JPH04263696A - Resin for paper coating and composition for paper coating - Google Patents
Resin for paper coating and composition for paper coatingInfo
- Publication number
- JPH04263696A JPH04263696A JP4080191A JP4080191A JPH04263696A JP H04263696 A JPH04263696 A JP H04263696A JP 4080191 A JP4080191 A JP 4080191A JP 4080191 A JP4080191 A JP 4080191A JP H04263696 A JPH04263696 A JP H04263696A
- Authority
- JP
- Japan
- Prior art keywords
- water
- resin
- hours
- soluble resin
- epihalohydrin
- 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 154
- 239000011347 resin Substances 0.000 title claims abstract description 154
- 239000011248 coating agent Substances 0.000 title claims abstract description 46
- 238000000576 coating method Methods 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- -1 alicyclic amino compound Chemical class 0.000 claims abstract description 69
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 239000004593 Epoxy Substances 0.000 claims abstract description 37
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 37
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 84
- 235000013877 carbamide Nutrition 0.000 claims description 47
- 239000004202 carbamide Substances 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 35
- 229920001281 polyalkylene Polymers 0.000 claims description 28
- 239000007795 chemical reaction product Substances 0.000 claims description 25
- 229920000768 polyamine Polymers 0.000 claims description 25
- 239000008199 coating composition Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 12
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 10
- 239000000049 pigment Substances 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 150000003672 ureas Chemical class 0.000 claims description 5
- 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 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 59
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 38
- 239000007864 aqueous solution Substances 0.000 description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 20
- 229910021529 ammonia Inorganic materials 0.000 description 18
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 18
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 9
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- 238000007639 printing Methods 0.000 description 8
- 229960001124 trientine Drugs 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 5
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 5
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229920000881 Modified starch Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 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 2
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000007796 conventional method Methods 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
- 150000004985 diamines Chemical class 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- ITZPOSYADVYECJ-UHFFFAOYSA-N n'-cyclohexylpropane-1,3-diamine Chemical compound NCCCNC1CCCCC1 ITZPOSYADVYECJ-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 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
- 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
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-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
- 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
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 101001053395 Arabidopsis thaliana Acid beta-fructofuranosidase 4, vacuolar Proteins 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- 108010058643 Fungal Proteins Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 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
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 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
- 229910004879 Na2S2O5 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- 239000002174 Styrene-butadiene Substances 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
- 125000001931 aliphatic group Chemical group 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
- 229910000147 aluminium phosphate Inorganic materials 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
- 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
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 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 compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 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
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 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
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process 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
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 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
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003287 optical effect Effects 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
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing 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
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、インキ受理性、耐水性
及び耐ブリスター性の３性能をバランスよく向上させた
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。[Industrial Application Field] The present invention provides a paper coating resin that provides a coated paper that improves the three performances of ink receptivity, water resistance, and blister resistance in a well-balanced manner, and a paper coating resin containing the paper coating resin. The present invention relates to a paper coating composition.
【０００２】0002
【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、従来より原紙にクレー、炭酸カルシウム等の顔料
やラテックス、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。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、塗工紙により高度な印刷適性が要求
されるようになった。特に印刷時のインキの着肉状態を
示すインキ受理性、オフセット印刷時の湿し水に対する
耐水性、及びオフセット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。[Prior Art] Coated paper, which is widely used as printing paper, is produced by coating a base paper with a composition whose main components are pigments such as clay and calcium carbonate, and adhesives such as latex and starch. Manufactured. In recent years, with the remarkable progress in printing technology represented by increased speed, precision, multicolor, etc., coated paper has come to be required to have higher printability. In particular, there is a strong need to improve ink receptivity, which indicates the state of ink adhesion during printing, water resistance to dampening water during offset printing, and blister resistance, which is required during ink drying during offset rotary printing. .
【０００３】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ルキレンポリアミン−尿素
−アルデヒド樹脂やポリアルキレンポリアミン−尿素−
アルデヒド樹脂とジアルデヒド類を併用すること（特開
昭５１−１２１０４１ 号公報）が提案されている。ま
た、発明者らは、以前よりポリアルキレンポリアミン−
尿素−アルデヒド樹脂とアミン−エピハロヒドリン樹脂
を併用（混合または反応）も試みてきた。In response to this, conventionally, polyalkylene polyamine-urea-aldehyde resins and polyalkylene polyamine-urea-
It has been proposed to use an aldehyde resin and dialdehydes in combination (Japanese Patent Application Laid-open No. 121041/1983). In addition, the inventors have previously discovered that polyalkylene polyamine-
Attempts have also been made to use urea-aldehyde resins and amine-epihalohydrin resins in combination (mixing or reaction).
【０００４】0004
【発明が解決しようとする課題】しかしながら、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
リスター性の３性能をバランスよく向上せしめる点につ
いては十分ではなく、より優れた樹脂の開発が望まれて
いる。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る。たとえば、
湿し水の塗工層内部への浸透を促進してインキ受理性を
向上させようとすると、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
トピッキングが生じ）易くなる。[Problem to be Solved by the Invention] However, none of these conventional techniques is sufficient in improving the three performances of ink receptivity, water resistance, and blister resistance in a well-balanced manner, and it is necessary to develop a more excellent resin. is desired. In particular, it is extremely difficult to improve both ink receptivity and water resistance in a well-balanced manner. for example,
If an attempt is made to improve ink receptivity by promoting the penetration of dampening water into the coating layer, the water resistance will be insufficient and part of the coating layer surface will be stripped off by the ink roll (so-called wet damping). picking occurs) becomes easier.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記課題
を解決するため鋭意検討の結果、ポリアルキレンポリア
ミン−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方又はいずれかに脂環
式アミノ化合物又は／及び脂環式エポキシ化合物を導入
し、両者を反応させるか、又は混合することにより目的
が達成できることを見いだし本発明に到達した。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors, as a result of intensive studies, have developed an alicyclic resin for polyalkylene polyamine-urea-aldehyde (epihalohydrin) resin and/or amine-epihalohydrin resin. The present invention was achieved by discovering that the object can be achieved by introducing a formula amino compound and/or an alicyclic epoxy compound and reacting or mixing the two.
【０００６】すなわち、本発明は、ポリアルキレンポリ
アミンと脂環式アミノ化合物又は／及び脂環式エポキシ
化合物と尿素類とホルムアルデヒド、エピハロヒドリン
もしくはジアルデヒド類の１種又は２種以上との反応生
成物からなる水溶性樹脂（Ｉ）、又はポリアルキレンポ
リアミンと尿素類とホルムアルデヒド，エピハロヒドリ
ンもしくはジアルデヒド類の１種又は２種以上との反応
生成物からなる水溶性樹脂（ＩＩ）のいずれかからなる
ポリアミン−尿素−アルデヒド（エピハロヒドリン）樹
脂（イ）と、エピハロヒドリンと脂肪族アミノ化合物と
脂環式アミノ化合物又は／及び脂環式エポキシ化合物と
の反応生成物である水溶性樹脂（ＩＩＩ ）、エピハロ
ヒドリンと脂肪族アミノ化合物との反応生成物である水
溶性樹脂（ＩＶ）、エピハロヒドリンと脂肪族アミノ化
合物と脂環式アミノ化合物又は／及び脂環式エポキシ化
合物と亜硫酸塩類又は／及び酸類との反応生成物である
水溶性樹脂（Ｖ）、エピハロヒドリンと脂肪族アミノ化
合物と亜硫酸塩類又は／及び酸類との反応生成物である
水溶性樹脂（ＶＩ）の以上（ＩＩＩ ）〜（ＶＩ）から
選ばれるアミン−エピハロヒドリン樹脂（ロ）とを反応
させて得た（但し該反応生成物（ＩＩ）と（ＩＶ）及び
（ＩＩ）と（ＶＩ）からなる反応生成物は除く）紙塗工
用樹脂、及び上記に記載された水溶性樹脂（イ）と（ロ
）の混合物（但し該反応生成物（ＩＩ）と（ＩＶ）及び
（ＩＩ）と（ＶＩ）からなる混合物は除く）からなる紙
塗工用樹脂、並びにこれらを含有する紙塗工用組成物を
提供するものである。以下、本発明を詳細に説明する。That is, the present invention provides a reaction product of a polyalkylene polyamine, an alicyclic amino compound or/and an alicyclic epoxy compound, ureas, and one or more of formaldehyde, epihalohydrin, or dialdehyde. or a water-soluble resin (II) consisting of a reaction product of a polyalkylene polyamine, ureas, and one or more types of formaldehyde, epihalohydrin, or dialdehydes. Urea-aldehyde (epihalohydrin) resin (a), water-soluble resin (III) which is a reaction product of epihalohydrin, an aliphatic amino compound, an alicyclic amino compound or/and an alicyclic epoxy compound, epihalohydrin and aliphatic A water-soluble resin (IV) which is a reaction product with an amino compound, a reaction product between epihalohydrin, an aliphatic amino compound, an alicyclic amino compound or/and an alicyclic epoxy compound, and sulfites or/and acids. Water-soluble resin (V), amine-epihalohydrin resin selected from the above (III) to (VI) of water-soluble resin (VI), which is a reaction product of epihalohydrin, an aliphatic amino compound, sulfites or/and acids; b) (However, the reaction products (II) and (IV) and the reaction products consisting of (II) and (VI) are excluded), and the paper coating resins described above. A paper coating resin consisting of a mixture of water-soluble resins (a) and (b) (excluding the reaction products (II) and (IV) and a mixture of (II) and (VI)), and The present invention provides a paper coating composition containing the following. The present invention will be explained in detail below.
【０００７】本発明に用いられるポリアルキレンポリア
ミンとしては、分子中に少なくとも２個の第一アミノ基
と少なくとも１個の第二アミノ基とを有する化合物が好
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
アミンなどであるが、そのうちでもポリエチレンポリア
ミンが好ましく、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 used in the present invention is preferably a compound having at least two primary amino groups and at least one secondary amino group in the molecule. Typical examples thereof include polyethylene polyamine, polypropylene polyamine, polybutylene polyamine, etc., among which polyethylene polyamine is preferred, and diethylene triamine, triethylene tetramine, and tetraethylene pentamine are more preferred.
【０００８】これらポリアルキレンポリアミンは一種類
のみでもよく、また、二種類以上の併用でもよい。また
、エチレンジアミン、プロピレンジアミン、ヘキサメチ
レンジアミンなどのジアミンやジメチルアミン、モノエ
タノールアミン、ベンジ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できる。本発明に用いられる
尿素類としては、尿素、チオ尿素、グアニル尿素、メチ
ル尿素、ジメチル尿素等があげられるが、特に尿素が好
ましい。[0008] These polyalkylene polyamines may be used alone or in combination of two or more types. Further, diamines such as ethylene diamine, propylene diamine, and hexamethylene diamine, and monoamines such as dimethylamine, monoethanolamine, and benzylamine may be used together in an amount of 60 moles or less per 100 moles of polyalkylene polyamine. Examples of the ureas used in the present invention include urea, thiourea, guanylurea, methylurea, dimethylurea, and the like, with urea being particularly preferred.
【０００９】本発明に用いられる脂環式アミノ化合物と
しては、分子中に少なくとも１個の活性水素基を有する
脂環式アミノ化合物であり、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−ジアミノシクロ
ヘキサン、１，４−ジアミノシクロヘキサン、４，４’
−ジアミノ−３，３’−ジメチル−ジシクロヘキシルメ
タン、４，４’−ジアミノ−３，３’−ジメチルジシク
ロヘキサン、４，４’−ビス（パラアミノシクロヘキシ
ル）メタン、イソホロンジアミン、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−１（２），５（６）−ジメタ
ンアミン、２，２’−ビス−（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’−スルホンビス（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、２，４’−ま
たは４，４’−ジアミノ−３，３’，５，５’−テトラ
アルキルジシクロヘキシルアルカン等が挙げられる。The alicyclic amino compound used in the present invention is an alicyclic amino compound having at least one active hydrogen group in the molecule, such as cyclohexylamine, dicyclohexylamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4'
-Diamino-3,3'-dimethyl-dicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexane, 4,4'-bis(para-aminocyclohexyl)methane, isophorone diamine, 1,3 (or 2 ，
4) -Bis-(aminomethyl)cyclohexane, N-aminopropylcyclohexylamine, octahydro-
4,7-methanoindene-1(2),5(6)-dimethaneamine, 2,2'-bis-(4-aminocyclohexyl)propane, bis-(4-aminocyclohexyl)methane, 4,4'-oxybis( cyclohexylamine)
, 4,4'-sulfonebis(cyclohexylamine),
Examples include 1,3,5-triaminocyclohexane, 2,4'- or 4,4'-diamino-3,3',5,5'-tetraalkyldicyclohexylalkane.
【００１０】本発明に用いられる脂環式エポキシ化合物
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
キサイド、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−エポキシ−シクロヘキサン−カルボキシレート、
２−（３，４−エポキシシクロヘキシル−５，５−スピ
ロ−３，４−エポキシ）シクロヘキサン−メタ−ジオキ
サンなどが挙げられる。The alicyclic epoxy compound used in the present invention refers to a compound in which an epoxy group is bonded directly or indirectly to a cyclohexane ring. As a specific example of direct combination,
Cyclohexene oxide, vinyl cyclohexene dioxide, bis(3,4-epoxycyclohexyl)adipate, 3,4-epoxycyclohexylmethyl-3
, 4-epoxy-cyclohexane-carboxylate,
Examples include 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane.
【００１１】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ともに含有
することを表す。具体例として、ビス−グリシジル−ヘ
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
。[0011] 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.
【００１２】本発明に用いられるエピハロヒドリンとし
ては、エピクロロヒドリン、エピブロモヒドリンが挙げ
られ、これらは単独または複数混合して使用される。本
発明に用いられるジアルデヒド類としては、グリオキザ
ール、グルタルアルデヒドなどが挙げられる。[0012] The epihalohydrin used in the present invention includes epichlorohydrin and epibromohydrin, and these may be used alone or in combination. Examples of the dialdehydes used in the present invention include glyoxal and glutaraldehyde.
【００１３】本発明に用いられる脂肪族アミノ化合物と
しては、アンモニアあるいは、第一アミノ基、第二アミ
ノ基又は第三アミノ基のいずれかを単数又は複数含む化
合物であり、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
ミン等のモノアミン、エチレンジアミン、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
ポリアミンがあげられる。The aliphatic amino compound used in the present invention is ammonia or a compound containing one or more of primary, secondary, or tertiary amino groups, and in addition to ammonia, for example, methyl Monoamines such as amines, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, butylamine, ethanolamine, 3-ethoxypropylamine, diamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc. Polyamines include:
【００１４】本発明に用いられる亜硫酸塩類としては、
例えば、亜硫酸塩（Ｍ１ ２ ＳＯ３ 、Ｍ１ は１価
の金属、以下同様）、亜硫酸水素塩（Ｍ１ ＨＳＯ３
）、ピロ亜硫酸塩（Ｍ１ ２ Ｓ２ Ｏ５ ）等が例示
され、Ｍ１ としてはアルカリ金属が挙げられる。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Ｍ１ ＳＯ３ −
、亜硫酸水素イオンＨＳＯ３ − 、ピロ亜硫酸イオ
ンＳ２ Ｏ５ ２−、亜硫酸イオンＳ２ Ｏ５ ２−、
ピロ亜硫酸金属イオンＭ１ Ｓ２ Ｏ５ − 、ピロ亜
硫酸水素イオンＨＳ２ Ｏ５ − 等が挙げられる。具
体的には亜硫酸ナトリウム（Ｎａ２ ＳＯ３ ）、亜硫
酸水素ナトリウム（ＮａＨＳＯ３ ）、無水重亜硫酸ナ
トリウム（Ｎａ２ Ｓ２ Ｏ５ ）等が例示される。[0014] The sulfites used in the present invention include:
For example, sulfite (M1 2 SO3, M1 is a monovalent metal, the same applies hereinafter), hydrogen sulfite (M1 HSO3
), pyrosulfite (M1 2 S2 O5), etc., and M1 includes an alkali metal. These are used singly or in combination, and the sulfite ions generated from them include sulfite metal ions M1 SO3 −
, bisulfite ion HSO3 − , pyrosulfite ion S2 O5 2−, sulfite ion S2 O5 2−,
Examples include metal pyrosulfite ion M1 S2 O5 -, hydrogen pyrosulfite ion HS2 O5 -, and the like. Specific examples include sodium sulfite (Na2SO3), sodium hydrogensulfite (NaHSO3), anhydrous sodium bisulfite (Na2S2O5), and the like.
【００１５】本発明に用いられる酸類とは、例えば硫酸
、塩酸、燐酸等の無機酸、ギ酸、酢酸等の有機酸があげ
られる。亜硫酸塩類を使用すると、紙塗工用樹脂のカオ
チン性を低下させ、紙塗工用組成物の増粘を防止するこ
とができる。また、酸類を使用す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、エピハロヒド
リンと反応せしめることにより低分子量のアミン−エピ
ハロヒドリン樹脂を得ることができ、これより紙塗工用
組成物の増粘を防止することができる。Examples of the acids used in the present invention include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as formic acid and acetic acid. When sulfites are used, the cationic properties of the paper coating resin can be reduced and thickening of the paper coating composition can be prevented. In addition, by using acids to convert some or all of the amino groups into amine salts, and then reacting with epihalohydrin, a low molecular weight amine-epihalohydrin resin can be obtained, and from this a paper coating composition can be obtained. It is possible to prevent the increase in viscosity.
【００１６】本発明におけるポリアルキレンポリアミン
−尿素−アルデヒド（エピハロヒドリン）樹脂のポリア
ルキレンポリアミン、尿素類、脂環式アミノ化合物、脂
環式エポキシ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モルに対して、尿素類０．５〜１０モ
ル、脂環式アミノ化合物又は／及び脂環式アミノ化合物
０．０２〜５モル（併用の場合は両方の和）の範囲が好
ましい。[0016] The ratio of each reaction component of the polyalkylene polyamine, urea, alicyclic amino compound, and alicyclic epoxy compound of the polyalkylene polyamine-urea-aldehyde (epihalohydrin) resin in the present invention is 1 mole of the polyalkylene polyamine. On the other hand, the preferred range is 0.5 to 10 mol of urea and 0.02 to 5 mol of alicyclic amino compound or/and 0.02 to 5 mol (in case of combined use, the sum of both).
【００１７】また、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類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０．１〜３モルが
好ましく、２種以上を併用するときの使用量としては０
．１〜４モルが好ましい。反応順序に関しては、ポリア
ルキレンポリアミン、尿素類、脂環式アミノ化合物、脂
環式エポキシ化合物は任意の順序で反応させることがで
きる。反応生成物（Ｉ）については、例えば下記（Ｉ）
−１ないし（Ｉ）−５により得られる。Further, the amount of formaldehyde, epihalohydrin or dialdehyde used alone is preferably 0.1 to 3 mol per 1 mol of polyalkylene polyamine, and when two or more types are used in combination, the amount used is 0.
．． 1 to 4 moles are preferred. Regarding the reaction order, the polyalkylene polyamine, urea, alicyclic amino compound, and alicyclic epoxy compound can be reacted in any order. Regarding the reaction product (I), for example, the following (I)
-1 to (I)-5.
【００１８】（Ｉ）−１ ポリアルキレンポリアミン
と、脂環式アミノ化合物又は／及び脂環式エポキシ化合
物と尿素類を８０〜２００℃で０．５〜１０時間脱アン
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類の１種
又は２種以上を公知の方法で任意の順序で反応させ反応
性基を導入する。(I)-1 Polyalkylene polyamine, alicyclic amino compound or/and alicyclic epoxy compound, and urea are subjected to a deammonia reaction at 80 to 200°C for 0.5 to 10 hours, and then water After diluting with water, one or more of formaldehyde, epihalohydrin, or dialdehydes are reacted in any order by a known method to introduce a reactive group.
【００１９】（Ｉ）−２ ポリアルキレンポリアミン
、尿素類、脂環式アミノ化合物及び脂環式エポキシ化合
物を２度に分けて反応させることもできる。例えば、ポ
リアルキレンポリアミンと、脂環式アミノ化合物又は／
及び脂環式エポキシ化合物と尿素類を８０〜２００℃で
０．５〜１０時間脱アンモニア反応を行い、更にポリア
ルキレンポリアミン又は／及び尿素類又は／及び脂環式
アミノ化合物又は／及び脂環式エポキシ化合物を加え８
０〜２００℃で０．５〜１０時間反応を行った。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類の１種又は２種以上を公知の方法
で任意の順序で反応させ反応性基を導入する。(I)-2 It is also possible to react the polyalkylene polyamine, urea, alicyclic amino compound and alicyclic epoxy compound in two steps. For example, polyalkylene polyamine and alicyclic amino compound or/
and alicyclic epoxy compound and urea are subjected to a deammonification reaction at 80 to 200°C for 0.5 to 10 hours, and further polyalkylene polyamine or/and urea or/and alicyclic amino compound or/and alicyclic Add epoxy compound 8
The reaction was carried out at 0 to 200°C for 0.5 to 10 hours. Next, after diluting with water, one or more of formaldehyde, epihalohydrin, or dialdehydes are reacted in any order by a known method to introduce a reactive group.
【００２０】（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を反応させた後、尿素類を反応
させることもできる。例えば、ポリアルキレンポリアミ
ンと脂環式エポキシ化合物を６０〜２００℃で０．５〜
５時間反応させた後、尿素類を加え８０〜２００℃で０
．５〜１０時間脱アンモニア反応を行った。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
はジアルデヒド類の１種又は２種以上を公知の方法で任
意の順序で反応させ反応性基を導入する。(I)-3 After reacting the polyalkylene polyamine with the alicyclic epoxy compound, it is also possible to react with urea. For example, polyalkylene polyamine and alicyclic epoxy compound are mixed at 60 to 200°C for 0.5 to
After reacting for 5 hours, add ureas and heat at 80 to 200°C.
．． The deammoniation reaction was carried out for 5 to 10 hours. Next, after diluting with water, one or more of formaldehyde, epihalohydrin, or dialdehydes are reacted in any order by a known method to introduce a reactive group.
【００２１】（Ｉ）−４ ポリアルキレンポリアミン
と尿素類と脂環式アミノ化合物又は／及び脂環式エポキ
シ化合物を反応させた後、脂環式アミノ化合物又は／及
び脂環式エポキシ化合物を反応させ、その後さらに尿素
を反応させることもできる。例えば、ポリアルキレンポ
リアミンと尿素類と脂環式アミノ化合物又は／及び脂環
式エポキシ化合物を８０〜２００℃で０．５〜１０時間
脱アンモニア反応させた後、脂環式アミノ化合物又は／
及び脂環式エポキシ化合物を加え８０〜２００℃で０．
５〜５時間反応させ、さらに尿素類を加え８０〜２００
℃で０．５〜５時間脱アンモニア反応を行った。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類の１種又は２種以上を公知の方法
で任意の順序で反応させ反応性基を導入する。(I)-4 After reacting the polyalkylene polyamine, urea, and alicyclic amino compound or/and alicyclic epoxy compound, reacting the alicyclic amino compound or/and alicyclic epoxy compound. , it is also possible to further react with urea after that. For example, after deammonizing a polyalkylene polyamine, urea, and alicyclic amino compound or/and alicyclic epoxy compound at 80 to 200°C for 0.5 to 10 hours, the alicyclic amino compound or/and
and an alicyclic epoxy compound at 80 to 200°C.
React for 5 to 5 hours, then add urea to 80 to 200
The deammoniation reaction was carried out at 0.5 to 5 hours. Next, after diluting with water, one or more of formaldehyde, epihalohydrin, or dialdehydes are reacted in any order by a known method to introduce a reactive group.
【００２２】（Ｉ）−５ ポリアルキレンポリミンと
尿素類を反応させた後、脂環式アミノ化合物又は／及び
脂環式エポキシ化合物と尿素類を同時に反応させること
もできる。例えば、ポリアルキレンポリアミンと尿素類
を８０〜２００℃で０．５〜１０時間反応させた後、脂
環式アミノ化合物又は／及び脂環式エポキシ化合物と尿
素類を加え８０〜２００℃で０．５〜１０時間反応させ
た。ついで水で希釈した後、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類の１種又は２種以上
を公知の方法で任意の順序で反応させ反応性基を導入す
る。(I)-5 After reacting the polyalkylene polymine with the urea, it is also possible to react the alicyclic amino compound or/and the alicyclic epoxy compound with the urea at the same time. For example, after a polyalkylene polyamine and a urea are reacted at 80 to 200°C for 0.5 to 10 hours, an alicyclic amino compound or/and an alicyclic epoxy compound and a urea are added to the reactor at 80 to 200°C for 0.5 to 10 hours. The reaction was allowed to proceed for 5 to 10 hours. After diluting with water, one or more of formaldehyde, epihalohydrin, or dialdehydes are reacted in any order by a known method to introduce a reactive group.
【００２３】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）−
２と同様に反応することができる。Regarding the reaction product (II), the above (I)-1, (I)-
It can react in the same way as 2.
【００２４】本発明におけるアミン−エピハロヒドリン
樹脂（ロ）の脂肪族アミノ化合物、脂環式エポキシ化合
物、脂環式アミノ化合物、エピハロヒドリン、亜硫酸塩
類、酸類の各反応成分の比率は、脂肪族アミノ化合物の
アミノ基１モルに対し脂環式アミノ化合物又は／及び脂
環式エポキシ化合物０．０１〜０．５モル（（ＩＩＩ
），（Ｖ）のみ。併用の場合は両方の和）、エピハロヒ
ドリン０．０５〜３モル、亜硫酸塩類０．０３〜１．５
モル（（Ｖ），（ＶＩ）のみ）、酸類０．１〜０．５モ
ル（（Ｖ），（ＶＩ）のみ。）の範囲が好ましい。[0024] The ratio of each reaction component of the aliphatic amino compound, alicyclic epoxy compound, alicyclic amino compound, epihalohydrin, sulfites, and acids in the amine-epihalohydrin resin (b) in the present invention is as follows: 0.01 to 0.5 mol of alicyclic amino compound or/and alicyclic epoxy compound per 1 mol of amino group ((III
), (V) only. If used in combination, the sum of both), epihalohydrin 0.05-3 mol, sulfites 0.03-1.5
mol ((V), (VI) only), acids in the range of 0.1 to 0.5 mol ((V), (VI) only).
【００２５】反応順序に関しては、脂環式エポキシ化合
物、脂環式アミノ化合物、脂肪族アミノ化合物、エピハ
ロヒドリン、亜硫酸塩類及び酸類は、任意の順序で反応
させることができる。反応生成物（ＩＩＩ ）について
は、下記（ＩＩＩ ）−１ないし（ＩＩＩ ）−２によ
り得られる。Regarding the reaction order, the alicyclic epoxy compound, alicyclic amino compound, aliphatic amino compound, epihalohydrin, sulfites and acids can be reacted in any order. The reaction product (III) can be obtained by the following steps (III)-1 and (III)-2.
【００２６】（ＩＩＩ ）−１ 脂環式エポキシ化合
物又は／及び脂環式アミノ化合物を含む脂肪族アミノ化
合物にエピハロヒドリンを４０℃以下で０．５〜３時間
かけて滴下後、４０〜８０℃で０〜４時間保持する。(III)-1 Epihalohydrin is added dropwise to an alicyclic epoxy compound or/and an aliphatic amino compound containing an alicyclic amino compound at a temperature below 40°C over a period of 0.5 to 3 hours, and then at a temperature of 40 to 80°C. Hold for 0-4 hours.
【００２７】（ＩＩＩ ）−２ 脂肪族アミノ化合物
と脂環式エポキシ化合物又は／及び脂環式アミノ化合物
を同時に反応させず、分けて反応させることもできる。
例えば、脂肪族アミノ化合物にエピハロヒドリンを４０
℃以下で０．５〜３時間かけて滴下し、その後脂環式ア
ミノ化合物又は／及び脂環式エポキシ化合物を加え４０
〜８０℃で０．５〜４時間保持する。(III)-2 The aliphatic amino compound and the alicyclic epoxy compound and/or the alicyclic amino compound may not be reacted simultaneously, but may be reacted separately. For example, add 40% epihalohydrin to an aliphatic amino compound.
℃ or less over 0.5 to 3 hours, then add the alicyclic amino compound or/and alicyclic epoxy compound to 40°C.
Hold at ~80°C for 0.5-4 hours.
【００２８】反応生成物（ＩＶ）については、例えば、
脂肪族アミノ化合物にエピハロヒドリンを４０℃以下で
０．５〜３時間かけて滴下し、滴下終了後４０〜８０℃
で０〜４時間保持することができる。反応生成物（Ｖ）
については、下記（Ｖ−１）ないし（Ｖ−４）により得
られる。Regarding the reaction product (IV), for example,
Epihalohydrin is added dropwise to the aliphatic amino compound at a temperature below 40°C over a period of 0.5 to 3 hours, and after the dropwise addition is completed, the temperature is reduced to 40°C to 80°C.
It can be maintained for 0 to 4 hours. Reaction product (V)
can be obtained by the following (V-1) to (V-4).
【００２９】（Ｖ）−１ 脂環式エポキシ化合物又は
／及び脂環式アミノ化合物を含む脂肪族アミノ化合物に
エピハロヒドリンを４０℃以下で０．５〜３時間かけて
滴下後、４０〜８０℃で０〜４時間保持し、さらに亜硫
酸塩類を加え４０〜８０℃で０．５〜４時間保持する。(V)-1 Epihalohydrin is added dropwise to an alicyclic epoxy compound or/and an aliphatic amino compound containing an alicyclic amino compound over a period of 0.5 to 3 hours at a temperature below 40°C, and then at a temperature of 40 to 80°C. Hold for 0 to 4 hours, add sulfites, and hold at 40 to 80°C for 0.5 to 4 hours.
【００３０】（Ｖ）−２ 脂環式エポキシ化合物又は
／及び脂環式アミノ化合物を含む脂肪族アミノ化合物と
亜硫酸塩類の混合物にエピハロヒドリンを４０℃以下で
０．５〜３時間かけて滴下し、その後４０〜８０℃で０
〜４時間保持する。(V)-2 Adding epihalohydrin dropwise to a mixture of an alicyclic epoxy compound or/and an aliphatic amino compound containing an alicyclic amino compound and sulfites at a temperature below 40° C. over a period of 0.5 to 3 hours, After that, 0 at 40-80℃
Hold for ~4 hours.
【００３１】（Ｖ）−３ エピハロヒドリンと亜硫酸
塩類を４０〜８０℃で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硫酸
塩類の混合物に、脂環式エポキシ化合物又は／及び脂環
式アミノ化合物を含む脂肪族アミノ化合物を加え４０〜
８０℃で０．５〜４時間反応させる。(V)-3 Adding an alicyclic epoxy compound or/to a reaction product obtained by reacting epihalohydrin and sulfites at 40 to 80°C for 0.5 to 4 hours or a mixture of epihalohydrin and sulfites. and an aliphatic amino compound including an alicyclic amino compound and 40 to
React at 80°C for 0.5 to 4 hours.
【００３２】（Ｖ）−４ 脂環式エポキシ化合物又は
／及び脂環式アミノ化合物を含む脂肪族アミノ化合物に
予め酸を加えておき、アミノ基の活性を抑えてから反応
することもできる。例えば、脂環式エポキシ化合物又は
／及び脂環式アミノ化合物を含む脂肪族アミノ化合物に
酸類を加えた後、エピハロヒドリンを５０℃以下で０．
５〜２時間かけて滴下し、さらに５０〜８０℃で０．５
〜４時間保持する。反応生成物（ＶＩ）については、下
記（ＶＩ−１）ないし（ＶＩ−４）により得られる。(V)-4 It is also possible to react after adding an acid to the alicyclic epoxy compound and/or the aliphatic amino compound containing the alicyclic amino compound in advance to suppress the activity of the amino group. For example, after adding an acid to an alicyclic epoxy compound or/and an aliphatic amino compound including an alicyclic amino compound, epihalohydrin is added at 50° C. or lower to 0.000° C.
Dropwise over 5 to 2 hours, and then at 50 to 80℃
Hold for ~4 hours. The reaction product (VI) can be obtained by the following steps (VI-1) to (VI-4).
【００３３】（ＶＩ）−１ 脂肪族アミノ化合物にエ
ピハロヒドリンを４０℃以下で０．５〜３時間かけて滴
下し、滴下終了後４０〜８０℃で０〜４時間保持し、さ
らに亜硫酸塩類を加え４０〜８０℃で０．５〜４時間保
持する。(VI)-1 Epihalohydrin is added dropwise to the aliphatic amino compound at a temperature below 40°C over a period of 0.5 to 3 hours, and after the dropwise addition is completed, it is held at 40 to 80°C for 0 to 4 hours, and then sulfites are added. Hold at 40-80°C for 0.5-4 hours.
【００３４】（ＶＩ）−２ 脂肪族アミノ化合物と亜
硫酸塩類の混合物にエピハロヒドリンを４０℃以下で０
．５〜３時間かけて滴下し、その後４０〜８０℃で０〜
４時間保持する。(VI)-2 Adding epihalohydrin to a mixture of aliphatic amino compounds and sulfites at 40°C or less
．． Dropped over 5 to 3 hours, then heated to 0 to 80℃ at 40 to 80℃
Hold for 4 hours.
【００３５】（ＶＩ）−３ エピハロヒドリンと亜硫
酸塩類を４０〜８０℃で０．５〜４時間反応させること
により得られた反応生成物またはエピハロヒドリンと亜
硫酸塩類の混合物に、脂肪族アミノ化合物を加え４０〜
８０℃で０．５〜４時間反応させる。(VI)-3 An aliphatic amino compound is added to the reaction product obtained by reacting epihalohydrin and sulfites at 40 to 80°C for 0.5 to 4 hours or to a mixture of epihalohydrin and sulfites. ~
React at 80°C for 0.5 to 4 hours.
【００３６】（ＶＩ）−４ 脂肪族アミノ化合物にあ
らかじめ酸を加えておき、アミノ基の活性を抑えてから
反応することもできる。例えば、脂肪族アミノ化合物に
酸類を加えた後、エピハロヒドリンを５０℃以下で０．
５〜２時間かけて滴下し、さらに５０〜８０℃で０．５
〜４時間保持する。(VI)-4 It is also possible to react after adding an acid to the aliphatic amino compound in advance to suppress the activity of the amino group. For example, after adding acids to an aliphatic amino compound, epihalohydrin is added at a temperature of 50° C. or less at 0.05°C.
Dropwise over 5 to 2 hours, and then at 50 to 80℃
Hold for ~4 hours.
【００３７】上記のようにして得られたポリアルキレン
ポリアミン−尿素−アルデヒド（エピハロヒドリン）樹
脂（イ）とアミン−エピハロヒドリン樹脂（ロ）は、更
に反応させるか、混合して使用される。また、両者を別
々に紙用塗工組成物に添加してもよい。両者を反応させ
るときは反応温度３０〜９０℃で２０分〜１０時間行わ
れる。また、（イ），（ロ）を反応および混合するとき
の（イ）と（ロ）の使用比率は任意である。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
、塗工液の配合によっては、紙用塗工組成物の増粘が著
しく好ましくない。The polyalkylene polyamine-urea-aldehyde (epihalohydrin) resin (a) and amine-epihalohydrin resin (b) obtained as described above are further reacted or used as a mixture. Moreover, both may be added separately to the paper coating composition. When the two are reacted, the reaction is carried out at a reaction temperature of 30 to 90°C for 20 minutes to 10 hours. Furthermore, when reacting and mixing (a) and (b), the ratio of use of (a) and (b) is arbitrary. Incidentally, the more (b) there is, the better the ink receptivity and blister resistance are, but depending on the formulation of the coating liquid, the viscosity of the paper coating composition is significantly undesirable.
【００３８】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。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、サチンホワイト
、二酸化チタン、水酸化アルミニウム、硫酸バリウム、
亜硫酸カルシウム、合成シリカ、酸化亜鉛等の無機顔料
及びスチレン系ポリマー、尿素系ポリマー等の有機顔料
があり、これらのうち１種類または２種類以上を混合し
て使用することができる。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. Pigments used in this case include clay, talc, heavy calcium carbonate, light calcium carbonate, satin white, titanium dioxide, aluminum hydroxide, barium sulfate,
There are inorganic pigments such as calcium sulfite, synthetic silica, and zinc oxide, and organic pigments such as styrene polymers and urea polymers, and one type or a mixture of two or more of these can be used.
【００３９】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）、カゼイン
、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−ブタジエン系樹脂、（メタ）アク
リレート−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が例示される。[0039] As adhesives, starch, modified starch (oxidized starch, esterified starch, etherified starch, enzyme-modified starch, pregelatinized starch, cationized starch, etc.), casein, gelatin, soybean protein, yeast protein, cellulose can be used. Natural polymer compounds such as derivatives (carboxymethyl cellulose, hydroxyethyl cellulose, etc.) or their derivatives, styrene-butadiene resins, (meth)acrylate-butadiene resins, (meth)acrylate resins, polyvinyl alcohol, vinyl acetate resins, Examples include synthetic polymer compounds such as acrylamide resins, styrene-(meth)acrylate resins, styrene-maleic acid resins, and ethylene-vinyl acetate resins.
【００４０】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
ことができる。組成物中のそれぞれの配合量は顔料を１
００重量部としたときに、紙塗工用樹脂が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
あることが好ましい。In addition to the above-mentioned pigments and adhesives, the paper coating composition of the present invention also contains dispersants, lubricants, thickeners, thinners, antifoaming agents, foam inhibitors, preservatives, and antifungal agents. , water retention agents, optical brighteners, dyes, conductive agents, and other various auxiliary agents may also be blended as needed. The amount of each pigment in the composition is 1
00 parts by weight, paper coating resin is 0.05 to 5
It is preferable that the solid content of the adhesive is in the range of 5 to 50 parts by weight.
【００４１】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ともに水中に分散させ、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
れに本発明の印刷適性向上剤を加え、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。[0041] To produce the paper coating composition of the present invention,
For example, a pigment is dispersed in water together with a dispersant, an adhesive and, if necessary, auxiliary agents such as a viscosity modifier are added thereto, the printability improver of the present invention is added thereto, the mixture is stirred, and then, if necessary, the pigment is dispersed in water. Adjust pH with caustic soda, ammonia, etc.
Adjust and prepare.
【００４２】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、ロールコーター、
サイズプレスコーター、ドクトルコーター、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であってもよい。また、一層塗工
であっても多層塗工であってもよく、さらに片面塗工、
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. Namely, blade coater, air knife coater, bar coater, roll coater,
Coating is performed by a commonly used method such as a size press coater, doctor coater, brush coater, curtain coater, gravure coater, cast coater, or champlex coater, and may be either on-machine coating or off-machine coating. In addition, it may be single-layer coating or multi-layer coating, and furthermore, single-sided coating,
Both sides coating is possible.
【００４３】塗工後の乾燥は例えばガスヒーター、電気
ヒーター、蒸気加熱ヒーター、赤外線ヒーター、熱風加
熱ヒーター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、水カレンダー、グロスカレン
ダー等の仕上げ工程によって光沢度を付与することが可
能であり、その他一般的な加工手段はいずれも使用可能
である。また、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。Drying after coating is carried out using a conventional method such as a gas heater, electric heater, steam heater, infrared heater, or hot air heater. After drying, use a super calendar, water calendar, or gloss calendar as necessary. Glossiness can be imparted through finishing steps such as, and any other general processing means can be used. Furthermore, this paper coating resin can be used for purposes other than paper chemicals.
【００４４】[0044]
【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。
参考例１
温度計、コンデンサー及び攪拌棒を備えた四つ口フラス
コにトリエチレンテトラミン２９２ｇ、シクロヘキセン
オキサイド９８ｇ及び尿素３００ｇを仕込み、１２０℃
で３時間脱アンモニア反応を行い、ついでこれに水を加
えて６０％水溶液とした。次に３７％ホルマリン水溶液
８１ｇを加え５０％硫酸水溶液にてｐＨ５に調整し、８
０℃で３時間攪拌しながら保持した。反応終了後２８％
アンモニア水にてｐＨ７に調整し、水を加えて固形分５
０％の水溶性樹脂を得た。以下、この樹脂水溶液を（ａ
−１）と略記する。[Examples] Next, the present invention will be explained by referring to reference examples, working examples, and comparative examples. Reference Example 1 292 g of triethylenetetramine, 98 g of cyclohexene oxide, and 300 g of urea were placed in a four-necked flask equipped with a thermometer, condenser, and stirring bar, and heated to 120°C.
Ammonia removal reaction was carried out for 3 hours, and then water was added to make a 60% aqueous solution. Next, 81 g of a 37% formalin aqueous solution was added, and the pH was adjusted to 5 with a 50% sulfuric acid aqueous solution.
The mixture was maintained at 0° C. for 3 hours with stirring. 28% after completion of reaction
Adjust the pH to 7 with ammonia water and add water to make the solid content 5.
0% water-soluble resin was obtained. Below, this resin aqueous solution (a
-1).
【００４５】参考例２
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−１（
２），５（６）−ジメタンアミン５９ｇおよび尿素９０
ｇを仕込み、１６０℃で２時間脱アンモニア反応を行い
、さらに尿素１２０ｇを加え１２０℃で２．５時間脱ア
ンモニア反応を行った。ついでこれに水を加えて６０％
の水溶液とした。次に３７％ホルマリン水溶液１２２ｇ
を加え９８％硫酸にてｐＨ６に調整し、８０℃で５時間
攪拌しながら保持した。反応終了後３０％水酸化ナトリ
ウム水溶液にてｐＨ８に調整し、水を加えて固形分５０
％の水溶性樹脂を得た。以下、これを樹脂水溶液（ａ−
２）と略記する。Reference Example 2 In a reaction vessel similar to Reference Example 1, 20% diethylenetriamine was added.
6g and octahydro-4,7-methanoindene-1 (
2),5(6)-dimethaneamine 59g and urea 90g
g was charged and a deammonification reaction was carried out at 160°C for 2 hours, and then 120g of urea was added and ammonia removal reaction was carried out at 120°C for 2.5 hours. Then add water to this to make it 60%
An aqueous solution of Next, 122g of 37% formalin aqueous solution
was added, the pH was adjusted to 6 with 98% sulfuric acid, and the mixture was maintained at 80° C. for 5 hours with stirring. After the reaction was completed, the pH was adjusted to 8 with a 30% aqueous sodium hydroxide solution, and water was added to reduce the solid content to 50.
% water-soluble resin was obtained. Hereinafter, this resin aqueous solution (a-
It is abbreviated as 2).
【００４６】参考例３
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３，４−エ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７６ｇを
仕込み、発熱に注意しながら１２０℃で１時間反応させ
、ついで尿素１８０ｇを加え１６０℃で３時間脱アンモ
ニア反応を行った。ついでこれに水を加えて６０％の水
溶液とした。次に３７％ホルマリン水溶液８１ｇを加え
３０％硫酸水溶液にてｐＨ５．５に調整し、７０℃で３
時間攪拌しながら保持した。反応終了後２８％アンモニ
ア水にてｐＨ８に調整し、水を加えて固形分５０％の水
溶性樹脂を得た。以下、これを樹脂水溶液（ａ−３）と
略記する。Reference Example 3 In a reaction vessel similar to Reference Example 1, 20% diethylenetriamine was added.
6g and 3,4-epoxycyclohexylmethyl-3,4
-Epoxycyclohexane-carboxylate (76 g) was charged and reacted at 120°C for 1 hour while being careful not to generate heat. Then, 180 g of urea was added and ammonia removal reaction was carried out at 160°C for 3 hours. Then, water was added to this to make a 60% aqueous solution. Next, 81 g of 37% formalin aqueous solution was added, the pH was adjusted to 5.5 with 30% sulfuric acid aqueous solution, and the pH was adjusted to 5.5 at 70°C.
Hold with stirring for an hour. After the reaction was completed, the pH was adjusted to 8 with 28% aqueous ammonia, and water was added to obtain a water-soluble resin with a solid content of 50%. Hereinafter, this will be abbreviated as resin aqueous solution (a-3).
【００４７】参考例４
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と尿素６０ｇを仕込み、１５０℃で１．５時間脱
アンモニア反応させた後、尿素２４０ｇとＮ−アミノプ
ロピルシクロヘキシルアミン５２ｇを加え１２０℃で４
時間脱アンモニア反応させた。ついでこれに水を加え６
０％水溶液とした。次に発熱に注意しながらエピクロロ
ヒドリン９３ｇを滴下した。滴下終了後７０℃で２時間
保持した。反応終了後これに水を加え固形分５０％の水
溶性樹脂を得た。以下、これを樹脂水溶液（ａ−４）と
略記する。Reference Example 4 Triethylenetetramine 2 was placed in the same reaction vessel as Reference Example 1.
92g of urea and 60g of urea were charged, and the ammonia was removed at 150°C for 1.5 hours. Then, 240g of urea and 52g of N-aminopropylcyclohexylamine were added, and the mixture was heated at 120°C for 4 hours.
Ammonia removal reaction was carried out for a period of time. Then add water to this and
It was made into a 0% aqueous solution. Next, 93 g of epichlorohydrin was added dropwise while being careful not to generate heat. After completion of the dropwise addition, the temperature was maintained at 70°C for 2 hours. After the reaction was completed, water was added to this to obtain a water-soluble resin with a solid content of 50%. Hereinafter, this will be abbreviated as resin aqueous solution (a-4).
【００４８】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
６ｇとモノエタノールアミン６１ｇとシクロヘキシルア
ミン４９ｇを仕込み、１２０℃で２時間反応させた後、
尿素３６０ｇを加え１２０℃で３時間脱アンモニア反応
させた。ついでこれに水を加え６０％の水溶液とした。
次に３７％ホルマリン水溶液１６２ｇを加え、９８％硫
酸にてｐＨ５に調整し、７０℃で２時間保持した。反応
終了後水を加え５０％の水溶性樹脂を得た。以下、これ
を樹脂水溶液（ａ−５）と略記する。Reference Example 5 In the same reaction vessel as in Reference Example 1, 20% diethylenetriamine was added.
After preparing 6g of monoethanolamine, 61g of monoethanolamine, and 49g of cyclohexylamine and reacting at 120°C for 2 hours,
360 g of urea was added and ammonia removal reaction was carried out at 120°C for 3 hours. Then, water was added to this to make a 60% aqueous solution. Next, 162 g of a 37% formalin aqueous solution was added, the pH was adjusted to 5 with 98% sulfuric acid, and the mixture was maintained at 70° C. for 2 hours. After the reaction was completed, water was added to obtain a 50% water-soluble resin. Hereinafter, this will be abbreviated as resin aqueous solution (a-5).
【００４９】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
９２ｇとイソホロンジアミン８５ｇとシクロヘキセンオ
キサイド４９ｇと尿素１２０ｇを仕込み、１５０℃で２
時間脱アンモニア反応させ、さらに尿素２４０ｇを加え
１２０℃で４時間脱アンモニア反応を行わせた。ついで
これに水を加え６０％の水溶液とした。次に３７％ホル
マリン水溶液１２２ｇを加え９８％の硫酸にてｐＨ５に
調整し、７０℃で２時間保持した。反応終了後これに水
を加え２８％アンモニア水にてｐＨ７に調整し、水を加
え固形分５０％の水溶性樹脂を得た。以下、これを水溶
性樹脂（ａ−６）と略記する。Reference Example 6 Triethylenetetramine 2 was placed in the same reaction vessel as Reference Example 1.
92g, isophoronediamine 85g, cyclohexene oxide 49g and urea 120g were prepared, and heated at 150℃ for 2 hours.
Ammonia removal reaction was carried out for a period of time, and 240 g of urea was further added thereto, and ammonia removal reaction was carried out at 120° C. for 4 hours. Then, 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 98% sulfuric acid, and the mixture was maintained at 70° C. for 2 hours. After the reaction was completed, water was added thereto and the pH was adjusted to 7 with 28% aqueous ammonia, and water was added to obtain a water-soluble resin with a solid content of 50%. Hereinafter, this will be abbreviated as water-soluble resin (a-6).
【００５０】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とシクロヘキセンオキサイド９８ｇを仕込み発熱
に注意しながら１２０℃で１．５時間保持した。その後
尿素６０ｇを加え１５０℃で１．５時間脱アンモニア反
応を行った。さらに尿素２４０ｇを加えて１２０℃で１
．５時間脱アンモニア反応を行った。ついでこれに水を
加えて６０％の水溶液とした。次に３７％ホルマリン水
溶液８１ｇを加え、９８％硫酸にてｐＨ５に調整し、７
０℃で２時間反応させた。その後エピクロロヒドリン４
６ｇを滴下し４０℃で１時間保持した。反応終了後これ
に水を加え固形分５０％の水溶性樹脂を得た。以下、こ
れを水溶液樹脂（ａ−７）と略記する。Reference Example 7 Triethylenetetramine 2 was placed in the same reaction vessel as Reference Example 1.
92 g and 98 g of cyclohexene oxide were charged and held at 120° C. for 1.5 hours while being careful not to generate heat. Thereafter, 60 g of urea was added and ammonia removal reaction was carried out at 150° C. for 1.5 hours. Furthermore, add 240g of urea and heat at 120°C.
．． Ammonia removal reaction was carried out for 5 hours. Then, water was added to this to make a 60% aqueous solution. Next, 81 g of 37% formalin aqueous solution was added, the pH was adjusted to 5 with 98% sulfuric acid, and the pH was adjusted to 7.
The reaction was carried out at 0°C for 2 hours. Then epichlorohydrin 4
6g was added dropwise and kept at 40°C for 1 hour. After the reaction was completed, water was added to this to obtain a water-soluble resin with a solid content of 50%. Hereinafter, this will be abbreviated as aqueous resin (a-7).
【００５１】参考例８
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と尿素２４０ｇを仕込み１５０℃で２時間脱アンモ
ニア反応を行い、さらにシクロヘキセンオキサイド４９
ｇと尿素９０ｇを加えて１２０℃で３時間反応を行った
。ついでこれに水を加え６０％水溶液とした。次に３７
％ホルマリン水溶液８１ｇを加え９８％硫酸でｐＨ５に
調整し、７０℃で２時間反応させた。反応終了後これに
水を加え固形分５０％の水溶性樹脂を得た。以下、これ
を水溶性樹脂（ａ−８）と略記する。Reference Example 8 In a reaction vessel similar to Reference Example 1, 20% of diethylenetriamine was added.
6g of urea and 240g of urea were charged, and ammonia removal reaction was carried out at 150°C for 2 hours.
g and 90 g of urea were added, and the reaction was carried out at 120° C. for 3 hours. Then, water was added to this to make a 60% aqueous solution. Next 37
% formalin aqueous solution was added, the pH was adjusted to 5 with 98% sulfuric acid, and the mixture was reacted at 70° C. for 2 hours. After the reaction was completed, water was added to this to obtain a water-soluble resin with a solid content of 50%. Hereinafter, this will be abbreviated as water-soluble resin (a-8).
【００５２】参考例９
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と尿素１２０ｇ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９８
ｇを仕込み１６０℃で２時間脱アンモニア反応を行い、
次いでシクロヘキセンオキサイド４９ｇを加え１２０℃
で１．５時間反応させた。さらに尿素１８０ｇを加え１
２０℃で２時間脱アンモニア反応を行った。ついでこれ
に水を加え６０％水溶液とした。次に３７％ホルマリン
水溶液８１ｇを加え９８％硫酸でｐＨ５に調整し、７０
℃で３時間反応させた。反応終了後これに水を加え固形
分５０％の水溶性樹脂を得た。以下、これを水溶性樹脂
（ａ−９）と略記する。Reference Example 9 Triethylenetetramine 2 was placed in the same reaction vessel as Reference Example 1.
92 g and 120 g of urea and octahydro-4,7-methanoindene-1(2),5(6)-dimethaneamine 98
g was charged and ammonia removal reaction was carried out at 160°C for 2 hours.
Next, 49 g of cyclohexene oxide was added and heated to 120°C.
The reaction was carried out for 1.5 hours. Furthermore, add 180g of urea and
Deammonification reaction was carried out at 20°C for 2 hours. Then, water was added to this to make a 60% aqueous solution. Next, 81 g of a 37% formalin aqueous solution was added, and the pH was adjusted to 5 with 98% sulfuric acid.
The reaction was carried out at ℃ for 3 hours. After the reaction was completed, water was added to this to obtain a water-soluble resin with a solid content of 50%. Hereinafter, this will be abbreviated as water-soluble resin (a-9).
【００５３】参考例１０
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と尿素６０ｇを仕込み、１５０℃で２時間脱アン
モニア反応を行い、さらに尿素３６０ｇを加え１２０℃
で３時間脱アンモニア反応を行った。ついでこれに水を
加え６０％水溶液とした。次に３７％ホルマリン水溶液
１２２ｇを加え、９８％硫酸にてｐＨ６に調整し８０℃
で３時間保持した。反応終了後３０％水酸化ナトリウム
水溶液でｐＨ８に調整し、水を加え固形分５０％の水溶
性樹脂を得た。以下、これを水溶性樹脂（ａ−１０）と
略記する。Reference Example 10 Triethylenetetramine 2 was placed in the same reaction vessel as Reference Example 1.
92g of urea and 60g of urea were charged, and ammonia removal reaction was carried out at 150℃ for 2 hours.Additionally, 360g of urea was added and the mixture was heated to 120℃.
Ammonia removal reaction was carried out for 3 hours. Then, water was added to this to make a 60% aqueous solution. Next, 122 g of 37% formalin aqueous solution was added, the pH was adjusted to 6 with 98% sulfuric acid, and the mixture was heated to 80°C.
It was held for 3 hours. After the reaction was completed, the pH was adjusted to 8 with a 30% aqueous sodium hydroxide solution, and water was added to obtain a water-soluble resin with a solid content of 50%. Hereinafter, this will be abbreviated as water-soluble resin (a-10).
【００５４】参考例１１
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と尿素２４０ｇを仕込み、１６０℃で２時間脱アン
モニア反応を行い、反応終了後水を加えて６０％の水溶
液とした。次に３７％ホルマリン水溶液８１ｇを加え、
９８％の硫酸にてｐＨ５に調整し、７０℃２時間保持し
た。ついでこれに水を加え固形分５０％の水溶性樹脂を
得た。以下、これを水溶性樹脂（ａ−１１）と略記する
。Reference Example 11 In the same reaction vessel as in Reference Example 1, 20% diethylenetriamine was added.
6 g of urea and 240 g of urea were charged, and ammonia removal reaction was carried out at 160° C. for 2 hours. After the reaction was completed, water was added to make a 60% aqueous solution. Next, add 81 g of 37% formalin aqueous solution,
The pH was adjusted to 5 with 98% sulfuric acid and maintained at 70°C for 2 hours. Then, water was added to this to obtain a water-soluble resin with a solid content of 50%. Hereinafter, this will be abbreviated as water-soluble resin (a-11).
【００５５】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１０
３ｇ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１０ｇを仕込み、水１
７０ｇにて希釈し、９８％硫酸１０ｇを加え十分攪拌し
ながらエピクロロヒドリン９３ｇを３０〜４０℃で２時
間かけて滴下した。滴下終了後６０℃で２時間保持した
後、水を加えて固形分４０％の水溶性樹脂を得た。以下
、これを水溶性樹脂（ｂ−１）と略記する。Reference Example 12 In a reaction vessel similar to Reference Example 1, 10% of diethylenetriamine was added.
3g and octahydro-4,7-methanoindene-1 (
2) Pour 10 g of ,5(6)-dimethaneamine, and add 1 g of water.
The mixture was diluted with 70 g, 10 g of 98% sulfuric acid was added, and 93 g of epichlorohydrin was added dropwise at 30 to 40° C. over 2 hours with sufficient stirring. 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 with a solid content of 40%. Hereinafter, this will be abbreviated as water-soluble resin (b-1).
【００５６】参考例１３
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１０ｇを仕込み、水１
９８ｇにて希釈し、十分攪拌しながら、無水重亜硫酸ナ
トリウム１９ｇを投入し、さらにエピクロロヒドリン１
８ｇを３０〜４０℃で２時間かけて滴下した。滴下終了
後６０℃で２時間保持した後、水を加え固形分４０％の
水溶性樹脂を得た。以下、これを水溶性樹脂（ｂ−２）
と略記する。Reference Example 13 In a reaction vessel similar to Reference Example 1, 10 diethylenetriamine was added.
3g and octahydro-4,7-methanoindene-1 (
2) Pour 10 g of ,5(6)-dimethaneamine, and add 1 g of water.
diluted with 98 g, add 19 g of anhydrous sodium bisulfite while stirring thoroughly, and add 1 ml of epichlorohydrin.
8 g was added dropwise over 2 hours at 30 to 40°C. 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 with a solid content of 40%. Hereinafter, this will be referred to as water-soluble resin (b-2).
It is abbreviated as
【００５７】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１０
３ｇと１，３−ビス−（アミノメチル）シクロヘキサン
７ｇを仕込み、水１６６ｇにて希釈し、十分攪拌しなが
らエピクロロヒドリン９３ｇを３０〜４０℃で２時間か
けて滴下した。滴下終了後６０℃で２時間保持した後、
水を加えて固形分４０％の水溶性樹脂を得た。以下、こ
れを水溶性樹脂（ｂ−３）と略記する。Reference Example 14 In a reaction vessel similar to Reference Example 1, 10% of diethylenetriamine was added.
3 g and 7 g of 1,3-bis-(aminomethyl)cyclohexane were charged, diluted with 166 g of water, and 93 g of epichlorohydrin was added dropwise at 30 to 40° C. over 2 hours with thorough stirring. After the dropwise addition was completed and held at 60°C for 2 hours,
Water was added to obtain a water-soluble resin with a solid content of 40%. Hereinafter, this will be abbreviated as water-soluble resin (b-3).
【００５８】参考例１５
参考例１と同様の反応容器にモノエタノールアミン２４
ｇ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２０ｇを仕込み、水１４
１ｇにて希釈した後、十分攪拌しながら亜硫酸ナトリウ
ム５０ｇを加え、さらにエピクロロヒドリン９３ｇを３
０〜４０℃で２時間かけて滴下した。滴下終了後６０℃
で２時間保持した後、水を加えて固形分３０％の水溶性
樹脂を得た。以下、これを水溶性樹脂（ｂ−４）と略記
する。Reference Example 15 Monoethanolamine 24 was placed in the same reaction vessel as Reference Example 1.
g and octahydro-4,7-methanoindene-1 (2
), 5(6)-dimethaneamine 20g, water 14g
After diluting with 1 g, add 50 g of sodium sulfite with sufficient stirring, and add 3 g of epichlorohydrin.
The mixture was added dropwise at 0 to 40°C over 2 hours. 60℃ after completion of dripping
After holding for 2 hours, water was added to obtain a water-soluble resin with a solid content of 30%. Hereinafter, this will be abbreviated as water-soluble resin (b-4).
【００５９】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１０
３ｇと３，４−エ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１３ｇ
を仕込み、水１７４ｇにて希釈し、十分攪拌しながらエ
ピクロロヒドリン９３ｇを３０〜４０℃で２時間かけて
滴下した。滴下終了後６０℃で１．５時間保持した後、
水を加えて固形分４０％の水溶性樹脂を得た。以下、こ
れを水溶性樹脂（ｂ−５）と略記する。Reference Example 16 In the same reaction vessel as in Reference Example 1, 10% of diethylenetriamine was added.
3g and 3,4-epoxycyclohexylmethyl-3,4
-Epoxy-cyclohexane-carboxylate 13g
was prepared, diluted with 174 g of water, and 93 g of epichlorohydrin was added dropwise at 30 to 40° C. over 2 hours with thorough stirring. After the completion of the dropwise addition, the temperature was maintained at 60°C for 1.5 hours.
Water was added to obtain a water-soluble resin with a solid content of 40%. Hereinafter, this will be abbreviated as water-soluble resin (b-5).
【００６０】参考例１７
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を仕込み、水２２１ｇにて希釈し、十分攪拌しなが
らエピクロロヒドリン９３ｇを３０〜４０℃で３時間か
けて滴下した。滴下終了後６０℃で２時間保持した後、
水を加えて固形分４０％の水溶性樹脂を得た。以下、こ
れを水溶性樹脂（ｂ−６）と略記する。Reference Example 17 In a reaction vessel similar to Reference Example 1, 10% of diethylenetriamine was added.
3 g was charged, diluted with 221 g of water, and 93 g of epichlorohydrin was added dropwise at 30 to 40° C. over 3 hours with sufficient stirring. After the dropwise addition was completed and held at 60°C for 2 hours,
Water was added to obtain a water-soluble resin with a solid content of 40%. Hereinafter, this will be abbreviated as water-soluble resin (b-6).
【００６１】参考例１８
参考例１と同様の反応容器にジメチルアミン（５０％）
９０ｇを仕込み、水２２ｇにて希釈し、十分攪拌しなが
らエピクロロヒドリン９３ｇを３０〜４０℃で２時間か
けて滴下した。滴下終了後６０℃で２時間保持した後、
水を加えて固形分４０％の水溶性樹脂を得た。以下、こ
れを水溶性樹脂（ｂ−７）と略記する。Reference Example 18 Dimethylamine (50%) was placed in the same reaction vessel as in Reference Example 1.
90 g of the solution was charged, diluted with 22 g of water, and 93 g of epichlorohydrin was added dropwise at 30 to 40° C. over 2 hours with sufficient stirring. After the dropwise addition was completed and held at 60°C for 2 hours,
Water was added to obtain a water-soluble resin with a solid content of 40%. Hereinafter, this will be abbreviated as water-soluble resin (b-7).
【００６２】実施例１
上記参考例に示した水溶性樹脂（ａ−１）９０ｇと水溶
性樹脂（ｂ−１）１０ｇを混合し、６０℃で５時間保持
することにより固形分４９％の紙塗工用樹脂を得た。以
下、これを樹脂Ａと略記する。Example 1 90 g of the water-soluble resin (a-1) shown in the above reference example and 10 g of the water-soluble resin (b-1) were mixed and held at 60°C for 5 hours to produce paper with a solid content of 49%. A coating resin was obtained. Hereinafter, this will be abbreviated as resin A.
【００６３】実施例２
上記参考例に示した水溶性樹脂（ａ−２）８０ｇと水溶
性樹脂（ｂ−２）２０ｇを混合し、８０℃で５時間保持
することにより固形分４８％の紙塗工用樹脂を得た。以
下、これを樹脂Ｂと略記する。Example 2 80 g of water-soluble resin (a-2) shown in the above reference example and 20 g of water-soluble resin (b-2) were mixed and held at 80°C for 5 hours to produce paper with a solid content of 48%. A coating resin was obtained. Hereinafter, this will be abbreviated as resin B.
【００６４】実施例３
上記参考例に示した水溶性樹脂（ａ−３）７０ｇと水溶
性樹脂（ｂ−３）３０ｇを混合し、８０℃で２時間保持
することにより固形分４７％の紙塗工用樹脂を得た。以
下、これを樹脂Ｃと略記する。Example 3 70 g of water-soluble resin (a-3) shown in the above reference example and 30 g of water-soluble resin (b-3) were mixed and held at 80°C for 2 hours to produce paper with a solid content of 47%. A coating resin was obtained. Hereinafter, this will be abbreviated as resin C.
【００６５】実施例４
上記参考例に示した水溶性樹脂（ａ−６）９５ｇと水溶
性樹脂（ｂ−７）５ｇを混合し、５０℃で８時間保持す
ることにより固形分４９．５％の紙塗工用樹脂を得た。
以下、これを樹脂Ｄと略記する。Example 4 95 g of the water-soluble resin (a-6) shown in the above reference example and 5 g of the water-soluble resin (b-7) were mixed and held at 50°C for 8 hours, resulting in a solid content of 49.5%. A paper coating resin was obtained. Hereinafter, this will be abbreviated as resin D.
【００６６】実施例５
上記参考例に示した水溶性樹脂（ａ−１０）７０ｇと水
溶性樹脂（ｂ−３）３０ｇを混合し、７０℃で４時間保
持することにより固形分４７％の紙塗工用樹脂を得た。
以下、これを樹脂Ｅと略記する。Example 5 70 g of the water-soluble resin (a-10) shown in the above reference example and 30 g of the water-soluble resin (b-3) were mixed and held at 70°C for 4 hours to produce paper with a solid content of 47%. A coating resin was obtained. Hereinafter, this will be abbreviated as resin E.
【００６７】実施例６
上記参考例に示した水溶性樹脂（ａ−４）９５ｇと水溶
性樹脂（ｂ−４）５ｇを混合することにより固形分４９
％の紙塗工用樹脂を得た。以下、これを樹脂Ｆと略記す
る。Example 6 By mixing 95 g of the water-soluble resin (a-4) and 5 g of the water-soluble resin (b-4) shown in the above reference example, the solid content was reduced to 49.
% paper coating resin was obtained. Hereinafter, this will be abbreviated as resin F.
【００６８】実施例７
上記参考例に示した水溶性樹脂（ａ−７）８０ｇと水溶
性樹脂（ｂ−６）２０ｇを混合することにより固形分４
８％の紙塗工用樹脂を得た。以下、これを樹脂Ｇと略記
する。Example 7 By mixing 80 g of the water-soluble resin (a-7) and 20 g of the water-soluble resin (b-6) shown in the above reference example, the solid content was reduced to 4.
An 8% paper coating resin was obtained. Hereinafter, this will be abbreviated as resin G.
【００６９】実施例８
上記参考例に示した水溶性樹脂（ａ−８）７０ｇと水溶
性樹脂（ｂ−５）３０ｇを混合することにより固形分４
４％の紙塗工用樹脂を得た。以下、これを樹脂Ｈと略記
する。Example 8 By mixing 70 g of water-soluble resin (a-8) shown in the above reference example and 30 g of water-soluble resin (b-5), the solid content was reduced to 4.
A 4% paper coating resin was obtained. Hereinafter, this will be abbreviated as resin H.
【００７０】実施例９
上記参考例に示した水溶性樹脂（ａ−９）９５ｇと水溶
性樹脂（ｂ−４）５ｇを混合することにより固形分４９
％の紙塗工用樹脂を得た。以下、これを樹脂Ｉと略記す
る。Example 9 By mixing 95 g of the water-soluble resin (a-9) shown in the above reference example and 5 g of the water-soluble resin (b-4), the solid content was reduced to 49.
% paper coating resin was obtained. Hereinafter, this will be abbreviated as resin I.
【００７１】実施例１０
上記参考例に示した水溶性樹脂（ａ−５）９０ｇと水溶
性樹脂（ｂ−５）１０ｇを混合することにより固形分４
９％の紙塗工用樹脂を得た。以下、これを樹脂Ｊと略記
する。Example 10 By mixing 90 g of the water-soluble resin (a-5) shown in the above reference example and 10 g of the water-soluble resin (b-5), the solid content was reduced to 4.
A 9% paper coating resin was obtained. Hereinafter, this will be abbreviated as resin J.
【００７２】実施例１１
上記参考例に示した水溶性樹脂（ａ−１１）７０ｇと水
溶性樹脂（ｂ−２）３０ｇを混合することにより固形分
４７％の紙塗工用樹脂を得た。以下、これを水溶性樹脂
Ｋと略記する。Example 11 A paper coating resin having a solid content of 47% was obtained by mixing 70 g of the water-soluble resin (a-11) and 30 g of the water-soluble resin (b-2) shown in the above reference example. Hereinafter, this will be abbreviated as water-soluble resin K.
【００７３】比較例１
上記参考例に示した水溶性樹脂（ａ−１０）９０ｇと水
溶性樹脂（ｂ−６）１０ｇを混合し、６０℃で４時間保
持することにより固形分４９％の紙塗工用樹脂を得た。
以下、これを水溶性樹脂ａと略記する。Comparative Example 1 90 g of the water-soluble resin (a-10) shown in the above reference example and 10 g of the water-soluble resin (b-6) were mixed and held at 60°C for 4 hours to produce paper with a solid content of 49%. A coating resin was obtained. Hereinafter, this will be abbreviated as water-soluble resin a.
【００７４】比較例２
上記参考例に示した水溶性樹脂（ａ−１１）８０ｇと水
溶性樹脂（ｂ−７）２０ｇを混合することにより固形分
４８％の紙塗工用樹脂を得た。以下、これを水溶性樹脂
ｂと略記する。Comparative Example 2 A paper coating resin having a solid content of 48% was obtained by mixing 80 g of the water-soluble resin (a-11) and 20 g of the water-soluble resin (b-7) shown in the above reference example. Hereinafter, this will be abbreviated as water-soluble resin b.
【００７５】比較例３
上記参考例に示した水溶性樹脂（ａ−１１）８０ｇとグ
リオキザール２０ｇを混合することにより固形分４８％
の紙塗工用樹脂を得た。以下、これを水溶性樹脂ｃと略
記する。Comparative Example 3 By mixing 80 g of the water-soluble resin (a-11) shown in the above reference example and 20 g of glyoxal, the solid content was 48%.
A paper coating resin was obtained. Hereinafter, this will be abbreviated as water-soluble resin c.
【００７６】実施例１２
実施例１〜１１，比較例１〜３及び参考例１０に示す樹
脂Ａ〜Ｋ，ａ〜ｃ，（ａ−１０）を用いて下記に示す紙
塗工用組成物を調製し、さらに固形分濃度が５０％とな
るように水を加えた後、３０％水酸化ナトリウム水溶液
によりｐＨ１１に調整して紙塗工用組成物を調製した。
なお、紙塗工用樹脂を添加しない紙用塗工組成物（比較
例４）も同様に調製した。また、参考例１７に示す樹脂
（ｂ−６）についても同様に紙塗工用組成物を調製した
が、紙塗工用組成物が増粘し調製できなかった。Example 12 The following paper coating composition was prepared using the resins A to K, a to c, and (a-10) shown in Examples 1 to 11, Comparative Examples 1 to 3, and Reference Example 10. After adding water so that the solid content concentration was 50%, the pH was adjusted to 11 with a 30% aqueous sodium hydroxide solution to prepare a paper coating composition. Note that a paper coating composition (Comparative Example 4) to which no paper coating resin was added was also prepared in the same manner. Further, a paper coating composition was similarly prepared for the resin (b-6) shown in Reference Example 17, but the paper coating composition thickened and could not be prepared.
【００７７】
「ウルトラホワイト９０」
６０部（米国エンゲルハルト・ミネラルズ社製クレー
）「カービタル９０」
４０部（イー・シー・シー・ジャパン（株）
製炭酸カルシウム）「ＪＳＲ−０６９７」
１２部（日本合成ゴム（株）
製ラテックス）
「ＭＳ−４６００」
４部（日本食品化工（株）製澱粉）
「アロン Ｔ−４０」
０．２部（東亞合成化学工業（株）製分散
剤）
「カーボミュールＳ−１０」
０．６部（ディック・ハーキュレス（株）製滑剤）
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 90”
60 parts (clay manufactured by Engelhardt Minerals, USA) "Carbital 90"
40 copies (ECC Japan Co., Ltd.)
calcium carbonate) “JSR-0697”
12 parts (Japan Synthetic Rubber Co., Ltd.)
(Made latex) “MS-4600”
Part 4 (starch manufactured by Nihon Shokuhin Kako Co., Ltd.) “Aron T-40”
0.2 parts (dispersant manufactured by Toagosei Chemical Industry Co., Ltd.) "Carbo Mule S-10"
0.6 parts (Lubricant manufactured by Dick Hercules Co., Ltd.)
Resin for paper coating
0.5 part Note that the above "part" indicates the weight of solid content.
【００７８】この塗工組成物を日本精機（株）製ラボ用
ブレードコータを使用して坪量９５ｇ／ｍ２ の原紙に
塗工量が１０ｇ／ｍ２ となるように片面に塗布した。
その後直ちに１１０℃で５秒間熱風乾燥し、ついで９０
℃で５秒間シリンダー乾燥した。さらにロール温度６０
℃、線圧７５ｋｇ／ｃｍなる条件で２回カレンダー処理
をした。得られた片面塗工紙は、２０℃６５％ＲＨ（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、ウェット・ピック、
ドライ・ピック等のＲＩ印刷適性検査を行った。さらに
塗工組成物の塗工時の粘度についても測定した。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
。This coating composition was applied to one side of a base paper having a basis weight of 95 g/m 2 using a laboratory blade coater manufactured by Nippon Seiki Co., Ltd. so that the coating amount was 10 g/m 2 . Thereafter, it was immediately dried with hot air at 110°C for 5 seconds, and then heated to 90°C.
Cylinder dry for 5 seconds at °C. Furthermore, the roll temperature is 60
Calendar treatment was carried out twice under the conditions of temperature and linear pressure of 75 kg/cm. The obtained single-sided coated paper was conditioned for 24 hours at 20°C and 65% RH (relative humidity), and then the ink receptivity, wet pick,
RI printing aptitude tests such as dry pick were conducted. Furthermore, the viscosity of the coating composition during application was also measured. The results of these measurements are shown in Table 1. Each test method is as follows.
【００７９】■塗工液の粘度
Ｂ型粘度計（形式：ＢＭ型、東京計器製作所製）を用い
て、６０ｒｐｍ にて塗工液調製直後に２５℃で測定し
た。① Viscosity of Coating Liquid Viscosity was measured at 25° C. immediately after preparation of the coating liquid using a B-type viscometer (model: BM type, manufactured by Tokyo Keiki Seisakusho) at 60 rpm.
【００８０】■インキ受理性
ＲＩ印刷試験機（明製作所製）を使用し、コート面を給
水ロールで湿潤させた後、印刷をして、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), after moistening the coated surface with a water supply roll, print and observe the ink receptivity with the naked eye. Grades up to 1 were determined in stages.
【００８１】■ウェット・ピック
ＲＩ印刷試験機を使用し、コート面を給水ロールで湿潤
させた後、印刷をして、紙むけ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。■Using a Wet Pick RI printing tester, after moistening the coated surface with a water supply roll, print, observe the paper peeling condition with the naked eye, and grade from Excellent 5 to Poor 1. It was determined that
【００８２】■耐ブリスター性
ＲＩ印刷試験機を用いて、オフ輪用インキを両面コート
の両面に「ベタ刷り」した後、シリコンオイルを満たし
た恒温槽に３秒間浸漬した。このときのブリスターの発
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。(2) Blister Resistance Using an RI printing tester, the ink for off-wheels was printed on both sides of the double-sided coating, and then immersed in a constant temperature bath filled with silicone oil for 3 seconds. The state of blistering at this time was observed with the naked eye, and grades ranging from excellent 5 to poor 1 were determined in stages.
【００８３】■ウェット・ラブ
コート紙表面上にイオン交換水約０．１ｍｌを滴下し、
指先で３回、５回、１０回、１５回および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、
そのさい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。■Approximately 0.1 ml of ion-exchanged water is dropped onto the surface of the wet love coated paper,
Rub it with your fingertips 3 times, 5 times, 10 times, 15 times and 20 times to move the elution area to the black paper according to each number of times,
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.
【００８４】上記の結果より、実施例の水溶性樹脂はい
ずれも、インキ受理性，ウェットピック，耐ブリスター
性，ウェットラブに優れていることがわかる。これに比
べ、脂環式アミノ化合物、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 water-soluble resins of Examples are excellent in ink receptivity, wet pick, blister resistance, and wet rub. In comparison, it is clear that the comparative example containing neither an alicyclic amino compound nor an alicyclic epoxy compound is inferior in ink receptivity, wet pick, blister resistance, and wet rub.
【００８５】[0085]
【表１】[Table 1]
【００８６】[0086]
【発明の効果】以上説明したように、本発明によれば、
ポリアルキレンポリアミン−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
方又はいずれかに脂環式アミノ化合物又は／及び脂環式
エポキシ化合物を導入し、両者を反応させるか、又は混
合することにより得られる水溶性樹脂を紙用印刷適性向
上剤として紙用塗工組成物に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せることがで
き、その工業的効果は大きい。[Effects of the Invention] As explained above, according to the present invention,
By introducing an alicyclic amino compound or/and an alicyclic epoxy compound into both or either of the polyalkylene polyamine-urea-aldehyde (epihalohydrin) resin and the amine-epihalohydrin resin and reacting or mixing the two. By using the obtained water-soluble resin in a paper coating composition as a paper printability improver, the properties of coated paper such as ink receptivity, wet pick, blister resistance, and wet rub can be improved in a well-balanced manner. can be achieved, and its industrial effects are significant.
Claims (3)
ミノ化合物又は／及び脂環式エポキシ化合物と尿素類と
ホルムアルデヒド、エピハロヒドリンもしくはジアルデ
ヒド類の１種又は２種以上との反応生成物からなる水溶
性樹脂（Ｉ）、又はポリアルキレンポリアミンと尿素類
とホルムアルデヒド，エピハロヒドリンもしくはジアル
デヒド類の１種又は２種以上との反応生成物からなる水
溶性樹脂（ＩＩ）のいずれかからなるポリアミン−尿素
−アルデヒド（エピハロヒドリン）樹脂（イ）と、エピ
ハロヒドリンと脂肪族アミノ化合物と脂環式アミノ化合
物又は／及び脂環式エポキシ化合物との反応生成物であ
る水溶性樹脂（ＩＩＩ ）、エピハロヒドリンと脂肪族
アミノ化合物との反応生成物である水溶性樹脂（ＩＶ）
、エピハロヒドリンと脂肪族アミノ化合物と脂環式アミ
ノ化合物又は／及び脂環式エポキシ化合物と亜硫酸塩類
又は／及び酸類との反応生成物である水溶性樹脂（Ｖ）
、エピハロヒドリンと脂肪族アミノ化合物と亜硫酸塩類
又は／及び酸類との反応生成物である水溶性樹脂（ＶＩ
）の以上（ＩＩＩ ）〜（ＶＩ）から選ばれるアミン−
エピハロヒドリン樹脂（ロ）とを反応させて得た（但し
該反応生成物（ＩＩ）と（ＩＶ）及び（ＩＩ）と（ＶＩ
）からなる反応生成物は除く）紙塗工用樹脂。Claim 1: A water-soluble resin comprising a reaction product of a polyalkylene polyamine, an alicyclic amino compound or/or an alicyclic epoxy compound, a urea, and one or more of formaldehyde, epihalohydrin, or dialdehyde. A polyamine-urea-aldehyde (I), or a water-soluble resin (II) consisting of a reaction product of a polyalkylene polyamine, ureas, and one or more types of formaldehyde, epihalohydrin, or dialdehydes ( (epihalohydrin) resin (a), a water-soluble resin (III) which is a reaction product of epihalohydrin, an aliphatic amino compound, an alicyclic amino compound or/and an alicyclic epoxy compound, Water-soluble resin (IV) which is a reaction product
, a water-soluble resin (V) which is a reaction product of epihalohydrin, an aliphatic amino compound, an alicyclic amino compound or/and an alicyclic epoxy compound, and a sulfite or/and an acid.
, a water-soluble resin (VI
amine selected from the above (III) to (VI)
obtained by reacting epihalohydrin resin (b) (however, the reaction products (II) and (IV) and (II) and (VI
) (excluding reaction products consisting of ) paper coating resins.
）と（ロ）の混合物（但し該反応生成物（ＩＩ）と（Ｉ
Ｖ）及び（ＩＩ）と（ＶＩ）からなる混合物は除く）か
らなる紙塗工用樹脂。2. A mixture of the water-soluble resins (a) and (b) according to claim 1 (provided that the reaction products (II) and (I)
V) and a mixture of (II) and (VI)).
は２記載の紙塗工用樹脂０．０５〜５重量部、接着剤５
〜５０重量部（固形分として）を含む紙塗工用組成物。3. 0.05 to 5 parts by weight of the paper coating resin according to claim 1 or 2, and 5 parts by weight of the adhesive per 100 parts by weight of the pigment.
-50 parts by weight (as solids) of a paper coating composition.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4080191A JP2636530B2 (en) | 1991-02-14 | 1991-02-14 | Paper coating resin and paper coating composition |
| US07/819,859 US5270355A (en) | 1991-01-14 | 1992-01-13 | Paper coating resin and paper coating composition |
| EP92100464A EP0499032B1 (en) | 1991-01-14 | 1992-01-13 | Paper coating resin and paper coating composition |
| CA002059216A CA2059216C (en) | 1991-01-14 | 1992-01-13 | Paper coating resin and paper coating composition |
| FI920141A FI107175B (en) | 1991-01-14 | 1992-01-13 | Paper coating resin and paper coating composition |
| AU10142/92A AU643865B2 (en) | 1991-01-14 | 1992-01-13 | Paper coating resin and paper coating composition |
| DE69205596T DE69205596T2 (en) | 1991-01-14 | 1992-01-13 | Resin and composition for coating paper. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4080191A JP2636530B2 (en) | 1991-02-14 | 1991-02-14 | Paper coating resin and paper coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04263696A true JPH04263696A (en) | 1992-09-18 |
| JP2636530B2 JP2636530B2 (en) | 1997-07-30 |
Family
ID=12590738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4080191A Expired - Fee Related JP2636530B2 (en) | 1991-01-14 | 1991-02-14 | Paper coating resin and paper coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2636530B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0691432A2 (en) | 1994-07-01 | 1996-01-10 | Sumitomo Chemical Company, Limited | Paper coating composition |
-
1991
- 1991-02-14 JP JP4080191A patent/JP2636530B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0691432A2 (en) | 1994-07-01 | 1996-01-10 | Sumitomo Chemical Company, Limited | Paper coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2636530B2 (en) | 1997-07-30 |
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