JPH04363301A - Modified starch, its producton and papermakers sizing agent using the samie agent - Google Patents
Modified starch, its producton and papermakers sizing agent using the samie agentInfo
- Publication number
- JPH04363301A JPH04363301A JP19136191A JP19136191A JPH04363301A JP H04363301 A JPH04363301 A JP H04363301A JP 19136191 A JP19136191 A JP 19136191A JP 19136191 A JP19136191 A JP 19136191A JP H04363301 A JPH04363301 A JP H04363301A
- Authority
- JP
- Japan
- Prior art keywords
- starch
- modified starch
- sizing agent
- chloride
- chloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 39
- 238000004513 sizing Methods 0.000 title claims abstract description 38
- 229920000881 Modified starch Polymers 0.000 title claims abstract description 26
- 235000019426 modified starch Nutrition 0.000 title claims abstract description 26
- 239000004368 Modified starch Substances 0.000 title claims abstract description 24
- 229920002472 Starch Polymers 0.000 claims abstract description 44
- 235000019698 starch Nutrition 0.000 claims abstract description 43
- 239000008107 starch Substances 0.000 claims abstract description 42
- 230000007935 neutral effect Effects 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- -1 alkenyl succinic anhydride Chemical compound 0.000 claims description 56
- 238000006467 substitution reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 238000006266 etherification reaction Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- WVJVHUWVQNLPCR-UHFFFAOYSA-N octadecanoyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(=O)CCCCCCCCCCCCCCCCC WVJVHUWVQNLPCR-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000003292 glue Substances 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 13
- YLBJPLYVSAAUDL-UHFFFAOYSA-M (3-chloro-2-hydroxypropyl)-triphenylazanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[N+](C=1C=CC=CC=1)(CC(CCl)O)C1=CC=CC=C1 YLBJPLYVSAAUDL-UHFFFAOYSA-M 0.000 abstract description 4
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 150000001450 anions Chemical class 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 125000002091 cationic group Chemical group 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 230000000977 initiatory effect Effects 0.000 description 7
- 240000003183 Manihot esculenta Species 0.000 description 6
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920002261 Corn starch Polymers 0.000 description 5
- AAZVLNHLLNLZEE-UHFFFAOYSA-M benzyl-(3-chloro-2-hydroxypropyl)-dimethylazanium;chloride Chemical compound [Cl-].ClCC(O)C[N+](C)(C)CC1=CC=CC=C1 AAZVLNHLLNLZEE-UHFFFAOYSA-M 0.000 description 5
- 239000008120 corn starch Substances 0.000 description 5
- 229940099112 cornstarch Drugs 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- 229920006319 cationized starch Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001592 potato starch Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- QVGQSEOEWHLURI-UHFFFAOYSA-M [Cl-].ClCC(C[N+](C1CCCCC1)(C)C)O Chemical compound [Cl-].ClCC(C[N+](C1CCCCC1)(C)C)O QVGQSEOEWHLURI-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000013055 pulp slurry Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RRWSMBHKMILYPA-UHFFFAOYSA-M (3-chloro-2-hydroxypropyl)-dimethyl-phenylazanium;chloride Chemical compound [Cl-].ClCC(O)C[N+](C)(C)C1=CC=CC=C1 RRWSMBHKMILYPA-UHFFFAOYSA-M 0.000 description 1
- HBBCOMVWDLGCAZ-UHFFFAOYSA-N 1-chloro-3-(diethylamino)propan-2-ol;hydrochloride Chemical compound Cl.CCN(CC)CC(O)CCl HBBCOMVWDLGCAZ-UHFFFAOYSA-N 0.000 description 1
- TURGQPDWYFJEDY-UHFFFAOYSA-N 1-hydroperoxypropane Chemical compound CCCOO TURGQPDWYFJEDY-UHFFFAOYSA-N 0.000 description 1
- YMDNODNLFSHHCV-UHFFFAOYSA-N 2-chloro-n,n-diethylethanamine Chemical compound CCN(CC)CCCl YMDNODNLFSHHCV-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-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
- LYKRIFJRHXXXDZ-UHFFFAOYSA-N 4-(4-hydroxybutoxy)butan-1-ol Chemical compound OCCCCOCCCCO LYKRIFJRHXXXDZ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- AZTTYKSNKVFVIW-UHFFFAOYSA-N N=C=O.C1NC1 Chemical class N=C=O.C1NC1 AZTTYKSNKVFVIW-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- MKRNVBXERAPZOP-UHFFFAOYSA-N Starch acetate Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)OC(C)=O)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 MKRNVBXERAPZOP-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- SDDBDXPFOIAAQO-UHFFFAOYSA-M [Cl-].Cl[N+](CC1=C(C=CC=C1)CC(C)O)(C)C Chemical compound [Cl-].Cl[N+](CC1=C(C=CC=C1)CC(C)O)(C)C SDDBDXPFOIAAQO-UHFFFAOYSA-M 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- VSECRMMAKHKQCN-UHFFFAOYSA-M dimethyl-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ylmethyl)-propylazanium chloride Chemical compound [Cl-].C(CC)[N+](CC1=C2C(=CC=C1)O2)(C)C VSECRMMAKHKQCN-UHFFFAOYSA-M 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JXBPSENIJJPTCI-UHFFFAOYSA-N ethyl cyanate Chemical compound CCOC#N JXBPSENIJJPTCI-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- FPBBPRPSGHHFSV-UHFFFAOYSA-N icos-1-en-1-one Chemical class CCCCCCCCCCCCCCCCCCC=C=O FPBBPRPSGHHFSV-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940116317 potato starch Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical group CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、新規変性澱粉とそれを
用いた中性抄紙用サイズ剤に関し、さらに詳しくは、乳
化安定性が良好である中性抄紙用サイズ剤に関する。TECHNICAL FIELD The present invention relates to a novel modified starch and a neutral paper sizing agent using the same, and more particularly to a neutral paper sizing agent having good emulsion stability.
【０００２】0002
【従来の技術】製紙工業界において中性抄紙サイズが確
立されつつある。中性サイズ剤の使用は紙の耐久性を増
すという点で好ましいばかりでなく、経済的にも有利で
ある。すなわち、ロジン系サイズ剤は石油樹脂サイズと
共に硫酸バンドを用いて酸性で抄紙されているが、酸性
抄紙系では填量として安価な炭酸カルシウムが分解、発
泡するため使用できないが、中性抄紙系では使用できる
。高充填により繊維原料を減少することができるとか、
機械のさびも防げる等の利点が挙げられている。中性抄
紙用サイズ剤には、セルロースと直接反応する反応性サ
イズ剤がある。これらの代表的なものとして、アルケニ
ル無水コハク酸、アルキルケテンダイマー、アルキルケ
テンダイマー誘導体、イソシアナートアジリジン誘導体
、コハク酸イミド誘導体、ロジン無水物、カルボニル誘
導体、脂肪酸無水物等が挙げられる。これらの反応性サ
イズ剤を水中に分散させて水性乳化剤を得る際の分散剤
として、カチオン化澱粉を用いることは、特公昭３９−
２３０５号公報及び特開昭５８−１９７３９７号公報に
より開示されている。BACKGROUND OF THE INVENTION Neutral paper sizes are becoming established in the paper industry. The use of neutral sizing agents is not only desirable in that it increases the durability of the paper, but is also economically advantageous. In other words, rosin-based sizing agents are used in acidic papermaking using sulfuric acid bands together with petroleum resin sizing agents, but in acidic papermaking systems, cheap calcium carbonate as filler decomposes and foams, so they cannot be used, but in neutral papermaking systems, rosin-based sizing agents cannot be used. Can be used. It is said that high filling can reduce the amount of fiber raw materials.
Benefits include preventing machinery from rusting. Neutral paper-making sizing agents include reactive sizing agents that react directly with cellulose. Representative examples of these include alkenyl succinic anhydride, alkyl ketene dimer, alkyl ketene dimer derivative, isocyanate aziridine derivative, succinimide derivative, rosin anhydride, carbonyl derivative, fatty acid anhydride, and the like. The use of cationized starch as a dispersing agent when dispersing these reactive sizing agents in water to obtain an aqueous emulsifier has been proposed in Japanese Patent Publication No. 39-1989.
This method is disclosed in Japanese Patent Application Laid-open No. 2305 and Japanese Patent Application Laid-open No. 197397/1983.
【０００３】0003
【発明が解決しようとする課題】従来、用いられてきた
カチオン化澱粉では、カチオン性を発現するアミノ基の
窒素原子に結合しているアルキル基の炭素数が１〜３と
短いために、反応性サイズ剤に対する充分な乳化安定性
が得られないという問題点がある。[Problems to be Solved by the Invention] In conventionally used cationized starch, the number of carbon atoms of the alkyl group bonded to the nitrogen atom of the amino group that exhibits cationic properties is short, 1 to 3, so that the reaction is difficult. However, there is a problem in that sufficient emulsion stability cannot be obtained with respect to the sizing agent.
【０００４】0004
【課題を解決するための手段】本発明者等は、上記の問
題点を解決するため、鋭意研究を重ねた結果、カチオン
化澱粉のカチオン性を発現するアミノ基の窒素原子にフ
ェニル基、ベンジル基及び／又はシクロヘキシル基を結
合させることにより、反応性サイズ剤に対する乳化安定
性が改善されることを見出し、本発明を完成するに至っ
た。すなわち、化４で表わされるカチオン変性澱粉は大
きな疎水基をもつために澱粉本来の親水性により強い乳
化性を示す。従って、反応性サイズ剤の乳化安定性が良
好な分散液が得られるのである。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have conducted intensive research and found that a phenyl group and a benzyl group are added to the nitrogen atom of the amino group that expresses the cationic properties of cationized starch. The present inventors have discovered that emulsion stability against reactive sizing agents can be improved by bonding groups and/or cyclohexyl groups, and have completed the present invention. That is, since the cationically modified starch represented by Chemical Formula 4 has a large hydrophobic group, it exhibits strong emulsifying properties due to the inherent hydrophilicity of starch. Therefore, a dispersion of the reactive sizing agent with good emulsion stability can be obtained.
【化４】[C4]
【０００５】本発明に使用され得るカチオン化剤は、化
５で表わされる。化５で表わされる化合物としては、例
えば、３−クロロ−２−ヒドロキシプロピルトリフェニ
ルアンモニウムクロライド、３−クロロ−２−ヒドロキ
シプロピルトリベンジルアンモニウムクロライド、３−
クロロ−２−ヒドロキシプロピルトリシクロヘキシルア
ンモニウムクロライド、３−クロロ−２−ヒドロキシプ
ロピルジフェニルメチルアンモニウムクロライド、３−
クロロ−２−ヒドロキシプロピルジベンジルメチルアン
モニウムクロライド、３−クロロ−２−ヒドロキシプロ
ピルジシクロヘキシルメチルアンモニウムクロライド、
３−クロロ−２−ヒドロキシプロピルジフェニルエチル
アンモニウムクロライド、３−クロロ−２−ヒドロキシ
プロピルジベンジルエチルアンモニウムクロライド、３
−クロロ−２−ヒドロキシプロピルジシクロヘキシルエ
チルアンモニウムクロライド、３−クロロ−２−ヒドロ
キシプロピルジメチルフェニルアンモニウムクロライド
、３−クロロ−２−ヒドロキシプロピルジエチルフェニ
ルアンモニウムクロライド、３−クロロ−２−ヒドロキ
シプロピルジメチルベンジルアンモニウムクロライド、
３−クロロ−２−ヒドロキシプロピルジエチルベンジル
アンモニウムクロライド、３−クロロ−２−ヒドロキシ
プロピルジメチルシクロヘキシルアンモニウムクロライ
ド、３−クロロ−２−ヒドロキシプロピルジエチルアン
モニウムクロライド、２，３−エポキシプロピルトリフ
ェニルアンモニウムクロライド、２，３−エポキシプロ
ピルトリベンジルアンモニウムクロライド、２，３−エ
ポキシプロピルトリシクロヘキシルアンモニウムクロラ
イド、２，３−エポキシプロピルジフェニルメチルアン
モニウムクロライド、２，３−エポキシプロピルジベン
ジルメチルアンモニウムクロライド、２，３−エポキシ
プロピルジシクロヘキスルメチルアンモニウムクロライ
ド、２，３−エポキシプロピルジフェニルエチルアンモ
ニウムクロライド、２，３−エポキシプロピルジベンジ
ルエチルアンモニウムクロライド、２，３−エポキシプ
ロピルジシクロヘキシルエチルアンモニウムクロライド
、２，３−エポキシプロピルジメチルフェニルアンモニ
ウムクロライド、２，３−エポキシプロピルジエチルフ
ェニルアンモニウムクロライド、２，３−エポキシプロ
ピルジメチルベンジルアンモニウムクロライド、２，３
−エポキシプロピルジエチルベンジルアンモニウムクロ
ライド、２，３−エポキシプロピルジメチルシクロヘキ
シルアンモニウムクロライド、２，３−エポキシプロピ
ルジエチルシクロヘキシルアンモニウムクロライド等の
４級アンモニウム塩、３−クロロ−２−ヒドロキシプロ
ピルジフェニルアミノクロライド、３−クロロ−２−ヒ
ドロキシプロピルジベンジルアミノクロライド、３−ク
ロロ−２−ヒドロキシプロピルジシクロヘキシルアミノ
クロライド、３−クロロ−２−ヒドロキシプロピルメチ
ルフェニルアミノクロライド、３−クロロ−２−ヒドロ
キシプロピルメチルベンジルアミノクロライド、３−ク
ロロ−２−ヒドロキシプロピルメチルシクロヘキシルア
ミノクロライド、３−クロロ−２−ヒドロキシプロピル
エチルフェニルアミノクロライド、３−クロロ−２−ヒ
ドロキシプロピルエチルベンジルアミノクロライド、３
−クロロ−２−ヒドロキシプロピルエチルシクロヘキシ
ルアミノクロライド、２，３−エポキシプロピルジフェ
ニルアミノクロライド、２，３−エポキシプロピルジベ
ンジルアミノクロライド、２，３−エポキシプロピルジ
シクロヘキシルアミノクロライド、２，３−エポキシプ
ロピルメチルフェニルアミノクロライド、２，３−エポ
キシプロピルメチルベンジルアミノクロライド、２，３
−エポキシプロピルメチルシクロヘキシルアミノクロラ
イド、２，３−エポキシプロピルエチルフェニルアミノ
クロライド、２，３−エポキシプロピルエチルベンジル
アミノクロライド、２，３−エポキシプロピルエチルシ
クロヘキシルアミノクロライド、等の３級アミン塩が挙
げられる。The cationizing agent that can be used in the present invention is represented by the following formula. Examples of the compound represented by Chemical Formula 5 include 3-chloro-2-hydroxypropyltriphenylammonium chloride, 3-chloro-2-hydroxypropyltribenzylammonium chloride, 3-chloro-2-hydroxypropyltriphenylammonium chloride,
Chloro-2-hydroxypropyltricyclohexylammonium chloride, 3-chloro-2-hydroxypropyldiphenylmethylammonium chloride, 3-
Chloro-2-hydroxypropyldibenzylmethylammonium chloride, 3-chloro-2-hydroxypropyldicyclohexylmethylammonium chloride,
3-chloro-2-hydroxypropyldiphenylethylammonium chloride, 3-chloro-2-hydroxypropyldibenzylethylammonium chloride, 3
-Chloro-2-hydroxypropyldicyclohexylethylammonium chloride, 3-chloro-2-hydroxypropyldimethylphenylammonium chloride, 3-chloro-2-hydroxypropyldiethylphenylammonium chloride, 3-chloro-2-hydroxypropyldimethylbenzylammonium chloride ,
3-chloro-2-hydroxypropyldiethylbenzylammonium chloride, 3-chloro-2-hydroxypropyldimethylcyclohexylammonium chloride, 3-chloro-2-hydroxypropyldiethylammonium chloride, 2,3-epoxypropyltriphenylammonium chloride, 2 , 3-Epoxypropyltribenzyl ammonium chloride, 2,3-epoxypropyltricyclohexylammonium chloride, 2,3-epoxypropyldiphenylmethylammonium chloride, 2,3-epoxypropyldibenzylmethylammonium chloride, 2,3-epoxypropyl Dicyclohexylmethylammonium chloride, 2,3-epoxypropyldiphenylethylammonium chloride, 2,3-epoxypropyldibenzylethylammonium chloride, 2,3-epoxypropyldicyclohexylethylammonium chloride, 2,3-epoxypropyldimethylphenylammonium Chloride, 2,3-epoxypropyldiethylphenylammonium chloride, 2,3-epoxypropyldimethylbenzylammonium chloride, 2,3
- Quaternary ammonium salts such as epoxypropyldiethylbenzylammonium chloride, 2,3-epoxypropyldimethylcyclohexylammonium chloride, 2,3-epoxypropyldiethylcyclohexylammonium chloride, 3-chloro-2-hydroxypropyldiphenylaminochloride, 3- Chloro-2-hydroxypropyldibenzylaminochloride, 3-chloro-2-hydroxypropyldicyclohexylaminochloride, 3-chloro-2-hydroxypropylmethylphenylaminochloride, 3-chloro-2-hydroxypropylmethylbenzylaminochloride, 3 -Chloro-2-hydroxypropylmethylcyclohexylaminochloride, 3-chloro-2-hydroxypropylethylphenylaminochloride, 3-chloro-2-hydroxypropylethylbenzylaminochloride, 3
-Chloro-2-hydroxypropylethylcyclohexylaminochloride, 2,3-epoxypropyldiphenylaminochloride, 2,3-epoxypropyldibenzylaminochloride, 2,3-epoxypropyldicyclohexylaminochloride, 2,3-epoxypropylmethyl Phenylaminochloride, 2,3-epoxypropylmethylbenzylaminochloride, 2,3
- Tertiary amine salts such as epoxypropylmethylcyclohexylaminochloride, 2,3-epoxypropylethylphenylaminochloride, 2,3-epoxypropylethylbenzylaminochloride, 2,3-epoxypropylethylcyclohexylaminochloride, etc. .
【０００６】本発明に使用され得る澱粉原料としては、
例えば、小麦澱粉、馬鈴薯澱粉、トウモロコシ澱粉、甘
藷澱粉、タピオカ澱粉、サゴ澱粉、米澱粉、モチトウモ
ロコシ澱粉、高アミロース含量トウモロコシ澱粉等の未
処理澱粉、またはこれらのエーテル化、エステル化、酸
化、酸処理化等を行ったものも挙げられる。[0006] Starch raw materials that can be used in the present invention include:
For example, unprocessed starches such as wheat starch, potato starch, corn starch, sweet potato starch, tapioca starch, sago starch, rice starch, waxy corn starch, high amylose content corn starch, or their etherification, esterification, oxidation, acid Also included are those that have been processed.
【０００７】本発明のカチオン変性澱粉のカチオン化法
は、通常のカチオン化剤の反応と同様に行なわれる。す
なわち、アルカリ触媒存在下の澱粉懸濁液に上記のカチ
オン化剤を滴下して反応を行う。反応温度は澱粉の糊化
開始温度以下、好ましくは３０℃以上、ｐＨ１０．５以
上、好ましくはｐＨ１１以上で行なわれる。必要ならば
、適量の硫酸ナトリウムの存在下で反応を行ってもよい
。反応後、公知の方法により、水洗、脱水、乾燥するこ
とにより、本発明の変性澱粉を得ることができる。また
、適当な混合または捏和装置を用いて、アルカリ触媒の
存在下、上記のカチオン化剤と澱粉を２〜５０％の水分
で混合、加熱することにより反応を行なうことができる
。The method of cationizing the cationically modified starch of the present invention is carried out in the same manner as the reaction of a conventional cationizing agent. That is, the reaction is carried out by dropping the above cationizing agent into a starch suspension in the presence of an alkali catalyst. The reaction temperature is below the gelatinization start temperature of starch, preferably above 30°C, and at a pH of above 10.5, preferably above pH 11. If necessary, the reaction may be carried out in the presence of an appropriate amount of sodium sulfate. After the reaction, the modified starch of the present invention can be obtained by washing with water, dehydrating, and drying by a known method. The reaction can also be carried out by mixing the above cationizing agent and starch at a moisture content of 2 to 50% and heating in the presence of an alkali catalyst using a suitable mixing or kneading device.
【０００８】このカチオン化の度合は置換度として表わ
し（無水グルコース残基１モル当り置換基Ｄ．Ｓ．モル
）Ｄ．Ｓ．＝０．０１〜０．２、好ましくは、０．０１
５〜０．０７が良い。糊化開始温度は２０〜７０℃が良
い。ここに糊化開始温度とは、澱粉の１５％（Ｗ／Ｖ）
水懸濁液４５０ｇをアミログラフ（ブラベンダー社製二
枚翼パドル式、メジャーリングヘッド：７００ｃｍｇ、
回転数：７５ｒｐｍ、温度上昇：１．５℃／分）に付し
た際に、アミログラフの基線から立ち上る処の温度をい
う。当該カチオン変性澱粉は高い糊液の安定性が求めら
れる。上記カチオン化によってもかなりの安定性がはか
れるのであるが、より安定な糊液が要求される時には、
カチオン化すると共にグルコースの水酸基をエーテル化
及び／又はエステル化することにより部分的にノニオン
性の官能基に置換する必要がある。また、この処理によ
り乳化安定性が増すと共に、紙力強度が増加することも
判明した。澱粉のエーテル化、エステル化は常法に従っ
てなされるが、例えば、エーテル化澱粉として、ジメチ
ル硫酸やヨウ化メチルと反応させた澱粉メチルエーテル
、塩化アリルと反応させた澱粉アリルエーテル、アクリ
ロニトリルと反応させた澱粉シアノエチルエーテル、ア
クリルアミドと反応させた澱粉カルバモイルエチルエー
テル、エチレンオキシドと反応させた澱粉ヒドロキシエ
チルエーテル、プロピレンオキシドと反応させた澱粉ヒ
ドロキシプロピルエーテル、ブチレンオキシドと反応さ
せた澱粉ヒドロキシブチルエーテル等が挙げられる。ま
た、エステル化澱粉として、ぎ酸、プロピオン酸、ラウ
リン酸、ミリスチン酸、パルミチン酸、ステアリン酸等
の脂肪酸と反応させた澱粉ぎ酸エステル、澱粉プロピオ
ン酸エステル、澱粉ラウリン酸エステル、澱粉ミリスチ
ン酸エステル、澱粉パルミチン酸エステル、澱粉ステア
リン酸エステル、無水酢酸や酢酸ビニルと反応させた澱
粉酢酸エステル等が挙げられる。これらの処理により、
カチオン化すると共に、エーテル化及び／又はエステル
化することにより部分的にノニオン化した澱粉は安定性
が向上し、糊化開始温度が低下する。その糊化開始温度
は２０〜７０℃、好ましくは３０〜５５℃であるThe degree of cationization is expressed as the degree of substitution (DS mole of substituent per mole of anhydroglucose residue). S. =0.01-0.2, preferably 0.01
5 to 0.07 is good. The gelatinization start temperature is preferably 20 to 70°C. Here, the gelatinization start temperature is 15% (W/V) of starch.
Add 450 g of water suspension to Amylograph (brabender two-blade paddle type, measuring head: 700 cm),
It refers to the temperature that rises from the base line of the amylograph when subjected to rotation speed: 75 rpm, temperature rise: 1.5° C./min). The cationically modified starch is required to have high stability of the size liquid. The cationization described above also provides considerable stability, but when a more stable size solution is required,
It is necessary to partially substitute nonionic functional groups by cationizing and etherifying and/or esterifying the hydroxyl group of glucose. It was also found that this treatment increased emulsion stability and paper strength. Etherification and esterification of starch are carried out according to conventional methods. For example, starch methyl ether reacted with dimethyl sulfate or methyl iodide, starch allyl ether reacted with allyl chloride, and starch reacted with acrylonitrile are used as etherified starch. starch cyanoethyl ether, starch carbamoylethyl ether reacted with acrylamide, starch hydroxyethyl ether reacted with ethylene oxide, starch hydroxypropyl ether reacted with propylene oxide, starch hydroxybutyl ether reacted with butylene oxide, etc. In addition, as esterified starch, starch formate ester, starch propionate ester, starch laurate ester, starch myristic ester reacted with fatty acids such as formic acid, propionic acid, lauric acid, myristic acid, palmitic acid, stearic acid, etc. , starch palmitate, starch stearate, starch acetate reacted with acetic anhydride or vinyl acetate, and the like. Through these processes,
Starch that is partially nonionized by cationization and etherification and/or esterification has improved stability and a lower gelatinization initiation temperature. Its gelatinization initiation temperature is 20-70°C, preferably 30-55°C.
【０００９】また、当該中性抄紙用サイズエマルジョン
を高濃度にするためには、カチオン性澱粉誘導体を低分
子化しなければならない。この低分子化の方法としては
、鉱酸によって酸加水分解する方法、酸化剤により酸化
すると共に分子の切断を行う方法、澱粉分解酵素により
酸素分解する方法、熱、超音波、放射線等によって物理
的に分子の切断を行う方法等が挙げられる。このときの
分子量は５０００〜５００００、好ましくは８０００〜
３００００で、粘度は２０重量％水懸濁液を８５℃以上
１０分間湯浴中で加熱糊化し、３０℃迄冷却後、Ｂ型回
転粘度計で測定したとき１０〜１０００センチポイズ、
好ましくは２０〜７００センチポイズである。[0009] Furthermore, in order to make the neutral size emulsion for papermaking highly concentrated, the cationic starch derivative must be reduced in molecular weight. Methods for reducing the molecular weight include acid hydrolysis using mineral acids, oxidation and molecular cleavage using oxidizing agents, oxygen decomposition using starch-degrading enzymes, and physical decomposition using heat, ultrasound, radiation, etc. Examples include methods of cutting molecules. The molecular weight at this time is 5,000 to 50,000, preferably 8,000 to 50,000.
30,000, and the viscosity is 10 to 1,000 centipoise when a 20% by weight aqueous suspension is gelatinized by heating in a water bath above 85°C for 10 minutes, cooled to 30°C, and measured with a B-type rotational viscometer.
Preferably it is 20 to 700 centipoise.
【００１０】本発明の製紙用サイズ剤は主成分としての
前記反応性サイズ剤の有効成分に対し、乳化安定剤とし
てのカチオン性澱粉誘導体を１０〜１５０％添加してエ
マルジョン化することにより得られる。本発明の反応性
サイズ剤として好適に用いられるものとして、アルケニ
ル無水コハク酸、アルキルケテンダイマー、アルキルケ
テンダイマー誘導体、無水ステアリン酸等を挙げること
ができる。本発明の中性抄紙用サイズエマルジョンの濃
度は５〜６０％、好ましくは１０〜４０％である。本発
明の中性抄紙用サイズ剤は、もし必要ならばリグニンス
ルホン酸ナトリウム、ポリオキシエチレンラウリン酸ア
ミド等の界面活性剤、ポリビニルアルコール、アクリル
アミド系ポリマー等の水溶性高分子を添加してもよい。
かくして得られるサイズ剤は、パルプスラリー中に添混
し内添用サイズ剤として、またシート表面に添加し表面
サイズ剤としても使用できる。The paper sizing agent of the present invention is obtained by adding 10 to 150% of a cationic starch derivative as an emulsion stabilizer to the active ingredient of the reactive sizing agent as the main component and emulsifying the active ingredient. . Examples of the reactive sizing agent suitably used in the present invention include alkenyl succinic anhydride, alkyl ketene dimer, alkyl ketene dimer derivatives, and stearic anhydride. The concentration of the neutral papermaking size emulsion of the present invention is 5 to 60%, preferably 10 to 40%. The neutral paper sizing agent of the present invention may contain surfactants such as sodium ligninsulfonate and polyoxyethylene lauric acid amide, and water-soluble polymers such as polyvinyl alcohol and acrylamide polymers, if necessary. . The sizing agent thus obtained can be used as an internal sizing agent by adding it to the pulp slurry, or as a surface sizing agent by adding it to the sheet surface.
【００１１】[0011]
【実施例】次に実施例を挙げて本発明を更に詳しく説明
するが、これらに限定されるものではない。
実施例１
水１３０部、水酸化ナトリウム２部、硫酸ナトリウム５
０部にタピオカ澱粉１００部を添加し、次に３−クロロ
−２−ヒドロキシプロピルジメチルベンジルアンモニウ
ムクロライド（４０％水溶液）１３部を加え、３％水酸
化ナトリウム水溶液でｐＨ１１に保ちながら４０℃で５
時間反応する。５時間後、プロピレンオキシド３部を加
え４０℃で６時間反応する。反応終了後、３０℃まで温
度を下げ、次亜塩素酸ナトリウム（有効塩素量１４％）
３０部を加え１時間反応する。反応終了後、希塩酸でｐ
Ｈ４．５に中和し脱水、水洗、乾燥してカチオン変性澱
粉を得た。得られた澱粉のカチオン性基の置換度（Ｄ．
Ｓ．）＝０．０３、糊化開始温度４９℃、粘度は２０％
、３０℃で４２センチポイズであった。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 130 parts of water, 2 parts of sodium hydroxide, 5 parts of sodium sulfate
Add 100 parts of tapioca starch to 0 parts, then add 13 parts of 3-chloro-2-hydroxypropyldimethylbenzyl ammonium chloride (40% aqueous solution), and add 100 parts of tapioca starch to 0 parts.
Time reacts. After 5 hours, 3 parts of propylene oxide was added and reacted at 40°C for 6 hours. After the reaction is complete, lower the temperature to 30°C and add sodium hypochlorite (available chlorine amount: 14%).
Add 30 parts and react for 1 hour. After the reaction is complete, purge with dilute hydrochloric acid.
The starch was neutralized to H4.5, dehydrated, washed with water, and dried to obtain a cationically modified starch. Degree of substitution of cationic groups in the obtained starch (D.
S. )=0.03, gelatinization start temperature 49℃, viscosity 20%
, 42 centipoise at 30°C.
【００１２】実施例２
実施例１においてタピオカ澱粉をコーンスターチに３−
クロロー２−ヒドロキシプロピルジメチルベンジルアン
モニウムクロライドを２，３−エポキシプロピルジフェ
ニルメチルアンモニウムクロライドにした以外は実施例
１と同様にしてカチオン変性澱粉を得た。得られた澱粉
のカチオン性基の置換度（Ｄ．Ｓ．）＝０．０３、糊化
開始温度５０℃、粘度は２０％、３０℃で４８センチポ
イズであった。
実施例３
実施例１においてタピオカ激粉を馬鈴薯澱粉に３−クロ
ロ−２−ヒドロキシプロピルジメチルベンジルアンモニ
ウムクロライドを３−クロロー２−ヒドロキシプロピル
ジメチルシクロヘキシルアンモニウムクロライドにした
以外は実施例１と同様にしてカチオン変性澱粉を得た。
得られた澱粉のカチオン性基の置換度（Ｄ．Ｓ．）＝０
．０２５、糊化開始温度４９℃、粘度は２０％、３０℃
で４６センチポイズであった。
実施例４
水１３０部、水酸化ナトリウム１．８部、硫酸ナトリウ
ム５０部の溶液にタピオカ澱粉１００部を加え、アクリ
ロニトリル８部添加し、４０℃で８時間反応する。次に
３−クロロ−２−ヒドロキシプロピルトリベンジルアン
モニウムクロライド１０部を加え、３％水酸化ナトリウ
ムでｐＨ１１．５に保ちながら４０℃で６時間反応する
。これに３５％過酸化水素水１８部を加え４時間反応す
る。反応終了後、希塩酸でｐＨ４．５に中和し脱水、水
洗、乾燥してカチオン変性澱粉を得た。得られた澱粉の
カチオン性基の置換度（Ｄ．Ｓ．）＝０．０２、糊化開
始温度５０℃、粘度は２０％、３０℃で１００センチポ
イズであった。
実施例５
コーンスターチ１００部に水８部、メタノール８．２部
、５０％水酸化ナトリウム２部の混合溶液を加え、分散
後エチレンオキシド１０部を加え、３８℃で１０時間反
応する。１０時間後、水１２０部の中に反応物を投入し
温度を４３℃まで上げ３−クロロ−２−ヒドロキシプロ
ピルトリフェニルアンモニウムクロライド８部を加え、
３％水酸化ナトリウム水溶液でｐＨ１１に保ちながら５
時間反応する。反応後、希塩酸でＰＨ５まで下げ２０％
塩酸１８部を加えて、４０℃で１５時間反応した後、３
％水酸化ナトリウム水溶液でｐＨ４．５に中和し、脱水
、水洗、乾燥してカチオン変性澱粉を得た。得られた澱
粉のカチオン性基の置換度（Ｄ．Ｓ．）＝０．０２、糊
化開始温度４９℃、粘度は２０％、３０℃で８０センチ
ポイズであった。
実施例６
水１３０部、水酸化ナトリウム１．５部、硫酸ナトリウ
ム５０部に酸化澱粉１００部を添加し、次に２，３−エ
ポキシプロピルジベンジルアミノクロライド１０部を加
え、３％水酸化ナトリウム水溶液でｐＨ１１．２に保ち
ながら４０℃で５時間反応する。反応液を３０℃まで下
げて、希塩酸でｐＨ８〜９に調整後、酢酸ビニル６部を
加え３０℃、ｐＨ８〜９で１０時間反応させる。反応終
了後、希塩酸でｐＨ４．５に中和し脱水、水洗、乾燥し
てカチオン変性澱粉を得た。得られた澱粉のカチオン性
基の置換度（Ｄ．Ｓ．）＝０．０４、糊化開始温度４６
℃、粘度は２０％、３０℃で６０センチポイズであった
。Example 2 In Example 1, tapioca starch was mixed with cornstarch.
A cationically modified starch was obtained in the same manner as in Example 1 except that 2,3-epoxypropyldiphenylmethylammonium chloride was used instead of chloro-2-hydroxypropyldimethylbenzylammonium chloride. The resulting starch had a degree of substitution (D.S.) of cationic groups of 0.03, a gelatinization initiation temperature of 50°C, a viscosity of 20%, and 48 centipoise at 30°C. Example 3 A cation was prepared in the same manner as in Example 1 except that in Example 1, tapioca flour was replaced with potato starch and 3-chloro-2-hydroxypropyldimethylbenzylammonium chloride was replaced with 3-chloro-2-hydroxypropyldimethylcyclohexylammonium chloride. Modified starch was obtained. Degree of substitution (D.S.) of cationic groups in the obtained starch = 0
．． 025, gelatinization start temperature 49℃, viscosity 20%, 30℃
It was 46 centipoise. Example 4 100 parts of tapioca starch is added to a solution of 130 parts of water, 1.8 parts of sodium hydroxide, and 50 parts of sodium sulfate, 8 parts of acrylonitrile are added, and the mixture is reacted at 40° C. for 8 hours. Next, 10 parts of 3-chloro-2-hydroxypropyltribenzyl ammonium chloride is added, and the mixture is reacted at 40° C. for 6 hours while maintaining the pH at 11.5 with 3% sodium hydroxide. 18 parts of 35% hydrogen peroxide solution was added to this and reacted for 4 hours. After the reaction was completed, the mixture was neutralized to pH 4.5 with diluted hydrochloric acid, dehydrated, washed with water, and dried to obtain cationically modified starch. The resulting starch had a degree of substitution (D.S.) of cationic groups of 0.02, a gelatinization initiation temperature of 50°C, a viscosity of 20%, and a viscosity of 100 centipoise at 30°C. Example 5 A mixed solution of 8 parts of water, 8.2 parts of methanol, and 2 parts of 50% sodium hydroxide is added to 100 parts of cornstarch, and after dispersion, 10 parts of ethylene oxide is added and reacted at 38° C. for 10 hours. After 10 hours, the reactant was poured into 120 parts of water, the temperature was raised to 43°C, and 8 parts of 3-chloro-2-hydroxypropyltriphenylammonium chloride was added.
5 while maintaining pH 11 with 3% sodium hydroxide aqueous solution.
Time reacts. After the reaction, lower the pH to 5 with dilute hydrochloric acid to 20%.
After adding 18 parts of hydrochloric acid and reacting at 40°C for 15 hours, 3
% sodium hydroxide aqueous solution to pH 4.5, dehydrated, washed with water, and dried to obtain a cationically modified starch. The resulting starch had a degree of substitution (D.S.) of cationic groups of 0.02, a gelatinization initiation temperature of 49°C, and a viscosity of 20% and 80 centipoise at 30°C. Example 6 100 parts of oxidized starch was added to 130 parts of water, 1.5 parts of sodium hydroxide, and 50 parts of sodium sulfate, then 10 parts of 2,3-epoxypropyldibenzylaminochloride was added, and 3% sodium hydroxide was added. The reaction was carried out at 40° C. for 5 hours while maintaining the pH at 11.2 with an aqueous solution. The reaction solution was lowered to 30°C, and after adjusting the pH to 8 to 9 with dilute hydrochloric acid, 6 parts of vinyl acetate was added, and the mixture was reacted at 30°C and pH 8 to 9 for 10 hours. After the reaction was completed, the mixture was neutralized to pH 4.5 with diluted hydrochloric acid, dehydrated, washed with water, and dried to obtain cationically modified starch. Degree of substitution (D.S.) of cationic groups in the obtained starch = 0.04, gelatinization initiation temperature 46
The viscosity was 20% and 60 centipoise at 30°C.
【００１３】比較例１
実施例１において３−クロロ−２−ヒドロキシプロピル
ジメチルベンジルアンモニウムクロライドを３−クロロ
−２−ヒドロキシプロピルトリメチルアンモニウムクロ
ライドにした以外は実施例１と同様にしてカチオン変性
澱粉を得た。得られた澱粉のカチオン性基の置換度（Ｄ
．Ｓ．）＝０．０４、糊化開始温度４８℃、粘度は２０
％、３０℃で９０センチポイズであった。
比較例２
実施例１において３−クロロ−２−ヒドロキシプロピル
ジメチルベンジルアンモニウムクロライドを２−ジエチ
ルアミノエチルクロライドにする以外は実施例１と同様
にしてカチオン変性澱粉を得た。得られた澱粉のカチオ
ン性基の置換度（Ｄ．Ｓ．）＝０．０５、糊化開始温度
４５℃、粘度は２０％、３０℃で８０センチポイズであ
った。Comparative Example 1 Cationically modified starch was obtained in the same manner as in Example 1 except that 3-chloro-2-hydroxypropyldimethylbenzylammonium chloride was replaced with 3-chloro-2-hydroxypropyltrimethylammonium chloride. Ta. Degree of substitution of cationic groups (D
．． S. )=0.04, gelatinization start temperature 48℃, viscosity 20
%, 90 centipoise at 30°C. Comparative Example 2 Cationically modified starch was obtained in the same manner as in Example 1 except that 2-diethylaminoethyl chloride was used instead of 3-chloro-2-hydroxypropyldimethylbenzyl ammonium chloride. The resulting starch had a degree of substitution (D.S.) of cationic groups of 0.05, a gelatinization initiation temperature of 45°C, a viscosity of 20%, and 80 centipoise at 30°C.
【００１４】実施例７
ドデセニル無水コハク酸２４部、上記実施例１〜６、比
較例１〜２で得られたカチオン変性澱粉の２０％水溶液
３０部及びイオン交換水１４６部を８０℃に加熱しホモ
ミキサーにて予備分散し同温度を保ちながらホモジナイ
ザーを２回通して分散させ、冷却後、３５０メッシユの
篩にて▲ろ▼過し水性エマルジョンを得た。得られた水
性エマルジョンを１００ｍｌメスシリンダーに移し、室
温で放置した。乳化層の容積（ｍｌ）の経時変化で保存
安定性の試験を行った。また、ブランクとしてカチオン
変性澱粉を添加しないものについても同様に行った。結
果は表１に示した。Example 7 24 parts of dodecenyl succinic anhydride, 30 parts of the 20% aqueous solution of the cationically modified starch obtained in Examples 1 to 6 and Comparative Examples 1 to 2, and 146 parts of ion-exchanged water were heated to 80°C. The mixture was preliminarily dispersed in a homomixer, passed through a homogenizer twice while maintaining the same temperature, and after cooling was filtered through a 350 mesh sieve to obtain an aqueous emulsion. The resulting aqueous emulsion was transferred to a 100 ml graduated cylinder and left at room temperature. A storage stability test was conducted based on changes in the volume (ml) of the emulsified layer over time. In addition, a blank sample to which cationically modified starch was not added was also tested in the same manner. The results are shown in Table 1.
【表１】
実施例７
叩解済みパルプスラリー（ＬＢＫＰ，４００ｃ・ｓ．ｆ
）に実施例７で調製したサイズ剤を、気乾パルプ重量に
対して、それぞれ固形換算し、３重量％に相当する量を
添加し、常法に従い手抄試験器（ＴＡＰＰＩ・スタンダ
ードマシン）を用い、坪量６０ｇ／ｍ２相当の手抄紙を
調製し、ステキヒトサイズ度試験をし保存安定性をみて
、表２の結果を得た。[Table 1] Example 7 Beaten pulp slurry (LBKP, 400 c.s.f.
) was added in an amount equivalent to 3% by weight of the sizing agent prepared in Example 7 based on the weight of the air-dried pulp, and the sizing agent was added to the sizing agent prepared in Example 7 in an amount equivalent to 3% by weight of the air-dried pulp. Using this method, handmade paper with a basis weight of 60 g/m2 was prepared, and the Steckcht sizing test was performed to determine storage stability, and the results shown in Table 2 were obtained.
【表２】[Table 2]
【００１５】実施例９
実施例７においてドデセニル無水コハク酸の代わりにス
テアリルケテンダイマーを用いる以外は実施例７と同様
にして水性エマルジョンを得て、その保存安定性試験を
行ない表３に結果を示した。Example 9 An aqueous emulsion was obtained in the same manner as in Example 7, except that stearyl ketene dimer was used instead of dodecenyl succinic anhydride, and a storage stability test was conducted. The results are shown in Table 3. Ta.
【表３】
実施例１０
実施例９で調製したサイズ剤を用いて実施例８と同様に
してステキヒトサイズ度試験を行い結果を表４に示した
。[Table 3] Example 10 Using the sizing agent prepared in Example 9, a Stekicht sizing test was conducted in the same manner as in Example 8, and the results are shown in Table 4.
【表４】[Table 4]
【００１６】[0016]
【発明の効果】表１〜表４より判る様に本発明のサイズ
剤は、従来品に比べて乳化安定性が高く、サイズ度も高
くかつ経時変化によるサイズ度の低下も従来品の様に著
しくないので極めて実用的価値の高いものである。[Effects of the Invention] As can be seen from Tables 1 to 4, the sizing agent of the present invention has higher emulsion stability and higher sizing degree than conventional products, and the sizing agent does not decrease in sizing degree due to changes over time like conventional products. Since it is not noticeable, it has extremely high practical value.
【化５】[C5]
Claims (5)
．Ｓ．）が０．０１〜０．２でその平均分子量が５００
０〜５００００，３０℃における糊液粘度が２０％水溶
液において１０〜１０００センチポイズである請求項１
記載の変性澱粉。2. Degree of substitution (D) of cationization of the modified starch
．． S. ) is 0.01 to 0.2 and its average molecular weight is 500
Claim 1: The viscosity of the paste liquid at 30°C is 10 to 1000 centipoise in a 20% aqueous solution.
Modified starch as described.
カリ触媒を用いて反応させることを特徴とする変性澱粉
の製造方法。 【化２】3. A method for producing modified starch, which comprises reacting starch with a compound represented by Chemical Formula 2 using an alkali catalyst. [Case 2]
ニル無水コハク酸、アルキルケテンダイマー、アルキル
ケテンダイマー誘導体及び無水ステアリン酸から選ばれ
る中性抄紙用サイズ剤に添加することを特徴とする製紙
用サイズ剤。 【化３】4. A method for paper manufacturing, characterized in that the modified starch represented by formula 3 is added to a neutral paper sizing agent selected from alkenyl succinic anhydride, alkyl ketene dimer, alkyl ketene dimer derivative, and stearic anhydride. Sizing agent. [Chemical formula 3]
（Ｄ．Ｓ．）が０．０１〜０．２であると共に、エーテ
ル化及び／又はエステル化することにより部分的にノニ
オン化した糊化開始温度が２０〜７０℃、平均分子量が
５０００〜５００００、３０℃における糊液粘度が２０
％水溶液において１０〜１０００センチポイズである請
求項３記載の製紙用サイズ剤。5. A glue in which the modified starch has a cationization degree (D.S.) of 0.01 to 0.2 and is partially nonionized by etherification and/or esterification. The starting temperature is 20 to 70°C, the average molecular weight is 5000 to 50000, and the viscosity of the paste at 30°C is 20.
4. The paper sizing agent according to claim 3, which has a sizing agent of 10 to 1000 centipoise in an aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03191361A JP3085739B2 (en) | 1991-04-25 | 1991-04-25 | Modified starch and sizing agent for paper making using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03191361A JP3085739B2 (en) | 1991-04-25 | 1991-04-25 | Modified starch and sizing agent for paper making using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04363301A true JPH04363301A (en) | 1992-12-16 |
| JP3085739B2 JP3085739B2 (en) | 2000-09-11 |
Family
ID=16273303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03191361A Expired - Fee Related JP3085739B2 (en) | 1991-04-25 | 1991-04-25 | Modified starch and sizing agent for paper making using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3085739B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997035068A1 (en) * | 1996-03-21 | 1997-09-25 | Betzdearborn Inc. | Paper size and paper sizing process |
| EP1008306A3 (en) * | 1998-12-10 | 2001-04-18 | Nissin Shokuhin Kabushiki Kaisha | Polysaccharide which can reduce viscosity resulting from psyllium, and foods containing the polysaccharide and psyllium |
| US6682770B2 (en) | 1998-12-10 | 2004-01-27 | Nissin Shokuhin Kabushiki Kaisha | Polysaccharide capable of reducing the viscosity of a hydrated psyllium, and foods containing the polysaccharide and psyllium |
| US7488402B2 (en) | 2000-08-07 | 2009-02-10 | Akzo Nobel N.V. | Process for production of paper |
| JP2013507464A (en) * | 2009-10-07 | 2013-03-04 | アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップ | Superhydrophilic amphiphilic copolymer and process for producing the same |
| US9114154B2 (en) | 2009-10-07 | 2015-08-25 | Johnson & Johnson Consumer Inc. | Compositions comprising superhydrophilic amphiphilic copolymers and methods of use thereof |
| US9243074B2 (en) | 2009-10-07 | 2016-01-26 | Akzo Nobel Chemicals International B.V. | Superhydrophilic amphiphilic copolymers and processes for making the same |
| CN109651517A (en) * | 2018-12-29 | 2019-04-19 | 广州天赐高新材料股份有限公司 | AKD emulsification amphoteric starch and its preparation method and application |
| US11173106B2 (en) | 2009-10-07 | 2021-11-16 | Johnson & Johnson Consumer Inc. | Compositions comprising a superhydrophilic amphiphilic copolymer and a micellar thickener |
-
1991
- 1991-04-25 JP JP03191361A patent/JP3085739B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997035068A1 (en) * | 1996-03-21 | 1997-09-25 | Betzdearborn Inc. | Paper size and paper sizing process |
| US6159339A (en) * | 1996-03-21 | 2000-12-12 | Betzdearborn Inc. | Paper size and paper sizing process |
| EP1008306A3 (en) * | 1998-12-10 | 2001-04-18 | Nissin Shokuhin Kabushiki Kaisha | Polysaccharide which can reduce viscosity resulting from psyllium, and foods containing the polysaccharide and psyllium |
| US6682770B2 (en) | 1998-12-10 | 2004-01-27 | Nissin Shokuhin Kabushiki Kaisha | Polysaccharide capable of reducing the viscosity of a hydrated psyllium, and foods containing the polysaccharide and psyllium |
| US7488402B2 (en) | 2000-08-07 | 2009-02-10 | Akzo Nobel N.V. | Process for production of paper |
| JP2013507464A (en) * | 2009-10-07 | 2013-03-04 | アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップ | Superhydrophilic amphiphilic copolymer and process for producing the same |
| US9114154B2 (en) | 2009-10-07 | 2015-08-25 | Johnson & Johnson Consumer Inc. | Compositions comprising superhydrophilic amphiphilic copolymers and methods of use thereof |
| US9243074B2 (en) | 2009-10-07 | 2016-01-26 | Akzo Nobel Chemicals International B.V. | Superhydrophilic amphiphilic copolymers and processes for making the same |
| JP2016053170A (en) * | 2009-10-07 | 2016-04-14 | アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップＡｋｚｏ Ｎｏｂｅｌ Ｃｈｅｍｉｃａｌｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｂ．Ｖ． | Superhydrophilic amphiphilic copolymer and method for making the same |
| US11173106B2 (en) | 2009-10-07 | 2021-11-16 | Johnson & Johnson Consumer Inc. | Compositions comprising a superhydrophilic amphiphilic copolymer and a micellar thickener |
| CN109651517A (en) * | 2018-12-29 | 2019-04-19 | 广州天赐高新材料股份有限公司 | AKD emulsification amphoteric starch and its preparation method and application |
| CN109651517B (en) * | 2018-12-29 | 2021-07-27 | 广州天赐高新材料股份有限公司 | Amphoteric starch for AKD emulsification and preparation method and application thereof |
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