JPH045080B2 - - Google Patents
Info
- Publication number
- JPH045080B2 JPH045080B2 JP59192948A JP19294884A JPH045080B2 JP H045080 B2 JPH045080 B2 JP H045080B2 JP 59192948 A JP59192948 A JP 59192948A JP 19294884 A JP19294884 A JP 19294884A JP H045080 B2 JPH045080 B2 JP H045080B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- spray
- detergent
- manufacturing
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002245 particle Substances 0.000 claims description 45
- 239000003599 detergent Substances 0.000 claims description 43
- 239000000843 powder Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 20
- 230000005484 gravity Effects 0.000 claims description 15
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 14
- 238000005469 granulation Methods 0.000 claims description 13
- 230000003179 granulation Effects 0.000 claims description 13
- 239000003607 modifier Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011164 primary particle Substances 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 description 38
- 125000004432 carbon atom Chemical group C* 0.000 description 29
- -1 alkylbenzene sulfonate Chemical class 0.000 description 28
- 125000003342 alkenyl group Chemical group 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- 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 4
- 229920002472 Starch Polymers 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004157 Hydrolases Human genes 0.000 description 3
- 108090000604 Hydrolases Proteins 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000004365 Protease Substances 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
- 239000011362 coarse particle Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- ABPJHHHWWYDYFZ-UHFFFAOYSA-N 2-methylidenebutanedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)CC(=C)C(O)=O ABPJHHHWWYDYFZ-UHFFFAOYSA-N 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- 108090000371 Esterases Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000001000 anthraquinone dye Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 108010089934 carbohydrase Proteins 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 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
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 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
- 238000000227 grinding Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- DCEMCPAKSGRHCN-UHFFFAOYSA-N oxirane-2,3-dicarboxylic acid Chemical compound OC(=O)C1OC1C(O)=O DCEMCPAKSGRHCN-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001444 polymaleic acid Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000429 sodium aluminium silicate Substances 0.000 description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 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
- 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
- MXYOPVWZZKEAGX-UHFFFAOYSA-N 1-phosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)P(O)(O)=O MXYOPVWZZKEAGX-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- BFMVMMMQVFULDO-UHFFFAOYSA-N 2-(sulfomethylidene)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)=CS(O)(=O)=O BFMVMMMQVFULDO-UHFFFAOYSA-N 0.000 description 1
- KIWDTIKAPYQWII-UHFFFAOYSA-N 2-[2-(2-phenylethenyl)phenyl]benzo[e][1,3]benzothiazole Chemical class C=1C=CC=C(C=2SC3=C(C4=CC=CC=C4C=C3)N=2)C=1C=CC1=CC=CC=C1 KIWDTIKAPYQWII-UHFFFAOYSA-N 0.000 description 1
- HECHAOUMONWDAO-UHFFFAOYSA-N 2-[4-[2-[4-(triazol-2-yl)phenyl]ethenyl]phenyl]triazole Chemical class C=1C=C(N2N=CC=N2)C=CC=1C=CC(C=C1)=CC=C1N1N=CC=N1 HECHAOUMONWDAO-UHFFFAOYSA-N 0.000 description 1
- INJFRROOFQOUGJ-UHFFFAOYSA-N 2-[hydroxy(methoxy)phosphoryl]butanedioic acid Chemical compound COP(O)(=O)C(C(O)=O)CC(O)=O INJFRROOFQOUGJ-UHFFFAOYSA-N 0.000 description 1
- ZILZQZGAJNDJIY-UHFFFAOYSA-N 2-chloro-5-[2-[4-[4-[2-(4-chloro-3-sulfophenyl)ethenyl]phenyl]phenyl]ethenyl]benzenesulfonic acid Chemical group C1=C(Cl)C(S(=O)(=O)O)=CC(C=CC=2C=CC(=CC=2)C=2C=CC(C=CC=3C=C(C(Cl)=CC=3)S(O)(=O)=O)=CC=2)=C1 ZILZQZGAJNDJIY-UHFFFAOYSA-N 0.000 description 1
- OOOLSJAKRPYLSA-UHFFFAOYSA-N 2-ethyl-2-phosphonobutanedioic acid Chemical compound CCC(P(O)(O)=O)(C(O)=O)CC(O)=O OOOLSJAKRPYLSA-UHFFFAOYSA-N 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- WOZHZOLFFPSEAM-UHFFFAOYSA-N 3-butene-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(=C)C(O)=O WOZHZOLFFPSEAM-UHFFFAOYSA-N 0.000 description 1
- UQJGJKYHBGUYJO-UHFFFAOYSA-N 3-tert-butyl-2-[1-(2-tert-butyl-6-hydroxy-3-methylphenyl)butyl]-4-methylphenol Chemical compound OC=1C=CC(C)=C(C(C)(C)C)C=1C(CCC)C1=C(O)C=CC(C)=C1C(C)(C)C UQJGJKYHBGUYJO-UHFFFAOYSA-N 0.000 description 1
- MYWGVBFSIIZBHJ-UHFFFAOYSA-N 4-phosphonobutane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(C(O)=O)CP(O)(O)=O MYWGVBFSIIZBHJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- 102000004400 Aminopeptidases Human genes 0.000 description 1
- 108090000915 Aminopeptidases Proteins 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 102000003670 Carboxypeptidase B Human genes 0.000 description 1
- 108090000087 Carboxypeptidase B Proteins 0.000 description 1
- 102000000496 Carboxypeptidases A Human genes 0.000 description 1
- 108010080937 Carboxypeptidases A Proteins 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 108090000322 Cholinesterases Proteins 0.000 description 1
- 102000003914 Cholinesterases Human genes 0.000 description 1
- 108090000317 Chymotrypsin Proteins 0.000 description 1
- 102000029816 Collagenase Human genes 0.000 description 1
- 108060005980 Collagenase Proteins 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 101000874334 Dalbergia nigrescens Isoflavonoid 7-O-beta-apiosyl-glucoside beta-glycosidase Proteins 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 101000757733 Enterococcus faecalis (strain ATCC 700802 / V583) Autolysin Proteins 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 102100031416 Gastric triacylglycerol lipase Human genes 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- 102000004195 Isomerases Human genes 0.000 description 1
- 108090000769 Isomerases Proteins 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004317 Lyases Human genes 0.000 description 1
- 108090000856 Lyases Proteins 0.000 description 1
- 108010014251 Muramidase Proteins 0.000 description 1
- 102000016943 Muramidase Human genes 0.000 description 1
- 101000757734 Mycolicibacterium phlei 38 kDa autolysin Proteins 0.000 description 1
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 description 1
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- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
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Landscapes
- Detergent Compositions (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、高密度でしかも流動性に優れた粉末
洗剤の製法に関する。
〔従来の技術及び問題点〕
従来より家庭で使用される洗剤は、生産性が良
好で、消費者が使用する際に、取り扱いやすくし
かも溶解性の良いことが求められ、そのため噴霧
乾燥法によつて製造された粉末洗剤が大部分であ
つた。ここで、取り扱い易さとは、粉末の自由流
動性が高く固結し難いこと、および粉塵の発生が
無い事を指す。
しかし乍ら、近年、省資源的観点での合理性、
および消費者の持ち運び易さといつた便利性か
ら、高密度の粉末洗剤への需要が高まつてきてい
る。高密度とは、粉末の見掛け比重が0.5g/cm3
以上を指す。従来の噴霧乾燥法によつて、このよ
うに高密度の粉末洗剤を得る事は極めて困難であ
る。
一般に噴霧乾燥された洗剤粒子の見掛け比重は
0.4g/cm3以下で、平均粒子径が200〜1000μm程
度であつて、直接、高密度の洗剤粒子を得ること
は困難である。
他方、噴霧乾燥法は、熱的に不安定な成分以外
は、水分を多量に含むアニオン性界面活性剤を始
めとする種々の原料を含む任意の組成について容
易に乾燥できる利点を有する。従つて、噴霧乾燥
された洗剤粒子を加工して、高密度でしかも流動
性の優れた粒子を得る製造法の確立が望まれてい
た。
噴霧乾燥された洗剤粒子を加工して、高密度の
粉末洗剤を得る試みは、例えば特開昭51−67302
がある。
特開昭51−67302では、商品名マルメライザー
と言う、実質的に垂直な平滑壁面の内部かつ底部
に位置する実質的に水平で回転自在の粗面テーブ
ルを含む顆粒化装置によつて、噴霧乾燥した粉末
洗剤を高密度化する製造法が開示されており、本
発明の先駆をなす技術ではあるが、粉末の流動性
に対して考慮が払われておらず、そのため製品の
流動性が元の粉末洗剤より悪くなり、消費者にと
つての便利性が不充分となる。
〔問題点を解決するための手段〕
以上の技術的背景から、良好な流動性を示す高
密度の粉末洗剤を製造するために研究を行つた結
果、以下に述べる本発明を完成した。
本発明は、堅形の混合槽の内部に垂直な攪拌
軸、例えば底部より突出した攪拌軸を持ち、この
軸に攪拌羽根を取り付けて粉末の混合、転動を行
う形式のミキサー又はこれの槽内に解砕あるいは
転動用チヨツパーを持つミキサーによつて、少な
くとも1種の界面活性剤と少なくとも1種のビル
ダーを含有する洗剤の噴霧乾燥生成物を撹拌粉砕
後、表面改質剤とバインダーの存在の下に撹拌造
粒処理を行う事によつて、高密度でしかも流動性
に優れた粉末洗剤を製造することを特徴とする。
表面改質剤としては、アルミノ珪酸塩が洗濯時
にカルシウムイオン捕捉剤として働くので望まし
い。特に一次粒子の平均粒子径が10μm以下のア
ルミノ珪酸塩が望ましい。表面改質剤としては、
アルミノ珪酸塩の外に、平均粒子径が10μm以下
の、二酸化珪素,ベントナイト,タルク,クレイ
のような無機微粉末を使う事ができる。また、平
均粒子径が10μm以下の金属石鹸も同様に使う事
ができる。
表面改質剤は、噴霧乾燥された洗剤粒子100重
量部に対して0.5〜35重量部を用いる事により目
的を達成する。表面改質剤が0.5重量部未満では、
良好な流動性を示す粉末を得る事が困難であり、
また35重量部を越えると、流動性が低下し、また
不必要にバインダーの量を増加しないと粉塵が発
生し消費者の使用感を損なう恐れがある。
更にその高密度洗剤粒子の見掛け比重は0.5〜
1.2g/cm3である。これ以上に見掛け比重が大き
いと粉末の溶解性に悪影響を与える傾向が見られ
るからである。しかも、平均粒子径は200から
800μmであることが望ましい。何故なら200μm未
満の平均粒子径では粉塵の発生が見られ、また、
800μmを越えると溶解性が悪化する傾向が見られ
るからである。
本発明で用いる事のできる界面活性剤には次の
ような物がある。
1 平均炭素数10〜16のアルキル基を有する直鎖
又は分枝鎖アルキルベンゼンスルホン酸塩
2 平均炭素数10〜20の直鎖又は分枝鎖のアルキ
ル基又はアルケニル基を有し、1分子内に平均
0.5〜8モルのエチレンオキサイドあるいはプ
ロピレンオキサイドあるいはブチレンオキサイ
ドあるいはエチレンオキサイド/プロピレンオ
キサイド=0.1/9.9〜9.9/0.1の比であるいは
エチレンオキサイド/ブチレンオキサイド=
0.1/9.9〜9.9/0.1の比で付加したアルキル又
はアルケニルエーテル硫酸塩
3 平均炭素数10〜20のアルキル基又はアルケニ
ル基を有するアルキル又はアルケニル硫酸塩
4 平均10〜20の炭素原子を1分子中に有するホ
レフインスルホン酸塩
5 平均10〜20の炭素原子を1分子中に有するア
ルカンスルホン酸塩
6 平均10〜24の炭素原子を1分子中に有する飽
和又は不飽和脂肪酸塩
7 平均炭素数10〜20のアルキル基又はアルケニ
ル基を有し、1分子中に平均0.5〜8モルのエ
チレンオキサイドあるいはプロピレンオキサイ
ドあるいはブチレンオキサイドあるいはエチレ
ンオキサイド/プロピレンオキサイド=0.1/
9.9〜9.9/0.1の比であるいはエチレンオキサイ
ド/ブチレンオキサイド=0.1/9.9〜9.9/0.1
の比で付加したアルキル又はアルケニルエーテ
ルカルボン酸塩
8 下記の式で表わされるα−スルホ脂肪酸塩又
はエステル
(式中Yは炭素数1〜3のアルキル基又は対
イオン、Zは対イオンである。Rは炭素数10〜
20のアルキル基又はアルケニル基を表わす。)
9 下記一般式で表わされるアミノ酸型界面活性
剤
(ここでR1′は炭素数8〜24のアルキル基又
はアルケニル基を、R2′は水素又は炭素数1〜
2のアルキル基を、R3′はアミノ酸残基を、X
はアルカリ金属又はアルカリ土類金属イオンを
示す。)
(R1′,R2′及びXは前述の通り。nは1〜5
の整数の示す。)
(R1′は前述の通り。mは1〜8の整数を示
す。)
(R1′,R3′及びXは前述の通り。R4は水素又
は炭素数1〜2のアルキル又はヒドロキシアル
キル基を示す。)
(R1′,R3′及びXは前述の通り。R5は炭素数
6〜28のβ−ヒドロキシアルキル又はβ−ヒド
ロキシアルケニル基を示す。)
(R3′,R5及びXは前述の通り。)
10 平均炭素数10〜20のアルキル基又はアルケニ
ル基を有し、1〜20モルのエチレンオキサイド
を付加したポリオキシエチレンアルキル又はア
ルケニルエーテル
11 平均炭素数6〜12のアルキル基を有し、1〜
20モルのエチレンオキサイドを付加たポリオキ
シエチレンアルキルフエニルエーテル
12 平均炭素数10〜20のアルキル基又はアルケニ
ル基を有し、1〜20モルのプロピレンオキサイ
ドを付加したポリオキシプロピレンアルキル又
はアルケニルエーテル
13 平均炭素数10〜20のアルキル基又はアルケニ
ル基を有し、1〜20モルのブチレンオキサイド
を付加したポリオキシブチレンアルキル又はア
ルケニルエーテル
14 平均炭素数10〜20のアルキル基又はアルケニ
ル基を有し、総和で1〜30モルのエチレンオキ
サイドとプロピレンオキサイドあるいはエチレ
ンオキサイドとブチレンオキサイドを付加した
非イオン性活性剤(エチレンオキサイドとプロ
ピレンオキサイド又はブチレンオキサイドとの
比は0.1/9.9〜9.9/0.1)
15 下記の一般式で表される高級脂肪酸アルカノ
ールアミド又はそのアルキレンオキサイド付加
物
(式中R11′は炭素数10〜20のアルキル基又は
アルケニル基であり、R12′はH又はCH3であ
り、n3は1〜3の整数、m3は0〜3の整数で
ある。)
16 平均炭素数10〜20の脂肪酸とシヨ糖から成る
シヨ糖脂肪酸エステル
17 平均炭素数10〜20の脂肪酸とグリセリンから
成る脂肪酸グリセリンモノエステル
18 下記の一般式で表わされるアルキルアミンオ
キサイド
(式中R13′は炭素数10〜20のアルキル基又は
アルケニル基であり、R14′,R15′は炭素数1〜
3のアルキル基である。)
19 下記の一般式で示されるベタイン型両性活性
剤
(ここでR21は炭素数8〜24のアルキル又は
アルケニル又はβ−ヒドロキシアルキル又はβ
−ヒドロキシアルケニル基、R22は炭素数1〜
4のアルキル基、R23は炭素数1〜6のアルキ
ル又はヒドロキシアルキル基を示す。)
(ここでR21及びR23は前述の通り。n2は1〜
20の整数を示す。)
(ここでR21及びR23は前述の通り。R24は炭
素数2〜5のカルボキシアルキル又はヒドロキ
シアルキル基を示す。)
20 下記一般式で示されるスルホン酸型両性界面
活性剤
(ここでR11は炭素数3〜24のアルキル又は
アルケニル基、R12は炭素数1〜4のアルキル
基、R13は炭素数1〜5のアルキル基、R14は
炭素数1〜4のアルキル又はヒドロキシアルキ
ル基を示す。)
(ここでR11及びR14は前述の通り。R15,
R16は炭素数8〜24又は1〜5のアルキル又は
アルケニル基を示す。)
(ここでR11及びR14は前述の通り、n1は1〜
20の整数を示す。)
21 リン酸エステル系活性剤
No.1 アルキル(又はアルケニル)酸性リン酸
エステル
(R′は炭素数8〜24のアルキル基、又は
アルケニル基、n′+m′=3,n′=1〜2)
No.2 アルキル(又はアルケニル)リン酸エス
テル
(R′は前述の通り、n″+m″=3,n″=1〜3)
No.3 アルキル(又はアルケニル)リン酸エス
テル塩
(R′,n″,m″は前述の通り、M′はNa,K,
Ca)
22 下記の一般式で示されるカチオン界面活性剤
(ここでR1′,R2′,R3′,R4′のうち少なくと
も1つは炭素数8〜24のアルキル又はアルケニ
ル基、他は炭素数1〜5のアルキル基を示す。
X′はハロゲンを示す。)
(ここでR1′,R2′,R3′及びX′は前述の通り。)
(ここでR1′,R2′及びX′は前述の通り。
R5′は炭素数2〜3のアルキレン基、n4は1〜
20の整数を示す。)
界面活性剤の含有量は10〜70重量%、好まし
くは25〜50重量%である。
また、本発明で用いる事のできる無機ビルダー
類には次の様な物がある。
炭酸ソーダ、セスキ炭酸ソーダ、ケイ酸ソーダ
などのアルカリ性塩、芒硝などの中性塩、オルソ
リン酸塩、ピロリン酸塩、トリポリリン酸塩、メ
タリン酸塩、ヘキサメタリン酸塩、フイチン酸塩
などのリン酸塩の外以下のアルミノケイ酸塩も含
むことができる。
No.1 次式で示される結晶性アルミノケイ酸塩
x′(M2′O又はM″O)・Al2O3・y′(SiO2)・
w′(H2O)
(式中、M′はアルカリ金属原子、M″はカルシ
ウムと交換可能なアルカリ土類金属原子、x′,
y′,w′は各成分のモル数を表わし、一般的に
は、0.7≦x′≦1.5、0.8≦y′≦6、w′は任意の整
数である。)
No.2 洗浄剤ビルダーとしては、特に次の一般式
で示されるものが好ましい。
Na2O・Al2O3・nSiO2・wH2O
(ここで、nは1.8〜3.0、wは1〜6の数を表
わす。)
No.3 次式で示される無定形アルミノケイ酸塩
x(M2O)・Al2O3・y(SiO2)・=(H2O)
(式中、Mはナトリウム及び/又はカリウム原
子を表わし、x,y,wは次の微値範囲内にあ
る各成分のモル数を表わすものである。
0.7≦x≦1.2
1.6≦y≦2.8
wは0を含む任意の正数)
No.4 次式で示される無定形アルミノケイ酸塩
X(M2O)・Al2O3・Y(SiO2)・Z(P2O5)・ω
(H2O)
式中、MはNa又はKを、X,Y,Z,Wは次
の数値の範囲内にある各成分のモル数を表わ
す。
0.20≦X≦1.10
0.20≦Y≦4.00
0.001≦Z≦0.80
W:0を含む任意の正数)
更に、本発明では次のような添加物を用いるこ
とができる。
(1) 二価金属イオン捕捉剤
1 エタン−1,1−ジホスホン酸、エタン−
1,2−トリホスホン酸、エタン−1−ヒド
ロキシ−1,1−ジホスホン酸及びその誘導
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
スホン酸等のホスホン酸塩。
2 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塩。
3 アスパラギン酸、グルタミン酸等のアミノ
酸塩。
4 ニトリロ三酢酸塩、エチレンジアミン四酢
酸塩、ジエチレントリアミン五酢酸塩等のア
ミノポリ酢酸塩。
5 ポリアクリル酸、ポリアコニツト酸、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−アコニツト酸共重合体、
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
ン酸共重合体、メタコン酸−フマル酸共重合
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、1−ブテン−2,3,4−ト
リカルボン酸.イタコン酸−アクリル酸共重
合体、第四アンモニウム基を有するポリエス
テルポリアルデヒドカルボン酸、エポキシコ
ハク酸のcis−異性体、ポリ〔N,N−ビス
(カルボキシメチル)アクリルアミド〕、ポリ
(オキシカルボン酸)、デンプンコハク酸ある
いはマレイン酸あるいはテレフタル酸エステ
ル、デンプンリン酸エステル、ジカルボキシ
デンプン、ジカルボキシメチルデンプン、カ
ルボキシメチルセルロース、コハク酸エステ
ルなどの高分子電解質
6 ポリエチレングリコール、ポリビニルアル
コール、ポリビニルピロリドン、冷水可溶性
ウレタン化ポリビニルアルコールなどの非解
離高分子。
7 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、シクロペンタ
ン−1,2,3,4−テトラカルボン酸、テ
トラヒドロフラン−1,2,3,4−テトラ
カルボン酸、テトラヒドロフラン−2,2,
5,5−テトラカルボン酸、クエン酸、乳
酸、酒石酸、シヨ糖、ラクトース、ラフイノ
ースなどのカルボキシメチル化物、ペンタエ
リスリトールのカルボキシメチル化物、グル
コン酸のカルボキシメチル化物、多価アルコ
ールあるいは糖類と無水マレイン酸あるいは
無水コハク酸との縮合物、オキシカルボン酸
と無水マレイン酸あるいは無水コハク酸との
縮合物、メリツト酸で代表されるベンゼンポ
リカルボン酸、エタン−1,1,2,2−テ
トラカルボン酸、エテン−1,1,2,2−
テトラカルボン酸、ブタン−1,2,3,4
−テトラカルボン酸、プロパン−1,2,3
−トリカルボン酸、ブタン−1,4−ジカル
ボン酸、シユウ酸、スルホコハク酸、デカン
−1,10−ジカルボン酸、スルホトリカルバ
リン酸、スルホイタコン酸、リンゴ酸、オキ
シジコハク酸、グルコン酸、CMOS、ビル
ダーMなどの有機酸塩。
(2) 再汚染防止剤
更に再汚染防止剤として次に示す化合物の1種
又は2種以上を組成物中に0.1〜5%含有するこ
とができる。ポリエチレングリコール、ポリビニ
ルアルコール、ポリビニルピロリドン、カルボキ
シメチルセルロースなど。
(3) 漂白剤
過炭酸ソーダ、過ホウ酸ソーダ、硫酸ナトリウ
ム過酸化水素付加体など。
(4) 酵素(本来的酵素作用を洗浄行程中になす酵
素である。)
酵素の反応性から分類すると、ヒドロラーゼ
類、ヒドラーゼ類、オキシドレダクターゼ類、デ
スモラーゼ類、トランスフエラーゼ類及びイソメ
ラーゼ類が挙げられるが、本発明にはいずれも適
用できる。特に好ましいのはヒドロラーゼ類であ
り、プロテアーゼ、エステラーゼ、カルボヒドラ
ーゼ及びヌクレアーゼが含まれる。
プロテアーゼの具体例は、ペプシン、トリペプ
シン、キモトリプシン、コラーゲナーゼ、ケラチ
ナーゼ、エラスターゼ、スプチリシン、BPN、
パパイン、プロメリン、カルボキシペプチターゼ
A及びB、アミノペプチターゼ、アスパーギロペ
プチターゼA及びBである。
エステラーゼの具体例は、ガストリツクリパー
ゼ、パンクレアチツクリパーゼ、植物リパーゼ
類、ホスホリパーゼ類、コリンエステラーゼ類及
びホスターゼ類がある。
カルボヒドラーゼは、セルラーゼ、マルター
ゼ、サツカラーゼ、アミラーゼ、ペクチナーゼ、
リゾチーム、α−グリコシダーゼおよびβ−グリ
コシダーゼが挙げられる。
(5) 青味付剤
各種の青味付剤も必要に応じて配合できる。
例えば次の構造のものが奨用される:
(式中Dは青色乃至紫色のモノアゾ、ジスア
ゾ又はアントラキノン系色素残基を表わし、X
及びYは水酸基、アミノ基、水酸基、スルホン
酸基、カルボン酸基、アルコキシ基で置換され
ていることもある脂肪族アミノ基、ハロゲン原
子、水酸基,スルホン酸基,カルボン酸基,低
級アルキル基,低級アルコキシ基で置換されて
いることもある芳香族アミノ基又は環状脂肪族
アミノ基である。Rは水素原子又は低級アルキ
ル基である。ただし、Rが水素原子を表わす場
合であつてX及びYが同時に水酸基又はアル
カノールアミノ基を表わす場合並びにX及び
Yのいずれか一方が水酸基であり、他方がアル
カノールアミノ基である場合を除く。nは2以
上の整数を表わす。)
(式中、Dは青色乃至紫色のアゾ又はアント
ラキノン系色素残基を表わし、X及びYは同一
又は相異なるアルカノールアミノ残基又は水酸
基を表わす。)
(6) ケーキング防止剤
パラトルエンスルホン酸塩、キシレンスルホン
酸塩、酢酸塩、スルホコハク酸塩、タルク、微粉
末シリカ、粘土、カルシウム−シリケート(例え
ばJohns Manvill社のマイクロセルなど)、酸化
マグネシウム等。
(7) 酸化防止剤
第3ブチルヒドロキシトルエン、4,4′−ブチ
リデンビス−(6−第3ブチル−3−メチルフエ
ノール)、2,2′−ブチリデンビス−(−第3ブチ
ル−4−メチルフエノール)、モノスチレン化ク
レゾール、ジスチレン化クレゾール、モノスチレ
ン化フエノール、ジスチレン化フエノール、1,
1′−ビス−(4−ヒドロキシフエニル)シクロヘ
キサン等の酸化防止剤。
(8) 蛍光染料
4,4′−ビス−(2−スルホスチリル)−ビフエ
ニル塩、4,4′−ビス−(4−クロロ−3−スル
ホスチリル)−ビフエニル塩、2−(スチリルフエ
ニル)ナフトチアゾール誘導体、4,4′−ビス
(トリアゾール−2−イル)スチルベン誘導体、
ビス(トリアジニルアミノ)スチルベンジスルホ
ン酸誘導体の1種又は2種以上を、組成物中に0
〜1重量%含有することができる。
(9) 光活性化漂白剤
スルホン化アルミニウムフタロシアニン、スル
ホン化亜鉛フタロシアニンの1種又は2種を組成
物中に0〜0.2重量%含有することができる。
(10) 香料
本発明で用いることのできるバインダーにはカ
ルボキシセルロース、ポリエチレングリコール、
ポリアクリル酸ソーダの如きポリカルボン酸塩等
の水溶性ポリマー溶液、ポリオキシエチレンアル
キルエーテル、脂肪酸モノエタノールアミド、脂
肪酸ジエタノールアミドなどのノニオン性物質、
珪酸ソーダ水溶液、水等を挙げることができる。
本発明の実施に当たつては噴霧乾燥された洗剤
粒子は次の様に得ることが出来る。即ち、熱的に
不安定な原料、例えば酵素や漂白剤、及び乾燥の
不必要な無機ビルダー、例えば炭酸ナトリウム硫
酸ナトリウムを除き、乾燥が必要な陰イオン性界
面活性剤溶液やアルミノ珪酸塩のスラリー、螢光
染料、色素等からなるスラリーを噴霧乾燥する。
噴霧乾燥した粒子の粘着性が強い場合には、洗剤
スラリーに炭酸ナトリウムや硫酸ナトリウム、珪
酸ソーダ、その他を混合することは任意である。
噴霧乾燥された洗剤粒子の見掛け比重と粒子径
は間わない。その水分は12%以下が好ましい。そ
れ以上に水分があると、造粒後の粒子の流動性に
悪影響を及ぼす。
次に本発明の方法における造粒処理について説
明する。本発明における造粒処理法には、基本的
に次の二つのステツプからなる。
破砕工程
噴霧乾燥された洗剤粒子を、堅形の混合槽の内
部に垂直な撹拌軸、例えば底部より突出した撹拌
軸を持ち、この軸に撹拌羽根を取り付けて粉末の
混合を行う形式のミキサーに投入し、見掛け比重
が元の粒子よりも0.05〜0.3g/cm3大きくなるま
で粉砕する。この時粉末の温度が摂氏60度以上に
なると、粉末の粘着性が高くなり、凝集が起きる
ので、これを避けるためにはミキサーの回りにジ
ヤケツトを設けて冷水を流すことが有効である。
本工程に於いて、噴霧乾燥生成物以外の洗剤の
他の無機原料又は(及び)有機原料を混合しても
よい。
撹拌造粒工程
上記の工程に引き続き、表面改質剤とバインダ
ーを加えながら撹拌造粒する。表面改質剤とバイ
ンダーは同時に加えても、あるいはどちらかを先
に加えても、あるいは交互に加えても良い。
本工程に於いて、洗剤の他の無機原料又は(及
び)有機原料を混合することは任意である。
本発明で用いられるミキサーの例としては、ハ
イスピードミキサー(撹拌転動造粒機)やヘンシ
エルミキサー(高速撹拌造粒機)のいずれもが使
用できる。
本発明によつて製造された洗剤粒子は、次の二
つの特徴を併せ持つ事により、他の製法による洗
剤粒子と容易に区別出来る。
その一つは、粒子表面が、表面改質剤によつて
覆われている点にあり、電子顕微鏡での観察によ
り容易に確認出来る。
もう一つの特徴は、機械的に破壊された噴霧乾
燥粒子によつて、本発明の洗剤粒子が構成されて
いることである。これは、エチルアルコールに洗
剤粒子を浸せきすると、本発明の洗剤粒子は微粉
末となつて分散するのに対し、単に噴霧乾燥され
た衣料用洗剤の粒子はこのようには分散しないこ
とから容易に確認出来る。
〔実施例〕
以下に本発明の実施例を示すが、これら実施例
は本発明を制限するものでは無い。
実施例 1
次に示す組成の洗剤を噴霧乾燥した。
直鎖アルキルベンゼンスルホン酸塩 35重量部
アルキル硫酸エステル塩 10 〃
炭酸ナトリウム 21.5 〃
珪酸ナトリウム 7 〃
アルミノ珪酸ナトリウム 14 〃
硫酸ナトリウム 3 〃
非イオン性界面活性剤 3.5 〃
水分 6 〃
得られた洗剤粒子の平均粒径は600μmで、見掛
け比重は0.31g/cm3であつた。
この噴霧乾燥された洗剤粒子100重量部を、ハ
イスピードミキサー(深江工業株式会社製)に入
れ、10分間撹拌粉砕し、見掛け比重0.43g/ml、
平均粒径130μmになつた。次いで、2重量部の水
と、平均粒径2.7μmのアルミノ珪酸塩微粉末を4
重量部加え、撹拌造粒を行つた後、16メツシユの
篩で粗粒子を除いた。
この様にして得た洗剤の見掛け比重、平均粒
径、流動性を測定し、他の実施例及び比較例と共
に表1に示した。
ここで、粉末の流動性は、JIS K3362に規定さ
れた見掛け比重測定用のホツパーから、100mlの
粉末が流出するのに要する時間を測定し、その時
間が短い程、流動性が良いと判定する。
実施例 2
次に示す組成の洗剤を噴霧乾燥した。
直鎖アルキルベンゼンスルホン酸塩 35重量部
アルキル硫酸エステル塩 10 〃
炭酸ナトリウム 30 〃
珪酸ナトリウム 7 〃
アルミノ珪酸ナトリウム 9 〃
硫酸ナトリウム 3 〃
水分 6 〃
得られた洗剤粒子の平均粒径は500μm、見掛け
比重は0.34g/mlであつた。この洗剤粒子100重
量部をハイスピードミキサー(深江工業株式会社
製)に入れ、10分間撹拌粉砕し、見掛け比重0.44
g/ml、平均粒径110μmになつた。次いで、非イ
オン界面活性剤4.6重量部と、平均粒径2.7μmのア
ルミノ珪酸塩微粉末を17重量部加え、撹拌造粒を
行つた。16メツシユの篩で粗粒子を除いた後、比
重、平均粒径、流動性を測定した。
実施例 3
実施例1に使用した噴霧乾燥された洗剤粒子
100重量部をハイスピードミキサー(深江工業株
式会社製)に入れ、10分間撹拌粉砕し、見掛け比
重0.43g/ml、平均粒径130μmになつた。次い
で、2重量部の水と、20mμ(0.02μm)の粒径の
二酸化珪素微粉末を1重量部加え、撹拌造粒を行
つた後、16メツシユの篩で粗粒子を除いた。
実施例 4
実施例3において、二酸化珪素微粉末の代わり
に、同じアルミノ珪酸塩2重量部と平均粒径の
1.5μmのタルク微粉末2重量部とを合わせて用い
た。
比較例 1
実施例1に於いて、表面改質剤を加えることな
く、撹拌造粒を行つた。
比較例 2
実施例1に於いて、実施例1と同じアルミノ珪
酸塩を40重量部加え、撹拌造粒を行つた。
以上実施例及び比較例から明らかな様に本発明
の製法によれば、高密度でしかも流動性に優れた
粒状洗剤を得ることができる。
【表】DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a powder detergent having high density and excellent fluidity. [Prior art and problems] Detergents used in households have been required to have good productivity, be easy to handle, and have good solubility when used by consumers. Most of the detergents were powdered detergents manufactured by Here, ease of handling refers to the fact that the powder has high free-flowing properties and is difficult to solidify, and that no dust is generated. However, in recent years, rationality from a resource saving perspective,
Demand for high-density powder detergents is increasing due to consumer convenience and portability. High density means that the apparent specific gravity of the powder is 0.5 g/cm 3
Refers to the above. It is extremely difficult to obtain powder detergents with such high density by conventional spray drying methods. Generally, the apparent specific gravity of spray-dried detergent particles is
It is difficult to directly obtain high-density detergent particles with a particle size of 0.4 g/cm 3 or less and an average particle diameter of about 200 to 1000 μm. On the other hand, the spray drying method has the advantage that any composition containing various raw materials including an anionic surfactant containing a large amount of water can be easily dried, except for thermally unstable components. Therefore, it has been desired to establish a manufacturing method for processing spray-dried detergent particles to obtain particles with high density and excellent fluidity. Attempts to obtain high-density powder detergent by processing spray-dried detergent particles have been made, for example, in JP-A-51-67302.
There is. In Japanese Patent Application Laid-open No. 51-67302, atomization is carried out using a granulation device called Marmerizer, which includes a substantially horizontal, rotatable, rough-surfaced table located inside and at the bottom of a substantially vertical, smooth-walled surface. Although a manufacturing method for densifying dry powder detergent has been disclosed, and is a pioneering technology of the present invention, no consideration is given to the fluidity of the powder, and as a result, the fluidity of the product is powder detergent, and the convenience for consumers is insufficient. [Means for Solving the Problems] Based on the above technical background, research was conducted to produce a high-density powder detergent that exhibits good fluidity, and as a result, the present invention described below was completed. The present invention relates to a mixer or a tank thereof having a vertical stirring shaft inside a solid mixing tank, for example, a stirring shaft protruding from the bottom, and stirring blades attached to the shaft to mix and roll powder. After stirring and grinding the spray-dried product of the detergent containing at least one surfactant and at least one builder by means of a mixer having a grinding or rolling chopper in the presence of surface modifiers and binders. It is characterized by producing a powdered detergent with high density and excellent fluidity by performing stirring granulation treatment under the above conditions. Aluminosilicates are preferred as surface modifiers because they act as calcium ion scavengers during washing. In particular, an aluminosilicate having an average primary particle diameter of 10 μm or less is desirable. As a surface modifier,
In addition to aluminosilicates, inorganic fine powders such as silicon dioxide, bentonite, talc, and clay with an average particle size of 10 μm or less can be used. Furthermore, metal soaps having an average particle size of 10 μm or less can be used in the same manner. The purpose of the surface modifier is achieved by using 0.5 to 35 parts by weight per 100 parts by weight of spray-dried detergent particles. If the surface modifier is less than 0.5 parts by weight,
It is difficult to obtain a powder that exhibits good fluidity;
Moreover, if it exceeds 35 parts by weight, the fluidity will decrease, and unless the amount of binder is increased unnecessarily, dust may be generated and the usability of the consumer may be impaired. Furthermore, the apparent specific gravity of the high-density detergent particles is 0.5~
It is 1.2g/ cm3 . This is because if the apparent specific gravity is larger than this, it tends to have an adverse effect on the solubility of the powder. Moreover, the average particle size starts from 200
Preferably it is 800 μm. This is because dust is generated when the average particle size is less than 200μm, and
This is because when the diameter exceeds 800 μm, solubility tends to deteriorate. Surfactants that can be used in the present invention include the following. 1 A straight-chain or branched alkylbenzene sulfonate having an alkyl group with an average of 10 to 16 carbon atoms 2 A straight-chain or branched alkyl benzene sulfonate having an average of 10 to 20 carbon atoms average
0.5 to 8 moles of ethylene oxide or propylene oxide or butylene oxide or ethylene oxide/propylene oxide = 0.1/9.9 to 9.9/0.1 ratio or ethylene oxide/butylene oxide =
Alkyl or alkenyl ether sulfate added in a ratio of 0.1/9.9 to 9.9/0.1 3 Alkyl or alkenyl sulfate having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms 4 An average of 10 to 20 carbon atoms per molecule Holefin sulfonate 5 having an average of 10 to 20 carbon atoms per molecule 6 Saturated or unsaturated fatty acid salt having an average of 10 to 24 carbon atoms per molecule 7 Average carbon number 10 It has ~20 alkyl or alkenyl groups, and an average of 0.5 to 8 moles of ethylene oxide, propylene oxide, or butylene oxide in one molecule, or ethylene oxide/propylene oxide = 0.1/
At a ratio of 9.9 to 9.9/0.1 or ethylene oxide/butylene oxide = 0.1/9.9 to 9.9/0.1
Alkyl or alkenyl ether carboxylic acid salt added in a ratio of 8 α-sulfo fatty acid salt or ester represented by the following formula (In the formula, Y is an alkyl group having 1 to 3 carbon atoms or a counter ion, Z is a counter ion, and R is an alkyl group having 1 to 3 carbon atoms.
20 alkyl or alkenyl groups. ) 9 Amino acid type surfactant represented by the following general formula (Here, R 1 ' is an alkyl group or alkenyl group having 8 to 24 carbon atoms, and R 2 ' is hydrogen or an alkyl group having 1 to 24 carbon atoms.
2 alkyl group, R 3 ' is an amino acid residue,
represents an alkali metal or alkaline earth metal ion. ) (R 1 ′, R 2 ′ and X are as described above. n is 1 to 5
Indicates an integer. ) (R 1 ' is as described above. m represents an integer from 1 to 8.) (R 1 ', R 3 ' and X are as described above. R 4 represents hydrogen or an alkyl or hydroxyalkyl group having 1 to 2 carbon atoms.) (R 1 ′, R 3 ′ and X are as described above. R 5 represents a β-hydroxyalkyl or β-hydroxyalkenyl group having 6 to 28 carbon atoms.) (R 3 ′, R 5 and It has an alkyl group with an average carbon number of 6 to 12, and 1 to
Polyoxyethylene alkyl phenyl ether 12 with 20 moles of ethylene oxide added Polyoxypropylene alkyl or alkenyl ether 13 with an alkyl or alkenyl group having an average carbon number of 10 to 20 and with 1 to 20 moles of propylene oxide added Polyoxybutylene alkyl or alkenyl ether 14 having an alkyl group or alkenyl group with an average carbon number of 10 to 20 and to which 1 to 20 moles of butylene oxide has been added, A nonionic surfactant with a total of 1 to 30 moles of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide added (ratio of ethylene oxide and propylene oxide or butylene oxide is 0.1/9.9 to 9.9/0.1) 15 The following: Higher fatty acid alkanolamide or its alkylene oxide adduct represented by the general formula (In the formula, R11 ' is an alkyl group or alkenyl group having 10 to 20 carbon atoms, R12 ' is H or CH3 , n3 is an integer of 1 to 3, and m3 is an integer of 0 to 3. ) 16 Sucrose fatty acid ester consisting of a fatty acid with an average carbon number of 10 to 20 and sucrose17 Fatty acid glycerin monoester consisting of a fatty acid with an average carbon number of 10 to 20 and glycerin18 Alkylamine oxide represented by the general formula below (In the formula, R 13 ′ is an alkyl group or alkenyl group having 10 to 20 carbon atoms, and R 14 ′ and R 15 ′ are groups having 1 to 20 carbon atoms.
3 is an alkyl group. ) 19 Betaine type amphoteric activator represented by the general formula below (Here, R 21 is alkyl or alkenyl having 8 to 24 carbon atoms, β-hydroxyalkyl or β
-Hydroxyalkenyl group, R 22 has 1 or more carbon atoms
The alkyl group of 4 and R23 represent an alkyl or hydroxyalkyl group having 1 to 6 carbon atoms. ) (Here, R 21 and R 23 are as described above. n 2 is 1 to
Indicates an integer of 20. ) (Here, R 21 and R 23 are as described above. R 24 represents a carboxyalkyl or hydroxyalkyl group having 2 to 5 carbon atoms.) 20 Sulfonic acid type amphoteric surfactant represented by the following general formula (Here, R 11 is an alkyl or alkenyl group having 3 to 24 carbon atoms, R 12 is an alkyl group having 1 to 4 carbon atoms, R 13 is an alkyl group having 1 to 5 carbon atoms, and R 14 is an alkyl group having 1 to 4 carbon atoms. (Indicates an alkyl or hydroxyalkyl group.) (Here, R 11 and R 14 are as described above. R 15 ,
R16 represents an alkyl or alkenyl group having 8 to 24 carbon atoms or 1 to 5 carbon atoms. ) (Here, R 11 and R 14 are as mentioned above, and n 1 is 1 to
Indicates an integer of 20. ) 21 Phosphate ester activator No. 1 Alkyl (or alkenyl) acid phosphate ester (R' is an alkyl group or alkenyl group having 8 to 24 carbon atoms, n'+m'=3, n'=1 to 2) No.2 Alkyl (or alkenyl) phosphate ester (R′ is as mentioned above, n″+m″=3, n″=1~3) No.3 Alkyl (or alkenyl) phosphate ester salt (R′, n″, m″ are as mentioned above, M′ is Na, K,
Ca) 22 Cationic surfactant represented by the general formula below (Here, at least one of R 1 ′, R 2 ′, R 3 ′, and R 4 ′ represents an alkyl or alkenyl group having 8 to 24 carbon atoms, and the others represent an alkyl group having 1 to 5 carbon atoms.
X′ represents halogen. ) (Here, R 1 ′, R 2 ′, R 3 ′, and X′ are as described above.) (Here, R 1 ′, R 2 ′, and X′ are as described above.
R 5 ' is an alkylene group having 2 to 3 carbon atoms, and n 4 is 1 to 3.
Indicates an integer of 20. ) The content of surfactant is 10-70% by weight, preferably 25-50% by weight. Further, inorganic builders that can be used in the present invention include the following. Alkaline salts such as soda carbonate, sodium sesquicarbonate, and sodium silicate, neutral salts such as mirabilite, phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, and phytate. In addition to the following aluminosilicates may also be included. No. 1 Crystalline aluminosilicate x′ (M 2 ′O or M″O)・Al 2 O 3・y′(SiO 2 )・
w′(H 2 O) (where M′ is an alkali metal atom, M″ is an alkaline earth metal atom exchangeable with calcium, x′,
y' and w' represent the number of moles of each component, and generally, 0.7≦x'≦1.5, 0.8≦y'≦6, and w' is any integer. ) No. 2 As the detergent builder, those represented by the following general formula are particularly preferred. Na 2 O・Al 2 O 3・nSiO 2・wH 2 O (Here, n represents a number from 1.8 to 3.0, and w represents a number from 1 to 6.) No. Amorphous aluminosilicate x expressed by the cubic formula (M 2 O)・Al 2 O 3・y(SiO 2 )・=(H 2 O) (In the formula, M represents a sodium and/or potassium atom, and x, y, and w are within the following marginal value range. 0.7≦x ≦ 1.2 1.6≦y≦2.8 w is any positive number including 0) No. 4 Amorphous aluminosilicate O )・Al2O3・Y( SiO2 )・Z ( P2O5 )・ω
(H 2 O) In the formula, M represents Na or K, and X, Y, Z, and W represent the number of moles of each component within the following numerical range. 0.20≦X≦1.10 0.20≦Y≦4.00 0.001≦Z≦0.80 W: Any positive number including 0) Furthermore, the following additives can be used in the present invention. (1) Divalent metal ion scavenger 1 Ethane-1,1-diphosphonic acid, Ethane-
1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-
Phosphonates such as 1,2-diphosphonic acid and methanehydroxyphosphonic acid. 2 Phosphonocarboxylic acid salts such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, and α-methylphosphonosuccinic acid. 3 Amino acid salts such as aspartic acid and glutamic acid. 4 Aminopolyacetates such as nitrilotriacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, etc. 5 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 crosslink copolymer, maleic anhydride-vinyl acetate copolymer, Maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylic ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride-isoprene copolymer, polyamide derived from maleic anhydride and carbon monoxide. −β−
Ketocarboxylic acid, itaconic acid, ethylene copolymer, itaconic acid-aconitic acid copolymer,
Itaconic acid-maleic acid copolymer, itaconic acid-acrylic acid copolymer, malonic acid-methylene acid copolymer, methaconic acid-fumaric acid copolymer, ethylene glycol-ethylene terephthalate copolymer, vinylpyrrolidone-vinyl acetate Copolymer, 1-butene-2,3,4-tricarboxylic acid. Itaconic acid-acrylic acid copolymer, polyester polyaldehyde carboxylic acid with quaternary ammonium groups, cis-isomer of epoxysuccinic acid, poly[N,N-bis(carboxymethyl)acrylamide], poly(oxycarboxylic acid) , starch succinic acid or maleic acid or terephthalic acid ester, starch phosphate ester, dicarboxy starch, dicarboxymethyl starch, carboxymethyl cellulose, succinic acid ester, etc. Polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, cold water soluble urethane Non-dissociated polymers such as polyvinyl alcohol. 7 Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-2,2,
Carboxymethylated products of 5,5-tetracarboxylic acid, citric acid, lactic acid, tartaric acid, sucrose, lactose, raffinose, etc., carboxymethylated products of pentaerythritol, carboxymethylated products of gluconic acid, polyhydric alcohols or sugars, and maleic anhydride. Or a condensate with succinic anhydride, a condensate of oxycarboxylic acid with maleic anhydride or succinic anhydride, benzene polycarboxylic acid represented by mellitic acid, ethane-1,1,2,2-tetracarboxylic acid, Ethene-1,1,2,2-
Tetracarboxylic acid, butane-1,2,3,4
-tetracarboxylic acid, propane-1,2,3
-Tricarboxylic acid, butane-1,4-dicarboxylic acid, oxalic acid, sulfosuccinic acid, decane-1,10-dicarboxylic acid, sulfotricarbalic acid, sulfoitaconic acid, malic acid, oxydisuccinic acid, gluconic acid, CMOS, Builder M organic acid salts such as (2) Anti-restaining agent Furthermore, one or more of the following compounds can be contained in the composition in an amount of 0.1 to 5% as an anti-restaining agent. Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, etc. (3) Bleach Soda percarbonate, sodium perborate, sodium sulfate hydrogen peroxide adduct, etc. (4) Enzymes (enzymes that perform their original enzymatic action during the cleaning process) Classified based on their reactivity, they include hydrolases, hydrolases, oxidoreductases, desmolases, transferases, and isomerases. However, any of them can be applied to the present invention. Particularly preferred are hydrolases, including proteases, esterases, carbohydrases and nucleases. Specific examples of proteases include pepsin, tripepsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN,
papain, promeline, carboxypeptidase A and B, aminopeptidase, and aspargylopeptidase A and B. Specific examples of esterases include gastric lipase, pancreatic lipase, plant lipases, phospholipases, cholinesterases, and hostases. Carbohydrases include cellulase, maltase, satucarase, amylase, pectinase,
Includes lysozyme, α-glycosidase and β-glycosidase. (5) Blue-tinging agent Various types of blue-tinging agents can be added as necessary. For example, the following structure is recommended: (In the formula, D represents a blue to purple monoazo, disazo or anthraquinone dye residue, and
and Y is a hydroxyl group, an amino group, a hydroxyl group, a sulfonic acid group, a carboxylic acid group, an aliphatic amino group that may be substituted with an alkoxy group, a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxylic acid group, a lower alkyl group, It is an aromatic amino group or a cycloaliphatic amino group which may be substituted with a lower alkoxy group. R is a hydrogen atom or a lower alkyl group. However, this excludes cases where R represents a hydrogen atom and X and Y simultaneously represent a hydroxyl group or an alkanolamino group, and cases where either one of X and Y is a hydroxyl group and the other is an alkanol-amino group. n represents an integer of 2 or more. ) (In the formula, D represents a blue to purple azo or anthraquinone dye residue, and X and Y represent the same or different alkanol amino residues or hydroxyl groups.) (6) Anti-caking agent para-toluenesulfonate, Xylene sulfonates, acetates, sulfosuccinates, talc, finely powdered silica, clays, calcium-silicates (such as Microcell from Johns Manvill), magnesium oxide, etc. (7) Antioxidant Tertiary-butylhydroxytoluene, 4,4'-butylidenebis-(6-tert-butyl-3-methylphenol), 2,2'-butylidenebis-(-tert-butyl-4-methylphenol) , monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,
Antioxidants such as 1'-bis-(4-hydroxyphenyl)cyclohexane. (8) Fluorescent dye 4,4'-bis-(2-sulfostyryl)-biphenyl salt, 4,4'-bis-(4-chloro-3-sulfostyryl)-biphenyl salt, 2-(styrylphenyl)naphthothiazole derivative, 4,4'-bis(triazol-2-yl)stilbene derivative,
One or more bis(triazinylamino)stilbene disulfonic acid derivatives are present in the composition.
It can be contained in an amount of up to 1% by weight. (9) Photoactivated bleaching agent The composition may contain 0 to 0.2% by weight of one or both of sulfonated aluminum phthalocyanine and sulfonated zinc phthalocyanine. (10) Fragrance Binders that can be used in the present invention include carboxycellulose, polyethylene glycol,
Water-soluble polymer solutions such as polycarboxylic acid salts such as sodium polyacrylate, nonionic substances such as polyoxyethylene alkyl ether, fatty acid monoethanolamide, fatty acid diethanolamide,
Examples include aqueous sodium silicate solution and water. In practicing the present invention, spray-dried detergent particles can be obtained as follows. That is, excluding thermally unstable raw materials such as enzymes and bleaching agents, and inorganic builders that do not require drying, such as sodium carbonate and sodium sulfate, anionic surfactant solutions and aluminosilicate slurries that require drying. , a fluorescent dye, a pigment, etc., is spray-dried.
If the spray-dried particles are highly sticky, it is optional to incorporate sodium carbonate, sodium sulfate, sodium silicate, etc. into the detergent slurry. The apparent specific gravity and particle size of spray-dried detergent particles are similar. The moisture content is preferably 12% or less. If there is more water than that, it will have a negative effect on the fluidity of the particles after granulation. Next, the granulation process in the method of the present invention will be explained. The granulation treatment method in the present invention basically consists of the following two steps. Crushing process Spray-dried detergent particles are placed in a mixer that has a vertical stirring shaft inside a solid mixing tank, such as a stirring shaft that protrudes from the bottom, and that mixes the powder by attaching stirring blades to this shaft. and grind until the apparent specific gravity becomes 0.05 to 0.3 g/cm 3 larger than the original particles. At this time, if the temperature of the powder exceeds 60 degrees Celsius, the powder will become more sticky and cause agglomeration, so to avoid this, it is effective to install a jacket around the mixer and run cold water through it. In this step, other inorganic and/or organic raw materials of the detergent other than the spray-dried product may be mixed. Stirring granulation process Following the above steps, stirring granulation is carried out while adding a surface modifier and a binder. The surface modifier and the binder may be added at the same time, one of them may be added first, or they may be added alternately. In this step, it is optional to mix other inorganic and/or organic raw materials of the detergent. As an example of the mixer used in the present invention, either a high-speed mixer (stirring rolling granulator) or a Henschel mixer (high-speed stirring granulator) can be used. The detergent particles produced by the present invention can be easily distinguished from detergent particles produced by other methods because they have the following two characteristics. One of these is that the particle surface is covered with a surface modifier, which can be easily confirmed by observation with an electron microscope. Another feature is that the detergent particles of the present invention are composed of mechanically broken, spray-dried particles. This is because when detergent particles are soaked in ethyl alcohol, the detergent particles of the present invention become a fine powder and disperse, whereas simply spray-dried laundry detergent particles do not disperse in this way. I can confirm. [Examples] Examples of the present invention are shown below, but these Examples do not limit the present invention. Example 1 A detergent having the following composition was spray-dried. Linear alkylbenzene sulfonate 35 parts by weight Alkyl sulfate ester salt 10 Sodium carbonate 21.5 Sodium silicate 7 Sodium aluminosilicate 14 Sodium sulfate 3 Nonionic surfactant 3.5 Water 6 Average of detergent particles obtained The particle size was 600 μm and the apparent specific gravity was 0.31 g/cm 3 . 100 parts by weight of the spray-dried detergent particles were placed in a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), stirred and pulverized for 10 minutes, and the apparent specific gravity was 0.43 g/ml.
The average particle size was 130μm. Next, 2 parts by weight of water and 4 parts of aluminosilicate fine powder with an average particle size of 2.7 μm were added.
After adding part by weight and stirring to granulate, coarse particles were removed using a 16-mesh sieve. The apparent specific gravity, average particle size, and fluidity of the detergent thus obtained were measured and are shown in Table 1 along with other Examples and Comparative Examples. Here, the fluidity of the powder is determined by measuring the time required for 100ml of powder to flow out from a hopper for measuring apparent specific gravity specified in JIS K3362, and the shorter the time, the better the fluidity is determined. . Example 2 A detergent having the following composition was spray dried. Linear alkylbenzene sulfonate 35 parts by weight Alkyl sulfate ester salt 10 〃 Sodium carbonate 30 〃 Sodium silicate 7 〃 Sodium aluminosilicate 9 〃 Sodium sulfate 3 〃 Water 6 〃 The average particle size of the obtained detergent particles is 500 μm, and the apparent specific gravity is It was 0.34g/ml. 100 parts by weight of these detergent particles were placed in a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), stirred and pulverized for 10 minutes, and the apparent specific gravity was 0.44.
g/ml, and the average particle size was 110 μm. Next, 4.6 parts by weight of a nonionic surfactant and 17 parts by weight of aluminosilicate fine powder having an average particle size of 2.7 μm were added, and granulation was performed with stirring. After removing coarse particles using a 16-mesh sieve, specific gravity, average particle size, and fluidity were measured. Example 3 Spray-dried detergent particles used in Example 1
100 parts by weight was placed in a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.) and pulverized with stirring for 10 minutes, resulting in an apparent specific gravity of 0.43 g/ml and an average particle size of 130 μm. Next, 2 parts by weight of water and 1 part by weight of silicon dioxide fine powder having a particle size of 20 mμ (0.02 μm) were added, and after granulation with stirring, coarse particles were removed using a 16-mesh sieve. Example 4 In Example 3, 2 parts by weight of the same aluminosilicate and the average particle size were used instead of the silicon dioxide fine powder.
2 parts by weight of 1.5 μm fine talc powder were used together. Comparative Example 1 In Example 1, stirring granulation was performed without adding a surface modifier. Comparative Example 2 In Example 1, 40 parts by weight of the same aluminosilicate as in Example 1 was added and granulation was performed with stirring. As is clear from the above Examples and Comparative Examples, according to the production method of the present invention, a granular detergent with high density and excellent fluidity can be obtained. 【table】
Claims (1)
この軸に攪拌羽根を取り付けて粉末の混合を行う
形式のミキサーによつて、少なくとも1種の界面
活性剤と少なくとも1種のビルダーを含有する洗
剤の噴霧乾燥生成物を攪拌粉砕後、表面改質剤と
バインダーの存在の下に攪拌造粒処理を行つて見
掛け比重が0.5〜1.2g/cm3の高密度洗剤粒子を得
る事を特徴とする流動性の改良された高密度の粒
状洗剤の製法。 2 表面改質剤がアルミノ珪酸塩である特許請求
の範囲第1項記載の製法。 3 アルミノ珪酸塩が1次粒子の平均径が10μm
以下のものである特許請求の範囲第2項記載の製
法。 4 表面改質剤が平均径が10μm以下の二酸化珪
素、ベントナイト、タルク、クレイのような無機
微粉末である特許請求の範囲第1項記載の製法。 5 表面改質剤が平均径が10μm以下の金属石鹸
である特許請求の範囲第1項記載の製法。 6 噴霧乾燥生成物100重量部に対し表面改質剤
が0.5から35重量部である特許請求の範囲第1項
乃至第5項の何れか1項に記載の製法。 7 噴霧乾燥生成物以外の粉末あるいは粒状の無
機原料又は(及び)有機原料を添加して同時に造
粒処理を行う特許請求の範囲第1項乃至第6項の
何れか1項に記載の製法。[Claims] 1. A vertical stirring shaft is provided inside a rigid mixing tank,
After stirring and pulverizing the spray-dried detergent product containing at least one type of surfactant and at least one type of builder using a mixer with a stirring blade attached to the shaft for mixing powder, surface modification is performed. A method for producing a high-density granular detergent with improved fluidity, characterized in that high-density detergent particles with an apparent specific gravity of 0.5 to 1.2 g/cm 3 are obtained by performing an agitation granulation process in the presence of an agent and a binder. . 2. The manufacturing method according to claim 1, wherein the surface modifier is an aluminosilicate. 3 The average diameter of primary particles of aluminosilicate is 10 μm
The manufacturing method according to claim 2, which is as follows. 4. The manufacturing method according to claim 1, wherein the surface modifier is an inorganic fine powder such as silicon dioxide, bentonite, talc, or clay having an average diameter of 10 μm or less. 5. The manufacturing method according to claim 1, wherein the surface modifier is a metal soap with an average diameter of 10 μm or less. 6. The method according to any one of claims 1 to 5, wherein the surface modifier is used in an amount of 0.5 to 35 parts by weight per 100 parts by weight of the spray-dried product. 7. The manufacturing method according to any one of claims 1 to 6, in which a powder or granular inorganic raw material or (and) organic raw material other than the spray-dried product is added and granulation is performed at the same time.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19294884A JPS6169897A (en) | 1984-09-14 | 1984-09-14 | Production of high density detergent improved in flowability |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19294884A JPS6169897A (en) | 1984-09-14 | 1984-09-14 | Production of high density detergent improved in flowability |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6169897A JPS6169897A (en) | 1986-04-10 |
JPH045080B2 true JPH045080B2 (en) | 1992-01-30 |
Family
ID=16299673
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP19294884A Granted JPS6169897A (en) | 1984-09-14 | 1984-09-14 | Production of high density detergent improved in flowability |
Country Status (1)
Country | Link |
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JP (1) | JPS6169897A (en) |
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CA1334389C (en) * | 1986-03-26 | 1995-02-14 | Ernest H. Brumbaugh | Machine dishwasher water spot control composition |
JP2617507B2 (en) * | 1988-01-29 | 1997-06-04 | 花王株式会社 | High density granular concentrated detergent composition |
US5318714A (en) * | 1988-03-14 | 1994-06-07 | Novo Nordisk A/S | Stabilized particulate composition |
DE3812530A1 (en) * | 1988-04-15 | 1989-10-26 | Henkel Kgaa | PROCESS FOR INCREASING THE DENSITY OF SPREADY DRY, PHOSPHATE-REDUCED DETERGENT |
GB8810193D0 (en) * | 1988-04-29 | 1988-06-02 | Unilever Plc | Detergent compositions & process for preparing them |
GB8810821D0 (en) * | 1988-05-06 | 1988-06-08 | Unilever Plc | Detergent compositions & process for preparing them |
IN170991B (en) * | 1988-07-21 | 1992-06-27 | Lever Hindustan Ltd | |
GB8826110D0 (en) * | 1988-11-08 | 1988-12-14 | Unilever Plc | Enzyme-containing detergent compositions |
GB8907187D0 (en) * | 1989-03-30 | 1989-05-10 | Unilever Plc | Detergent compositions and process for preparing them |
US5045238A (en) * | 1989-06-09 | 1991-09-03 | The Procter & Gamble Company | High active detergent particles which are dispersible in cold water |
GB8924294D0 (en) * | 1989-10-27 | 1989-12-13 | Unilever Plc | Detergent compositions |
GB8926718D0 (en) * | 1989-11-27 | 1990-01-17 | Unilever Plc | Process for the preparation of detergent compositions |
JP3192469B2 (en) * | 1991-05-17 | 2001-07-30 | 花王株式会社 | Method for producing nonionic detergent particles |
US5691294A (en) * | 1993-03-30 | 1997-11-25 | The Procter & Gamble Company | Flow aids for detergent powders comprising sodium aluminosilicate and hydrophobic silica |
US5780410A (en) * | 1993-07-14 | 1998-07-14 | The Procter & Gamble Company | Detergent compositions containing percarbonate and making processes thereof |
CA2167158C (en) * | 1993-07-14 | 1999-11-02 | Gerard Marcel Baillely | Detergent compositions containing percarbonate and making processes thereof |
DE69532586T3 (en) | 1994-09-13 | 2014-03-13 | Kao Corp. | WASHING PROCEDURE |
JPH11509263A (en) * | 1996-05-07 | 1999-08-17 | ザ、プロクター、エンド、ギャンブル、カンパニー | PROCESS FOR PRODUCING AGENT DETERGENT COMPOSITIONS WITH IMPROVED FLOW |
US6017867A (en) * | 1998-06-05 | 2000-01-25 | The Procter & Gamble Company | Detergent compositions containing percarbonate and making processes thereof |
GB0125653D0 (en) | 2001-10-25 | 2001-12-19 | Unilever Plc | Process for the production of detergent granules |
BR0213432A (en) | 2001-10-25 | 2004-11-09 | Unilever Nv | Process for the preparation of detergent granules |
JP4515239B2 (en) * | 2004-12-08 | 2010-07-28 | 花王株式会社 | Hand washing laundry detergent |
CN118339271A (en) | 2022-03-16 | 2024-07-12 | 宝洁公司 | Detergent granule coated with precipitated calcium carbonate |
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Also Published As
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