JPH0913295A - Liquid agent for improving surface quality of paper - Google Patents
Liquid agent for improving surface quality of paperInfo
- Publication number
- JPH0913295A JPH0913295A JP17798395A JP17798395A JPH0913295A JP H0913295 A JPH0913295 A JP H0913295A JP 17798395 A JP17798395 A JP 17798395A JP 17798395 A JP17798395 A JP 17798395A JP H0913295 A JPH0913295 A JP H0913295A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- acid
- maleic acid
- styrene
- meth
- 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.)
- Pending
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 85
- 229920005989 resin Polymers 0.000 claims abstract description 85
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 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 claims abstract description 9
- MKALOVJHPRAZRE-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=CC=CC1=CC=CC=C1 MKALOVJHPRAZRE-UHFFFAOYSA-N 0.000 claims abstract description 8
- GPEBATBEGCDEFK-PAMPIZDHSA-N (z)-but-2-enedioic acid;2-methylprop-1-ene Chemical compound CC(C)=C.OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O GPEBATBEGCDEFK-PAMPIZDHSA-N 0.000 claims abstract description 6
- VJAKQOZUHPALOQ-VHUAPCKSSA-N C(C=C/C(=O)O)(=O)O.C(=CC1=CC=CC=C1)/C(=C/C(=O)O)/C(=O)O Chemical compound C(C=C/C(=O)O)(=O)O.C(=CC1=CC=CC=C1)/C(=C/C(=O)O)/C(=O)O VJAKQOZUHPALOQ-VHUAPCKSSA-N 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims description 13
- 150000003926 acrylamides Chemical class 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- LZDDXRWBWZUFHD-ODZAUARKSA-N (z)-but-2-enedioic acid;2-methylprop-1-ene Chemical compound CC(C)=C.OC(=O)\C=C/C(O)=O LZDDXRWBWZUFHD-ODZAUARKSA-N 0.000 claims description 5
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 4
- 150000003009 phosphonic acids Chemical class 0.000 claims description 4
- 150000003460 sulfonic acids Chemical class 0.000 claims description 4
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 4
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- -1 acrylamide compound Chemical class 0.000 abstract description 27
- 239000011976 maleic acid Substances 0.000 abstract description 10
- 238000004513 sizing Methods 0.000 abstract description 5
- 239000000123 paper Substances 0.000 description 37
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000005476 size effect Effects 0.000 description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000003863 ammonium salts Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 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 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 159000000001 potassium salts Chemical class 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-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
- 239000002585 base Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- KPHXZEMRIVKEIQ-UHFFFAOYSA-N N-[3-[dimethoxy(2-methylpropyl)silyl]propyl]prop-2-enamide Chemical compound C(C=C)(=O)NCCC[Si](OC)(OC)CC(C)C KPHXZEMRIVKEIQ-UHFFFAOYSA-N 0.000 description 2
- 229920001800 Shellac Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000004208 shellac Substances 0.000 description 2
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 2
- 229940113147 shellac Drugs 0.000 description 2
- 235000013874 shellac Nutrition 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- IDXCKOANSQIPGX-UHFFFAOYSA-N (acetyloxy-ethenyl-methylsilyl) acetate Chemical compound CC(=O)O[Si](C)(C=C)OC(C)=O IDXCKOANSQIPGX-UHFFFAOYSA-N 0.000 description 1
- STGNLGBPLOVYMA-TZKOHIRVSA-N (z)-but-2-enedioic acid Chemical compound OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O STGNLGBPLOVYMA-TZKOHIRVSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- GSSDUXHQPXODCN-UHFFFAOYSA-N 1-phenylethenylphosphonic acid Chemical compound OP(O)(=O)C(=C)C1=CC=CC=C1 GSSDUXHQPXODCN-UHFFFAOYSA-N 0.000 description 1
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- ZZHQUFIOKFFEAC-UHFFFAOYSA-N 18-triacetyloxysilyloctadecyl prop-2-enoate Chemical compound C(C=C)(=O)OCCCCCCCCCCCCCCCCCC[Si](OC(C)=O)(OC(C)=O)OC(C)=O ZZHQUFIOKFFEAC-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 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
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- RSROEZYGRKHVMN-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.CCC(CO)(CO)CO RSROEZYGRKHVMN-UHFFFAOYSA-N 0.000 description 1
- HGJDNBZIDQOMEU-UHFFFAOYSA-N 2-methyl-n,n-bis(prop-2-enyl)prop-2-enamide Chemical compound CC(=C)C(=O)N(CC=C)CC=C HGJDNBZIDQOMEU-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- HHHPYRGQUSPESB-UHFFFAOYSA-N 3-(dimethoxymethylsilyl)propyl prop-2-enoate Chemical compound COC(OC)[SiH2]CCCOC(=O)C=C HHHPYRGQUSPESB-UHFFFAOYSA-N 0.000 description 1
- BXAAQNFGSQKPDZ-UHFFFAOYSA-N 3-[1,2,2-tris(prop-2-enoxy)ethoxy]prop-1-ene Chemical compound C=CCOC(OCC=C)C(OCC=C)OCC=C BXAAQNFGSQKPDZ-UHFFFAOYSA-N 0.000 description 1
- GBAQKTTVWCCNHH-UHFFFAOYSA-N 3-[dichloro(methyl)silyl]propyl prop-2-enoate Chemical compound C[Si](Cl)(Cl)CCCOC(=O)C=C GBAQKTTVWCCNHH-UHFFFAOYSA-N 0.000 description 1
- NMBCRAXGCAEIGZ-UHFFFAOYSA-N 3-[ethenyl(dimethyl)silyl]oxyaniline Chemical compound C=C[Si](C)(C)OC1=CC=CC(N)=C1 NMBCRAXGCAEIGZ-UHFFFAOYSA-N 0.000 description 1
- WOZHZOLFFPSEAM-UHFFFAOYSA-N 3-butene-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(=C)C(O)=O WOZHZOLFFPSEAM-UHFFFAOYSA-N 0.000 description 1
- VLRGXXKFHVJQOL-UHFFFAOYSA-N 3-chloropentane-2,4-dione Chemical compound CC(=O)C(Cl)C(C)=O VLRGXXKFHVJQOL-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- VFKZECOCJCGZQK-UHFFFAOYSA-M 3-hydroxypropyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCO VFKZECOCJCGZQK-UHFFFAOYSA-M 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- SWZBNMRGWLZHGE-UHFFFAOYSA-N 4-[ethenyl(dimethyl)silyl]oxyaniline Chemical compound C=C[Si](C)(C)OC1=CC=C(N)C=C1 SWZBNMRGWLZHGE-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- YJQVMTGDHQCLGL-UHFFFAOYSA-N C(C=C)(=O)NCCC[Si](OC(C)=O)(OC(C)=O)CCCCCCCC Chemical compound C(C=C)(=O)NCCC[Si](OC(C)=O)(OC(C)=O)CCCCCCCC YJQVMTGDHQCLGL-UHFFFAOYSA-N 0.000 description 1
- MBADEJCVXKMKQU-UHFFFAOYSA-N C(C=C)(=O)NCCC[Si](OCC)(OCC)CC1=CC=CC=C1 Chemical compound C(C=C)(=O)NCCC[Si](OCC)(OCC)CC1=CC=CC=C1 MBADEJCVXKMKQU-UHFFFAOYSA-N 0.000 description 1
- GRPDKQBJIAHIEY-UHFFFAOYSA-N C(C=C)(=O)NCCC[Si](OCCNC)(OCCNC)OCCNC Chemical compound C(C=C)(=O)NCCC[Si](OCCNC)(OCCNC)OCCNC GRPDKQBJIAHIEY-UHFFFAOYSA-N 0.000 description 1
- YAQNMHKUHVNSNU-UHFFFAOYSA-N C(C=C)(=O)NCO[Si](OC)(Cl)CC(C)C Chemical compound C(C=C)(=O)NCO[Si](OC)(Cl)CC(C)C YAQNMHKUHVNSNU-UHFFFAOYSA-N 0.000 description 1
- TWUNLFOKRYHVRI-UHFFFAOYSA-N C(C=C)(=O)NC[Si](OC(C)=O)(OC(C)=O)C1=CC=CC=C1 Chemical compound C(C=C)(=O)NC[Si](OC(C)=O)(OC(C)=O)C1=CC=CC=C1 TWUNLFOKRYHVRI-UHFFFAOYSA-N 0.000 description 1
- RADIZGQSFSEOQU-UHFFFAOYSA-N CC(C[Si](OC)(OC)OC)C.C(C=C)(=O)N Chemical compound CC(C[Si](OC)(OC)OC)C.C(C=C)(=O)N RADIZGQSFSEOQU-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
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Landscapes
- Paper (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、紙の表面強度、内部強
度、サイズ効果をバランス良く向上させ、製品安定性に
優れる表面紙質向上液剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface paper quality improving liquid agent which improves the surface strength, internal strength and size effect of paper in a well-balanced manner and is excellent in product stability.
【0002】[0002]
【従来の技術】近年の印刷技術の発展は目覚ましく、印
刷の高速化、高品質化に伴い、印刷用紙に対して高度な
要求、例えば表面強度、内部強度、サイズ性等の印刷適
性の向上が求められるようになってきた。これらの要求
に対応するため製紙用薬品をパルプの水性スラリーに添
加(内添)したり、紙の表面に塗工(外添)することが
行われている。これらのうち内添剤は薬品の歩留りが十
分ではなく、一方、外添剤は薬品の歩留りがほぼ100
%であり、紙の表面に直接作用することから、より有利
なことが知られている。紙の表面強度、内部強度、サイ
ズ性を向上させ、印刷適性を向上させることを目的とす
る表面紙質向上剤としては、従来よりアルケニルコハク
酸塩とポリアクリルアミド系物質の混合物(特公昭60
−10160号公報)が知られている。2. Description of the Related Art In recent years, the development of printing technology has been remarkable, and with the increase in printing speed and quality, it has become more and more demanding for printing paper to improve its printability such as surface strength, internal strength and size. It has come to be demanded. In order to meet these requirements, papermaking chemicals have been added (internally added) to an aqueous pulp slurry or coated (externally added) on the surface of paper. Of these, the internal additive has an insufficient chemical yield, while the external additive has a chemical yield of almost 100.
%, Which is known to be more advantageous because it acts directly on the surface of the paper. Conventionally, a mixture of alkenyl succinate and polyacrylamide type substances (Japanese Patent Publication No. 60
No. 10160) is known.
【0003】[0003]
【発明が解決しようとする課題】しかしながら、最近の
高度な表面紙質向上の要求に対して、従来の表面紙質向
上剤では十分に満足な効果が得られておらず、特に、表
面強度、内部強度、サイズ性をバランス良く向上させる
点が不十分であった。例えば、無サイズ紙に上記従来技
術の表面紙質向上剤をゲートロールコーター、サイズプ
レス等で表面塗工した場合は、表面強度、内部強度は向
上するが、サイズ性の向上は十分とは言えない。また、
強サイズ紙に同様に塗工した場合には、サイズ効果は向
上せずむしろ低下することがあり問題視されている。However, the conventional surface paper quality improvers have not been sufficiently satisfactory in response to the recent demand for a high degree of surface paper quality improvement. However, it was insufficient to improve the size property in a well-balanced manner. For example, when the above-mentioned conventional surface paper quality improver is applied to a non-sized paper by a gate roll coater, a size press, etc., the surface strength and internal strength are improved, but the sizing property is not sufficiently improved. . Also,
When the same is applied to strong size paper, the size effect is not improved but rather deteriorated, which is regarded as a problem.
【0004】そこで、サイズ効果を向上させるべく、上
記従来技術の表面紙質向上剤の疎水性成分(アルケニル
コハク酸塩)の混合比率を増加させると、サイズ性は改
善されるが、一方、表面強度、内部強度は著しく低下す
るので好ましくない。また、上記混合比率を変えずに、
疎水性成分自身(アルケニルコハク酸塩)の疎水性を上
げサイズ効果を高めるという方法は、併用するポリアク
リルアミド系物質との相溶性の低下をもたらし好ましく
ない。このため、表面強度、内部強度と共にサイズ性を
バランス良く向上させる表面紙質向上剤の出現が強く望
まれていた。本発明は上記課題を解決するための表面紙
質向上液剤を提供するものである。Therefore, if the mixing ratio of the hydrophobic component (alkenyl succinate) of the above-mentioned surface paper quality improver of the prior art is increased in order to improve the size effect, the size property is improved, while the surface strength is improved. However, the internal strength is significantly reduced, which is not preferable. Also, without changing the mixing ratio,
The method of increasing the hydrophobicity of the hydrophobic component itself (alkenyl succinate) to enhance the size effect is not preferable because it reduces the compatibility with the polyacrylamide-based substance used in combination. Therefore, it has been strongly desired to develop a surface paper quality improving agent that improves the surface strength and the internal strength as well as the size property in a well-balanced manner. The present invention provides a surface paper quality improving liquid agent for solving the above problems.
【0005】[0005]
【課題を解決するための手段】本発明者等は、その要望
に答えるべく鋭意研究を行った結果、スチレン−アクリ
ル酸樹脂、スチレン−アクリル酸−アクリル酸エステル
樹脂、スチレン−マレイン酸樹脂、スチレン−マレイン
酸−マレイン酸半エステル樹脂、(ジ)イソブチレン−
マレイン酸樹脂、(ジ)イソブチレン−マレイン酸−マ
レイン酸半エステル樹脂からなる群から選ばれた少なく
とも一種の樹脂〔A〕1〜50重量部と、アクリルアミ
ド類(a)100重量部と、アニオン性ビニルモノマー
(b)0.5〜50重量部および必要に応じて架橋剤
(c)0.005〜10重量部を反応して得られるアク
リルアミド系樹脂〔B〕の混合水溶液を含有する表面紙
質向上液剤を用いることにより、表面強度、内部強度と
共にサイズ効果をバランス良く向上させることを見い出
し、本発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted diligent research to meet the demand, and as a result, styrene-acrylic acid resin, styrene-acrylic acid-acrylic acid ester resin, styrene-maleic acid resin, styrene. -Maleic acid-Maleic acid half ester resin, (di) isobutylene-
1 to 50 parts by weight of at least one resin [A] selected from the group consisting of maleic acid resin and (di) isobutylene-maleic acid-maleic acid half-ester resin, 100 parts by weight of acrylamides (a), and anionic Surface paper quality improvement containing a mixed aqueous solution of an acrylamide resin [B] obtained by reacting 0.5 to 50 parts by weight of a vinyl monomer (b) and optionally 0.005 to 10 parts by weight of a crosslinking agent (c). By using a liquid agent, it was found that the size effect can be improved in a well-balanced manner as well as the surface strength and the internal strength, and the present invention has been completed.
【0006】すなわち本発明は、スチレン−アクリル酸
樹脂、スチレン−アクリル酸−アクリル酸エステル樹
脂、スチレン−マレイン酸樹脂、スチレン−マレイン酸
−マレイン酸半エステル樹脂、(ジ)イソブチレン−マ
レイン酸樹脂、(ジ)イソブチレン−マレイン酸−マレ
イン酸半エステル樹脂からなる群から選ばれた少なくと
も一種の樹脂〔A〕1〜50重量部と、アクリルアミド
類(a)100重量部と、アニオン性ビニルモノマー
(b)0.5〜50重量部を反応して得られるアクリル
アミド系樹脂〔B〕の混合水溶液を含有する表面紙質向
上液剤、That is, the present invention relates to a styrene-acrylic acid resin, a styrene-acrylic acid-acrylic acid ester resin, a styrene-maleic acid resin, a styrene-maleic acid-maleic acid half-ester resin, a (di) isobutylene-maleic acid resin, (Di) 1 to 50 parts by weight of at least one resin [A] selected from the group consisting of isobutylene-maleic acid-maleic acid half ester resin, 100 parts by weight of acrylamides (a), and anionic vinyl monomer (b). ) A surface paper quality improving liquid agent containing a mixed aqueous solution of an acrylamide resin [B] obtained by reacting 0.5 to 50 parts by weight,
【0007】あるいはスチレン−アクリル酸樹脂、スチ
レン−アクリル酸−アクリル酸エステル樹脂、スチレン
−マレイン酸樹脂、スチレン−マレイン酸−マレイン酸
半エステル樹脂、(ジ)イソブチレン−マレイン酸樹
脂、(ジ)イソブチレン−マレイン酸−マレイン酸半エ
ステル樹脂からなる群から選ばれた少なくとも一種の樹
脂〔A〕1〜50重量部と、アクリルアミド類(a)1
00重量部と、アニオン性ビニルモノマー(b)0.5
〜50重量部と、架橋剤(c)0.005〜10重量部
を反応して得られるアクリルアミド系樹脂〔B〕の混合
水溶液を含有する表面紙質向上液剤を提供するものであ
る。Alternatively, styrene-acrylic acid resin, styrene-acrylic acid-acrylic acid ester resin, styrene-maleic acid resin, styrene-maleic acid-maleic acid half ester resin, (di) isobutylene-maleic acid resin, (di) isobutylene 1-50 parts by weight of at least one resin [A] selected from the group consisting of maleic acid-maleic acid half-ester resin, and acrylamides (a) 1
00 parts by weight and 0.5 of the anionic vinyl monomer (b)
A surface paper quality improving liquid agent containing a mixed aqueous solution of acrylamide resin [B] obtained by reacting ˜50 parts by weight with 0.005 to 10 parts by weight of a crosslinking agent (c) is provided.
【0008】なお、上記樹脂〔A〕がスチレン−アクリ
ル酸樹脂であることが好ましく、上記アクリルアミド類
(a)がアクリルアミド、メタクリルアミドであること
が好ましい。また、上記アニオン性ビニルモノマー
(b)が不飽和モノカルボン酸、不飽和ジカルボン酸、
不飽和トリカルボン酸、不飽和テトラカルボン酸、不飽
和スルホン酸、不飽和ホスホン酸、およびそれらの塩類
からなる群から選ばれた少なくとも一種であることが好
ましい。The resin [A] is preferably a styrene-acrylic acid resin, and the acrylamides (a) are preferably acrylamide or methacrylamide. Further, the anionic vinyl monomer (b) is an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid,
It is preferably at least one selected from the group consisting of unsaturated tricarboxylic acid, unsaturated tetracarboxylic acid, unsaturated sulfonic acid, unsaturated phosphonic acid, and salts thereof.
【0009】次に本発明を詳細に説明する。本発明で使
用する樹脂〔A〕であるスチレン−アクリル酸樹脂、ス
チレン−アクリル酸−アクリル酸エステル樹脂、スチレ
ン−マレイン酸樹脂、スチレン−マレイン酸−マレイン
酸半エステル樹脂、(ジ)イソブチレン−マレイン酸樹
脂、(ジ)イソブチレン−マレイン酸−マレイン酸半エ
ステル樹脂は、塊状重合、溶液重合、乳化重合等のいず
れの方法で重合したものでも良いが、特に塊状重合品が
好ましい。粉末の樹脂を用いる場合には、重合前あるい
は重合中に水溶液とするためケン化する必要がある。Next, the present invention will be described in detail. The resin [A] used in the present invention is styrene-acrylic acid resin, styrene-acrylic acid-acrylic acid ester resin, styrene-maleic acid resin, styrene-maleic acid-maleic acid half ester resin, (di) isobutylene-malein. The acid resin and the (di) isobutylene-maleic acid-maleic acid half ester resin may be polymerized by any method such as bulk polymerization, solution polymerization and emulsion polymerization, but a bulk polymerization product is particularly preferable. When a powdered resin is used, it needs to be saponified to form an aqueous solution before or during the polymerization.
【0010】ケン化時に用いるアルカリとしては、水酸
化ナトリウム、水酸化カリウム、アンモニア、珪酸ナト
リウム、アルミン酸ナトリウム、モノエタノールアミ
ン、トリエタノールアミン等から選ばれる1種または2
種以上の有機または無機アルカリを用いることができ
る。また、スチレンとアクリル酸、スチレンとアクリル
酸とアクリル酸エステル、スチレンとマレイン酸、スチ
レンとマレイン酸とマレイン酸半エステル、(ジ)イソ
ブチレンとマレイン酸、(ジ)イソブチレンとマレイン
酸とマレイン酸半エステルの組成比、分子量について
は、アクリルアミド系樹脂〔B〕との相溶性を阻害しな
い範囲内であれば、特に限定するものではない。The alkali used for saponification is one or two selected from sodium hydroxide, potassium hydroxide, ammonia, sodium silicate, sodium aluminate, monoethanolamine, triethanolamine and the like.
More than one organic or inorganic alkali can be used. Also, styrene and acrylic acid, styrene and acrylic acid and acrylic ester, styrene and maleic acid, styrene and maleic acid and maleic acid half ester, (di) isobutylene and maleic acid, (di) isobutylene and maleic acid and maleic acid half ester. The composition ratio and molecular weight of the ester are not particularly limited as long as they do not impair the compatibility with the acrylamide resin [B].
【0011】樹脂〔A〕としては、GSA2302(ス
チレン−アクリル酸樹脂:岐阜セラック社製)、GSA
2303(スチレン−アクリル酸−アクリル酸エステル
樹脂:岐阜セラック社製)、SMA3000(スチレン
−マレイン酸樹脂:エルフ・アトケム社製)、SMA2
000(スチレン−マレイン酸樹脂:エルフ・アトケム
社製)、イソバン10(イソブチレン−マレイン酸樹
脂:クラレ社製)等が挙げられる。特に、スチレン−ア
クリル酸樹脂が好ましい。As the resin [A], GSA2302 (styrene-acrylic acid resin: manufactured by Gifu Shellac), GSA
2303 (styrene-acrylic acid-acrylic acid ester resin: manufactured by Gifu Shellac), SMA3000 (styrene-maleic acid resin: manufactured by Elf Atchem), SMA2
000 (styrene-maleic acid resin: manufactured by Elf Atchem), isoban 10 (isobutylene-maleic acid resin: manufactured by Kuraray Co., Ltd.) and the like. Particularly, styrene-acrylic acid resin is preferable.
【0012】次に、本発明で使用するアクリルアミド系
樹脂〔B〕について説明する。アクリルアミド系樹脂
〔B〕に使用する(a)成分のアクリルアミド類として
は、アクリルアミド、メタクリルアミドが好ましく、ま
た、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,N−ジメチル(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−t−オクチル(メタ)アクリルアミド等のN置
換アクリルアミド類のいずれか一種以上をアクリルアミ
ド、メタクリルアミドと併用して使用することもでき
る。Next, the acrylamide resin [B] used in the present invention will be described. As the acrylamides of the component (a) used in the acrylamide resin [B], acrylamide and methacrylamide are preferable, and N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl ( Any one or more of N-substituted acrylamides such as (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nt-octyl (meth) acrylamide can be used in combination with acrylamide and methacrylamide.
【0013】アクリルアミド系樹脂〔B〕に使用する
(b)成分のアニオン性ビニルモノマーである不飽和モ
ノカルボン酸、不飽和ジカルボン酸、不飽和トリカルボ
ン酸、不飽和テトラカルボン酸、不飽和スルホン酸、不
飽和ホスホン酸およびそれらの塩類について以下に例示
する。Unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated tricarboxylic acid, unsaturated tetracarboxylic acid, unsaturated sulfonic acid, which is the anionic vinyl monomer of the component (b) used in the acrylamide resin [B], The unsaturated phosphonic acid and salts thereof are exemplified below.
【0014】不飽和モノカルボン酸及びそれらの塩類と
しては、アクリル酸、メタクリル酸及びそれらのナトリ
ウム、カリウム塩等のアルカリ金属塩類またはアンモニ
ウム塩等が挙げられる。Examples of the unsaturated monocarboxylic acid and salts thereof include acrylic acid, methacrylic acid and their alkali metal salts such as sodium and potassium salts, ammonium salts and the like.
【0015】不飽和ジカルボン酸およびそれらの塩類と
しては、マレイン酸、フマル酸、イタコン酸、シトラコ
ン酸およびそれらのナトリウム、カリウム塩等のアルカ
リ金属塩類またはアンモニウム塩等が挙げられる。Examples of unsaturated dicarboxylic acids and salts thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid and their alkali metal salts such as sodium and potassium salts, or ammonium salts.
【0016】不飽和トリカルボン酸及びそれらの塩類と
してはアコニット酸、3−ブテン−1,2,3−トリカ
ルボン酸、4−ペンテン−1,2,4−トリカルボン酸
およびそれらのナトリウム、カリウム塩等のアルカリ金
属塩類またはアンモニウム塩等が挙げられる。Examples of unsaturated tricarboxylic acids and salts thereof include aconitic acid, 3-butene-1,2,3-tricarboxylic acid, 4-pentene-1,2,4-tricarboxylic acid and their sodium and potassium salts. Examples thereof include alkali metal salts and ammonium salts.
【0017】不飽和テトラカルボン酸及びそれらの塩類
としては、1−ペンテン−1,1,4,4−テトラカル
ボン酸、4−ペンテン−1,2,3,4−テトラカルボ
ン酸、3−ヘキセン−1,1,6,6−テトラカルボン
酸およびそれらのナトリウム、カリウム塩等のアルカリ
金属塩類またはアンモニウム塩等が挙げられる。The unsaturated tetracarboxylic acid and salts thereof include 1-pentene-1,1,4,4-tetracarboxylic acid, 4-pentene-1,2,3,4-tetracarboxylic acid and 3-hexene. Examples thereof include -1,1,6,6-tetracarboxylic acid and their alkali metal salts such as sodium and potassium salts or ammonium salts.
【0018】不飽和スルホン酸としては、ビニルスルホ
ン酸、スチレンスルホン酸、アリルスルホン酸、2−ア
クリルアミド−2−メチルプロパンスルホン酸およびそ
れらのナトリウム、カリウム塩等のアルカリ金属塩類ま
たはアンモニウム塩等が挙げられる。Examples of the unsaturated sulfonic acid include vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid and their alkali metal salts such as sodium and potassium salts or ammonium salts. To be
【0019】不飽和ホスホン酸としては、ビニルホスホ
ン酸、α−フェニルビニルホスホン酸およびそれらのナ
トリウム、カリウム塩等のアルカリ金属塩類またはアン
モニウム塩等が挙げられる。Examples of the unsaturated phosphonic acid include vinylphosphonic acid, α-phenylvinylphosphonic acid and their alkali metal salts such as sodium and potassium salts or ammonium salts.
【0020】上記アニオン性ビニルモノマーのうちイタ
コン酸、アクリル酸及びその塩類が好ましく、特に、イ
タコン酸およびその塩類が好ましい。アニオン性基の導
入方法として、アニオン性ビニルモノマーを用いる方法
以外に、アクリルアミド系樹脂〔B〕を酸またはアルカ
リで加水分解することにより、アニオン基を導入する方
法も使用できる。Of the above anionic vinyl monomers, itaconic acid, acrylic acid and salts thereof are preferable, and itaconic acid and salts thereof are particularly preferable. As a method of introducing the anionic group, a method of introducing the anionic group by hydrolyzing the acrylamide resin [B] with an acid or an alkali can be used in addition to the method of using the anionic vinyl monomer.
【0021】上記(a)および(b)成分以外にジメチ
ルアミノプロピル(メタ)アクリルアミド及びその4級
化物等の共重合可能なカチオン性ビニルモノマー、ある
いは得られたアクリルアミド系樹脂〔B〕の相溶性、水
溶性を害しない程度の量のノニオン性ビニルモノマーも
使用できる。In addition to the above components (a) and (b), the compatibility of the copolymerizable cationic vinyl monomers such as dimethylaminopropyl (meth) acrylamide and its quaternary products, or the obtained acrylamide resin [B]. Also, nonionic vinyl monomers in an amount that does not impair the water solubility can be used.
【0022】カチオン性ビニルモノマーとしては、例え
ばジメチルアミノエチル(メタ)アクリレート、ジエチ
ルアミノエチル(メタ)アクリレート、ジメチルアミノ
プロピル(メタ)アクリレート、ジエチルアミノプロピ
ル(メタ)アクリレート、ジメチルアミノプロピル(メ
タ)アクリルアミドもしくはジエチルアミノプロピル
(メタ)アクリルアミド、アルキルジアリルアミン、ジ
アルキルアリルアミン、ジアリルアミン、アリルアミン
等の3級アミノ基、2級アミノ基、1級アミノ基を有す
るビニルモノマーまたは、それらの塩類、硫酸、ギ酸、
酢酸などの無機酸ないしは有機酸の塩類、Examples of the cationic vinyl monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide or diethylamino. Vinyl monomers having tertiary amino groups such as propyl (meth) acrylamide, alkyldiallylamine, dialkylallylamine, diallylamine and allylamine, secondary amino groups and primary amino groups, or salts thereof, sulfuric acid, formic acid,
Salts of inorganic or organic acids such as acetic acid,
【0023】または該3級アミノ基含有ビニルモノマー
とメチルクロライド、メチルブロマイド等のアルキルハ
ライド、ベンジルクロライド、ベンジルブロマイド等の
アリールアルキルハライド、ジメチル硫酸、ジエチル硫
酸、エピクロロヒドリン、3−クロロ−2−ヒドロキシ
プロピルトリメチルアンモニウムクロライド、グリシジ
ルトリアルキルアンモニウムクロライド等の4級化剤と
の反応によって得られる第4級アンモニウム塩を含有す
るビニルモノマー、例えば2−ヒドロキシ−N,N,
N,N’,N’−ペンタメチル−N’−[3−{(1−
オキソ−2−プロペニル)アミノ}プロピル]−1,3
−プロパンジアミニウムジクロライド等が例示され、こ
れらの一種を単独でまたは二種以上を併用して使用する
ことができる。Alternatively, the vinyl monomer containing a tertiary amino group and an alkyl halide such as methyl chloride or methyl bromide, an arylalkyl halide such as benzyl chloride or benzyl bromide, dimethylsulfate, diethylsulfate, epichlorohydrin or 3-chloro-2. A vinyl monomer containing a quaternary ammonium salt obtained by reaction with a quaternizing agent such as hydroxypropyltrimethylammonium chloride or glycidyltrialkylammonium chloride, eg 2-hydroxy-N, N,
N, N ', N'-pentamethyl-N'-[3-{(1-
Oxo-2-propenyl) amino} propyl] -1,3
-Propanediaminium dichloride and the like are exemplified, and these can be used alone or in combination of two or more.
【0024】ノニオン性ビニルモノマーとしては、アク
リロニトリル、メタアクリロニトリル、スチレン、メチ
ルビニルエーテル、(メタ)アクリル酸のアルキルエス
テル、2−ヒドロキシエステルまたはグリシジルエステ
ル等が例示され、これらの一種を単独でまたは二種以上
を併用して使用することができる。Examples of the nonionic vinyl monomer include acrylonitrile, methacrylonitrile, styrene, methyl vinyl ether, alkyl ester of (meth) acrylic acid, 2-hydroxy ester, glycidyl ester and the like, and one of these may be used alone or two of them may be used. The above can be used in combination.
【0025】本発明で使用する架橋剤(c)としては、
エチレングリコールジ(メタ)アクリレート、ジエチレ
ングリコールジ(メタ)アクリレート、トリエチレング
リコールジ(メタ)アクリレート、プロピレングリコー
ルジ(メタ)アクリレート等のジ(メタ)アクリレート
類、グリセリンジ(メタ)アクリレート、トリメチロー
ルプロパン・エチレンオキサイド付加物トリアクリレー
ト、メチレンビス(メタ)アクリルアミド、エチレンビ
ス(メタ)アクリルアミド、ヘキサメチレンビス(メ
タ)アクリルアミド、N,N’−ビスアクリルアミド酢
酸、N,N’−ビスアクリルアミド酢酸メチル、N,N
−ベンジリデンビスアクリルアミド等のビス(メタ)ア
クリルアミド類、The cross-linking agent (c) used in the present invention includes
Di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane -Ethylene oxide adduct triacrylate, methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, hexamethylenebis (meth) acrylamide, N, N'-bisacrylamidoacetic acid, N, N'-bisacrylamidoacetate methyl, N, N
-Bis (meth) acrylamides such as benzylidene bisacrylamide,
【0026】アジピン酸ジビニル、セバシン酸ジビニル
等のジビニルエステル類、エポキシアクリレート類、ウ
レタンアクリレート類、アリル(メタ)アクリレート、
ジアリルフタレート、ジアリルマレート、ジアリルサク
シネート、ジアリルアクリルアミド、ジビニルベンゼ
ン、ジイソプロピルベンゼン、N,N−ジアリルメタク
リルアミド、ジアリルジメチルアンモニウム、ジアリル
クロレンデート、グリシジル(メタ)アクリレート等の
2官能性ビニルモノマー、1,3,5−トリアクリロイ
ルヘキサヒドロ−S−トリアジン、トリアリルイソシア
ヌレート、N,N−ジアリルアクリルアミド、トリアリ
ルアミン、トリアリルトリメリテート等の3官能性ビニ
ルモノマー、Divinyl esters such as divinyl adipate and divinyl sebacate, epoxy acrylates, urethane acrylates, allyl (meth) acrylate,
Bifunctional vinyl monomers such as diallyl phthalate, diallyl malate, diallyl succinate, diallyl acrylamide, divinyl benzene, diisopropyl benzene, N, N-diallyl methacrylamide, diallyl dimethyl ammonium, diallyl chlorendate and glycidyl (meth) acrylate, Trifunctional vinyl monomers such as 1,3,5-triacryloylhexahydro-S-triazine, triallyl isocyanurate, N, N-diallyl acrylamide, triallylamine and triallyl trimellitate,
【0027】テトラメチロールメタンテトラアクリレー
ト、テトラアリルピロメリテート、N,N,N’,N’
−テトラアリル−1,4−ジアミノブタン、テトラアリ
ルアミン塩、テトラアリルオキシエタン等の4官能性ビ
ニルモノマー、テトラメチロールメタン−トリ−β−ア
ジリジニルプロピオネート、トリメチロールプロパン−
トリ−β−アジリジニルプロピオンエート、4,4’−
ビス(エチレンイミンカルボニルアミノ)ジフェニルメ
タン等の水溶性アジリジニル化合物、(ポリ)エチレン
グリコールジグリシジルエーテル、(ポリ)プロピレン
グリコールジグリシジルエーテル、(ポリ)グリセリン
ジグリシジルエーテル、(ポリ)グリセリントリグリシ
ジルエーテル等の水溶性の多官能エポキシ化合物、Tetramethylolmethane tetraacrylate, tetraallyl pyromellitate, N, N, N ', N'
-Tetrafunctional vinyl monomers such as tetraallyl-1,4-diaminobutane, tetraallylamine salt and tetraallyloxyethane, tetramethylolmethane-tri-β-aziridinylpropionate, trimethylolpropane-
Tri-β-aziridinyl propionate, 4,4′-
Water-soluble aziridinyl compounds such as bis (ethyleneiminecarbonylamino) diphenylmethane, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, (poly) glycerin triglycidyl ether, etc. Water-soluble polyfunctional epoxy compound,
【0028】及び3−(メタ)アクリロキシメチルトリ
メトキシシラン、3−(メタ)アクリロキシプロピルジ
メトキシメチルシラン、3−(メタ)アクリロキシプロ
ピルトリメトキシシラン、3−(メタ)アクリロキシプ
ロピルメチルジクロロシラン、3−(メタ)アクリロキ
シオクタデシルトリアセトキシシラン、3−(メタ)ア
クリロキシ−2,5−ジメチルヘキシルジアセトキシメ
チルシラン、3−(メタ)アクリルアミドプロピルトリ
メトキシシラン、2−(メタ)アクリルアミドエチルト
リメトキシシラン、1−(メタ)アクリルアミドメチル
トリメトキシシラン、2−(メタ)アクリルアミド−2
−メチルプロピルトリメトキシシラン、2−(メタ)ア
クリルアミド−2−メチルエチルトリメトキシシラン、And 3- (meth) acryloxymethyltrimethoxysilane, 3- (meth) acryloxypropyldimethoxymethylsilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldi Chlorosilane, 3- (meth) acryloxyoctadecyltriacetoxysilane, 3- (meth) acryloxy-2,5-dimethylhexyldiacetoxymethylsilane, 3- (meth) acrylamidopropyltrimethoxysilane, 2- (meth) acrylamidoethyl. Trimethoxysilane, 1- (meth) acrylamidemethyltrimethoxysilane, 2- (meth) acrylamide-2
-Methylpropyltrimethoxysilane, 2- (meth) acrylamido-2-methylethyltrimethoxysilane,
【0029】2−(メタ)アクリルアミドイソプロピル
トリメトキシシラン、3−(メタ)アクリルアミドプロ
ピルトリエトキシシラン、N−(2−(メタ)アクリル
アミドエチル)アミノプロピルトリメトキシシラン、
(3−(メタ)アクリルアミドプロピル)オキシプロピ
ルトリメトキシシラン、3−(N−メチル(メタ)アク
リルアミド)プロピルトリメトキシシラン、3−((メ
タ)アクリルアミド−メトキシ)−3−ヒドロキシプロ
ピルトリメトキシシラン、3−((メタ)アクリルアミ
ド−メトキシ)プロピルトリメトキシシラン、3−(ビ
ニルベンジルアミノプロピル)トリメトキシシラン、2- (meth) acrylamidoisopropyltrimethoxysilane, 3- (meth) acrylamidopropyltriethoxysilane, N- (2- (meth) acrylamidoethyl) aminopropyltrimethoxysilane,
(3- (meth) acrylamidopropyl) oxypropyltrimethoxysilane, 3- (N-methyl (meth) acrylamide) propyltrimethoxysilane, 3-((meth) acrylamide-methoxy) -3-hydroxypropyltrimethoxysilane, 3-((meth) acrylamide-methoxy) propyltrimethoxysilane, 3- (vinylbenzylaminopropyl) trimethoxysilane,
【0030】ジメチル−3−(メタ)アクリルアミド−
プロピル−3−(トリメトキシシリル)−プロピルアン
モニウムクロライド、ジメチル−2−(メタ)アクリル
アミド−2−メチルプロピル−3−(トリメトキシシリ
ル)−プロピルアンモニウムクロライド、3−(メタ)
アクリルアミドプロピルメチルジメトキシシラン、3−
(メタ)アクリルアミドプロピルジメチルメトキシシラ
ン、3−(メタ)アクリルアミドプロピルイソブチルジ
メトキシシラン、2−(メタ)アクリルアミドプロピル
イソブチルジメトキシシラン、2−(メタ)アクリルア
ミド−2−メチルプロピルモノクロロジメトキシシラ
ン、2−(メタ)アクリルアミド−2−メチルプロピル
ハイドロジエンジメトキシシラン、Dimethyl-3- (meth) acrylamide-
Propyl-3- (trimethoxysilyl) -propylammonium chloride, dimethyl-2- (meth) acrylamido-2-methylpropyl-3- (trimethoxysilyl) -propylammonium chloride, 3- (meth)
Acrylamidopropylmethyldimethoxysilane, 3-
(Meth) acrylamidopropyldimethylmethoxysilane, 3- (meth) acrylamidopropylisobutyldimethoxysilane, 2- (meth) acrylamidopropylisobutyldimethoxysilane, 2- (meth) acrylamido-2-methylpropylmonochlorodimethoxysilane, 2- (meta ) Acrylamido-2-methylpropylhydrogendimethoxysilane,
【0031】3−(メタ)アクリルアミドプロピルベン
ジルジエトキシシラン、3−(メタ)アクリルアミドプ
ロピルトリアセトキシシラン、2−(メタ)アクリルア
ミドエチルトリアセトキシシラン、4−(メタ)アクリ
ルアミドブチルトリアセトキシシラン、2−(メタ)ア
クリルアミド−2−メチルプロピルトリアセトキシシラ
ン、N−(2−(メタ)アクリルアミドエチル)アミノ
プロピルトリアセトキシシラン、2−(N−エチル(メ
タ)アクリルアミド)エチルトリアセトキシシラン、3
−(メタ)アクリルアミドプロピルオクチルジアセトキ
シシラン、1−(メタ)アクリルアミドメチルフェニル
ジアセトキシシラン、3- (meth) acrylamidopropylbenzyldiethoxysilane, 3- (meth) acrylamidopropyltriacetoxysilane, 2- (meth) acrylamidoethyltriacetoxysilane, 4- (meth) acrylamidobutyltriacetoxysilane, 2- (Meth) acrylamido-2-methylpropyltriacetoxysilane, N- (2- (meth) acrylamidoethyl) aminopropyltriacetoxysilane, 2- (N-ethyl (meth) acrylamide) ethyltriacetoxysilane, 3
-(Meth) acrylamidopropyloctyldiacetoxysilane, 1- (meth) acrylamidomethylphenyldiacetoxysilane,
【0032】3−(メタ)アクリルアミドプロピルトリ
プロピオニロキシシラン、3−(メタ)アクリルアミド
プロピルトリ(N−メチルアミノエトキシ)シラン、ビ
ニルトリクロロシラン、ビニルメチルジクロロシラン、
ジビニルジクロロシラン、ビニルフェニルジクロロシラ
ン、ビニルジメチルクロロシラン、ビニルメチルフェニ
ルクロロシラン、ビニルジフェニルクロロシラン、ビニ
ルトリメトキシシラン、ビニルメチルジメトキシシラ
ン、ビニルイソブチルジメトキシシラン、ビニルジメチ
ルメトキシシラン、ビニルトリエトキシシラン、3−ビ
ニルベンジルアミノプロピルトリエトキシシラン、ビニ
ルメチルジエトキシシラン、3- (meth) acrylamidopropyltripropionyloxysilane, 3- (meth) acrylamidopropyltri (N-methylaminoethoxy) silane, vinyltrichlorosilane, vinylmethyldichlorosilane,
Divinyldichlorosilane, vinylphenyldichlorosilane, vinyldimethylchlorosilane, vinylmethylphenylchlorosilane, vinyldiphenylchlorosilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinylisobutyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, 3-vinyl Benzylaminopropyltriethoxysilane, vinylmethyldiethoxysilane,
【0033】ジビニルジエトキシシラン、ビニルジメチ
ルエトキシシラン、ビニルジフェニルエトキシシラン、
ビニルトリイソプロポキシシラン、ビニルトリブトキシ
シラン、ビニルジメチルイソブトキシシラン、ビニルト
リフェノキシシラン、ビニルジメチル(3−アミノフェ
ノキシ)シラン、ビニルジメチル(4−アミノフェノキ
シ)シラン、ビニルジメチル(3−メチル−4−クロロ
フェノキシ)シラン、ビニルジメチル(2−メチル−4
−クロロフェノキシ)シラン、ビニルトリアセトキシシ
ラン、ビニルメチルジアセトキシシラン、ビニルジメチ
ルアセトキシシラン等のシリコン系化合物が例示でき
る。Divinyldiethoxysilane, vinyldimethylethoxysilane, vinyldiphenylethoxysilane,
Vinyltriisopropoxysilane, vinyltributoxysilane, vinyldimethylisobutoxysilane, vinyltriphenoxysilane, vinyldimethyl (3-aminophenoxy) silane, vinyldimethyl (4-aminophenoxy) silane, vinyldimethyl (3-methyl-4) -Chlorophenoxy) silane, vinyldimethyl (2-methyl-4)
Examples thereof include silicon compounds such as -chlorophenoxy) silane, vinyltriacetoxysilane, vinylmethyldiacetoxysilane, and vinyldimethylacetoxysilane.
【0034】本発明で用いる樹脂〔A〕の使用量は、ア
クリルアミド系樹脂〔B〕に使用するアクリルアミド類
(a)100重量部に対し、1〜50重量部であり、3
〜30重量部が好ましい。The amount of the resin [A] used in the present invention is 1 to 50 parts by weight based on 100 parts by weight of the acrylamide (a) used in the acrylamide resin [B].
-30 parts by weight is preferred.
【0035】本発明のアクリルアミド系樹脂〔B〕の反
応は適当な重合開始剤を使用し、40〜100℃の温度
で、0.5〜10時間の反応を行う。アクリルアミド類
(a)100重量部に対して、各成分(b)、(c)の
重量比は、次の通りである。アニオン性ビニルモノマー
(b)は0.5〜50重量部、好ましくは2〜20重量
部であり、架橋剤(c)は0.005〜10重量部、好
ましくは0.01〜2重量部である。The reaction of the acrylamide resin [B] of the present invention is carried out by using a suitable polymerization initiator at a temperature of 40 to 100 ° C. for 0.5 to 10 hours. The weight ratio of each of the components (b) and (c) to 100 parts by weight of the acrylamides (a) is as follows. The anionic vinyl monomer (b) is 0.5 to 50 parts by weight, preferably 2 to 20 parts by weight, and the crosslinking agent (c) is 0.005 to 10 parts by weight, preferably 0.01 to 2 parts by weight. is there.
【0036】樹脂〔A〕、アニオン性ビニルモノマー
(b)、架橋剤(c)の重量比がこの範囲以外の場合
は、表面強度、内部強度、サイズ効果をバランス良く向
上させることができず好ましくない。特に、樹脂〔A〕
が50重量部を越える場合には、得られるアクリルアミ
ド系樹脂〔B〕との混合水溶液としての安定性が悪く好
ましくない。When the weight ratio of the resin [A], the anionic vinyl monomer (b) and the cross-linking agent (c) is out of this range, the surface strength, internal strength and size effect cannot be improved in a good balance, which is preferable. Absent. In particular, resin [A]
When it exceeds 50 parts by weight, the stability as an aqueous solution mixed with the resulting acrylamide resin [B] is poor, which is not preferable.
【0037】本発明において使用する重合開始剤は、特
に限定されるものではなく、公知慣用のものが使用でき
る。例えば、過硫酸ナトリウム、過硫酸カリウム、過硫
酸アンモニウム、過酸化水素、第二セリウム塩などのラ
ジカル重合開始剤をアクリルアミド類(a)とアニオン
性ビニルモノマー(b)の合計重量に対して0.01〜
5重量%使用する。また、ジメチルアミン、亜硫酸水素
ナトリウム、ナトリウムホルムアルデヒドスルホキシレ
ートなどの還元剤を併用してレドックス重合することも
できる。The polymerization initiator used in the present invention is not particularly limited, and known and commonly used ones can be used. For example, a radical polymerization initiator such as sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, and a ceric salt is added in an amount of 0.01 with respect to the total weight of the acrylamides (a) and the anionic vinyl monomer (b). ~
Use 5% by weight. Further, redox polymerization can be carried out by using a reducing agent such as dimethylamine, sodium hydrogen sulfite and sodium formaldehyde sulfoxylate in combination.
【0038】また、必要に応じて公知慣用の連鎖移動剤
を使用してもよい。例えば、アリルアルコール、アリル
アミンなどのアリル化合物、メルカプトエタノール、チ
オグリコール酸またはそのアルカリ金属塩またはアンモ
ニウム塩、イソプロピルアルコール、次亜リン酸ナトリ
ウム等が挙げられる。If necessary, a known and commonly used chain transfer agent may be used. Examples thereof include allyl compounds such as allyl alcohol and allylamine, mercaptoethanol, thioglycolic acid or its alkali metal salts or ammonium salts, isopropyl alcohol, and sodium hypophosphite.
【0039】本発明の表面紙質向上液剤あるいはこれを
含有する塗工液に防滑剤、離型剤、防錆剤、防腐剤、消
泡剤、粘度調整剤、染料、表面サイズ剤、撥水剤等の添
加剤を加えてもかまわない。また、澱粉類、ポリビニル
アルコール、カルボキシメチルセルロース等の天然また
は合成高分子との併用、さらには、他の表面紙質向上剤
との併用も制限されるものではない。なお、塗工液の固
形分濃度は通常0.1〜15%である。The surface paper quality improving liquid of the present invention or the coating liquid containing the same is added to an anti-slip agent, a release agent, a rust preventive, a preservative, an antifoaming agent, a viscosity modifier, a dye, a surface sizing agent, a water repellent. You may add additives, such as. Further, the combination with natural or synthetic polymers such as starches, polyvinyl alcohol and carboxymethyl cellulose, and the combination with other surface paper quality improvers are not limited. In addition, the solid content concentration of the coating liquid is usually 0.1 to 15%.
【0040】本発明の表面紙質向上液剤を含有する表面
塗工液を、紙や板紙に塗工するにあたり、サイズプレ
ス、フィルムプレス、ゲートロールコーター、ブレード
コーターあるいはキャレンダー等の方法で、実施するこ
とが好ましい。また、バーコーター、ナイフコーター、
エアーナイフコーターなどによって塗工することもでき
る。The surface coating solution containing the surface paper quality improving liquid agent of the present invention is applied to paper or paperboard by a method such as size press, film press, gate roll coater, blade coater or calender. It is preferable. Also, bar coater, knife coater,
It can also be coated with an air knife coater or the like.
【0041】また、本発明の表面紙質向上液剤を含有す
る塗工液は、酸性紙あるいは中性紙に塗工することがで
きる。酸性紙あるいは中性紙の種類としては、コート原
紙、新聞用紙、ライナー、コートボール、印刷筆記用
紙、フォーム用紙、PPC用紙、インクジェット用紙、
熱転写用紙、感熱紙等の各種原紙が挙げられる。原紙の
サイズ度も任意であるが、サイズプレス等を用いて塗工
する場合は、原紙の吸液量を調整する目的で内添サイズ
剤を使用することが望ましい。The coating liquid containing the surface paper quality improving liquid agent of the present invention can be applied to acidic paper or neutral paper. Types of acid paper or neutral paper include coated base paper, newsprint, liner, coated ball, printing writing paper, foam paper, PPC paper, inkjet paper,
Examples include various base papers such as thermal transfer paper and thermal paper. The sizing degree of the base paper is also arbitrary, but when applying using a size press or the like, it is desirable to use an internal sizing agent for the purpose of adjusting the liquid absorption of the base paper.
【0042】[0042]
【実施例】以下、実施例および比較例を挙げて本発明を
詳細に説明するが、本発明に下記実施例に限定されるも
のではない。なお、部、%は特に断わりがない限り重量
部、重量%を意味する。The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, parts and% mean parts by weight and% by weight.
【0043】合成例1(アクリルアミド系樹脂[B]の
合成) 撹拌機、温度計、還流冷却管および窒素ガス導入管を付
した1リットルの四つ口フラスコに水251部、50%
アクリルアミド水溶液200部、イタコン酸4部、イソ
プロピルアルコール40部を仕込み、60℃に昇温し
た。次いで、窒素ガス導入下で5%過硫酸アンモニウム
水溶液3.3部を添加し、80℃に昇温し、2時間反応
させた。得られた反応生成物に水22部を加え、固形分
20.3%、粘度4100cpsの水溶性樹脂を得た。
これを樹脂mとする。Synthesis Example 1 (Synthesis of Acrylamide Resin [B]) 251 parts of water, 50% in a 1 liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube.
200 parts of an acrylamide aqueous solution, 4 parts of itaconic acid, and 40 parts of isopropyl alcohol were charged, and the temperature was raised to 60 ° C. Then, 3.3 parts of a 5% ammonium persulfate aqueous solution was added under the introduction of nitrogen gas, the temperature was raised to 80 ° C., and the reaction was carried out for 2 hours. 22 parts of water was added to the obtained reaction product to obtain a water-soluble resin having a solid content of 20.3% and a viscosity of 4100 cps.
This is designated as resin m.
【0044】合成例2〜6 アニオン性ビニルモノマーの種類および使用量を表1の
通り適宜変えること以外は、合成例1と同様に行い、樹
脂n〜rを得た。Synthetic Examples 2 to 6 Resins n to r were obtained in the same manner as in Synthetic Example 1 except that the type and amount of the anionic vinyl monomer were changed as shown in Table 1.
【0045】実施例1 樹脂m104部とGSA2302(スチレン−アクリル
酸樹脂)の20%アンモニア水溶液10部を混合した。
得られた混合水溶液を樹脂Aとする。Example 1 104 parts of resin m and 10 parts of 20% aqueous ammonia solution of GSA2302 (styrene-acrylic acid resin) were mixed.
The obtained mixed aqueous solution is referred to as Resin A.
【0046】実施例2〜6、比較例1〜4 表2に示す樹脂[A]とアクリルアミド系樹脂[B]を
実施例1と同様に混合し、樹脂B〜F、樹脂x〜z(比
較例)を得た。また、樹脂mのみの場合を比較例1とす
る。Examples 2 to 6 and Comparative Examples 1 to 4 Resin [A] and acrylamide resin [B] shown in Table 2 were mixed in the same manner as in Example 1 to prepare resins BF and resins x to z (comparative). I got) Further, Comparative Example 1 is a case where only the resin m is used.
【0047】実施例7 上記樹脂A〜F、樹脂mおよびx〜z(比較例)を水で
希釈し、固形分濃度が3%の塗工液を調製した。この塗
工液を未塗工新聞用紙(坪量43.5〔g/m2 〕)に
No.3バーコーターを用いて片面塗工し、ドラムドラ
イヤー(80℃、50秒間)にて乾燥した。乾燥後、2
0℃、相対湿度65%RHの恒温恒湿室中で24時間調
湿し、その後、各種評価試験を供した。結果を表3に示
す。なお、水のみを塗工した例を表3に記載した。ま
た、樹脂A〜F、mおよびx〜zの保存安定性について
の評価結果を表2に記載した。Example 7 The above resins A to F, resins m and x to z (comparative example) were diluted with water to prepare a coating liquid having a solid content concentration of 3%. This coating solution was applied to uncoated newsprint paper (basis weight: 43.5 [g / m 2 ]). One side was coated using a 3 bar coater and dried with a drum dryer (80 ° C., 50 seconds). After drying 2
The humidity was controlled for 24 hours in a constant temperature and humidity room at 0 ° C. and a relative humidity of 65% RH, and then various evaluation tests were performed. Table 3 shows the results. An example in which only water is applied is shown in Table 3. Further, Table 2 shows the evaluation results of the storage stability of the resins A to F, m and x to z.
【0048】なお、評価試験は以下の測定方法で行っ
た。 表面強度: ドライピック ;RI印刷試験機、ニップ幅10mm インキ:FINE INK.(大日本インキ化学工業
製)インキT.V.=24 いずれも印刷後の紙のむけ状態を肉眼で観察し、5を
優、1を劣として5段階評価を行った。 内部強度: スコットボンド(kgf・cm);インターナルボンド
テスター(熊谷理機工業社製)を使用し接着強度5kg
/cm2 、30秒の条件で測定した。 サイズ度: ドロップテスト(秒);J.TAPPI 33(水5μ
l)に準じて行った。 保存安定性:40℃にて静置し、製品の分離、白濁、凝
集物の発生等を観察した。 ○:優 △:良 ×:劣The evaluation test was carried out by the following measuring method. Surface strength: Dry pick; RI printing tester, nip width 10 mm Ink: FINE INK. (Manufactured by Dainippon Ink and Chemicals, Inc.) V. = 24 In all cases, the peeled state of the paper after printing was observed with the naked eye, and 5 was evaluated as excellent and 1 was inferior, and a 5-level evaluation was performed. Internal strength: Scott bond (kgf · cm); Internal bond tester (manufactured by Kumagai Riki Kogyo Co., Ltd.) is used for adhesive strength 5 kg.
/ Cm 2 , 30 seconds was measured. Size: Drop test (seconds); TAPPI 33 (water 5μ
It carried out according to l). Storage stability: The product was allowed to stand at 40 ° C., and product separation, white turbidity, generation of aggregates, etc. were observed. ○: Excellent △: Good ×: Poor
【0049】表3の試験結果から明らかなように、実施
例の樹脂はいずれも、表面強度、内部強度、サイズ効果
がバランス良く優れ、安定性に優れていた。一方、比較
例の樹脂は表面強度、内部強度およびサイズ効果をバラ
ンス良く向上させていなかった(例えば比較例1の樹脂
mは、表面強度、内部強度は、実施例の樹脂と同様に優
れた効果を示したが、サイズ効果が明らかに劣ってい
た)。As is clear from the test results in Table 3, all the resins of the examples were excellent in surface strength, internal strength, and size effect in good balance and excellent in stability. On the other hand, the resin of Comparative Example did not improve the surface strength, the internal strength and the size effect in a well-balanced manner (for example, the resin m of Comparative Example 1 had the same excellent surface strength and internal strength as the resin of the Example). , But the size effect was clearly inferior).
【0050】[0050]
【表1】 [Table 1]
【0051】[0051]
【表2】 [Table 2]
【0052】[0052]
【表3】 [Table 3]
【0053】[0053]
【発明の効果】本発明の表面紙質向上液剤は、紙の表面
強度、内部強度、サイズ効果をバランス良く向上させ、
かつ優れた安定性を示すものである。The surface paper quality improving liquid agent of the present invention improves the surface strength, internal strength and size effect of paper in a well-balanced manner.
It also exhibits excellent stability.
Claims (5)
アクリル酸−アクリル酸エステル樹脂、スチレン−マレ
イン酸樹脂、スチレン−マレイン酸−マレイン酸半エス
テル樹脂、(ジ)イソブチレン−マレイン酸樹脂、
(ジ)イソブチレン−マレイン酸−マレイン酸半エステ
ル樹脂からなる群から選ばれた少なくとも一種の樹脂
〔A〕1〜50重量部と、アクリルアミド類(a)10
0重量部と、アニオン性ビニルモノマー(b)0.5〜
50重量部を反応して得られるアクリルアミド系樹脂
〔B〕の混合水溶液を含有することを特徴とする表面紙
質向上液剤。1. Styrene-acrylic acid resin, styrene-
Acrylic acid-acrylic acid ester resin, styrene-maleic acid resin, styrene-maleic acid-maleic acid half ester resin, (di) isobutylene-maleic acid resin,
1 to 50 parts by weight of at least one resin [A] selected from the group consisting of (di) isobutylene-maleic acid-maleic acid half-ester resin, and acrylamides (a) 10
0 parts by weight and an anionic vinyl monomer (b) 0.5 to
A surface paper quality improving liquid agent comprising a mixed aqueous solution of an acrylamide resin [B] obtained by reacting 50 parts by weight.
アクリル酸−アクリル酸エステル樹脂、スチレン−マレ
イン酸樹脂、スチレン−マレイン酸−マレイン酸半エス
テル樹脂、(ジ)イソブチレン−マレイン酸樹脂、
(ジ)イソブチレン−マレイン酸−マレイン酸半エステ
ル樹脂からなる群から選ばれた少なくとも一種の樹脂
〔A〕1〜50重量部と、アクリルアミド類(a)10
0重量部と、アニオン性ビニルモノマー(b)0.5〜
50重量部と、架橋剤(c)0.005〜10重量部を
反応して得られるアクリルアミド系樹脂〔B〕の混合水
溶液を含有することを特徴とする表面紙質向上液剤。2. Styrene-acrylic acid resin, styrene-
Acrylic acid-acrylic acid ester resin, styrene-maleic acid resin, styrene-maleic acid-maleic acid half ester resin, (di) isobutylene-maleic acid resin,
1 to 50 parts by weight of at least one resin [A] selected from the group consisting of (di) isobutylene-maleic acid-maleic acid half-ester resin, and acrylamides (a) 10
0 parts by weight and an anionic vinyl monomer (b) 0.5 to
A surface paper quality improving liquid agent comprising 50 parts by weight and a mixed aqueous solution of an acrylamide resin [B] obtained by reacting 0.005 to 10 parts by weight of a crosslinking agent (c).
和モノカルボン酸、不飽和ジカルボン酸、不飽和トリカ
ルボン酸、不飽和テトラカルボン酸、不飽和スルホン
酸、不飽和ホスホン酸およびそれらの塩類からなる群か
ら選ばれた少なくとも一種である請求項1または2記載
の表面紙質向上液剤。3. The anionic vinyl monomer (b) is composed of unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated tricarboxylic acid, unsaturated tetracarboxylic acid, unsaturated sulfonic acid, unsaturated phosphonic acid and salts thereof. The surface paper quality improving liquid agent according to claim 1 or 2, which is at least one selected from the group.
である請求項1ないし3のいずれか記載の表面紙質向上
液剤。4. The surface paper quality improving liquid agent according to claim 1, wherein the resin [A] is a styrene-acrylic acid resin.
ド、メタクリルアミドである請求項1ないし4のいずれ
か記載の表面紙質向上液剤。5. The surface paper quality improving liquid agent according to claim 1, wherein the acrylamides (a) are acrylamide and methacrylamide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17798395A JPH0913295A (en) | 1995-06-22 | 1995-06-22 | Liquid agent for improving surface quality of paper |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17798395A JPH0913295A (en) | 1995-06-22 | 1995-06-22 | Liquid agent for improving surface quality of paper |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0913295A true JPH0913295A (en) | 1997-01-14 |
Family
ID=16040490
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17798395A Pending JPH0913295A (en) | 1995-06-22 | 1995-06-22 | Liquid agent for improving surface quality of paper |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0913295A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002173894A (en) * | 2000-09-28 | 2002-06-21 | Nippon Paper Industries Co Ltd | Offset printing paper |
JP2009041145A (en) * | 2007-08-09 | 2009-02-26 | Seiko Pmc Corp | Coating liquid composition and paper and hardboard |
-
1995
- 1995-06-22 JP JP17798395A patent/JPH0913295A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002173894A (en) * | 2000-09-28 | 2002-06-21 | Nippon Paper Industries Co Ltd | Offset printing paper |
JP4712239B2 (en) * | 2000-09-28 | 2011-06-29 | 日本製紙株式会社 | Offset printing paper |
JP2009041145A (en) * | 2007-08-09 | 2009-02-26 | Seiko Pmc Corp | Coating liquid composition and paper and hardboard |
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