JPH064958B2 - Resin for paper coating and composition for paper coating - Google Patents
Resin for paper coating and composition for paper coatingInfo
- Publication number
- JPH064958B2 JPH064958B2 JP20798090A JP20798090A JPH064958B2 JP H064958 B2 JPH064958 B2 JP H064958B2 JP 20798090 A JP20798090 A JP 20798090A JP 20798090 A JP20798090 A JP 20798090A JP H064958 B2 JPH064958 B2 JP H064958B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- hours
- aqueous solution
- water
- 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.)
- Expired - Lifetime
Links
- 229920005989 resin Polymers 0.000 title claims description 155
- 239000011347 resin Substances 0.000 title claims description 155
- 239000011248 coating agent Substances 0.000 title claims description 47
- 238000000576 coating method Methods 0.000 title claims description 47
- 239000000203 mixture Substances 0.000 title claims description 36
- -1 carboxylic acid compound Chemical class 0.000 claims description 69
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 239000007795 chemical reaction product Substances 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 34
- 239000004593 Epoxy Substances 0.000 claims description 28
- 125000002723 alicyclic group Chemical group 0.000 claims description 26
- 239000004202 carbamide Substances 0.000 claims description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 23
- 229920000768 polyamine Polymers 0.000 claims description 22
- 229920001281 polyalkylene Polymers 0.000 claims description 16
- 239000008199 coating composition Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 7
- 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
- 239000000047 product Substances 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 65
- 235000013877 carbamide Nutrition 0.000 description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 238000006482 condensation reaction Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- 238000007639 printing Methods 0.000 description 11
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 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 description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 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
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 150000003672 ureas Chemical class 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
- 238000001816 cooling Methods 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 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
- 238000001035 drying Methods 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
- 238000003490 calendering Methods 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 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 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- MPYOXCAHVAWKKU-UHFFFAOYSA-N ethanamine tricyclo[5.2.1.02,6]decane Chemical compound CCN.CCN.C1CC2C3CCC(C3)C2C1 MPYOXCAHVAWKKU-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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
- 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
- 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
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-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
- 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-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
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 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
- 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
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 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
- 238000010828 elution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229940079826 hydrogen sulfite Drugs 0.000 description 2
- 150000002500 ions Chemical class 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
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000019426 modified starch Nutrition 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 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
- 239000011734 sodium Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 239000002562 thickening agent Substances 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
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-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
- 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
- KSMVBYPXNKCPAJ-UHFFFAOYSA-N 4-Methylcyclohexylamine Chemical compound CC1CCC(N)CC1 KSMVBYPXNKCPAJ-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
- 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 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 108010058643 Fungal Proteins Proteins 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
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-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 Proteins 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 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
- 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
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 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
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- YFRNYWVKHCQRPE-UHFFFAOYSA-N buta-1,3-diene;prop-2-enoic acid Chemical compound C=CC=C.OC(=O)C=C YFRNYWVKHCQRPE-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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-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
- 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
- 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
- 238000004040 coloring Methods 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
- 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
- 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
- DNWBGZGLCKETOT-UHFFFAOYSA-N cyclohexane;1,3-dioxane Chemical compound C1CCCCC1.C1COCOC1 DNWBGZGLCKETOT-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- 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
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007789 gas Substances 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
- 229910052739 hydrogen Inorganic materials 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 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
- 150000002739 metals Chemical class 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
- 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
- 238000007645 offset printing Methods 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide 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
- 239000003755 preservative agent 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
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 241000894007 species Species 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
- 239000000126 substance Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920006174 synthetic rubber latex 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
- 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
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
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 [Industrial field of application] The present invention contains a paper coating resin which provides a coated paper excellent in printability, particularly ink acceptability, and a paper coating resin. The present invention relates to a paper coating composition.
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
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。Coated paper, which is widely used as printing paper, is produced by coating a base paper that has been made up to now with a composition containing clay, a pigment such as calcium carbonate, a latex, and an adhesive such as starch as a main component. Has been done.
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が要求されるようになった。In recent years, with the remarkable progress of printing technology represented by speeding up, precision and multi-coloring, the coated paper is required to have higher printability. .
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 improvement in ink acceptability, which indicates the ink inking state during printing, water resistance against dampening water during offset printing, and blister resistance required during ink drying in rotary printing.
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61-42931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62-101621号公報参照）が
提案されている。In response, polyamide-urea-formaldehyde resin (see JP-B-44-11667) and polyamide-urea-epihalohydrin-formaldehyde resin (JP-B-61-42931) have been conventionally used to impart the above-mentioned various performances required for printing. It is also proposed to use an alicyclic dibasic carboxylic acid as the acid component of the polyamide of the polyamide-urea-formaldehyde resin (see JP-A-62-101621).
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た。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、インキ受理性が低下する。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
のである。However, none of these conventional techniques is sufficient in improving the ink receptivity, water resistance and blister resistance in a well-balanced manner, and development of a better resin has been desired. In particular, it has been extremely difficult to improve both ink acceptability and water resistance in a well-balanced manner. That is, when the water resistance of the coating layer is promoted, the penetration of dampening water from the surface of the coating layer to the inside is suppressed, the dampening water easily remains on the surface, and the transfer of the ink to the surface of the coating layer is suppressed. It becomes defective and the ink acceptability decreases. On the other hand, if the water resistance of the coating layer is relaxed, the penetration of dampening water into the interior is promoted and the ink acceptability is improved, but the water resistance becomes insufficient, so part of the surface of the coating layer becomes an ink roll. This is because it is likely to be peeled off (so-called wet picking occurs).
Therefore, the present invention is intended to solve the above-mentioned difficult problems.
本発明者らは、該課題を解決するため鋭意検討の結果、
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方又はいずれか
に脂環式エポキシ化合物又は／及び脂環式アミノ化合物
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出し本発明に到達した。The present inventors, as a result of earnest study to solve the problem,
By introducing an alicyclic epoxy compound and / or an alicyclic amino compound into either or both of a polyamide-urea-aldehyde (epihalohydrin) resin and an amine-epihalohydrin resin, and reacting or mixing them, the purpose is The inventors have reached the present invention by finding out what can be achieved.
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
ノ化合物（Ｅ）とホルムアルデヒド（Ｆ１）、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
アミノ化合物（Ｇ）と（Ｆ２）よりなる反応生成物（II
I）、上記の（Ｄ）または／および（Ｅ）と（Ｇ）と
（Ｆ２）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（Ｆ２）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、並びにこれらを含有
する紙塗工用組成物を提供するものである。That is, the present invention relates to a polyalkylene polyamine (A)
And dibasic carboxylic acid compound (B), ureas (C), alicyclic epoxy compound (D) or / and alicyclic amino compound (E) and formaldehyde (F 1 ), epihalohydrin (F 2 ) and A reaction product (I) consisting of one or more kinds (F) selected from dialdehydes (F 3 ), or the above (A), (B), (C) and (F). From the polyamide-urea-aldehyde (epihalohydrin) resin (a) comprising any of the reaction products (II), and the above (D) or / and (E) and the aliphatic amino compound (G) and (F 2 ). Reaction product (II
I), the above (D) or / and (E), (G), (F 2 ) and sulfites (H) or / and acids (J)
Of the reaction product (IV), the reaction product (V) of the above (G) and (F 2 ) and the above (G) and (F
2 ) and the reaction product (VI) consisting of (H) and / or (J) and an amine-epihalohydrin resin (b) which is one reaction product selected from the above (III) to (VI). Resins for paper coating obtained by reaction (excluding those obtained by reaction of reaction products (II) and (V) and (II) and (VI)), and resins described above ( A resin for paper coating which is a mixture of a) and a resin (b) (excluding the mixture of the reaction products (II) and (V) and (II) and (VI)), and a paper coating containing them. An industrial composition is provided.
以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
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
ン等であるが、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 (A) 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 and the like. Among them, polyethylene polyamine is preferable, and diethylenetriamine, triethylenetetramine and tetraethylenepentamine are more preferable.
これらポリアルキレンポリアミンは一種のみでもよく、
また、二種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等の
ジアミンやメチルアミン、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。These polyalkylene polyamines may be only one kind,
Further, two or more kinds may be used in combination. Further, diamines such as ethylenediamine, propylenediamine and hexamethylenediamine and monoamines such as methylamine, monoethanolamine and benzylamine may be used in combination within a range of 60 mol or less relative to 100 mol 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が挙げられる。Dibasic carboxylic acid compound (B) used in the present invention
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、例えばコハク酸、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、テトラヒドロフタル酸、ヘキサ
ヒドロフタル酸、シクロヘキサン−1,4−ジカルボン
酸、メチルテトラヒドロフタル酸、メチルヘキサヒドロ
フタル酸等の二塩基性カルボン酸が挙げられる。また、
二塩基性カルボン酸無水物および半エステルとしては、
上記の二塩基性カルボン酸の無水物および半エステルが
挙げられる。Examples of the dibasic carboxylic acid include succinic acid, glutaric acid, adipic acid, maleic acid, isophthalic acid, phthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane-1,4-dicarboxylic acid and methyl. Examples thereof include dibasic carboxylic acids such as tetrahydrophthalic acid and methylhexahydrophthalic acid. Also,
As the dibasic carboxylic acid anhydride and half ester,
Included are the anhydrides and half-esters of the above dibasic carboxylic acids.
二塩基性カルボン酸ジエステルとしては、コハク酸ジメ
チル、グルタル酸ジメチル、アジピン酸ジメチル、アジ
ピン酸ジエチルなど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
ジオクチルなどの芳香族二塩基性カルボン酸ジエステル
等が挙げられるが、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 the dibasic carboxylic acid diester include aliphatic dibasic carboxylic acid diesters such as dimethyl succinate, dimethyl glutarate, dimethyl adipate, and diethyl adipate, and further aromatic dibasic carboxylic acid diesters such as dimethyl isophthalate and dioctyl terephthalate. Examples thereof include basic carboxylic acid diesters, and lower alcohol esters having 1 to 3 carbon atoms are particularly preferable.
これら二塩基性カルボン酸系化合物（Ｂ）は、１種のみ
で用いても、２種以上併用してもよい。These dibasic carboxylic acid compounds (B) 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／及びその無水物又は／及びそのエステ
ルを併用することもできる。Further, a monobasic carboxylic acid such as acetic acid, stearic acid or benzoic acid or / and its anhydride or / and its ester can be used together.
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、ジメチル尿素等が挙
げられるが、特に尿素が好ましい。Examples of ureas (C) used in the present invention include urea, thiourea, guanylurea, methylurea, dimethylurea, etc., with urea being particularly preferable.
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性、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−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。The alicyclic epoxy compound (D) used in the present invention refers to a compound in which an epoxy group is directly or indirectly bonded to a cyclohexane ring. Specific examples of directly bonded, cyclohexene oxide, vinyl cyclohexene dioxide, bis (3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexane-carboxylate, 2- (3, 4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)
Examples thereof include cyclohexane-meta-dioxane.
In addition, the term “indirect” as used herein means containing an epoxy group such as a glycidyl group together with a cyclohexane ring. As a specific example, bis-glycidyl-hexahydro-
Examples thereof include 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３4,4′−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いまたは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 (E) used in the present invention is an alicyclic amino compound having at least one active hydrogen in the molecule, such as cyclohexylamine, dicyclohexylamine, 1,3-diaminocyclohexane, 1 , 4-Diaminocyclohexane 34,4'-diamino-
3,3'-Dimethyl-dicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexane, 4,4'-bis (paraaminocyclohexyl) methane, isophoronediamine, 1,3 or 2,4) -Bis- (aminomethyl) cyclohexane, N-aminopropylcyclohexylamine, octahydro-4,7-methanoindene-1 (2), 5
(6) -Dimethanamine, 2,2'-bis- (4-aminocyclohexyl) propane, bis- (4-aminocyclohexyl) methane, 4,4'-oxybis (cyclohexylamine), 4,4'-sulfonebis (cyclohexyl) Amine), 1,3,5-triaminocyclohexane, 2,4'- or 4,4'-diamino-3,3 ', 5,5'-tetraalkyldicyclohexylalkane, and the like.
本発明に用いられる脂肪族アミノ化合物（Ｇ）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
アミンが挙げられる。The aliphatic amino compound (G) used in the present invention is ammonia or a compound containing one or more of a primary amino group, a secondary amino group or a tertiary amino group. Amine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, butylamine, ethanolamine, monoamines such as 3-ethoxypropylamine, ethylenediamine, diamines such as hexamethylenediamine and diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc. The polyamines of
本発明に用いられるエピハロヒドリン（Ｆ２）としては
エピクロロヒドリン、エピブロモヒドリンが例示され、
これらは１種のみでもよく、また、２種以上の併用でも
よい。Examples of epihalohydrin (F 2 ) used in the present invention include epichlorohydrin and epibromohydrin,
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が挙げられる。The dialdehydes (F 3) used in the present invention include:
Glyoxal, glutaraldehyde, etc. are mentioned.
本発明に用いられる亜硫酸塩類（Ｈ）としては、例えば
亜硫酸塩（Ｍ１ ２ＳＯ３，Ｍ１は１価の金属、以下同
じ）、亜硫酸水素塩（Ｍ１ＨＳＯ３）、ピロ亜硫酸塩
（Ｍ１ ２Ｓ２Ｏ５）等が例示され、Ｍ１としてはアルカ
リ金属があげられる。Examples of the sulfites (H) used in the present invention include sulfites (M 1 2 SO 3 and M 1 are monovalent metals, the same applies hereinafter), bisulfites (M 1 HSO 3 ) and pyrosulfites (M). 1 2 S 2 O 5 ) and the like, and examples of M 1 include an alkali metal.
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Ｍ１Ｓ
Ｏ３ −、亜硫酸水素イオンＨＳＯ３ −、ピロ亜硫酸イオ
ンＳ２Ｏ５ 2-、亜硫酸イオンＳＯ３ 2-、ピロ亜硫酸金属
イオンＭ１Ｓ２Ｏ５ −、ピロ亜硫酸水素イオンＨＳ２Ｏ
５ −等が挙げられる。具体的な化合物としては亜硫酸ナ
トリウム（Ｎａ２ＳＯ３）、亜硫酸水素ナトリウム（Ｎ
ａＨＳＯ３）、無水重亜硫酸ナトリウム（Ｎａ２Ｓ２Ｏ
５）等が例示される。These are used singly or in a plural number, and as sulfite ions generated from them, metal sulfite ion M 1 S
O 3 − , hydrogen sulfite ion HSO 3 − , pyrosulfite ion S 2 O 5 2− , sulfite ion SO 3 2− , metal pyrosulfite ion M 1 S 2 O 5 − , hydrogen sulfite hydrogen ion HS 2 O
5- and the like. Specific compounds include sodium sulfite (Na 2 SO 3 ) and sodium hydrogen sulfite (N
aHSO 3 ), anhydrous sodium bisulfite (Na 2 S 2 O
5 ) etc. are illustrated.
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、ギ酸、酢酸等の有機酸が挙げら
れる。Examples of the acids (J) used in the present invention include sulfuric acid,
Examples thereof include inorganic acids such as hydrochloric acid and phosphoric acid, and organic acids such as formic acid and acetic acid.
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ができ
る。The use of sulfites can reduce the cationic property of the paper coating resin and prevent thickening of the paper coating composition.
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、これにより紙塗工用組成物の増
粘を防止することができる。In addition, a low molecular weight amine-epihalohydrin resin can be obtained by reacting with epihalohydrin after converting a part or all of amino groups to amine salts by using an acid, and thereby a composition for paper coating. Can be prevented from increasing in viscosity.
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、脂環式アミノ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／及び脂環式アミノ化合物0.02〜
４モル（併用の場合は両方の和）の範囲が好ましい。Polyalkylene polyamine of polyamide-urea-aldehyde (epihalohydrin) resin (a) in the present invention,
The ratio of the reaction components of the dibasic carboxylic acid compound, urea, alicyclic epoxy compound, and alicyclic amino compound is 0.1 to 2 mol of the dibasic carboxylic acid compound and urea to 1 mol of the polyalkylene polyamine. 0.5 to 10 mol, and alicyclic epoxy compound or / and alicyclic amino compound 0.02 to
A range of 4 moles (the sum of both when used in combination) is preferred.
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。The amount of formaldehyde, epihalohydrin or dialdehyde used alone is preferably 0.1 to 3 mol per 1 mol of polyalkylene polyamine, and the amount used when two or more of them are used in combination is preferably 0.1 to 4 mol.
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、及び脂環式アミノ化合物は任意の順序で反応させる
ことができる。Regarding the reaction order, the polyalkylene polyamine, the dibasic carboxylic acid compound, the ureas, the alicyclic epoxy compound, and the alicyclic amino 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 following method.
（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／及び脂環式アミノ化合物と二塩基性カ
ルボン酸系化合物を60〜300℃、好ましくは80〜200℃で
１〜10時間反応させて縮合を行った後、尿素を加えて90
〜180℃で脱アンモニア反応を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) -1: Polyalkylene polyamine, alicyclic epoxy compound or / and alicyclic amino compound and dibasic carboxylic acid compound are reacted at 60 to 300 ° C, preferably 80 to 200 ° C for 1 to 10 hours. After performing condensation, urea is added to
The deammonification reaction is carried out at ˜180 ° C. for 0.5 to 10 hours, then diluted with water, and then one or more of formaldehyde, epihalohydrin or dialdehyde is reacted by a known method to introduce a reactive group.
（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／及び脂環式アミノ化合物と尿素類を90
〜180℃で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60〜300℃、好ましく
は80〜200℃で１〜10時間縮合反応を行い、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。(I) -2: 90% of polyalkylene polyamine, alicyclic epoxy compound or / and alicyclic amino compound and urea
After deammonification reaction at ~ 180 ° C for 0.5-10 hours, add dibasic carboxylic acid compound to perform condensation reaction at 60-300 ° C, preferably 80-200 ° C for 1-10 hours, and then with water. After the dilution, one or more of formaldehyde, epihalohydrin or dialdehyde is reacted by a known method to introduce a reactive group.
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でき
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／及び脂環式アミノ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, the alicyclic epoxy compound, the alicyclic amino compound, the dibasic carboxylic acid compound, and the ureas can also be divided and reacted. That is, (I) -3: a polyalkylene polyamine, an alicyclic epoxy compound or / and an alicyclic amino compound, and a urea are subjected to a deammonification reaction, and then a dibasic carboxylic acid compound is added to carry out a condensation reaction. Then, urea is added again to carry out a deammonification reaction, and then diluted with water, and then one or more of formaldehyde, epihalohydrin or dialdehyde is reacted by a known method to form a reactive group. Introduce.
（Ｉ）−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／及び脂環式アミノ化合物と二塩基性カ
ルボン酸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、次いで、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、その後水
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) -4: Polyalkylene polyamine, alicyclic epoxy compound or / and alicyclic amino compound and a dibasic carboxylic acid compound are subjected to a condensation reaction, and then urea is added to carry out a deammonification reaction. Then, the dibasic carboxylic acid compound is added again to carry out the condensation reaction, and after diluting with water, one or more of formaldehyde, epihalohydrin or dialdehyde is reacted by a known method to give a reactive group. To introduce.
（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
び脂環式アミノ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、その後水で希釈した後、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 polyammonium polyamine and ureas are subjected to deammonification reaction, alicyclic epoxy compound or / and alicyclic amino compound and dibasic carboxylic acid compound are added to carry out condensation reaction, then Then, urea is added again to carry out a deammonification reaction, and after diluting with water, one or more of formaldehyde, epihalohydrin or dialdehyde is reacted by a known method to introduce a reactive group.
（Ｉ）−６：ポリアルキレンポリアミンと、脂環式アミ
ノ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、その後水で希釈した後、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) -6: Polyalkylene polyamine and alicyclic amino compound are subjected to condensation reaction with different dibasic carboxylic acid compounds, respectively, and after mixing both, ureas are added to carry out deammonification reaction, and then with water. After dilution, formaldehyde, epihalohydrin or dialdehyde 1
One 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℃、好ましくは80〜200℃で0.5〜1
0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℃、好ましくは80〜200℃で１〜10時間縮合
反応させ、その後さらに、尿素類を加えて90〜180℃で
脱アンモニア反応を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 at 60 to 300 ° C, preferably 80 to 200 ° C, 0.5 to 1
After reacting for 0 hours, a dibasic carboxylic acid compound is added and a condensation reaction is performed at 60 to 300 ° C, preferably 80 to 200 ° C for 1 to 10 hours, and then urea is further added at 90 to 180 ° C. Deammonification reaction is carried out for 0.5 to 10 hours, diluted with water, and then reacted with one or more of formaldehyde, epihalohydrin or dialdehyde by a known method,
Introduce a reactive group.
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
応することができる。The reaction product (II) can be reacted in the same manner as in the above (I) -1 to (I) -5 except that the 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
ルに対し脂環式エポキシ化合物又は／及び脂環式アミノ
化合物（反応生成物III，IVの場合）0.01〜0.5モル（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、酸類0.1〜0.5モルの範
囲が好ましい。The ratio of each reaction component of the alicyclic epoxy compound, the alicyclic amino compound, the aliphatic amino compound, the epihalohydrin, the sulfites, and the acids of the amine-epihalohydrin resin (b) in the present invention is the amino group 1 of the aliphatic amino compound. Aliphatic epoxy compound or / and alicyclic amino compound (in the case of reaction products III and IV) 0.01 to 0.5 mol (the sum of both in the case of combined use), epihalohydrin 0.05 to 3 mol, and sulfites 0.03 to mol The range of 1.5 mol and 0.1-0.5 mol of acids is preferable.
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。Regarding the reaction sequence, an alicyclic epoxy compound, an alicyclic amino compound, an aliphatic amino compound, epihalohydrin,
The sulfites and acids can be reacted in any order.
例えば、反応生成物（III）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 (III) can be produced by the following method.
（III）−１：脂環式エポキシ化合物又は／及び脂環式
アミノ化合物と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時間反応する。(III) -1: Epihalohydrin is added dropwise to an alicyclic epoxy compound or / and an alicyclic amino compound and an aliphatic amino compound at 40 ° C. or lower over 0.5 to 3 hours, and then 0 at 40 to 80 ° C.
React for ~ 4 hours.
また、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、 （III）−２：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時間反応する。Further, the aliphatic amino compound and the alicyclic epoxy compound or / and the alicyclic amino compound may be reacted separately instead of simultaneously. For example, (III) -2: epihalohydrin is added dropwise to an aliphatic amino compound at 40 ° C. or lower over 0.5 to 3 hours, and then an alicyclic amino compound or / and an alicyclic epoxy compound is added thereto.
React at ~ 80 ° C for 0.5-4 hours.
反応生成物（IV）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。The reaction product (IV) can be produced by the method shown below.
（IV）−１：脂環式エポキシ化合物又は／及び脂環式ア
ミノ化合物と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時間反応する。(IV) -1: an alicyclic epoxy compound or / and an alicyclic amino compound and an aliphatic amino compound with epihalohydrin
After dropping at 40 ° C or below for 0.5 to 3 hours, 0 to 40 to 80 ° C
Hold for 4 hours, add sulfites to 0.5 at 40-80 ℃
React for ~ 4 hours.
（IV）−２：脂環式エポキシ化合物又は／及び脂環式ア
ミノ化合物と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時間反応する。(IV) -2: Epihalohydrin is added dropwise to a mixture of an alicyclic epoxy compound or / and an alicyclic amino compound, an aliphatic amino compound and a sulfite at 40 ° C or lower over 0.5 to 3 hours, and then 40 to 80 ° C. React for 0 to 4 hours.
（IV）−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と脂肪
族アミノ化合物を加え40〜80℃で0.5〜４時間反応させ
る。(IV) -3: Epihalohydrin and sulfites at 40-80 ° C
To a reaction product or a mixture of epihalohydrin and sulfites obtained by reacting for 0.5 to 4 hours with an alicyclic epoxy compound or / and an alicyclic amino compound and an aliphatic amino compound at 40 to 80 ° C. Allow to react for ~ 4 hours.
又、脂環式エポキシ化合物又は／及び脂環式アミノ化合
物と脂肪族アミノ化合物にあらかじめ酸類を加えてお
き、アミノ基の活性を抑えてから反応することもでき
る。It is also possible to add acids to the alicyclic epoxy compound or / and the alicyclic amino compound and the aliphatic amino compound in advance to suppress the activity of the amino group before the reaction.
例えば、（IV）−４：脂環式エポキシ化合物又は／及び
脂環式アミノ化合物と脂肪族アミノ化合物に硫酸を加え
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時間反応する。For example, (IV) -4: after adding sulfuric acid to an alicyclic epoxy compound or / and an alicyclic amino compound and an aliphatic amino compound, epihalohydrin is added dropwise at 50 ° C. or lower over 0.5 to 2 hours, and further 50 React at ~ 80 ° C for 0.5-4 hours.
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が
できる。The reaction product (V) can be reacted in the same manner as in the above (III) -1 except that the 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 the above (IV) -1 to (IV) -4 except that the 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（エピハロヒドリン）樹脂（イ）とアミン−エピハロ
ヒドリン樹脂（ロ）は、さらに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
合わせは除く）。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。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おきこれを紙塗工用組成
物に添加してもよい。The polyamide-urea-aldehyde (epihalohydrin) resin (a) and amine-epihalohydrin resin (b) obtained as described above are further reacted or used as a mixture (however, (II) and (V), (Excluding the combination of (II) and (VI)). When reacting both, the reaction temperature is 30
It is carried out at ℃ ~ 90 ℃ for 20 minutes ~ 10 hours. Upon mixing, both may be added separately to the paper coating composition, or both may be mixed in advance and 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、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, when (a) and (b) are reacted and mixed, (a),
The usage ratio of (b) is arbitrary. It should be noted that the larger the amount (b) is, the more excellent the ink acceptability and the blister resistance are, but depending on the composition, the thickening of the paper coating composition is not so preferable.
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。Further, 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。The paper coating resin of the present invention can be used alone, but is preferably used as a paper coating composition by adding a pigment, an adhesive and, if necessary, other components.
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。Pigments used in this case include clay, talc,
There are inorganic pigments such as heavy calcium carbonate, light calcium carbonate, satin white, titanium dioxide, aluminum hydroxide, barium sulfate, calcium sulfite, synthetic silica, zinc oxide, and organic pigments such as styrene-based polymers and urea-based polymers. Of these, one kind or a mixture of two or more kinds can be used.
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。As the adhesive, starch, modified starch (oxidized starch, esterified starch, etherified starch, enzyme modified starch, pregelatinized starch, cationized starch, etc.), casein, gelatin,
Natural polymer compounds such as soybean protein, yeast protein, cellulose derivatives (carboxymethyl cellulose, hydroxyethyl cellulose, etc.) or their derivatives, and styrene-butadiene resin, (meth) acrylate-butadiene resin, (meth) acrylate resin, polyvinyl Examples thereof include synthetic polymer compounds such as alcohols, vinyl acetate resins, acrylamide resins, styrene- (meth) acrylate resins, styrene-maleic acid resins, ethylene-vinyl acetate resins.
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。In the paper coating composition of the present invention, in addition to the above-mentioned pigments and adhesives, dispersants, lubricants, thickeners, thickeners, defoamers, defoamers, preservatives, fungicides, water retention agents. Various auxiliaries such as a fluorescent whitening agent, a dye, and a conductive agent can be appropriately blended 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。The amount of each compound in the composition is preferably in the range of 0.05 to 5 parts by weight for the paper coating resin and 5 to 50 parts by weight for the solid content of the adhesive when the pigment is 100 parts by weight.
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
塗工用樹脂を加え撹拌し、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。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, an auxiliary agent such as a viscosity modifier are added to the composition, and the present invention is added thereto. The resin for paper coating is added and stirred, and if necessary, the pH is adjusted with caustic soda, ammonia, etc. to prepare.
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、オフマシンコーテイング
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 on a base paper by a known method. That is, a blade coater, an air knife coater, a bar coater, a roll coater, a size press coater, a dock coater, a brush coater, a curtain coater, a gravure coater, a cast coater, a Chanplex coater, etc. , Or off-machine coating. Further, it may be one-layer coating or multi-layer coating, and either single-side coating or double-side coating is possible.
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することができる。Drying after coating is carried out by a usual method such as a gas heater, an electric heater, a steam heating heater, an infrared heater, hot air heating, etc., and after drying, if necessary, a finishing step such as super calendering, water calendering, gloss calendering, etc. It is possible to impart gloss, and any other general processing means can be used.
次に本発明を参考例、実施例、比較例によって説明す
る。Next, the present invention will be described with reference to Reference Examples, Examples and Comparative Examples.
参考例 １ 温度計、コンデンサー及び撹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219ｇとイソホロンジアミ
ン85ｇおよびアジピン酸37ｇを加えて160℃で1.5時間縮
合反応を行い、発生する水を系外に除去した。次いでこ
れに尿素120ｇを加え120℃で５時間脱アンモニア反応を
行った。しかる後に、これに水を加ええ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℃で４時間撹拌しながら保持
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Ｉ）を得た。この樹脂水溶液を（ａ−１）とす
る。Reference Example 1 Add 219 g of triethylenetetramine, 85 g of isophoronediamine and 37 g of adipic acid to a four-necked flask equipped with a thermometer, a condenser and a stir bar and carry out a condensation reaction at 160 ° C for 1.5 hours to generate water out of the system. Removed. Next, 120 g of urea was added thereto, and a deammonification reaction was performed at 120 ° C. for 5 hours. After that, water was added to this to prepare a 60% aqueous solution. Next, 122 g of 37% formalin aqueous solution was added to adjust the pH to 5 with 50% sulfuric acid aqueous solution, and the mixture was maintained at 70 ° C. for 4 hours while stirring. Further, water was added to obtain a water-soluble resin (reaction product I) having a solid content of 50%. Let this resin aqueous solution be (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35
0ｇおよび尿素72ｇを仕込み、撹拌しながら150℃で90分
間脱アンモニア反応を行った。次いで、これを120℃ま
で冷却してからアジピン酸175ｇとシクロヘキセンオキ
サイド59ｇとを加えて160℃で２時間縮合反応を行い、
発生する水を系外に除去した。次いでこれを120℃に冷
却した後、尿素288ｇを加えて120℃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50％
硫酸水溶液にてpH５調整し、70℃で３時間撹拌しながら
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Ｉ）を得た。この樹脂水溶液を（ａ−
２）とする。Reference Example 2 Triethylenetetramine 35 was placed in the same reaction vessel as in Reference Example 1.
0 g and 72 g of urea were charged, and a deammonification reaction was performed at 150 ° C. for 90 minutes while stirring. Then, after cooling this to 120 ° C., 175 g of adipic acid and 59 g of cyclohexene oxide were added and a condensation reaction was carried out at 160 ° C. for 2 hours,
The generated water was removed outside the system. Next, this was cooled to 120 ° C., 288 g of urea was added, and a deammonification reaction was carried out at 120 ° C. for 5 hours. Thereafter, water was added to this to prepare a 70% aqueous solution. Next, add 146 g of 37% formalin aqueous solution and add 50%.
The pH was adjusted to 5 with an aqueous sulfuric acid solution, and the mixture was kept at 70 ° C. for 3 hours with stirring. Thereafter, water was added to obtain a water-soluble resin (reaction product I) having a solid content of 60%. This resin aqueous solution is (a-
2).
参考例 ３ 参考例１と同様の反応容器にトリエチレンテトラミン23
4ｇとシクロヘキセンオキサイド20ｇを仕込み、120℃で
１時間撹拌を行った。次いでアジピン酸37ｇとジシクロ
ヘキシルアミン36ｇを加え160℃昇温し、1.5時間縮合反
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360ｇを加えて120℃で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122
ｇを加えて50％硫酸水溶液でpH５に調整し、70℃で３時
間撹拌しながら保持した。Reference Example 3 Triethylenetetramine 23 in the same reaction vessel as in Reference Example 1
4 g and 20 g of cyclohexene oxide were charged, and the mixture was stirred at 120 ° C. for 1 hour. Then, 37 g of adipic acid and 36 g of dicyclohexylamine were added, the temperature was raised to 160 ° C., the condensation reaction was carried out for 1.5 hours, and the generated water was removed to the outside of the system. Further this
After cooling to 120 ° C., 360 g of urea was added and a deammonification reaction was carried out at 120 ° C. for 4 hours. Then, water was added to this to make a 60% aqueous solution. Next, 37% formalin aqueous solution 122
g was added, the pH was adjusted to 5 with a 50% aqueous sulfuric acid solution, and the mixture was maintained at 70 ° C. for 3 hours with stirring.
さらに水を加えて固形分50％の水溶性樹脂（反応生成物
Ｉ）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 I) having a solid content of 50%. Let this resin aqueous solution be (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165
ｇとモノエタノールアミン12ｇ、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19
4ｇを仕込み、135℃で2.5時間縮合反応を行い、発生す
るメタノールを系外に除去した。次いで、これを120℃
に冷却した後、尿素176ｇを加えて、120℃で３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。次にエピクロロヒドリン117ｇを加え
て55℃で２時間反応を続けた。しかる後に、30℃に冷却
して37％ホルマリン水溶液68ｇを加え、50％硫酸水溶液
にてpH４に調整し、65℃で３時間保ちつつ撹拌した。さ
らに水を加えて固形分50％の水溶性樹脂（反応生成物
Ｉ）を得た。この樹脂水溶液を（ａ−４）とする。Reference Example 4 A reaction vessel similar to Reference Example 1 was charged with diethylenetriamine 165.
g, monoethanolamine 12 g, 4,4-oxybis (cyclohexylamine) 85 g and dimethyl terephthalate 19
4 g was charged and a condensation reaction was carried out at 135 ° C. for 2.5 hours to remove generated methanol out of the system. Then this is 120 ℃
After cooling to 1, 176 g of urea was added, and a deammonification reaction was performed at 120 ° C. for 3 hours. Then add water to this and 60
% Aqueous solution. Next, 117 g of epichlorohydrin was added and the reaction was continued at 55 ° C. for 2 hours. Thereafter, the mixture was cooled to 30 ° C., 68 g of a 37% aqueous formalin solution was added, the pH was adjusted to 4 with a 50% aqueous sulfuric acid solution, and the mixture was stirred at 65 ° C. for 3 hours. Further, water was added to obtain a water-soluble resin (reaction product I) having a solid content of 50%. Let this resin aqueous solution be (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206
ｇと2,2−ビス（４′−グリシジルオキシシクロヘキシ
ル）プロパン70ｇと尿素90ｇ仕込み、撹拌しながら150
℃で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160ｇを加えて160℃で２時間縮合反応を行
い、発生するメタノールを系外に除去した。その後さら
に、尿素60ｇを加えて120℃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℃で３時間撹拌しながら保
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Ｉ）を得た。この樹脂水溶液を（ａ−５）とす
る。Reference Example 5 A reaction vessel similar to that of Reference Example 1 was charged with diethylenetriamine 206.
g, 70 g of 2,2-bis (4'-glycidyloxycyclohexyl) propane and 90 g of urea were charged, and 150 with stirring
A deammonification reaction was performed at ℃ for 3 hours. Next, 160 g of dimethyl glutarate was added and a condensation reaction was performed at 160 ° C. for 2 hours to remove generated methanol out of the system. Thereafter, 60 g of urea was further added, and a deammonification reaction was carried out at 120 ° C. for 5 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 5 with 50% sulfuric acid aqueous solution, and the mixture was kept at 70 ° C. for 3 hours while stirring. Further, water was added to obtain a water-soluble resin (reaction product I) having a solid content of 50%. Let this resin aqueous solution be (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29
2ｇと尿素120ｇを仕込み、150℃で２時間脱アンモニア
反応を行った。次いでアジピン酸146ｇを加え160℃昇温
し、３時間縮合反応を行い、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℃で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％硫酸水溶液でpH５に調
整し、70℃で４時間撹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II）を得
た。この樹脂水溶液を（ａ−６）とする。Reference Example 6 Triethylenetetramine 29 was placed in the same reaction vessel as in Reference Example 1.
2 g and 120 g of urea were charged and a deammonification reaction was carried out at 150 ° C. for 2 hours. Next, 146 g of adipic acid was added, the temperature was raised to 160 ° C., the condensation reaction was performed for 3 hours, and the generated water was removed to the outside of the system. Further, after cooling this to 120 ° C., 120 g of urea was added and a deammonification 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 37% formalin aqueous solution was added, the pH was adjusted to 5 with 50% sulfuric acid aqueous solution, and the mixture was maintained at 70 ° C. for 4 hours with stirring. Further, water was added to obtain a water-soluble resin (reaction product II) having a solid content of 50%. Let this resin aqueous solution be (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29
2ｇとアジピン酸146ｇを仕込み、170℃で2.5時間撹拌を
行った。次いで、120℃まで冷却した後、尿素300ｇを加
えて120℃で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162ｇを加えて50％硫酸水溶液でpH５に調
整し、80℃で２時間撹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II）を得
た。この樹脂水溶液を（ａ−７）とする。Reference Example 7 Triethylenetetramine 29 was placed in the same reaction vessel as in Reference Example 1.
2 g and adipic acid (146 g) were charged, and the mixture was stirred at 170 ° C. for 2.5 hours. Then, after cooling to 120 ° C., 300 g of urea was added and a deammonification reaction was carried out at 120 ° C. for 4 hours. Then, water was added to this to make a 60% aqueous solution. Next, 162 g of 37% formalin aqueous solution was added, the pH was adjusted to 5 with a 50% sulfuric acid aqueous solution, and the mixture was kept at 80 ° C. for 2 hours with stirring. Further, water was added to obtain a water-soluble resin (reaction product II) having a solid content of 50%. Let this resin aqueous solution be (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29
2ｇとグルタル酸132ｇを仕込み、撹拌しながら170℃で
３時間縮合反応を行い、発生する水を系外に除去した。
次いで、尿素120ｇを加えて120℃で２時間脱アンモニア
反応を行った。その後さらに、アジピン酸ジメチル174
ｇを加えて170℃で２時間縮合反応を行い、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。次に37％ホルマリン水溶液162ｇ
を加え、50％硫酸水溶液にてpH５に調整し、70℃で３時
間撹拌しながら保持した。更に水を加えて固形分50％の
水溶性樹脂（反応生成物II）を得た。この樹脂水溶液を
（ａ−８）とする。Reference Example 8 Triethylenetetramine 29 was placed in the same reaction vessel as in Reference Example 1.
2 g and 132 g of glutaric acid were charged, a condensation reaction was carried out at 170 ° C. for 3 hours while stirring, and the generated water was removed to the outside of the system.
Then, 120 g of urea was added and a deammonification reaction was performed at 120 ° C. for 2 hours. Then dimethyl adipate 174
g was added and a condensation reaction was carried out at 170 ° C. for 2 hours to remove generated methanol out of the system. Then, water was added to this to make a 60% aqueous solution. Next, 162 g of 37% formalin aqueous solution
Was added to adjust the pH to 5 with a 50% aqueous solution of sulfuric acid, and the mixture was maintained at 70 ° C. for 3 hours with stirring. Further, water was added to obtain a water-soluble resin (reaction product II) having a solid content of 50%. Let this resin aqueous solution be (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206
ｇと1,3−ビス−（アミノメチル）シクロヘキサン14ｇ
を仕込み、水331ｇにて希釈した後、十分撹拌しながら
エピクロロヒドリン183ｇを35℃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（反応生成物III）を得た。この
樹脂水溶液を（ｂ−１）とする。Reference Example 9 Diethylenetriamine 206 was placed in the same reaction vessel as in Reference Example 1.
g and 14 g of 1,3-bis- (aminomethyl) cyclohexane
Was charged, diluted with 331 g of water, and 183 g of epichlorohydrin was added dropwise at 35 ° C. over 2 hours with sufficient stirring. After the dropping was completed, the mixture was kept at 60 ° C. for 2 hours and then water was added to obtain a water-soluble resin (reaction product III) having a solid content of 40%. Let this resin aqueous solution be (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206
ｇ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25ｇを仕込み、水
347ｇにて希釈した後、十分撹拌しながらエピクロロヒ
ドリン185ｇを35℃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（反応生成物III）を得た。この樹脂水溶液
を（ｂ−２）とする。Reference Example 10 Diethylenetriamine 206 was placed in the same reaction vessel as in Reference Example 1.
and 25 g of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane-carboxylate were added, and water was added.
After diluting with 347 g, 185 g of epichlorohydrin was added dropwise at 35 ° C. over 2 hours with sufficient stirring. After the dropping was completed, the mixture was kept at 60 ° C. for 1.5 hours, and then water was added to obtain a water-soluble resin (reaction product III) having a solid content of 40%. Let this resin aqueous solution be (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29
2ｇとＮ−アミノプロピルシクロヘキシルアミン16ｇを
仕込み、水462ｇにて希釈した後、十分撹拌しながらエ
ピクロロヒドリン93ｇを35℃で２時間かけて滴下した。
滴下終了後60℃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III）を得た。この樹脂
水溶液を（ｂ−３）とする。Reference Example 11 Triethylenetetramine 29 was placed in the same reaction vessel as in Reference Example 1.
After charging 2 g and N-aminopropylcyclohexylamine 16 g and diluting with 462 g of water, 93 g of epichlorohydrin was added dropwise at 35 ° C. over 2 hours with sufficient stirring.
After the completion of dropping, hold at 60 ° C for 2 hours, and then add water to solid content.
40% water-soluble resin (reaction product III) was obtained. Let this resin aqueous solution be (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206
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396ｇにて希釈し
た後、十分撹拌しながら無水重亜硫酸ナトリウム40ｇを
加え、さらにエピクロロヒドリン36ｇを35℃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（反応生成物IV）を得
た。この樹脂水溶液を（ｂ−４）とする。Reference Example 12 Diethylenetriamine 206 was placed in the same reaction vessel as in Reference Example 1.
g and octahydro-4,7-methanoindene-1 (2), 5
(6) -Dimethanamine (20 g) was charged, diluted with water (396 g), anhydrous sodium bisulfite (40 g) was added with sufficient stirring, and epichlorohydrin (36 g) was added dropwise at 35 ° C. over 2 hours. After the dropping was completed, the mixture was kept at 60 ° C. for 2 hours, and then water was added to obtain a water-soluble resin (reaction product IV) having a solid content of 40%. Let this resin aqueous solution be (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24ｇ
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141ｇにて希釈した
後、十分撹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92ｇを35℃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（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 24 g of monoethanolamine in the same reaction vessel as in Reference Example 1.
And Octahydro-4,7-methanoindene-1 (2), 5 (6)
-Dimethanamine (20 g) was charged, diluted with water (141 g), sodium sulfite (50 g) was added with sufficient stirring, and epichlorohydrin (92 g) was added dropwise at 35 ° C over 2 hours. After the dropping was completed, the mixture was kept at 60 ° C. for 2 hours, and then water was added to obtain a water-soluble resin (reaction product IV) having a solid content of 40%. Let this resin aqueous solution be (b-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206
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394ｇにて希釈
し、十分撹拌しながら酢酸37ｇを加え、さらにエピクロ
ロヒドリン185ｇを35℃で１時間かけて滴下した。滴下
終了後80℃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−６）とする。Reference Example 14 Diethylenetriamine 206 was placed in the same reaction vessel as in Reference Example 1.
g and octahydro-4,7-methanoindene-1 (2), 5
20 g of (6) -dimethanamine was charged, diluted with 394 g of water, 37 g of acetic acid was added with sufficient stirring, and 185 g of epichlorohydrin was further added dropwise at 35 ° C. over 1 hour. After dripping, hold at 80 ℃ for 2 hours, then add water to solid content 40%
Of water-soluble resin (reaction product IV) was obtained. Let this resin aqueous solution be (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21
9ｇを仕込み、水256ｇにて希釈した後、十分撹拌しなが
らエピクロロヒドリン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38ｇを加えて、60℃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 21 was placed in the same reaction vessel as in Reference Example 1.
After 9 g was charged and diluted with 256 g of water, 93 g of epichlorohydrin was added dropwise at 35 ° C. over 2 hours with sufficient stirring. After completion of the dropping, 10 g of cyclohexene oxide and 38 g of anhydrous sodium bisulfite were added, and the mixture was kept at 60 ° C. for 3 hours. Then, water was added to obtain a water-soluble resin (reaction product IV) having a solid content of 40%. Let this resin aqueous solution be (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206
ｇを仕込み、水503ｇにて希釈した後、十分撹拌しなが
らエピクロロヒドリン370ｇを滴下した。滴下終了後65
℃で２時間保持した後、水を加えて固形分50％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 A reaction vessel similar to Reference Example 1 was charged with diethylenetriamine 206.
After charging g, diluting with 503 g of water, 370 g of epichlorohydrin was added dropwise with sufficient stirring. 65 after completion of dropping
After keeping at 0 ° C for 2 hours, water was added to obtain a water-soluble resin (reaction product V) having a solid content of 50%. This resin aqueous solution is (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
189ｇと無水重亜硫酸ナトリウム38ｇを仕込み、水368ｇ
にて希釈した後、十分撹拌しながらエピクロロヒドリン
222ｇを滴下した。滴下終了後55℃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V
I）を得た。この樹脂水溶液を（ｂ−９）とする。Reference Example 17 Tetraethylenepentamine was placed in the same reaction vessel as in Reference Example 1.
Charge 189g and anhydrous sodium bisulfite 38g, water 368g
After diluting with, mix well with epichlorohydrin
222 g was added dropwise. After the dropping was completed, the mixture was kept at 55 ° C for 4 hours, and then water was added to the mixture to prepare a water-soluble resin with a solid content of 40% (reaction product V
I) got. This resin aqueous solution is referred to as (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103
ｇと50％ジメチルアミン90ｇを仕込み、水552ｇで希釈
した後、十分撹拌しながらエピクロロヒドリン278ｇを2
5℃で滴下した。滴下終了後35℃で30分間保持した後、
亜硫酸ナトリウム63ｇを加え50℃で２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V
I）を得た。この樹脂水溶液を（ｂ−10）とする。Reference Example 18 Diethylenetriamine 103 was placed in the same reaction vessel as in Reference Example 1.
g and 50 g of 50% dimethylamine were added, diluted with 552 g of water, and 2 well of 278 g of epichlorohydrin with sufficient stirring.
It was added dropwise at 5 ° C. After holding for 30 minutes at 35 ℃ after completion of dropping,
63 g of sodium sulfite was added and the mixture was kept at 50 ° C. for 2 hours. After that, water is added to add a water-soluble resin with a solid content of 40% (reaction product V
I) got. Let this resin aqueous solution be (b-10).
実施例１ 上記参考例に示した樹脂水溶液（ａ−１）90ｇと樹脂水
溶液（ｂ−１）10ｇを60℃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Ａとする。Example 1 A resin for paper coating was obtained by reacting 90 g of the resin aqueous solution (a-1) shown in the above Reference Example with 10 g of the resin aqueous solution (b-1) at 60 ° C. for 5 hours. This is designated as resin A.
実施例２ 上記参考例に示した樹脂水溶液（ａ−２）80ｇと樹脂水
溶液（ｂ−８）20ｇ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Ｂとする。Example 2 A resin for paper coating was obtained by reacting 80 g 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 is designated as Resin B.
実施例３ 上記参考例に示した樹脂水溶液（ａ−６）70ｇと樹脂水
溶液（ｂ−４）30ｇを80℃で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 resin for paper coating was obtained by reacting 70 g of the resin aqueous solution (a-6) shown in the above Reference Example with 30 g of the resin aqueous solution (b-4) at 80 ° C. for 2 hours. This is designated as Resin C.
実施例４ 上記参考例に示した樹脂水溶液（ａ−３）95ｇと樹脂水
溶液（ｂ−２）５ｇを50℃で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Ｄとする。Example 4 A resin for paper coating was obtained by reacting 95 g of the resin aqueous solution (a-3) shown in the above Reference Example with 5 g of the resin aqueous solution (b-2) at 50 ° C. for 8 hours. This is designated as resin D.
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）10ｇを70℃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Ｅとする。Example 5 A resin for paper coating was obtained by reacting 90 g of the resin aqueous solution (a-4) shown in the above Reference Example with 10 g of the resin aqueous solution (b-9) at 70 ° C. for 4 hours. This is designated as resin E.
実施例６ 上記参考例に示した樹脂水溶液（ａ−７）90ｇと樹脂水
溶液（ｂ−５）10ｇを40℃で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 90 g of the resin aqueous solution (a-7) shown in the above Reference Example with 10 g of the resin aqueous solution (b-5) at 40 ° C. for 10 hours. This is designated as resin 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℃で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 paper coating resin was obtained by reacting 85 g of the resin aqueous solution (a-1) shown in the above Reference Example with 15 g of the resin aqueous solution (b-6) at 60 ° C. for 2 hours. This is designated as resin 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℃で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 80 g of the resin aqueous solution (a-5) shown in the above Reference Example with 20 g of the resin aqueous solution (b-7) at 80 ° C. for 2 hours. This is referred to as resin H.
比較例１ 上記参考例に示した樹脂水溶液（ａ−６）90ｇと樹脂水
溶液（ｂ−８）10ｇを70℃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ａとする。Comparative Example 1 A resin for paper coating was obtained by reacting 90 g of the resin aqueous solution (a-6) shown in the above Reference Example with 10 g of the resin aqueous solution (b-8) at 70 ° C. for 4 hours. This is designated 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ｂとする。Comparative Example 2 A paper coating resin was obtained by reacting 90 g of the resin aqueous solution (a-7) shown in the above Reference Example with 10 g of the resin aqueous solution (b-9) at 80 ° C. for 5 hours. This is designated as resin b.
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）20ｇ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ｃとする。Comparative Example 3 A resin for paper coating was obtained by reacting 80 g of the resin aqueous solution (a-8) shown in the above Reference Example with 20 g of the resin aqueous solution (b-10) at 80 ° C. for 5 hours. This is designated as resin c.
実施例９ 上記参考例に示した樹脂水溶液（ａ−１）90ｇと樹脂水
溶液（ｂ−８）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Ｉとする。Example 9 A resin for paper coating was obtained by mixing 90 g of the resin aqueous solution (a-1) and 10 g of the resin aqueous solution (b-8) shown in the above Reference Example. This is 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）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Ｊとする。Example 10 A resin for paper coating was obtained by mixing 90 g of the resin aqueous solution (a-2) shown in the above reference example with 10 g of the resin aqueous solution (b-5). This is 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（ｂ−１）15ｇを混合することにより紙塗工用樹脂
を得た。これを樹脂Ｋとする。Example 11 A paper coating resin was obtained by mixing 85 g of the resin aqueous solution (a-6) shown in the above Reference Example with 15 g of the resin aqueous solution (b-1). This is designated as resin K.
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）15ｇを混合することにより紙塗工用樹脂
を得た。これを樹脂Ｌとする。Example 12 A paper coating resin was obtained by mixing 85 g of the resin aqueous solution (a-3) shown in the above Reference Example with 15 g of the resin aqueous solution (b-10). This is referred to as resin L.
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 resin for paper coating was obtained by mixing 90 g of the resin aqueous solution (a-4) and 10 g of the resin aqueous solution (b-2) shown in the above Reference Example. This is 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 resin for paper coating was obtained by mixing 70 g of the resin aqueous solution (a-7) shown in the above Reference Example with 30 g of the resin aqueous solution (b-6). This is designated 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 90 g of the resin aqueous solution (a-8) shown in the above Reference Example with 10 g of the resin aqueous solution (b-3). This is designated 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 resin for paper coating was obtained by mixing 80 g of the resin aqueous solution (a-6) shown in the above Reference Example with 20 g of the resin aqueous solution (b-9). This is designated 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）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ｅとする。Comparative Example 5 A paper coating resin was obtained 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. This is designated 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〜Ｏ，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），（ｂ−１），（ｂ
−８）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 O and a to e shown in Examples 1 to 15 and Comparative Examples 1 to 5 and Reference Examples 1, 6, 9 and 16 as Comparative Example 7.
Resin (a-1), (a-6), (b-1), (b
-8) was used to prepare the following composition for paper coating, and water was added to make the solid content concentration 50%, and then 30%
The pH was adjusted to 11 with an aqueous sodium hydroxide solution to prepare a paper coating composition. A paper coating composition containing no resin for paper coating (Comparative Example 6) was similarly prepared.
「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） 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 made by Engelhard Minerals, Inc. in the United States) "Carbital 90" 40 parts (Calcium Carbonate manufactured by EC Japan Japan Ltd.) "JSR-0697" 12 parts (Japan Synthetic Rubber) Latex manufactured by Co., Ltd. "MS-4600" 4 parts (Starch manufactured by Nippon Shokuhin Kako Co., Ltd.) 0.2 parts Aron T-40 "Dispersant manufactured by Toagosei Kagaku Kogyo Co., Ltd. 0.5 parts paper coating resin In addition, the above-mentioned "part" shows solid content weight.
この塗工組成物をアプリケーターを使用して坪量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。（耐ブリスター性測定用塗工紙については、片面塗
布後裏面にも同様に塗布した）100℃で１分間熱風乾燥
機中で乾燥させてからロール温度60℃、線圧75Kg／cmな
る条件で２回カレンダー処理を行った。得られた塗工紙
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・ピック等のＲＩ印刷適性試験を行った。Using this applicator, the basis weight is 95 g /
It was coated on one side so that the coating amount was 10 g / m 2 on m 2 base paper. (For coated paper for blister resistance measurement, apply the same on the back side after applying on one side) After drying in a hot air dryer at 100 ° C for 1 minute, roll temperature 60 ° C, linear pressure 75Kg / cm Calendar processing was performed twice. The coated paper obtained is conditioned for 24 hours at 20 ° C and 65% RH (relative humidity), and then the ink acceptability of the coated paper and RI printability test such as wet picking are performed. It was
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、コート面を給
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 acceptability Using an RI printing tester (manufactured by Ming Seisakusho), after moistening the coated surface with a water supply roll, printing is performed, and the acceptability of the ink is observed with the naked eye, and grades ranging from excellent to poor 1 are obtained. It was judged in stages.
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、印刷を行い、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, the coated surface was wetted with a water supply roll, printing was performed, and the peeled state was visually observed, and grades ranging from excellent to inferior 1 were determined stepwise.
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
紙の両面に「ベタ刷り」を行った後、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。Blister resistance A double-sided coated paper was subjected to "solid printing" with the ink for off wheels using a RI printing tester, and then immersed in a thermostatic bath filled with silicone oil for 3 seconds. The blister generation state at this time was visually observed, and grades ranging from excellent to inferior 1 were determined stepwise.
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。Wet Love Coat Approximately 0.1 ml of deionized water was dripped onto the surface of the paper and rubbed with your fingertips for 3, 5, 10, 15 and 20 times, and the elution part according to the number of times became black paper. It was moved, and the amount of elution at that time was visually observed, and water resistance excellent 5 to poor 1 was determined.
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
比べ脂環式アミノ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 acceptability, wet pick, dry pick, blister resistance, and wet rub. In comparison, a comparative example containing neither an alicyclic amino compound nor an alicyclic epoxy compound shows ink acceptability, wet
Inferior to picks, blister resistance and wet rubs.
〔発明の効果〕 以上説明したように、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方又はいずれかに脂環式エポキ
シ化合物又は／及び脂環式アミノ化合物を導入し、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 described above, according to the present invention, a cycloaliphatic epoxy compound or / and a cycloaliphatic amino compound is contained in either or both of a polyamide-urea-aldehyde (epihalohydrin) resin and an amine-epihalohydrin resin. The paper-receiving resin obtained by introducing or reacting the two with each other or by mixing them is used in the paper-coating composition, whereby the ink-receptive property of the coated paper, the wet pick, and the blister resistance ,
The performance of wet rub etc. can be improved in a well-balanced manner, and its industrial effect is great.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 平山 治香 千葉県市原市八幡海岸通17番地２ ディッ ク・ハーキュレス株式会社内 (72)発明者 小保方 隆夫 千葉県市原市八幡海岸通17番地２ ディッ ク・ハーキュレス株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Haruka Hirayama, Inventor Harukares, Ichihara, Ichihara, Chiba 2 2 Dick Hercules Co., Ltd. (72) Takao Obokata, 17 Yawata, Ichihara, Chiba, 2 Ku Hercules Co., Ltd.
Claims (3)
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／および脂環式アミノ化合物
（Ｅ）とホルムアルデヒド（Ｆ１）、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）と脂肪族アミノ化合物
（Ｇ）と（Ｆ２）よりなる反応生成物（III）、上記の
（Ｄ）または／および（Ｅ）と（Ｇ）と（Ｆ２）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（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
（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）の反応によって得られたものは除く）紙塗工用樹
脂。1. A polyalkylene polyamine (A), a dibasic carboxylic acid compound (B), a urea (C), an alicyclic epoxy compound (D) and / or an alicyclic amino compound (E) and formaldehyde. 1 selected from (F 1 ), epihalohydrin (F 2 ) and dialdehydes (F 3 ).
Or a reaction product (I) consisting of two or more kinds (F) or a reaction product (II) consisting of the above (A), (B), (C) and (F). Reaction product (III) consisting of urea-aldehyde (epihalohydrin) resin (a), the above (D) or / and (E), an aliphatic amino compound (G) and (F 2 ), the above (D) Or / and a reaction product (IV) consisting of (E), (G), (F 2 ) and sulfites (H) or / and acids (J), and a reaction consisting of (G) and (F 2 ) above A product (V) and a reaction product (VI) consisting of the above (G), (F 2 ) and (H) or / and (J) selected from the above (III) to (VI) 1 It was obtained by reacting with an amine-epihalohydrin resin (II) consisting of a reaction product of Resins for paper coating (excluding those obtained by the reaction of (II) and (V) and (II) and (VI)).
（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。2. From the mixture of the resin (a) and the resin (b) according to claim 1, except for the reaction products (II) and (V) and the mixture of (II) and (VI). Resin for paper coating.
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。3. The method according to claim 1 or 2 with respect to 100 parts by weight of the pigment.
A paper coating composition containing 0.05 to 5 parts by weight of the paper coating resin described above and 5 to 50 parts by weight of an adhesive (as a solid content).
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 JPH04100996A (en) | 1992-04-02 |
| JPH064958B2 true 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) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ264007A (en) * | 1993-07-16 | 1995-09-26 | Sumitomo Chemical Co | Paper-coating composition comprising an aqueous binder; a water-soluble resin obtained from at least alkylamine and urea; and an amine or a quaternary ammonium salt or a polyamide |
| JPWO2018056459A1 (en) * | 2016-09-26 | 2019-07-04 | 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
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04100996A (en) | 1992-04-02 |
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