JP4841976B2 - Detergent composition for dishwasher - Google Patents
Detergent composition for dishwasher Download PDFInfo
- Publication number
- JP4841976B2 JP4841976B2 JP2006066007A JP2006066007A JP4841976B2 JP 4841976 B2 JP4841976 B2 JP 4841976B2 JP 2006066007 A JP2006066007 A JP 2006066007A JP 2006066007 A JP2006066007 A JP 2006066007A JP 4841976 B2 JP4841976 B2 JP 4841976B2
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- Prior art keywords
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- polymer compound
- monomer
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- 239000000203 mixture Substances 0.000 title claims description 86
- 239000003599 detergent Substances 0.000 title claims description 25
- 239000002245 particle Substances 0.000 claims description 140
- 239000000178 monomer Substances 0.000 claims description 93
- 150000001875 compounds Chemical class 0.000 claims description 47
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 229920000642 polymer Polymers 0.000 claims description 37
- 238000004140 cleaning Methods 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 125000002091 cationic group Chemical group 0.000 claims description 21
- 239000000470 constituent Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 125000000129 anionic group Chemical group 0.000 claims description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 15
- 239000011976 maleic acid Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- -1 alkali metal salt Chemical class 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 27
- 150000003839 salts Chemical class 0.000 description 24
- 238000003860 storage Methods 0.000 description 23
- 239000007787 solid Substances 0.000 description 20
- 229910017053 inorganic salt Inorganic materials 0.000 description 19
- 150000002894 organic compounds Chemical class 0.000 description 18
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical group [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 10
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 7
- 108090000790 Enzymes Proteins 0.000 description 7
- 239000004115 Sodium Silicate Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000796 flavoring agent Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 102000013142 Amylases Human genes 0.000 description 6
- 108010065511 Amylases Proteins 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 108091005804 Peptidases Proteins 0.000 description 6
- 239000004365 Protease Substances 0.000 description 6
- 125000004103 aminoalkyl group Chemical group 0.000 description 6
- 235000019418 amylase Nutrition 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004382 Amylase Substances 0.000 description 5
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 235000010338 boric acid Nutrition 0.000 description 5
- 229960002645 boric acid Drugs 0.000 description 5
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 5
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 5
- 229940008406 diethyl sulfate Drugs 0.000 description 5
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 5
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 5
- 229940088598 enzyme Drugs 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 125000005429 oxyalkyl group Chemical group 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 229940045872 sodium percarbonate Drugs 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-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
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 150000001449 anionic compounds Chemical class 0.000 description 3
- 229920006317 cationic polymer Polymers 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229960003330 pentetic acid Drugs 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229960001922 sodium perborate Drugs 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical class OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- RBPIYINIVXGGFY-UHFFFAOYSA-N 4-(dimethylazaniumyl)-2-methylidenebutanoate Chemical compound CN(C)CCC(=C)C(O)=O RBPIYINIVXGGFY-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 235000011054 acetic acid Nutrition 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory 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
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 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
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000010079 rubber tapping Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 229940117986 sulfobetaine Drugs 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- DCCWEYXHEXDZQW-BYPYZUCNSA-N (2s)-2-[bis(carboxymethyl)amino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)N(CC(O)=O)CC(O)=O DCCWEYXHEXDZQW-BYPYZUCNSA-N 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
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
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- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- GAVHQOUUSHBDAA-UHFFFAOYSA-N 3-butyl-1-ethenylaziridin-2-one Chemical compound CCCCC1N(C=C)C1=O GAVHQOUUSHBDAA-UHFFFAOYSA-N 0.000 description 1
- RYKZRKKEYSRDNF-UHFFFAOYSA-N 3-methylidenepentane Chemical compound CCC(=C)CC RYKZRKKEYSRDNF-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- XZQWWHBLXRBQKI-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanoic acid Chemical compound CN(C)CCCC(=C)C(O)=O XZQWWHBLXRBQKI-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 102100026189 Beta-galactosidase Human genes 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 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 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
- 108090000371 Esterases Proteins 0.000 description 1
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- 229910021538 borax Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
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- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 108010093305 exopolygalacturonase Proteins 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 239000011361 granulated particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229940116108 lactase Drugs 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000019419 proteases Nutrition 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- FHLDWQLHDYCXKI-UHFFFAOYSA-N sodium;4-(3,5-dichloro-4-hydroxyphenyl)iminocyclohexa-2,5-dien-1-one Chemical compound [Na+].C1=C(Cl)C(O)=C(Cl)C=C1N=C1C=CC(=O)C=C1 FHLDWQLHDYCXKI-UHFFFAOYSA-N 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- Y02P60/216—
Landscapes
- Detergent Compositions (AREA)
Description
本発明は食器洗浄機用洗浄剤組成物に関する。 The present invention relates to a detergent composition for a dishwasher.
近年、自動食器洗浄機は急速に普及しており、また、省エネルギー、省資源の観点から使用する洗浄水の量を低減化し、且つ一回に洗浄する食器の量を増加させる洗浄機が主流を占めている。しかしながら、このような洗浄機で汚れ量が多い食器を洗浄すると、洗浄／乾燥後の食器にいわゆるウォータースポットとして知られている白い付着物が形成されることが多々起こるという問題があり、この解決が強く求められる。 In recent years, automatic dishwashers have rapidly spread, and washing machines that reduce the amount of washing water used from the viewpoint of energy saving and resource saving and increase the amount of tableware to be washed at one time have become mainstream. is occupying. However, when a dish with a large amount of dirt is washed by such a washing machine, there is a problem that white deposits known as water spots are often formed on the dish after washing / drying. Is strongly demanded.
このウォータースポットの形成を抑制する洗浄剤の技術として特許文献１に陽イオン性高分子化合物又は両性高分子化合物を応用する技術が開示されている。また、特許文献２にはリン酸スケール形成抑制剤として、特許文献３には褪色又は腐食抑制剤として陽イオン性高分子化合物又は両性高分子化合物を応用する技術が開示されている。特許公報４及び特許公報５には、ジアリルアンモニウム型モノマー、酸性官能基を有するモノマー及びその他モノマーの共重合体を汚れ再付着防止剤として用いる技術が開示されており、特には特許公報５には、該ポリマーを水溶性の無機担体に吸着及び／又は吸収させた状態で含む固体状予備配合製品として配合する台所用品及び食器の機械洗浄用洗浄剤が記載されている。特許公報６及び特許公報７には、アクリル酸／マレイン酸共重合体又はそのアルカリ金属塩を食器洗浄機用洗浄剤組成物に用いる技術が開示されている。
上記のように、特許文献１〜７には、食器洗浄機用洗浄剤組成物に陽イオン性基及び陰イオン性基を有する高分子化合物や、アクリル酸／マレイン酸共重合体を配合することが開示されているが、粉末状ないし粒状の食器洗浄機用洗浄剤組成物に陽イオン性高分子化合物又は両性高分子化合物を配合する場合、ケーキングするなどの組成物の貯蔵安定性が著しく低下すると共に、一般に用いられる無機過酸化物の貯蔵安定性に悪影響を及ぼし、貯蔵後の洗浄性能が著しく低下するという課題がある。また、本発明者らは、粉末状ないし粒状の食器洗浄機用洗浄剤組成物において、陽イオン性基を有するモノマー構成単位を含む高分子化合物を、炭酸ナトリウムや珪酸ナトリウムなどのアルカリ剤と混合すると、貯蔵保存後に、香料による匂いとは異なる異臭が発生することを見出した。この点、特許文献１〜７は、固体、粉末状ないし粒状中の洗浄剤組成物中に所定の高分子化合物を存在させた場合のこのような問題点について何ら言及していない。 As described above, Patent Documents 1 to 7 include blending a polymer compound having a cationic group and an anionic group or an acrylic acid / maleic acid copolymer into a detergent composition for a dishwasher. However, when a cationic polymer compound or an amphoteric polymer compound is added to a powdery or granular dishwasher detergent composition, the storage stability of the composition such as caking is significantly reduced. At the same time, there is a problem that the storage stability of generally used inorganic peroxides is adversely affected, and the cleaning performance after storage is significantly reduced. Further, the present inventors mixed a polymer compound containing a monomer constituent unit having a cationic group with an alkaline agent such as sodium carbonate or sodium silicate in a powdery or granular dishwasher detergent composition. Then, after storage preservation | save, it discovered that a different odor different from the smell by a fragrance | flavor generate | occur | produces. In this respect, Patent Documents 1 to 7 do not mention any such problems when a predetermined polymer compound is present in a cleaning composition in a solid, powder or granular form.
本発明の課題は、ウォータースポット形成抑制効果に優れ、ケーキングなどの貯蔵安定性に問題がなく、貯蔵後の洗浄性能、特に無機過酸化物を含有する組成物の貯蔵後の洗浄性能に問題がなく、且つ異臭の発生が抑制された食器洗浄機用洗浄剤組成物を提供することにある。 The problem of the present invention is that it has an excellent water spot formation suppressing effect, has no problem in storage stability such as caking, and has a problem in cleaning performance after storage, particularly cleaning performance after storage of a composition containing an inorganic peroxide. The object is to provide a detergent composition for a dishwasher that is free from the occurrence of off-flavors.
本発明は、陽イオン性基を有するモノマー構成単位（ａ−１）及び陰イオン性基を有するモノマー構成単位（ａ−２）を含み、〔陽イオン性基の総モル数〕／〔陰イオン性基の総モル数〕がモル比として３０／７０〜９０／１０である高分子化合物（ａ）、カルボン酸基を有するモノマー構成単位（ｂ−１）を含むが陽イオン性基を有するモノマー構成単位を含まない高分子化合物であって、１質量％水溶液の２５℃でのｐＨが３〜８である高分子化合物（ｂ）、並びに、アルカリ剤（ｃ）を含有し、（ａ）／（ｂ）の質量比が０．０１〜３である食器洗浄機用洗浄剤組成物に関する。 The present invention includes a monomer structural unit (a-1) having a cationic group and a monomer structural unit (a-2) having an anionic group, and [total number of moles of cationic group] / [anion] Monomer having a cationic group, but comprising a polymer compound (a) having a molar ratio of 30/70 to 90/10 as a molar ratio and a monomer structural unit (b-1) having a carboxylic acid group A polymer compound containing no structural unit, the polymer compound (b) having a pH of 3 to 8 at 25 ° C. in a 1% by mass aqueous solution, and an alkali agent (c), (a) / It is related with the cleaning composition for dishwashers whose mass ratio of (b) is 0.01-3.
本発明によれば、ウォータースポット形成抑制効果に優れ、ケーキングなどの貯蔵安定性に問題がなく、貯蔵後の洗浄性能、特に無機過酸化物を含有する組成物の貯蔵後の洗浄性能に問題に問題がなく、且つ貯蔵保存後の異臭の発生が抑制された食器洗浄機用洗浄剤組成物が提供される。 According to the present invention, the water spot formation inhibiting effect is excellent, there is no problem in storage stability such as caking, and there is a problem in cleaning performance after storage, particularly cleaning performance after storage of a composition containing an inorganic peroxide. There is provided a detergent composition for a dishwasher that is free from problems and that suppresses the generation of off-flavors after storage.
＜（ａ）成分＞
本発明では陽イオン性基を有するモノマー構成単位（ａ−１）〔以下モノマー構成単位（ａ−１）という〕及び陰イオン性基を有するモノマー構成単位（ａ−２）〔以下モノマー構成単位（ａ−２）という〕を含有する高分子化合物（ａ）〔以下、（ａ）成分という〕を用いる。
<(A) component>
In the present invention, the monomer structural unit (a-1) having a cationic group (hereinafter referred to as monomer structural unit (a-1)) and the monomer structural unit (a-2) having an anionic group (hereinafter referred to as monomer structural unit ( a high molecular compound (a) [hereinafter referred to as component (a)].
モノマー構成単位（ａ−１）としては下記一般式（１）及び／又は一般式（２）のモノマー構成単位が好適である。 The monomer structural unit (a-1) is preferably a monomer structural unit represented by the following general formula (1) and / or general formula (2).
〔式中、Ｒ11は水素原子又はメチル基であり、Ｒ12は水素原子、メチル基、又はヒドロキシ基であり、Ｒ13は炭素数１〜３のアルキル基又はヒドロキシアルキル基である。Ｘは−ＣＯＯＲ14−、−ＣＯＮ（Ｒ15）Ｒ16−であり、ここでＲ14、Ｒ16は炭素数２〜５のアルキレン基であり、Ｒ15は水素原子又はメチル基である。Ｒ21は炭素数１〜３のアルキル基又はヒドロキシアルキル基であり、ｎは０又は１の数である。Ｙ-は陰イオン基である。〕 [Wherein, R 11 is a hydrogen atom or a methyl group, R 12 is a hydrogen atom, a methyl group, or a hydroxy group, and R 13 is an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms. X is —COOR 14 —, —CON (R 15 ) R 16 —, wherein R 14 and R 16 are alkylene groups having 2 to 5 carbon atoms, and R 15 is a hydrogen atom or a methyl group. R 21 is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and n is a number of 0 or 1. Y - is an anionic group. ]
一般式（１）においてＲ11は水素原子が好ましく、Ｒ12は水素原子、メチル基が好ましい。Ｘは−ＣＯＮ（Ｒ15）Ｒ16−が好ましく、Ｒ15は水素原子が好適である。Ｒ13はメチル基が好ましく、Ｙ-はハロゲンイオン、硫酸イオン、炭素数１〜３のアルキル硫酸エステルイオン、燐酸イオン、炭素数１〜１２の脂肪酸イオン、炭素数１〜３のアルキル基が１〜３個置換していてもよいベンゼンスルホン酸イオンが好適であり、特にクロルイオンが好ましい。 In the general formula (1), R 11 is preferably a hydrogen atom, and R 12 is preferably a hydrogen atom or a methyl group. X is preferably —CON (R 15 ) R 16 —, and R 15 is preferably a hydrogen atom. R 13 is preferably a methyl group, Y - is a halogen ion, sulfate ion, alkyl sulfate ion having 1 to 3 carbon atoms, phosphate ions, fatty acid ion having 1 to 12 carbon atoms, an alkyl group having 1 to 3 carbon atoms 1 A benzenesulfonic acid ion which may be substituted by 3 is preferable, and a chloro ion is particularly preferable.
一般式（２）においてＲ21はメチル基が好ましく、Ｙ-はハロゲンイオン、硫酸イオン、燐酸イオン、炭素数１〜１２の脂肪酸イオン、炭素数１〜３のアルキル基が１〜３個置換していてもよいベンゼンスルホン酸イオンが好適であり、特にクロルイオンが好ましい。ｎは０が好適である。 In general formula (2), R 21 is preferably a methyl group, and Y − is substituted by 1 to 3 halogen ions, sulfate ions, phosphate ions, fatty acid ions having 1 to 12 carbon atoms, and alkyl groups having 1 to 3 carbon atoms. Benzenesulfonic acid ions which may be present are preferred, and chloro ions are particularly preferred. n is preferably 0.
モノマー構成単位（ａ−２）としては下記一般式（３）のモノマー構成単位が好適である。 As the monomer structural unit (a-2), a monomer structural unit represented by the following general formula (3) is preferable.
〔式中、Ｒ31は水素原子、メチル基、又は−ＣＯＯＭであり、Ｒ32は水素原子、メチル基、又はヒドロキシ基である。Ｚは−ＣＯＯＭ、−ｐｈ−ＳＯ3Ｍである。ここでＭは水素原子、アルカリ金属又はアルカリ土類金属であり、ｐｈはベンゼン環を示す。〕 [Wherein, R 31 represents a hydrogen atom, a methyl group, or —COOM, and R 32 represents a hydrogen atom, a methyl group, or a hydroxy group. Z is -COOM, a -ph-SO 3 M. Here, M is a hydrogen atom, an alkali metal or an alkaline earth metal, and ph represents a benzene ring. ]
本発明の（ａ）成分は、陽イオン性基及び陰イオン性基を１つのモノマー構成単位に有する構造（ａ−１２）であっても差し支えない。具体的には下記一般式（４）又は一般式（５）のモノマー構成単位が好適である。 The component (a) of the present invention may be a structure (a-12) having a cationic group and an anionic group in one monomer constituent unit. Specifically, the monomer structural unit of the following general formula (4) or general formula (5) is preferable.
〔式中Ｒ41、Ｒ51は水素原子又はメチル基であり、Ｒ42、Ｒ52は水素原子、メチル基、又はヒドロキシ基である。Ｘ、Ｙ-、Ｍは上述と同一の意味であり、Ｒ43、Ｒ53は炭素数１〜３のアルキル基又はヒドロキシアルキル基であり、Ｒ54は−ＣＨ2ＣＯＯ-、−Ｃ3Ｈ6ＳＯ3 -、−ＣＨ2ＣＨ（ＯＨ）ＣＨ2−ＳＯ3 -から選ばれる基である。〕 [Wherein R 41 and R 51 are a hydrogen atom or a methyl group, and R 42 and R 52 are a hydrogen atom, a methyl group or a hydroxy group. X, Y − and M have the same meaning as described above, R 43 and R 53 are an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, and R 54 is —CH 2 COO − , —C 3 H 6. It is a group selected from SO 3 − and —CH 2 CH (OH) CH 2 —SO 3 — . ]
本発明の（ａ）成分は、（ａ）成分を構成するモノマー構成単位に対応する単量体を通常の重合反応を行って製造することができる。あるいは、高分子化合物に後処理を施すことにより、最終的に（ａ）成分を得ても良い。例えば、陽イオン性基として４級アンモニウム基を有する高分子化合物の場合は、当初の単量体中に４級アンモニウム基を有する単量体を重合反応により得る方法の他に、アミノ基を有する単量体を用いて重合反応を行った物に４級化処理を施すことによって（ａ）成分を得てもよい。もちろん陰イオン性基についても同様である。当然ながら、後処理を必要とする高分子化合物を得るために用いられる単量体は、後処理を考慮した構造のものが選ばれる。 The component (a) of the present invention can be produced by subjecting a monomer corresponding to the monomer structural unit constituting the component (a) to a normal polymerization reaction. Or you may finally obtain (a) component by performing a post-process to a high molecular compound. For example, in the case of a polymer compound having a quaternary ammonium group as a cationic group, it has an amino group in addition to a method of obtaining a monomer having a quaternary ammonium group in the initial monomer by a polymerization reaction. The component (a) may be obtained by subjecting a product subjected to a polymerization reaction using a monomer to quaternization treatment. Of course, the same applies to anionic groups. Naturally, the monomer used for obtaining the polymer compound that requires post-treatment is selected to have a structure that takes post-treatment into consideration.
具体的な一般式（１）のモノマー構成単位に対応する単量体としてはアクリロイル（又はメタクリロイル、α−ヒドロキシアキリロイル、もしくはクロトノイル）アミノアルキル（炭素数２〜５）−Ｎ，Ｎ，Ｎ−トリアルキル（炭素数１〜３）４級アンモニウム塩、アクリロイル（又はメタクリロイル、α−ヒドロキシアキリロイル、もしくはクロトノイル）オキシアルキル（炭素数２〜５）−Ｎ，Ｎ，Ｎ−トリアルキル（炭素数１〜３）４級アンモニウム塩を挙げることができる。塩としては上述のＹ−に相当する塩が好ましい。また、アクリロイル（又はメタクリロイル、α−ヒドロキシアキリロイル、もしくはクロトノイル）アミノアルキル（炭素数２〜５）−Ｎ，Ｎ−ジアルキル（炭素数１〜３）アミン、アクリロイル（又はメタクリロイル、α−ヒドロキシアキリロイル、もしくはクロトノイル）オキシアルキル（炭素数２〜５）−Ｎ，Ｎ−ジアルキル（炭素数１〜３）アミンを重合させたモノマー構成単位に、メチルクロリド、ジメチル硫酸、ジエチル硫酸、エチレンオキシド、プロピレンオキシドなどの４級化剤を用いてアルキル化することで製造することもできる。なお、エチレンオキシド及び／又はプロピレンオキシドを用いる場合にはＹＨ（Ｙは上記陰イオン化合物）で示される酸でアミノ基を中和して反応させる必要がある。 Specific examples of the monomer corresponding to the monomer structural unit represented by the general formula (1) include acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 5 carbon atoms) -N, N, N— Trialkyl (1 to 3 carbon atoms) quaternary ammonium salt, acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) oxyalkyl (2 to 5 carbon atoms) -N, N, N-trialkyl (1 carbon atom) -3) A quaternary ammonium salt can be mentioned. As the salt, a salt corresponding to the above-mentioned Y- is preferable. Also, acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 5 carbon atoms) -N, N-dialkyl (1 to 3 carbon atoms) amine, acryloyl (or methacryloyl, α-hydroxyacryloyl) , Or crotonoyl) oxyalkyl (2 to 5 carbon atoms) -N, N-dialkyl (1 to 3 carbon atoms) monomer monomer units, methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, propylene oxide, etc. It can also manufacture by alkylating using the quaternizing agent of these. In addition, when using ethylene oxide and / or propylene oxide, it is necessary to neutralize and react an amino group with the acid shown by YH (Y is the said anionic compound).
一般式（２）に対応する単量体としてはＮ，Ｎ−ジアリル−Ｎ，Ｎ−ジアルキル（炭素数１〜３）４級アンモニウム塩を用いることができる。また、Ｎ，Ｎ−ジアリル−Ｎ−アルキル（炭素数１〜３）アミンを重合させたモノマー構成単位に、メチルクロリド、ジメチル硫酸、ジエチル硫酸、エチレンオキシド、プロピレンオキシドなどの４級化剤を用いてアルキル化することで製造することもできる。なお、エチレンオキシド及び／又はプロピレンオキシドを用いる場合にはＹＨ（Ｙは上記陰イオン化合物）で示される酸でアミノ基を中和して反応させる必要がある。 N, N-diallyl-N, N-dialkyl (C1-3) quaternary ammonium salt can be used as the monomer corresponding to the general formula (2). In addition, a quaternizing agent such as methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, or propylene oxide is used for the monomer structural unit obtained by polymerizing N, N-diallyl-N-alkyl (carbon number 1 to 3) amine. It can also be produced by alkylation. In addition, when using ethylene oxide and / or propylene oxide, it is necessary to neutralize and react an amino group with the acid shown by YH (Y is the said anionic compound).
一般式（３）に対応する単量体としてはアクリル酸又はその塩、メタクリル酸又はその塩、クロトン酸又はその塩、α−ヒドロキシアクリル酸又はその塩、マレイン酸又はその塩、無水マレイン酸、スチレンスルホン酸塩を挙げることができる。また、スチレンスルホン酸塩を重合して得られるモノマー構成単位は、スチレンを重合して得られた化合物に３酸化イオウ、クロルスルホン酸、硫酸などのスルホン化剤を用いてスルホン化し、中和することでも得ることができる。 As monomers corresponding to the general formula (3), acrylic acid or a salt thereof, methacrylic acid or a salt thereof, crotonic acid or a salt thereof, α-hydroxyacrylic acid or a salt thereof, maleic acid or a salt thereof, maleic anhydride, Mention may be made of styrene sulfonates. The monomer structural unit obtained by polymerizing styrene sulfonate is neutralized by sulfonating a compound obtained by polymerizing styrene with a sulfonating agent such as sulfur trioxide, chlorosulfonic acid, sulfuric acid or the like. Can also be obtained.
一般式（４）のモノマー構成単位を有する高分子化合物は、無水マレイン酸を予め重合したモノマー構成単位にアミノアルキル（炭素数２〜５）ジアルキル（炭素数１〜３）アミン、又はＮ，Ｎ−ジアルキル（炭素数１〜３）−Ｎ−アルカノール（炭素数２〜５）アミンを反応させ、続いてメチルクロリド、ジメチル硫酸、ジエチル硫酸、エチレンオキシド、プロピレンオキシドなどの４級化剤を用いてアルキル化することで製造することもできる。なお、エチレンオキシド及び／又はプロピレンオキシドを用いる場合にはＹＨ（Ｙは上記陰イオン化合物）で示される酸でアミノ基を中和して反応させる必要がある。 The polymer compound having the monomer structural unit of the general formula (4) is an aminoalkyl (2 to 5 carbon atoms) dialkyl (1 to 3 carbon atoms) amine, or N, N -Dialkyl (1 to 3 carbon atoms)-N-alkanol (2 to 5 carbon atoms) amine is reacted, followed by alkylation using a quaternizing agent such as methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, propylene oxide Can also be manufactured. In addition, when using ethylene oxide and / or propylene oxide, it is necessary to neutralize and react an amino group with the acid shown by YH (Y is the said anionic compound).
一般式（５）に対応する単量体としてはＮ−〔アクリロイル（又はメタクリロイル、α−ヒドロキシアクリロイル、もしくはクロトノイル）アミノアルキル（炭素数２〜３）〕−Ｎ，Ｎ−ジアルキル（炭素数１〜３）−Ｎ−カルボキシメチル アンモニウムカルボベタイン、Ｎ−〔アクリロイル（又はメタクリロイル、α−ヒドロキシアクリロイル、もしくはクロトノイル）アミノアルキル（炭素数２〜３）〕−Ｎ，Ｎ−ジアルキル（炭素数１〜３）−Ｎ−〔２−ヒドロキシスルホプロピル〕 アンモニウムスルホベタイン、Ｎ−〔アクリロイル（又はメタクリロイル、α−ヒドロキシアクリロイル、もしくはクロトノイル）アミノアルキル（炭素数２〜３）〕−Ｎ，Ｎ−ジアルキル（炭素数１〜３）−Ｎ−スルホプロピル〕 アンモニウムスルホベタイン、Ｎ−〔アクリロイル（又はメタクリロイル、α−ヒドロキシアクリロイル、もしくはクロトノイル）オキシアルキル（炭素数２〜３）〕−Ｎ，Ｎ−ジアルキル（炭素数１〜３）−Ｎ−カルボキシメチル アンモニウムカルボベタイン、Ｎ−〔アクリロイル（又はメタクリロイル、α−ヒドロキシアクリロイル、もしくはクロトノイル）オキシアルキル（炭素数２〜３）〕−Ｎ，Ｎ−ジアルキル（炭素数１〜３）−Ｎ−〔２−ヒドロキシスルホプロピル〕 アンモニウムスルホベタイン、Ｎ−〔アクリロイル（又はメタクリロイル、α−ヒドロキシアクリロイル、もしくはクロトノイル）オキシアルキル（炭素数２〜３）〕−Ｎ，Ｎ−ジアルキル（炭素数１〜３）−Ｎ−スルホプロピル〕 アンモニウムスルホベタインを挙げることができる。 As a monomer corresponding to the general formula (5), N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 to 3 carbon atoms) 3) -N-carboxymethyl ammonium carbobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 3 carbon atoms)] -N, N-dialkyl (1 to 3 carbon atoms) -N- [2-hydroxysulfopropyl] ammonium sulfobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 carbon atom) -3) -N-sulfopropyl] ammonium Betaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) oxyalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 to 3 carbon atoms) -N-carboxymethyl ammonium carbobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) oxyalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 to 3 carbon atoms) -N- [2-hydroxysulfopropyl] ammonium Sulfobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) oxyalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 to 3 carbon atoms) -N-sulfopropyl] ammonium sulfone Named betaine Kill.
本発明では陽イオン性基を有するモノマー構成単位として、特にＮ，Ｎ−ジアリル−Ｎ，Ｎ−ジアルキル（炭素数１〜３）４級アンモニウム塩を重合して得られるモノマー構成単位、またはＮ，Ｎ−ジアリル−Ｎ−アルキル（炭素数１〜３）アミンを重合させたモノマー構成単位をメチルクロリド、ジメチル硫酸、ジエチル硫酸、エチレンオキシド、プロピレンオキシドなどの４級化剤を用いてアルキル化したモノマー構成単位が好ましく、陰イオン性基を有するモノマー構成単位としてアクリル酸又はその塩、メタクリル酸又はその塩、マレイン酸又はその塩、無水マレイン酸から選ばれる単量体を重合して得られるモノマー構成単位が好ましい。 In the present invention, as a monomer structural unit having a cationic group, a monomer structural unit obtained by polymerizing an N, N-diallyl-N, N-dialkyl (C 1-3 quaternary ammonium salt), or N, Monomer composition in which N-diallyl-N-alkyl (1 to 3 carbon atoms) monomer structural unit is alkylated using a quaternizing agent such as methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, propylene oxide. Monomer constituent unit obtained by polymerizing a monomer selected from acrylic acid or a salt thereof, methacrylic acid or a salt thereof, maleic acid or a salt thereof, or maleic anhydride as a monomer constituent unit having an anionic group. Is preferred.
本発明の（ａ）成分は、〔陽イオン性基の総モル数〕／〔陰イオン性基の総モル数〕のモル比が３０／７０〜９０／１０、好ましくは４０／６０〜７０／３０、より好ましくは５０／５０〜７０／３０の高分子化合物を用いる。また、陰イオン性基がカルボン酸基である場合に好適なモル比は好ましくは３０／７０〜７０／３０、特には５０／５０〜７０／３０である。 Component (a) of the present invention has a molar ratio of [total number of cationic groups] / [total number of anionic groups] of 30/70 to 90/10, preferably 40/60 to 70 /. 30, More preferably, a polymer compound of 50/50 to 70/30 is used. Further, when the anionic group is a carboxylic acid group, the preferred molar ratio is preferably 30/70 to 70/30, particularly 50/50 to 70/30.
本発明の（ａ）成分は陽イオン性基を有するモノマー構成単位、及び陰イオン性基を有するモノマー構成単位、好ましくは一般式（１）〜一般式（５）から選ばれるモノマー構成単位、の合計が、（ａ）成分を構成する全モノマー構成単位中、５０〜１００モル％、好ましくは７０〜１００モル％、より好ましくは８０〜１００モル％、特に好ましくは９０〜１００モル％の高分子化合物が好ましい。 The component (a) of the present invention comprises a monomer constituent unit having a cationic group and a monomer constituent unit having an anionic group, preferably a monomer constituent unit selected from the general formulas (1) to (5). A polymer having a total of 50 to 100 mol%, preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and particularly preferably 90 to 100 mol% in all monomer constituent units constituting the component (a) Compounds are preferred.
本発明では陽イオン性基を有するモノマー構成単位、及び陰イオン性基を有するモノマー構成単位、好ましくは一般式（１）〜一般式（５）から選ばれるモノマー構成単位以外に、本発明の効果を損なわない程度にこれらと共重合可能な単量体を共重合させて得られるモノマー構成単位（ａ−３）［以下モノマー構成単位（ａ−３）という］を含んでいてもよい。具体的にはアクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピルアクリル酸（又はメタクリル酸）アミド、Ｎ，Ｎ−ジメチルアクリル（又はメタクリル）アミド、Ｎ，Ｎ−ジメチルアミノエチルアクリル酸（又はメタクリル酸）アミド、Ｎ，Ｎ−ジメチルアミノエチルアクリル酸（又はメタクリル酸）アミド、Ｎ−ビニル−２−カプロラクタム、Ｎ−ビニル−２−ピロリドン、アクリル酸（又はメタクリル酸）アルキル（炭素数１〜５）、アクリル酸（又はメタクリル酸）２−ヒドロキシエチル、アクリル酸（又はメタクリル酸）−Ｎ，Ｎ−ジメチルアミノアルキル（炭素数１〜５）、酢酸ビニル、エチレン、プロピレン、Ｎ−ブチレン、イソブチレン、Ｎ−ペンテン、イソプレン、２−メチル−１−ブテン、Ｎ−ヘキセン、２−メチル−１−ペンテン、３−メチル−１−ペンテン、４−メチル−１−ペンテン、２−エチル−１−ブテン、スチレン、ビニルトルエン、α−メチルスチレン、アリルアミン、Ｎ，Ｎ−ジアリルアミン、Ｎ，Ｎ−ジアリル−Ｎ−アルキル（炭素数１〜５）アミン、エチレンオキシド、プロピレンオキシド、２−ビニルピリジン、４−ビニルピリジン、二酸化硫黄を挙げることができる。 In the present invention, in addition to the monomer structural unit having a cationic group and the monomer structural unit having an anionic group, preferably the monomer structural unit selected from the general formula (1) to the general formula (5), the effect of the present invention. The monomer constituent unit (a-3) [hereinafter referred to as the monomer constituent unit (a-3)] obtained by copolymerizing a monomer copolymerizable with these may be included so as not to impair the above. Specifically, acrylamide, N, N-dimethylaminopropylacrylic acid (or methacrylic acid) amide, N, N-dimethylacrylic (or methacrylic) amide, N, N-dimethylaminoethylacrylic acid (or methacrylic acid) amide, N, N-dimethylaminoethyl acrylic acid (or methacrylic acid) amide, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone, acrylic acid (or methacrylic acid) alkyl (1 to 5 carbon atoms), acrylic acid (Or methacrylic acid) 2-hydroxyethyl, acrylic acid (or methacrylic acid) -N, N-dimethylaminoalkyl (1 to 5 carbon atoms), vinyl acetate, ethylene, propylene, N-butylene, isobutylene, N-pentene, Isoprene, 2-methyl-1-butene, N-hexene, 2-methyl-1- Nthene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, styrene, vinyltoluene, α-methylstyrene, allylamine, N, N-diallylamine, N, N-diallyl- N-alkyl (C1-C5) amine, ethylene oxide, propylene oxide, 2-vinylpyridine, 4-vinylpyridine, and sulfur dioxide can be mentioned.
本発明では特に二酸化硫黄を（ａ）成分中に１〜１５モル％共重合させた化合物が最も好ましい。 In the present invention, a compound obtained by copolymerizing 1 to 15 mol% of sulfur dioxide in the component (a) is most preferable.
本発明の（ａ）成分はいかなる重合法によって得てもよいが、ラジカル重合法が特に好ましく、塊状、溶液、又は乳化系にてこれを行うことができる。ラジカル重合は加熱によりこれを開始してもよいが、開始剤として、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩、２，２’−アゾビス（Ｎ，Ｎ−ジメチレンイソブチルアミジン）二塩酸塩、などのアゾ系開始剤、過酸化水素及び、過酸化ベンゾイル、ｔ−ブチルヒドロパーオキシド、クメンヒドロパーオキシド、メチルエチルケトンパーオキシド、過安息香酸などの有機過酸化物、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウムなどの過硫酸塩、過酸化水素−Ｆｅ3+などのレドックス開始剤、など既存のラジカル開始剤を用いてもよいし、光増感剤の存在／又は非存在下での光照射や、放射線照射により重合を開始させてもよいが、特に安全性、反応性の点から過硫酸アンモニウムを用いることが好ましい。 The component (a) of the present invention may be obtained by any polymerization method, but a radical polymerization method is particularly preferred, and this can be carried out in a lump, solution or emulsion system. Radical polymerization may be initiated by heating, but as an initiator, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (N, N-dimethyleneisobutylamidine) Azo initiators such as dihydrochloride, hydrogen peroxide and organic peroxides such as benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide, perbenzoic acid, sodium persulfate, Existing radical initiators such as persulfates such as potassium persulfate and ammonium persulfate, and redox initiators such as hydrogen peroxide-Fe 3+ may be used, and in the presence or absence of a photosensitizer. The polymerization may be initiated by irradiation with light or radiation, but ammonium persulfate is preferably used from the viewpoint of safety and reactivity.
本発明の（ａ）成分は、重量平均分子量が好ましくは１，０００〜６，０００，０００、より好ましくは１，０００〜５００，０００、さらに好ましくは１，０００〜１００，０００、特に好ましくは５，０００〜６０，０００であり、この重量平均分子量はアセトニトリルと水の混合溶媒（リン酸緩衝液）を展開溶媒とし、ゲルパーミエーションクロマトグラフィーでポリエチレングリコールを標準物質として求めたものである。 The component (a) of the present invention preferably has a weight average molecular weight of 1,000 to 6,000,000, more preferably 1,000 to 500,000, still more preferably 1,000 to 100,000, particularly preferably. The weight average molecular weight is determined by gel permeation chromatography using polyethylene glycol as a standard substance with a mixed solvent of acetonitrile and water (phosphate buffer solution) as a developing solvent.
本発明の食器洗浄機用洗浄剤組成物は、上記（ａ）成分を、該（ａ）成分を０．０５〜１０質量％、更に０．３〜１０質量％、更に０．４〜８質量％、特に０．４質量％以上、５質量％未満を含有する粒子〔以下、粒子（Ａ）という〕として含有することが好ましい。 The detergent composition for a dishwasher of the present invention comprises the component (a), the component (a) at 0.05 to 10% by mass, further 0.3 to 10% by mass, and further 0.4 to 8% by mass. %, Particularly 0.4% by mass or more and less than 5% by mass, and preferably contained as particles (hereinafter referred to as particles (A)).
なお、組成物が無リン系の食器洗浄機用洗浄剤の場合、粒子（Ａ）の担体としてリン酸塩を使用することができない。安定性を考慮すると、無リン系の食器洗浄機用洗浄剤の場合の粒子（Ａ）中の（ａ）成分の濃度は０．４〜２質量％であることが好ましい。 When the composition is a phosphorus-free dishwasher detergent, phosphate cannot be used as the carrier for the particles (A). In consideration of stability, the concentration of the component (a) in the particles (A) in the case of a phosphorus-free dishwasher detergent is preferably 0.4 to 2% by mass.
また、粒子（Ａ）は、１質量％水溶液の２０℃におけるｐＨが３〜１２、好ましくは４〜１０、より好ましくは５〜１０の固体状水溶性有機化合物又は水溶性無機塩を含有する粒子が好適である。固体状水溶性有機化合物及び／又は水溶性無機塩の含有量は、乾燥状態のもの或いは結晶水又は配位水を持たないものとして、粒子（Ａ）中に好ましくは６０〜９９．９質量％、より好ましくは７０〜９９質量％であり、最も好ましくは８５〜９８質量％である。なお無リン系の場合、好ましくは９０質量％以上である。 Further, the particle (A) is a particle containing a solid water-soluble organic compound or water-soluble inorganic salt having a pH of 3 to 12, preferably 4 to 10, more preferably 5 to 10 in a 1% by mass aqueous solution. Is preferred. The content of the solid water-soluble organic compound and / or water-soluble inorganic salt is preferably 60 to 99.9% by mass in the particles (A), assuming that it is in a dry state or does not have crystal water or coordination water. More preferably, it is 70-99 mass%, Most preferably, it is 85-98 mass%. In the case of a phosphorus-free system, it is preferably 90% by mass or more.
固体状水溶性有機化合物としては分子量４０〜４００、好ましくは９０〜３６０、より好ましくは１００〜３００の水溶性有機酸、特に分子中に２つ以上、好ましくは２〜６個のカルボン酸基を有する多価カルボン酸又はそれらの塩が好ましい。具体的にはギ酸、酢酸、グルコン酸、リンゴ酸、酒石酸、乳酸、クエン酸、コハク酸、マレイン酸、フマル酸から選ばれるカルボン酸、エチレンジアミン４酢酸、ジエチレントリアミン５酢酸、メチルグリシン２酢酸、グルタミン酸２酢酸、セリン２酢酸、アスパラギン酸２酢酸から選ばれるアミノカルボン酸、及びこれらの塩が好適であり、特にクエン酸、メチルグリシン２酢酸、エチレンジアミン４酢酸、ジエチレントリアミン５酢酸が好ましい。塩としてはナトリウム塩、カリウム塩が好ましい。 As the solid water-soluble organic compound, a water-soluble organic acid having a molecular weight of 40 to 400, preferably 90 to 360, more preferably 100 to 300, particularly 2 or more, preferably 2 to 6 carboxylic acid groups in the molecule. Preferred are polyvalent carboxylic acids or salts thereof. Specifically, formic acid, acetic acid, gluconic acid, malic acid, tartaric acid, lactic acid, citric acid, succinic acid, maleic acid, fumaric acid, carboxylic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, methylglycine diacetic acid, glutamic acid 2 An aminocarboxylic acid selected from acetic acid, serine diacetic acid, aspartic acid diacetic acid, and salts thereof are preferred, and citric acid, methylglycine diacetic acid, ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid are particularly preferred. The salt is preferably a sodium salt or a potassium salt.
水溶性無機塩としては硫酸塩、塩酸塩、リン酸塩が好ましく、特に結晶水を持ちうる塩が好ましい。具体的には硫酸ナトリウム、硫酸カリウム、トリポリリン酸ナトリウムが好適である。 As the water-soluble inorganic salt, sulfates, hydrochlorides, and phosphates are preferable, and salts that can have crystal water are particularly preferable. Specifically, sodium sulfate, potassium sulfate, and sodium tripolyphosphate are preferable.
本発明の粒子（Ａ）には、固体状水溶性有機化合物及び水溶性無機塩を併用してもよく、無リン系の場合は固体状水溶性有機化合物／水溶性無機塩の質量比は、好ましくは９０／１０〜１０／９０、より好ましくは７０／３０〜１０／９０、特に好ましくは５０／５０〜１０／９０が好適である。また、水溶性無機塩がリン酸塩の場合は、固体状水溶性有機化合物／水溶性無機塩の質量比は、好ましくは０／１００〜２０／８０、特に好ましくは０／１００が好適である。 The particles (A) of the present invention may be used in combination with a solid water-soluble organic compound and a water-soluble inorganic salt. In the case of a phosphorus-free system, the mass ratio of the solid water-soluble organic compound / water-soluble inorganic salt is: 90/10 to 10/90 is preferable, 70/30 to 10/90 is more preferable, and 50/50 to 10/90 is particularly preferable. When the water-soluble inorganic salt is a phosphate, the mass ratio of solid water-soluble organic compound / water-soluble inorganic salt is preferably 0/100 to 20/80, particularly preferably 0/100. .
本発明の食器洗浄機用洗浄剤組成物が無リン系の場合、粒子（Ａ）の１質量％水溶液の２５℃におけるｐＨが５〜１０、更に６〜９であることが好ましい。無リン系の組成物では、固体状水溶性有機化合物と水溶性無機塩とを併用することが好ましく、粒子（Ａ）が上記ｐＨを示すようにこれらを用いることが好ましい。すなわち粒子（Ａ）が酸性物質を含むものであってもよいが、最終的な粒子（Ａ）の設計において、他にアルカリ性粒子を併用することでこれらｐＨ範囲に設定することが好ましい。例えば中和度の異なる弱酸強塩基の有機酸又は塩が上げられる。もちろん或いは有機酸塩と中性塩との組み合わせであってもよい。但し前記したように、固体状水溶性有機化合物と水溶性無機塩のそれぞれは１質量％の濃度の水溶液のｐＨが２５℃で３〜１２の範囲に入るものが用いられる。 When the cleaning composition for a dishwasher of the present invention is phosphorus-free, the pH at 25 ° C. of a 1% by mass aqueous solution of particles (A) is preferably 5 to 10, and more preferably 6 to 9. In a phosphorus-free composition, it is preferable to use a solid water-soluble organic compound and a water-soluble inorganic salt in combination, and it is preferable to use them so that the particles (A) exhibit the above pH. That is, the particles (A) may contain an acidic substance, but in the final design of the particles (A), it is preferable to set these pH ranges by using other alkaline particles together. For example, organic acids or salts of weak acids and strong bases having different degrees of neutralization can be raised. Of course, it may be a combination of an organic acid salt and a neutral salt. However, as described above, each of the solid water-soluble organic compound and the water-soluble inorganic salt is used when the pH of the aqueous solution having a concentration of 1% by mass falls within the range of 3 to 12 at 25 ° C.
本発明において、上記（ａ）成分と固体状水溶性有機化合物、水溶性無機塩又はそれらの混合物を混合して粒子（Ａ）を得るが、洗浄性能及びウォータースポット形成抑制効果の点から（ａ）成分を５〜８０質量％、好ましくは８〜５０質量％、特に好ましくは２０〜５０質量％含有する水溶液と、固体状水溶性有機化合物及び／又は水溶性無機塩とを混合する方法で粒子（Ａ）を製造する方法が好ましい。（ａ）成分を水溶液として用いる場合、（ａ）成分を５〜８０質量％含有する水溶液の２５℃におけるｐHを８以下、特には２〜７に調整して用いることが、配合適性、洗浄性能及びウォータースポット形成抑制効果及び安定性の点で好ましい。（ａ）成分を含有する水溶液の水の量が本発明の効果に影響を及ぼし、水溶液中の（ａ）成分濃度が上記範囲以下では、貯蔵安定性が低下し、貯蔵後の洗浄効果が低下する傾向にあり、また、（ａ）成分の濃度が上記範囲を超えると洗浄効果が低下する傾向にある。 In the present invention, the component (a) is mixed with a solid water-soluble organic compound, a water-soluble inorganic salt or a mixture thereof to obtain particles (A). From the viewpoint of cleaning performance and water spot formation inhibiting effect (a ) Particles by a method in which an aqueous solution containing 5 to 80% by mass, preferably 8 to 50% by mass, particularly preferably 20 to 50% by mass of a component, and a solid water-soluble organic compound and / or a water-soluble inorganic salt are mixed. The method for producing (A) is preferred. When the component (a) is used as an aqueous solution, the aqueous solution containing 5 to 80% by mass of the component (a) is adjusted to a pH of 25 or less, particularly 2 to 7 at 25 ° C. In addition, it is preferable from the viewpoint of water spot formation suppression effect and stability. The amount of water in the aqueous solution containing the component (a) affects the effect of the present invention. When the concentration of the component (a) in the aqueous solution is not more than the above range, the storage stability decreases and the cleaning effect after storage decreases. In addition, when the concentration of the component (a) exceeds the above range, the cleaning effect tends to decrease.
本発明では上記（ａ）成分の水溶液（Ｘ）と、固体状水溶性有機化合物、水溶性無機塩又はそれらの混合物（Ｙ）との混合比率は、（Ｘ）／（Ｙ）質量比で好ましくは０．２／９９．８〜４０／６０、より好ましくは０．５／９９．５〜２０／８０、特に好ましくは１／９９〜１５／８５である。 In the present invention, the mixing ratio between the aqueous solution (X) of the component (a) and the solid water-soluble organic compound, water-soluble inorganic salt or mixture (Y) is preferably (X) / (Y) mass ratio. Is 0.2 / 99.8 to 40/60, more preferably 0.5 / 99.5 to 20/80, and particularly preferably 1/99 to 15/85.
通常、活性物質の製剤化にはバインダー物質を用いることが行われるが、本発明では上記（ａ）成分水溶液中の少量の水がバインダーとして作用する。その他バインダー物質としては分子量２０００〜２００００のポリエチレングリコール、炭素数１０〜２０の脂肪酸、炭素数１０〜２０の脂肪アルコールを挙げることができる。このようなバインダー物質は粒子（Ａ）中に１０質量％以下、好ましくは５質量％以下、特に３質量％以下が好適である。しかしながら、最も好ましくは（ａ）成分を溶解させる際の水をバインダーとして用いることが好ましい。 Usually, a binder substance is used for formulation of an active substance, but in the present invention, a small amount of water in the aqueous solution (a) acts as a binder. Other binder materials include polyethylene glycol having a molecular weight of 2000 to 20000, fatty acids having 10 to 20 carbon atoms, and fatty alcohols having 10 to 20 carbon atoms. Such a binder substance is suitably 10% by mass or less, preferably 5% by mass or less, particularly 3% by mass or less in the particles (A). However, it is most preferable to use water at the time of dissolving the component (a) as a binder.
本発明では上記（ａ）成分の水溶液と固体状水溶性有機化合物及び／又は水溶性無機塩とを混合した後、粒子物性を改善させる目的から該混合物と水不溶性無機粉体を混合することが好ましい。水不溶性無機粉体としては一次粒子径５ｎｍ〜２００μｍ、好ましくは２０ｎｍ〜１００μｍ、特に好ましくは２０ｎｍ〜５０μｍのものが好ましく、具体的には、結晶性ケイ酸塩、アルミノシリケート、シリカ、アルミナが好ましい。本発明では、上記混合物（Ｙ）に対する水不溶性無機粉体（Ｚ）の質量比（Ｚ）／（Ｙ）は、好ましくは９９．９／０．１〜９５／５、より好ましくは９９．５／０．５〜９７．５／２．５、特に好ましくは９９．３／０．７〜９８／２である。 In the present invention, after mixing the aqueous solution of the component (a) with a solid water-soluble organic compound and / or a water-soluble inorganic salt, the mixture and the water-insoluble inorganic powder may be mixed for the purpose of improving particle physical properties. preferable. The water-insoluble inorganic powder preferably has a primary particle size of 5 nm to 200 μm, preferably 20 nm to 100 μm, particularly preferably 20 nm to 50 μm. Specifically, crystalline silicate, aluminosilicate, silica and alumina are preferable. . In the present invention, the mass ratio (Z) / (Y) of the water-insoluble inorganic powder (Z) to the mixture (Y) is preferably 99.9 / 0.1 to 95/5, more preferably 99.5. /0.5 to 97.5 / 2.5, particularly preferably 99.3 / 0.7 to 98/2.
水不溶性無機粉体としてシリカを用いる場合には、アエロジル（日本アエロジル（株）製）、トクシール、ファインシール、レオロシール（（株）トクヤマ製）、サイロピュア（富士シリシア（株）製）等を用いること好ましい。 When silica is used as the water-insoluble inorganic powder, Aerosil (produced by Nippon Aerosil Co., Ltd.), Toxeal, Fine Seal, Leoroseal (produced by Tokuyama Co., Ltd.), Silo Pure (produced by Fuji Silysia Co., Ltd.), etc. are used. It is preferable.
本発明では上記混合工程を例えば、ヘンシェルミキサー（三井鉱山株式会社製）、ハイスピードミキサー（深江工業株式会社製）、ナウターミキサー（ホソカワミクロン株式会社製）等の周知の混合機を用いることができ、特に攪拌時にせん断力があまりかからないナウターミキサーを用いることが好ましい。 In the present invention, a known mixer such as Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), high speed mixer (manufactured by Fukae Kogyo Co., Ltd.), Nauter mixer (manufactured by Hosokawa Micron Co., Ltd.), or the like can be used for the mixing step. In particular, it is preferable to use a Nauter mixer that does not require much shearing force during stirring.
本発明の粒子（Ａ）は、（ａ）成分を０．０５〜１０質量％、好ましくは０．３〜１０質量％、より好ましくは０．４〜８質量％、固体状水溶性有機化合物及び／又は水溶性無機塩を、乾燥状態のもの或いは結晶水又は配位水を持たないものとして６０〜９９．９質量％、より好ましくは７０〜９９質量％であり、最も好ましくは８５〜９８質量％、水不溶性無機粉体を０．１〜３質量％、好ましくは０．５〜２．５質量％、特に好ましくは０．７〜２質量％を含有する粒子であり、また、水分の含有量は０．０５〜１５質量％、好ましくは０．３〜１５質量％、特に好ましくは０．３〜１０質量％が好適である。 In the particles (A) of the present invention, the component (a) is 0.05 to 10% by mass, preferably 0.3 to 10% by mass, more preferably 0.4 to 8% by mass, a solid water-soluble organic compound and The water-soluble inorganic salt is 60 to 99.9% by mass, more preferably 70 to 99% by mass, most preferably 85 to 98% by mass in the dry state or without crystal water or coordination water. %, Particles containing 0.1 to 3% by weight of water-insoluble inorganic powder, preferably 0.5 to 2.5% by weight, particularly preferably 0.7 to 2% by weight, and containing water The amount is 0.05 to 15% by mass, preferably 0.3 to 15% by mass, particularly preferably 0.3 to 10% by mass.
粒子（Ａ）の平均粒径は、好ましくは５０〜１０００μｍ、より好ましくは１００〜８００μｍ、特に好ましくは１００〜６００μｍである。 The average particle diameter of the particles (A) is preferably 50 to 1000 μm, more preferably 100 to 800 μm, and particularly preferably 100 to 600 μm.
粒子（Ａ）は、好ましくは１０〜８００μｍ、より好ましくは５０〜８００μｍ、特に好ましくは１００〜５００μｍの固体状水溶性有機化合物、水溶性無機塩又はそれらの混合物を含有する粒子から得られることが好ましい。 The particles (A) are preferably obtained from particles containing 10 to 800 μm, more preferably 50 to 800 μm, particularly preferably 100 to 500 μm of a solid water-soluble organic compound, a water-soluble inorganic salt or a mixture thereof. preferable.
粒子（Ａ）はこれら固体状水溶性有機化合物や水溶性無機塩の粒子表面に（ａ）成分が付着した粒子であってもよく、更にその表面に上記の水不溶性無機粉体が塗布された状態（ないし被覆された状態）になっているものが流動性に富むため理想的である。なお固体状水溶性有機化合物や水溶性無機塩の種類あるいはバインダーの種類やその濃度によっては、（ａ）成分を含む水溶液の添加後、あるいは上記バインダー物質を添加した場合、凝集して（ａ）成分を包含する凝集した粒子になる場合もある。更にその凝集粒子表面が水不溶性無機粉体により被覆された状態になっていてもよい。 The particles (A) may be particles in which the component (a) is attached to the surface of the solid water-soluble organic compound or water-soluble inorganic salt, and the water-insoluble inorganic powder is coated on the surface. What is in a state (or in a coated state) is ideal because of its high fluidity. Depending on the type of the solid water-soluble organic compound or water-soluble inorganic salt or the type and concentration of the binder, it may aggregate after the addition of the aqueous solution containing the component (a) or when the binder material is added (a) In some cases, the agglomerated particles contain the components. Further, the surface of the aggregated particles may be covered with a water-insoluble inorganic powder.
本発明の洗浄剤組成物は、（ａ）成分を組成物中に０．０５〜１．５質量％、好ましくは０．２〜１．５質量％、より好ましくは０．３〜１．４質量％含有する。粒子（Ａ）は、（ａ）成分の含有量がこの範囲となるように用いられる。組成物中の全（ａ）成分のうち、８０質量％以上、更に９０質量％以上、特には実質的には１００質量％が、粒子（Ａ）中に存在することが好ましい。粒子（Ａ）を製造する際には、（ａ）成分は水溶液で添加することが好ましい。その場合、粒子（Ａ）と他の粒子との混合後に（ａ）成分が他の粒子に少量移行する可能性もあるが、本発明の粒子（Ａ）が本発明の範囲で存在すればよい。 In the cleaning composition of the present invention, the component (a) in the composition is 0.05 to 1.5% by mass, preferably 0.2 to 1.5% by mass, more preferably 0.3 to 1.4%. Contains by mass%. The particles (A) are used so that the content of the component (a) falls within this range. Of all the components (a) in the composition, 80% by mass or more, more preferably 90% by mass or more, and particularly substantially 100% by mass is preferably present in the particles (A). When producing the particles (A), the component (a) is preferably added as an aqueous solution. In that case, although there is a possibility that the component (a) migrates to other particles after mixing of the particles (A) with other particles, the particles (A) of the present invention should be present within the scope of the present invention. .
＜（ｂ）成分＞
本発明の食器洗浄機用洗浄剤組成物は、カルボン酸基を有するモノマー構成単位（ｂ−１）を含むが陽イオン性基を有するモノマー構成単位を含まない高分子化合物であって、１質量％水溶液の２５℃でのｐＨが３〜８、好ましくは異臭抑制の観点から７以下、より好ましくは６以下であり、洗浄力の点から好ましくは５以上である高分子化合物（ｂ）〔以下、（ｂ）成分という〕を用いる。
<(B) component>
The cleaning composition for a dishwasher according to the present invention is a polymer compound containing a monomer constituent unit (b-1) having a carboxylic acid group but not containing a monomer constituent unit having a cationic group. % Of aqueous solution having a pH of 3 to 8, preferably 7 or less, more preferably 6 or less from the viewpoint of suppressing bad smell, and preferably 5 or more from the viewpoint of detergency, And (b) component].
本発明の（ｂ）成分は、中和度を調整することで前記ｐＨを調整することができる、（ｂ）成分は、アルカリ金属水酸化物、好ましくは水酸化ナトリウム、水酸化カリウムによる部分中和物が好ましく、特にこれらにより分子中のカルボン酸部分が１０〜７０ｍｏｌ％、更に１０〜６０ｍｏｌ％、特に２０〜５０ｍｏｌ％の範囲で部分中和されていることが、洗浄剤組成物としての溶解性、保存安定性、貯蔵後の異臭抑制効果の点で好ましい。 In the component (b) of the present invention, the pH can be adjusted by adjusting the degree of neutralization. The component (b) is contained in an alkali metal hydroxide, preferably sodium hydroxide or potassium hydroxide. It is preferable that the solvate is dissolved as a detergent composition, in particular that the carboxylic acid moiety in the molecule is partially neutralized in the range of 10 to 70 mol%, more preferably 10 to 60 mol%, particularly 20 to 50 mol%. Is preferable in terms of the property, storage stability, and the effect of suppressing odor after storage.
カルボン酸基を有するモノマー構成単位（ｂ−１）［以下モノマー構成単位（ｂ−１）という］は、前記（ａ−２）から選ぶことができ、前記一般式（３）で示される化合物のうちＺが−ＣＯＯＭのものが挙げられる。特には、アクリル酸系モノマー及び／又はマレイン酸系モノマー由来のモノマー構成単位であるものが好ましい。 The monomer structural unit (b-1) having a carboxylic acid group (hereinafter referred to as monomer structural unit (b-1)) can be selected from the above (a-2), and is a compound represented by the general formula (3). Among them, those in which Z is —COOM can be mentioned. In particular, a monomer constituent unit derived from an acrylic acid monomer and / or a maleic acid monomer is preferable.
（ｂ）成分は、アクリル酸系モノマー及び／又はマレイン酸系モノマー以外の単量体を共重合させた共重合体であってもよい。但し、陽イオン性基を有する単量体は除かれる。モノマー構成単位（ｂ−１）以外のモノマー構成単位（ｂ−２）［以下、モノマー構成単位（ｂ−２）という］としては、非イオン性の不飽和基を有する単量体を重合して得られるモノマー構成単位を上げることができる。モノマー構成単位（ｂ−２）は前記モノマー構成単位（ａ−３）を得るために挙げられた単量体と同じ化合物由来のものであってもよい。なおモノマー構成単位（ｂ−１）は、（ｂ）成分の全モノマー構成単位中に、７０ｍｏｌ％以上、更に９０％以上、特には実質１００ｍｏｌ％を占めることが望ましい。 The component (b) may be a copolymer obtained by copolymerizing a monomer other than an acrylic acid monomer and / or a maleic acid monomer. However, monomers having a cationic group are excluded. As monomer structural unit (b-2) other than monomer structural unit (b-1) [hereinafter referred to as monomer structural unit (b-2)], a monomer having a nonionic unsaturated group is polymerized. The monomer structural unit obtained can be raised. The monomer structural unit (b-2) may be derived from the same compound as the monomer listed for obtaining the monomer structural unit (a-3). In addition, it is desirable that the monomer structural unit (b-1) occupies 70 mol% or more, further 90% or more, particularly 100 mol% in the total monomer structural unit of the component (b).
本発明では、（ｂ）成分として最も好ましい化合物は、アクリル酸及びマレイン酸の共重合体［以下、アクリル酸−マレイン酸共重合体という］である。 In the present invention, the most preferable compound as the component (b) is a copolymer of acrylic acid and maleic acid [hereinafter referred to as acrylic acid-maleic acid copolymer].
（ｂ）成分がアクリル酸−マレイン酸共重合体の場合、アクリル酸／マレイン酸のモル比が１０／９０〜９０／１０、好ましくは２０／８０〜８０／２０、より好ましくは５０／５０〜８０／２０の高分子化合物を用いる。 When the component (b) is an acrylic acid-maleic acid copolymer, the molar ratio of acrylic acid / maleic acid is 10/90 to 90/10, preferably 20/80 to 80/20, more preferably 50/50 to An 80/20 polymer compound is used.
本発明の（ｂ）成分の重量平均分子量は、１，０００〜５０，０００、より好ましくは１，０００〜５００，０００、さらに好ましくは１，０００〜１００，０００、特に好ましくは１０，０００〜１００，０００であり、この重量平均分子量はアセトニトリルと水の混合溶媒（リン酸緩衝液）を展開溶媒とし、ゲルパーミエーションクロマトグラフィーでポリエチレングリコールを標準物質として求めたものである。 The weight average molecular weight of (b) component of this invention is 1,000-50,000, More preferably, it is 1,000-500,000, More preferably, it is 1,000-100,000, Most preferably, it is 10,000- The weight average molecular weight was determined by gel permeation chromatography using polyethylene glycol as a standard substance using a mixed solvent of acetonitrile and water (phosphate buffer) as a developing solvent.
本発明では、（ａ）成分と（ｂ）成分の質量比は、（ａ）／（ｂ）＝０．０１〜３であり、好ましくは０．０２〜２、より好ましくは０．０３〜１．５であることが、異臭発生の抑制効果の点で好ましい。 In the present invention, the mass ratio of the component (a) and the component (b) is (a) / (b) = 0.3-1, preferably 0.02-2, more preferably 0.03-1. .5 is preferable in terms of the effect of suppressing the generation of off-flavors.
本発明では、貯蔵保存後の異臭発生の抑制のために、高分子化合物（ｂ）は、高分子化合物（ａ）と異なる粉末状ないし粒状のものとして配合されることが望ましい。その場合、（ａ）成分は後述する粒子（Ａ）として配合されることがより好ましい。 In the present invention, it is desirable that the polymer compound (b) is blended in a powder or granular form different from the polymer compound (a) in order to suppress the generation of a strange odor after storage and storage. In this case, the component (a) is more preferably blended as particles (A) described later.
（ｂ）成分は、（ｂ）成分を含有する粒子（Ｂ）として組成物に配合することが好ましく、（ｂ）成分として、粉末状ないし粒状のものを用いる場合、これをそのまま粒子（Ｂ）とすることができる。粉末状ないし粒状のものを用いる場合、平均粒径が５０〜１０００μｍ、更に１００〜８００μｍのものが好ましい。このような粒径を得るためには、例えば（ｂ）成分を含有するスラリーないし溶液を乾燥して固化し、粉砕して整粒や分級する方法、粉末化したものを造粒により目的の粒径に調整する方法、又は（ｂ）成分を含むスラリーないし溶液を噴霧乾燥する方法などを挙げることができる。粒子（Ｂ）中の（ｂ）成分濃度は、粒子（Ａ）と異なり、その殆どが（ｂ）成分で占めていることが好ましく、具体的には８０質量％以上、好ましくは９０質量％以上である。また粒子（Ｂ）に配合可能な他の成分としては、（ｂ）成分に規定のｐＨ範囲に影響を与えない化合物であることが望ましく、少量の水分の他に、界面活性剤、溶解補助剤、造粒補助剤、増量剤など、粒状化の点で公知の化合物を配合することができる。 The component (b) is preferably blended in the composition as particles (B) containing the component (b). When the powder (b) is used as the component (b), the particles (B) are used as they are. It can be. When using a powder form or a granular thing, an average particle diameter is 50-1000 micrometers, Furthermore, the thing of 100-800 micrometers is preferable. In order to obtain such a particle size, for example, a slurry or a solution containing the component (b) is dried and solidified, pulverized and sized and classified, and the powdered product is granulated to obtain the desired particles. Examples thereof include a method of adjusting the diameter or a method of spray drying a slurry or solution containing the component (b). Unlike the particle (A), the concentration of the component (b) in the particle (B) is preferably mostly occupied by the component (b), specifically 80% by mass or more, preferably 90% by mass or more. It is. As other components that can be blended in the particles (B), it is desirable that the component (b) does not affect the specified pH range. In addition to a small amount of water, surfactants and solubilizing agents In addition, known compounds such as granulation aids and extenders can be blended in terms of granulation.
＜（ｃ）成分＞
本発明の食器洗浄機用洗浄剤組成物は、アルカリ剤（ｃ）〔以下、（ｃ）成分という〕を含有する。
<(C) component>
The cleaning composition for a dishwasher of the present invention contains an alkaline agent (c) [hereinafter referred to as component (c)].
（ｃ）成分としては、粉末状ないし粒状のものが好ましく、特に炭酸アルカリ金属塩［以下（ｃ−１）成分という］、珪酸アルカリ金属塩［以下（ｃ−２）成分という］を用いることができる。（ｃ）成分は、（ｃ）成分を含有する粒子（Ｃ）として組成物に配合することが好ましく、（ｃ）成分として、粉末状ないし粒状のものを用いる場合、これをそのまま粒子（Ｃ）とすることができる。粒子（Ｃ）もその殆どが（ｃ）成分で占めていることが好ましく、粒子（Ｃ）中の（ｃ）成分の含有量は、８０質量％以上、更に９０質量％以上が好ましい。 The component (c) is preferably in the form of powder or granule, and in particular, an alkali metal carbonate (hereinafter referred to as (c-1) component) or an alkali metal silicate (hereinafter referred to as (c-2) component) is used. it can. The component (c) is preferably blended in the composition as particles (C) containing the component (c). When the powder (c) is used as the component (c), the particles (C) are used as they are. It can be. Most of the particles (C) are preferably occupied by the component (c), and the content of the component (c) in the particles (C) is preferably 80% by mass or more, and more preferably 90% by mass or more.
（ｃ−１）成分の炭酸アルカリ金属塩としては、炭酸ナトリウム（ライト灰、デンス灰）、炭酸カリウムを用いることができ、特に平均粒径５０〜６００μｍ、好ましくは１００〜５００μｍの粉末状ないし粒状のものとして配合することが望ましく、具体的にはデンス灰を用いることが好適である。 As the alkali metal carbonate of component (c-1), sodium carbonate (light ash, dense ash) and potassium carbonate can be used, and in particular, powdery or granular with an average particle size of 50 to 600 μm, preferably 100 to 500 μm. It is desirable to mix as a thing, specifically, it is suitable to use dense ash.
（ｃ−２）成分の珪酸アルカリ金属塩としては、１〜３号珪酸ナトリウム等の非晶質珪酸ナトリウム、特開平７−８９７１２号公報、特開昭６０−２２７８９５号公報及び Phys. Chem. Glasses. 7, p127-p138(1966)、Z.Kristallogr., 129, p396-p404(1969)に記載されている結晶性珪酸塩、並びに（株）トクヤマシルテックより商品名「プリフィード」（δ−Ｎａ2Ｓｉ2Ｏ5）として市販されている結晶性層状珪酸ナトリウムが好ましい。本発明では結晶性層状珪酸ナトリウムが最も好適である。 Examples of the alkali metal silicate of component (c-2) include amorphous sodium silicates such as Nos. 1-3 sodium silicate, JP-A-7-89712, JP-A-60-227895, and Phys. Chem. Glasses. 7, p127-p138 (1966), Z. Kristallogr., 129, p396-p404 (1969), and the product name “Prefeed” (δ−) from Tokuyama Siltech Co., Ltd. Crystalline layered sodium silicate marketed as Na 2 Si 2 O 5 ) is preferred. In the present invention, crystalline layered sodium silicate is most preferred.
（ｃ−２）成分は、平均粒径５０〜１０００μｍ、好ましくは１００〜８００μｍの粉末状ないし粒状のものが好ましく、粒状化したものが市販されており、それを用いることができる。 The component (c-2) is preferably a powder or granule having an average particle diameter of 50 to 1000 μm, preferably 100 to 800 μm, and is granulated and is commercially available.
（ｃ）成分の組成物中の含有量は、好ましくは２〜８０質量％、より好ましくは５〜７０質量％、特に好ましくは８〜５０質量％である。 The content of the component (c) in the composition is preferably 2 to 80% by mass, more preferably 5 to 70% by mass, and particularly preferably 8 to 50% by mass.
また本発明では（ｃ）成分として（ｃ−１）成分及び（ｃ−２）成分を併用することが好ましく、それぞれの組成物中の含有量は、（ｃ−１）成分は、好ましくは１〜７９質量％、より好ましくは３〜６０質量％、特に好ましくは５〜４０質量％であり、（ｃ−２）成分は、好ましくは１〜２０質量％、より好ましくは３〜１５質量％、特に好ましくは３〜１０質量％である。 Moreover, in this invention, it is preferable to use together the (c-1) component and the (c-2) component as the (c) component, and the content in each composition is preferably 1 (c-1). -79 mass%, More preferably, it is 3-60 mass%, Most preferably, it is 5-40 mass%, (c-2) component becomes like this. Preferably it is 1-20 mass%, More preferably, it is 3-15 mass%, Especially preferably, it is 3-10 mass%.
本発明の食器洗浄機用洗浄剤組成物は、粉末状ないし粒状の場合、（ａ）成分を含む粒子（Ａ）と、（ｂ）成分を含む粒子（Ｂ）と、（ｃ）成分を含む粒子（Ｃ）とを混合することで得られる。すなわち、本発明の食器洗浄機用洗浄剤組成物は、（ａ）成分を含有する粒子（Ａ）と、カルボン酸基を有するモノマー構成単位（ｂ−１）を含むが陽イオン性基を有するモノマー構成単位を含まない高分子化合物であって、１質量％水溶液の２５℃でのｐＨ３〜８である高分子化合物（ｂ）を含有する粒子（Ｂ）と、アルカリ剤（ｃ）を含有する粒子（Ｃ）とを混合する工程を有する、食器洗浄機用洗浄剤組成物である。本発明者らは、まず粉末状ないし粒状（ａ）成分の一部と（ｃ）成分のアルカリ剤が接触した状態で貯蔵された場合、洗浄剤組成物の香りが不良、すなわち異臭が発生することを見出した。その上で、異臭を抑制するために１質量％水溶液の２５℃でのｐＨが３〜８、具体的には部分中和された（ｂ）成分を該洗浄剤組成物に混合することにより、異臭の発生を抑制することができることを見出し、そして、その具体的な態様として、前記した粒子条件が好ましいことを見出したのである。 In the case of powder or granular form, the detergent composition for a dishwasher of the present invention comprises particles (A) containing component (a), particles (B) containing component (b), and component (c). It is obtained by mixing the particles (C). That is, the detergent composition for a dishwasher according to the present invention includes a particle (A) containing the component (a) and a monomer structural unit (b-1) having a carboxylic acid group, but has a cationic group. A polymer (B) containing no monomer constituent unit and containing a polymer (b) having a pH of 3 to 8 at 25 ° C. in a 1% by mass aqueous solution, and an alkali agent (c) A detergent composition for a dishwasher, comprising a step of mixing particles (C). First, when the present invention is stored in a state where a part of the powdery or granular component (a) and the alkali agent of the component (c) are in contact with each other, the scent of the cleaning composition is poor, that is, a strange odor is generated. I found out. Then, in order to suppress off-flavors, the pH at 3 ° C. of the 1% by weight aqueous solution is 3 to 8, specifically, by partially mixing the component (b) that is partially neutralized with the cleaning composition, It has been found that generation of off-flavors can be suppressed, and as a specific embodiment thereof, it has been found that the above-described particle conditions are preferable.
本発明の食器洗浄機用洗浄剤組成物には、粒子（Ａ）、粒子（Ｂ）、粒子（Ｃ）以外の粒子として、無機過酸化物を含有する粒子（Ｄ）、酵素を含有する粒子（Ｅ）から選ばれる一種以上の粒子を含有することが好ましく、特には粒子（Ｄ）と粒子（Ｅ）をすべて含有することが好ましい。またこれらの粒子以外に、任意の粒子（Ｆ）を含有してもよい。 In the detergent composition for a dishwasher of the present invention, particles other than particles (A), particles (B) and particles (C), particles containing inorganic peroxide (D), particles containing enzymes It is preferable to contain one or more particles selected from (E), and it is particularly preferable to contain all of the particles (D) and particles (E). Moreover, you may contain arbitrary particles (F) other than these particles.
粒子（Ｄ）は無機過酸化物を含有する粒子である。具体的には過炭酸塩、好ましくは過炭酸ナトリウム（以下、ＰＣと表記することもある）、過ホウ酸塩、好ましくは過ホウ酸ナトリウムである。また、過炭酸塩を採用する場合には、貯蔵安定性の点から被覆された過炭酸塩を用いることが好適である。 The particles (D) are particles containing an inorganic peroxide. Specifically, it is percarbonate, preferably sodium percarbonate (hereinafter sometimes referred to as PC), perborate, preferably sodium perborate. Moreover, when employ | adopting a percarbonate, it is suitable to use the coated percarbonate from the point of storage stability.
被覆された過炭酸塩としては、好ましくは水溶性ポリマーや無機塩等で被覆したものが好適である。具体的な例としては、公知の方法で被覆された過炭酸ナトリウムを用いることができ、例えば、特公昭47−32200号（ＰＣをパラフィンで被覆）、特公昭53−15717号（ＰＣを過ホウ酸ソーダで被覆）、米国特許第4131562 号（ＰＣを過ホウ酸ソーダとアルコールのエチレンオキサイド付加物で被覆）、米国特許第4120812号（ＰＣと過ホウ酸ソーダをポリエチレングリコールで被覆）、ドイツ特許第2712139号（ＰＣをシリケートで被覆）、ドイツ特許第2800916号（ＰＣをホウ酸で被覆）、欧州特許第30759号（ＰＣをワックスで被覆）、特開昭58−217599号（ＰＣをホウ酸塩で被覆）、特開昭59−196399号（ＰＣをホウ酸塩で被覆）、特開平４−31498号（ＰＣをホウ酸とケイ酸塩で別々に噴霧して被覆）等に記載された方法により得られたものが使用できる。 The coated percarbonate is preferably one coated with a water-soluble polymer or inorganic salt. As specific examples, sodium percarbonate coated by a known method can be used. For example, Japanese Patent Publication No. 47-32200 (PC coated with paraffin), Japanese Patent Publication No. 53-15717 (PC US Pat. No. 4,131,562 (PC coated with sodium perborate and alcohol ethylene oxide adduct), US Pat. No. 4120812 (PC coated with sodium perborate with polyethylene glycol), German patent No. 2712139 (PC coated with silicate), German Patent No. 2800916 (PC coated with boric acid), European Patent No. 30759 (PC coated with wax), JP-A-58-217599 (PC coated with boric acid) Coated with salt), JP-A-59-196399 (PC coated with borate), JP-A-4-31498 (PC coated with boric acid and silicate separately), etc. What was obtained by the method can be used.
これらのなかでも特に、（ｉ）ホウ酸ナトリウム、好ましくはメタホウ酸ナトリウム、オルトホウ酸ナトリウムを過炭酸塩に対して０．１〜３０質量％の割合で被覆した過炭酸塩、（ii）オルトホウ酸、メタホウ酸及び４ホウ酸から選ばれるホウ酸を過炭酸塩に対して０．３〜２０質量％、好ましくは０．５〜１０質量％、特に好ましくは１〜８質量％被覆した過炭酸塩、及び（iii）（ii）にさらにメタ珪酸ナトリウム、オルト珪酸ナトリウム、水ガラス１号、２号、３号のナトリウム塩、メタ珪酸カリウム、オルト珪酸カリウム、好ましくは水ガラス１号、２号、３号のナトリウム塩を過炭酸塩に対してＳｉＯ２に換算して０．１〜１０質量％、０．２〜７質量％、特に好ましくは０．３〜５質量％を被覆させた過炭酸塩が好ましい。特に貯蔵安定性の点から（ｉ）の過炭酸塩が好ましい。過炭酸塩としては過炭酸ナトリウムが好ましい。 Among these, (i) sodium borate, preferably sodium metaborate, percarbonate coated with sodium orthoborate in a proportion of 0.1 to 30% by mass with respect to the percarbonate, (ii) orthoboric acid Percarbonate coated with 0.3 to 20% by mass, preferably 0.5 to 10% by mass, particularly preferably 1 to 8% by mass of boric acid selected from metaboric acid and tetraboric acid with respect to the percarbonate And (iii) and (ii) further sodium metasilicate, sodium orthosilicate, water glass No. 1, No. 2, sodium salt, potassium metasilicate, ortho orthosilicate, preferably water glass No. 1, No. 2, No. 3 sodium carbonate converted to SiO2 with respect to the percarbonate, 0.1 to 10 mass%, 0.2 to 7 mass%, particularly preferably 0.3 to 5 mass% percarbonate Is preferred. In particular, the percarbonate of (i) is preferable from the viewpoint of storage stability. As the percarbonate, sodium percarbonate is preferred.
本発明の被覆された過炭酸塩は通常の方法で製造することができる。例えば湿潤状態もしくは乾燥状態の過炭酸塩に上記被覆剤を含有する溶液もしくは粉末を混合吸着させて乾燥させる方法が使用できる。 The coated percarbonate of the present invention can be prepared by conventional methods. For example, a method can be used in which a solution or powder containing the above-mentioned coating agent is mixed and adsorbed on a percarbonate in a wet state or a dry state and dried.
被覆された過炭酸塩は平均粒径が１００〜２０００μｍ、更に２５０〜１０００μｍであることが、漂白洗浄効果の点から好ましい。 The average particle size of the coated percarbonate is preferably 100 to 2000 μm, more preferably 250 to 1000 μm, from the viewpoint of the bleaching washing effect.
また、粒子（Ｄ）の組成物中の含有量は、好ましくは０．５〜９９質量％、より好ましくは５〜７０質量％、特に好ましくは５〜５０質量％である。 Moreover, content in the composition of particle | grains (D) becomes like this. Preferably it is 0.5-99 mass%, More preferably, it is 5-70 mass%, Most preferably, it is 5-50 mass%.
本発明では酵素を含有する粒子（Ｅ）を含有することが好適であり、セルラーゼ、プロテアーゼ、リパーゼ、アミラーゼ、エステラーゼ、ペクチナーゼ、ラクターゼおよびペルオキシダーゼを挙げることができ、特にプロテアーゼ、アミラーゼが好適である。 In the present invention, it is preferable to contain an enzyme-containing particle (E), and examples include cellulase, protease, lipase, amylase, esterase, pectinase, lactase and peroxidase, and protease and amylase are particularly preferable.
プロテアーゼとしては使用できる市販の酵素としては、アルカラーゼ、サビナーゼ、エバラーゼ、カンナーゼ、エスペラーゼ（ノボノルディスクバイオインダストリー（株））、オボザイム、プラフェクト、プロペラーゼ、プラフェクトＯＸ（ジェネンコア・インターナショナル社）を挙げることができる。 Examples of commercially available enzymes that can be used as proteases include alcalase, sabinase, evalase, cannase, esperase (Novo Nordisk Bioindustry Co., Ltd.), ovozyme, plafect, properase, and perfect OX (Genencore International). .
アミラーゼとしては使用できる市販の酵素としてはラピダーゼ（ギスト−ブロカーズ）、およびターマミル、デュラミル、ステインザイム（ノボノルディスクバイオインダストリー（株））、プラスターＳＴ、プラスターＯｘＡｍ（ジェネンコア・インターナショナル社）を挙げることができる。 Examples of commercially available enzymes that can be used as amylases include Lapidase (Gist-Brokers), Termamyl, Duramil, Steinzyme (Novo Nordisk Bioindustry Co., Ltd.), Plaster ST, Plaster OxAm (Genencor International). it can.
本発明ではプロテアーゼとアミラーゼを併用することが好ましく、酵素タンパク量としてアミラーゼ／プロテアーゼの質量比は、好ましくは１／９９〜９４／６、より好ましくは２／９８〜９０／１０、特に好ましくは２０／８０〜８０／２０である。 In the present invention, it is preferable to use protease and amylase in combination, and the mass ratio of amylase / protease as the amount of enzyme protein is preferably 1/99 to 94/6, more preferably 2/98 to 90/10, and particularly preferably 20. / 80 to 80/20.
本発明ではこれら酵素を造粒した粒子として含有することが好ましい。造粒物中の酵素タンパク量は粒子（Ｅ）中に１〜３０質量％、好ましくは２〜２５質量％である。また、粒子（Ｅ）の平均粒径は５０〜１０００μｍ、好ましくは１５０〜８００μｍである。 In the present invention, these enzymes are preferably contained as granulated particles. The amount of enzyme protein in the granulated product is 1 to 30% by mass, preferably 2 to 25% by mass in the particles (E). Moreover, the average particle diameter of particle | grains (E) is 50-1000 micrometers, Preferably it is 150-800 micrometers.
また、粒子（Ｅ）の組成物中の含有量は、好ましくは０．１〜１０質量％、より好ましくは０．２〜７質量％、特に好ましくは０．２〜５質量％である。 The content of the particles (E) in the composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 7% by mass, and particularly preferably 0.2 to 5% by mass.
本発明の食器洗浄機用洗浄剤組成物は、界面活性剤を含有することができる。界面活性剤を含有する場合は、ウォータースポット形成抑制効果の点からできるだけ低減化させることが好適であり、界面活性剤の含有量は組成物中、好ましくは１０質量％以下、より好ましくは５質量％以下が好適である。なお、界面活性剤において、オキシプロピレンとオキシエチレンの共重合体型の非イオン界面活性剤は、０．０１重量％未満であることが好ましい。 The cleaning composition for a dishwasher of the present invention can contain a surfactant. In the case of containing a surfactant, it is preferable to reduce it as much as possible from the viewpoint of the water spot formation suppressing effect, and the content of the surfactant is preferably 10% by mass or less, more preferably 5% by mass in the composition. % Or less is preferred. In the surfactant, the copolymer type nonionic surfactant of oxypropylene and oxyethylene is preferably less than 0.01% by weight.
本発明では、重量平均分子量が６００〜５０００、好ましくは２０００〜４０００のポリプロピレングリコールを該組成物に配合することが洗浄効果を付与し、且つ洗浄後の食器への残香性を抑制できるため好ましい。ポリプロピレングリコールは組成物中に好ましくは０．１〜１０質量％、更に０．５〜５質量％、特に１〜５質量％含有することが好適である。 In the present invention, it is preferable to add polypropylene glycol having a weight average molecular weight of 600 to 5,000, preferably 2,000 to 4,000, to the composition because it provides a cleaning effect and can suppress the remaining fragrance of the tableware after the cleaning. Polypropylene glycol is preferably contained in the composition in an amount of 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, particularly 1 to 5% by mass.
その他、色素、香料、消泡剤、テトラアセチルエチレンジアミン（ＴＡＥＤ）等の漂白活性化剤を任意の成分としてあげることができる。 In addition, bleaching activators such as pigments, fragrances, antifoaming agents, and tetraacetylethylenediamine (TAED) can be mentioned as optional components.
これら任意に配合可能な化合物は各粒子に安定性や該成分の性質を損なわない程度で添加してもよく、別途粒子（Ｆ）として配合してもよい。あるいは粒子（Ａ）〜（Ｅ）の１種または２種以上の混合物に添加したり、微粒子（ないし粉末）として添加してもよい。 These arbitrarily compoundable compounds may be added to each particle to such an extent that the stability and properties of the component are not impaired, or may be added separately as particles (F). Alternatively, it may be added to one kind or a mixture of two or more kinds of particles (A) to (E), or may be added as fine particles (or powder).
なお本発明の食器洗浄機用洗浄剤組成物の剤形として、粉末状ないし粒状の他に、前記規定を満たした粉末状ないし粒状を固めたタブレット状もまた挙げることができるが、好ましくは粉末状ないし粒状である。 As the dosage form of the dishwasher cleaning composition of the present invention, in addition to the powder form or granular form, a powder form satisfying the above regulations or a tablet form obtained by solidifying the granule can also be exemplified, but preferably a powder form It is shaped or granular.
好ましい本発明の食器洗浄機用洗浄剤組成物は、平均粒径が１００〜１０００μｍ、更に２００〜７００μｍであることが好ましい。また、組成物の嵩密度は０．８〜１．５ｇ／ｃｍ3、更に０．８〜１．２ｇ／ｃｍ3であることが好ましい。 The preferred detergent composition for a dishwasher of the present invention preferably has an average particle size of 100 to 1000 μm, more preferably 200 to 700 μm. Further, it is preferable that the bulk density of the composition is 0.8 to 1.5 g / cm 3, a further 0.8~1.2g / cm 3.
本発明に記載の平均粒径、一次粒子径及び嵩密度の測定は下記の通りである。
＜平均粒径の測定法＞
平均粒径はメジアン径であり、ＪＩＳ Ｚ ８８０１に規定の篩を用いて求める。例えば、目開きが２０００μｍ、１４００μｍ、１０００μｍ、７１０μｍ、５００μｍ、３５０μｍ、２５０μｍ、１８０μｍ、１２５μｍである９段階の篩と受け皿を用い、ロータップマシーン（ＨＥＩＫＯＳＥＩＳＡＫＵＳＨＯ製、タッピング：１５６回／分、ローリング：２９０回／分）に取り付け、１００ｇの試料を５分間振動させた後、篩目開きのサイズによる質量分率から各粒径の粒子の割合を測定し、平均粒径を求める。
The average particle diameter, primary particle diameter, and bulk density described in the present invention are measured as follows.
<Measuring method of average particle size>
The average particle diameter is a median diameter, and is determined using a sieve specified in JIS Z 8801. For example, using a 9-stage sieve and a saucer having openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, 180 μm, and 125 μm, a low-tapping machine (made by HEIKOSEISAKUSHO, tapping: 156 times / minute, rolling: 290 And a 100 g sample is vibrated for 5 minutes, and then the proportion of particles of each particle size is measured from the mass fraction according to the size of the sieve opening to determine the average particle size.
＜一次粒子径の測定法＞
走査型または透過型電子顕微鏡により粒子３，０００個の粒径を計測し、個数で平均した粒径を求める。
<Measurement method of primary particle size>
The particle size of 3,000 particles is measured with a scanning or transmission electron microscope, and the average particle size is obtained.
＜嵩密度の測定法＞
嵩密度は、ＪＩＳ Ｋ ３３６２により規定された方法で測定する。
<Method for measuring bulk density>
The bulk density is measured by a method defined by JIS K 3362.
本発明の最も好ましい態様を以下に示す。
まず（ａ）成分は、
陽イオン性基を有するモノマー構成単位（ａ−１）として、Ｎ，Ｎ−ジアリル−Ｎ，Ｎ−ジアルキル（炭素数１〜３）４級アンモニウム塩を重合して得られるモノマー構成単位、またはＮ，Ｎ−ジアリル−Ｎ−アルキル（炭素数１〜３）アミンを重合させたモノマー構成単位をメチルクロリド、ジメチル硫酸、ジエチル硫酸、エチレンオキシド、プロピレンオキシドなどの４級化剤を用いてアルキル化したモノマー構成単位、
陰イオン性基を有するモノマー構成単位（ａ−２）として、アクリル酸又はその塩（塩は共重合後の中和により生成したものを含む、以下同様）、メタクリル酸又はその塩、マレイン酸又はその塩、無水マレイン酸から選ばれる単量体に由来するモノマー構成単位、及び
その他の共重合可能な単量体（ａ−３）に由来するモノマー構成単位
を有し、
モル比〔陽イオン性基の総モル数〕／〔陰イオン性基の総モル数〕が５０／５０〜７０／３０であって、
陽イオン性基を有するモノマー構成単位（ａ−１）、及び陰イオン性基を有するモノマー構成単位（ａ−２）の合計が（ａ）成分を構成する全モノマー構成単位中、９０〜１００モル％を占め、
重量平均分子量５０００〜１００万の高分子化合物〔以下、（ａ’）成分という〕が好ましい。この好ましい（ａ’）成分は、該（ａ’）成分を２０〜５０質量％含有し、２５℃におけるｐＨが８以下、特には２〜７の水溶液として粒子（Ａ）の製造に用いることが好ましい。更に、具体的な粒子条件を以下に示す。
・粒子（Ａ）：（ａ）成分として組成物中に０．４〜１．０質量％となる量で含有される。
但し、粒子（Ａ）は、平均粒径１００〜５００μｍであって、（ａ）成分、更に（ａ’）成分を０．５〜８質量％、硫酸ナトリウム、トリポリ燐酸ナトリウム、硫酸カリウムから選ばれ、平均粒径が１００〜５００μｍの水溶性無機塩一種以上を７〜５０質量％、クエン酸、メチルグリシン２酢酸、エチレンジアミン４酢酸、ジエチレントリアミン５酢酸及びこれらの塩から選ばれる平均粒径１００〜５００μｍの固体状水溶性有機化合物を７〜５０質量％、結晶性ケイ酸塩、アルミノシリケート、シリカ、アルミナから選ばれる粒子（Ａ）を被覆している水不溶性無機粉体を０．５〜２質量％含有し、固体状水溶性有機化合物／水溶性無機塩の比率が質量比で５０／５０〜１０／９０で配合されてなる粒子である。
・粒子（Ｂ）：（ｂ）成分として、アクリル酸／マレイン酸のモル比が２０／８０〜８０／２０のアクリル酸／マレイン酸共重合体を水酸化ナトリウムで１０〜７０ｍｏｌ％部分中和した重量平均分子量が１，０００〜１００，０００の高分子化合物を９０質量％以上含有し、平均粒径が１００〜８００μｍの粉末状ないし粒状体として用いられる。
なお（ａ）成分と（ｂ）成分は質量比で（ａ）／（ｂ）＝０．０２〜２である。
・粒子（Ｃ）：（ｃ）成分濃度として組成物中の含有量が２〜８０質量％である。
最も好適には、（ｃ−１）成分及び（ｃ−２）成分を併用する。（ｃ−１）成分として、平均粒径１００〜５００μｍであるライト灰、デンス灰を、組成物中の含有量が５〜４０質量％となるように用いる。また（ｃ−２）成分として、平均粒径１００〜８００μｍである結晶性層状珪酸ナトリウムを、組成物中の含有量が３〜１０質量％となるように用いる。
・粒子（Ｄ）：組成物中の含有量が５〜５０質量％である。
但し、粒子（Ｄ）は平均粒径２５０〜１０００μｍであって、表面を珪酸塩やホウ酸塩などにより被覆することで安定化された過炭酸ナトリウムである。
・粒子（Ｅ）：組成物中の含有量が０．２〜５質量％である。
但し、粒子（Ｆ）はアミラーゼとプロテアーゼとを含有し、平均粒径１５０〜８００μｍである。
・粒子（Ｆ）：組成物中の含有量が０〜５質量％である。
但し、粒子（Ｆ）は任意の粒子であり、平均粒径５０〜１５００μｍであって、その他補助剤や付加価値を高めるための粒子であり、例えば消臭性能を示すような香料粒子を提案することができる。
更に、上記に示される性質の異なる粒子群を含有し、該粒子（Ａ）〜（Ｆ）は振動などによって粒子が層状に分かれること（一般的に分級）を抑制するために、なるべく他の粒子と粒径や嵩密度が揃ったものとして配合されている食器洗浄機用洗浄剤組成物である。
The most preferred embodiment of the present invention is shown below.
First, component (a)
As a monomer structural unit (a-1) having a cationic group, a monomer structural unit obtained by polymerizing an N, N-diallyl-N, N-dialkyl (carbon number 1 to 3) quaternary ammonium salt, or N , N-diallyl-N-alkyl (C1-C3) monomer-polymerized monomer structural unit using a quaternizing agent such as methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, propylene oxide, etc. Composition unit,
As a monomer structural unit (a-2) having an anionic group, acrylic acid or a salt thereof (salt includes those produced by neutralization after copolymerization, the same applies hereinafter), methacrylic acid or a salt thereof, maleic acid or A monomer constituent unit derived from a monomer selected from its salt, maleic anhydride, and a monomer constituent unit derived from another copolymerizable monomer (a-3),
The molar ratio [total number of moles of cationic groups] / [total number of moles of anionic groups] is 50/50 to 70/30,
90 to 100 mol of the monomer constituent unit (a-1) having a cationic group and the monomer constituent unit (a-2) having an anionic group in the total monomer constituent units constituting the component (a) %
A polymer compound having a weight average molecular weight of 5,000 to 1,000,000 [hereinafter referred to as component (a ′)] is preferred. This preferable component (a ′) contains 20 to 50% by mass of the component (a ′) and is used for the production of the particles (A) as an aqueous solution having a pH at 25 ° C. of 8 or less, particularly 2 to 7. preferable. Furthermore, specific particle conditions are shown below.
-Particle | grain (A): It contains in the quantity used as 0.4-1.0 mass% in a composition as (a) component.
However, the particles (A) have an average particle size of 100 to 500 μm, and are selected from 0.5 to 8% by mass of component (a) and further component (a ′), sodium sulfate, sodium tripolyphosphate and potassium sulfate. 7 to 50% by mass of one or more water-soluble inorganic salts having an average particle size of 100 to 500 μm, an average particle size of 100 to 500 μm selected from citric acid, methylglycine diacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and salts thereof 7 to 50% by mass of a solid water-soluble organic compound, and 0.5 to 2% by mass of a water-insoluble inorganic powder covering particles (A) selected from crystalline silicate, aluminosilicate, silica, and alumina. It is a particle | grain formed by mix | blending the ratio of solid water-soluble organic compound / water-soluble inorganic salt by mass ratio 50/50-10/90.
Particle (B): As component (b), an acrylic acid / maleic acid copolymer having an acrylic acid / maleic acid molar ratio of 20/80 to 80/20 was partially neutralized with sodium hydroxide at 10 to 70 mol%. It contains 90% by mass or more of a polymer compound having a weight average molecular weight of 1,000 to 100,000 and is used as a powder or granule having an average particle size of 100 to 800 μm.
In addition, (a) component and (b) component are (a) / (b) = 0.02-2 by mass ratio.
-Particle | grain (C): Content in a composition is 2-80 mass% as (c) component density | concentration.
Most preferably, the component (c-1) and the component (c-2) are used in combination. As the component (c-1), light ash or dense ash having an average particle size of 100 to 500 μm is used so that the content in the composition is 5 to 40% by mass. As the component (c-2), crystalline layered sodium silicate having an average particle diameter of 100 to 800 μm is used so that the content in the composition is 3 to 10% by mass.
-Particle | grain (D): Content in a composition is 5-50 mass%.
However, the particles (D) are sodium percarbonate having an average particle size of 250 to 1000 μm and stabilized by coating the surface with silicate or borate.
-Particle | grain (E): Content in a composition is 0.2-5 mass%.
However, the particles (F) contain amylase and protease and have an average particle size of 150 to 800 μm.
-Particle | grain (F): Content in a composition is 0-5 mass%.
However, the particles (F) are arbitrary particles, and have an average particle diameter of 50 to 1500 μm, and are particles for enhancing other additives and added values. For example, a perfume particle that exhibits deodorizing performance is proposed. be able to.
Furthermore, it contains particles having different properties as described above, and the particles (A) to (F) are preferably other particles as much as possible in order to prevent the particles from being separated into layers by vibration or the like (generally classification). And a dishwasher detergent composition that is formulated as having a uniform particle size and bulk density.
＜粒子（Ａ）の製法＞
３０Ｌナウターミキサー（自転：１１０ｒ／ｍｉｎ、公転：４ｒ／ｍｉｎ）に硫酸ナトリウム及びクエン酸３ナトリウムを添加し、１分間混合した。次に表１中の高分子化合物（ａ）としてＮ，Ｎ−ジアリル−Ｎ，Ｎ−ジメチルアンモニウムクロリド／マレイン酸／二酸化硫黄＝６６．７／２６．７／６．６のモル比で重合させた共重合体（重量平均分子量２万、２５％水溶液のｐＨ２．０）の水溶液を添加し、５分間混合した。次に表面改質剤（洗浄剤組成物中に添加する量の半量）を添加し、さらに１分間混合して粒子（Ａ）を得た。なお、各成分の添加量は、洗浄剤組成物３０ｋｇに相当する表１に示す配合比率より計算される量とした。
<Production method of particles (A)>
Sodium sulfate and trisodium citrate were added to a 30 L Nauter mixer (rotation: 110 r / min, revolution: 4 r / min) and mixed for 1 minute. Next, the polymer compound (a) in Table 1 was polymerized at a molar ratio of N, N-diallyl-N, N-dimethylammonium chloride / maleic acid / sulfur dioxide = 66.7 / 26.7 / 6.6. An aqueous solution of a copolymer (weight average molecular weight 20,000, pH of 25% aqueous solution) was added and mixed for 5 minutes. Next, a surface modifier (half the amount to be added to the cleaning composition) was added and further mixed for 1 minute to obtain particles (A). In addition, the addition amount of each component was made into the quantity calculated from the mixture ratio shown in Table 1 corresponding to 30 kg of cleaning composition.
＜洗浄剤組成物の製法＞
粒子（Ａ）を製造後、表１に示す配合比率にてさらに（ｂ）成分〔高分子化合物（ｂ）、粒子（Ｂ）〕、（ｃ−１）成分及び（ｃ−２）成分を粒子（Ｃ）として添加して１分間混合した。次にポリプロピレングリコールを添加し、３分間混合し、表面改質剤（洗浄剤組成物中に添加する量の半量）を添加し、さらに１分間混合した。次に粒子（Ｄ）及び粒子（Ｅ）を添加し、香料を添加してさらに３分間混合して洗浄剤組成物３０ｋｇを得た。得られた洗浄剤組成物を以下の洗浄条件で用いた場合の評価を以下のように行った。結果を表１に示す。
<Production method of cleaning composition>
After the production of the particles (A), the components (b) [polymer compound (b), particles (B)], (c-1) and (c-2) are further mixed in the mixing ratio shown in Table 1. Added as (C) and mixed for 1 minute. Next, polypropylene glycol was added and mixed for 3 minutes, a surface modifier (half the amount added to the cleaning composition) was added, and further mixed for 1 minute. Next, particles (D) and particles (E) were added, a fragrance was added, and the mixture was further mixed for 3 minutes to obtain 30 kg of a cleaning composition. Evaluation when the obtained cleaning composition was used under the following cleaning conditions was performed as follows. The results are shown in Table 1.
＜洗浄条件＞
使用洗浄機：松下電器産業株式会社製自動食器洗い機（機種ＮＰ−６０ＳＳ５）を用い、下記食器、表１の洗浄剤組成物を入れて標準コースで運転した。この洗浄機は、２．２Ｌの水を２０℃から６０℃まで徐々に昇温して洗浄し、その後すすぎを３回（昇温しない）行い、最終すすぎ（２０℃から７０℃まで徐々に昇温してすすぎ）後、乾燥する形式のものである。
汚染皿：１０枚（下記方法で調製されたもの）
未汚染ガラスコップ：９個
未汚染スライドガラス：３枚
使用水：３．５°ＤＨの水
洗浄剤組成物添加量：６ｇ
<Cleaning conditions>
Washing machine used: An automatic dishwasher (model NP-60SS5) manufactured by Matsushita Electric Industrial Co., Ltd. was used, and the following tableware and the detergent composition shown in Table 1 were put in and operated on a standard course. This washer was cleaned by gradually warming 2.2 L of water from 20 ° C. to 60 ° C., and then rinsing three times (no temperature rise), and finally rinsing (gradually rising from 20 ° C. to 70 ° C.). It is of a type that dries after warming and rinsing).
Contaminated dishes: 10 (prepared by the following method)
Uncontaminated glass cup: 9 Uncontaminated slide glass: 3 Water used: Water at 3.5 ° DH Detergent composition added amount: 6 g
＜汚染皿の調製＞
半熟目玉焼きをすりつぶし、口径１ｍｍのネットで濾過し、濾液を直径１１ｃｍの磁性皿に１枚当たり１．８ｇできるだけ均一に塗布し、１時間放置したものを洗浄に用いた。
<Preparation of contaminated dishes>
The half-boiled fried egg was ground and filtered through a 1 mm diameter net, and the filtrate was applied as uniformly as possible to a magnetic dish having a diameter of 11 cm, and 1.8 g per piece was allowed to stand for 1 hour.
＜ガラスコップの仕上がり評価方法＞
洗浄後のガラスコップに形成されたウォータースポットの数を蛍光灯にかざして数えた。結果を表１に示した。ガラスコップは、サイズがφ64×H100、210mLのものを用いた。
<Finished glass cup evaluation method>
The number of water spots formed on the washed glass cup was counted over a fluorescent lamp. The results are shown in Table 1. A glass cup having a size of φ64 × H100 and 210 mL was used.
ウォータースポット数は、被洗浄物の個体により多少の違いが生じる。本評価では９個のガラスコップに生じたウォータースポット数の平均値とした。大体、ウォータースポット数が４０個以内なら、気にならない仕上がり具合であり、２０個以内になると、優れた仕上がり具合であるといえる。 The number of water spots varies slightly depending on the object to be cleaned. In this evaluation, the average number of water spots generated in the nine glass cups was used. In general, if the number of water spots is 40 or less, it is an unfinished finish, and if it is 20 or less, it is an excellent finish.
＜接触角の測定＞
洗浄後、スライドガラス３枚分の蒸留水の接触角を測定し、平均値を算出した。
<Measurement of contact angle>
After washing, the contact angle of distilled water for 3 slide glasses was measured, and the average value was calculated.
＜貯蔵安定性＞
表１の洗浄剤組成物７００ｇを箱型容器（花王株式会社製キッチンクイックル容器）に入れ、４０℃、湿度８０％の恒温槽で３０日間保存し、保存後の組成物の様子を観察し、保存前と変化ない場合を◎、やや組成物粒子の凝集が見られるが、性能上問題ない場合を○、やや組成物粒子の凝集が見られ、性能の低下が見られる場合を△、かなり組成物粒子の凝集が見られる場合を×として評価した。
<Storage stability>
700 g of the detergent composition shown in Table 1 is put in a box-type container (a kitchen quill container manufactured by Kao Corporation), stored in a thermostatic bath at 40 ° C. and 80% humidity for 30 days, and the state of the composition after storage is observed. ◎ when the storage is unchanged and ◎, slightly aggregated composition particles are observed, ○ if there is no problem in performance, △ slightly aggregated composition particles, if there is a decrease in performance △, considerably The case where aggregation of the composition particles was observed was evaluated as x.
＜異臭の評価＞
表１の洗浄剤組成物７００ｇを箱型容器（花王株式会社製キッチンクイックル容器）に入れ、室温で１ヶ月保存した。保存後、洗剤の匂いを３０歳代の男性及び女性４人（各２人ずつ）のパネルに嗅いでもらい、当初の香料による臭いとは異なる異臭の有無につき官能評価を行った。異臭が感じられない場合を４点、ほとんど感知されない場合を３点、やや感知される場合を２点、はっきりと感知される場合を１点とし、パネル４名の平均点を算出した。
<Evaluation of off-flavors>
700 g of the detergent composition shown in Table 1 was placed in a box-type container (a kitchen quill container manufactured by Kao Corporation) and stored at room temperature for 1 month. After storage, the smell of the detergent was sniffed by a panel of men and four women in their 30s (two each), and sensory evaluation was performed for the presence or absence of a different odor different from the original odor. The average score of 4 panelists was calculated with 4 points when no strange smell was felt, 3 points when almost undetected, 2 points when slightly detected, and 1 point when clearly detected.
（注）
１）トクシールＮＲ（（株）トクヤマ製、吸油能：２１０〜２７０ｍＬ／１００ｇ）、一次粒子径約２０ｎｍ
２）アクリル酸／マレイン酸＝７０／３０のモル比で重合させた重量平均分子量７万の共重合体の塩。平均粒径４００μｍの顆粒として混合、水酸化ナトリウムによる中和度と１質量％水溶液の２５℃でのｐＨを、表１のように変更した。
３）メタホウ酸ナトリウムで表面を被覆した過炭酸ナトリウム。平均粒径７００μｍ
４）デュラミル６０Ｔ（ノボノルディスクバイオインダストリー株式会社）、平均粒径６００μｍ
５）サビナーゼ１８．０Ｔ（ノボノルディスクバイオインダストリー株式会社）、平均粒径６００μｍ
６）重量平均分子量約３０００、平均縮合度約５０（ジオールタイプ、和光純薬工業株式会社）
(note)
1) Tokuseal NR (manufactured by Tokuyama Corporation, oil absorption capacity: 210 to 270 mL / 100 g), primary particle diameter of about 20 nm
2) A salt of a copolymer having a weight average molecular weight of 70,000 polymerized at a molar ratio of acrylic acid / maleic acid = 70/30. As a granule having an average particle diameter of 400 μm, the degree of neutralization with sodium hydroxide and the pH of a 1 mass% aqueous solution at 25 ° C. were changed as shown in Table 1.
3) Sodium percarbonate whose surface is coated with sodium metaborate. Average particle size 700μm
4) Duramil 60T (Novo Nordisk Bioindustry Co., Ltd.), average particle size 600 μm
5) Sabinase 18.0T (Novo Nordisk Bioindustry Co., Ltd.), average particle size 600 μm
6) Weight average molecular weight of about 3000, average condensation degree of about 50 (diol type, Wako Pure Chemical Industries, Ltd.)
Claims (8)
〔式中、Ｒ11は水素原子又はメチル基であり、Ｒ12は水素原子、メチル基、又はヒドロキシ基であり、Ｒ13は炭素数１〜３のアルキル基又はヒドロキシアルキル基である。Ｘは−ＣＯＯＲ14−、−ＣＯＮ（Ｒ15）Ｒ16−であり、ここでＲ14、Ｒ16は炭素数２〜５のアルキレン基であり、Ｒ15は水素原子又はメチル基である。Ｒ21は炭素数１〜３のアルキル基又はヒドロキシアルキル基であり、ｎは０又は１の数である。Ｙ-は陰イオン基である。
〕
〔式中、Ｒ31は水素原子、メチル基、又は−ＣＯＯＭであり、Ｒ32は水素原子、メチル基、又はヒドロキシ基である。Ｚは−ＣＯＯＭ、−ｐｈ−ＳＯ3Ｍである。ここでＭは水素原子又はアルカリ金属であり、ｐｈはベンゼン環を示す。〕 Monomer constituent unit (a-1) having a cationic group represented by the following general formula (1) and / or general formula (2), and a monomer having an anionic group represented by the following general formula (3) 1 to 15 mol% of the structural unit (a-2) and the monomer structural unit (a-3) derived from sulfur dioxide, [total number of moles of cationic group] / [total number of moles of anionic group] The polymer compound (a) having a molar ratio of 30/70 to 90/10 includes a monomer structural unit (b-1) having a carboxylic acid group derived from acrylic acid and / or maleic acid, but has a cationic group A polymer compound containing no monomer structural unit, the polymer compound (b) having a pH of 3 to 8 at 25 ° C. in a 1% by mass aqueous solution, and an alkali agent (c), (a) / (B) mass ratio of 0.01 to 3 for dishwashers Composition.
[Wherein, R 11 is a hydrogen atom or a methyl group, R 12 is a hydrogen atom, a methyl group, or a hydroxy group, and R 13 is an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms. X is —COOR 14 —, —CON (R 15 ) R 16 —, wherein R 14 and R 16 are alkylene groups having 2 to 5 carbon atoms, and R 15 is a hydrogen atom or a methyl group. R 21 is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and n is a number of 0 or 1. Y - is an anionic group.
]
[Wherein, R 31 represents a hydrogen atom, a methyl group, or —COOM, and R 32 represents a hydrogen atom, a methyl group, or a hydroxy group. Z is -COOM, a -ph-SO 3 M. Wherein M is a hydrogen atom or an alkali metals, ph represents a benzene ring. ]
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