JPH07189174A - Rosin emulsion composition, its production, sizing agent and sizing method - Google Patents
Rosin emulsion composition, its production, sizing agent and sizing methodInfo
- Publication number
- JPH07189174A JPH07189174A JP5346803A JP34680393A JPH07189174A JP H07189174 A JPH07189174 A JP H07189174A JP 5346803 A JP5346803 A JP 5346803A JP 34680393 A JP34680393 A JP 34680393A JP H07189174 A JPH07189174 A JP H07189174A
- Authority
- JP
- Japan
- Prior art keywords
- rosin
- emulsion composition
- composition according
- sizing
- reaction product
- 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
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 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 title claims abstract description 77
- 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 title claims abstract description 77
- 238000004513 sizing Methods 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000000839 emulsion Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title description 17
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 59
- 239000002253 acid Substances 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 150000001414 amino alcohols Chemical class 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 6
- 150000003141 primary amines Chemical class 0.000 claims abstract description 5
- 229920000768 polyamine Polymers 0.000 claims abstract 2
- -1 alkenyl succinic acid derivative Chemical class 0.000 claims description 87
- 150000005846 sugar alcohols Polymers 0.000 claims description 21
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 229940014800 succinic anhydride Drugs 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 14
- 150000008064 anhydrides Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000001384 succinic acid Substances 0.000 claims description 12
- 150000001298 alcohols Chemical class 0.000 claims description 10
- 150000001735 carboxylic acids Chemical class 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043276 diisopropanolamine Drugs 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000000123 paper Substances 0.000 abstract description 61
- 230000007935 neutral effect Effects 0.000 abstract description 14
- 238000001035 drying Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 239000000084 colloidal system Substances 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 4
- 150000007513 acids Chemical class 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000003784 tall oil Substances 0.000 abstract description 3
- 239000005018 casein Substances 0.000 abstract description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 abstract description 2
- 235000021240 caseins Nutrition 0.000 abstract description 2
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 abstract 1
- 239000003995 emulsifying agent Substances 0.000 abstract 1
- 239000003755 preservative agent Substances 0.000 abstract 1
- 230000002335 preservative effect Effects 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 12
- 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 11
- 230000001804 emulsifying effect Effects 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 125000002091 cationic group Chemical group 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229920002401 polyacrylamide Polymers 0.000 description 9
- 125000000129 anionic group Chemical group 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000001530 fumaric acid Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000007764 o/w emulsion Substances 0.000 description 5
- 239000013055 pulp slurry Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 230000005476 size effect Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 4
- 229940055577 oleyl alcohol Drugs 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- KLAIOABSDQUNSA-WUKNDPDISA-N 3-[(e)-octadec-2-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCC\C=C\CC1CC(=O)OC1=O KLAIOABSDQUNSA-WUKNDPDISA-N 0.000 description 2
- KAYAKFYASWYOEB-UHFFFAOYSA-N 3-octadec-1-enyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCCC=CC1CC(=O)OC1=O KAYAKFYASWYOEB-UHFFFAOYSA-N 0.000 description 2
- BNDWRWFZSMPKQP-UHFFFAOYSA-N 3-pentadec-1-enyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCC=CC1CC(=O)OC1=O BNDWRWFZSMPKQP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229920006318 anionic polymer Polymers 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 229920006319 cationized starch Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
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- 239000004815 dispersion polymer Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
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- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 2
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
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- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- FBFIDNKZBQMMEQ-UHFFFAOYSA-N 3-(3-phenylpentan-3-yl)benzene-1,2-diamine Chemical compound C=1C=CC(N)=C(N)C=1C(CC)(CC)C1=CC=CC=C1 FBFIDNKZBQMMEQ-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- XYUINKARGUCCQJ-UHFFFAOYSA-N 3-imino-n-propylpropan-1-amine Chemical compound CCCNCCC=N XYUINKARGUCCQJ-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- 229930185605 Bisphenol Natural products 0.000 description 1
- JIXZPVOOTNKLQO-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)(=O)O.C(CO)O.C(=CCCCCCCCCCCCCC)C1C(=O)OC(C1)=O Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)O.C(CO)O.C(=CCCCCCCCCCCCCC)C1C(=O)OC(C1)=O JIXZPVOOTNKLQO-UHFFFAOYSA-N 0.000 description 1
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- 239000008186 active pharmaceutical agent Substances 0.000 description 1
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
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- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 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
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 1
- LFRGVKPZDIYAQV-UHFFFAOYSA-N cyclopenta-2,4-diene-1,1-diamine Chemical compound NC1(N)C=CC=C1 LFRGVKPZDIYAQV-UHFFFAOYSA-N 0.000 description 1
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- FLISWPFVWWWNNP-BQYQJAHWSA-N dihydro-3-(1-octenyl)-2,5-furandione Chemical compound CCCCCC\C=C\C1CC(=O)OC1=O FLISWPFVWWWNNP-BQYQJAHWSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KMBPCQSCMCEPMU-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-methylpropane-1,3-diamine Chemical compound NCCCN(C)CCCN KMBPCQSCMCEPMU-UHFFFAOYSA-N 0.000 description 1
- ITZPOSYADVYECJ-UHFFFAOYSA-N n'-cyclohexylpropane-1,3-diamine Chemical compound NCCCNC1CCCCC1 ITZPOSYADVYECJ-UHFFFAOYSA-N 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013054 paper strength agent Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- JMHCCAYJTTWMCX-QWPJCUCISA-M sodium;(2s)-2-amino-3-[4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl]propanoate;pentahydrate Chemical compound O.O.O.O.O.[Na+].IC1=CC(C[C@H](N)C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 JMHCCAYJTTWMCX-QWPJCUCISA-M 0.000 description 1
- HLPHHOLZSKWDAK-UHFFFAOYSA-M sodium;formaldehyde;naphthalene-1-sulfonate Chemical compound [Na+].O=C.C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HLPHHOLZSKWDAK-UHFFFAOYSA-M 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Colloid Chemistry (AREA)
- Paper (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ロジン系エマルション
組成物、その製造方法、サイズ剤、サイジング方法に係
わり、特にエマルション固形分中にアルケニルコハク酸
誘導体とロジン系物質と分散剤を含有したロジン系エマ
ルション組成物であって、酸性系はもちろん中性領域で
の抄紙系において優れたサイズ効果を発現し、特に抄紙
速度が高速で乾燥条件の穏やかな場合、すなわち湿紙に
付与される熱量が相対的に低い抄紙系、例えばヤンキー
ドライヤーを有する抄紙機の乾燥条件において製造され
た紙にも優れたサイズ効果を発揮し、しかもそれ自体の
機械的安定性及び保存安定性に優れたサイズ剤に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rosin emulsion composition, a process for producing the same, a sizing agent and a sizing method, and more particularly to a rosin containing an alkenylsuccinic acid derivative, a rosin substance and a dispersant in the emulsion solids. A system emulsion composition, which exhibits an excellent size effect not only in an acidic system but also in a papermaking system in a neutral region, particularly when the papermaking speed is high and the drying conditions are mild, that is, the amount of heat applied to the wet paper is The present invention relates to a sizing agent that exhibits excellent sizing effect even on paper produced under the drying conditions of a paper machine having a relatively low papermaking system, for example, a Yankee dryer, and has excellent mechanical stability and storage stability of itself. .
【０００２】[0002]
【従来の技術】製紙業界では、紙質の向上、抄紙系のク
ローズド化及び製紙原料として炭酸カルシウムを含んだ
古紙や損紙を使用することに伴う諸問題を抱えており、
一方生産性向上のために抄紙機はより高速化され、その
結果として乾燥を比較的低温条件下で急速に行うことが
多くなってきている。後者に関しては、従来のサイズ剤
では紙に十分なサイズ度が付与できない傾向が見られ
る。2. Description of the Related Art In the papermaking industry, there are problems associated with improving paper quality, closing papermaking systems, and using waste paper and broke containing calcium carbonate as a raw material for papermaking.
On the other hand, in order to improve productivity, paper machines have been made faster, and as a result, drying has been often performed rapidly under relatively low temperature conditions. Regarding the latter, there is a tendency that conventional sizing agents cannot give sufficient sizing degree to paper.
【０００３】[0003]
【発明が解決しようとする課題】例えばアニオン性ロジ
ン系サイズ剤、特に強化ロジンのアルカリ中和物である
溶液型ロジンサイズ剤を使用した場合、また、溶液型ロ
ジンサイズ剤よりもサイズ効果に優れ、抄紙適用ｐＨ範
囲の広い分散型ロジン系サイズ剤を使用した場合、高速
抄紙機による抄造の際には乾燥条件が十分とは言えず、
所定のサイズ度を得るためにはサイズ剤の添加量を増や
さなければならず、そのためにコストアップになるばか
りでなく、抄紙工程中で発泡が著しいという問題を生じ
る。このような事情から、抄紙速度が高速で、乾燥条件
が比較的穏やかな場合、例えばヤンキードライヤーを有
する抄紙機（例えは純白ロール紙用等の抄紙機）あるい
は超高速の新聞用紙用抄紙機の乾燥条件下において抄造
された紙にも優れたサイズ効果を発揮するロジン系エマ
ルションサイズ剤が強く求められている。For example, when an anionic rosin-based sizing agent, particularly a solution-type rosin-sizing agent which is an alkali-neutralized product of a toughened rosin, is used, it is also superior in size effect to the solution-type rosin-sizing agent. When a dispersion type rosin-based sizing agent having a wide pH range applicable to papermaking is used, it cannot be said that the drying conditions are sufficient during papermaking using a high-speed papermaking machine.
In order to obtain a predetermined sizing degree, it is necessary to increase the amount of the sizing agent added, which not only raises the cost but also causes a problem of remarkable foaming in the papermaking process. Under such circumstances, when the papermaking speed is high and the drying conditions are relatively gentle, for example, a paper machine having a Yankee dryer (for example, a paper machine for pure white roll paper) or an ultra-high speed paper machine for newsprint is used. There is a strong demand for a rosin-based emulsion sizing agent that exerts an excellent sizing effect on paper made under dry conditions.
【０００４】本発明の目的は、高速抄紙機で抄紙する場
合のように、乾燥条件が比較的穏やかな抄紙系で抄造さ
れる紙のみならず、酸性から中性までの幅広い抄紙ｐＨ
領域の抄紙系において抄造された紙に優れたサイズ効果
を発揮し、しかも機械的安定性及び保存安定性に優れた
ロジン系エマルション組成物、その製造方法、この組成
物を含有するサイズ剤、サイジング方法を提供すること
にある。The object of the present invention is not only to make paper in a papermaking system in which drying conditions are relatively mild, as in the case of making paper in a high-speed papermaking machine, but also to a wide range of papermaking pH from acidic to neutral.
Rosin emulsion composition exhibiting excellent sizing effect on paper produced in the papermaking system of the domain, and having excellent mechanical stability and storage stability, a method for producing the same, a sizing agent containing this composition, and sizing To provide a method.
【０００５】[0005]
【課題を解決するための手段】本発明は、上記課題を解
決するために、（Ａ）アルケニルコハク酸誘導体と、
（Ｂ）ロジン系物質と、（Ｃ）分散剤を含有する分散質
を水中に安定に分散させたロジン系エマルション組成物
を提供するものである。In order to solve the above problems, the present invention provides (A) an alkenylsuccinic acid derivative,
It is intended to provide a rosin-based emulsion composition in which a dispersoid containing (B) a rosin-based substance and (C) a dispersant is stably dispersed in water.
【０００６】また、本発明は、これらのロジン系エマル
ション組成物の製造方法、この組成物を含有するサイズ
剤、サイジング方法を提供する。The present invention also provides a method for producing these rosin emulsion compositions, a sizing agent containing this composition, and a sizing method.
【０００７】以下に本発明を詳細に説明する。本発明を
構成する（Ａ）のアルケニルコハク酸誘導体とは、
一級アミン類、二級アミン類、多価アミン類及びアミノ
アルコール類からなる群から選ばれた少なくとも１種
と、アルケニルコハク酸無水物及びアルケニルコハク酸
の少なくとも１種との反応生成物、 二級アミン類、
多価アミン類及びアミノアルコール類からなる群から選
ばれた少なくとも１種と、アルケニルコハク酸無水物及
びアルケニルコハク酸の少なくとも１種との反応生成物
にさらに一価アルコール類、多価アルコール類及び一級
カルボン酸類からなる群から選ばれた少なくとも１種を
反応させて得られた反応生成物、 一価アルコール
と、アルケニルコハク酸無水物及びアルケニルコハク酸
の少なくとも１種との反応生成物、 一価アルコール
と、アルケニルコハク酸無水物及びアルケニルコハク酸
の少なくとも１種との反応生成物に多価アルコール類を
反応させて得られた反応生成物、 多価アルコール類
と、アルケニルコハク酸無水物及びアルケニルコハク酸
の少なくとも１種との反応生成物、 多価アルコール
類と、アルケニルコハク酸無水物及びアルケニルコハク
酸の少なくとも１種との反応生成物に一価アルコール類
及び一級カルボン酸類の少なくとも１種を反応させて得
られた反応生成物であり、これらは各群内単独又は２種
以上併用しても良く、また任意の２以上の群の各群少な
くとも１種を併用してもよい。The present invention will be described in detail below. The alkenylsuccinic acid derivative (A) that constitutes the present invention is
Reaction product of at least one selected from the group consisting of primary amines, secondary amines, polyvalent amines and amino alcohols with at least one of alkenyl succinic anhydride and alkenyl succinic acid, secondary Amines,
The reaction product of at least one selected from the group consisting of polyhydric amines and amino alcohols with at least one of alkenyl succinic anhydride and alkenyl succinic acid is further added to monohydric alcohols, polyhydric alcohols, and A reaction product obtained by reacting at least one selected from the group consisting of primary carboxylic acids, a reaction product of a monohydric alcohol with at least one of alkenyl succinic anhydride and alkenyl succinic acid, monovalent Reaction product obtained by reacting polyhydric alcohol with reaction product of alcohol and at least one of alkenyl succinic anhydride and alkenyl succinic acid, polyhydric alcohol, alkenyl succinic anhydride and alkenyl Reaction products with at least one succinic acid, polyhydric alcohols, alkenyl succinic anhydride and And a reaction product of at least one kind of alkenyl succinic acid with at least one kind of a monohydric alcohol and a primary carboxylic acid, and these are reaction products obtained individually or in combination of two or more kinds in each group. Alternatively, at least one of each of two or more groups may be used in combination.
【０００８】ここで、アルケニルコハク酸無水物、アル
ケニルコハク酸とは、それぞれ炭素数６〜３０のオレフ
ィンと無水マレイン酸、炭素数６〜３０のオレフィンと
マレイン酸の反応生成物であり、両者は単独で用いられ
るが、混合して用いられても良い。オレフィンとして
は、炭素数が好ましくは８〜２０、さらに好ましくは１
２〜１８である。そのオレフィンの代表的なものとして
は、直鎖α─オレフィン、直鎖内部オレフィン、分岐オ
レフィンのいずれも使用でき、また、それらの任意の２
種以上の混合物でも良い。上記アルケニルコハク酸無水
物は、下記一般式で示され、上記アルケニルコハク酸は
その開環したものである。Here, the alkenylsuccinic anhydride and the alkenylsuccinic acid are reaction products of an olefin having 6 to 30 carbon atoms and maleic anhydride, and an olefin having 6 to 30 carbon atoms and maleic acid, respectively. Although they are used alone, they may be used in combination. The olefin preferably has 8 to 20 carbon atoms, and more preferably 1 carbon atom.
2-18. As typical olefins, any of linear α-olefins, linear internal olefins, and branched olefins can be used.
It may be a mixture of two or more species. The alkenylsuccinic anhydride is represented by the following general formula, and the alkenylsuccinic acid is a ring-opened product thereof.
【０００９】[0009]
【化１】 [Chemical 1]
【００１０】式中、Ｒ8 〜 Ｒ12はそれぞれ水素原子又
は同一若しくは異なっても良い炭素数１〜２７の直鎖若
しくは分岐のアルキル基を示す。In the formula, R 8 to R 12 each represent a hydrogen atom or a linear or branched alkyl group having 1 to 27 carbon atoms which may be the same or different.
【００１１】アルケニルコハク酸誘導体を製造するに当
たり、アルケニルコハク酸無水物とアルケニルコハク酸
とでは、反応の容易さの点で前者を使用することが好ま
しい。上記の反応生成物は、アミド化反応、イミド化
反応、エステル化反応あるいはこれらの反応が複数組み
合わさって起こることによって得られる化合物である。
実際には、上記のアミン類のそれぞれの物質と、アル
ケニルコハク酸無水物及びアルケニルコハク酸の少なく
とも１種を混合し、あるいは一方の成分に他方の成分を
滴下しながら、室温ないし２００℃程度で３０分〜２４
時間程度付加付加及び／又は脱水反応を起こして製造さ
れる。一般的には、発熱反応であるため、一方の成分に
他方の成分を滴下する方法が好ましい。これらアミン類
は２種以上併用しても良く、この場合、２種以上のアミ
ン類を同時にアルケニルコハク酸無水物及びアルケニル
コハク酸の少なくとも１種と反応させても良いし、ある
いは１種類のアミンを反応させてから次のアミンを反応
させるように段階的に反応を行っても良い。In producing the alkenylsuccinic acid derivative, it is preferable to use the former of the alkenylsuccinic anhydride and the alkenylsuccinic acid in terms of easiness of reaction. The above reaction product is a compound obtained by amidation reaction, imidization reaction, esterification reaction or a combination of these reactions.
In practice, each of the above amines is mixed with at least one of alkenylsuccinic anhydride and alkenylsuccinic acid, or one component is added dropwise while the other component is added at room temperature to about 200 ° C. 30 minutes to 24
It is produced by adding addition and / or dehydration reaction for about time. Generally, since the reaction is exothermic, the method of dropping the other component in one component is preferable. Two or more kinds of these amines may be used in combination, and in this case, two or more kinds of amines may be simultaneously reacted with at least one of alkenylsuccinic anhydride and alkenylsuccinic acid, or one kind of amine. The reaction may be carried out in a stepwise manner so that the following amine is reacted.
【００１２】本発明で使用される一級アミン類として
は、一般式Ｒ1 ＮＨ2 で表され、二級アミン類として
は、一般式Ｒ2 Ｒ3 ＮＨで表され、Ｒ1 、Ｒ2 、Ｒ3 は
同一又は異なる炭素数１〜３０の鎖状又は環状炭化水素
基を示す化合物が好ましい。Ｒ1、Ｒ2 、Ｒ3 のそれぞ
れの具体例としては、メチル、エチル、プロピル、イソ
プロピル、アリル、ブチル、イソブチル、ｓ−ブチル、
ｔ─ブチル、ヘキシル、シクロヘキシル、オクチル、２
─エチルヘキシル、ノニル、デシル、ラウリル、ミリス
チル、パルミチル、ステアリル、オレイル等の鎖状炭化
水素基、フェニル、ナフチル、デヒドロアビエチル等を
挙げることができる。The primary amines used in the present invention are represented by the general formula R 1 NH 2 , and the secondary amines are represented by the general formula R 2 R 3 NH, R 1 , R 2 and R 3 is preferably a compound which is the same or different and represents a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms. Specific examples of R 1 , R 2 and R 3 include methyl, ethyl, propyl, isopropyl, allyl, butyl, isobutyl, s-butyl,
t-butyl, hexyl, cyclohexyl, octyl, 2
—Chain hydrocarbon groups such as ethylhexyl, nonyl, decyl, lauryl, myristyl, palmityl, stearyl, oleyl, phenyl, naphthyl, dehydroabietyl, etc.
【００１３】また、多価アミン類としては、一般式Ｈ2
Ｎ─Ｒ4 （ＮＲ5 ─Ｒ4 ）ｎ─ＮＨ2 で表され、Ｒ4 が
炭素数２〜１３の鎖状又は環状アルキレン基、Ｒ5 が水
素又はメチル基であってｎが０〜５の整数値で示される
化合物が好ましい。例えば、エチレンジアミン、ヘキサ
メチレンジアミン、ジエチレントリアミン、トリエチレ
ンテトラミン、テトラエチレンペンタミン、イミノビス
プロピルアミン、メチルイミノビスプロピルアミン、ト
リメチルヘキサメチレンジアミン、イソホロンジアミ
ン、シクロペンタジエンジアミン、ビス（パラアミノシ
クロヘキシル）メタン、ビスアミノメチルシクロヘキサ
ン、Ｎ−アミノプロピルシクロヘキシルアミン、キシレ
ンジアミン、ジアミノジエチルジフェニルメタン、ｏ−
トリジン、トルイレンジアミン、フェニレンジアミン、
ビスアミノプロピルピペラジン、ジアミノジフェニルエ
ーテル、ジアミノベンズアニリド、ジアニシジン等を挙
げることができる。また、アミノアルコール類として
は、例えばモノエタノールアミン、ジエタノールアミ
ン、トリエタノールアミン、モノイソプロパノールアミ
ン、ジイソプロパノールアミン、トリイソプロパノール
アミン等を挙げることができる。Further, as the polyvalent amine, general formula H 2
N—R 4 (NR 5 —R 4 ) n—NH 2 , R 4 is a chain or cyclic alkylene group having 2 to 13 carbon atoms, R 5 is hydrogen or a methyl group, and n is 0 to 5 The compound represented by the integer value of is preferable. For example, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, methyliminobispropylamine, trimethylhexamethylenediamine, isophoronediamine, cyclopentadienediamine, bis (paraaminocyclohexyl) methane, bis Aminomethylcyclohexane, N-aminopropylcyclohexylamine, xylenediamine, diaminodiethyldiphenylmethane, o-
Trizine, toluylenediamine, phenylenediamine,
Examples thereof include bisaminopropylpiperazine, diaminodiphenyl ether, diaminobenzanilide, and dianisidine. Examples of amino alcohols include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and the like.
【００１４】アルケニルコハク酸無水物及びアルケニル
コハク酸の少なくとも１種と、上記アミン類の反応を行
う際、使用したアミン類の種類及び仕込み比率によって
未反応のカルボキシル基、水酸基、アミノ基を１つ以上
もつアルケニルコハク酸誘導体が合成される。したがっ
てこれらの反応生成物にさらに一価アルコール類、多価
アルコール類、一級カルボン酸類を単独又は複数併用し
て、エステル化反応あるいはアミド化反応を行ったアル
ケニルコハク酸誘導体を合成することができ、本発明は
これらも使用できる。このようなアルコール類、一級カ
ルボン酸類は、アルケニルコハク酸無水物及びアルケニ
ルコハク酸の少なくとも１種とアミン類を反応させた
後、加えて反応させることが好ましいが、あるいはアル
ケニルコハク酸無水物及びアルケニルコハク酸の少なく
とも１種とアルコール類、一級カルボン酸類を混合して
反応させてからアミン類を加えてさらに反応させても良
いし、さらには全部を同時に混合して反応させても良
い。When at least one of alkenylsuccinic anhydride and alkenylsuccinic acid is reacted with the above amines, one unreacted carboxyl group, hydroxyl group or amino group is selected depending on the type of amines used and the charging ratio. The alkenyl succinic acid derivative having the above is synthesized. Therefore, further monohydric alcohols, polyhydric alcohols, primary carboxylic acids may be used alone or in combination with these reaction products to synthesize an alkenylsuccinic acid derivative that has undergone an esterification reaction or an amidation reaction, The present invention can also use these. Such alcohols and primary carboxylic acids are preferably obtained by reacting at least one of alkenyl succinic anhydride and alkenyl succinic acid with amines, and then adding and reacting them. Alternatively, alkenyl succinic anhydride and alkenyl succinic acid are used. At least one kind of succinic acid may be mixed and reacted with alcohols and primary carboxylic acids, and then amines may be added and further reacted, or all of them may be simultaneously mixed and reacted.
【００１５】上記一価アルコール類としては、一般式Ｒ
6 ＯＨで表され、Ｒ6 は炭素数１〜３０の鎖状又は環状
炭化水素基を示す化合物が好ましい。例えは、メチルア
ルコール、エチルアルコール、ブチルアルコール、オク
チルアルコール、ラウリルアルコール、パルミチルアル
コール、ステアリルアルコール、オレイルアルコール、
エイコシルアルコール等の脂肪族アルコール、シクロペ
ンタノール、シクロヘキサノール、ベンジルアルコール
あるいはロジンアルコール等の環状アルコールが代表的
なものであり、これらは単独又は２種以上併用して使用
できる。多価アルコールとしては、ＯＨ基を２〜１０個
有する化合物からなり、代表的なものとしては、例えは
エチレングリコール、ジエチレングリコール、プロピレ
ングリコール、ネオペンチルグリコール、グリセリン、
ジグリセリン、トリメチロールエタン、トリメチロール
プロパン、ペンタエリスリトール、ジペンタエリスリト
ール、ビスフェノール等が挙げられ、これらは単独又は
２種以上併用して使用できる。The above-mentioned monohydric alcohols have the general formula R
A compound represented by 6 OH, wherein R 6 represents a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms is preferable. For example, methyl alcohol, ethyl alcohol, butyl alcohol, octyl alcohol, lauryl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol,
Typical examples are aliphatic alcohols such as eicosyl alcohol, and cyclic alcohols such as cyclopentanol, cyclohexanol, benzyl alcohol and rosin alcohol, and these can be used alone or in combination of two or more kinds. The polyhydric alcohol is composed of a compound having 2 to 10 OH groups, and typical examples thereof include ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, glycerin,
Examples thereof include diglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and bisphenol. These can be used alone or in combination of two or more.
【００１６】一級カルボン酸類としては、一般式Ｒ7 Ｃ
ＯＯＨで表され、Ｒ7 は炭素数４〜２４の鎖又は環状の
炭化水素基である化合物が好ましい。例えば、ラウリル
酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレ
イン酸、ベヘン酸等が挙げられ、これらは単独又は２種
以上併用して使用できる。なお、これら一級カルボン酸
類の代わりに対応する一級カルボン酸無水物も使用で
き、本発明の一級カルボン酸類にはこれも含む。The primary carboxylic acids are represented by the general formula R 7 C
A compound represented by OOH and R 7 is a chain or cyclic hydrocarbon group having 4 to 24 carbon atoms is preferable. Examples thereof include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid, and these can be used alone or in combination of two or more kinds. Incidentally, corresponding primary carboxylic acid anhydrides can be used instead of these primary carboxylic acids, and the primary carboxylic acids of the present invention also include these.
【００１７】本発明において、アルケニルコハク酸無水
物及びアルケニルコハク酸の少なくとも１種と一価アル
コール類との反応生成物とは、これら物質の付加反応及
び／又は脱水反応により生成するモノエステル、ジエス
テル誘導体及びこれらの混合物である。一価アルコール
類は単独又は２種以上併用しても良いが、アルケニルコ
ハク酸無水物及びアルケニルコハク酸の少なくとも１種
と混合後、あるいは一方の成分に他方の成分を滴下しな
がら、室温ないし２５０℃程度で３０分〜２４時間程度
反応させるいずれの方法でも良い。その一価アルコール
類としては上記一般式Ｒ6 ＯＨで表されるもの、その具
体的例示物はそのまま適用できる。上記アルケニルコハ
ク酸無水物及びアルケニルコハク酸の少なくとも１種と
一価アルコール類との反応生成物がモノエステル及び未
反応のカルボキシル基を含む場合、さらに多価アルコー
ルを加えてエステル化反応を行ってアルケニルコハク酸
誘導体を合成できる。この際の反応温度は１２０〜２５
０℃、反応時間は２〜２４時間が好ましい。その多価ア
ルコールとしては上記の多価アルコールについて述べた
ものが適用できる。In the present invention, the reaction product of at least one of alkenyl succinic anhydride and alkenyl succinic acid with a monohydric alcohol is a monoester or diester produced by an addition reaction and / or a dehydration reaction of these substances. Derivatives and mixtures thereof. The monohydric alcohols may be used singly or in combination of two or more, but after mixing with at least one of alkenylsuccinic anhydride and alkenylsuccinic acid, or while dropping the other component into one component, the temperature may range from room temperature to 250. Any method in which the reaction is carried out at about C for about 30 minutes to 24 hours may be used. As the monohydric alcohols, those represented by the above general formula R 6 OH, and specific examples thereof can be applied as they are. When the reaction product of at least one of the above alkenyl succinic anhydride and alkenyl succinic acid and a monohydric alcohol contains a monoester and an unreacted carboxyl group, a polyhydric alcohol is further added to carry out an esterification reaction. Alkenyl succinic acid derivatives can be synthesized. The reaction temperature at this time is 120 to 25.
The reaction time is preferably 0 ° C. and 2 to 24 hours. As the polyhydric alcohol, those described above for the polyhydric alcohol can be applied.
【００１８】また、本発明において、アルケニルコハク
酸無水物及びアルケニルコハク酸の少なくとも１種と多
価アルコール類との反応生成物とは、これら物質の付加
反応及び／又は脱水反応により生成するエステル誘導体
である。多価アルコール類は単独又は２種以上併用して
も良いが、アルケニルコハク酸無水物及びアルケニルコ
ハク酸の少なくとも１種と混合後、あるいは一方の成分
に他方の成分を滴下しながら、室温ないし２５０℃程度
で３０分〜２４時間程度反応させるいずれの方法でも良
い。その多価アルコールとしては上記の多価アルコール
について述べたものが適用できる。上記アルケニルコハ
ク酸無水物及びアルケニルコハク酸の少なくとも１種と
多価アルコール類との反応を行う際、使用した多価アル
コールの種類及び仕込み比率によって、未反応のカルボ
キシル基、水酸基及びこれら官能基を複数持つアルケニ
ルコハク酸誘導体が合成される。したがってこれら反応
生成物に、一価アルコール類や一級カルボン酸類を単独
又は２種以上併用して、さらにエステル化反応を行った
アルケニルコハク酸誘導体を合成することができ、本発
明ではこれも使用できる。その一価アルコール類として
は上記一般式Ｒ6 ＯＨで表されるもの、その具体的例示
物はそのまま適用できる。また、その一級カルボン酸類
としては上記一般式Ｒ7 ＣＯＯＨで表されるもの、その
例示物はそのまま使用できる。In the present invention, the reaction product of at least one of alkenylsuccinic anhydride and alkenylsuccinic acid with a polyhydric alcohol is an ester derivative produced by an addition reaction and / or a dehydration reaction of these substances. Is. The polyhydric alcohols may be used alone or in combination of two or more kinds, but after mixing with at least one of alkenylsuccinic anhydride and alkenylsuccinic acid, or while dropping the other component into one component, the temperature may range from room temperature to 250 ° C. Any method in which the reaction is carried out at about C for about 30 minutes to 24 hours may be used. As the polyhydric alcohol, those described above for the polyhydric alcohol can be applied. When carrying out the reaction of at least one of the above-mentioned alkenyl succinic anhydride and alkenyl succinic acid with polyhydric alcohols, unreacted carboxyl group, hydroxyl group and these functional groups are changed depending on the type of polyhydric alcohol used and the charging ratio. A plurality of alkenyl succinic acid derivatives are synthesized. Therefore, these reaction products can be used alone or in combination of two or more kinds of monohydric alcohols and primary carboxylic acids to synthesize an alkenylsuccinic acid derivative which has been subjected to an esterification reaction, which can also be used in the present invention. . As the monohydric alcohols, those represented by the above general formula R 6 OH, and specific examples thereof can be applied as they are. As the primary carboxylic acids, those represented by the above general formula R 7 COOH, and the exemplified products can be used as they are.
【００１９】本発明における（Ｂ）成分のロジン系物質
とは、ガムロジン、トール油ロジン、ウッドロジン及び
これらロジンの変性物であり、これらは単独あるいは２
種以上の混合物として用いられる。このロジンの変性物
としては、一部あるいは実質的に完全に水素化されたも
の、不均化されたもの、重合化されたもの、あるいはホ
ルムアルデヒドで変性されたものなどが挙げられる。ま
た、これらロジン系物質に、α，β─不飽和カルボン酸
を付加反応した強化ロジンもロジン系物質に含まれる。
ここで用いられるα，β─不飽和カルボン酸の代表的な
ものは、フマル酸、マレイン酸、無水マレイン酸、イタ
コン酸、無水イタコン酸、シトラコン酸、無水シトラコ
ン酸等の不飽和二塩基酸、アクリル酸、メタクリル酸等
の不飽和一塩基酸等が挙げられ、これらは１種又は２種
以上併用して用いられる。さらにロジンとグリセリン、
ペンタエリスリトール等の多価アルコールとのエステ
ル、ロジンとエポキシ化合物との反応生成物も上記ロジ
ン系物質に包含される。The rosin-based substance as the component (B) in the present invention is gum rosin, tall oil rosin, wood rosin and modified products of these rosins, which may be used alone or in combination with 2
Used as a mixture of two or more species. Examples of the modified rosin include a partially or substantially completely hydrogenated product, a disproportionated product, a polymerized product, and a formaldehyde-modified product. Further, the rosin-based substance also includes a reinforced rosin obtained by addition-reacting an α, β-unsaturated carboxylic acid with these rosin-based substances.
Typical examples of the α, β-unsaturated carboxylic acid used here are unsaturated dibasic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride. Examples thereof include unsaturated monobasic acids such as acrylic acid and methacrylic acid, and these may be used alone or in combination of two or more. Furthermore, rosin and glycerin,
Esters of polyhydric alcohols such as pentaerythritol and reaction products of rosin and epoxy compounds are also included in the rosin-based substance.
【００２０】本発明における（Ｃ）成分の分散剤は、乳
化分散剤及び／又は保護コロイドからなるものであり、
特に限定されるものではないが、各種低分子界面活性
剤、高分子系乳化分散剤の少なくとも１種の乳化分散
剤、カゼイン、レシチン、ポリビニルアルコール、変性
澱粉などの保護コロイドが使用でき、これらは単独ある
いは２種以上組合わせて使用しても良い。各種低分子界
面活性剤としては、ロジンのアルカリ金属塩、強化ロジ
ンのアルカリ金属塩、アルキルベンゼンスルホン酸塩、
ポリオキシエチレンアルキルエーテル硫酸エステル塩、
ポリオキシエチレンアルキルフェニルエーテル硫酸エス
テル塩、ポリオキシエチレンモノ及びジスチリルフェニ
ルエーテル硫酸エステル塩、アルキル硫酸エステル塩、
アルキルナフタレンスルホン酸塩、ナフタレンスルホン
酸塩ホルムアルデヒド縮合物、ポリオキシエチレンアル
キルエーテルスルホコハク酸モノエステル塩、ポリオキ
シエチレンアルキルフェニルエーテルスルホコハク酸モ
ノエステル塩、ポリオキシエチレンモノ及びジスチリル
フェニルエーテルスルホコハク酸モノエステル塩、アル
キルフェノキシポリオキシエチレンプロピルスルホン酸
塩などのアニオン性界面活性剤、ポリオキシエチレンア
ルキルエーテル、ポリオキシエチレンアルキルフェニル
エーテル、ポリオキシエチレンモノ及びジスチリルフェ
ニルエーテル、ポリオキシプロピレンポリオキシエチレ
ングリコールグリセリン脂肪酸エステル、ソルビタン脂
肪酸エステル、ポリエチレングリコール脂肪酸エステ
ル、ポリオキシエチレンソルビタン脂肪酸エステル、シ
ヨ糖脂肪酸エステル、ペンタエリスリトール脂肪酸エス
テル、プロピレングリコール脂肪酸エステル、脂肪酸ジ
エタノールアミド、ポリオキシプロピレンポリオキシエ
チレングリコール等の非イオン性の界面活性剤、さらに
はテトラアルキルアンモニウムクロライド、トリアルキ
ルベンジルアンモニウムクロライド、アルキルアミン、
モノ及びポリオキシエチレンアルキルアミン等のカチオ
ン性界面活性剤を例示することができる。The dispersant of the component (C) in the present invention comprises an emulsifying dispersant and / or a protective colloid,
Although not particularly limited, various low-molecular-weight surfactants, at least one emulsifying dispersant of a polymeric emulsifying dispersant, protective colloids such as casein, lecithin, polyvinyl alcohol, and modified starch can be used. You may use it individually or in combination of 2 or more types. As various low-molecular-weight surfactants, alkali metal salts of rosin, alkali metal salts of reinforced rosin, alkylbenzene sulfonates,
Polyoxyethylene alkyl ether sulfate ester salt,
Polyoxyethylene alkyl phenyl ether sulfate ester salt, polyoxyethylene mono- and distyryl phenyl ether sulfate ester salt, alkyl sulfate ester salt,
Alkyl naphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, polyoxyethylene alkyl ether sulfosuccinic acid monoester salt, polyoxyethylene alkylphenyl ether sulfosuccinic acid monoester salt, polyoxyethylene mono and distyryl phenyl ether sulfosuccinic acid monoester Salts, anionic surfactants such as alkylphenoxy polyoxyethylene propyl sulfonate, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene mono- and distyryl phenyl ethers, polyoxypropylene polyoxyethylene glycol glycerin Fatty acid ester, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethyl ester Non-ionic surfactants such as sorbitan fatty acid ester, sucrose fatty acid ester, pentaerythritol fatty acid ester, propylene glycol fatty acid ester, fatty acid diethanolamide, polyoxypropylene polyoxyethylene glycol, and tetraalkylammonium chloride, trialkyl Benzyl ammonium chloride, alkylamine,
Examples include cationic surfactants such as mono- and polyoxyethylene alkylamines.
【００２１】また、高分子系乳化分散剤としては、特に
限定しないが基本的には疎水性基、非イオン性基及び／
又はイオン性基を持つ合成高分子あるいは一般の天然高
分子系乳化分散剤が使用でき、一例を挙げればアニオン
性スチレン─（メタ）アクリル酸系共重合体の部分ある
いは完全中和物、アニオン性あるいはカチオン性の（メ
タ）アクリル酸エステル系共重合体あるいは（メタ）ア
クリルアミド系共重合体、カチオン性のポリアミノポリ
アミド─エピクロルヒドリン樹脂、アルキレンポリアミ
ン─エピクロルヒドリン樹脂、ポリ（ジアリルアミン）
─エピクロルヒドリン樹脂等を例示することができる。
また、これらの高分子系乳化分散剤は保護コロイドとし
て単独あるいは２種以上を組み合わせて使用しても良
い。The polymeric emulsifying dispersant is not particularly limited, but basically, a hydrophobic group, a nonionic group and / or
Alternatively, a synthetic polymer having an ionic group or a general natural polymer-based emulsifying dispersant can be used. For example, a partially or completely neutralized product of anionic styrene- (meth) acrylic acid-based copolymer, anionic Alternatively, cationic (meth) acrylic acid ester-based copolymer or (meth) acrylamide-based copolymer, cationic polyaminopolyamide-epichlorohydrin resin, alkylenepolyamine-epichlorohydrin resin, poly (diallylamine)
—Epichlorohydrin resin and the like can be exemplified.
These polymeric emulsifying dispersants may be used alone or in combination of two or more as a protective colloid.
【００２２】本発明のエマルション組成物は、前記
（Ａ）、（Ｂ）、（Ｃ）成分からなり、（Ｂ）成分のロ
ジン系物質を５０〜９８重量部、（Ａ）成分のアルケニ
ルコハク酸誘導体を１〜４９重量部、より好ましくは２
〜２０重量部及び（Ｃ）成分の分散剤を１〜２０重量
部、より好ましくは３〜１０重量部含有することが好ま
しい。（Ａ）成分が１重量部未満ではサイズ性能などに
及ぼす効果が上記範囲のものよりは低下し、また、５０
重量部以上ではサイズ性能などへの影響が頭打ちになる
傾向が見られ、経済的には好ましくない。また、（Ｃ）
成分が１重量部より少ないと、（Ｂ）成分のロジン系物
質と（Ａ）成分のアルケニルコハク酸誘導体との混合物
を乳化分散させる作用及び貯蔵安定性が上記範囲のもの
より低下し、２０重量部より多くしても乳化分散作用が
格別に良くなることはなく、またサイズ性能及び発泡性
の点でも上記範囲のものよりは良くなることはない。The emulsion composition of the present invention comprises the above-mentioned components (A), (B) and (C), 50 to 98 parts by weight of the rosin substance as the component (B), and alkenylsuccinic acid as the component (A). 1 to 49 parts by weight of the derivative, more preferably 2
˜20 parts by weight and 1 to 20 parts by weight, more preferably 3 to 10 parts by weight of the component (C) dispersant. When the amount of the component (A) is less than 1 part by weight, the effect on the size performance and the like is lower than that in the above range, and 50
When the amount is more than the weight part, the influence on the size performance tends to reach a peak, which is economically unfavorable. Also, (C)
If the amount of the component is less than 1 part by weight, the action of emulsifying and dispersing the mixture of the rosin-based substance of the component (B) and the alkenylsuccinic acid derivative of the component (A) and the storage stability are lower than those in the above range, and 20 parts by weight Even if the amount is larger than the above range, the emulsifying and dispersing action is not particularly improved, and the size performance and foamability are not better than those in the above range.
【００２３】（Ａ）成分をエマルション固形分中に上記
含有量含める方法としては、特に限定されないが、
（Ａ）成分１〜４９重量部と（Ｂ）成分、好ましくは
α，β─不飽和カルボン酸により強化したロジン系物質
９８〜５０重量部を熔融混合した後、（Ｃ）成分の分散
剤で水中に乳化分散するか、（Ｂ）成分、好ましくは
α，β─不飽和カルボン酸により強化したロジン系物質
を（Ｃ）成分で乳化分散させたものと、（Ａ）成分を
（Ｃ）成分で乳化分散させたものを混合するか、いずれ
の方法で行うこともできる。前者はサイズ性能の点で好
ましい。乳化分散後のエマルションの全固形分は２０〜
６０重量％が好ましく、より好ましく３０〜５０重量％
である。There are no particular restrictions on the method of incorporating the above-mentioned content of the component (A) into the emulsion solids,
After 1 to 49 parts by weight of the component (A) and 98 to 50 parts by weight of the rosin-based substance fortified with the component (B), preferably α, β-unsaturated carboxylic acid, are melt-mixed, and then the dispersant of the component (C) is used. A dispersion obtained by emulsifying and dispersing in water or a component (B), preferably a rosin-based substance fortified with an α, β-unsaturated carboxylic acid, which is dispersed in the component (C), and a component (A) in the component (C). It is also possible to mix or emulsify and disperse the mixture, or to carry out by any method. The former is preferable in terms of size performance. The total solid content of the emulsion after emulsification and dispersion is 20 to
60% by weight is preferred, more preferably 30-50% by weight
Is.
【００２４】本発明のロジン系エマルション組成物の製
造法は、特に限定されるものではないが、例えば特公昭
５４─３６２４２号公報に記載されている方法に準じ
て、（Ｂ）及び（Ａ）成分を溶剤に溶かし、（Ｃ）成分
を添加した後ホモジナイザーを通して水中油型エマルシ
ョンを製造する方法（溶剤法）、特開昭５４─７７２０
９号公報に記載されている方法に準じて、熔融した
（Ｂ）成分に（Ａ）成分を混合し、この混合物に（Ｃ）
成分を混合して油中水型エマルジョンを形成し、反転水
を添加し水中油型エマルジョンに相転移させる方法（転
相法）、特公昭５３─３２３８０号公報に記載されてい
る方法に準じて、（Ａ）、（Ｂ）成分を熔融混合し、さ
らに（Ｃ）成分を混合した後、高圧下でホモジナイザー
を通して水中油型エマルジョンを製造する方法（メカニ
カル法）等が用いられる。The method for producing the rosin emulsion composition of the present invention is not particularly limited, but, for example, according to the method described in JP-B-54-36242, (B) and (A). A method of dissolving the components in a solvent, adding the component (C), and then producing an oil-in-water emulsion through a homogenizer (solvent method), JP-A-54-7720.
According to the method described in Japanese Patent Publication No. 9, the component (A) is mixed with the melted component (B), and the mixture (C) is added to the mixture.
A method of mixing the components to form a water-in-oil emulsion and adding inversion water to cause a phase transition to an oil-in-water emulsion (phase inversion method) according to the method described in JP-B-53-32380. , (A) and (B) are melt-mixed, and further (C) is mixed, and then an oil-in-water emulsion is produced through a homogenizer under high pressure (mechanical method).
【００２５】かくして得られたロジン系エマルション組
成物は、サイズ剤として用いると、保存安定性及び機械
的安定性に優れており、高速抄紙機で比較的温和な乾燥
条件下、すなわち湿紙に付与する熱量が比較的少ない、
例えばヤンキードライヤーを有する抄紙機あるいは超高
速の新聞用紙用抄紙機の場合に特に酸性ないし中性抄紙
系（ｐＨ４〜８）で従来のサイズ剤に比べて紙に付与す
るサイズ性能が優れているばかりでなく、弱サイズ度か
ら強サイズ度までの調節が可能であるという利点を有し
ている。また、本発明のサイズ剤は、プレスロール、ド
ライヤーキャンバスなどの抄紙用具の汚れが少ないこと
等の特徴がある。The rosin emulsion composition thus obtained, when used as a sizing agent, has excellent storage stability and mechanical stability, and is applied to a wet paper under relatively mild drying conditions on a high-speed paper machine. Relatively less heat
For example, in the case of a paper machine having a Yankee dryer or a paper machine for ultra-high speed newsprint, especially in an acidic or neutral paper making system (pH 4 to 8), the size performance imparted to paper is superior to that of the conventional size. In addition, it has an advantage that it can be adjusted from weak size to strong size. Further, the sizing agent of the present invention is characterized in that a papermaking tool such as a press roll or a dryer canvas is less contaminated.
【００２６】本発明のサイジング方法は、本発明のロジ
ン径エマルション組成物を含有するサイズ剤を、紙や板
紙の製造工程において、例えばウェット・エンド部に添
加することにより実施される。具体的には、本発明のサ
イズ剤をパルプの水性分散液にその乾燥重量に対して
０．０１〜５固形分重量％、好ましくは０．０５〜２固
形分重量％添加する。また、（Ａ）成分を（Ｃ）成分で
乳化分散させたものと、（Ｂ）成分を（Ｃ）成分で乳化
分散させたものを別々にパルプスラリーに添加すること
もできるが、本発明のサイズ剤を用いる方がサイズ効果
も良いし、取扱いも容易である。The sizing method of the present invention is carried out by adding a sizing agent containing the rosin diameter emulsion composition of the present invention to, for example, the wet end portion in the process of producing paper or paperboard. Specifically, the sizing agent of the present invention is added to an aqueous dispersion of pulp in an amount of 0.01 to 5% by solid weight, preferably 0.05 to 2% by solid weight, based on its dry weight. Further, it is also possible to separately add a component obtained by emulsifying and dispersing the component (A) with the component (C) and a component obtained by emulsifying and dispersing the component (B) with the component (C) to the pulp slurry. The use of a sizing agent has a better sizing effect and is easier to handle.
【００２７】本発明のサイズされた紙は、本発明のサイ
ズ剤を硫酸バン土の多い抄紙系で使用して得られたサイ
ズ紙において優れたサイズ効果を発揮し、さらに 硫
酸バン土を使用できないか、その使用量が少量に限定さ
れる抄紙系、例えは中性純白ロール紙、中性ライナー、
防錆ライナー及び金属合紙、 古紙原料から炭酸カル
シウムが混入する抄紙系，例えば石膏ボード原紙、白
板、コート原紙、中性紙、一般ライナー及び中芯、
填料として炭酸カルシウムを使用する抄紙系、例えば中
性印刷筆記用紙、中性コート原紙、中性ＰＰＣ用紙、中
性感熱原紙、中性感圧原紙、中性インクジェット用紙及
び中性情報用紙、 定着剤の使用量が限定される抄紙
系、例えばクラフト紙などにおいて本発明のサイズ剤を
用いて得られ、従来のロジン系サイズ剤にはない優れた
サイズ性能を発揮する。The sized paper of the present invention exhibits excellent sizing effect in sizing paper obtained by using the sizing agent of the present invention in a papermaking system rich in sulphate sulphate, and further sulphate of sulphate cannot be used. Or papermaking system whose usage is limited to a small amount, such as neutral pure white roll paper, neutral liner,
Anticorrosion liner and metal interleaving paper, papermaking system in which calcium carbonate is mixed from used paper materials, such as gypsum board base paper, white board, coated base paper, neutral paper, general liner and core,
Paper-making systems that use calcium carbonate as a filler, such as neutral printing writing paper, neutral coated base paper, neutral PPC paper, neutral thermosensitive base paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, and fixing agent It is obtained by using the sizing agent of the present invention in a paper-making system whose amount used is limited, for example, kraft paper, and exhibits excellent sizing performance not found in conventional rosin-based sizing agents.
【００２８】上記サイジング方法、サイズ剤は、表面サ
イジング方法、表面サイズ剤としても使用可能であり、
この場合、抄紙された湿紙に噴霧、浸漬、塗布などの慣
用的方法が適用される。The above sizing method and sizing agent can also be used as a surface sizing method and surface sizing agent.
In this case, a conventional method such as spraying, dipping, coating or the like is applied to the wet paper thus made.
【００２９】本発明のサイズされた紙は、少なくとも
（Ａ）成分と、（Ｂ）成分を含有し、さらに（Ｃ）成分
を含有しても良いが、その含有量は紙の種類により異な
るが、０．０１〜５固形重量％の範囲が挙げられる。そ
れぞれの成分は分析することにより特定される。その分
析法としては例えば熱分解ＧＣ−ＭＳ（ガスクロマトグ
ラフィー質量分析）が挙げられる。The sized paper of the present invention contains at least the component (A), the component (B), and may further contain the component (C), but the content varies depending on the type of paper. , And a range of 0.01 to 5% by solid weight. Each component is identified by analysis. Examples of the analysis method include thermal decomposition GC-MS (gas chromatography mass spectrometry).
【００３０】紙あるいは板紙を製造するに当たって、パ
ルプ原料としては、クラフトパルプあるいはサルファイ
トパルプなどの晒あるいは未晒化学パルプ、砕木パル
プ、機械パルプあるいはサーモメカニカルパルプなどの
晒あるいは未晒高収率パルプ、新聞古紙、雑誌古紙、段
ボール古紙あるいは脱墨古紙などの古紙パルプのいずれ
も使用することができる。また、上記パルプ原料と石綿
などの無機物繊維、あるいはポリアミド、ポリイミド、
ポリエステル、ポリオレフィン、ポリビニルアルコール
等の合成繊維との混合物も使用することができる。In the production of paper or paperboard, pulp raw materials are bleached or unbleached pulp such as bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp or thermomechanical pulp. Any of used pulp such as used newspaper, used magazine, used corrugated cardboard or deinked used paper can be used. Further, the pulp material and inorganic fibers such as asbestos, or polyamide, polyimide,
Mixtures with synthetic fibers such as polyesters, polyolefins, polyvinyl alcohol and the like can also be used.
【００３１】填料、染料、乾燥紙力向上剤、湿潤紙力向
上剤、歩留り向上剤、濾水性向上剤などの添加物も、各
々紙種に要求される物性を発現するために、必要に応じ
て使用しても良い。填料としては、クレー、タルク、重
質又は軽質炭酸カルシウム等が挙げられ、これらは単独
で用いても良く、併用しても良い。 乾燥紙力向上剤と
しては、アニオン性ポリアクリルアミド、カチオン性ポ
リアクリルアミド、両性ポリアクリルアミド、カチオン
化澱粉等が挙げられ、これらは単独で用いてもよく、併
用しても良い。湿潤紙力向上剤としては、ポリアミド・
エピクロルヒドリン樹脂、メラミン・ホルムアルデヒド
樹脂、尿素・ホルムアルデヒド樹脂等が挙げられ、これ
らは単独で用いてもよく、アニオン性ポリアクリルアミ
ドと併用しても良い。歩留り向上剤としては、アニオン
性又はカチオン性高分子量ポリアクリルアミド、シリカ
ゾルとカチオン化澱粉の併用、ベントナイトとカチオン
性高分子量ポリアクリルアミドの併用等が挙げられる。
濾水性向上剤としては、ポリエチレンイミン、カチオン
性又はアニオン性ポリアクリルアミド等が挙げられる。
また、サイズプレス、ゲートロールコーター、ビルブレ
ードコーター、キャレンダーなどで、澱粉、ポリビニル
アルコール、染料、コーテイングカラー、表面サイズ
剤、防滑剤などを必要に応じて塗布しても良い。また、
硫酸バン土は本発明のサイズ剤を添加する前、添加した
後、あるいは同時に添加して使用しても良い。Additives such as a filler, a dye, a dry paper strength improver, a wet paper strength improver, a retention improver, and a drainage improver may be used as necessary in order to express the physical properties required for each paper type. You may use it. Examples of the filler include clay, talc, heavy or light calcium carbonate, etc. These may be used alone or in combination. Examples of the dry paper strength improver include anionic polyacrylamide, cationic polyacrylamide, amphoteric polyacrylamide, and cationized starch, which may be used alone or in combination. Wet paper strength improvers include polyamide
Examples thereof include epichlorohydrin resin, melamine / formaldehyde resin, urea / formaldehyde resin, which may be used alone or in combination with anionic polyacrylamide. Examples of the yield improver include anionic or cationic high molecular weight polyacrylamide, a combination of silica sol and cationized starch, a combination of bentonite and cationic high molecular weight polyacrylamide, and the like.
Examples of the drainage improving agent include polyethyleneimine, cationic or anionic polyacrylamide, and the like.
If necessary, starch, polyvinyl alcohol, dye, coating color, surface sizing agent, anti-slip agent, etc. may be applied with a size press, gate roll coater, bill blade coater, calender or the like. Also,
Bansulfate may be used before, after, or simultaneously with the addition of the sizing agent of the present invention.
【００３２】[0032]
【実施例】以下、上記（Ａ）、（Ｂ）、（Ｃ）成分の製
造例、これを用いた実施例及び比較例を挙げて本発明を
より具体的に説明するが、本発明はこれらの例に限定さ
れるものではない。なお、各例中、部及び％は特記しな
いかぎりすべて重量基準である。EXAMPLES The present invention will be described in more detail below with reference to production examples of the above components (A), (B) and (C), and examples and comparative examples using the same. It is not limited to the example of. In the examples, parts and% are based on weight unless otherwise specified.
【００３３】 アルケニルコハク酸誘導体の製造 −１ ドデセニルコハク酸無水物─ステアリルアミン
反応物（Ａ−１） 約１００℃のドデセニルコハク酸無水物（三洋化成工業
（株）製商品名ＤＤＳＡ）５１．４部にステアリルアミ
ン５２．１部を滴下し、滴下後徐々に１５０℃まで昇温
した。１５０℃で５時間反応を行い、生成する水（３．
５部）を留去してアルケニルコハク酸誘導体であるイミ
ド化合物のドデセニルコハク酸無水物─ステアリルアミ
ン反応物（Ａ−１）１００部を得た。 −２ ドデセニルコハク酸無水物─ジエチルアミン反
応物（Ａ−２） 約１００℃のドデセニルコハク酸無水物（三洋化成工業
（株）製商品名ＤＤＳＡ）７８．４部にジエチルアミン
２１．６部を滴下し、滴下後徐々に１５０℃まで昇温し
た。１５０℃で１時間反応を行い、アルケニルコハク酸
モノアミド化合物であるドデセニルコハク酸無水物─ジ
エチルアミン反応物（Ａ−２）１００部を得た。Production of Alkenyl Succinic Acid Derivative -1 Dodecenyl succinic anhydride-stearyl amine reaction product (A-1) 51.4 parts of dodecenyl succinic anhydride (trade name DDSA manufactured by Sanyo Kasei Co., Ltd.) at about 100 ° C 52.1 parts of stearylamine was added dropwise, and after the addition, the temperature was gradually raised to 150 ° C. The reaction is carried out at 150 ° C. for 5 hours to produce water (3.
(5 parts) was distilled off to obtain 100 parts of a dodecenylsuccinic anhydride-stearylamine reaction product (A-1) of an imide compound which is an alkenylsuccinic acid derivative. -2 Dodecenyl succinic anhydride-diethylamine reaction product (A-2) 21.6 parts of diethylamine was added dropwise to 78.4 parts of dodecenyl succinic anhydride (trade name DDSA manufactured by Sanyo Chemical Industry Co., Ltd.) at about 100 ° C. After that, the temperature was gradually raised to 150 ° C. The reaction was carried out at 150 ° C for 1 hour to obtain 100 parts of a dodecenylsuccinic anhydride-diethylamine reaction product (A-2) which was an alkenylsuccinic acid monoamide compound.
【００３４】−３ ペンタデセニルコハク酸無水物−
ジエチレントリアミン反応物（Ａ−３） ドデセニルコハク酸無水物、エチレンジアミンの代わり
に、ペンタデセニルコハク酸無水物（三洋化成工業
（株）製商品名ＰＤＳＡ−ＤＡ）９３．５部、ジエチレ
ントリアミン１０部を使用し、上記−１の製造例と同
様に反応を行った。留去した水は３．５部で、アルケニ
ルコハク酸誘導体のペンタデセニルコハク酸無水物−ジ
エチレントリアミン反応物（Ａ−３）１００部が得ら
れ、このものは酸価５５を有する、アルケニルコハク酸
のモノアミド及びイミド誘導体であった。 −４ ドデセニルコハク酸無水物−エチレンジアミン
反応物（Ａ−４） 約１００℃のドデセニルコハク酸無水物（三洋化成工業
（株）製商品名ＤＤＳＡ）９５．７部にエチレンジアミ
ン１０．８部を滴下し、滴下後徐々に１５０℃まで昇温
した。１５０℃で５時間反応を行い、生成する水（６．
５部）を留去してアルケニルコハク酸誘導体であるイミ
ド化合物のドデセニルコハク酸無水物─エチレンジアミ
ン反応物（Ａ−４）１００部を得た。 −５ ドデセニルコハク酸無水物−モノイソプロパノ
ールアミン反応物（Ａ−５） 約１００℃のドデセニルコハク酸無水物（三洋化成工業
（株）製商品名ＤＤＳＡ）９０．３部にモノイソプロパ
ノールアミン１２．７部を滴下し、滴下後徐々に１５０
℃まで昇温した。１５０℃で５時間反応を行い、生成す
る水（３部）を留去してアルケニルコハク酸誘導体であ
るドデセニルコハク酸無水物─モノイソプロパノールア
ミン反応物（Ａ−５）１００部を得た。-3 Pentadecenylsuccinic anhydride-
Diethylenetriamine reaction product (A-3) 93.5 parts of pentadecenylsuccinic anhydride (trade name PDSA-DA manufactured by Sanyo Kasei Co., Ltd.) and 10 parts of diethylenetriamine were used in place of dodecenylsuccinic anhydride and ethylenediamine. Then, the reaction was carried out in the same manner as in the production example of -1 above. The distilled water was 3.5 parts, and 100 parts of pentadecenyl succinic anhydride-diethylenetriamine reaction product (A-3) of the alkenyl succinic acid derivative was obtained, which has an acid value of 55. It was a monoamide and imide derivative of the acid. -4 Dodecenyl succinic anhydride-ethylenediamine reaction product (A-4) 10.8 parts of ethylenediamine was added dropwise to 95.7 parts of dodecenyl succinic anhydride (trade name DDSA manufactured by Sanyo Chemical Industry Co., Ltd.) at about 100 ° C. After that, the temperature was gradually raised to 150 ° C. The reaction is carried out at 150 ° C. for 5 hours to produce water (6.
5 parts) was distilled off to obtain 100 parts of a dodecenylsuccinic anhydride-ethylenediamine reaction product (A-4) of an imide compound which is an alkenylsuccinic acid derivative. -5 Dodecenyl succinic anhydride-monoisopropanolamine reaction product (A-5) Dodecenyl succinic anhydride (Sanyo Kasei Kogyo KK, trade name DDSA) 90.3 parts at about 100 ° C. and 12.7 parts monoisopropanolamine. Drop, and gradually after dropping 150
The temperature was raised to ° C. The reaction was carried out at 150 ° C. for 5 hours, and the produced water (3 parts) was distilled off to obtain 100 parts of a dodecenylsuccinic anhydride-monoisopropanolamine reaction product (A-5) which is an alkenylsuccinic acid derivative.
【００３５】−６ ドデセニルコハク酸無水物−ジエ
チルアミン−オレイルアルコール反応物（Ａ−６） 上記−２により得られたドデセニルコハク酸無水物─
ジエチルアミン反応物（Ａ−２）５７．５部にオレイル
アルコール４５．５部を加え、１８０℃で６時間脱水反
応を行い（留出した水は３部であった）、この（Ａ−
２）のエステル化物であるドデセニルコハク酸無水物−
ジエチルアミン−オレイルアルコール反応物（Ａ−６）
１００部を得た。-6 Dodecenyl succinic anhydride-diethylamine-oleyl alcohol reaction product (A-6) Dodecenyl succinic anhydride obtained by the above-mentioned -2
Oleyl alcohol (45.5 parts) was added to diethylamine reaction product (A-2) (57.5 parts), and dehydration reaction was performed at 180 ° C. for 6 hours (distilled water was 3 parts).
Dodecenyl succinic anhydride which is an esterified product of 2)-
Diethylamine-oleyl alcohol reaction product (A-6)
100 parts were obtained.
【００３６】−７ ペンタデセニルコハク酸無水物−
ジエチレントリアミン−ビスフェノールＡ反応物（Ａ−
７） 上記−３により得られたペンタデセニルコハク酸無水
物−ジエチレントリアミン反応物（Ａ−３）９１．６部
にビスフェノールＡ１０部を加え、２００℃で１２時間
脱水反応を行い（留出した水は１．６部であった）、こ
の（Ａ−３）のエステル化物であるペンタデセニルコハ
ク酸無水物−ジエチレントリアミン−ビスフェノールＡ
反応物（Ａ−７）１００部を得た。 −８ ペンタデセニルコハク酸無水物−ジエチレント
リアミン−グリセリン反応物（Ａ−８） 上記−３により得られたペンタデセニルコハク酸無水
物−ジエチレントリアミン反応物（Ａ−３）９８．８部
にグリセリン３部を加え、２００℃で１２時間脱水反応
を行い（留去した水は１．８部あった）、この（Ａ−
３）のエステル化物であるペンタデセニルコハク酸無水
物−ジエチレントリアミン−グリセリン反応物（Ａ−
８）１００部を得た。-7 Pentadecenylsuccinic anhydride-
Diethylenetriamine-bisphenol A reaction product (A-
7) 10 parts of bisphenol A was added to 91.6 parts of the pentadecenylsuccinic anhydride-diethylenetriamine reaction product (A-3) obtained in -3 above, and dehydration reaction was carried out at 200 ° C for 12 hours (distillation). Water was 1.6 parts), and pentadecenylsuccinic anhydride-diethylenetriamine-bisphenol A which is an esterified product of (A-3).
100 parts of the reaction product (A-7) was obtained. -8 Pentadecenylsuccinic anhydride-diethylenetriamine-glycerin reaction product (A-8) In 98.8 parts of pentadecenylsuccinic anhydride-diethylenetriamine reaction product (A-3) obtained in -3 above. Glycerin (3 parts) was added, and dehydration reaction was performed at 200 ° C. for 12 hours (the amount of distilled water was 1.8 parts).
Pentadecenyl succinic anhydride-diethylenetriamine-glycerin reaction product (A-
8) 100 parts were obtained.
【００３７】−９ オクタデセニルコハク酸無水物−
ロジンアルコール反応物（Ａ−９） 約１５０℃のオクタデセニルコハク酸無水物（Ｄｉｘｉ
ｅ Ｃｈｅｍ．社製商品名ＯＤＳＡ）５０部にロジンア
ルコール（理化ハーキュレス社製商品名アビトール）５
０部を加え、１５０℃で６時間反応を行い、アルケニル
コハク酸モノエステル化物（Ａ−９）１００を得た。 −１０ オクテニルコハク酸無水物−エチルヘキシル
アルコール反応物（Ａ−１０） 約１５０℃のオクテニルコハク酸無水物（Ｄｉｘｉｅ
Ｃｈｅｍ．社製商品名ＯＤＳＡ）６２部にエチルヘキシ
ルアルコール３８部を加え、１５０℃で６時間反応を行
い、アルケニルコハク酸モノエステル化合物であるオク
テニルコハク酸無水物−エチルヘキシルアルコール反応
物（Ａ−１０）１００部を得た。 −１１ オクタデセニルコハク酸無水物−エチルヘキ
シルアルコール−ビスフェノールＡ反応物（Ａ−１１） 上記−１０に従い、オクタデセニルコハク酸無水物６
０．７部とエチルヘキシルアルコール２２．６部から、
アルケニルコハク酸モノエステル誘導体８３．３部を得
た。このものに、さらにビスフェノールＡ１９．８部を
加え、２００℃で８時間脱水反応を行い（留出した水は
３．１部であった）、オクタデセニルコハク酸無水物−
エチルヘキシルアルコール−ビスフェノールＡ反応物
（Ａ−１１）１００部を得た。-9 Octadecenyl succinic anhydride-
Rosin alcohol reaction product (A-9) Octadecenyl succinic anhydride (Dixi) at about 150 ° C.
e Chem. Rosin alcohol (product name: Abitol, manufactured by Rika Hercules Co., Ltd.) in 50 parts of product name: ODSA manufactured by the company
0 part was added and the reaction was carried out at 150 ° C. for 6 hours to obtain an alkenylsuccinic acid monoester product (A-9) 100. -10 Octenyl succinic anhydride-ethylhexyl alcohol reaction product (A-10) Octenyl succinic anhydride (Dixie) at about 150 ° C.
Chem. 38 parts of ethylhexyl alcohol was added to 62 parts of trade name ODSA manufactured by the company, and the reaction was carried out at 150 ° C. for 6 hours to obtain 100 parts of octenylsuccinic anhydride-ethylhexyl alcohol reaction product (A-10) which was an alkenylsuccinic acid monoester compound. Obtained. -11 Octadecenyl succinic anhydride-Ethylhexyl alcohol-Bisphenol A reaction product (A-11) According to the above-mentioned -10, octadecenyl succinic anhydride 6
From 0.7 parts and 22.6 parts of ethylhexyl alcohol,
83.3 parts of alkenyl succinic acid monoester derivative were obtained. To this product, 19.8 parts of bisphenol A was further added, and dehydration reaction was carried out at 200 ° C. for 8 hours (distilled water was 3.1 parts) to obtain octadecenyl succinic anhydride-
100 parts of an ethylhexyl alcohol-bisphenol A reaction product (A-11) was obtained.
【００３８】−１２ ペンタデセニルコハク酸無水物
−エチレングリコール反応物（Ａ−１２） 約１５０℃のペンタデセニルコハク酸無水物（三洋化成
工業（株）製商品名ＰＤＳＡ−ＤＡ）９２．１部にエチ
レングリコール８．８部を加え、１５０℃で６時間反応
を行い、ペンタデセニルコハク酸無水物−エチレングリ
コール反応物（Ａ−１２）１００部を得た。 −１３ ペンタデセニルコハク酸無水物−エチレング
リコール−ステアリン酸反応物（Ａ−１３） 上記−１２により得られたペンタデセニルコハク酸無
水物−エチレングリコール反応物（Ａ−１２）５７．０
部にステアリン酸４５．９部を加え、２００℃で８時間
脱水反応を行い（留出した水は２．９部であった）、こ
の（Ａ−１２）のエステル化物であるペンタデセニルコ
ハク酸無水物−エチレングリコール−ステアリン酸反応
物（Ａ−１３）１００部を得た。-12 Pentadecenylsuccinic anhydride-Ethylene glycol reaction product (A-12) Pentadecenylsuccinic anhydride at about 150 ° C (trade name PDSA-DA manufactured by Sanyo Kasei Co., Ltd.) 92 Ethylene glycol 8.8 parts was added to 0.1 part and reacted at 150 ° C. for 6 hours to obtain 100 parts of pentadecenylsuccinic anhydride-ethylene glycol reaction product (A-12). -13 Pentadecenyl succinic anhydride-ethylene glycol-stearic acid reaction product (A-13) Pentadecenyl succinic anhydride-ethylene glycol reaction product (A-12) 57. 0
45.9 parts of stearic acid was added to 10 parts, and dehydration reaction was carried out at 200 ° C. for 8 hours (the distilled water was 2.9 parts), and pentadecenyl which was an esterified product of (A-12). 100 parts of a succinic anhydride-ethylene glycol-stearic acid reaction product (A-13) was obtained.
【００３９】 ロジン系物質（Ｂ）の製造 −１ フマル酸強化ロジンの製造 約２００℃で熔融状態にあるガムロジン４５０部にフマ
ル酸８０部を徐々に加えていき、ほとんど全部のフマル
酸が反応し終わった後、さらにホルムアルドヒド処理
（変性率３％）トール油ロジンを４７０部加え、熔融撹
拌して均質化し、その後に反応生成物を室温に冷却し
た。この反応生成物（強化ロジン）はロジンにフマル酸
が８％付加されたものであった。Production of rosin-based substance (B) -1 Production of fumaric acid fortified rosin 80 parts of fumaric acid was gradually added to 450 parts of gum rosin in a molten state at about 200 ° C., and almost all fumaric acid reacted. After the completion, 470 parts of tall oil rosin treated with formaldehyde (modification rate 3%) was added, and the mixture was melted and stirred for homogenization, after which the reaction product was cooled to room temperature. The reaction product (toughened rosin) was 8% fumaric acid added to rosin.
【００４０】 高分子系乳化分散剤の製造 以下のようにして、ロジン系物質を分散安定化するため
の実施例用高分子系乳化分散剤（Ｃ─１）及び（Ｃ−
２）を製造した。 ─１ 実施例用アニオン性高分子系分散剤（Ｃ─１）
の製造 特開昭６１─１０８７９６号公報の参考例１０の製造方
法に従い、以下のようにしてスチレン─メタクリル酸系
共重合体中和物（Ｃ─１）を製造した。スチレン５５
部、メタクリル酸３０部、イタコン酸５部、アクリル酸
ラウリル１０部、１０％ナフタレンスルホン酸ナトリウ
ムホルムアルデヒド縮合物５０部、過硫酸アンモニウム
１部及び水２００部を混合撹拌し、加圧下、１５０℃で
３０分間加熱した。ついで７０℃まで冷却し、４８．５
％水酸化ナトリウム３５．５部と水７部を徐々に滴下
し、３０分間撹拌した後室温まで冷却することにより、
固形分３０％のアニオン性ポリマー分散液（Ｃ─１）を
得た。Production of Polymer Emulsified Dispersant Polymer emulsified dispersants (C-1) and (C- for Examples for dispersing and stabilizing a rosin-based substance are prepared as follows.
2) was produced. -1 Anionic Polymer Dispersant for Examples (C-1)
Manufacture of a styrene-methacrylic acid copolymer neutralized product (C-1) was manufactured in the following manner according to the manufacturing method of Reference Example 10 of JP-A No. 61-108796. Styrene 55
Parts, methacrylic acid 30 parts, itaconic acid 5 parts, lauryl acrylate 10 parts, 10% sodium naphthalene sulphonate formaldehyde condensate 50 parts, ammonium persulfate 1 part and water 200 parts by mixing and stirring, and at 30 ° C. under pressure at 30 ° C. Heated for minutes. Then it was cooled to 70 ° C. and 48.5.
By gradually adding 35.5 parts of sodium hydroxide and 7 parts of water, stirring for 30 minutes, and then cooling to room temperature,
An anionic polymer dispersion liquid (C-1) having a solid content of 30% was obtained.
【００４１】─２ 実施例用カチオン系高分子系分散
剤（Ｃ─２）の製造 特開平２─１７７５３４号公報の実施例１に記載の疎水
性基を有するカチオン性ポリ（メタ）アクリルアミドの
製造方法に従い、以下のようにして高分子系分散剤（Ｃ
−２）を製造した。撹拌機、温度計、還流冷却器及び窒
素ガス導入管を備えた１リットル容の４つ口フラスコ
に、ジメチルアミノエチルメタクリレート３１．４部、
５０％アクリルアミド水溶液８５．３部、スチレン２
０．８部、イオン交換水１００．６部、イソプロピルア
ルコール１４３．３部、ｎ−ドデシルメルカプタン０．
６部を仕込み、２０％酢酸水溶液にてｐＨを４．５に調
節した。この混合液を撹拌しながら窒素ガス雰囲気下
で、６０℃まで昇温した。重合開始剤として５％過硫酸
アンモニウム水溶液を２．３部を加え、８０℃まで昇温
し、１．５時間保持した後、過硫酸アンモニウムの５％
水溶液０．７部を追加した。さらに１時間同温度に保持
した後、イオン交換水１００部を加え、次いでイソプロ
ピルアルコールを留去し、さらにイオン交換水を加えて
固形分濃度２０．４％のカチオン性ポリマー分散液（Ｃ
─２）を製造した。-2 Production of Cationic Polymer Dispersant (C-2) for Examples Production of cationic poly (meth) acrylamide having a hydrophobic group described in Example 1 of JP-A-2-177534. According to the method, the polymeric dispersant (C
-2) was produced. A 1 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 31.4 parts of dimethylaminoethyl methacrylate.
85.3 parts of 50% acrylamide aqueous solution, styrene 2
0.8 parts, ion-exchanged water 100.6 parts, isopropyl alcohol 143.3 parts, n-dodecyl mercaptan 0.
6 parts were charged and the pH was adjusted to 4.5 with a 20% aqueous acetic acid solution. The temperature of this mixed solution was raised to 60 ° C. under a nitrogen gas atmosphere while stirring. 2.3 parts of 5% ammonium persulfate aqueous solution was added as a polymerization initiator, and the temperature was raised to 80 ° C. and kept for 1.5 hours.
0.7 part of the aqueous solution was added. After holding at the same temperature for 1 hour, 100 parts of ion-exchanged water was added, isopropyl alcohol was then distilled off, and ion-exchanged water was further added to the cationic polymer dispersion liquid having a solid content concentration of 20.4% (C
-2) was manufactured.
【００４２】 ロジン系エマルション組成物の製造 ─１ 実施例１〜１５ で得たフマル酸強化ロジンとで得たアルケニルコハ
ク酸誘導体を表１に示した割合で混合し、約１５０℃に
加熱溶融し、激しく撹拌しながら、で得た分散剤を同
表に記載のように添加混合して油中水型のエマルション
とした。これに熱水を徐々に加えて転相させ水中油型の
エマルションとし、これにさらに熱水を素早く添加して
安定な水中油型エマルションとした後、室温まで冷却し
た。かくして得られたエマルションの固形分は約４５〜
５０％であり、Ｍａｓｔｅｒ Ｓｉｚｅｒ（マルバーン
社製）で測定した重量基準粒径分布における累積５０％
径（以下、平均粒子径と称す）は０．２〜０．４μｍで
あり、長期間安定なものであった。Production of Rosin-Based Emulsion Composition -1 The fumaric acid-enhanced rosin obtained in Examples 1 to 15 and the alkenylsuccinic acid derivative obtained in Example 1 were mixed in the proportions shown in Table 1, and heated and melted at about 150 ° C. While stirring vigorously, the dispersant obtained in (4) was added and mixed as shown in the same table to give a water-in-oil emulsion. Hot water was gradually added to this to invert the phase to form an oil-in-water emulsion, and hot water was further quickly added to this to form a stable oil-in-water emulsion, which was then cooled to room temperature. The emulsion thus obtained has a solid content of about 45-
50%, cumulative 50% in weight-based particle size distribution measured by Master Sizer (Malvern)
The diameter (hereinafter referred to as the average particle diameter) was 0.2 to 0.4 μm, which was stable for a long period of time.
【００４３】─２ 比較例１、２ アルケニルコハク酸誘導体を使用せず、表１に示した組
成にした以外は上記実施例と同様の方法でロジン系エマ
ルション組成物（サイズ剤）を得た。上記実施例、比較
例のロジン系エマルション組成物の組成及び性状を表１
に示す。-2-Comparative Examples 1 and 2 A rosin emulsion composition (size) was obtained in the same manner as in the above Examples except that the alkenylsuccinic acid derivative was not used and the composition shown in Table 1 was used. Table 1 shows the composition and properties of the rosin emulsion compositions of the above Examples and Comparative Examples.
Shown in.
【００４４】[0044]
【表１】 [Table 1]
【００４５】以上の実施例及び比較例で得られたロジン
系エマルション組成物をサイズ剤として用いて下記の試
験条件でサイズ効果試験を行った結果を表２に示す。添
加薬品はすべてパルプ絶乾重量に対する固形分重量比で
示した。Table 2 shows the results of a size effect test conducted under the following test conditions using the rosin emulsion compositions obtained in the above Examples and Comparative Examples as a sizing agent. All the added chemicals are shown by the weight ratio of solid content to absolute dry weight of pulp.
【００４６】─１ サイズ効果試験１ 晒クラフトパルプ（針葉樹対広葉樹のパルプ比が１対４
である混合パルプ）のパルプ濃度を２．５％になるよう
に硬度１００ｐｐｍの希釈用水で希釈し、ビーターを用
いて３５０ｍｌのカナディアンスタンダードフリーネス
まで叩解した。このパルプスラリー１．２リットルを離
解機に秤取し、上記実施例、比較例のサイズ剤を表２に
示す量（０．３％あるいは０．４％）と１．５％の硫酸
バン土を同時に添加し、その後３０分間撹拌した。次い
でｐＨ４．５の希釈水でこのパルプスラリーを濃度０．
２５％まで希釈し、次いで定着剤としてカチオン性ポリ
アクリルアミド（日本ＰＭＣ（株）製紙力剤ＤＳ４１
０）を０．０５％添加し、ノーブルアンドウッド抄紙機
で抄紙ｐＨ４．５で抄紙し、坪量６５ｇ／ｍ2 の試験紙
を得た。湿紙の乾燥は、ドラムドライヤーを用いて所定
の乾燥条件で行った。得られた試験紙を恒温恒湿環境下
（２０℃、６５％相対湿度）で２４時間調湿した後、サ
イズ度をステキヒト法で測定した。その結果を表２に示
した。表中、乾燥条件のうち、８０℃、１００秒の条件
が「乾燥条件が比較的穏やかな場合」に相当する。-1 Size effect test 1 Bleached kraft pulp (pulp ratio of softwood to hardwood is 1: 4
Was mixed with water for dilution having a hardness of 100 ppm so as to have a pulp concentration of 2.5%, and beaten up to 350 ml of Canadian standard freeness using a beater. 1.2 liters of this pulp slurry was weighed in a disintegrator, and the sizing agents of the above Examples and Comparative Examples were added in the amounts shown in Table 2 (0.3% or 0.4%) and 1.5% vanadium sulfate. Were added simultaneously and then stirred for 30 minutes. The pulp slurry is then diluted to a concentration of 0.
Dilute to 25% and then use cationic polyacrylamide as a fixing agent (Paper Strength Agent DS41 manufactured by Nippon PMC Co., Ltd.)
0) was added in an amount of 0.05%, and the paper was made at a paper making pH of 4.5 with a Noble and Wood paper making machine to obtain a test paper having a basis weight of 65 g / m 2 . The wet paper web was dried under a predetermined drying condition using a drum dryer. The obtained test paper was conditioned under a constant temperature and constant humidity environment (20 ° C., 65% relative humidity) for 24 hours, and then the sizing degree was measured by the Steckit method. The results are shown in Table 2. In the table, among the drying conditions, the conditions of 80 ° C. and 100 seconds correspond to “when the drying conditions are relatively gentle”.
【００４７】[0047]
【表２】 [Table 2]
【００４８】─２ サイズ効果試験２ 前項の─１の試験と同一条件で叩解したパルプスラリ
ー１．２リットルを離解機に秤取し、上記実施例、比較
例のサイズ剤を表２に示す量（０．４％あるいは０．８
％）と１．０％の硫酸バン土及び定着剤として上記ＤＳ
４１０を０．２％添加し、その後１０分間撹拌した。次
いでｐＨ８の希釈水でこのパルプスラリーを濃度０．２
５％まで希釈し、軽質炭酸カルシウム（奥多摩工業
（株）製タマパール１２１Ｓ）を２％、及び歩留り剤と
して高分子量カチオン性ポリアクリルアミド（日本ＰＭ
Ｃ（株）歩留剤ＲＤ８１４）を０．０１％添加し、ノー
ブルアンドウッド抄紙機で抄紙ｐＨ８で抄紙し、坪量６
５ｇ／ｍ2 の試験紙を得た。湿紙の乾燥は、ドラムドラ
イヤーを用いて所定の乾燥条件で行った。得られた試験
紙を恒温恒湿環境下（２０℃、６５％相対湿度）で２４
時間調湿した後、サイズ度をステキヒト法で測定した。
その結果を表３に示した。-2 Size effect test 2 1.2 liters of pulp slurry beaten under the same conditions as in the test of -1 in the preceding paragraph were weighed in a disintegrator, and the sizing agents of the above Examples and Comparative Examples were used in the amounts shown in Table 2. (0.4% or 0.8
%) And 1.0% vanadium sulfate and the above DS as a fixing agent
0.2% of 410 was added and then stirred for 10 minutes. The pulp slurry is then diluted to a concentration of 0.2 with diluted water of pH 8.
Diluted to 5%, 2% of light calcium carbonate (Tamapearl 121S manufactured by Okutama Industry Co., Ltd.), and high molecular weight cationic polyacrylamide as a retention agent (Japan PM
0.01% of retention agent RD814) of C Co., Ltd. was added, paper was made at a paper making pH of 8 with a Noble and Wood paper machine, and the basis weight was 6
A test paper of 5 g / m 2 was obtained. The wet paper web was dried under a predetermined drying condition using a drum dryer. The obtained test paper is placed in a constant temperature and humidity environment (20 ° C, 65% relative humidity) for 24 hours.
After conditioned for time, the sizing degree was measured by the Steckit method.
The results are shown in Table 3.
【００４９】[0049]
【表３】 [Table 3]
【００５０】 静置安定性試験 長さ３０ｃｍ、内径２．１ｃｍの試験管に１００ｍｌの
上記実施例、比較例のサイズ剤を入れ、６ケ月静置後、
底部に沈澱した沈澱物の高さ（ｃｍ）を測定した。その
測定結果を表４に示す。Stationary Stability Test 100 ml of the sizing agents of the above Examples and Comparative Examples were placed in a test tube having a length of 30 cm and an inner diameter of 2.1 cm, and allowed to stand for 6 months.
The height (cm) of the precipitate deposited on the bottom was measured. The measurement results are shown in Table 4.
【００５１】 機械的安定性試験 前記実施例、比較例の各サイズ剤５０ｇをカップに入
れ、温度２５℃、荷重２０Ｋｇ、回転数８００ｒｐｍに
て５分間マーロン式安定性試験を行った。生成した凝集
物を３２５メッシュの金網にて濾過して全固形分に対す
る析出量を測定し百分率で表した。その測定結果を表４
に示す。Mechanical Stability Test 50 g of each sizing agent of the above Examples and Comparative Examples was put in a cup, and a Marlon type stability test was conducted at a temperature of 25 ° C., a load of 20 Kg and a rotation speed of 800 rpm for 5 minutes. The generated agglomerates were filtered through a wire mesh of 325 mesh, and the amount of precipitation with respect to the total solid content was measured and expressed as a percentage. The measurement results are shown in Table 4.
Shown in.
【００５２】[0052]
【表４】 [Table 4]
【００５３】[0053]
【発明の効果】本発明によれば、アルケニルコハク酸誘
導体を含有するロジン系エマルション組成物、その製造
方法、サイズ剤、サイジング方法を提供できるので、こ
のロジン系エマルション組成物を含有するサイズ剤を用
いてサイジングを行うと、特に抄紙速度が高速で乾燥条
件が穏やかな条件下においても従来のアニオン性あるい
はカチオン性ロシンエマルションには見られない優れた
サイズ効果を発揮する紙を提供できる。また、このサイ
ズ剤は保存安定性及び機械的安定性に優れている。According to the present invention, since a rosin emulsion composition containing an alkenylsuccinic acid derivative, a method for producing the same, a sizing agent and a sizing method can be provided, a sizing agent containing this rosin emulsion composition can be provided. When used for sizing, it is possible to provide a paper exhibiting an excellent sizing effect not found in conventional anionic or cationic rosin emulsions even under conditions of high papermaking speed and mild drying conditions. Further, this sizing agent has excellent storage stability and mechanical stability.
Claims (21)
（Ｂ）ロジン系物質と、（Ｃ）分散剤を含有する分散質
を水中に安定に分散させたロジン系エマルション組成
物。1. An (A) alkenyl succinic acid derivative,
A rosin-based emulsion composition in which a dispersoid containing (B) a rosin-based substance and (C) a dispersant is stably dispersed in water.
アミン類、二級アミン類、多価アミン類及びアミノアル
コール類からなる群から選ばれた少なくとも１種と、ア
ルケニルコハク酸無水物及びアルケニルコハク酸の少な
くとも１種との反応生成物である請求項１記載のロジン
系エマルション組成物。2. An alkenyl succinic anhydride and an alkenyl, wherein the alkenyl succinic acid derivative (A) is at least one selected from the group consisting of primary amines, secondary amines, polyvalent amines and amino alcohols. The rosin-based emulsion composition according to claim 1, which is a reaction product with at least one succinic acid.
し、Ｒ1 は炭素数１〜３０の鎖状又は環状炭化水素基を
示す）で表される化合物である請求項２記載のロジン系
エマルション組成物。3. The rosin according to claim 2, wherein the primary amine is a compound represented by the general formula R 1 NH 2 (wherein R 1 represents a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms). System emulsion composition.
アミン類、多価アミン類及びアミノアルコール類からな
る群から選ばれた少なくとも１種と、アルケニルコハク
酸無水物及びアルケニルコハク酸の少なくとも１種との
反応生成物にさらに一価アルコール類、多価アルコール
類及び一級カルボン酸類からなる群から選ばれた少なく
とも１種を反応させて得られた反応生成物である請求項
１記載のロジン系エマルション組成物。4. An alkenyl succinic acid derivative of (A) at least one selected from the group consisting of secondary amines, polyamines and amino alcohols, and at least alkenyl succinic anhydride and alkenyl succinic acid. The rosin according to claim 1, which is a reaction product obtained by reacting a reaction product with one kind with at least one kind selected from the group consisting of monohydric alcohols, polyhydric alcohols and primary carboxylic acids. System emulsion composition.
2 、Ｒ3 は同一又は異なる炭素数１〜３０の鎖状又は環
状炭化水素基を示す）で表される化合物である請求項２
ないし４のいずれかに記載のロジン系エマルション組成
物。5. The secondary amines are R 2 R 3 NH (provided that R 2 R 3 NH
2 and R 3 are the same or different and each represents a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms).
The rosin-based emulsion composition according to any one of 1 to 4.
Ｒ5 ─Ｒ4 ）ｎ─ＮＨ2 （但し、Ｒ4 が炭素数２〜１３
の鎖状又は環状アルキレン基、Ｒ5 が水素又はメチル基
であってｎが０〜５の整数値で示される）で表される請
求項２ないし５のいずれかに記載のロジン系エマルショ
ン組成物。6. A polyvalent amine is represented by the general formula H 2 N--R 4 (N
R 5 --R 4 ) n--NH 2 (provided that R 4 has 2 to 13 carbon atoms
A chain or cyclic alkylene group, R 5 is hydrogen or a methyl group, and n is represented by an integer value of 0 to 5). .
ミン、ジエタノールアミン、トリエタノールアミン、モ
ノイソプロパノールアミン、ジイソプロパノールアミ
ン、及びトリイソプロパノールアミンからなる群から選
ばれた少なくとも１種である請求項２ないし６のいずれ
かに記載のロジン系エマルション組成物。7. The amino alcohol is at least one selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine. A rosin-based emulsion composition as described in 1.
アルコールと、アルケニルコハク酸無水物及びアルケニ
ルコハク酸の少なくとも１種との反応生成物である請求
項１記載のロジン系エマルション組成物。8. The rosin emulsion composition according to claim 1, wherein the alkenylsuccinic acid derivative (A) is a reaction product of a monohydric alcohol and at least one of alkenylsuccinic anhydride and alkenylsuccinic acid.
アルコール類と、アルケニルコハク酸無水物及びアルケ
ニルコハク酸の少なくとも１種との反応生成物にさらに
多価アルコール類を反応させて得られた反応生成物であ
る請求項１記載のロジン系エマルション組成物。9. An alkenyl succinic acid derivative of (A) is obtained by further reacting a reaction product of a monohydric alcohol with at least one of alkenyl succinic anhydride and alkenyl succinic acid with a polyhydric alcohol. The rosin-based emulsion composition according to claim 1, which is a reaction product.
価アルコール類と、アルケニルコハク酸無水物及びアル
ケニルコハク酸の少なくとも１種との反応生成物である
請求項１記載のロジン系エマルション組成物。10. The rosin emulsion composition according to claim 1, wherein the alkenylsuccinic acid derivative (A) is a reaction product of a polyhydric alcohol and at least one of alkenylsuccinic anhydride and alkenylsuccinic acid. .
価アルコール類と、アルケニルコハク酸無水物及びアル
ケニルコハク酸の少なくとも１種との反応生成物に一価
アルコール類及び一級カルボン酸類の少なくとも１種を
反応させて得られた反応生成物である請求項１記載のロ
ジン系エマルション組成物。11. A reaction product of the alkenylsuccinic acid derivative of (A) with a polyhydric alcohol and at least one of an alkenylsuccinic anhydride and an alkenylsuccinic acid, and at least one of a monohydric alcohol and a primary carboxylic acid. The rosin-based emulsion composition according to claim 1, which is a reaction product obtained by reacting seeds.
Ｒ6 は炭素数１〜３０の鎖状又は環状炭化水素基を示
す）で表される化合物である請求項４ないし１１のいず
れかに記載のロジン系エマルション組成物。12. The monohydric alcohol is R 6 OH (provided that
R 6 is rosin emulsion composition according to any one of claims 4 is a compound represented by showing a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms) 11.
個有する化合物である請求項４ないし７のいずれか又は
９ないし１１のいずれかにに記載のロジン系エマルショ
ン組成物。13. The polyhydric alcohol has an OH group of 2 to 10.
The rosin-based emulsion composition according to any one of claims 4 to 7 or 9 to 11, which is a compound having an individual group.
Ｈ（但し、Ｒ7 が炭素数４〜２４の鎖状又は環状炭化水
素基を示す）で表される請求項４ないし７のいずれか又
は１１に記載のロジン系エマルション組成物。14. The primary carboxylic acid has the general formula R 7 COO.
The rosin-based emulsion composition according to any one of claims 4 to 7 or 11, which is represented by H (however, R 7 represents a chain or cyclic hydrocarbon group having 4 to 24 carbon atoms).
求項２ないし１４に記載されたアルケニルコハク酸誘導
体の２種以上である請求項１記載のロジン系エマルショ
ン組成物。15. The rosin emulsion composition according to claim 1, wherein the alkenylsuccinic acid derivative (A) is at least two kinds of the alkenylsuccinic acid derivatives described in any one of claims 2 to 14.
アルケニルコハク酸がそれぞれ炭素数６〜３０のオレフ
ィンと無水マレイン酸、炭素数６〜３０のオレフィンと
マレイン酸との反応生成物である請求項２ないし１５の
いずれかに記載のロジン系エマルション組成物。16. An alkenyl succinic anhydride in (A),
The rosin-based emulsion composition according to any one of claims 2 to 15, wherein the alkenylsuccinic acid is a reaction product of an olefin having 6 to 30 carbon atoms and maleic anhydride, or an olefin having 6 to 30 carbon atoms and maleic acid. .
を形成して分散されている請求項１ないし１６記載のロ
ジン系エマルション組成物。17. The rosin-based emulsion composition according to claim 1, wherein the component (A) and the component (B) are dispersed by forming a mixture particle.
分が５０〜９８重量部及び（Ｃ）成分が１〜２０重量部
の合計１００重量部を水中に安定に分散させ、固形分濃
度２０〜６０重量％の分散液とする請求項１ないし１８
のいずれかに記載のロジン系エマルション組成物。18. A total of 100 parts by weight of 1 to 49 parts by weight of component (A), 50 to 98 parts by weight of component (B) and 1 to 20 parts by weight of component (C) are stably dispersed in water, 19. A dispersion having a solid content concentration of 20 to 60% by weight.
The rosin-based emulsion composition according to any one of 1.
合物を（Ｃ）成分を用いて水中に分散させる請求項１な
いし１８のいずれかに記載のロジン系エマルション組成
物の製造方法。19. A rosin emulsion composition according to claim 1, wherein the components (A) and (B) are mixed and the mixture is dispersed in water using the component (C). Method.
のロジン系エマルション組成物を含有するサイズ剤。20. A sizing agent containing the rosin-based emulsion composition according to any one of claims 1 to 18.
されたロジン系エマルション組成物をサイズ剤として用
いるサイジング方法。21. A sizing method using the rosin-based emulsion composition according to any one of claims 1 to 18 as a sizing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34680393A JP3304584B2 (en) | 1993-12-27 | 1993-12-27 | Rosin emulsion composition, production method thereof, sizing agent, sizing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34680393A JP3304584B2 (en) | 1993-12-27 | 1993-12-27 | Rosin emulsion composition, production method thereof, sizing agent, sizing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07189174A true JPH07189174A (en) | 1995-07-25 |
| JP3304584B2 JP3304584B2 (en) | 2002-07-22 |
Family
ID=18385921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34680393A Expired - Fee Related JP3304584B2 (en) | 1993-12-27 | 1993-12-27 | Rosin emulsion composition, production method thereof, sizing agent, sizing method |
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| Country | Link |
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| JP (1) | JP3304584B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002129494A (en) * | 2000-08-16 | 2002-05-09 | Bayer Ag | Cationic polymer dispersion for paper sizing treatment |
| JP2014208653A (en) * | 2008-01-25 | 2014-11-06 | ロディア オペレーションズＲｈｏｄｉａ Ｏｐｅｒａｔｉｏｎｓ | Use of esteramide as solvent, novel esteramide and process for preparing esteramide |
| JP2016197207A (en) * | 2015-04-06 | 2016-11-24 | 花王株式会社 | Toner for electrostatic charge image development |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102888782B (en) * | 2011-09-09 | 2014-12-17 | 山东鲁南纸业股份有限公司 | Production method of chemical fiber wallpaper base |
-
1993
- 1993-12-27 JP JP34680393A patent/JP3304584B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002129494A (en) * | 2000-08-16 | 2002-05-09 | Bayer Ag | Cationic polymer dispersion for paper sizing treatment |
| JP2014208653A (en) * | 2008-01-25 | 2014-11-06 | ロディア オペレーションズＲｈｏｄｉａ Ｏｐｅｒａｔｉｏｎｓ | Use of esteramide as solvent, novel esteramide and process for preparing esteramide |
| JP2016197207A (en) * | 2015-04-06 | 2016-11-24 | 花王株式会社 | Toner for electrostatic charge image development |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3304584B2 (en) | 2002-07-22 |
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