JP4400202B2 - Surface sizing agent for papermaking - Google Patents
Surface sizing agent for papermaking Download PDFInfo
- Publication number
- JP4400202B2 JP4400202B2 JP2003413055A JP2003413055A JP4400202B2 JP 4400202 B2 JP4400202 B2 JP 4400202B2 JP 2003413055 A JP2003413055 A JP 2003413055A JP 2003413055 A JP2003413055 A JP 2003413055A JP 4400202 B2 JP4400202 B2 JP 4400202B2
- Authority
- JP
- Japan
- Prior art keywords
- sizing agent
- paper
- surface sizing
- papermaking
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004513 sizing Methods 0.000 title claims description 62
- 239000003795 chemical substances by application Substances 0.000 claims description 46
- 239000000178 monomer Substances 0.000 claims description 42
- -1 succinic anhydride alkali salt Chemical class 0.000 claims description 39
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 239000000839 emulsion Substances 0.000 claims description 22
- 229940014800 succinic anhydride Drugs 0.000 claims description 16
- 230000002209 hydrophobic effect Effects 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- 229920003169 water-soluble polymer Polymers 0.000 claims description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 239000000123 paper Substances 0.000 description 60
- 238000000576 coating method Methods 0.000 description 33
- 239000011248 coating agent Substances 0.000 description 25
- 229920000642 polymer Polymers 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 230000005476 size effect Effects 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 230000000740 bleeding effect Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 235000013808 oxidized starch Nutrition 0.000 description 8
- 239000001254 oxidized starch Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical class ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 5
- 150000001447 alkali salts Chemical class 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000007641 inkjet printing Methods 0.000 description 4
- 239000011087 paperboard Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003926 acrylamides Chemical class 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000001739 density measurement Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003890 succinate salts Chemical class 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 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 1
- 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 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
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- 239000004368 Modified starch Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
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- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 1
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- 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
- 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
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
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- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 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
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000001256 steam distillation Methods 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
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 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
- 239000002562 thickening agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Paper (AREA)
Description
本発明は、エマルジョン型の製紙用表面サイズ剤に関する。具体的には、ゲートロール塗工及びサイズプレス塗工時におけるサイズ効果に優れ、かつ、系の発泡が少ないエマルジョン型の製紙用表面サイズ剤に関する。さらには、インクジェット印刷におけるフェザリング適性およびブリーディング適性にも優れる製紙用表面サイズ剤に関する。 The present invention relates to an emulsion-type surface sizing agent for papermaking. Specifically, the present invention relates to an emulsion-type surface sizing agent for papermaking that is excellent in size effect during gate roll coating and size press coating, and has less foaming of the system. Furthermore, the present invention relates to a surface sizing agent for papermaking that is excellent in feathering suitability and bleeding suitability in ink jet printing.
製紙工程においては、成紙にサイズ性を付与するべくパルプスラリーに内添サイズ剤を添加する内添サイズ法が広く行われているが、紙表面に直接サイズ剤を塗工する表面サイズ法によれば、紙表面にサイズ剤をほぼ１００％歩留らせることができるため、印刷適性や筆記性、耐水性、耐油性（バリア性）等の通常のサイズ性能や、インクジェット記録方式における印刷適性（フェザリング適性やブリーディング適性等）といった、内添サイズ法では得られ難い各種の効果を得ることが可能となる。表面サイズ剤としては各種のものが知られており、特に近年では中性紙において優れたサイズ効果を発揮する中性紙用表面サイズ剤として、アルキル又はアルケニル置換コハク酸塩の水溶液にアニオン性スチレン系ポリマーを配合してなる組成物を有効成分とする表面サイズ剤（例えば、特許文献１を参照）が知られている。 In the papermaking process, an internal sizing method is widely used in which an internal sizing agent is added to pulp slurry in order to impart sizing properties to the finished paper. According to this, since the sizing agent can be almost 100% retained on the paper surface, normal size performance such as printability, writing property, water resistance, oil resistance (barrier property), and printability in the ink jet recording method. It is possible to obtain various effects such as (feathering suitability and bleeding suitability) that are difficult to obtain by the internally added size method. Various surface sizing agents are known, and in recent years, an anionic styrene in an aqueous solution of an alkyl or alkenyl-substituted succinate as a surface sizing agent for neutral paper that exhibits an excellent sizing effect on neutral paper. 2. Description of the Related Art A surface sizing agent (for example, see Patent Document 1) containing a composition formed by blending a polymer as an active ingredient is known.
表面サイズ剤は湿紙の乾燥工程（ドライヤーパート）の中間において、サイズプレス塗工、ゲートロール塗工、ダブサイジング塗工、シムサイズプレス塗工、カレンダー塗工やブレード塗工等の各種塗工方式で紙表面に塗布されるが、これらのなかでも特に２本のアプリケーターロールを用いるサイズプレス塗工や高速抄紙に対応できるゲートロール塗工が一般的である。サイズプレス塗工はアプリケーターロール間に溜めた比較的低濃度のサイズ液に紙を浸漬・進入させた後に該ロールで紙を絞る方式であり、サイズ剤が紙の深部にまでサイズ液が浸透してパルプ繊維と結合することによりサイズ効果が発現する。一方、ゲートロール塗工は比較的高濃度のサイズ液を溜めたロールから該ロールと接するアプリケーターロールを介してサイズ液のフィルムを紙表面に転写する方式であり、紙表面に塗工液をほぼ１００％定着させることができるため、紙表面の大幅な改質が可能となる。 Surface sizing agent is applied in various ways such as size press coating, gate roll coating, dove sizing coating, shim size press coating, calendar coating and blade coating in the middle of the wet paper drying process (dryer part). Although it is applied to the paper surface by a method, gate roll coating that can cope with size press coating using two applicator rolls and high-speed papermaking is generally used. Size press coating is a method in which the paper is immersed in a relatively low concentration liquid stored between applicator rolls and then squeezed with the roll. The size liquid penetrates deep into the paper. The size effect is manifested by binding to the pulp fiber. On the other hand, gate roll coating is a system in which a film of size liquid is transferred to the paper surface from a roll in which a relatively high concentration of size liquid is stored via an applicator roll in contact with the roll. Since it can be fixed 100%, the paper surface can be greatly modified.
上述のように表面サイズ剤の塗工方式は多様であるが、すべての方式において適応できる表面サイズ剤は少なく、塗工装置切り替えの際にサイズ効果が発現し難くなるものもあった。そのため、塗工方式の変更に伴い、目的とする紙質効果（サイズ性、印刷適性、筆記性、インクジェット適性等）を考慮しつつ、表面サイズ剤の組成を変更しなければならないといった煩雑さがあった。 As described above, there are various surface sizing agent coating methods. However, there are few surface sizing agents that can be applied to all methods, and there are some cases where it is difficult to realize the size effect when the coating apparatus is switched. Therefore, with the change of the coating method, there is a trouble that the composition of the surface sizing agent has to be changed in consideration of the desired paper quality effect (size property, printability, writing property, inkjet property, etc.). It was.
本発明が解決しようとする課題は、近年中性サイズ剤の原料として広く賞用されているアルキル又はアルケニル置換コハク酸塩を用いて、現在主流のサイズプレス塗工方式とゲートロール塗工方式の両方式において良好なサイズ効果を発現し得る、エマルジョン型の製紙用表面サイズ剤を提供することにある。さらには、インクジェット印刷におけるフェザリングおよびブリーディング適性にも優れる製紙用表面サイズ剤を提供することにある。 The problem to be solved by the present invention is the use of an alkyl or alkenyl-substituted succinate that has been widely used as a raw material for neutral sizing agents in recent years, and the current mainstream size press coating method and gate roll coating method. An object of the present invention is to provide an emulsion-type surface sizing agent for papermaking, which can exhibit a good sizing effect in both systems. Furthermore, it is providing the surface sizing agent for paper manufacture which is excellent also in the feathering and bleeding ability in inkjet printing.
本出願人は前記課題を解決するべく鋭意検討を重ねた結果、特定量の炭素数８〜３６のアルキル又はアルケニル置換無水コハク酸のアルカリ塩の存在下において、特定量の各種ビニル系単量体を乳化重合して得られる水性エマルジョン組成物を用いた製紙用表面サイズ剤によれば、前記課題を悉く解決し得ることを見出した。 As a result of intensive studies to solve the above problems, the present applicant has found that a specific amount of various vinyl monomers in the presence of a specific amount of an alkali salt of alkyl or alkenyl-substituted succinic anhydride having 8 to 36 carbon atoms. It has been found that according to the paper sizing agent using an aqueous emulsion composition obtained by emulsion polymerization, the above problems can be solved.
即ち、本発明は、疎水性不飽和単量体８０〜９８重量％、（メタ）アクリル酸１〜１５重量％及びアクリルアミド系単量体１〜１０重量％からなるビニル系単量体混合物１００重量部と、これに対し２〜８重量部（固形分換算）となる炭素数１６〜２０のアルキル又はアルケニル置換無水コハク酸アルカリ塩とを乳化重合して得られる水性エマルジョン組成物を含有してなる製紙用表面サイズ剤；当該製紙用表面サイズ剤に、さらに疎水性不飽和単量体およびカルボキシル基含有不飽和単量体を重合させて得られる水溶性重合体を混合してなる製紙用表面サイズ剤、に関する。 That is, the present invention is 100 wt % of a vinyl monomer mixture comprising 80 to 98 wt% of a hydrophobic unsaturated monomer, 1 to 15 wt% of (meth) acrylic acid and 1 to 10 wt% of an acrylamide monomer. And an aqueous emulsion composition obtained by emulsion polymerization of an alkyl or alkenyl-substituted succinic anhydride alkali salt having 16 to 20 carbon atoms, which is 2 to 8 parts by weight (in terms of solid content). Paper-making surface sizing agent; paper-making surface sizing agent, and a water-soluble polymer obtained by further polymerizing a hydrophobic unsaturated monomer and a carboxyl group-containing unsaturated monomer to the paper-making surface sizing agent Agent.
本発明に係る製紙用表面サイズ剤によれば、塗工方式に左右されず、一定のサイズ効果を得ることができる。特にゲートロール、サイズプレス塗工時においてバランス良いサイズ効果が得られる。また、系の発泡が少ないという特徴もある。さらには、インクジェット印刷におけるフェザリングおよびブリーディング適性にも優れるという特徴もある。 According to the surface sizing agent for papermaking according to the present invention, a certain size effect can be obtained regardless of the coating method. In particular, a well-balanced size effect can be obtained during gate roll and size press coating. Moreover, there is also a feature that the foaming of the system is small. Furthermore, it is also characterized by excellent feathering and bleeding suitability in ink jet printing.
まず、本発明に係る製紙用表面サイズ剤の有効成分である水性エマルジョン組成物について説明する。該エマルジョンの基幹ポリマーは各種公知のビニル系単量体、特に疎水性不飽和単量体、（メタ）アクリル酸及びアクリルアミド系単量体を構成成分とするビニル重合体である。 First, the aqueous emulsion composition which is an active ingredient of the paper sizing agent according to the present invention will be described. The basic polymer of the emulsion is a vinyl polymer having various known vinyl monomers, particularly hydrophobic unsaturated monomers, (meth) acrylic acid and acrylamide monomers as constituent components.
該疎水性不飽和単量体としては、スチレン、α−メチルスチレン、ビニルトルエン等のスチレン類、アルキル基が炭素数６〜２２の直鎖または分岐鎖であるα−オレフィン、アルキル基の炭素数が１〜１８の（メタ）アクリル酸アルキルエステル、エステル置換基が２−ヒドロキシエチル基、２−ヒドロキシプロピル基等のヒドロキシアルキル基、ベンジル基、アリル基等の各種（メタ）アクリル酸エステル、（メタ）アクリロニトリル、酢酸ビニル、プロピオン酸ビニル等のビニルエステル類、炭素数１〜２２のアルキルビニルエーテル等が挙げられる。これら疎水性不飽和単量体は１種を単独で、または２種以上を併用して用いることができるが、その中でもスチレン類および／または（メタ）アクリル酸アルキルエステルが好ましい。上記の（メタ）アクリル酸エステルの中では、アルキル基の炭素数が１〜１８の（メタ）アクリル酸アルキルエステルが好ましい。特にアルキル基の炭素数が１〜１２の場合が好ましい。かかる炭素数が１〜１８のアルキル基としては、直鎖、分岐鎖または環状のものを例示でき、たとえばメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｔ−ブチル基、ネオペンチル基、ｎ−ヘキシル基、シクロヘキシル基、２−エチルヘキシル基、デシル基、パルミチル基、ステアリル基等があげられる。 Examples of the hydrophobic unsaturated monomer include styrenes such as styrene, α-methylstyrene, vinyltoluene, α-olefins whose alkyl group is a straight chain or branched chain having 6 to 22 carbon atoms, and carbon number of the alkyl group. 1 to 18 (meth) acrylic acid alkyl ester, the ester substituent is a hydroxyalkyl group such as 2-hydroxyethyl group and 2-hydroxypropyl group, various (meth) acrylic acid esters such as benzyl group and allyl group, ( Examples thereof include vinyl esters such as (meth) acrylonitrile, vinyl acetate and vinyl propionate, and alkyl vinyl ethers having 1 to 22 carbon atoms. These hydrophobic unsaturated monomers can be used alone or in combination of two or more. Among them, styrenes and / or (meth) acrylic acid alkyl esters are preferable. Among the above (meth) acrylic acid esters, (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms in the alkyl group are preferable. In particular, the case where the alkyl group has 1 to 12 carbon atoms is preferable. Examples of the alkyl group having 1 to 18 carbon atoms include straight chain, branched chain and cyclic groups, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- Examples thereof include a butyl group, a t-butyl group, a neopentyl group, an n-hexyl group, a cyclohexyl group, a 2-ethylhexyl group, a decyl group, a palmityl group, and a stearyl group.
（メタ）アクリル酸の他、該カルボキシル基含有単量体として、マレイン酸、マレイン酸半エステル、イタコン酸、イタコン酸半エステル、シトラコン酸、フマル酸、クロトン酸等が挙げられる。特に好ましくは（メタ）アクリル酸および／またはその塩である。 Only (meth) acrylic acid, and with the carboxyl-containing monomers, maleic acid, maleic half esters, itaconic acid, itaconic Sanhan ester, citraconic acid, fumaric acid, Ru crotonic acid and the like. Particularly preferred is (meth) acrylic acid and / or a salt thereof.
該アクリルアミド系単量体としては、アクリルアミド、メタクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ−ターシャリーブチル(メタ)アクリルアミド、Ｎ−ラウリル（メタ）アクリルアミド、及びＮ−シクロヘキシル置換アルキル（メタ）アクリルアミド等のＮ−置換モノアルキル（メタ）アクリルアミド類、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジイソプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジターシャリーブチル（メタ）アクリルアミド、Ｎ，Ｎ−ジラウリル（メタ）アクリルアミド、Ｎ，Ｎ−ジターシャリーオクチル（メタ）アクリルアミド、及びＮ，Ｎ−ジシクロヘキシル（メタ）アクリルアミド等のＮ−置換ジアルキル（メタ）アクリルアミド、ダイアセトンアクリルアミド等、が挙げられる。これらのなかでも、（メタ）アクリルアミドが好ましい。 Examples of the acrylamide monomers include acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-tertiary. N-substituted monoalkyl (meth) acrylamides such as butyl (meth) acrylamide, N-lauryl (meth) acrylamide, and N-cyclohexyl substituted alkyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diisopropyl (meth) acrylamide, N, N-ditertiary butyl (meth) acrylamide, N, N-dilauryl (meth) acrylamide, N, N-ditertiary octyl (meth) acrylamide, and N, N-dicyclohexyl ( Data) acrylamide, N- substituted dialkyl (meth) acrylamide, diacetone acrylamide, and the like. Among these, (meth) acrylamide is preferable.
前記した各ビニル系単量体に加え、必要に応じてビニルピロリドン等のノニオン性不飽和単量体や、ビニルスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸等のスルホン酸含有アニオン性不飽和単量体またはそのアルカリ塩などを使用することもできる。その使用量は得られる本発明にかかるエマルジョン型の製紙用表面サイズ剤のサイズ性能を低下させない範囲とされ、通常、前記基幹ポリマー総重量の１０重量％以下とされる。 In addition to the above-mentioned vinyl monomers, nonionic unsaturated monomers such as vinyl pyrrolidone, and sulfonic acid-containing anionic impurities such as vinyl sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid as necessary. A saturated monomer or an alkali salt thereof can also be used. The amount used is in a range that does not reduce the size performance of the resulting emulsion-type paper surface sizing agent according to the present invention, and is usually 10% by weight or less of the total weight of the basic polymer.
基幹ポリマーにおける疎水性不飽和単量体、（メタ）アクリル酸及びアクリルアミド類のそれぞれの使用量は、疎水性不飽和単量体８０〜９８重量％、好ましくは８４〜９６重量％、（メタ）アクリル酸１〜１５重量％程度、好ましくは２〜８重量％、アクリルアミド類１〜１０重量％程度、好ましくは１〜６重量％である。疎水性不飽和単量体の使用量が８０重量％に満たない場合には良好なサイズ効果が得られ難くなる傾向があり、９８重量％を超えるとエマルジョンの安定性が低下する傾向にある。また、（メタ）アクリル酸の使用量が１重量％に満たない場合にはエマルジョンの貯蔵安定性が低下するという傾向にあり、１０重量％を超えるとサイズ効果が低下し、かつエマルジョンを構成する粒子にアニオン性官能基が相対的に多く含有されることになるためエマルジョンの粘度が上昇して作業性が低下するという傾向にある。また、アクリルアミド類の使用量が１重量％に満たない場合には硬水系における希釈時の貯蔵安定性および機械的安定性が低下するという傾向にあり、１０重量％を超えるとサイズ効果が低下するという傾向にある。 The amount of each of the hydrophobic unsaturated monomer, (meth) acrylic acid and acrylamides used in the basic polymer is 80 to 98% by weight , preferably 84 to 96% by weight, (meth). Acrylic acid is about 1 to 15% by weight , preferably 2 to 8% by weight, and acrylamides are about 1 to 10% by weight , preferably 1 to 6% by weight. When the amount of the hydrophobic unsaturated monomer used is less than 80% by weight, it tends to be difficult to obtain a good size effect, and when it exceeds 98% by weight, the stability of the emulsion tends to be lowered. Further, when the amount of (meth) acrylic acid used is less than 1% by weight, the storage stability of the emulsion tends to be lowered, and when it exceeds 10% by weight, the size effect is lowered and the emulsion is constituted. Since the particles contain a relatively large amount of anionic functional groups, the viscosity of the emulsion tends to increase and workability tends to decrease. Further, when the amount of acrylamide used is less than 1% by weight, the storage stability and mechanical stability at the time of dilution in a hard water system tend to decrease, and when the amount exceeds 10% by weight, the size effect decreases. It tends to be.
なお、前記基幹ポリマーは水に分散させるために、当該基幹ポリマー中に含まれるカルボキシル基の少なくとも５０％以上、より好ましくは８０〜１００％が中和されている必要がある。かかる中和はカルボキシル基含有不飽和単量体の段階で行ない得るのはもちろんのこと、基幹ポリマーの製造後に行なうこともできる。中和塩としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属塩や、またアンモニウム塩及び／又は揮発性アミン塩が好ましい。 In order to disperse the basic polymer in water, at least 50% or more, more preferably 80 to 100%, of the carboxyl groups contained in the basic polymer needs to be neutralized. Such neutralization can be performed at the stage of the carboxyl group-containing unsaturated monomer as well as after the production of the basic polymer. As the neutralized salt, alkali metal salts such as sodium hydroxide and potassium hydroxide, and ammonium salts and / or volatile amine salts are preferable.
アンモニウム塩を形成するものとしては、アンモニアの他、炭酸アンモニウム塩等のアンモニウム塩を使用できる。また、揮発性アミンとしては炭素数１〜１２程度の脂肪族、脂環族又は芳香族アミン塩、同様のアリールアミン塩、アルカノールアミン塩等をあげることができる。具体的には、たとえば、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、モノブチルアミン等の脂肪族アミン、シクロヘキシルアミン等の脂環族アミン、アニリン等の芳香族アミン、アリールアミン、アルカノールアミン等の第１級及び第２級アミン等があげられる。これらの中和塩のなかでも、特にアンモニアによるアンモニウム塩が好ましい。 As for the ammonium salt, an ammonium salt such as ammonium carbonate can be used in addition to ammonia. Examples of the volatile amine include aliphatic, alicyclic or aromatic amine salts having about 1 to 12 carbon atoms, similar arylamine salts, alkanolamine salts and the like. Specifically, for example, aliphatic amines such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine and monobutylamine, alicyclic amines such as cyclohexylamine, aromatic amines such as aniline, arylamines, alkanolamines, etc. And primary amines and secondary amines. Among these neutralized salts, an ammonium salt with ammonia is particularly preferable.
次に、炭素数数１６〜２０のアルキル又はアルケニル置換無水コハク酸のアルカリ塩について説明する。このものは、本発明において前記基幹ポリマーの乳化剤（保護コロイド）的な作用を奏するものであり、アルカリ塩としては、アルカリ金属、アンモニア又は有機アミン類の塩が挙げられる。このものを使用することにより、特にゲートロール塗工時およびサイズプレス塗工時のサイズ効果が良好となり、かつ系の発泡を抑制することが可能となる。しかし、このものを必要量以上に用いるとサイズプレス時のサイズ効果がむしろ低下する傾向にあるため、その使用量は、前述した基幹ポリマーを構成するビニル系単量体混合物１００重量部に対して２〜８重量部、特に好ましくは３〜６重量部である。使用量が少なすぎるとゲートロール塗工時において満足なサイズ効果が得られず、また８重量部以上であると前記したようにサイズプレス時のサイズ効果が得られ難くなる傾向にある。 Next, an alkali salt of an alkyl or alkenyl substituted succinic anhydride having 16 to 20 carbon atoms will be described. This material is intended in the present invention exhibits an emulsifier (protective colloid) effects of the backbone polymer, the alkali salts include salts of alkali metals, ammonia or organic amines. By using this, the size effect at the time of gate roll coating and size press coating is improved, and foaming of the system can be suppressed. However, since the size effect at the time of size press tends to decrease if this amount is used more than necessary, the amount used is 100 parts by weight of the vinyl monomer mixture constituting the basic polymer described above. 2 to 8 parts by weight , particularly preferably 3 to 6 parts by weight. If the amount used is too small, a satisfactory size effect cannot be obtained at the time of gate roll coating, and if it is 8 parts by weight or more, the size effect at the time of size pressing tends to be difficult to obtain as described above.
つぎに、本発明に係る製紙用表面サイズ剤を構成するエマルジョンの製造方法について説明する。該エマルジョンの製造は公知の手段によればよく、たとえば適当な加熱装置と攪拌機を備えた反応容器に前記炭素数１６〜２０のアルキル又はアルケニル置換無水コハク酸アルカリ塩を溶解した水溶液を仕込み、これに前記ビニル系単量体混合物および公知のラジカル重合開始剤を加え、ついで当該容器に水、有機溶剤および各種公知の乳化剤を仕込み、攪拌下に加温して重合を開始し、その後、重合体を中和する方法が挙げられる。なお、前記ビニル系単量体の仕込み方法は、一括仕込み、分割滴下のいずれの方法でもよく、ラジカル重合開始剤とともに滴下する方法であってもよい。なお、重合温度は通常４０〜１５０℃程度、反応時間は２〜１２時間程度とされる。 Below, the manufacturing method of the emulsion which comprises the surface sizing agent for paper manufacture which concerns on this invention is demonstrated. The emulsion may be produced by known means. For example, an aqueous solution in which the alkyl salt having 16 to 20 carbon atoms or the alkenyl-substituted succinic anhydride is dissolved is charged into a reaction vessel equipped with a suitable heating device and a stirrer. The vinyl monomer mixture and a known radical polymerization initiator are added to the container, and then water, an organic solvent and various known emulsifiers are charged into the container, and the mixture is heated with stirring to start polymerization. The method of neutralizing is mentioned. In addition, the charging method of the vinyl monomer may be either batch charging or divided dropping, or may be a dropping method together with a radical polymerization initiator. The polymerization temperature is usually about 40 to 150 ° C., and the reaction time is about 2 to 12 hours.
重合開始剤の種類については特に制限されず、過酸化水素、過硫酸アンモニウム、過硫酸カリウム等の無機過酸化物、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ラウリルパーオキサイド等の有機過酸化物、２，２’−アゾビスイソブチロニトリル、ジメチル−２，２’−アゾビスイソブチレイト等のアゾ系化合物等の公知の物を適宜選択して使用することができる。その使用量はビニル系単量体１００重量部に対して、通常０．０１〜５重量部程度である。なお、ラジカル重合開始剤の場合は亜硫酸水素ナトリウム、チオ硫酸ナトリウム等の還元剤を併用して反応系をレドックス系としてもよい。また重合に際して重合度を調節して所望の粘度とするためにドデシルメルカプタン、２−メルカプトベンゾチアゾール、ブロムトリクロルメタン等のような連鎖移動剤を用いることもでき、その使用量は、前記各単量体の混合物１００重量部(固形分)に対し、通常０．０１〜５重量部程度である。 The type of the polymerization initiator is not particularly limited, inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, organic peroxides such as benzoyl peroxide, dicumyl peroxide, lauryl peroxide, 2, Known substances such as azo compounds such as 2′-azobisisobutyronitrile and dimethyl-2,2′-azobisisobutyrate can be appropriately selected and used. The amount used is usually about 0.01 to 5 parts by weight per 100 parts by weight of the vinyl monomer. In the case of a radical polymerization initiator, the reaction system may be a redox system by using a reducing agent such as sodium bisulfite or sodium thiosulfate in combination. In addition, a chain transfer agent such as dodecyl mercaptan, 2-mercaptobenzothiazole, bromotrichloromethane and the like can be used to adjust the degree of polymerization to a desired viscosity during polymerization, The amount is usually about 0.01 to 5 parts by weight per 100 parts by weight (solid content) of the body mixture.
乳化重合の際に用いる有機溶剤としては、エチルアルコール、プロピルアルコール等のアルコール類、アセトン、メチルエチルケトン等の低級ケトン類、トルエン、ベンゼン等の芳香族炭化水素類、酢酸エチル、クロロホルム、ジメチルホルムアミド等を単独で又は適宜組み合わせて使用することができる。ただし、これらの有機溶剤は水蒸気蒸留又は減圧蒸留により留去するのが好ましい。 Examples of the organic solvent used in the emulsion polymerization include alcohols such as ethyl alcohol and propyl alcohol, lower ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as toluene and benzene, ethyl acetate, chloroform and dimethylformamide. They can be used alone or in appropriate combination. However, these organic solvents are preferably distilled off by steam distillation or vacuum distillation.
なお、乳化重合においては、本発明の目的を損なわない範囲において、各種公知のアニオン性もしくはノニオン性の界面活性剤を単独で又は混合して使用することもできる。該界面活性剤の使用量は前記基幹ポリマーを構成する全単量体の総重量に対して１０重量％以下、より好ましくは５重量％以下である。１０重量％を越える場合は、得られたエマルションの泡立ち性が強くなり、塗布液とした時に泡によるトラブルを引き起こすことがある。ノニオン性界面活性剤としては、例えばポリエチレングリコール、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スチリルフェニルエーテル、ポリオキシエチレンソルビタン脂肪酸エステル等があげられる。アニオン性界面活性剤としては、例えばアルキル硫酸塩、アルキルベンゼンスルフォン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、ジアルキルスルホコハク酸エステル塩、アルキルスルフォン酸塩、ポリオキシエチレンアルキルエーテルスルホコハク酸塩、ポリオキシエチレンスチリルフェニルエーテルスルホコハク酸エステル塩、ポリオキシエチレンアルキルエーテルリン酸塩エステル、α―オレフィンスルホン酸塩、ナフタリンスルホン酸ホルマリン縮合物、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等等があげられる。また、以下の一般式に示されるような、分子中に反応性官能基を有するノニオン性またはアニオン性界面活性剤等（特開２００３−２９３２８８号公報を参照）を使用してもよい。なお、カチオン性界面活性剤は、重合中に凝集物が発生するため、使用することはできない。 In the emulsion polymerization, various known anionic or nonionic surfactants can be used alone or in admixture as long as the object of the present invention is not impaired. The amount of the surfactant used is 10% by weight or less, more preferably 5% by weight or less, based on the total weight of all monomers constituting the basic polymer. When it exceeds 10% by weight, the foamability of the obtained emulsion becomes strong, and troubles due to foam may be caused when it is used as a coating solution. Examples of the nonionic surfactant include polyethylene glycol, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitan fatty acid ester and the like. Examples of the anionic surfactant include alkyl sulfates, alkyl benzene sulfonates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, dialkyl sulfosuccinates, alkyl sulfonates, polyoxyethylene alkyls. Ether sulfosuccinate, polyoxyethylene styryl phenyl ether sulfosuccinate ester salt, polyoxyethylene alkyl ether phosphate ester, α-olefin sulfonate, naphthalene sulfonate formalin condensate, polyoxyethylene alkyl phenyl ether sulfate ester, etc. Etc. Moreover, you may use the nonionic or anionic surfactant etc. which have a reactive functional group in a molecule | numerator (refer Unexamined-Japanese-Patent No. 2003-293288) as shown by the following general formula. A cationic surfactant cannot be used because aggregates are generated during polymerization.
（式中、Ｒ１、Ｒ２は水素原子または炭素数１〜２０の炭化水素基；Ｘは炭素―炭素二重結合を含有する共重合性の官能基；（ＡＯ）のうち、Ａは炭素数２〜４のアルキレン基もしくは置換アルキレン基；ｎは１〜１００の整数；Ｂは水素、スルホン酸基、リン酸基、スルホコハク酸基およびこれらの塩ならびにスルホコハク酸基エステルから選ばれる少なくとも一つを示す。） (Wherein R 1 and R 2 are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; X is a copolymerizable functional group containing a carbon-carbon double bond; A in (AO) is carbon N is an integer of 1 to 100; B is at least one selected from hydrogen, sulfonic acid group, phosphoric acid group, sulfosuccinic acid group and salts thereof, and sulfosuccinic acid group ester Is shown.)
（式中、Ｒ３は炭素数１〜２０の炭化水素基、または、少なくとも１つの炭素数１〜２０の炭化水素基により置換された芳香環；Ｘは炭素―炭素二重結合を含有する共重合性の官能基；（ＡＯ）のうちＡは炭素数２〜４のアルキレン基もしくは置換アルキレン基；ｎは１〜１００の整数；Ｂは水素、スルホン酸基、リン酸基、スルホコハク酸基およびこれらの塩ならびにスルホコハク酸基エステルから選ばれる少なくとも一つ；ｌは０または１の整数を示す。） (In the formula, R 3 is a hydrocarbon group having 1 to 20 carbon atoms or an aromatic ring substituted with at least one hydrocarbon group having 1 to 20 carbon atoms; X is a common group containing a carbon-carbon double bond; A polymerizable functional group; in (AO), A is an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group; n is an integer of 1 to 100; B is hydrogen, a sulfonic acid group, a phosphoric acid group, a sulfosuccinic acid group, and (At least one selected from these salts and sulfosuccinic acid group esters; l represents an integer of 0 or 1)
こうして得られたエマルジョン組成物は黄白濁状の外観を呈し、濃度２５重量％においてｐＨ７．５〜８．５、粘度５〜３０ｍＰａ・ｓ（２５℃）、６０〜２００ｎｍの粒子径を有するものである。 The emulsion composition thus obtained has a yellowish cloudy appearance, and has a pH of 7.5 to 8.5, a viscosity of 5 to 30 mPa · s (25 ° C.), and a particle size of 60 to 200 nm at a concentration of 25% by weight. is there.
本発明のエマルジョン型製紙用表面サイズ剤には、通常紙力増強剤として併用される酸化澱粉、リン酸エステル化澱粉、酵素変性澱粉、およびカチオン化澱粉などの澱粉類；カルボキシメチルセルロース等のセルロース類；ポリビニルアルコール類、ポリアクリルアミド類；およびアルギン酸ソーダ等の水溶性高分子；を添加使用できる。また、必要に応じて他の各種公知のサイズ剤、エマルジョン型サイズ剤、防滑剤、防腐剤、防錆剤、ｐＨ調整剤、消泡剤、増粘剤、充填剤、酸化防止剤、耐水化剤、造膜助剤、顔料、染料等を添加することができる。 In the surface sizing agent for emulsion type papermaking of the present invention, starches such as oxidized starch, phosphate esterified starch, enzyme-modified starch, and cationized starch that are usually used in combination as a paper strength enhancer; celluloses such as carboxymethylcellulose Polyvinyl alcohols, polyacrylamides, and water-soluble polymers such as sodium alginate can be added and used. In addition, if necessary, various other known sizing agents, emulsion type sizing agents, anti-slip agents, antiseptics, rust inhibitors, pH adjusters, antifoaming agents, thickeners, fillers, antioxidants, water resistance Agents, film-forming aids, pigments, dyes and the like can be added.
なお、本発明に係る製紙用表面サイズ剤に対する添加剤として、疎水性不飽和単量体およびカルボキシル基含有不飽和単量体を重合させて得られる水溶性重合体を配合することによりゲートロール塗工時におけるサイズ性の向上を得ることができ、加えて良好なカラーインクジェット適性、具体的にはバランスのとれたフェザリング適性とブリーディング適性の発現という効果を得ることができる。当該水溶性重合体は、前記した疎水性不飽和単量体と前記したカルボキシル基含有不飽和単量体とを各種公知の重合方法に従い重合してなる高分子水溶液（溶液）であり、単量体の組み合わせとしては例えば、スチレン−マレイン酸、スチレン−（メタ）アクリル酸等が好ましい。該疎水性不飽和単量体と該カルボキシル基含有不飽和単量体の使用量は特に制限されないが、基幹ポリマーにおいて前者が通常２０〜８０重量％程度、後者が通常８０〜２０重量％程度である。こうして得られた該水溶性重合体は、通常分子量（ゲルパーミエーションクロマトグラフィーによるポリスチレン換算値）が１０００〜１００００００程度、好ましくは２０００〜１０００００、通常固形分が１０〜３０重量％程度、また当該固形分濃度範囲における粘度が１０〜１００００ｍＰａ・ｓ（２５℃）程度、ｐＨが８．０〜９．５程度、通常酸価が１５０〜６００程度の物性を有するものである。本発明において、当該水溶性重合体は、本発明に係る製紙用表面サイズ剤１００重量部（固形分）に対して、通常３００重量部（固形分）未満、好ましくは２０〜２５０重量部（固形分）となるように用いる。混合の手段は特に制限されない。３００重量部を超えると、インクジェット適性のフェザリングがむしろ低下するという傾向にある。 In addition, as an additive for the paper sizing surface sizing agent according to the present invention, a gate roll coating is prepared by blending a water-soluble polymer obtained by polymerizing a hydrophobic unsaturated monomer and a carboxyl group-containing unsaturated monomer. It is possible to improve the sizing property at the time of processing, and in addition, it is possible to obtain good color ink jet aptitude, specifically, the effect of balanced feathering aptitude and bleeding aptitude. The water-soluble polymer is a polymer aqueous solution (solution) obtained by polymerizing the above-described hydrophobic unsaturated monomer and the above-described carboxyl group-containing unsaturated monomer according to various known polymerization methods. As the combination of the bodies, for example, styrene-maleic acid, styrene- (meth) acrylic acid and the like are preferable. The amount of the hydrophobic unsaturated monomer and the carboxyl group-containing unsaturated monomer is not particularly limited, but in the basic polymer, the former is usually about 20 to 80% by weight and the latter is usually about 80 to 20% by weight. is there. The water-soluble polymer thus obtained usually has a molecular weight (polystyrene conversion value by gel permeation chromatography) of about 1,000 to 1,000,000, preferably 2,000 to 100,000, and usually has a solid content of about 10 to 30% by weight. It has physical properties such that the viscosity in the partial concentration range is about 10 to 10000 mPa · s (25 ° C.), the pH is about 8.0 to 9.5, and the acid value is usually about 150 to 600. In the present invention, the water-soluble polymer is usually less than 300 parts by weight (solid content), preferably 20 to 250 parts by weight (solid) with respect to 100 parts by weight (solid content) of the paper sizing surface sizing agent according to the present invention. Minutes). The means for mixing is not particularly limited. If it exceeds 300 parts by weight, the feathering for ink jetting tends to be rather lowered.
本発明の製紙用表面サイズ剤は各種の紙及び板紙に特に制限なく適用できる。紙の種類としては、フォーム用紙、ＰＰＣ用紙、感熱記録原紙、感圧記録原紙等の記録用紙及びその原紙、アート紙、キャストコート紙、上質コート紙等のコート紙用の原紙、クラフト紙、純白ロール紙等の包装用紙、その他、ノート用紙、書籍用紙、印刷用紙、新聞用紙等の各種紙（洋紙）；マニラボール、白ボール、チップボール等の紙器用板紙及びライナー等の板紙があげられる。 The surface sizing agent for papermaking of the present invention can be applied to various papers and paperboards without any particular limitation. The types of paper include foam paper, PPC paper, thermal recording base paper, pressure sensitive recording base paper, etc., and base paper for coated paper such as base paper, art paper, cast coated paper, high quality coated paper, kraft paper, pure white Examples include wrapping paper such as roll paper, various papers (Western paper) such as notebook paper, book paper, printing paper, and newsprint paper; paperboard paperboard such as Manila ball, white ball, and chipball, and paperboard such as liner.
また、本発明の製紙用表面サイズ剤は、パルプ、填料、内添サイズ剤、内添紙力増強剤、歩留まり向上剤等の原料及び内添薬品による影響、及び抄紙ｐＨ、抄紙温度、抄紙マシンの形式等抄紙条件の影響はほとんど受けない。また、本発明の製紙用表面サイズ剤は、上記各種の紙に対して従来公知の塗布方法、例えば含浸法、サイズプレス法、ゲートロール法、ゲートロール法、カレンダー法、スプレー法により塗布されるが、特にサイズプレス法、ゲートロール法におけるサイズ効果が良好である。なお、紙への塗布量は通常は０．００１〜２ｇ／ｍ2 （固形分）、好ましくは０．００５〜０．５ｇ／ｍ2 である。 Further, the surface sizing agent for papermaking of the present invention includes the effects of raw materials such as pulp, filler, internal sizing agent, internal paper strength enhancer, yield improver, and internal chemicals, and papermaking pH, papermaking temperature, papermaking machine. This is almost unaffected by papermaking conditions such as the type of paper. The surface sizing agent for papermaking of the present invention is applied to the above-mentioned various papers by a conventionally known coating method, for example, an impregnation method, a size press method, a gate roll method, a gate roll method, a calendar method, or a spray method. However, the size effect in the size press method and the gate roll method is particularly good. The coating amount of the paper is usually 0.001~2g / m 2 (solid content), preferably from 0.005 to 0.5 / m 2.
以下、参考例および比較例をあげて本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお各例中、部および％は特記しない限りすべて重量基準である。 Hereinafter, the present invention will be specifically described with reference examples and comparative examples, but the present invention is not limited to these examples. In each example, all parts and% are based on weight unless otherwise specified.
合成例１
撹拌器、還流冷却管、窒素導入管付きの反応器に窒素を導入しながら軟水１００部およびイソプロピルアルコール７５部を仕込み、撹拌しながら系を加熱して８０℃まで昇温した。次いで系にスチレン４５部、アクリル酸５５部を混合した単量体混合液と、過硫酸カリウム５部を水１２０部に溶解した重合開始剤水溶液を約３時間かけて系内に滴下し、その後、系を２時間保温して反応を完結させた。その後、イソプロピルアルコールを留去し、冷却後２８％アンモニア水溶液４６．４部(アクリル酸に対して１００モル％)を加え水で希釈し共重合体の濃度が２０％になるように調整し、２５℃の粘度が１１００ｍＰａ・ｓである共重合体水溶液（以下、ポリマー（Ａ）という）を得た。
Synthesis example 1
While introducing nitrogen into a reactor equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, 100 parts of soft water and 75 parts of isopropyl alcohol were charged, and the system was heated to 80 ° C. while stirring. Next, a monomer mixed solution in which 45 parts of styrene and 55 parts of acrylic acid were mixed into the system, and an aqueous polymerization initiator solution in which 5 parts of potassium persulfate was dissolved in 120 parts of water were dropped into the system over about 3 hours. The system was incubated for 2 hours to complete the reaction. Thereafter, isopropyl alcohol was distilled off, and after cooling, 46.4 parts of 28% aqueous ammonia solution (100 mol% relative to acrylic acid) was added and diluted with water to adjust the concentration of the copolymer to 20%. A copolymer aqueous solution (hereinafter referred to as polymer (A)) having a viscosity at 25 ° C. of 1100 mPa · s was obtained.
合成例２
撹拌器、還流冷却管、窒素導入管付きの反応器に窒素を導入しながらイソプロピルアルコール６０部を仕込み、撹拌しながら系を加熱して還流温度まで昇温した。次いで系にスチレン５０部、メタアクリル酸メチル１５部、アクリル酸３０部、アクリルアミド５部およびアゾビスイソブチロニトリル１．５部を混合した単量体混合液を約２時間かけて系内に滴下し、その後、系を４時間保温して反応を完結させた。その後、７５℃に冷却、４８％苛性ソーダ水溶液２４部、水３６０部を添加した。添加終了後、イソプロピルアルコールを留去し、冷却後２８％アンモニア水溶液９部を加え水で希釈し共重合体の濃度が２０％になるように調整し、２５℃の粘度が３００ｍＰａ・ｓである共重合体水溶液（以下、ポリマー（Ｂ）という）を得た。
Synthesis example 2
While introducing nitrogen into a reactor equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, 60 parts of isopropyl alcohol was charged, and the system was heated to the reflux temperature while stirring. Next, a monomer mixed solution prepared by mixing 50 parts of styrene, 15 parts of methyl methacrylate, 30 parts of acrylic acid, 5 parts of acrylamide and 1.5 parts of azobisisobutyronitrile was added to the system over about 2 hours. Then, the system was kept warm for 4 hours to complete the reaction. Thereafter, the mixture was cooled to 75 ° C., and 24 parts of a 48% sodium hydroxide aqueous solution and 360 parts of water were added. After completion of the addition, isopropyl alcohol is distilled off, and after cooling, 9 parts of 28% aqueous ammonia solution is added and diluted with water to adjust the concentration of the copolymer to 20%, and the viscosity at 25 ° C. is 300 mPa · s. An aqueous copolymer solution (hereinafter referred to as polymer (B)) was obtained.
製造例１（水性エマルジョン組成物の製造）
攪拌機、温度計、還流冷却管及び窒素導入管をつけた１リットルの四つ口フラスコ（反応容器）に、水３００部、および保護コロイドとして、炭素数が１８のアルケニル無水コハク酸５.０部、４８％苛性ソーダ水溶液２．３８部（当該アルケニル無水コハク酸に対して１００モル％中和）からなる不揮発分が４０％であってｐＨが１３．０の水溶液を１２．５部（ビニル系単量体全量に対して５重量％）、α−メチルスチレン８部、ブチルメタクリレート８４部、メタクリル酸６部、アクリルアミド２部、Ｎ−ドデシルメルカプタン０.５部、４８％苛性ソーダ５．８部（メタクリル酸に対して１００モル％中和）、およびアニオン性界面活性剤（ネオハイテノールＳ−７０：第一工業製薬（株）製）４部からなる混合物を仕込んだ。反応系内の酸素を窒素で充分に置換し、次いで、前記混合物を７０℃まで昇温した後、反応容器にラジカル重合開始剤（過硫酸アンモニウム２.５部を水８ｇに溶解した水溶液）を投入した。次いで、２０分間乳化重合させた後、８０℃まで昇温し、８０〜８５℃の温度範囲で２時間重合反応を進行させた。このようにして、ｐＨ８．２、固形分濃度２５.５％、粘度１０ｍＰａ・ｓ／２５℃のエマルジョン組成物（製紙用表面サイズ剤）を得た。
Production Example 1 (Production of aqueous emulsion composition)
In a 1 liter four-necked flask (reaction vessel) equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube, 300 parts of water and 5.0 parts of alkenyl succinic anhydride having 18 carbon atoms as protective colloid 12.5 parts of an aqueous solution having a non-volatile content of 40% and a pH of 13.0 consisting of 2.38 parts of a 48% sodium hydroxide aqueous solution (100 mol% neutralized with respect to the alkenyl succinic anhydride). 5 parts by weight based on the total weight of the monomer, α-methylstyrene 8 parts, butyl methacrylate 84 parts, methacrylic acid 6 parts, acrylamide 2 parts, N-dodecyl mercaptan 0.5 parts, 48% caustic soda 5.8 parts (methacrylic) 100 mol% neutralization with respect to the acid) and an anionic surfactant (Neohaitenol S-70: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 4 parts were charged. After sufficiently replacing oxygen in the reaction system with nitrogen, the temperature of the mixture was raised to 70 ° C., and then a radical polymerization initiator (an aqueous solution in which 2.5 parts of ammonium persulfate was dissolved in 8 g of water) was added to the reaction vessel. did. Next, after emulsion polymerization for 20 minutes, the temperature was raised to 80 ° C., and the polymerization reaction was allowed to proceed in the temperature range of 80 to 85 ° C. for 2 hours. Thus, an emulsion composition (surface sizing agent for papermaking) having a pH of 8.2, a solid content concentration of 25.5%, and a viscosity of 10 mPa · s / 25 ° C. was obtained.
製造例２〜１１
表１に示す原料を用いた以外は同様の方法でエマルジョン組成物（製紙用表面サイズ剤）を得た。
Production Examples 2-11
An emulsion composition (surface sizing agent for papermaking) was obtained in the same manner except that the raw materials shown in Table 1 were used.
表中、αＳｔはα−メチルスチレンを、ＢＭＡはアクリル酸ブチルを、ＭＡＡはメタアクリル酸を、ＡＭはアクリルアミドを意味する。 In the table, αSt means α-methylstyrene, BMA means butyl acrylate, MAA means methacrylic acid, and AM means acrylamide.
表中、
※１・・・単量体全量（部）に対する乳化剤の使用重量％を意味する。
※２・・・エマルジョンをなす基幹ポリマー中におけるカルボキシル基の中和率（モル％）を意味する。
※３・・・エマルジョン組成物の固形分濃度（重量％）を意味する。
※４・・・２５℃におけるブルックフィールド型粘度計で測定した値（ｍＰａ・ｓ）を示す。
In the table,
* 1: Indicates the weight percentage of emulsifier used relative to the total amount (parts) of monomer.
* 2: This means the neutralization rate (mol%) of carboxyl groups in the backbone polymer that forms the emulsion.
* 3: Means the solid content concentration (% by weight) of the emulsion composition.
* 4: Indicates a value (mPa · s) measured with a Brookfield viscometer at 25 ° C.
表中、
Ｃ１８−３６ＡＳＡ：炭素数８〜３６のアルキル又はアルケニル置換無水コハク酸アルカリ塩を意味する。
ＯＤＳＡ；炭素数１８のアルケニル基（オクタデセニル基）で置換された無水コハク酸を意味する。
ＤＤＳＡ；炭素数１２のアルケニル基（ドデセニル基）で置換された無水コハク酸を意味する。
ＨＤＳＡ；炭素数１６のアルケニル基（ヘキサデセニル基）で置換された無水コハク酸を意味する。
Ｓ−７０；ハーフエステル型スルホコハク酸ナトリウム（商品名「ネオハイテノールＳ−７０」：第一工業製薬（株）製）
In the table,
C 18-36 ASA: An alkyl or alkenyl substituted succinic anhydride alkali salt having 8 to 36 carbon atoms.
ODSA: means succinic anhydride substituted with an alkenyl group having 18 carbon atoms (octadecenyl group).
DDSA: means succinic anhydride substituted with an alkenyl group having 12 carbon atoms (dodecenyl group).
HDSA: means succinic anhydride substituted with an alkenyl group having 16 carbon atoms (hexadecenyl group).
S-70; sodium half-ester sulfosuccinate (trade name “Neohaitenol S-70” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
＜表面サイズ液の調製：サイズプレス塗工用＞
表１に記載された製造例１のエマルジョン組成物を固形分濃度で０．１５％、酸化澱粉（商品名「王子エース」：王子コーンスターチ（株）製）を固形分濃度で５％含有し、残部は水からなる表面サイズ液を調製した。製造例２〜１１についても同様にして表面サイズ液２〜１１を調製した。
<Preparation of surface sizing solution: for size press coating>
The emulsion composition of Production Example 1 described in Table 1 contains 0.15% in solid concentration, and oxidized starch (trade name “Oji Ace”: manufactured by Oji Corn Starch Co., Ltd.) contains 5% in solid concentration. The balance was a surface sizing solution consisting of water. Surface sizes 2 to 11 were similarly prepared for Production Examples 2 to 11.
また、前記製造例１に係るエマルジョン組成物に前記合成例１で得られたポリマー（Ａ）を固形分比率が１／１になるように混合し、水で固形分濃度が０．１５％、前記酸化澱粉を固形分で５％含有し、残部は水からなる表面サイズ液１２を調整した。 In addition, the polymer (A) obtained in Synthesis Example 1 was mixed with the emulsion composition according to Production Example 1 so that the solid content ratio was 1/1, and the solid content concentration was 0.15% with water. A surface sizing solution 12 containing 5% of the oxidized starch in solid content and the balance comprising water was prepared.
前記合成例１で得られたポリマー（Ａ）に炭素数が１８のアルケニル無水コハク酸のナトリウム塩水溶液を固形分比が５／５となるように混合し、水で固形分濃度が０．１５％、前記酸化澱粉を固形分で５％含有し、残部は水からなる表面サイズ液１３を調製した。 An aqueous sodium salt solution of an alkenyl succinic anhydride having 18 carbon atoms is mixed with the polymer (A) obtained in Synthesis Example 1 so that the solid content ratio is 5/5, and the solid content concentration is 0.15 with water. %, A surface sizing solution 13 containing 5% of the above-mentioned oxidized starch in solid content and the balance comprising water was prepared.
前記合成例２で得られたポリマー（Ｂ）に炭素数が１８のアルケニル無水コハク酸のナトリウム塩水溶液を固形分比が９５／５となるように混合し、水で固形分濃度が０．１５％、前記酸化澱粉を固形分で５％含有し、残部は水からなる表面サイズ液１４を調製した。 An aqueous sodium salt solution of an alkenyl succinic anhydride having 18 carbon atoms is mixed with the polymer (B) obtained in Synthesis Example 2 so that the solid content ratio is 95/5, and the solid content concentration is 0.15 with water. %, And the oxidized starch was contained in a solid content of 5%, and the balance was prepared as a surface sizing solution 14 consisting of water.
前記合成例１で得られたポリマー（Ａ）のみを、水で固形分濃度が０．１５％、前記酸化澱粉を固形分で５％含有し、残部は水からなる表面サイズ液１５を調製した。 Only the polymer (A) obtained in Synthesis Example 1 was prepared with a surface concentration solution 15 containing a solid content concentration of 0.15% in water and the oxidized starch in a solid content of 5%, with the balance being water. .
＜表面サイズ液の調製：ゲートロール用＞
前記サイズプレス用の表面サイズ液１〜１１、１２、１３、１４及び１５の組成濃度を、酸化澱粉の固形分濃度が８％、酸化澱粉以外の固形分成分の濃度が３％となるように変更したものを、夫々表面サイズ液１６〜２６、２７、２８、２９及び３０とした。
<Preparation of surface sizing solution: for gate roll>
The composition concentration of the surface size liquids 1 to 11, 12, 13, 14, and 15 for the size press is such that the solid content concentration of oxidized starch is 8% and the concentration of solid content components other than oxidized starch is 3%. The changed ones were designated as surface size liquids 16 to 26, 27, 28, 29, and 30, respectively.
＜試験用紙の作成：サイズプレス法＞
中性上質用紙（秤量７０ｇ／ｍ２、ステキヒトサイズ度０秒）を原紙とし、前記表面サイズ液１〜１５のそれぞれを用いて、ラボサイズプレス塗工機（試験用サイズプレス、熊谷理機工業(株)）により塗工を行った。次いで、各塗工紙を回転式ドラムドライヤーにて１０５℃、１分間乾燥を行い、目的とする試験用紙を得た。
<Test paper preparation: size press method>
Neutral high-quality paper (weighing 70 g / m 2 , Steecht size degree 0 second) is used as a base paper, and each of the above surface size liquids 1 to 15 is used for a laboratory size press coating machine (size press for testing, Riki Kumagai). Coating was carried out by Kogyo Co., Ltd. Next, each coated paper was dried at 105 ° C. for 1 minute with a rotary drum dryer to obtain a target test paper.
＜試験用紙の作成：ゲートロール法＞
前記中性上質用紙を原紙とし、前記表面サイズ液１６〜３０のそれぞれを用いて、ラボゲートロール塗工機（（株）エスエムテー製）により塗工を行った。次いで、各塗工紙を回転式ドラムドライヤーにて１０５℃、１分間乾燥を行い、目的とする試験用紙を得た。
<Test paper preparation: gate roll method>
The neutral high-quality paper was used as a base paper, and coating was performed using a lab gate roll coating machine (manufactured by SMT Co., Ltd.) using each of the surface size liquids 16 to 30. Next, each coated paper was dried at 105 ° C. for 1 minute with a rotary drum dryer to obtain a target test paper.
実施例、比較例
（ステキヒトサイズ度の測定）
前記方法で得られた各塗工紙を用い、ＪＩＳ Ｐ ８１２２に準拠してステキヒトサイズ度を測定した。結果を表２に示す。
Examples, comparative examples (measurement of squeecht size)
Using each coated paper obtained by the above-mentioned method, the Steecht sizing degree was measured in accordance with JIS P8122. The results are shown in Table 2.
（ドロップサイズ度の測定）
前記方法で得られた各塗工紙を用い、脱イオン水０．５μＬを紙面に滴下し光沢がなくなるまでの時間を測定した。結果を表２に示す。
(Drop size measurement)
Using each coated paper obtained by the above method, 0.5 μL of deionized water was dropped on the paper surface, and the time until gloss was lost was measured. The results are shown in Table 2.
（発泡性の測定）
前記表面サイズ液１〜１６の夫々を５０℃に加熱したものを家庭用ミキサーで１分間処理を行ったときの泡立（ｍｍ）の高さを測定した。結果を表２に示す。
(Measurement of foamability)
The height of foaming (mm) was measured when each of the surface sizing liquids 1 to 16 was heated to 50 ° C. and treated with a household mixer for 1 minute. The results are shown in Table 2.
（インクジェット適性の評価（印字濃度測定））
前記サイズプレス法で得られた各塗工紙に、インクジェットプリンター（商品名「ＢＪＣ−４２０Ｊ」：キャノン（株）製）を用いてモノクロ・カラー（染料）でべた印刷した。次いで、反射濃度計（商品名「グレタグＤ１８６」：グレタグマクベス（株）製）を用いて得られた印刷部位の濃度測定を行った。数値が大きいほど印字濃度が高いことを示す。結果を、表２に示す。
(Evaluation of inkjet suitability (print density measurement))
Each coated paper obtained by the size press method was printed in monochrome color (dye) using an inkjet printer (trade name “BJC-420J” manufactured by Canon Inc.). Subsequently, the density measurement of the printing site | part obtained using the reflection densitometer (Brand name "Gretag D186": Gretag Macbeth Co., Ltd. product) was performed. The larger the value, the higher the print density. The results are shown in Table 2.
（インクジェット適性の評価（フェザーリング試験））
前記サイズプレス法で得られた各塗工紙に、インクジェットプリンター（商品名「ＢＪＣ−４２０Ｊ」：キャノン（株）製）を用いてモノクロ・カラー（染料）で直行する線幅一定の直線及び文字を印字し、目視にて直線及び文字の外縁のにじみを目し評価することで行った。フェザーリングの全くないものを６とし、インクがにじまって文字の判別がつかないものを０とした。結果を表２に示す。
(Evaluation of ink jet aptitude (feathering test))
Straight lines and characters with a constant line width that go straight in monochrome color (dye) using an inkjet printer (trade name “BJC-420J” manufactured by Canon Inc.) on each coated paper obtained by the size press method. This was done by visually observing blurring of straight lines and outer edges of characters. The case where there was no feathering was set to 6, and the case where ink could not be recognized due to ink bleeding was set to 0. The results are shown in Table 2.
（インクジェット適性の評価（ブリーディング試験））
前記サイズプレス法で得られた各塗工紙に、インクジェットプリンター（商品名「ＢＪＣ−４２０Ｊ」：キャノン（株）製）を用いてイエローとブラックが隣り合うように印字を行いイエロー印字部へのブラックインクのにじみを目視評価することで行った。フェザリングの全くないものを６とし、インクがにじんでしまって文字の判別がつかないものを０とした。結果を表２に示す。
(Evaluation of inkjet suitability (bleeding test))
On each coated paper obtained by the size press method, printing is performed so that yellow and black are adjacent to each other using an inkjet printer (trade name “BJC-420J” manufactured by Canon Inc.). This was performed by visually evaluating the bleeding of the black ink. The case where there was no feathering was set to 6, and the case where ink was blurred and the character could not be identified was set to 0. The results are shown in Table 2.
表２に示す結果から明らかなように、実施例１〜３は、サイズプレス法およびゲートロール法においても高いサイズ効果を発揮する。すなわちサイズプレス塗工方式とゲートロール塗工方式の両方式において良好なサイズ効果を発現し得、系内の泡立ちが非常に少ない。比較例１〜３、１０においては、保護コロイドたるアルケニル置換無水コハク酸アルカリ塩をビニル系単量体総量の８重量％を超えて使用されることから、ゲートロール法におけるサイズ効果は比較的高いが、サイズプレス法ではステキヒトサイズ度が低い。また比較例５は、アルケニル無水コハク酸のアルカリ塩と疎水性不飽和単量体、メタクリル酸及びアクリルアミド系単量体からなる重合体をブレンドしたものであるが、アルケニル無水コハク酸が同添加量である実施例１等と対比すると、ゲートロール法においてサイズが発現し難いことがわかる。 As is apparent from the results shown in Table 2, Examples 1 to 3 exhibit a high size effect even in the size press method and the gate roll method. That is, a good size effect can be expressed in both the size press coating method and the gate roll coating method, and foaming in the system is very small. In Comparative Examples 1 to 3 , and 10 , since the alkenyl-substituted succinic anhydride alkali salt as the protective colloid is used in excess of 8 % by weight of the total amount of the vinyl monomer, the size effect in the gate roll method is relatively high. However, the size press method has a low degree of steecht size. Comparative Example 5 is a blend of an alkali salt of alkenyl succinic anhydride and a polymer comprising a hydrophobic unsaturated monomer, methacrylic acid and an acrylamide monomer, but the alkenyl succinic anhydride is added in the same amount. Compared with Example 1 etc. which are these, it turns out that size is hard to express in a gate roll method.
また、表２の実施例４より、本発明に係る製紙用表面サイズ剤に対する添加剤として、疎水性不飽和単量体およびカルボキシル基含有不飽和単量体を重合させて得られる水溶性重合体を配合することにより、良好なカラーインクジェット適性、具体的にはフェザリングとブリーディングにバランスがとれるという効果を得ることができる。
Further, from Example 4 in Table 2, a water-soluble polymer obtained by polymerizing a hydrophobic unsaturated monomer and a carboxyl group-containing unsaturated monomer as an additive to the paper sizing agent according to the present invention. By blending, it is possible to obtain good color ink jet aptitude, specifically, an effect of balancing the feathering and bleeding.
Claims (7)
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