JPH04100996A - Resin for coating paper and composition for coating paper - Google Patents
Resin for coating paper and composition for coating paperInfo
- Publication number
- JPH04100996A JPH04100996A JP20798090A JP20798090A JPH04100996A JP H04100996 A JPH04100996 A JP H04100996A JP 20798090 A JP20798090 A JP 20798090A JP 20798090 A JP20798090 A JP 20798090A JP H04100996 A JPH04100996 A JP H04100996A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- water
- aqueous solution
- hours
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 157
- 239000011347 resin Substances 0.000 title claims abstract description 157
- 239000011248 coating agent Substances 0.000 title claims description 45
- 238000000576 coating method Methods 0.000 title claims description 45
- 239000000203 mixture Substances 0.000 title claims description 28
- -1 carboxylic acid compound Chemical class 0.000 claims abstract description 71
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 239000004593 Epoxy Substances 0.000 claims abstract description 28
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 28
- 239000004202 carbamide Substances 0.000 claims abstract description 24
- 229920000768 polyamine Polymers 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 46
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 22
- 229920001281 polyalkylene Polymers 0.000 claims description 17
- 239000008199 coating composition Substances 0.000 claims description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 9
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 abstract description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 63
- 235000013877 carbamide Nutrition 0.000 description 29
- 238000003756 stirring Methods 0.000 description 20
- 241000238557 Decapoda Species 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 238000007639 printing Methods 0.000 description 12
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229960001124 trientine Drugs 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 238000007865 diluting Methods 0.000 description 7
- 150000003672 ureas Chemical class 0.000 description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 150000003944 halohydrins Chemical class 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000000306 component Substances 0.000 description 4
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 4
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 229920000881 Modified starch Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 150000001334 alicyclic compounds Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 2
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- ITZPOSYADVYECJ-UHFFFAOYSA-N n'-cyclohexylpropane-1,3-diamine Chemical compound NCCCNC1CCCCC1 ITZPOSYADVYECJ-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 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
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- GZPRASLJQIBVDP-UHFFFAOYSA-N 2-[[4-[2-[4-(oxiran-2-ylmethoxy)cyclohexyl]propan-2-yl]cyclohexyl]oxymethyl]oxirane Chemical compound C1CC(OCC2OC2)CCC1C(C)(C)C(CC1)CCC1OCC1CO1 GZPRASLJQIBVDP-UHFFFAOYSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 description 1
- SZEWALYSKVMFAD-UHFFFAOYSA-N 4-(4-aminocyclohexyl)oxycyclohexan-1-amine Chemical compound C1CC(N)CCC1OC1CCC(N)CC1 SZEWALYSKVMFAD-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 108010058643 Fungal Proteins Chemical class 0.000 description 1
- 108010010803 Gelatin Chemical class 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 101150101999 IL6 gene Proteins 0.000 description 1
- 241001024304 Mino Species 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 108010073771 Soybean Proteins Chemical class 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- NIYNIOYNNFXGFN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound OCC1CCC(CO)CC1.C1C(C(=O)O)CCC2OC21.C1C(C(=O)O)CCC2OC21 NIYNIOYNNFXGFN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- IDSLNGDJQFVDPQ-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-yl) hexanedioate Chemical compound C1CC2OC2CC1OC(=O)CCCCC(=O)OC1CC2OC2CC1 IDSLNGDJQFVDPQ-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical class NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- UYAUGHKQCCCFDK-UHFFFAOYSA-N cyclohexane-1,3,5-triamine Chemical compound NC1CC(N)CC(N)C1 UYAUGHKQCCCFDK-UHFFFAOYSA-N 0.000 description 1
- DNWBGZGLCKETOT-UHFFFAOYSA-N cyclohexane;1,3-dioxane Chemical compound C1CCCCC1.C1COCOC1 DNWBGZGLCKETOT-UHFFFAOYSA-N 0.000 description 1
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000159 gelatin Chemical class 0.000 description 1
- 239000008273 gelatin Chemical class 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000000314 lubricant 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
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000003956 methylamines Chemical class 0.000 description 1
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 229920005615 natural polymer Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010971 suitability test Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Landscapes
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、優れた印刷適性、特にインキ受理性に優れた
塗工紙を提供する紙塗工用樹脂及び該紙塗工用樹脂を含
有した紙塗工用組成物に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a paper coating resin that provides coated paper with excellent printability, particularly excellent ink receptivity, and a paper coating resin containing the paper coating resin. The present invention relates to a paper coating composition.
（従来の技術〕
印刷用紙として広く用いられている塗工紙は、従来より
抄き上げた原紙にクレー、炭酸カルシウム等の顔料やラ
デツクス、デンプン等の接着剤を主成分とする組成物を
塗工することによって製造されている。(Prior art) Coated paper, which is widely used as printing paper, is made by coating a base paper with a composition whose main components are pigments such as clay and calcium carbonate, and adhesives such as radex and starch. It is manufactured by engineering.
この塗工紙にも近年、高速化・精密化・多色化等に代表
される印刷技術の目ざましい進歩に伴なって、塗工紙に
はより高度な印刷適性か要求されるようになった。Coated paper has also come to be required to have a higher level of printing suitability in recent years, due to the remarkable progress in printing technology represented by increased speed, precision, and multi-color printing. .
特に印刷時のインキの着肉状態を示すインキ受理性、オ
フセラ１〜印刷時の湿し水に対する耐水性、及び輪転印
刷におけるインキ乾燥の際に要求される耐ブリスター性
の向上が強く要求されている。In particular, there is a strong demand for improvements in ink receptivity, which indicates the state of ink adhesion during printing, water resistance to dampening water during printing, and blister resistance required during ink drying in rotary printing. There is.
これに応えて従来、印刷時に必要な上記諸性能を付与す
るためにポリアミド−尿素−ホルムアルデヒド樹脂（特
公昭４４−１１６６７号公報参照）やポリアミド−尿素
−エピハロヒドリン−ホルムアルデヒド樹脂（特公昭６
１−４２９３１号公報参照）或いはポリアミド−尿素−
ホルムアルデヒド樹脂のポリアミドの酸成分として脂環
式二塩基性カルボン酸を使用すること（特開昭６２−１
０１６２１号公報参照）か提案されている。In response to this, polyamide-urea-formaldehyde resin (see Japanese Patent Publication No. 44-11667) and polyamide-urea-epihalohydrin-formaldehyde resin (Japanese Patent Publication No. 11667-1983) have been used to provide the above-mentioned properties necessary for printing.
1-42931) or polyamide-urea-
Use of alicyclic dibasic carboxylic acid as the acid component of polyamide of formaldehyde resin (Japanese Unexamined Patent Publication No. 62-1
01621) has been proposed.
（発明か解決しようとする課題〕
しかしなから、これらの従来技術はいずれも、インキ受
理性、耐水性及び耐ブリスターの３性能をバランスよく
向上せしめる点については十分てはなく、より優れた樹
脂の開発が望まれていた。(Problem to be solved by the invention) However, none of these conventional technologies are sufficient in improving the three performances of ink receptivity, water resistance, and blister resistance in a well-balanced manner. development was desired.
特に、インキ受理性と耐水性の双方をバランスよく改善
することは極めて困難な課題であった。すなわち、塗工
層の耐水化を促進すると、湿し水の塗工層表面から内部
への浸透が抑制されて表面に湿し水が残留し易くなり、
塗工層表面へのインキの転移が不良となり、インキ受理
性か低下する。In particular, it has been extremely difficult to improve both ink receptivity and water resistance in a well-balanced manner. In other words, when the water resistance of the coating layer is promoted, the penetration of dampening water from the surface of the coating layer into the interior is suppressed, making it easier for dampening water to remain on the surface.
Transfer of ink to the surface of the coating layer becomes poor and ink receptivity decreases.
一方、塗工層の耐水化を緩和すると湿し水の内部への浸
透が促進されてインキ受理性は向上するものの、耐水化
が不十分になるため塗工層表面の一部がインキロールに
剥ぎ取られ（所謂ウェットピッキンが生じ）易くなるか
らである。而して本発明は上記の困難な課題を解決しよ
うとするもので必る。On the other hand, if the water resistance of the coating layer is relaxed, the penetration of dampening water into the interior will be promoted and the ink receptivity will be improved, but the water resistance will be insufficient and a part of the surface of the coating layer will be exposed to the ink roll. This is because it becomes easy to peel off (so-called wet picking occurs). Therefore, the present invention is intended to solve the above-mentioned difficult problem.
（課題を解決するための手段）
本発明考らは、該課題を解決するため鋭意検問の結果、
ポリアミド−尿素−アルデヒド（Ｔビハロじトリジ〉樹
脂とアミン−エピハロヒドリン樹脂の両力又はいずれか
に脂環式エポキシ化合物又は／及び脂環式アミン化合物
を導入し、両者を反応させるか、又は混合することによ
り目的か達成できることを見出し本発明に到達した。(Means for Solving the Problems) In order to solve the problems, the present invention has as a result of extensive investigation,
An alicyclic epoxy compound or/and an alicyclic amine compound are introduced into both or either of the polyamide-urea-aldehyde (T-bihaloditridi) resin and the amine-epihalohydrin resin, and the two are reacted or mixed. The inventors have discovered that the object can be achieved by doing so, and have arrived at the present invention.
すなわち、本発明は、ポリアルキレンポリアミン（Ａ＞
と二塩基性カルボン酸系化合物（Ｂ）と尿素類（Ｃ）と
脂環式エポキシ化合物（Ｄ＞または／および脂環式アミ
ン化合物（Ｅ）とホルムアルデヒド（「１）、エピハロ
ヒドリン（Ｆ２）およびジアルデヒド類（Ｆ３）より選
ばれた１種または２種以上（Ｆ）よりなる反応生成物（
Ｉ）、又は、上記の（Ａ）、（Ｂ）、（Ｃ）および（Ｆ
）よりなる反応生成物（ＩＩ）のいずれかからなるポリ
アミド−尿素−アルデヒド（エピハロヒドリン）樹脂（
イ）と、上記の（Ｄ＞または／および（Ｅ）と脂肪族７
ミノ化合物（Ｇ ）と（［２）よりなる反応生成物（Ｉ
ＩＩ）、上記の（Ｄ＞または７・′あよひ（「）と（Ｇ
）と（Ｆ２）と曲硫酸塩類（）−１＞または／および酸
類（Ｊ）よりなる反応生成物（ＩＶ）、上記の（Ｇ）と
（Ｆ２）よりなる反応生成物（Ｖ）、並びに、上記の（
Ｇ）と（Ｆ２）と（Ｈ）または／および（Ｊ）よりなる
反応生成物（ＶＩ ）の以上（１）〜（ＶＩ ）から選
ばれた１種の反応生成物であるアミン−エピハロヒドリ
ン樹脂（ロ）とを反応させて得た（但し反応生成物の（
ＩＩ＞と（Ｖ）及び（ＩＩ）と（ＶＩ ）の反応によっ
て得られたものは除く）紙塗工用樹脂、及び上記に記載
された樹脂（イ）と樹脂（ロ）の混合物（但し該反応生
成物（ＩＩ）と（Ｖ）及び（ＩＩ）と（ＶＩ ）の混合
物は除く）である紙塗工用樹脂、並びにこれらを含＠す
る紙塗工用組成物を提供するものである。That is, the present invention provides polyalkylene polyamine (A>
and dibasic carboxylic acid compound (B), urea (C), alicyclic epoxy compound (D> or/and alicyclic amine compound (E), formaldehyde (1), epihalohydrin (F2) and A reaction product (F) consisting of one or more selected aldehydes (F3)
I), or (A), (B), (C) and (F) above
) polyamide-urea-aldehyde (epihalohydrin) resin (
a) and the above (D> or/and (E) and aliphatic 7
Reaction product (I) consisting of mino compound (G) and ([2)
II), above (D> or 7・'Ayohi (") and (G
) and (F2), a reaction product (IV) consisting of a sulfate ()-1> or/and an acid (J), a reaction product (V) consisting of the above (G) and (F2), and above(
Amine-epihalohydrin resin (VI) which is one type of reaction product selected from the above (1) to (VI) of the reaction product (VI) consisting of G), (F2) and (H) or/and (J). b)) (However, the reaction product (
II> and (V) and (II) and (VI)), and mixtures of resins (a) and resins (b) described above (however, The present invention provides paper coating resins that are reaction products (excluding reaction products (II) and (V) and mixtures of (II) and (VI)), and paper coating compositions containing these.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に用いられるポリアルキレンポリアミン（Ａ）と
しては、分子中に少なくとも２個の第一アミン基と少な
くとも１個の第ニアミノ基とを有する化合物か好ましい
。その代表的な例を挙げるとポリエチレンポリアミン、
ポリプロピレンポリアミン、ポリブチレンポリアミン等
であるか、そのうちでもポリエチレンポリアミンか好ま
しく、さらに好ましくはジエチレントリアミン、トリエ
チレンテトラミン、テトラエチレンペンタミンである。The polyalkylene polyamine (A) used in the present invention is preferably a compound having at least two primary amine groups and at least one secondary amino group in the molecule. Typical examples are polyethylene polyamine,
Polypropylene polyamine, polybutylene polyamine, etc., among which polyethylene polyamine is preferred, and diethylene triamine, triethylene tetramine, and tetraethylene pentamine are more preferred.
これらポリアルキレンポリアミンは一種のみてもよく、
また、二種以上の併用でもよい。またエチレンシアミン
、プロピレンジアミン、ヘキサメチレンジアミン等のジ
アミンやジメチルアミン、モノエタノールアミン、ペン
シルアミンなどのモノアミンをポリアルキレンポリアミ
ン１００モルに対して６０モル以下の範囲で併用するこ
ともてきる。These polyalkylene polyamines may be used alone,
Moreover, two or more types may be used in combination. Further, diamines such as ethylenecyamine, propylene diamine, and hexamethylene diamine, and monoamines such as dimethylamine, monoethanolamine, and pencil amine may be used in combination in an amount of 60 moles or less per 100 moles of polyalkylene polyamine.
本発明に用いられる二塩基性カルボン酸系化合物（Ｂ）
としては、二塩基性カルボン酸、二塩基性カルボン酸無
水物、その半エステル及びジエステルか挙げられる。Dibasic carboxylic acid compound (B) used in the present invention
Examples include dibasic carboxylic acids, dibasic carboxylic acid anhydrides, half esters and diesters thereof.
その二塩基性カルボン酸としては、例えば］ハク酸、グ
ルタル酸、アジピン酸、マレイン酸、イソフタル酸、フ
タル酸、テレフタル酸、テ１ヘラじトロフタル酸、ヘキ
サヒドロフタル酸、シクロへキリン−１，４−ジカルボ
ン酸、メチルテ１〜ラヒトロフタル酸、メチルへキサヒ
ドロフタル酸等の二塩基性カルボン酸及びこれらの無水
物かある。また、二塩基性カルボン酸の半エステルとし
ては、上記の二塩基性カルボン酸の半エステルかある。Examples of the dibasic carboxylic acids include] uccinic acid, glutaric acid, adipic acid, maleic acid, isophthalic acid, phthalic acid, terephthalic acid, ditrophthalic acid, hexahydrophthalic acid, cyclohekyrin-1, These include dibasic carboxylic acids such as 4-dicarboxylic acid, methyltetrahydrophthalic acid, and methylhexahydrophthalic acid, and their anhydrides. Further, as the half ester of dibasic carboxylic acid, there are the above-mentioned half esters of dibasic carboxylic acid.
二塩基性カルボン酸ジエステルとしては、］ハク酸ジメ
チル、グルタル酸ジメチル、アジピン酸ジメチル、アジ
ピン酸ジエチルなとの脂肪族二塩基性カルボン酸ジエス
テル、さらには、イソフタル酸ジメチル、テレフタル酸
ジオクチルなとの芳香族二塩基性カルボン酸ジエステル
等か挙げられるが、特に炭素数１〜３の低級アルコール
エステルが好ましい。Examples of dibasic carboxylic acid diesters include aliphatic dibasic carboxylic acid diesters such as dimethyl uccinate, dimethyl glutarate, dimethyl adipate, and diethyl adipate, and dimethyl isophthalate and dioctyl terephthalate. Examples include aromatic dibasic carboxylic acid diesters, and lower alcohol esters having 1 to 3 carbon atoms are particularly preferred.
これらは、１種のみて用いても、２種以上併用してもよ
い。These may be used alone or in combination of two or more.
また、酢酸、ステアリン酸、安息香酸のような一塩基性
カルボン酸又は／及びそのエステルを併用することもて
きる。Furthermore, monobasic carboxylic acids such as acetic acid, stearic acid, and benzoic acid and/or esters thereof may be used in combination.
本発明に用いられる尿素類（Ｃ）としては、尿素、チオ
尿素、グアニル尿素、メチル尿素、ジメチル尿素等か挙
げられるか、特に尿素か好ましい。The ureas (C) used in the present invention include urea, thiourea, guanylurea, methylurea, dimethylurea, etc. Urea is particularly preferred.
本発明に用いられる、脂環式エポキシ化合物（Ｄ＞とし
ては、シクロヘキサン環に直接、間接にエポキシ基が結
合した化合物をいう。直接結合した具体例として、シク
ロヘキセンオキサイド、ビニルシクロヘキセンジオキサ
イト、ビス（３，４エポキシシクロヘキシル）アジペー
ト、３，４−エポキシシクロヘキシルメチル−３，４−
■ポキシシクロヘキサンー力ルポキシレート、２− （
３，４エポキシシクロへキシル−５，５−スピロ−３，
４エポキシ）シクロヘキサン−メタ−ジオキサンなどが
あげられる。また、ここで間接とは、例えばグリシジル
基のようなエポキシ基をシクロヘキサン環と共に含有す
ることを表す。具体例として、ビス−グリシジル−へキ
サヒドロ−フタレート、２．２−ビス（４′ −グリシ
ジルオキシシクロヘキシル）プロパンなどが挙げられる
。The alicyclic epoxy compound used in the present invention (D> refers to a compound in which an epoxy group is directly or indirectly bonded to a cyclohexane ring. Specific examples of directly bonded epoxy groups include cyclohexene oxide, vinyl cyclohexene dioxite, bis (3,4-epoxycyclohexyl)adipate, 3,4-epoxycyclohexylmethyl-3,4-
■Poxycyclohexane-lupoxylate, 2-(
3,4 epoxycyclohexyl-5,5-spiro-3,
(4epoxy) cyclohexane-meta-dioxane and the like. In addition, the term "indirect" here means that an epoxy group such as a glycidyl group is contained together with a cyclohexane ring. Specific examples include bis-glycidyl-hexahydro-phthalate and 2,2-bis(4'-glycidyloxycyclohexyl)propane.
本発明に用いられる脂環式アミノ化合物（Ｅ＞としては
、分子中に少なくとも１個の活性水素を有する脂環式ア
ミン化合物であり、例えばシクロヘキシルアミン、ジシ
クロヘキシルアミン、１，３シアミノシクロヘキ）ノン
、１，４−シアミノシクロヘキ）ノン、４，４′ −
ジアミノ−３，３′ −ジメチル−ジシクロへキシル
メタン、４，４′ −ジアミノ３３′ −ジメチルジ
シクロへキリン、４，４′ビス（バラアミノシクロヘキ
シル）メタン、イソホロンシアミン、１，３（または２
，４）−ビス＝（アミノメチル）シクロヘキサン、Ｎ−
アミノプロピルシクロヘキシルアミン、オクタハイドロ
−４，７メタノインデンー１（２）、 ５（６）−ジメ
タンアミン、２２′ −ヒス−（４−アミノシクロヘ
キシル）プロパン、ビス−（４−アミノシクロヘキシル
）メタン、４，４′ −オキシビス（シクロヘキシル
アミン）、４，４′ −スルホンヒス（シクロヘキシ
ルアミン）、１，３．５− トリアミノシクロヘキサン
、２４′ −または４．４′ −ジアミノ−３３’
、５．５’テトラアルキルジシクロへキシルアルカン等
か挙げられる。The alicyclic amino compound (E>) used in the present invention is an alicyclic amine compound having at least one active hydrogen in the molecule, such as cyclohexylamine, dicyclohexylamine, 1,3 cyaminocyclohexyl)non , 1,4-cyaminocyclohexynone, 4,4'-
Diamino-3,3'-dimethyl-dicyclohexylmethane, 4,4'-diamino33'-dimethyldicyclohexylmethane, 4,4'bis(baraminocyclohexyl)methane, isophoronecyamine, 1,3(or 2)
,4)-bis=(aminomethyl)cyclohexane, N-
Aminopropylcyclohexylamine, octahydro-4,7methanoindene-1(2),5(6)-dimethaneamine, 22'-his-(4-aminocyclohexyl)propane, bis-(4-aminocyclohexyl)methane, 4,4 ' -oxybis(cyclohexylamine), 4,4' -sulfonehis(cyclohexylamine), 1,3,5-triaminocyclohexane, 24' - or 4,4'-diamino-33'
, 5,5'tetraalkyldicyclohexylalkane, etc.
本発明に用いられる脂肪族アミン化合物（Ｇ）としては
、アンモニアあるいは、第一アミノ基、第ニアミノ基又
は第三アミン基のいずれかを単数又は複数含む化合物て
市り、アンモニアの他に例えばメチルアミン、ジメチル
アミン、トリメチルアミン、エチルアミン、ジエチルア
ミン、トリエチルアミン、プロピルアミン、ブチルアミ
ン、エタノールアミン、３−エトキシプロピルアミン等
の−Ｅノアミン、エチレンシアミン、ヘキサメチレンジ
アミン等のジアミン及びジエチレントリアミン、トリエ
チレンテトラミン、テトラエチレンペンタミン等のポリ
アミンが挙げられる。As the aliphatic amine compound (G) used in the present invention, ammonia or a compound containing one or more of a primary amino group, a secondary amino group, or a tertiary amine group is available, and in addition to ammonia, for example, methyl Amines, diamines such as dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, butylamine, ethanolamine, 3-ethoxypropylamine, diamines such as ethylenecyamine, hexamethylenediamine, and diethylenetriamine, triethylenetetramine, tetra Examples include polyamines such as ethylenepentamine.
本発明に用いられるエビハロヒドリン（Ｆ２）としては
エビクロロじドリノ、エビブロモヒドリンが例示され、
これらは１種のみてもよく、また、２種以上の併用でも
よい。Examples of shrimp halohydrin (F2) used in the present invention include shrimp chlorodydorino and shrimp bromohydrin,
These may be used alone or in combination of two or more.
本発明に用いられるジアルデヒド類（Ｆ３）としては、
グリオキザール、グルタルアルデヒド等か挙げられる。The dialdehydes (F3) used in the present invention include:
Examples include glyoxal and glutaraldehyde.
本発明に用いられる亜硫酸塩類（ト１）としては、例え
ば亜硫酸塩（Ｍ ２５０３９Ｍ１は１価の金属、以下同
じ）、亜硫酸水素塩（Ｍ’Ｈ３Ｏ・）、ピロ亜５Ａ酸塩
（Ｍ’ ２５２ｏ５）等か例示され、Ｍｌとしてはアル
カリ金属かあげられる。Examples of the sulfites (T1) used in the present invention include sulfites (M25039M1 is a monovalent metal, the same applies hereinafter), hydrogen sulfites (M'H3O.), and pyro5A salts (M'252o5). Examples include alkali metals as Ml.
これらは単独又は複数使用され、これらから生成する亜
硫酸イオン類としては、亜硫酸金属イオンＭＳＯ−１曲
硫酸水素イオンＨ３Ｏ３−？−
ピロ亜硫酸イオン５２０５ 、亜硫酸イオンＳＯ、ピロ
亜硫酸金属イオンＭ’ Ｓ２ ｏ５−１ピロ亜硫酸水素
イオンＨ８２０５−等か挙げられる。具体的な化合物と
しては亜硫酸ナトリウム（Ｎａ２３０３ ） 、亜硫酸
水素ナトリウム（ＮａＨ３Ｏ３） 、無水重亜硫酸ナト
リウム（Ｎａ２３２０５ ＞等が例示すレル。These are used singly or in combination, and the sulfite ions generated from them include sulfite metal ion MSO-1, hydrogen sulfate ion H3O3-? - Examples include pyrosulfite ion 5205, sulfite ion SO, pyrosulfite metal ion M' S2 o5-1 pyrosulfite hydrogen ion H8205-, and the like. Specific examples of the compounds include sodium sulfite (Na2303), sodium hydrogensulfite (NaH3O3), anhydrous sodium bisulfite (Na23205), and the like.
本発明に用いられる酸類（Ｊ）としては、例えば硫酸、
塩酸、燐酸等の無機酸、キ酸、酢酸等の有機酸が埜げら
れる。Examples of acids (J) used in the present invention include sulfuric acid,
Inorganic acids such as hydrochloric acid and phosphoric acid, and organic acids such as phosphoric acid and acetic acid are removed.
亜硫酸塩類を使用すると、紙塗工用樹脂のカチオン性を
低下させ、紙塗工用組成物の増粘を防止することかでき
る。When sulfites are used, the cationic nature of the paper coating resin can be reduced and thickening of the paper coating composition can be prevented.
また、酸類を使用量ることでアミノ基の一部あるいは全
部をアミンの塩類にした後、エビハロヒドリンと反応せ
しめることにより低分子量のアミンエビハロヒドリン樹
脂を得ることかでき、これにまり紙塗工用組成物の増結
を防止することかできる。In addition, by using acids in a certain amount, some or all of the amino groups can be converted into amine salts, and then by reacting with shrimp halohydrin, it is possible to obtain a low molecular weight amine shrimp halohydrin resin. It is possible to prevent the industrial composition from increasing.
本発明におけるポリアミド−尿素−アルデヒド（エピハ
ロヒドリン）樹脂（イ）のポリアルキレンポリアミン、
二塩基性カルボン酸系化合物、尿素類、脂環式エポキシ
化合物、脂環式アミン化合物の各反応成分の比率はポリ
アルキレンポリアミン１モルに対し、二塩基性カルボン
酸系化合物０、・１〜２モル、尿素類０．５〜１０モル
、及び脂環式エポキシ化合物又は／及び脂環式アミン化
合物０．０２〜４モル（併用の場合は両方の和〉の範囲
か好ましい。The polyalkylene polyamine of the polyamide-urea-aldehyde (epihalohydrin) resin (a) in the present invention,
The ratio of each reaction component of the dibasic carboxylic acid compound, urea, alicyclic epoxy compound, and alicyclic amine compound is 0, 1 to 2 of the dibasic carboxylic acid compound to 1 mole of polyalkylene polyamine. mol, 0.5 to 10 mol of the urea, and 0.02 to 4 mol of the alicyclic epoxy compound or/and the alicyclic amine compound (if used in combination, the sum of both).
また、ホルムアルデヒド、エビハロヒドリンもしくはジ
アルデヒドの単独使用量としては、ポリアルキレンポリ
アミン１モルに対して０１〜３−しルか好ましく、２種
以上を１ガ用するときの使用量としては０，１〜４モル
か好ましい。Further, the amount of formaldehyde, shrimp halohydrin or dialdehyde to be used alone is preferably 0.1 to 3-sol per mole of polyalkylene polyamine, and when two or more types are used in one mole, the amount to be used is 0.1-3. 4 mol is preferred.
反応順序に関しては、ポリアルキレンポリアミン、二塩
基性カルボン酸系化合物、尿素類、脂環式エポキシ化合
物、及び脂環式アミン化合物は任意の順序で反応させる
ことかできる。Regarding the reaction order, the polyalkylene polyamine, dibasic carboxylic acid compound, ureas, alicyclic epoxy compound, and alicyclic amine compound can be reacted in any order.
例えば、反応生成物＜Ｉ＞については、次に示す方法に
よって製造することができる。For example, the reaction product <I> can be produced by the method shown below.
（Ｉ）−１：ポリアルキレンポリアミンと、脂環式エポ
キシ化合物又は／及び脂環式アミン化合物と二塩基性カ
ルボン酸系化合物を６０〜３００ ’Ｃ１好ましくは８
０〜２００ ’Ｃて１〜１０時間反応させて縮合を行っ
た後、尿素を加えて９０’−１８０’Ｃて脱アンモア反
応を０．５〜１０時間行い、次に水で希釈した後、ホル
ムアルデヒド、エビハロヒドリンもしくはジアルデヒド
の１種または２種以上を公知の方法で反応させ、反応性
基を導入する。(I)-1: Polyalkylene polyamine, alicyclic epoxy compound or/and alicyclic amine compound, and dibasic carboxylic acid compound at 60 to 300' C1, preferably 8
After condensation by reacting at 0 to 200'C for 1 to 10 hours, urea was added and a deammoization reaction was carried out at 90' to 180'C for 0.5 to 10 hours, and then diluted with water. A reactive group is introduced by reacting one or more of formaldehyde, shrimp halohydrin, or dialdehyde by a known method.
（Ｉ＞−２：ポリアルキレンポリアミンと、脂環式エポ
キシ化合物又は／及び脂環式アミン化合物と尿素類を９
０〜１８０’Ｃて０．５〜１０時間脱アンモニア反応さ
せた後、二塩基性カルボン酸系化合物を加えて６０〜３
００ ’Ｃ１好ましくは８０〜２００°Ｃで１〜１０時
間縮時間窓を行い、次に水で希釈した後、ホルムアルデ
ヒド、エピハロヒドリンもしくはジアルデヒドの１種ま
たは２種以上を公知の方法で反応させ、反応性基を導入
する。(I>-2: polyalkylene polyamine, alicyclic epoxy compound or/and alicyclic amine compound, and urea)
After deammonizing at 0 to 180'C for 0.5 to 10 hours, a dibasic carboxylic acid compound was added and
00 'C1 preferably carried out at 80-200 °C for a 1-10 hour reduced time window, then after dilution with water, reacting with one or more formaldehyde, epihalohydrin or dialdehyde in a known manner, Introducing reactive groups.
また、ポリアルキレンポリアミン、脂環式エポキシ化合
物、脂環式アミノ化合物、二塩基性カルボン酸系化合物
及び尿素類はそれぞれ分割して反応させることもてきる
。即ち、
（Ｉ）−３：ポリアルキレンポリアミンと、脂環式エポ
キシ化合物又は／及び脂環式アミン化合物と尿素類とを
脱アンモニア反応させた後、二塩基性カルボン酸系化合
物を加えて縮合反応を行い、次いで、再び尿素類を加え
て脱アンモニア反応を行い、次に水で希釈した後、ホル
ムアルデヒド、エピハロヒドリンもしくはジアルデヒド
の１種または２種以上を公知の方法で反応させ、反応性
基を導入する。Further, the polyalkylene polyamine, alicyclic epoxy compound, alicyclic amino compound, dibasic carboxylic acid compound, and urea can be reacted separately. That is, (I)-3: After deammonizing the polyalkylene polyamine, the alicyclic epoxy compound or/and the alicyclic amine compound, and the urea, a dibasic carboxylic acid compound is added to perform a condensation reaction. Then, ureas are added again to perform a deammonification reaction, and then diluted with water, one or more of formaldehyde, epihalohydrin, or dialdehyde is reacted by a known method to remove the reactive group. Introduce.
（ＩＩ−４：ポリアルキレンポリアミンと、脂環式エポ
キシ化合物又は２′及び脂環式アミン化合物と二塩基性
カルボン醇系化合物により縮合反応を行った後、尿素類
を加えて脱アンモニア反応を行い、次いて、再び二塩基
性カルボン酸系化合物を加えて縮合反応を行い、その接
水で希釈した後、ホルムアルデヒド、エピハロヒドリン
もしくはシアルデヒ１−の１種又は２種以上を公知の方
法で反応させ、反応性基を導入する。(II-4: After performing a condensation reaction with a polyalkylene polyamine, an alicyclic epoxy compound or 2' and an alicyclic amine compound, and a dibasic carbonate compound, ureas are added and a deammonification reaction is performed. Then, a dibasic carboxylic acid compound is added again to perform a condensation reaction, and after diluting with water, one or more of formaldehyde, epihalohydrin, or sialdehyde 1- is reacted by a known method, Introducing reactive groups.
（Ｉ）−５：ポリアルキレンポリアミンと尿素類を脱ア
ンモニア反応させた後、脂環式エポキシ化合物又は／及
び脂環式アミン化合物と二塩基性カルボン酸系化合物を
加えて縮合反応を行い、次いで、再び尿素類を加えて脱
アンモニア反応を行い、その接水で希釈した後、ホルム
アルデヒド、エピハロヒドリンもしくはジアルデヒドの
１種又は２種以上を公知の方法で反応させ、反応性基を
導入する。(I)-5: After deammonizing the polyalkylene polyamine and urea, add an alicyclic epoxy compound or/and an alicyclic amine compound and a dibasic carboxylic acid compound to perform a condensation reaction, and then Then, ureas are added again to carry out a deammonification reaction, and after dilution with water, one or more of formaldehyde, epihalohydrin, or dialdehyde is reacted by a known method to introduce a reactive group.
（Ｉｌ−６：ポリアルキレンポリアミンと、脂環式アミ
ン化合物をそれぞれ異なる二塩基性カルボン酸系化合物
と縮合反応させ、両者を混合した後尿素類を加えて脱ア
ンモニア反応を行い、その接水で希釈した後、ホルムア
ルデヒド、エピハロヒドリンもしくはジアルデヒドの１
種又は２種以上を公知の方法で反応させ、反応性基を導
入する。(Il-6: Polyalkylene polyamine and alicyclic amine compound are each subjected to a condensation reaction with different dibasic carboxylic acid compounds, and after mixing the two, ureas are added to perform a deammonification reaction, and in contact with water, After dilution, one of formaldehyde, epihalohydrin or dialdehyde
The species or two or more species are reacted by a known method to introduce a reactive group.
＜Ｉ＞−７：ポリアルキレンポリアミンと、脂環式エポ
キシ化合物を６０〜３００ ’Ｃ１好ましくは８０〜２
００’Ｃて０．５〜１０時間反応させた後、二塩基性カ
ルボン酸系化合物を加えて６０〜３００°Ｃ１好ましく
は８０〜２００’Ｃで１〜１０時間縮時間窓させ、その
後さらに、尿素類を加えて９０〜１８０°Ｃて脱アンモ
ア反応を０．５〜１０時間行い、水で希釈した後、ホル
ムアルデヒド、エピハロヒドリンもしくはジアルデヒド
の１種又は２種以上を公知の方法で反応させ、反応性基
を導入する。<I>-7: Polyalkylene polyamine and alicyclic epoxy compound of 60 to 300' C1, preferably 80 to 2
After reacting at 00°C for 0.5 to 10 hours, a dibasic carboxylic acid compound is added and the time is reduced at 60 to 300°C, preferably 80 to 200°C, for 1 to 10 hours, and then further, After adding ureas and carrying out a deammoization reaction at 90 to 180 °C for 0.5 to 10 hours, diluting with water, reacting with one or more of formaldehyde, epihalohydrin or dialdehyde by a known method, Introducing reactive groups.
反応生成物（ＩＩ）については、脂環式化合物を使用し
ないことを除き、上記（Ｉ）−１〜（Ｉ＞５と同様に反
応することかできる。Reaction product (II) can be reacted in the same manner as in (I)-1 to (I>5) above, except that an alicyclic compound is not used.
本発明におけるアミン−エピハロヒドリン樹脂（ロ）の
脂環式エポキシ化合物、脂環式アミノ化合物、脂肪族ア
ミン化合物、エピハロヒドリン、亜硫酸塩類、酸類の各
艮［芯成分の比率（」、脂肪族アミノ化合物のアミノ基
１土ルに対し脂環式エポキシ化合物又は・′及び脂環式
アミン化合物（反応生成物１．ＩＶの場合）０．０１〜
０５モル（イガ川の場合は両方の和）、エピハロヒドリ
ン０．０５〜３［ル、亜硫酸塩類０．０３〜１．５モル
、酸類０１〜０．５モルの範囲か好ましい。In the amine-epihalohydrin resin (b) of the present invention, each of the alicyclic epoxy compounds, alicyclic amino compounds, aliphatic amine compounds, epihalohydrin, sulfites, and acids [ratio of core components ('), aliphatic amino compound Alicyclic epoxy compound or /' and alicyclic amine compound (in the case of reaction product 1.IV) 0.01 to 1 mil of amino group
The preferable range is 0.05 mole (in the case of Igakawa, the sum of both), 0.05 to 3 mole of epihalohydrin, 0.03 to 1.5 mole of sulfites, and 01 to 0.5 mole of acids.
反応順序に関しては、脂環式エポキシ化合物、脂環式ア
ミン化合物、脂肪族アミン化合物、エピハロヒドリン、
亜硫酸塩類及び酸類は、任愈の順序で反応させることか
できる。Regarding the reaction order, alicyclic epoxy compounds, alicyclic amine compounds, aliphatic amine compounds, epihalohydrin,
The sulfites and acids can be reacted in any order.
例えば、反応生成物（Ｉ［Ｉ）については、次に示す方
法によって製造することかできる。For example, the reaction product (I[I) can be produced by the following method.
（Ｉ［Ｉ）−１：脂環式エポキシ化合物又は／及び脂環
式アミン化合物と脂肪族アミノ化合物にエピハロヒドリ
ンを４０’Ｃ以下で０．５〜３時間かけて滴下後、４０
〜８０’ＣでＯ〜４時間反応する。(I[I)-1: After dropping epihalohydrin to an alicyclic epoxy compound or/and an alicyclic amine compound and an aliphatic amino compound over a period of 0.5 to 3 hours at 40'C or less,
React at ~80'C for ~4 hours.
また、脂肪族アミン化合物と脂環式エポキシ化合物又は
／及び脂環式アミン化合物を同時に反応させず、分【プ
て反応させることもできる。例えば、（Ｉ［［）−２：
脂肪族アミン化合物にエピハロヒドリンンを、ｌｌＯ’
Ｃ以下で０．５〜３時間かけて滴下し、その後脂環式ア
ミン化合物又は／′及び脂環式エポキシ化合物を加え４
０〜８０’Ｃて０．５〜４時間反応する。Further, the aliphatic amine compound and the alicyclic epoxy compound and/or the alicyclic amine compound may not be reacted simultaneously, but may be reacted separately. For example, (I[[)-2:
Adding epihalohydrin to an aliphatic amine compound, llO'
C or less over 0.5 to 3 hours, and then add the alicyclic amine compound or /' and the alicyclic epoxy compound.
React at 0-80'C for 0.5-4 hours.
反応生成物（１ｖ）については、次に示す方法によって
製造することかできる。The reaction product (1v) can be produced by the following method.
（ＩＶ）−１：脂環式エポキシ化合物又は／及び脂環式
アミン化合物と脂肪族アミン化合物にエピハロヒトリン
を４０’Ｃ以下で０．５〜３時間かけて滴下後、４０〜
８０°Ｃて０〜４時間保持し、さらに亜硫酸塩類を加え
４０〜８０’Ｃて０．５〜４時間反応する。(IV)-1: After dropping epihalophytrine to an alicyclic epoxy compound or/and an alicyclic amine compound and an aliphatic amine compound over a period of 0.5 to 3 hours at 40°C or less,
The mixture is maintained at 80°C for 0 to 4 hours, and further sulfites are added and reacted at 40 to 80'C for 0.5 to 4 hours.
（ＩＶ）−２：脂環式エポキシ化合物又は／及び脂環式
アミン化合物と脂肪族アミン化合物と亜硫酸塩類の混合
物にエピハロヒドリンを４０’Ｃ以下で０．５〜３時間
かけて滴下し、その後４０〜８０’ＣてＯ〜４時間反応
する。(IV)-2: Epihalohydrin is added dropwise to a mixture of an alicyclic epoxy compound or/and an alicyclic amine compound, an aliphatic amine compound, and sulfites at a temperature below 40'C over a period of 0.5 to 3 hours, and then React at ~80'C for ~4 hours.
（ＩＶ）−３：エピハロヒトリンと亜硫酸塩類を４０〜
８０’Ｃて０．５〜４時間反応させることにより得られ
た反応生成物又はエピハロヒドリンと亜ＦｆｆＬＭ塩類
の混合物に、脂環式エポキシ化合物又は５′及び脂環式
アミノ化合物と脂肪族アミノ化合物を加え４０〜８０°
Ｃて０．５〜４時間反応させる。(IV)-3: Epihalophytrine and sulfites from 40 to
An alicyclic epoxy compound or a 5' and alicyclic amino compound and an aliphatic amino compound are added to the reaction product obtained by reacting at 80'C for 0.5 to 4 hours or a mixture of epihalohydrin and sub-FffLM salts. addition 40~80°
React at C for 0.5 to 4 hours.
又、脂環式エポキシ化合物又は 及び脂環式アミン化合
物と脂肪族アミン化合物にあらかじめ酸類を加えておき
、アミン基の活性を抑えてから反応することもてきる。It is also possible to add an acid to the alicyclic epoxy compound or the alicyclic amine compound and the aliphatic amine compound in advance to suppress the activity of the amine group before reacting.
例えば、（ＩＶ）−４：脂環式エポキシ化合物又は／及
び脂環式アミン化合物と脂肪族アミン化合物に硫酸を加
えた後、エピハロヒドリンを５０’Ｃ以下で０．５〜２
時間かけて滴下し、ざらに５０〜８０’Ｃて０．５〜４
時間反応する。For example, (IV)-4: After adding sulfuric acid to an alicyclic epoxy compound or/and an alicyclic amine compound and an aliphatic amine compound, add 0.5 to 2
Drop over time and heat to 50-80'C for 0.5-4
Time reacts.
反応生成物（Ｖ）については、脂環式化合物を使用しな
いことを除き上記（ＩＩＩ）−１と同様に反応すること
かできる。The reaction product (V) can be reacted in the same manner as in (III)-1 above, except that an alicyclic compound is not used.
反応生成物（ＶＩ）については、脂環式化合物を使用し
ないことを除き上記（ＩＶ）−１〜（ＩＶ＞４と同様に
反応することができる。The reaction product (VI) can be reacted in the same manner as in (IV)-1 to (IV>4) above, except that an alicyclic compound is not used.
上記のようにして得られたポリアミド−尿素−アルデヒ
ド（エピハロじドリノ）樹脂（イ）とアミン−エピハロ
ヒトリン樹脂（ロ）は、ざら（反応させるか混合して使
用する（但し、（ＩＩ）と（Ｖ）、（ＩＩ）と（ＶＩ
）の組み合わけは除く）。The polyamide-urea-aldehyde (epihalodidolino) resin (a) and the amine-epihalohitrin resin (b) obtained as described above are used by reacting or mixing (however, (II) and ( V), (II) and (VI
) (excluding combinations).
両者を反応させるときは、肢応温度３０°Ｃ〜９０°Ｃ
て２０分〜１０時間行われる。混合に際しては、両者を
別々に紙塗工用組成物に添加してもよく、あるいは、あ
らかじめ両者を混合してあきこれを紙塗工用組成物に添
加してもよい。When reacting both, the limb temperature is 30°C to 90°C.
It lasts for 20 minutes to 10 hours. When mixing, both may be added separately to the paper coating composition, or both may be mixed in advance and then added to the paper coating composition.
又、（イ）、（ロ）を反応及び混合するときの（イ）、
（ロ）の使用比率は任意でおる。なお、（ロ）が多いほ
どインキ受理性、耐ブリスター性に優れるが、配合によ
っては、紙塗工用組成物の増粘が著しく好ましくない。Also, (a) when reacting and mixing (a) and (b),
The usage ratio of (b) is arbitrary. Incidentally, the more (b) there is, the better the ink receptivity and blister resistance are, but depending on the formulation, the viscosity of the paper coating composition is significantly undesirable.
又、この紙塗工用樹脂は紙薬品以外の用途にも使用する
ことができる。Moreover, this paper coating resin can be used for purposes other than paper chemicals.
本発明の紙塗工用樹脂は単独でも使用されるが、好まし
くは顔料、接着剤及び必要によりその他の成分を添加し
て紙塗工用組成物にして使用される。Although the paper coating resin of the present invention can be used alone, it is preferably used in the form of a paper coating composition by adding pigments, adhesives, and other components if necessary.
この場合に用いられる顔料としては、クレー、タルク、
重質炭酸カルシウム、軽質炭酸カルシウム、リチンホワ
イ）〜、二酸化チタン、水酸化アルミニウム、硫酸バリ
ウム、亜ｆｆ＋ｉ％カルシウム、合成シリカ、酸化曲鉤
等の無機顔料及びスチレン系ポリマー、尿素系ポリマー
等の有機顔料かあり、これらのうら１種類または２種類
以上を混合して使用することかできる。Pigments used in this case include clay, talc,
Inorganic pigments such as heavy calcium carbonate, light calcium carbonate, lithine white), titanium dioxide, aluminum hydroxide, barium sulfate, ff+i% calcium, synthetic silica, oxidized benthoku, and organic pigments such as styrene polymers and urea polymers. It is possible to use one type or a mixture of two or more of these types.
また、接着剤としては澱粉、変性澱粉〈酸化澱粉、エス
テル化澱粉、エーテル化澱粉、酵素変性澱粉、アルファ
ー化澱粉、カチオン化澱粉等〉、カセイン、ゼラチン、
大豆タンパク、酵母タンパク、セルロース誘導体（カル
ボキシメチルセルロース、ヒドロキシエチルセルロース
等）等の天然高分子化合物あるいはその誘導体、及びス
チレン−ブタジェン系樹脂、（メタ）アクリレトーブタ
ジエン系樹脂、（メタ）アクリレート系樹脂、ポリビニ
ルアルコール、酢酸ビニル系樹脂、アクリルアミド系樹
脂、スチレン−（メタ）アクリレート系樹脂、スチレン
−マレイン酸系樹脂、エチレン−酢酸ビニル系樹脂等の
合成高分子化合物か例示される。In addition, adhesives include starch, modified starch (oxidized starch, esterified starch, etherified starch, enzyme-modified starch, pregelatinized starch, cationized starch, etc.), casein, gelatin,
Soybean protein, yeast protein, natural polymer compounds such as cellulose derivatives (carboxymethyl cellulose, hydroxyethyl cellulose, etc.) or their derivatives, styrene-butadiene resin, (meth)acryletobutadiene resin, (meth)acrylate resin, polyvinyl Examples include synthetic polymer compounds such as alcohol, vinyl acetate resin, acrylamide resin, styrene-(meth)acrylate resin, styrene-maleic acid resin, and ethylene-vinyl acetate resin.
本発明の紙塗工用組成物には、上記の顔料、接着剤のほ
か分散剤、滑剤、増粘剤、減粘剤、消泡剤、抑泡剤、防
腐剤、防カビ剤、保水剤、蛍光増白剤、染料、導電剤な
どの各種助剤も必要に応じて適宜配合することかできる
。In addition to the above-mentioned pigments and adhesives, the paper coating composition of the present invention includes dispersants, lubricants, thickeners, thinners, antifoaming agents, foam inhibitors, preservatives, antifungal agents, and water retention agents. , a fluorescent brightener, a dye, a conductive agent, and other various auxiliary agents may be added as necessary.
組成物中のそれぞれの配合量は顔料を１００重量部とし
たときに、紙塗工用樹脂か０．０５〜５重量部、接着剤
が固形分として５〜５０重量部の範囲であることか好ま
しい。The amount of each compounded in the composition should be in the range of 0.05 to 5 parts by weight of the paper coating resin and 5 to 50 parts by weight of the adhesive as a solid content when the pigment is 100 parts by weight. preferable.
本発明の紙塗工用組成物を製造するには、例えば顔料を
分散剤と共に水中に分散させ、これに接着剤、及び必要
に応じて粘度調節剤等の助剤を加え、これに本発明の紙
塗工用樹脂を加え攪拌し、そしてさらに必要に応じて苛
性ソーダ、及びアンモニア等でｐＨを調節して調製する
。In order to produce the paper coating composition of the present invention, for example, the pigment is dispersed in water together with a dispersant, and an adhesive and, if necessary, auxiliary agents such as a viscosity modifier are added thereto. The paper coating resin is added and stirred, and the pH is further adjusted with caustic soda, ammonia, etc. as necessary.
本発明の紙塗工用組成物は、公知の方法で原紙上に塗工
される。すなわち、ブレードコーターエアーナイフコー
ター、バーコーター、ロールコター、サイズプレスコー
ター、ドクトル］−タ、ブラシコーター、カーテンコー
ター、グラビアコーター、キャストコーター、チャンプ
レックスコーター等通常用いられる方法で塗工され、オ
ンマシンコーティング、オフマシンコーティングのいず
れてあってｂよい。また、−層ｑ王であっても多層塗工
てあってもよく、さらに片面塗Ｔ、両面塗工のいずれも
可能である。The paper coating composition of the present invention is coated onto base paper by a known method. That is, coating is performed by a commonly used method such as a blade coater, an air knife coater, a bar coater, a roll coater, a size press coater, a doctor coater, a brush coater, a curtain coater, a gravure coater, a cast coater, and a champlex coater. , off-machine coating may be used. Further, it may be a -layer q layer or a multilayer coating, and both single-sided coating and double-sided coating are possible.
塗工後の乾燥は例えばカスヒーター、電気ヒター、蒸気
加熱ヒーター、赤外線ヒーター、熱風加熱等の通常の方
法で行われ、乾燥後は必要に応じてスーパーカレンダー
、水力レンダ−、クロスカレンダー等の什上げ工程によ
って光沢を付与することか可能であり、その他−船釣な
加工手段はいずれも使用することができる。Drying after coating is carried out using a conventional method such as a cast heater, an electric heater, a steam heater, an infrared heater, or a hot air heater. It is possible to impart gloss through the polishing process, and any other processing means can be used.
（実 施 例〕
次に本発明を参考例、実施例、比較例によって説明する
。(Example) Next, the present invention will be explained by reference examples, examples, and comparative examples.
参考例 １
温度計、コンデンサー及び攪拌捧を備えた四つロフラス
コにトリエチレンテトラミン２１９ｇとイソホロンジア
ミン８５ｇおよびアジピン酸３７７を加えて１６０°Ｃ
て１．５時間線合反応を行い、発生する水を系外に除去
した。次いてこれに尿素１２０９を加え１２０’Ｃて５
時間脱アンモニア反応を行った。Reference Example 1 Add 219 g of triethylenetetramine, 85 g of isophorone diamine, and 377 g of adipic acid to a four-bottle flask equipped with a thermometer, condenser, and stirring sprocket, and heat to 160°C.
Linearization reaction was carried out for 1.5 hours, and the generated water was removed from the system. Next, add urea 1209 to this and heat at 120'C for 5
A time deammonification reaction was performed.
しかる後、これに水を加えて６０％水溶液とした。Thereafter, water was added to this to make a 60% aqueous solution.
次に３７％ホルマリン水溶液１２２ｇを加え５０％硫酸
水溶液（てｐ１］５に調整し、７０’Ｃて４時間攪拌し
なから保持した。さらに水を加えて固形分５０％の水溶
性樹脂（反応生成物工）を得た。この樹脂水溶液を（ａ
−１＞とする。Next, 122 g of a 37% formalin aqueous solution was added to adjust the concentration to 50% sulfuric acid aqueous solution (p1), and the mixture was kept at 70'C for 4 hours without stirring.Additionally, water was added to make a water-soluble resin with a solid content of 50% (reacted). This resin aqueous solution was obtained as (a
−1>.
参考例 ２
参考例１と同様の反応容器にトリエチレンテトラミン３
５０ｇおよび尿素７２ｇを仕込み、攪拌しながら１５０
°Ｃて９０分間脱アンモニア反応を行った。Reference Example 2 Triethylenetetramine 3 was placed in the same reaction vessel as Reference Example 1.
Add 50g and 72g of urea and boil to 150g while stirring.
Deammonification reaction was carried out at °C for 90 minutes.
次いて、これを１２０’Ｃまて冷却してからアジピン１
１７５ｇとシクロヘキセンオキサイド５９ｇとを加えて
１６０°Ｃて２時間線合反応を行い、発生する水を系外
に除去した。次いでこれを１２０°Ｃに冷却した後、尿
素２８８ｇを加えて１２０°Ｃで５時間脱アンモニア反
応を行った。しかる後、これに水を加えて７０％水溶液
とした。次に３７％ホルマリン水溶液１４６ｇを加え５
０％硫酸水）ｄ液にてｏｆ（５に調整し、７０°Ｃて３
時間攪拌しながら保持した。しかる後、水を加えて固形
分６０％の水溶性樹脂（反応生成物■）を得た。この樹
脂水溶液を（ａ−２＞とする。Next, after cooling this to 120'C, adipine 1
175 g of cyclohexene oxide and 59 g of cyclohexene oxide were added, and a line combination reaction was carried out at 160°C for 2 hours, and the generated water was removed from the system. Next, after cooling this to 120°C, 288 g of urea was added and a deammonia reaction was carried out at 120°C for 5 hours. Thereafter, water was added to this to make a 70% aqueous solution. Next, add 146 g of 37% formalin aqueous solution and
0% sulfuric acid water) of (adjusted to 5 with d solution, 3 at 70°C
Hold with stirring for an hour. Thereafter, water was added to obtain a water-soluble resin (reaction product (2)) with a solid content of 60%. This resin aqueous solution is designated as (a-2>).
参考例 ３
参考例１と同様の反応容器にｉ〜リエチレンテトラミン
２３４ｇとシクロヘキセンオキ１ノイド２０９を仕込み
、１２０℃で１時間ａ拌を行った。次いてアジピン酸３
７９とジシクロヘキシルアミン３６９を加え１６０’Ｃ
昇温し、１．５時間線合反応を行い、発生する水を系外
に除去した。さらにこれを１２０’Ｃまて冷却した後、
尿素３６０ ｇを加えて１２０ ’Ｃて４時間脱アンモ
ニア反応を行った。しかる後、これに水を加えて６０％
水溶液とした。次に３７％ホルマリン水溶液１２２ｇを
加えて５０％硫酸水溶液てｐ）１５に調整し、７０’Ｃ
で３時間攪拌しなから保持した。Reference Example 3 234 g of i~lyethylenetetramine and 209 cyclohexene ochinoid were placed in the same reaction vessel as in Reference Example 1, and stirred at 120° C. for 1 hour. Then adipic acid 3
79 and dicyclohexylamine 369 and heated at 160'C.
The temperature was raised, a linear combination reaction was carried out for 1.5 hours, and the generated water was removed from the system. After further cooling this to 120'C,
360 g of urea was added and ammonia removal reaction was carried out at 120'C for 4 hours. After that, add water to this to make 60%
It was made into an aqueous solution. Next, add 122 g of 37% formalin aqueous solution, adjust to p) 15 with 50% sulfuric acid aqueous solution, and 70'C
The mixture was stirred and held for 3 hours.
さらに水を加えて固形分５０％の水溶性樹脂（反応生成
物■）を得た。この樹脂水溶液を（ａ〜３）とする。Further water was added to obtain a water-soluble resin (reaction product (2)) with a solid content of 50%. This resin aqueous solution is referred to as (a-3).
参考例 ４
参考例１と同様の反応容器にジエチレントリアミン１６
５ｇとモノエタノールアミン１２９．４．４オキシビス
（シクロヘキシルアミン）８５ｇ及び゛テレフタル酸ジ
メチル１９４９を付込み、１３５°Ｃて２．５時間給合
反応を行い、発生するメタノールを系外に除去した。次
いて、これを１２０°Ｃに冷却した後、尿素１７６ｇを
加えて１２０’Ｃて３時間脱アンモニア反応を行った。Reference Example 4 Diethylenetriamine 16 was added to the same reaction vessel as Reference Example 1.
5 g of monoethanolamine 129.4.4, 85 g of oxybis(cyclohexylamine) and 1949 dimethyl terephthalate were added, and a feeding reaction was carried out at 135° C. for 2.5 hours, and the generated methanol was removed from the system. Next, after cooling this to 120°C, 176 g of urea was added and a deammonia reaction was carried out at 120'C for 3 hours.
しかる後、これに水を加えて６０％水溶液とした。次に
エビクロロヒドリン１１７ｇを加えて５５°Ｃて２時間
反応を続けた。しかる後、３０’Ｃに冷却して３７％ホ
ルマリン水溶液６８９を加え、５０％硫酸水溶液にてｐ
Ｈ４に調整し、６５°Ｃて３時間保ちつつ攪拌した。ざ
らに水を加えて固形分５０％の水溶性樹脂（反応生成物
■）を得た。Thereafter, water was added to this to make a 60% aqueous solution. Next, 117 g of shrimp chlorohydrin was added and the reaction was continued at 55°C for 2 hours. After that, the temperature was cooled to 30'C, 37% formalin aqueous solution 689 was added, and 50% sulfuric acid aqueous solution was added.
The temperature was adjusted to H4, and the temperature was maintained at 65°C for 3 hours while stirring. Water was added to the colander to obtain a water-soluble resin (reaction product ■) with a solid content of 50%.
この樹脂水溶液を（ａ−４＞とする。This resin aqueous solution is designated as (a-4>).
参考例 ５
参考例１と同様の反応容器にジエチレントリアミン２０
６９と２，２−じス（４°−グリシジルオキシシクロヘ
キシル）プロパン７０９と尿素９０ｇ仕込み、攪拌しな
から１５０°Ｃて３時間脱アンモニア反応を行った。次
いで、グルタル酸ジメチル１６０ （ｊを加えて１６０
’Ｃて２時間線合艮応を行い、発生するメタノールを系
外に除去した。ぞの後ざらに、尿素６０ｇを加えて１２
０ ’Ｃて５時間脱アンモニア反応を行った。しかる後
、これに水を加えて６０％水溶液とした。次に３７％ホ
ルマリン水溶液１２２ｇを加え、５０％硫酸水溶液にて
ｐＨ５に調整し、７０’Ｃて３時間攪拌しなから保持し
た。さらに水を加えて固形分５０％の水溶性樹脂（反応
生成物Ｔ）を得た。この樹脂水溶液を（ａ−５）とする
。Reference Example 5 In a reaction vessel similar to Reference Example 1, diethylenetriamine 20
69, 2,2-disu(4°-glycidyloxycyclohexyl)propane (709) and 90 g of urea were charged, and ammonia removal reaction was carried out at 150°C for 3 hours without stirring. Next, add 160 dimethyl glutarate (j and add 160
The reaction mixture was heated for 2 hours at 100°C, and the generated methanol was removed from the system. Add 60g of urea to the back of the throat and make 12
Deammonization reaction was carried out at 0'C for 5 hours. Thereafter, water was added to this to make a 60% aqueous solution. Next, 122 g of a 37% formalin aqueous solution was added, the pH was adjusted to 5 with a 50% sulfuric acid aqueous solution, and the mixture was maintained at 70'C for 3 hours without stirring. Further water was added to obtain a water-soluble resin (reaction product T) with a solid content of 50%. This resin aqueous solution is referred to as (a-5).
参考例 ６
参考例１と同様の反応容器にトリエチレンテトラミン２
９２９と尿素１２０７を仕込み、１５０°Ｃて２時間脱
アンモニア反応を行った。次いてアジピン酸１４６ｇを
加え１６０°Ｃ昇温し、３時間線合反応を行い、発生す
る水を系外に除去した。さらにこれを１２０℃まで冷却
した後、尿素１２０ｇを加えて１２０°Ｃて４時間脱ア
ンモニア反応を行った。しかる１変、これに水を加えて
６０％水溶液とした。次に３７％ホルマリン水溶液１２
２９を加えて５０％ｆＡＭ水溶液で０１１５に調整し、
７０°Ｃて４時間攪拌しながら保持した。さら（水を加
えて固形分５０％の水溶性樹脂（反応生成物■）を得た
。この樹脂水溶液を（ａ−６）とする。Reference Example 6 Triethylenetetramine 2 was added to the same reaction vessel as Reference Example 1.
929 and urea 1207 were charged, and ammonia removal reaction was performed at 150°C for 2 hours. Next, 146 g of adipic acid was added, the temperature was raised to 160°C, a linear combination reaction was carried out for 3 hours, and the generated water was removed from the system. After further cooling this to 120°C, 120g of urea was added and a deammonia reaction was carried out at 120°C for 4 hours. In one change, water was added to this to make a 60% aqueous solution. Next, 37% formalin aqueous solution 12
29 and adjusted to 0115 with 50% fAM aqueous solution,
The mixture was maintained at 70°C for 4 hours with stirring. Further, water was added to obtain a water-soluble resin (reaction product (2)) with a solid content of 50%. This resin aqueous solution is referred to as (a-6).
参考例 ７
参考例１と同様の反応容器にトリエチレンテトラミン２
９２ｇとアジピンｌ １４６ｇを仕込み、１７０°Ｃて
２．５時間攪拌を行った。次いで、１２０°Ｃまて冷却
した後、尿素３００ｇを加えて１２０’Ｃて４時間脱ア
ンモニア反応を行った。しかる後、これに水を加えて６
０％水溶液とした。次に３７％ホルマリン水溶液１６２
ｇを加えて５０％硫酸水溶液でｐＨ５に調整し、８０’
Ｃで２時間攪拌しながら保持した。さらに水を加えて固
形分５０％の水溶性樹脂（反応生成物■）を得た。この
樹脂水溶液を（ａ−７＞とする。Reference Example 7 Triethylenetetramine 2 was added to the same reaction vessel as Reference Example 1.
92 g and 146 g of adipine 1 were charged, and the mixture was stirred at 170°C for 2.5 hours. Then, after cooling to 120°C, 300g of urea was added and a deammonia reaction was carried out at 120°C for 4 hours. After that, add water to this and make 6
It was made into a 0% aqueous solution. Next, 37% formalin aqueous solution 162
g, adjusted to pH 5 with 50% sulfuric acid aqueous solution, and heated to 80'
The mixture was maintained at C for 2 hours with stirring. Further water was added to obtain a water-soluble resin (reaction product (2)) with a solid content of 50%. This resin aqueous solution is designated as (a-7>).
参考例 ８
参考例１と同様の反応容器にトリエチレンテトラミン２
９２ｇとグルタル１１３２ ｇを仕込み、攪拌しなから
１７０°Ｃて３時間線合艮応を行い、発生する水を系外
に除去した。次いて、尿素１２０９を加えて１２０°Ｃ
て２時間ＪＪＲ７’ンモニア反応を行った。Reference example 8 Triethylenetetramine 2 was placed in the same reaction vessel as in reference example 1.
92 g of glutarium and 1132 g of glutarium were charged, and the mixture was reacted at 170° C. for 3 hours without stirring, and the generated water was removed from the system. Next, add urea 1209 and heat to 120°C.
JJR7' ammonia reaction was carried out for 2 hours.
その後さらに、アジピン酸ジメチル１７４ｇを加えて１
７０°Ｃて２時間線合反応を行い、発生するメタノール
を系外に除去した。しかる後、これに水を加えて６０％
水溶液とした。次（こ３７％ホルマリン水溶液１６２７
を加え、５０％硫酸水溶液にてｐｆ１５Ｍ調整し、７０
’Ｃて３時間攪拌しなから保持した。史に水を加えて固
形分５０％の水溶性樹脂（反応生成物■）を得た。この
樹脂水溶液を（ａ−８＞とする。Then, 174g of dimethyl adipate was added and 1
Linearization reaction was carried out at 70°C for 2 hours, and generated methanol was removed from the system. After that, add water to this to make 60%
It was made into an aqueous solution. Next (this 37% formalin aqueous solution 1627
was added, the pf was adjusted to 15M with 50% sulfuric acid aqueous solution, and the
The mixture was stirred and held at 'C for 3 hours. Water was added to the mixture to obtain a water-soluble resin (reaction product (2)) with a solid content of 50%. This resin aqueous solution is designated as (a-8>).
参考例 ９
参考例１と同様の反応容器にジエチレントリアミン２０
６ｇと１，３−ビス−（アミノメチル）シクロヘキサン
１４ｇを仕込み、水３３７ｇにて希釈した後、十分攪拌
しなからエビクロロヒドリン１８３Ｊを３５℃で２時間
かけて滴下した。滴下終了後６０°Ｃて２時間保持した
後、水を加えて固形分４０％の水溶性樹脂（反応生成物
■）を得た。この樹脂水溶液を（ｂ−１＞とする。Reference Example 9 In a reaction vessel similar to Reference Example 1, diethylenetriamine 20
6 g and 14 g of 1,3-bis-(aminomethyl)cyclohexane were added, diluted with 337 g of water, and then 183 J of shrimp chlorohydrin was added dropwise at 35° C. over 2 hours without sufficient stirring. After the dropwise addition was completed, the mixture was maintained at 60°C for 2 hours, and then water was added to obtain a water-soluble resin (reaction product ①) with a solid content of 40%. This resin aqueous solution is designated as (b-1>).
参考例 １０
参考例１と同様の反応容器にジエチレントリアミン２０
６９と３，４−■ポキシシクロヘキシルメチル３．４−
エポキシシクロヘキサン−カルボキシレート２５７を仕
込み、水３４７９にて希釈した後、十分攪拌しながらエ
ビクロロヒドリン１８５ｇを３５°Ｃて２時間かけて滴
下した。滴下終了後６０°Ｃて１．５時間保持した後、
水を加えて固形分４０％の水溶性樹脂（反応生成物■）
を得た。この樹脂水溶液を（ｂ−２＞とする。Reference Example 10 In a reaction vessel similar to Reference Example 1, diethylenetriamine 20
69 and 3,4-■Poxycyclohexylmethyl 3,4-
Epoxycyclohexane-carboxylate 257 was charged and diluted with water 3479, and then 185 g of shrimp chlorohydrin was added dropwise over 2 hours at 35° C. with sufficient stirring. After the completion of dropping, the temperature was maintained at 60°C for 1.5 hours,
Water-soluble resin with solid content of 40% by adding water (reaction product ■)
I got it. This resin aqueous solution is designated as (b-2>).
参考例 １１
参考例１と同様の反応容器にトリエチレンテトラミン２
９２ｇとＮ−アミノプロピルシクロへキシルアミン１６
ｇを仕込み、水４６２９にて希釈した後、十分攪拌しな
がらエビクロロヒドリン９３ｇを３５℃で２時間かけて
滴下した。滴下終了後６０’Ｃで２時間保持した後、水
を加えて固形分４０％の水溶性樹脂（反応生成物■）を
得た。この樹脂水溶液を（ｂ−３＞とする。Reference Example 11 Triethylenetetramine 2 was placed in the same reaction vessel as Reference Example 1.
92g and N-aminopropylcyclohexylamine 16
After diluting with 4,629 g of water, 93 g of shrimp chlorohydrin was added dropwise at 35° C. over 2 hours with sufficient stirring. After the completion of the dropwise addition, the mixture was maintained at 60'C for 2 hours, and then water was added to obtain a water-soluble resin (reaction product ■) with a solid content of 40%. This resin aqueous solution is designated as (b-3>).
参考例 １２
参考例１と同様の反応容器にジエチレントリアミン２０
６９とオクタハイドロ−４，７−メタノインデン−１（
２）、 ５（６）−ジメタンアミン２０９を仕込み、水
３９６ｇにて希釈した後、十分攪拌しながら無水重亜硫
酸ナトリウム４０ｇを加え、ざらにエビクロロヒドリン
３６ｇを３５°Ｃて２時間かけて滴下した。Reference Example 12 In a reaction vessel similar to Reference Example 1, diethylenetriamine 20
69 and octahydro-4,7-methanoindene-1 (
2), After preparing 5(6)-dimethanamine 209 and diluting it with 396 g of water, add 40 g of anhydrous sodium bisulfite while stirring thoroughly, and dropwise add 36 g of shrimp chlorohydrin to the colander over 2 hours at 35°C. did.
滴下終了後６０’Ｃて２時間保持した後、水を加えて固
形分４０％の水溶性樹脂（反応生成物ＩＶ ）を得た。After the dropwise addition was completed, the mixture was maintained at 60'C for 2 hours, and then water was added to obtain a water-soluble resin (reaction product IV) with a solid content of 40%.
この樹脂水溶液を（ｂ−４＞とする。This resin aqueous solution is designated as (b-4>).
参考例 １３
参考例１と同様の反応容器にモノエタノールアミン２４
９とオクタハイドロ−４，７−メタノインデン１（２）
、 ５（６）−ジメタンアミン２０７を仕込み、水１４
１ｇにて希釈した接、十分攪拌しなから亜硫酸ナトリウ
ム５０９を加え、さらにエビクロロヒドリン９２ｇを３
５°Ｃて２時間かけて滴下した。滴下終了後６０°Ｃで
２時間保持した後、水を加えて固形分４０％の水溶性樹
脂（反応生成物ＩＶ ＞を得た。この樹脂水溶液を（ｂ
−５＞とする。Reference Example 13 Monoethanolamine 24 was placed in the same reaction vessel as Reference Example 1.
9 and octahydro-4,7-methanoindene 1(2)
, 5(6)-dimethaneamine 207 was charged, water was added 14
After stirring thoroughly, sodium sulfite 509 was added, and then 92 g of shrimp chlorohydrin was added to the mixture.
The mixture was added dropwise at 5°C over 2 hours. After the dropwise addition was completed, the temperature was maintained at 60°C for 2 hours, and then water was added to obtain a water-soluble resin (reaction product IV) with a solid content of 40%.
−5>.
参考例 １４
参考例１と同様の反応容器にジエチレントリアミン２０
６ｇとオクタハイドロ−４，７−メタノインデン−Ｈ２
）、 ５（６）−ジメタンアミン２０ｇを付込み、水３
９４ｇにて希釈し、十分攪拌しなから酢酸３７ｇを加え
、さらにエビクロロヒドリン１８５ｇを３５°Ｃて１時
間かけて滴下した。滴下終了後８０°Ｃて２時間保持し
た後、水を加えて固形分４０％の水溶性樹脂（反応生成
物ＩＶ ）を得た。この樹脂水溶液を（ｂ−６＞とする
。Reference Example 14 In a reaction vessel similar to Reference Example 1, diethylenetriamine 20
6g and octahydro-4,7-methanoindene-H2
), add 20 g of 5(6)-dimethaneamine, add 3 ml of water
After stirring thoroughly, 37 g of acetic acid was added, and 185 g of shrimp chlorohydrin was added dropwise at 35° C. over 1 hour. After the dropwise addition was completed, the mixture was maintained at 80°C for 2 hours, and then water was added to obtain a water-soluble resin (reaction product IV) with a solid content of 40%. This resin aqueous solution is designated as (b-6>).
参考例 １５
参考例１と同様の反応容器にトリエチレンテトラミン２
１９９を仕込み、水２５６ｇにて希釈した後、十分攪拌
しながらエビクロロヒドリン９３ｇを３５°Ｃで２時間
かけて滴下した。滴下終了後シクロヘキセンオキサイド
１０ｇと無水重亜硫酸ナトリウム３８９を加えて、６０
°Ｃで３時間保持した。その後、水を加えて固形分４０
％の水溶性樹脂（反応生成物ＩＶ ）を得た。この樹脂
水溶液を（ｂ−７＞とする。Reference example 15 Triethylenetetramine 2 was placed in the same reaction vessel as in reference example 1.
After diluting with 256 g of water, 93 g of shrimp chlorohydrin was added dropwise at 35° C. over 2 hours with thorough stirring. After dropping, add 10 g of cyclohexene oxide and 389 g of anhydrous sodium bisulfite,
It was kept at °C for 3 hours. After that, add water to make the solid content 40.
% of water-soluble resin (reaction product IV) was obtained. This resin aqueous solution is designated as (b-7>).
参考例 １６
参考例１と同様の反応容器にジエチレントリアミン２０
６７を仕込み、水５ｏ３９にて希釈した後、十分攪拌し
ながらエビクロロヒドリン３７０Ｊを滴下した。滴下終
了後６５°Ｃて２時間保持した後、水を加えて固形分５
０％の水溶性樹脂（反応生成物Ｖ）を得た。この樹脂水
溶液を（ｂ−８＞とする。Reference Example 16 In a reaction vessel similar to Reference Example 1, diethylenetriamine 20
67 and diluted with 5 to 39 parts of water, 370 J of shrimp chlorohydrin was added dropwise with sufficient stirring. After the dropping was completed, the temperature was kept at 65°C for 2 hours, and water was added to reduce the solid content to 5.
A 0% water-soluble resin (reaction product V) was obtained. This resin aqueous solution is designated as (b-8>).
参考例 １７
参考例１と同様の反応容器にテトラエチレンペンタミン
１８９９と無水重亜硫酸ナトリウム３８ｇを仕込み、水
３６８９にて希釈した後、十分攪拌しながらエビクロロ
ヒドリン２２２ｇを滴下した。滴下終了後５５°Ｃで４
時間保持した後、水を加えて固形分４０％の水溶性樹脂
（反応生成物Ｖｌ）を得た。この樹脂水溶液を（ｂ−９
＞とする。Reference Example 17 In a reaction vessel similar to Reference Example 1, 1899 tetraethylene pentamine and 38 g of anhydrous sodium bisulfite were charged, and after diluting with 3689 water, 222 g of shrimp chlorohydrin was added dropwise with sufficient stirring. 4 at 55°C after completion of dripping.
After holding for a period of time, water was added to obtain a water-soluble resin (reaction product Vl) with a solid content of 40%. This resin aqueous solution (b-9
>.
参考例 １８
参考例１と同様の反応容器にジエチレントリアミン１０
３ｇと５０％ジメチルアミン９０ｇを仕込み、水５５２
ソで希釈した後、十分攪拌しながらエビクロロヒドリン
２７８ｇを２５°Ｃで滴下した。滴下終了１変３５°Ｃ
て３０分間保持した後、亜硫酸ナトリウム６３９を加え
５０’Ｃて２時間保持した。その復水を加えて固形分４
０％の水溶性樹脂（反応生成物Ｖｌ ）を得た。この樹
脂水溶液を（ｂ−１０＞とする。Reference Example 18 Diethylenetriamine 10 was added to the same reaction vessel as Reference Example 1.
Prepare 3g and 90g of 50% dimethylamine, and add 552g of water.
After diluting with SO, 278 g of shrimp chlorohydrin was added dropwise at 25°C while stirring thoroughly. Dripping completed 1 change 35°C
After holding for 30 minutes at 50'C, sodium sulfite 639 was added and held at 50'C for 2 hours. Add the condensate and the solid content is 4
0% water-soluble resin (reaction product Vl) was obtained. This resin aqueous solution is designated as (b-10>).
実施例１
上記参考例に示し１：樹脂水溶液（ａ−１）’ｔｏ９と
樹脂水溶液（ｂ−１）１０ｇを６０’Ｃて５時間反応す
ることにより、紙塗工用樹脂を得た。これを樹脂Ａとす
る。Example 1 As shown in the above reference example 1: Resin aqueous solution (a-1)'to9 and 10 g of resin aqueous solution (b-1) were reacted at 60'C for 5 hours to obtain a paper coating resin. This is called resin A.
実施例２
上記参考例に示した樹脂水溶液（ａ−２）８０９と樹脂
水溶液（ｂ−８）２０ｇを８０°Ｃで５時間反応するこ
とにより、紙塗工用樹脂を得た。これを樹脂Ｂとする。Example 2 A resin for paper coating was obtained by reacting 809 of the resin aqueous solution (a-2) shown in the above reference example with 20 g of the resin aqueous solution (b-8) at 80°C for 5 hours. This will be referred to as resin B.
実施例３
上記参考例に示した樹脂水溶液（ａ−６）７（１ｇと樹
脂水溶液（ｂ−４）３０ｇを８０’Ｃて２時間反応する
ことにより、紙塗工用樹脂を得た。これを樹脂Ｃとする
。Example 3 A paper coating resin was obtained by reacting 1 g of resin aqueous solution (a-6) 7 (7) shown in the above reference example and 30 g of resin aqueous solution (b-4) at 80'C for 2 hours. Let be resin C.
実施例４
上記参考例に示した樹脂水溶液（ａ−３＞９５９と樹脂
水溶液（ｂ−２＞５９を５０’Ｃて８時間反応すること
により、紙塗工用樹脂を得た。これを樹脂りとする。Example 4 A paper coating resin was obtained by reacting the resin aqueous solution (a-3>959 and the resin aqueous solution (b-2>59) shown in the above reference example at 50'C for 8 hours. I will do it.
実施例５
上記参考例に示した樹脂水溶液（ａ−４＞９０ｇと樹脂
水溶液（ｂ−９＞ｔＯｇを１０℃で４時間反応すること
により、紙塗工用樹脂を得た。これを樹脂Ｆとする。Example 5 A resin for paper coating was obtained by reacting the resin aqueous solution (a-4>90g and the resin aqueous solution (b-9>tOg) shown in the above reference example at 10°C for 4 hours. shall be.
実施例６
上記参考例に示した樹脂水溶液（ａ−７＞９０ｙと樹脂
水溶液（ｂ−５＞１０ｇを４０’Ｃて１０時間反応する
ことにより、紙塗工用樹脂を得た。これを樹脂Ｆとする
。Example 6 A resin for paper coating was obtained by reacting the aqueous resin solution (a-7>90y and the aqueous resin solution (b-5>10g) shown in the above reference example at 40'C for 10 hours. Let it be F.
実施例７
上記参考例に示した樹脂水溶液（ａ−１＞８５ｇと樹脂
水溶液（ｂ−６＞１５ｇを６０’Ｃて２時間反応するこ
とにより、紙塗工用樹脂を得た。これを樹脂Ｇとする。Example 7 A resin for paper coating was obtained by reacting the aqueous resin solution (a-1 > 85 g and the aqueous resin solution (b-6 > 15 g) shown in the above reference example at 60'C for 2 hours. Let it be G.
実施例８
上記参考例に示した樹脂水溶液（ａ−５＞８０ｇと樹脂
水溶液（ｂ−７＞２０ｇを８０’Ｃて２時間反応するこ
とにより、紙塗工用樹脂を得た。これを樹脂Ｈとする。Example 8 A resin for paper coating was obtained by reacting the aqueous resin solution (a-5>80g and the aqueous resin solution (b-7>20g) shown in the above reference example at 80'C for 2 hours. Let it be H.
比較例１
上記参考例に示した樹脂水溶′ｆｉ（ａ−６＞９０！７
と樹脂水溶液（ｂ−８）１０ｇを７０℃で４＠間及応す
ることｋより、紙塗工用樹脂を得た。これを樹脂ａとす
る。Comparative Example 1 Resin water soluble 'fi (a-6>90!7
A paper coating resin was obtained by reacting 10 g of the resin aqueous solution (b-8) at 70° C. for 4 hours. This will be referred to as resin a.
比較例２
上記参考例に示した樹脂水溶液（ａ−７＞９０ｇと樹脂
水溶液（ｂ−９＞１０ｇを８０℃で５時間反応すること
により、紙塗工用樹脂を得た。これを樹脂すとする。Comparative Example 2 A paper coating resin was obtained by reacting the resin aqueous solution (a-7 > 90 g and the resin aqueous solution (b-9 > 10 g) shown in the above reference example at 80°C for 5 hours. shall be.
比較例３
上記参考例に示した樹脂水溶液（ａ−８＞８０ｇと樹脂
水溶液（ｂ−１０＞ ２０９を８０’Ｃで５時間反応す
ることにより、紙塗工用樹脂を得た。これを樹脂Ｃとす
る。Comparative Example 3 A paper coating resin was obtained by reacting the resin aqueous solution (a-8>80g and the resin aqueous solution (b-10>209) shown in the above reference example at 80'C for 5 hours. Let it be C.
実施例９
上記参考例に示した樹脂水溶液（ａ−１＞９０７と樹脂
水溶液（ｂ〜８ ） １０７を混合することにより紙塗
工用樹脂を得た。これを樹脂Ｉとする。Example 9 A paper coating resin was obtained by mixing the resin aqueous solution (a-1>907) shown in the above reference example and the resin aqueous solution (b-8) 107. This is referred to as resin I.
実施例１０
上記参考例に示した樹脂水溶液＜ａ−２＞９０ｇと樹脂
水溶液（ｂ−５）１０９を混合することにまり紙塗工用
樹脂を得た。これを樹脂Ｊとする。Example 10 A paper coating resin was obtained by mixing 90 g of the resin aqueous solution <a-2> shown in the above reference example and 109 g of the resin aqueous solution (b-5). This will be referred to as resin J.
実施例１１
上記参考例に示した樹脂水溶液（ａ−６＞８５ｇと樹脂
水溶液（ｔ）−１＞１５９を混合することにより紙塗工
用樹脂を得た。これを樹脂にとする。Example 11 A paper coating resin was obtained by mixing the resin aqueous solution (a-6>85g and the resin aqueous solution (t)-1>159g shown in the above reference example).This was used as a resin.
実施例１２
上記参考例に示した樹脂水溶液（ａ−３＞８５ｇと樹脂
水溶液（ｂ−１０＞ １５！９を混合することにより紙
塗工用樹脂を得た。これを樹脂りとする。Example 12 A resin for paper coating was obtained by mixing the resin aqueous solution (a-3>85 g) shown in the above reference example and the resin aqueous solution (b-10>15!9). This was used as a resin resin.
実施例１３
上記参考例に示した樹脂水溶液（ａ−４＞９０ｇと樹脂
水溶液（ｂ−２）１０ｇを混合することにより紙塗工用
樹脂を得た。これを樹脂Ｍとする。Example 13 A paper coating resin was obtained by mixing 90 g of the resin aqueous solution (a-4>90 g) shown in the above reference example and 10 g of the resin aqueous solution (b-2). This was referred to as resin M.
実施例１４
上記参考例に示した樹脂水溶液（ａ−７＞７０ｇと樹脂
水溶液（ｂ−６＞３０ｇを混合することにより紙塗工用
樹脂を得た。これを樹脂Ｎとする。Example 14 A paper coating resin was obtained by mixing the resin aqueous solution (a-7 > 70 g) and the resin aqueous solution (b-6 > 30 g) shown in the above reference example. This is referred to as resin N.
実施例１５
上記参考例に示した樹脂水溶液（ａ−８＞９０ｇと樹脂
水溶液（ｂ−３＞１０ｇを混合することにより紙塗工用
樹脂を得た。これを樹脂Ｏとする。Example 15 A paper coating resin was obtained by mixing the resin aqueous solution (a-8>90 g and the resin aqueous solution (b-3>10 g) shown in the above reference example. This is referred to as resin O.
比較例４
上記参考例に示した樹脂水溶液（ａ−６＞８０ｇと樹脂
水溶液（ｂ−９＞２０ｇを混合することにより紙塗工用
樹脂を得た。これを樹脂ｄとする。Comparative Example 4 A paper coating resin was obtained by mixing the resin aqueous solution (a-6 > 80 g) and the resin aqueous solution (b-9 > 20 g) shown in the above reference example. This is referred to as resin d.
比較例５
上記参考例に示した樹脂水溶液（ａ−７）９０ｇと樹脂
水溶液（ｂ−１０） １０（ｊを混合することにまり紙
塗工用樹脂を得た。これを樹脂ｅとする。Comparative Example 5 By mixing 90 g of the resin aqueous solution (a-7) and 10 g of the resin aqueous solution (b-10) shown in the above reference example, a resin for paper coating was obtained. This is referred to as resin e.
実施例１６
実施例１〜１５及び比較例１〜５に示す樹脂Ａ〜Ｏ２お
よびａ−ｅ、並びに比較例７として参考例１．６，９．
１６に示す樹脂（ａ−１）、（ａ−６）（ｂｉ）、（ｂ
−８＞を用いて下記に示す紙塗工用組成物を調製し、ざ
らに固形分濃喚が５０％となるように水を加えた俊、３
０％水酸化ナトリウム水溶液によりｐ旧１に調整して紙
塗工用組成物を調製した。なお、紙塗工用樹脂を配合し
ない紙塗工用組成物（比較例６）も同様に調製した。Example 16 Resins A to O2 and ae shown in Examples 1 to 15 and Comparative Examples 1 to 5, and Reference Examples 1.6, 9. as Comparative Example 7.
Resins (a-1), (a-6) (bi), (b
-8> was used to prepare the paper coating composition shown below, and water was added to it so that the solid content concentration was 50%.
A paper coating composition was prepared by adjusting p to 1 with a 0% aqueous sodium hydroxide solution. A paper coating composition (Comparative Example 6) containing no paper coating resin was also prepared in the same manner.
「ウルトラホワイト９０Ｊ ６０部（
米国エングルハルト・ミネラルズ社製クレー）１カーど
タル９０Ｊ ４０部（イー・シ
ー・シー・ジャパン■製炭酸カルシウム）
ｒＪＳＲ−０６９７Ｊ １２
部（日本合成ゴム■製ラテックス）
ｒＭｓ −４６００Ｊ ４部（日
本食品化工■製澱粉）
［アロン Ｔ−４０Ｊ Ｏ，２部
（東◇合成化学工業■製分散剤）
紙塗工用樹脂 ０．５部なお、
上記の「部」は固形分重量を示す。“Ultra White 90J 60 copies (
(clay manufactured by Englehardt Minerals, USA) 1 card Tal 90J 40 parts (calcium carbonate manufactured by ECC Japan ■) rJSR-0697J 12
part (latex manufactured by Japan Synthetic Rubber ■) rMs -4600J 4 parts (starch manufactured by Nippon Shokuhin Kako ■) [Aron T-40J O, 2 parts (dispersant manufactured by Higashi◇ Synthetic Chemical Industry ■) Resin for paper coating 0.5 In addition,
The above "part" indicates the weight of solid content.
この塗工組成物をアプリケーターを使用して坪柵９５
’ｊ 、′ｍの原紙に塗工量か１０７ 、’ ７７ｊと
なるように６面に塗布した。１００°Ｃて１分間熱風乾
燥機中で乾燥させてからロール温度６０℃、線斤７５Ｋ
ｇ／ｃｍなる条件て２回カレンダー処理を行った。得ら
れた片面塗工紙は、２０°Ｃ１６５％Ｒ）−１（相対湿
度）の条件下で２４時間コンディショニングを行った後
、その塗工紙のインキ受理性、ウエツ１〜・ピック等の
ＲＩ印刷適性試験を行った。Apply this coating composition using an applicator.
It was applied to 6 sides of base paper 'j and 'm so that the coating amount was 107 and '77j. Dry in a hot air dryer at 100°C for 1 minute, then roll at 60°C and wire at 75K.
Calendar treatment was performed twice under the condition of g/cm. The resulting single-sided coated paper was conditioned for 24 hours at 20°C, 165%R)-1 (relative humidity), and then the ink receptivity of the coated paper, RI of wets 1~, pick, etc. A printing suitability test was conducted.
これらの測定結果を表１に示す。各試験方法は次の通り
である。The results of these measurements are shown in Table 1. Each test method is as follows.
■インキ受理性
ＲＩ印刷試験機（明製作所製）を使用し、コト面を給水
ロールで湿潤させた後、印刷を行い、インキの受理性を
肉眼で観察し、優５〜劣１に至る等級を段階的に判定し
た。■Ink receptivity Using an RI printing tester (manufactured by Mei Seisakusho), print after moistening the surface with a water supply roll, and observe the ink receptivity with the naked eye, which grades from excellent 5 to poor 1. was judged step by step.
■ウェット・ピック
ＲＩ印刷試験機を使用し、］−ト面を給水ロールで湿潤
させた後、印刷を行い、紙むけ状態を肉眼で観察し、ｆ
！！５〜劣１に至る等級を段階的に判定した。■Using a Wet Pick RI printing tester, wet the surface with a water supply roll, print, observe the paper peeling condition with the naked eye, and
! ! Grades ranging from 5 to poor 1 were determined in stages.
■耐ブリスター性
［印刷試験機を用いて、オフ輪用インキを両面］−１〜
紙の両面に「ベタ刷り」を行った債、シリコンオイルを
満たした恒温槽に３秒間浸漬した。■Blister resistance [using ink for off-wheels on both sides using a printing tester] -1~
The bonds, which were printed on both sides of the paper, were immersed in a constant temperature bath filled with silicone oil for 3 seconds.
このときの１リスターの発生状態を肉眼で観察し、優５
〜劣１に至る等級を段階的に判定した。At this time, the state of occurrence of 1 lister was observed with the naked eye, and
Grades ranging from ~Poor 1 were determined in stages.
■ウェット・ラブ
コート紙表面上にイオン交換本釣０．１ｍを滴下し、指
先で３回、５回、 １０回、１５回及び２０回摩擦して
、それぞれの回数に応じた溶出部を黒紙に移動させ、そ
の際の溶出量を肉眼で観察し、耐水性優５〜劣１の判定
を行った。■Drop 0.1 m of ion-exchanged rod onto the surface of wet rub coat paper and rub with your fingertips 3, 5, 10, 15 and 20 times to blacken the eluted area according to each number of times. The sample was transferred to paper, and the amount of elution at that time was observed with the naked eye, and the water resistance was judged as being excellent 5 to poor 1.
上記の結果より、実施例のものはいずれもインキ受理性
、ウェット・ピック、ドライ・ピック、耐ブリスター性
、ウェット・ラブに優れていることがわかる。これに比
へ脂環式アミン化合物及び脂環式エポキシ化合物のいず
れも含有しない比較例は、インキ受理性、ウェット・ピ
ック、耐ブリスター性、ウェット・ラブに劣ることは明
白である。From the above results, it can be seen that all of the examples are excellent in ink receptivity, wet pick, dry pick, blister resistance, and wet rub. In comparison, it is clear that the comparative example containing neither the alicyclic amine compound nor the alicyclic epoxy compound is inferior in ink receptivity, wet pick, blister resistance, and wet rub.
Ｃ発明の効果〕
以上説明したよう（、本発明によれば、ポリアミド−尿
素−アルデヒド（エピハロヒドリン）樹脂とアミン−エ
ピハロヒドリン樹脂の両り又はいずれかに脂環式エポキ
シ化合物又は／及び脂環式アミン化合物を導入し、両者
を反応させるか、又は混合することにより得られた紙塗
工用樹脂を紙塗工用組成物（使用することにより塗工紙
のインキ受理性、ウェット・ピック、耐ブリスター性、
ウェット・ラブ等の性能をバランス良く向上さゼること
ができ、その工業的効果は大きい。C Effects of the Invention] As explained above, according to the present invention, an alicyclic epoxy compound or/and an alicyclic amine is added to both or either of the polyamide-urea-aldehyde (epihalohydrin) resin and the amine-epihalohydrin resin. The paper coating resin obtained by introducing a compound and reacting or mixing the two can be used to improve the ink receptivity, wet pick, and blister resistance of coated paper. sex,
The performance of wet rubs, etc. can be improved in a well-balanced manner, and its industrial effects are significant.
Claims (1)
ン酸系化合物（Ｂ）と尿素類（Ｃ）と脂環式エポキシ化
合物（Ｄ）または／および脂環式アミノ化合物（Ｅ）と
ホルムアルデヒド（Ｆ＿１）、エピハロヒドリン（Ｆ＿
２）およびジアルデヒド類（Ｆ＿３）より選ばれた１種
または２種以上（Ｆ）よりなる反応生成物（ I ）、又
は上記の（Ａ）、（Ｂ）、（Ｃ）および（Ｆ）よりなる
反応生成物（II）のいずれかからなるポリアミド−尿素
−アルデヒド（エピハロヒドリン）樹脂（イ）と、上記
の（Ｄ）または／および（Ｅ）と脂肪族アミノ化合物（
Ｇ）と（Ｆ＿２）よりなる反応生成物（III）、上記の
（Ｄ）または／および（Ｅ）と（Ｇ）と（Ｆ＿２）と亜
硫酸塩類（Ｈ）または／および酸類（Ｊ）よりなる反応
生成物（IV）、上記の（Ｇ）と（Ｆ＿２）よりなる反応
生成物（Ｖ）、並びに、上記の（Ｇ）と（Ｆ＿２）と（
Ｈ）または／および（Ｊ）よりなる反応生成物（VI）の
以上（III）〜（VI）から選ばれた１種の反応生成物か
らなるアミン−エピハロヒドリン樹脂（ロ）とを反応さ
せて得た（但し反応生成物の（II）と（Ｖ）及び（II）
と（VI）の反応によつて得られたものは除く）紙塗工用
樹脂。 ２、請求項１に記載された樹脂（イ）と樹脂（ロ）の混
合物（但し該反応生成物（II）と（Ｖ）及び（II）と（
VI）の混合物は除く）からなる紙塗工用樹脂。 ３、顔料１００重量部に対し、請求項１または２記載の
紙塗工用樹脂０．０５〜５重量部と接着剤５〜５０重量
部（固形分として）を配合した紙塗工用組成物。[Claims] 1. Polyalkylene polyamine (A), dibasic carboxylic acid compound (B), urea (C), alicyclic epoxy compound (D) or/and alicyclic amino compound (E) ), formaldehyde (F_1), epihalohydrin (F_
2) and a reaction product (I) consisting of one or more types (F) selected from dialdehydes (F_3), or from the above (A), (B), (C) and (F) polyamide-urea-aldehyde (epihalohydrin) resin (A) consisting of any of the reaction products (II), the above (D) or/and (E), and an aliphatic amino compound (
Reaction product (III) consisting of G) and (F_2), reaction consisting of the above (D) or/and (E), (G), (F_2), sulfites (H) or/and acids (J) Product (IV), reaction product (V) consisting of the above (G) and (F_2), and the above (G), (F_2) and (
obtained by reacting the reaction product (VI) consisting of H) or/and (J) with the amine-epihalohydrin resin (b) consisting of one reaction product selected from the above (III) to (VI). (However, the reaction products (II), (V) and (II)
(excluding those obtained by the reaction of (VI) and (VI)).Resins for paper coating. 2. A mixture of resin (a) and resin (b) described in claim 1 (provided that the reaction products (II) and (V) and (II) and (
(excluding mixtures of VI)) for paper coating. 3. A paper coating composition containing 0.05 to 5 parts by weight of the paper coating resin according to claim 1 or 2 and 5 to 50 parts by weight (as solid content) of the adhesive to 100 parts by weight of the pigment. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20798090A JPH064958B2 (en) | 1990-08-08 | 1990-08-08 | Resin for paper coating and composition for paper coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20798090A JPH064958B2 (en) | 1990-08-08 | 1990-08-08 | Resin for paper coating and composition for paper coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04100996A true JPH04100996A (en) | 1992-04-02 |
| JPH064958B2 JPH064958B2 (en) | 1994-01-19 |
Family
ID=16548689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20798090A Expired - Lifetime JPH064958B2 (en) | 1990-08-08 | 1990-08-08 | Resin for paper coating and composition for paper coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH064958B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5654359A (en) * | 1993-07-16 | 1997-08-05 | Sumitomo Chemical Company, Limited | Paper coating composition |
| WO2018056459A1 (en) * | 2016-09-26 | 2018-03-29 | 日立化成株式会社 | Method for producing polyamide |
-
1990
- 1990-08-08 JP JP20798090A patent/JPH064958B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5654359A (en) * | 1993-07-16 | 1997-08-05 | Sumitomo Chemical Company, Limited | Paper coating composition |
| WO2018056459A1 (en) * | 2016-09-26 | 2018-03-29 | 日立化成株式会社 | Method for producing polyamide |
| WO2018056463A1 (en) * | 2016-09-26 | 2018-03-29 | 日立化成株式会社 | Polyamide, polyamide film, and film capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH064958B2 (en) | 1994-01-19 |
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