producing granular detergent |
| JP6092854B2 (en) * | 2011-06-17 | 2017-03-08 | ダウ グローバル テクノロジーズ エルエルシー | Fabric care granules and methods |
| JP6466199B2 (en) * | 2015-02-20 | 2019-02-06 | 四国化成工業株式会社 | Spherical granule containing chlorinated isocyanuric acid compound and method for producing the same |
| US10538720B2 (en) * | 2016-03-08 | 2020-01-21 | The Procter & Gamble Company | Particles including enzyme |
| JP6035447B1 (en) * | 2016-05-30 | 2016-11-30 | 株式会社ニイタカ | Cleaning composition for automatic cleaning machine |
| US11767495B2 (en) | 2020-03-13 | 2023-09-26 | YFY Consumer Products, Co. | Systems and methods for manufacturing solid granules |
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| JPH10279993A (en) * | 1997-04-01 | 1998-10-20 | Lion Corp | Detergent composition |
| JP2000017294A (en) * | 1998-06-30 | 2000-01-18 | Lion Corp | Preparation of high bulk density particulate detergent |
| JP4264713B2 (en) * | 2003-05-07 | 2009-05-20 | ライオン株式会社 | Bleach cleaning composition |
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