JP2013087398A - Resin composition for paper coating - Google Patents
Resin composition for paper coating Download PDFInfo
- Publication number
- JP2013087398A JP2013087398A JP2011231457A JP2011231457A JP2013087398A JP 2013087398 A JP2013087398 A JP 2013087398A JP 2011231457 A JP2011231457 A JP 2011231457A JP 2011231457 A JP2011231457 A JP 2011231457A JP 2013087398 A JP2013087398 A JP 2013087398A
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- JP
- Japan
- Prior art keywords
- resin composition
- parts
- paper coating
- paper
- polycondensate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000011342 resin composition Substances 0.000 title claims abstract description 107
- 238000000576 coating method Methods 0.000 title claims abstract description 95
- 239000011248 coating agent Substances 0.000 title claims abstract description 88
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000004202 carbamide Substances 0.000 claims abstract description 48
- 229920000768 polyamine Polymers 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 15
- 235000013877 carbamide Nutrition 0.000 claims description 63
- 239000007787 solid Substances 0.000 claims description 54
- 150000003672 ureas Chemical class 0.000 claims description 30
- 239000008199 coating composition Substances 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 17
- 239000000049 pigment Substances 0.000 claims description 17
- 150000003951 lactams Chemical class 0.000 claims description 14
- 150000001735 carboxylic acids Chemical class 0.000 claims description 12
- 150000002334 glycols Chemical class 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 72
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 126
- 229920005989 resin Polymers 0.000 description 53
- 239000011347 resin Substances 0.000 description 53
- 230000015572 biosynthetic process Effects 0.000 description 40
- 238000003786 synthesis reaction Methods 0.000 description 40
- 238000004519 manufacturing process Methods 0.000 description 37
- 229920000642 polymer Polymers 0.000 description 30
- 238000010992 reflux Methods 0.000 description 27
- 238000003756 stirring Methods 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 24
- -1 aliphatic alcohols Chemical class 0.000 description 23
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- LWMIDUUVMLBKQF-UHFFFAOYSA-N 4-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound CC1CC=CC2C(=O)OC(=O)C12 LWMIDUUVMLBKQF-UHFFFAOYSA-N 0.000 description 4
- JDBDDNFATWXGQZ-UHFFFAOYSA-N 5-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1=CC(C)CC2C(=O)OC(=O)C12 JDBDDNFATWXGQZ-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000005263 alkylenediamine group Chemical group 0.000 description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 4
- 238000007112 amidation reaction Methods 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 229920006122 polyamide resin Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 229960001124 trientine Drugs 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 229920001281 polyalkylene Polymers 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- TYKJILJOXAHUFO-UHFFFAOYSA-N 2-amino-1,4-dihydroimidazol-5-one Chemical compound NC1=NC(=O)CN1 TYKJILJOXAHUFO-UHFFFAOYSA-N 0.000 description 2
- NNTWKXKLHMTGBU-UHFFFAOYSA-N 4,5-dihydroxyimidazolidin-2-one Chemical compound OC1NC(=O)NC1O NNTWKXKLHMTGBU-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 2
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000001254 oxidized starch Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- 239000003232 water-soluble binding agent Substances 0.000 description 2
- 238000004078 waterproofing Methods 0.000 description 2
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- QXRRAZIZHCWBQY-UHFFFAOYSA-N 1,1-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1(CN=C=O)CCCCC1 QXRRAZIZHCWBQY-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- 229940051269 1,3-dichloro-2-propanol Drugs 0.000 description 1
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-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
- FQUYSHZXSKYCSY-UHFFFAOYSA-N 1,4-diazepane Chemical compound C1CNCCNC1 FQUYSHZXSKYCSY-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- PODSUMUEKRUDEI-UHFFFAOYSA-N 1-(2-aminoethyl)imidazolidin-2-one Chemical compound NCCN1CCNC1=O PODSUMUEKRUDEI-UHFFFAOYSA-N 0.000 description 1
- PWZDJIUQHUGFRJ-UHFFFAOYSA-N 1-(2-chlorophenyl)piperazine Chemical compound ClC1=CC=CC=C1N1CCNCC1 PWZDJIUQHUGFRJ-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 description 1
- KANVKUMQZXAJGG-UHFFFAOYSA-N 1-isocyanato-2-(3-isocyanatopropyl)cyclohexane Chemical compound O=C=NCCCC1CCCCC1N=C=O KANVKUMQZXAJGG-UHFFFAOYSA-N 0.000 description 1
- PKDPUENCROCRCH-UHFFFAOYSA-N 1-piperazin-1-ylethanone Chemical compound CC(=O)N1CCNCC1 PKDPUENCROCRCH-UHFFFAOYSA-N 0.000 description 1
- QLEIDMAURCRVCX-UHFFFAOYSA-N 1-propylpiperazine Chemical compound CCCN1CCNCC1 QLEIDMAURCRVCX-UHFFFAOYSA-N 0.000 description 1
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- XYUINKARGUCCQJ-UHFFFAOYSA-N 3-imino-n-propylpropan-1-amine Chemical compound CCCNCCC=N XYUINKARGUCCQJ-UHFFFAOYSA-N 0.000 description 1
- UIKUBYKUYUSRSM-UHFFFAOYSA-N 3-morpholinopropylamine Chemical compound NCCCN1CCOCC1 UIKUBYKUYUSRSM-UHFFFAOYSA-N 0.000 description 1
- UVLSCMIEPPWCHZ-UHFFFAOYSA-N 3-piperazin-1-ylpropan-1-amine Chemical compound NCCCN1CCNCC1 UVLSCMIEPPWCHZ-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
- SVLTVRFYVWMEQN-UHFFFAOYSA-N 5-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound CC1CC(C(O)=O)C(C(O)=O)C=C1 SVLTVRFYVWMEQN-UHFFFAOYSA-N 0.000 description 1
- GPYZZWFCOCCLQZ-UHFFFAOYSA-N 6-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound CC1CC=CC(C(O)=O)C1C(O)=O GPYZZWFCOCCLQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
- Paper (AREA)
- Polyamides (AREA)
Abstract
Description
本発明は、紙の塗工、特に顔料及び水性バインダーと混合して紙に塗工するのに有用な紙塗工用樹脂組成物、及びそれの紙塗工への適用に関するものである。さらに詳しくは、ホルムアルデヒドの発生がなく、紙に対して優れた耐水性、インキ受理性を付与することができ、かつコスト的に有利となる紙塗工用組成物、及びそれに有用な紙塗工用樹脂組成物を提供しようとするものである。なお、本明細書で用いる「紙」という語は広義の意味であり、狭義の意味でいう紙及び板紙を包含する。 TECHNICAL FIELD The present invention relates to a paper coating resin composition useful for coating paper, in particular, a paper and a pigment and an aqueous binder, and its application to paper coating. More specifically, a paper coating composition that does not generate formaldehyde, can impart excellent water resistance and ink acceptability to paper, and is advantageous in terms of cost, and paper coating useful for it. The resin composition for use is intended to be provided. The term “paper” used in the present specification has a broad meaning, and includes paper and paperboard in a narrow sense.
顔料と水性バインダーを主体とした塗工組成物を紙に塗布し、乾燥、カレンダー処理などの必要な処理を施して得られる塗工紙は、その優れた印刷効果などの特徴から、商業印刷物や雑誌・書籍などに広く用いられているが、品質要求の高度化、印刷の高速化などに伴って、塗工紙の品質改良努力が今もなお続けられている。とりわけ印刷の多くを占めるオフセット印刷においては、湿し水の影響下でのインキ受理性、ウェットピックなどの耐水性、及び輪転印刷での耐ブリスター性の改良・向上が、業界の重要な課題となっている。 A coated paper obtained by applying a coating composition mainly composed of a pigment and a water-based binder to paper and performing necessary treatments such as drying and calendering is used for commercial printed matter and Although it is widely used in magazines and books, efforts to improve the quality of coated paper are still ongoing as quality requirements become higher and printing speeds increase. Particularly in offset printing, which accounts for a large portion of printing, improving and improving ink acceptance under the influence of dampening water, water resistance such as wet pick, and blister resistance in rotary printing are important issues in the industry. It has become.
従来よりこうした課題に対して、メラミン−ホルムアルデヒド樹脂、尿素−ホルムアルデヒド樹脂、ポリアミドポリ尿素−ホルムアルデヒド樹脂（特許文献１）、ブロックグリオキザール樹脂（特許文献２）、アミン−エピハロヒドリン樹脂（特許文献３）、ポリアミドポリ尿素−エピハロヒドリン−ホルムアルデヒド樹脂（特許文献４）など、耐水化剤やバインダー用添加剤として添加する手法が開示されている。しかし、これら従来の耐水化剤やバインダー用添加剤は、最近の品質要求の高度化やそれに伴う配合組成の変化により現在では、一部の特性において重大な欠点又は効果の不十分さが認められることから、実用上必ずしも満足しうるものではない。 Conventionally, in response to such problems, melamine-formaldehyde resin, urea-formaldehyde resin, polyamide polyurea-formaldehyde resin (Patent Document 1), block glyoxal resin (Patent Document 2), amine-epihalohydrin resin (Patent Document 3), polyamide A technique of adding as a water resistance agent or an additive for a binder such as polyurea-epihalohydrin-formaldehyde resin (Patent Document 4) is disclosed. However, these conventional water-proofing agents and additives for binders currently have serious defects or insufficient effects in some properties due to recent sophistication of quality requirements and accompanying changes in formulation composition. Therefore, it is not always satisfactory in practical use.
例えば、メラミン−ホルムアルデヒド樹脂や尿素−ホルムアルデヒド樹脂などのいわゆるアミノプラスト樹脂は、作業時の、あるいは塗工紙からのホルムアルデヒドの発生が多いのみならず、インキ受理性や耐ブリスター性の改良効果がほとんど得られないことや、塗工組成物のｐＨが高くなると耐水化効果も発揮されにくくなることなどの問題がある。またポリアミドポリ尿素-ホルムアルデヒド樹脂はアミノプラスト樹脂同様、作業時の、あるいは塗工紙からのホルムアルデヒドの発生の問題がある。一方、ホルムアルデヒド不含のバインダー用添加剤として知られているブロックグリオキザール樹脂は、湿し水に対する耐水性をある程度付与できるものの、インキ受理性や耐ブリスター性などの塗工紙品質の改良にはほとんど効果がない。また、アミン−エピハロヒドリン樹脂も、耐水性やインキ受理性などの塗工紙品質の改良にあまり有効でないとともに、エピハロヒドリン由来の吸着性有機ハロゲン化合物が存在するため、その使用が差し控えられる傾向にある。 For example, so-called aminoplast resins such as melamine-formaldehyde resin and urea-formaldehyde resin not only generate a lot of formaldehyde during work or from coated paper, but also have an effect of improving ink acceptability and blister resistance. There are problems that it cannot be obtained, and that when the pH of the coating composition is increased, the water resistance effect is hardly exhibited. Polyamide polyurea-formaldehyde resins, like aminoplast resins, have the problem of formaldehyde generation during work or from coated paper. On the other hand, block glyoxal resin, which is known as an additive for formaldehyde-free binder, can give water resistance to fountain solution to some extent, but it is almost impossible to improve coated paper quality such as ink acceptability and blister resistance. has no effect. In addition, amine-epihalohydrin resins are not very effective in improving the quality of coated paper such as water resistance and ink acceptability, and use of epihalohydrin-derived adsorptive organic halogen compounds tends to be withheld.
こういう課題に対して、本発明者らは、先にインキ受理性および耐水性に優れた塗工紙を与える紙塗工用樹脂組成物として、グリコール類と脂環式二塩基性カルボン酸類との反応で得られる重合物、ポリアミン類、尿素類、アルキル化剤を反応せしめてなる樹脂組成物（特許文献５）を提案した。前記樹脂組成物は、従来の塗工用組成物よりはインキ受理性や耐水性が向上しているが、ポリアミン類や脂環式二塩基性カルボン酸類などは他の原料と比較して高価であり、それから成る樹脂組成物も高価なものと成らざるを得なかった。 In response to these problems, the present inventors have previously made glycols and alicyclic dibasic carboxylic acids as a resin composition for paper coating that gives coated paper excellent in ink acceptability and water resistance. A resin composition (Patent Document 5) obtained by reacting a polymer obtained by the reaction, polyamines, ureas, and an alkylating agent has been proposed. The resin composition has improved ink acceptability and water resistance compared to conventional coating compositions, but polyamines and alicyclic dibasic carboxylic acids are more expensive than other raw materials. There is no choice but to make the resin composition made of it expensive.
本発明の目的は、ホルムアルデヒドの発生がなく、優れた耐水性、インキ受理性を有し、かつコスト的に有利な塗工紙を与える紙塗工用樹脂組成物を提供することである。 An object of the present invention is to provide a resin composition for paper coating which does not generate formaldehyde, has excellent water resistance and ink acceptability, and gives a coated paper which is advantageous in terms of cost.
本発明者らは、上記課題を解決すべく鋭意検討した結果、グリコール類（ａ）と、脂環式二塩基性カルボン酸類（ｂ）との反応で得られる遊離カルボキシル基を有する重縮合物（Ａ）に、少なくともポリアミン類（ｃ）、尿素類（ｅ）及び架橋性化合物（ｄ）を反応させ重縮合物（Ｂ）を得て、さらに重縮合物（Ｂ）に他の使用原料よりも安価な尿素類（Ｃ）を添加する事で、尿素類（Ｃ）を添加しない重縮合物（Ｂ）と比較しても紙塗工用樹脂組成物としての性能は低下せず、優れた耐水性、インキ受理性を有する事を見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have found that a polycondensate having a free carboxyl group obtained by the reaction of glycols (a) and alicyclic dibasic carboxylic acids (b) ( A) is reacted with at least polyamines (c), ureas (e) and a crosslinkable compound (d) to obtain a polycondensate (B), and the polycondensate (B) is more than the other raw materials used. By adding inexpensive ureas (C), the performance as a resin composition for paper coating does not deteriorate even when compared with the polycondensate (B) without adding ureas (C), and excellent water resistance And the present invention was completed.
本発明の紙塗工用樹脂組成物は、ホルムアルデヒドの発生がなく、優れた耐水性、インキ受理性を有し、かつ他の使用原料よりも安価な尿素類を添加する事により、それらの性能を低下させず、コスト的に有利な紙塗工用樹脂組成物を提供する事ができる。また、本発明の紙塗工用樹脂組成物は印刷適性向上剤および耐水化剤にも使用し得る。 The resin composition for paper coating of the present invention has no performance of formaldehyde, has excellent water resistance, ink acceptability, and is less expensive than other raw materials used to add performance. Thus, it is possible to provide a resin composition for paper coating that is advantageous in terms of cost. The resin composition for paper coating of the present invention can also be used as a printability improver and a water-proofing agent.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
まず、重縮合物（Ａ）について説明する。
重縮合物（Ａ）に用いられるグリコール類（ａ）とは、分子中に水酸基を少なくとも２ 個有する脂肪族アルコールであり、例えば、エチレングリコール、プロピレングリコール、ブタンジオール等のアルキレングリコール類； ブテンジオール、シクロペンタンジオール、シクロヘキサンジオール等のシクロアルキレングリコール類； オクテンジオール等のアルケニレングリコール類； ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、ポリエチレングリコール、ポリテトラメチレングリコール等のポリアルキレングリコール類； グリセリン、ポリビニルアルコール等のアルキレン基を含有するポリアルキレングリコール； グルコース、フルクトース、マンニット、ソルビット等の糖類；ビスフェノールＡ のエチレンオキシド付加物等が挙げられる。
グリコール類として、２ 種類以上のグリコール類を併用してもよい。
グリコール類としては、中では、アルキレングリコール類、アルケニレングリコール類、
ポリアルキレングリコール類が好ましく、とりわけ、エチレングリコール、ジエチレング
リコール、グリセリンが工業的に有利である。
First, the polycondensate (A) will be described.
The glycols (a) used in the polycondensate (A) are aliphatic alcohols having at least two hydroxyl groups in the molecule, for example, alkylene glycols such as ethylene glycol, propylene glycol, and butanediol; butenediol , Cycloalkylene glycols such as cyclopentanediol and cyclohexanediol; alkenylene glycols such as octenediol; polyalkylene glycols such as diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol and polytetramethylene glycol; glycerin and polyvinyl alcohol Polyalkylene glycols containing alkylene groups such as: sugars such as glucose, fructose, mannitol, sorbit; Examples include adducts of lenoxide.
As glycols, two or more kinds of glycols may be used in combination.
As glycols, among them, alkylene glycols, alkenylene glycols,
Polyalkylene glycols are preferred, and ethylene glycol, diethylene glycol, and glycerin are particularly industrially advantageous.
重縮合物（Ａ）に用いられる脂環式二塩基性カルボン酸類（ｂ）とは、分子中に２ 個のカルボキシル基を有する化合物、それらのエステル類、又は、それらの酸無水物である。具体的には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、３−メチルテトラヒドロフタル酸、４−メチルテトラヒドロフタル酸等のカルボン酸及びこれらのエステル類、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、３−メチルテトラヒドロ無水フタル酸、４−メチルテトラヒドロ無水フタル酸等の酸無水物等が挙げられる。
脂環式二塩基性カルボン酸類（ｂ）として、２種以上の脂環式二塩基性カルボン酸類を用いてもよい。
脂環式二塩基性カルボン酸類（ｂ）としては、中でも、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、３−メチルテトラヒドロ無水フタル酸及び４−メチルテトラヒドロ無水フタル酸が好ましい。
The alicyclic dibasic carboxylic acids (b) used in the polycondensate (A) are compounds having two carboxyl groups in the molecule, esters thereof, or acid anhydrides thereof. Specifically, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane-1,4-dicarboxylic acid, 3-methyltetrahydrophthalic acid, carboxylic acids such as 4-methyltetrahydrophthalic acid and esters thereof, tetrahydrophthalic anhydride, And acid anhydrides such as hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, and the like.
Two or more alicyclic dibasic carboxylic acids may be used as the alicyclic dibasic carboxylic acids (b).
Among the alicyclic dibasic carboxylic acids (b), tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride and 4-methyltetrahydrophthalic anhydride are preferable.
本発明に用いられる重縮合物（Ａ）は、グリコール類（ａ）と脂環式二塩基性カルボン酸類（ｂ）との反応で得られる重縮合物（Ａ）である。
重縮合物（Ａ）の反応に用いられる単量体比率としては、グリコール類（ａ）に含有される水酸基１モルに対して、脂環式二塩基性カルボン酸類（ｂ）の分子数が０．１〜１モル程度、好ましくは０．３〜１．０モルである。
The polycondensate (A) used in the present invention is a polycondensate (A) obtained by the reaction of glycols (a) and alicyclic dibasic carboxylic acids (b).
As a monomer ratio used for the reaction of the polycondensate (A), the number of molecules of the alicyclic dibasic carboxylic acid (b) is 0 with respect to 1 mol of the hydroxyl group contained in the glycol (a). .About 1 to 1 mol, preferably 0.3 to 1.0 mol.
重縮合物（Ａ）の製造方法としては、グリコール類（ａ）と脂環式二塩基性カルボン酸類（ｂ）の反応は脂環式二塩基性カルボン酸類（ｂ）の種類によって、最適な反応温度および反応時間が異なるが、例えば、脂環式二塩基性カルボン酸類（ｂ）がエステルであれば、反応温度８０〜２５０℃で、発生するアルコールを留去しながら、２〜１０時間反応する方法等が挙げられ、脂環式二塩基性カルボン酸類（ｂ）が酸または酸無水物であれば、反応温度５０〜２００℃ で、発生する水を留去しながら、２〜１０時間反応する方法等が挙げられる。 As a method for producing the polycondensate (A), the reaction between the glycols (a) and the alicyclic dibasic carboxylic acids (b) depends on the type of the alicyclic dibasic carboxylic acids (b). For example, if the alicyclic dibasic carboxylic acid (b) is an ester, it reacts at a reaction temperature of 80 to 250 ° C. for 2 to 10 hours while distilling off the generated alcohol. If the alicyclic dibasic carboxylic acid (b) is an acid or an acid anhydride, the reaction is carried out at a reaction temperature of 50 to 200 ° C. for 2 to 10 hours while distilling off the generated water. Methods and the like.
次に、重縮合物（Ａ）に反応させる単量体について説明する。
本発明に用いられるポリアミン類（ｃ）とは、分子中に１ 級アミノ基（−ＮＨ２）又は２
級アミノ基（＝ＮＨ）を少なくとも２個有する脂肪族アミンであり、例えば、アルキレン
ジアミン、ポリアルキレンポリアミン、脂環式ポリアミン、複素環ポリアミン等が挙げら
れる。
Next, the monomer reacted with the polycondensate (A) will be described.
The polyamines (c) used in the present invention are primary amino groups (—NH 2 ) or 2 in the molecule.
It is an aliphatic amine having at least two secondary amino groups (= NH), and examples thereof include alkylene diamine, polyalkylene polyamine, alicyclic polyamine, and heterocyclic polyamine.
ここで、アルキレンジアミンとは、通常、炭素数１〜１０程度のアルキレン基を含有するアルキレンジアミンであり、具体的には、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が例示される。
ポリアルキレンポリアミンとは、アルキレンジアミンを脱アンモニア反応せしめて縮合し
たものであり、具体的には、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、ペンタエチレンヘキサミン、イミノビスプロピルアミン、３−アザヘ
キサン−１，６−ジアミン等が例示される。脂環式ポリアミンとしては、例えば、イソホ
ロンジアミン、ビス（アミノメチル）シクロヘキサン、４，７−ジアザデカン−１，１０
−ジアミンなどが例示される。
Here, the alkylene diamine is usually an alkylene diamine containing an alkylene group having about 1 to 10 carbon atoms, and specific examples include ethylene diamine, propylene diamine, and hexamethylene diamine.
The polyalkylene polyamine is a product obtained by condensing alkylene diamine with deammonia reaction, and specifically, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, iminobispropylamine, 3-azahexane-1 , 6-diamine and the like. Examples of the alicyclic polyamine include isophorone diamine, bis (aminomethyl) cyclohexane, 4,7-diazadecane-1,10.
-A diamine etc. are illustrated.
複素環ポリアミンとは、通常、分子内に、窒素原子、酸素原子、硫黄原子などのヘテロ原
子を少なくとも１ 個含有する脂環式炭化水素基である複素環を含み、かつ、１級アミノ基及び／ 又は２級アミノ基を少なくとも２ 個有するアミンのことである。具体的には、ピペラジン、ホモピペラジン、Ｎ−メチルピペラジン、Ｎ−エチルピペラジン、Ｎ−プロピルピペラジン、Ｎ−アセチルピペラジン及び１−（クロロフェニル）ピペラジン等のような複素環ジアミン類；Ｎ−アミノエチルピペリジン、Ｎ−アミノプロピルピペリジン、Ｎ−アミノエチルピペラジン、Ｎ−アミノプロピルピペラジン、Ｎ−アミノエチルモルホリン、Ｎ−アミノプロピルモルホリン、Ｎ−アミノプロピル−２−ピペコリン、Ｎ−アミノプロピル−４−ピペコリン及び１，４−ビス（アミノプロピル）ピペラジンのようなアミノアルキルを含有した複素環アミンなどが例示される。
The heterocyclic polyamine usually includes a heterocyclic ring which is an alicyclic hydrocarbon group containing at least one hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom in the molecule, and a primary amino group and / Or an amine having at least two secondary amino groups. Specifically, heterocyclic diamines such as piperazine, homopiperazine, N-methylpiperazine, N-ethylpiperazine, N-propylpiperazine, N-acetylpiperazine and 1- (chlorophenyl) piperazine; N-aminoethylpiperidine N-aminopropylpiperidine, N-aminoethylpiperazine, N-aminopropylpiperazine, N-aminoethylmorpholine, N-aminopropylmorpholine, N-aminopropyl-2-pipecholine, N-aminopropyl-4-pipecholine and 1 And heterocyclic amines containing aminoalkyl such as 1,4-bis (aminopropyl) piperazine.
ポリアミン類（ｃ）として、異なる２種以上のポリアミン類を用いてもよい。ポリアミン
類（ｃ）の中でも、ポリアルキレンポリアミンが好ましく、とりわけ、ジエチレントリア
ミン、トリエチレンテトラミンが好適である。
Two or more different polyamines may be used as the polyamines (c). Among the polyamines (c), polyalkylene polyamines are preferable, and diethylenetriamine and triethylenetetramine are particularly preferable.
本発明に用いられる尿素類（ｄ）の具体例としては、尿素、メチル尿素、ジメチル尿素、チオ尿素、４，５−ジヒドロキシ−２−イミダゾリジノン、１−（２−アミノエチル）−２−イミダゾリジノン等が挙げられるが、工業的には尿素が有利である。 Specific examples of ureas (d) used in the present invention include urea, methylurea, dimethylurea, thiourea, 4,5-dihydroxy-2-imidazolidinone, 1- (2-aminoethyl) -2- Although imidazolidinone and the like are mentioned, urea is advantageous industrially.
本発明に用いられる架橋性化合物（ｅ）とは、エピハロヒドリン類、モノハロヒドリン類、α，γ−ジハロ−β−ヒドリン類、グリシジル化合物又はイソシアネート類等が挙げられる。架橋性化合物（ｅ）のうちのエピハロヒドリン類は、次の式（１）で示される。 Examples of the crosslinkable compound (e) used in the present invention include epihalohydrins, monohalohydrins, α, γ-dihalo-β-hydrins, glycidyl compounds or isocyanates. Epihalohydrins in the crosslinkable compound (e) are represented by the following formula (1).
エピハロヒドリン類としては、例えば、エピクロロヒドリン、エピブロモヒドリンなどが挙げられる。
架橋性化合物（ｅ）のうちのモノハロヒドリン類は、式（２）
Examples of epihalohydrins include epichlorohydrin and epibromohydrin.
The monohalohydrins in the crosslinkable compound (e) are represented by the formula (2)
モノハロヒドリンとしては、例えば、エチレンクロロヒドリン、エチレンブロモヒドリン等が挙げられる。 Examples of the monohalohydrin include ethylene chlorohydrin and ethylene bromohydrin.
架橋性化合物（ｅ）のうちのα，γ−ジハロ−β−ヒドリン類は、式（３） Among the crosslinkable compounds (e), α, γ-dihalo-β-hydrins are represented by the formula (3).
かかるα，γ−ジハロ−β−ヒドリン類としては、例えば１，３−ジクロロ−２−プロパノールなどが挙げられる。 Examples of such α, γ-dihalo-β-hydrins include 1,3-dichloro-2-propanol.
架橋性化合物（ｅ）のうちのグリシジル化合物は通常、分子内にグリシジル基を少なくとも２個有するものである。その具体例としては、エチレングリコールジグリシジルエーテルやプロピレングリコールジグリシジルエーテルのようなアルキレングリコールジグリシジルエーテル類、ポリエチレングリコールジグリシジルエーテルやポリプロピレングリコールジグリシジルエーテルのようなポリオキシアルキレングリコールジグリシジルエーテル類、レゾルシンジグリシジルエーテルやビスフェノールＡジグリシジルエーテルのような芳香族ジグリシジルエーテル類、トリメチロールプロパンジ−又はトリ−グリシジルエーテル、ソルビトールジ−、トリ−、テトラ−、ペンタ−又はヘキサ−グリシジルエーテル、ペンタエリスリトールジ−、トリ−又はテトラ−グリシジルエーテルなどが挙げられる。 The glycidyl compound in the crosslinkable compound (e) usually has at least two glycidyl groups in the molecule. Specific examples thereof include alkylene glycol diglycidyl ethers such as ethylene glycol diglycidyl ether and propylene glycol diglycidyl ether, polyoxyalkylene glycol diglycidyl ethers such as polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether, Aromatic diglycidyl ethers such as resorcin diglycidyl ether and bisphenol A diglycidyl ether, trimethylolpropane di- or tri-glycidyl ether, sorbitol di-, tri-, tetra-, penta- or hexa-glycidyl ether, penta And erythritol di-, tri- or tetra-glycidyl ether.
架橋性化合物（ｅ）のうちのイソシアネート類は通常、分子内にイソシアナト基を少なくとも２個有するものである。その具体例としては、イソホロンジイソシアネート、３−（２−イソシアナトシクロヘキシル）プロピルイソシアネート、ビス（イソシアナトメチル）シクロヘキサン、イソプロピリデンビス（シクロヘキシルイソシアネート）、トランスシクロヘキサン−１，４−ジイソシアネート、ビシクロヘプタントリイソシアネートのような脂環式イソシアネート類、ヘキサメチレンジイソシアネート、トリメチルヘキサン−１，６−ジイソシアネート、２，６−ジイソシアナトヘキサン酸メチル（リジンジイソシアネートとも呼ばれる）のような脂肪族イソシアネート類及び、トリレンジイソシアネート、トリフェニルメタントリイソシアネート、トリス（イソシアナトフェニル）チオフォスフェート、フェニレンジイソシアネート、ジアニシジンジイソシアネート、ジフェニルエーテルジイソシアネートのような芳香族イソシアネート類が挙げられる。 Of the crosslinkable compounds (e), the isocyanates usually have at least two isocyanato groups in the molecule. Specific examples thereof include isophorone diisocyanate, 3- (2-isocyanatocyclohexyl) propyl isocyanate, bis (isocyanatomethyl) cyclohexane, isopropylidenebis (cyclohexyl isocyanate), transcyclohexane-1,4-diisocyanate, and bicycloheptane triisocyanate. Aliphatic isocyanates such as hexamethylene diisocyanate, trimethylhexane-1,6-diisocyanate, aliphatic isocyanates such as methyl 2,6-diisocyanatohexanoate (also called lysine diisocyanate), and tolylene diisocyanate , Triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, phenylene diisocyanate, dianisidine Isocyanates, aromatic isocyanates such as diphenyl ether diisocyanate.
これらの架橋性化合物（ｅ）は、それぞれ単独で、又は２種以上組み合わせて用いることができる。もちろん、エピハロヒドリン類、α，γ−ジハロ−β−ヒドリン類、グリシジル化合物及びイソシアネート類のうちで、異なる種類に属するものを２種以上併用することもできる。中でもエピハロヒドリン類、及びα，γ−ジハロ−β−ヒドリン類が工業的に好ましく、とりわけエピハロヒドリン類、この中でもエピクロロヒドリン、エピブロモヒドリンが好適である。 These crosslinkable compounds (e) can be used alone or in combination of two or more. Of course, among epihalohydrins, α, γ-dihalo-β-hydrins, glycidyl compounds and isocyanates, two or more of those belonging to different types can be used in combination. Of these, epihalohydrins and α, γ-dihalo-β-hydrins are industrially preferable, and epihalohydrins are particularly preferable, and epichlorohydrin and epibromohydrin are particularly preferable.
本発明の重縮合物（Ｂ）の合成に用いられるポリアミン類（ｃ）は、重縮合物（Ａ）の酸価１モルに対して、通常１モルよりも多く、５モル以下、好ましくは１モルよりも多く、３モル以下使用される。ここで、重縮合物（Ａ）の酸価とは、重縮合物に含まれる遊離カルボキシル基の当量数である。ポリアミン類（ｃ）が重縮合物（Ａ）の酸価よりも過剰に使用することから、本発明の重縮合物（Ｂ）は、重縮合物（Ａ）を構成成分として含有する樹脂と、重縮合物（Ａ）を構成成分として含有しない樹脂との組成物となっている。 The polyamines (c) used in the synthesis of the polycondensate (B) of the present invention are usually more than 1 mol and 5 mol or less, preferably 1 with respect to 1 mol of the acid value of the polycondensate (A). More than 3 moles and less than 3 moles are used. Here, the acid value of the polycondensate (A) is the number of equivalents of free carboxyl groups contained in the polycondensate. Since polyamines (c) are used in excess of the acid value of the polycondensate (A), the polycondensate (B) of the present invention comprises a resin containing the polycondensate (A) as a constituent component, It is a composition with resin which does not contain a polycondensate (A) as a structural component.
本発明の重縮合物（Ｂ）の合成に用いられる尿素類（ｄ）は、ポリアミン類（ｃ）に含まれる１級アミノ基と２級アミノ基のそれぞれの物質量合計１モルに対して、通常、０．１〜１．０モル程度であり、好ましくは、０．３〜０．８モルである。
また、架橋性化合物（ｅ）の使用量としては、ポリアミン類（ｃ）１モルに対して、通常、０．１〜１．５モル程度、好ましくは０．２〜１．０モルである。
The ureas (d) used for the synthesis of the polycondensate (B) of the present invention are based on a total of 1 mol of each of the primary amino groups and secondary amino groups contained in the polyamines (c). Usually, it is about 0.1-1.0 mol, Preferably, it is 0.3-0.8 mol.
Moreover, as the usage-amount of a crosslinkable compound (e), it is about 0.1-1.5 mol normally with respect to 1 mol of polyamines (c), Preferably it is 0.2-1.0 mol.
本発明の重縮合物（Ｂ）は、重縮合物（Ａ）に、ポリアミン類（ｃ）、尿素類（ｄ）及び架橋性化合物（ｅ）を重縮合させた物であり、必要に応じて（ｃ）〜（ｅ）の単量体と共に、脂肪族カルボン酸類（ｆ）及び／ 又はラクタム類（ｇ）を重縮合させてもよい。 The polycondensate (B) of the present invention is a product obtained by polycondensation of polyamines (c), ureas (d) and a crosslinkable compound (e) to the polycondensate (A). The aliphatic carboxylic acids (f) and / or lactams (g) may be polycondensed together with the monomers (c) to (e).
脂肪族カルボン酸類（ｆ）を用いる場合、その使用量としては、ポリアミン類（ｃ）１ モルに対して、通常、０．０１〜０．５モル程度、好ましくは０．０５〜０．３モルである。また、ラクタム類（ｇ）を用いる場合、その使用量としては、ポリアミン類（ｃ）１モルに対して、通常、０．０１〜２モル程度、好ましくは０．０２〜１．２モルである。 When using aliphatic carboxylic acids (f), the amount used is usually about 0.01 to 0.5 mol, preferably 0.05 to 0.3 mol, per 1 mol of polyamines (c). It is. Moreover, when using lactam (g), as the usage-amount, it is about 0.01-2 mol normally with respect to 1 mol of polyamines (c), Preferably it is 0.02-1.2 mol. .
ここで、脂肪族カルボン酸類（ｆ）とは、モノカルボン酸、ポリカルボン酸、これらのエステル、これらの無水物である。
具体的には、例えば、酢酸、プロピオン酸、酪酸、吉草酸、オクタン酸、２−エチルヘキサン酸、ノナン酸、ラウリン酸、ミスチリン酸、パルミチン酸、ステアリン酸、リノール酸等の脂肪族モノカルボン酸； マロン酸、マレイン酸、フマル酸、コハク酸、アジピン酸、アゼライン酸、スベリン酸等の脂肪族ジカルボン酸； ブタンテトラカルボン酸等の脂肪族ポリカルボン酸等が挙げられ、カルボン酸エステルとしては、前記脂肪族モノカルボン酸、脂肪族ジカルボン酸あるいは脂肪族ポリカルボン酸と、メタノールあるいはエタノール等の低級アルコールとのエステルが挙げられる。さらに、カルボン酸無水物としては、例えば、無水酢酸、無水コハク酸、無水マレイン酸、無水アジピン酸等が挙げられる。
脂肪族カルボン酸類（ｆ）として、２種以上の脂肪族カルボン酸類を用いてもよい。
脂肪族カルボン酸類（ｆ）としては、中でも、酢酸、プロピオン酸、酪酸、吉草酸、オクタン酸、２−エチルヘキサン酸、ノナン酸等の炭素数１０以下の脂肪族カルボン酸が挙げられる。
Here, the aliphatic carboxylic acids (f) are monocarboxylic acids, polycarboxylic acids, esters thereof, and anhydrides thereof.
Specifically, for example, aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, lauric acid, myristylic acid, palmitic acid, stearic acid, linoleic acid, etc. Aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, adipic acid, azelaic acid, and suberic acid; and aliphatic polycarboxylic acids such as butanetetracarboxylic acid; Examples thereof include esters of the aliphatic monocarboxylic acid, aliphatic dicarboxylic acid or aliphatic polycarboxylic acid with a lower alcohol such as methanol or ethanol. Furthermore, examples of the carboxylic acid anhydride include acetic anhydride, succinic anhydride, maleic anhydride, and adipic anhydride.
As the aliphatic carboxylic acids (f), two or more aliphatic carboxylic acids may be used.
Examples of the aliphatic carboxylic acids (f) include aliphatic carboxylic acids having 10 or less carbon atoms such as acetic acid, propionic acid, butyric acid, valeric acid, octanoic acid, 2-ethylhexanoic acid, and nonanoic acid.
ラクタム類（ｇ）としては、例えば、γ−ラクタム、δ−ラクタム、ε−カプロラクタム
、ラウリルラクタム、グリコシアミジン、オキシドール、イサチン等が挙げられるが、工
業的にはε−カプロラクタムが有利である。
Examples of the lactams (g) include γ-lactam, δ-lactam, ε-caprolactam, lauryl lactam, glycocyanidine, oxidol, and isatin. Industrially, ε-caprolactam is advantageous.
本発明の重縮合物（Ｂ）の製造方法としては、例えば（ア）重縮合物（Ａ）とポリアミン類（ｃ）をアミド化反応させたのち水で希釈し、さらに尿素類（ｄ）と脱アンモニア反応をさせた後、架橋性化合物（ｅ）と反応をさせる方法；（イ）重縮合物（Ａ）とポリアミン類（ｃ）をアミド化反応させたのち水で希釈し、さらに架橋性化合物（ｅ）と反応させた後、尿素類（ｄ）と脱アンモニア反応をさせる方法；（ウ）重縮合物（Ａ）とポリアミン類（ｃ）及び脂肪族カルボン酸類（ｆ）をアミド化反応させたのち水で希釈し、さらに尿素類（ｄ）と脱アンモニア反応をさせた後、架橋性化合物（ｅ）と反応をさせる方法；（エ）あらかじめ、（ｃ）〜（ｅ）と、必要により（ｆ）及び／ 又は（ｇ）と重縮合させて得られた重縮合物（Ｄ）を予め製造し、別途、得られた重縮合物（Ａ）と重縮合物（Ｄ）とを混合した後、アミド化反応をさせる方法；（オ）重縮合物（Ａ）にポリアミン類（ｃ）と脂肪族カルボン酸類（ｆ）とラクタム類（ｇ）とを同時に重縮合させたのち水で希釈し、続いて、尿素類（ｄ）と脱アンモニア反応をさせた後、架橋性化合物（ｅ）を反応させる方法；（カ）重縮合物（Ａ）にポリアミン類（ｃ）と脂肪族カルボン酸類（ｆ）とラクタム類（ｇ）とを同時に重縮合させたのち水で希釈し、続いて、架橋性化合物（ｅ）を反応させたのち、尿素類（ｄ）と脱アンモニア反応をさせる方法；（キ）重縮合物（Ａ）と（ｃ）〜（ｅ）と、必要により（ｆ）及び／ 又は（ｇ）を同時に反応させ、アミド化反応と脱アンモニア反応と架橋反応を同時にさせる方法などが挙げられる。 As a method for producing the polycondensate (B) of the present invention, for example, (a) the polycondensate (A) and the polyamines (c) are amidated, diluted with water, and further ureas (d) and A method of reacting with the crosslinkable compound (e) after deammonia reaction; (a) The polycondensate (A) and the polyamines (c) are amidated, diluted with water, and further crosslinked. Method of reacting with compound (e) and then deammonia reaction with urea (d); (c) Amidation reaction of polycondensate (A) with polyamines (c) and aliphatic carboxylic acids (f) And then diluting with water and further deammonia reaction with urea (d), followed by reaction with crosslinkable compound (e); (e) In advance, (c) to (e), necessary The polycondensate (D) obtained by polycondensation with (f) and / or (g) by A method in which the polycondensate (A) and the polycondensate (D) obtained separately are mixed and then subjected to an amidation reaction; (e) a polyamine (c) is added to the polycondensate (A). And aliphatic carboxylic acids (f) and lactams (g) are simultaneously polycondensed and diluted with water, followed by deammonia reaction with ureas (d), and then a crosslinkable compound (e) (F) polycondensate (A), polyamines (c), aliphatic carboxylic acids (f) and lactams (g) are simultaneously polycondensed and diluted with water, A method of reacting the crosslinkable compound (e) and then deammonia with the urea (d); (g) polycondensates (A) and (c) to (e), and (f) and / Or And so on.
グリコール類（ａ）と脂環式二塩基性カルボン酸類（ｂ）との反応で得られる遊離カルボキシル基を有する重縮合物（Ａ）とポリアミン類（ｃ）との反応は、重縮合物（Ａ）の種類によって反応温度および反応時間が異なるが、例えば、重縮合物（Ａ）とポリアミン類（ｃ）とをアミド化反応させる場合、通常、１３０〜２５０℃程度、好ましくは１３０〜１６０℃で、発生する水等を留去しながら、２〜１０時間程度、好ましくは３〜５時間反応する方法等が挙げられる。 The reaction of the polycondensate (A) having a free carboxyl group obtained by the reaction of the glycols (a) with the alicyclic dibasic carboxylic acid (b) and the polyamines (c) is carried out by the polycondensate (A The reaction temperature and reaction time vary depending on the type of the above), but, for example, when the polycondensation product (A) and the polyamines (c) are subjected to an amidation reaction, the reaction temperature is usually about 130 to 250 ° C, preferably 130 to 160 ° C. And a method of reacting for about 2 to 10 hours, preferably 3 to 5 hours while distilling off generated water and the like.
ポリアミン類（ｃ）のアミノ基と尿素類（ｄ）との脱アンモニア反応は、通常、８０〜１８０℃程度、好ましくは９０〜１６０℃で、発生するアンモニアを留去しながら４〜３０時間程度、好ましくは５〜２０時間反応させる方法等が挙げられる。 The deammonia reaction between the amino group of the polyamines (c) and the ureas (d) is usually about 80 to 180 ° C., preferably 90 to 160 ° C., and the generated ammonia is distilled off for about 4 to 30 hours. Preferably, a method of reacting for 5 to 20 hours is used.
ポリアミン類（ｃ）のアミノ基と架橋性化合物との反応（ｅ）は、通常、３０〜１２０℃程度、好ましくは５０〜１００℃にて１〜２０時間程度、好ましくは２〜１０時間反応させる方法等が挙げられる。 The reaction (e) between the amino group of the polyamines (c) and the crosslinkable compound is usually about 30 to 120 ° C., preferably 50 to 100 ° C. for about 1 to 20 hours, preferably 2 to 10 hours. Methods and the like.
脂肪族カルボン酸類（ｆ）を用いる場合、ポリアミン類（ｃ）と脂肪族カルボン酸類（ｆ）とのアミド化反応は、通常、１３０〜２５０℃程度、好ましくは１３０〜１６０℃で、発生する水等を留去しながら、２〜１０時間程度、好ましくは３〜５時間反応する方法等が挙げられる。 When the aliphatic carboxylic acid (f) is used, the amidation reaction between the polyamine (c) and the aliphatic carboxylic acid (f) is usually about 130 to 250 ° C, preferably 130 to 160 ° C. For example, a method of reacting for about 2 to 10 hours, preferably 3 to 5 hours while distilling off and the like.
ラクタム類（ｇ）を用いる場合、ポリアミン類（ｃ）とラクタム類（ｇ）との開環付加反応は、通常、１３０〜２５０℃程度、好ましくは１３０〜１６０℃で、２〜１０時間程度、好ましくは３〜５時間反応する方法等が挙げられる。 When using the lactams (g), the ring-opening addition reaction between the polyamines (c) and the lactams (g) is usually about 130 to 250 ° C., preferably 130 to 160 ° C. for about 2 to 10 hours, Preferably, a method of reacting for 3 to 5 hours, and the like are included.
このようにして得られた重縮合物（Ｂ）は、必要に応じて、リン酸、硫酸、塩酸、硝酸などの無機酸や、蟻酸、酢酸、プロピオン酸、アジピン酸などの有機酸を用いて、ｐＨ６〜１０程度に調整してもよい。
その後、得られた重縮合物（Ｂ）は、尿素類（Ｃ）の添加に供される。
The polycondensate (B) thus obtained is obtained by using an inorganic acid such as phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid, or an organic acid such as formic acid, acetic acid, propionic acid or adipic acid as necessary. The pH may be adjusted to about 6 to 10.
Thereafter, the obtained polycondensate (B) is subjected to addition of ureas (C).
重縮合物（Ｂ）に添加される尿素類（Ｃ）の具体例としては、尿素、メチル尿素、ジメチル尿素、チオ尿素、４，５−ジヒドロキシ−２−イミダゾリジノン、１−（２−アミノエチル）−２−イミダゾリジノン等が挙げられるが、工業的には尿素が有利である。 Specific examples of ureas (C) added to the polycondensate (B) include urea, methylurea, dimethylurea, thiourea, 4,5-dihydroxy-2-imidazolidinone, 1- (2-amino Ethyl) -2-imidazolidinone and the like, and urea is advantageous industrially.
添加される尿素類（Ｃ）の重量比は、重縮合物（Ｂ）の固形分換算量に対して、１〜３０重量％、好ましくは２．５〜２０重量％である。１重量％未満であると、経済的な効果が少なく、本発明の効果が十分ではない。３０重量％より多いと、経済的な効果は大きいものの、温度によっては尿素類が完全に溶解しない、もしくは低温で尿素が析出するなど、低温での安定性が悪化する可能性がある。 The weight ratio of the ureas (C) to be added is 1 to 30% by weight, preferably 2.5 to 20% by weight with respect to the solid content converted amount of the polycondensate (B). If it is less than 1% by weight, the economic effect is small and the effect of the present invention is not sufficient. If the amount is more than 30% by weight, the economic effect is great, but depending on the temperature, the ureas may not be completely dissolved, or urea may precipitate at low temperatures, which may deteriorate the stability at low temperatures.
添加方法に関しては、特に限定される事はなく、例えば、重縮合物（Ｂ）に直接、尿素類（Ｃ）を添加する方法や、予め尿素類（Ｃ）を溶解した溶液を調整し、重縮合物（Ｂ）に添加する方法等が挙げられる。
また、尿素類（Ｃ）が低温で析出しないよう、添加前後に任意の濃度へ調整する事も可能である。
The addition method is not particularly limited. For example, a method in which ureas (C) are directly added to the polycondensate (B) or a solution in which ureas (C) are dissolved in advance is prepared, Examples include a method of adding to the condensate (B).
Moreover, it is also possible to adjust to arbitrary density | concentrations before and behind addition so that urea (C) may not precipitate at low temperature.
尿素類（Ｃ）もしくは尿素類（Ｃ）の溶解液を重縮合物（Ｂ）へ添加し、本発明の紙塗工用樹脂組成物を得る際、通常、１０〜８０℃程度、好ましくは３０〜６０℃で、０．５〜１０時間程度、好ましくは１〜３時間攪拌、混合が行われる。 When the urea (C) or urea (C) solution is added to the polycondensate (B) to obtain the resin composition for paper coating of the present invention, usually about 10 to 80 ° C., preferably 30 The mixture is stirred and mixed at -60 ° C for about 0.5 to 10 hours, preferably 1 to 3 hours.
このようにして得られた紙塗工用樹脂組成物は通常、水溶液であり、固形分１０〜７５％程度、好ましくは４０〜６５％に調整される。 The resin composition for paper coating thus obtained is usually an aqueous solution and is adjusted to a solid content of about 10 to 75%, preferably 40 to 65%.
かくして得られた紙塗工用樹脂組成物は、顔料および水性バインダーとともに紙用塗工組成物として調整される。ここで、顔料としては、例えば、白色無機顔料、白色有機顔料などが挙げられる。白色無機顔料の具体例としては、カオリン、タルク、炭酸カルシウム（重質又は軽質）、水酸化アルミニウム、サチンホワイト、酸化チタンなどが挙げられる。また白色有機顔料の具体例としては、例えば、ポリスチレン、メラミン−ホルムアルデヒド樹脂、尿素−ホルムアルデヒド樹脂などが挙げられる。顔料として、２種類以上の顔料を使用してもよい。 The resin composition for paper coating thus obtained is prepared as a paper coating composition together with a pigment and an aqueous binder. Here, examples of the pigment include white inorganic pigments and white organic pigments. Specific examples of the white inorganic pigment include kaolin, talc, calcium carbonate (heavy or light), aluminum hydroxide, satin white, titanium oxide, and the like. Specific examples of the white organic pigment include polystyrene, melamine-formaldehyde resin, urea-formaldehyde resin, and the like. Two or more types of pigments may be used as the pigment.
水性バインダーとしては、例えば、水溶性バインダー、水乳化系バインダーなどが挙げられる。水溶性バインダーの具体例としては、酸化でんぷん、無変性でんぷん、リン酸エステルなどで変性されたでんぷん等のでんぷん類；カゼイン、ゼラチンなどの水溶性プロテイン；カルボキシメチルセルロースなどの変性セルロース類；部分または完全けん化されたポリビニルアルコール、変性ポリビニルアルコール等が挙げられる。水乳化系バインダーの具体例としては、カルボキシル基やニトリル基を有することもあるスチレン−ブタジエン系樹脂（ＳＢＲラテックス）、アクリロニトリル−ブタジエン系樹脂（ＮＢＲラテックス）、クロロプレン系樹脂（ＣＲラテックス）、メチルメタクリレート−ブタジエン系樹脂（ＭＢＲラテックス）、アクリル系モノマー２種以上の共重合樹脂、アクリル系モノマーと酢酸ビニルとの共重合樹脂、アクリル系モノマーとスチレンとの共重合樹脂、酢酸ビニル樹脂、スチレン−酢酸ビニル樹脂、エチレン−酢酸ビニル樹脂などが挙げられる。水性バインダーとして、２種類以上の異なる水性バインダーを使用しても良い。 Examples of the aqueous binder include a water-soluble binder and a water-emulsified binder. Specific examples of the water-soluble binder include starches such as starch modified with oxidized starch, non-denatured starch and phosphate ester; water-soluble proteins such as casein and gelatin; modified celluloses such as carboxymethyl cellulose; partially or completely Examples thereof include saponified polyvinyl alcohol and modified polyvinyl alcohol. Specific examples of water-emulsifying binders include styrene-butadiene resins (SBR latex), acrylonitrile-butadiene resins (NBR latex), chloroprene resins (CR latex), and methyl methacrylate, which may have carboxyl groups or nitrile groups. -Butadiene resin (MBR latex), copolymer resin of two or more acrylic monomers, copolymer resin of acrylic monomers and vinyl acetate, copolymer resin of acrylic monomers and styrene, vinyl acetate resin, styrene-acetic acid Examples thereof include vinyl resins and ethylene-vinyl acetate resins. Two or more different aqueous binders may be used as the aqueous binder.
本発明の紙用塗工組成物における顔料、水性バインダー（固形分）および紙塗工用樹脂（固形分）の重量比率としては、通常、顔料１００重量部に対して、水性バインダーが１〜２００重量部程度、とりわけ好ましくは５〜５０重量部であり、紙塗工用樹脂組成物が０.０１〜５重量部程度、とりわけ好ましくは、０.０５〜２重量部である。 The weight ratio of the pigment, the aqueous binder (solid content) and the paper coating resin (solid content) in the paper coating composition of the present invention is usually 1 to 200 based on 100 parts by weight of the pigment. About 5 parts by weight, particularly preferably 5 to 50 parts by weight, and the resin composition for paper coating is about 0.01 to 5 parts by weight, and particularly preferably 0.05 to 2 parts by weight.
紙用塗工組成物を調製するにあたり、顔料、水性バインダー及び樹脂組成物の添加混合順序は任意であり、特に制限されない。例えば、樹脂組成物を顔料及び水性バインダーの混合物に添加混合する方法、樹脂組成物を予め顔料又は水性バインダーに添加混合しておき、これを残りの成分と配合する方法などが採用できる。 In preparing the paper coating composition, the order of addition and mixing of the pigment, the aqueous binder and the resin composition is arbitrary and is not particularly limited. For example, a method of adding and mixing a resin composition to a mixture of a pigment and an aqueous binder, a method of adding and mixing a resin composition in advance to a pigment or an aqueous binder, and blending it with the remaining components can be employed.
さらに、塗工組成物に、例えば、アロンＴ−４０（東亞合成社製）、スミレーズレジンＤＳ-１０（住友化学社製）などの分散剤、粘度・流動性調整剤、消泡剤、防腐剤、潤滑剤、保水剤、染料・有色顔料等の着色剤、ならびに、本発明の紙塗工用樹脂とは異なる印刷適性向上剤および耐水化剤などを含有せしめてもよい。 Furthermore, the coating composition includes, for example, a dispersant such as Aron T-40 (manufactured by Toagosei Co., Ltd.), Sumirez Resin DS-10 (manufactured by Sumitomo Chemical Co., Ltd.), viscosity / fluidity modifier, antifoaming agent, antiseptic A colorant such as an agent, a lubricant, a water retention agent, a dye or a colored pigment, and a printability improver and a water resistance agent different from the paper coating resin of the present invention may be contained.
本発明の塗工紙とは、前記紙塗工用組成物を片面または両面に含有する紙である。紙の製造方法としては、例えば、製紙科学（中外産業調査会発行（１９８２））、Ｐｕｌｐ ａｎｄ Ｐａｐｅｒ:Ｃｈｅｍｉｓｔｒｙ ａｎｄ Ｃｈｅｍｉｃａｌ Ｔｅｃｈｎｏｌｏｇｙ、 Ｖｏｌ．ＩＩ、 Ｊｏｈｎ Ｗｉｌｅｙ ＆ａｍｐ; Ｓｏｎｓ （１９８０）などに記載の方法により、化学パルプ、機械パルプ、故紙パルプなどを抄紙する方法などが挙げられる。本発明に用いられる紙に、必要により、填料、サイジング剤、バンド剤、紙力増強剤、染料などの添加剤を含有せしめた紙であってもよい。なお、本発明の紙とは広義の意味であって、狭義の意味でいう紙のほか、いわゆる板紙をも包含する。 The coated paper of the present invention is paper containing the paper coating composition on one side or both sides. Examples of paper manufacturing methods include papermaking science (published by Chugai Industry Research Council (1982)), Pulp and Paper: Chemistry and Chemical Technology, Vol. II, John Wiley & Sons (1980) and the like, and methods such as chemical pulping, mechanical pulping, waste paper pulping, and the like. The paper used in the present invention may be paper in which additives such as a filler, a sizing agent, a banding agent, a paper strength enhancer, and a dye are added as necessary. In addition, the paper of the present invention has a broad meaning, and includes so-called paperboard in addition to paper in a narrow sense.
本発明の塗工紙の製造方法としては、例えば、紙に塗工組成物を１回塗工する方法、塗工組成物の配合比率が同じまたは異なる塗工組成物を複数回塗工する方法などが挙げられる。ここで、塗工方法としては、例えば、ブレードコーター、エアーナイフコーター、バーコーター、サイズプレスコーター、ゲートロールコーター、キャストコーターなどのコーターを用いて塗工組成物を塗工原紙に塗布し、その後、必要な乾燥を行い、さらに必要に応じてスーパーカレンダーなどで平滑化処理を施す方法などが挙げられる。 Examples of the method for producing the coated paper of the present invention include, for example, a method in which a coating composition is applied to paper once, and a method in which a coating composition having the same or different blending ratio is applied multiple times. Etc. Here, as a coating method, for example, a coating composition is applied to a coating base paper using a coater such as a blade coater, an air knife coater, a bar coater, a size press coater, a gate roll coater, or a cast coater, and then And a method of performing necessary drying and further performing a smoothing treatment with a super calender or the like, if necessary.
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれらによって限定される物ではない。例中、部および％は、特に断わらないかぎり重量基準である。また、固形分は、ＪＩＳ Ｋ６８２８の４．９に準じて乾燥することにより求めた蒸発残分であり、ｐＨは、ガラス電極式水素イオン濃度計〔東亜電波工業社製〕を用い、調製直後の試料のｐＨを２５℃にて測定した値であり、粘度は、Ｂ型粘度計〔東京計器社製、ＢＬ型〕を用い、６０rpm 、２５℃で、調製直後の塗工組成物の粘度を測定した値である。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not a thing limited by these. In the examples, parts and% are based on weight unless otherwise specified. Moreover, solid content is the evaporation residue calculated | required by drying according to 4.9 of JISK6828, pH uses a glass electrode type hydrogen ion concentration meter (made by Toa Denpa Kogyo Co., Ltd.), and immediately after preparation. The pH of the sample was measured at 25 ° C., and the viscosity was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd., BL type) at 60 rpm and 25 ° C. to measure the viscosity of the coating composition immediately after preparation. It is the value.
＜製造例１＞
＜重合物（Ａ）の製造例１：樹脂１−１の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、３−メチルテトラヒドロ無水フタル酸および４−メチルテトラヒドロ無水フタル酸の混合物３９．４部（０．２４モル、ＨＮ−２０００ 日立化成工業（株）製）及びテトラヒドロ無水フタル酸９５．０部（０．６２モル）を仕込み（合計０．８６モル）、内温を１２０℃に昇温した。次に、内温１２０〜１４０℃に保温しながら、エチレングリコール２６．７部（０．４３モル）をゆっくりと滴下し、滴下終了後、内温１４０〜１５５℃でさらに１時間攪拌し、末端に遊離カルボキシル基を有する反応生成物１６０．７部（０．４３モル、遊離カルボキシル基としての物質量０．８６モル）を得た。これを樹脂組成物１−１とする。
<Production Example 1>
<Production Example 1 of Polymer (A) 1: Synthesis of Resin 1-1>
A reactor equipped with a thermometer, a reflux condenser and a stir bar was charged with 39.4 parts of a mixture of 3-methyltetrahydrophthalic anhydride and 4-methyltetrahydrophthalic anhydride (0.24 mol, HN-2000 Hitachi Chemical) Co., Ltd.) and 95.0 parts (0.62 mol) of tetrahydrophthalic anhydride were charged (total 0.86 mol), and the internal temperature was raised to 120 ° C. Next, 26.7 parts (0.43 mol) of ethylene glycol was slowly added dropwise while keeping the internal temperature at 120 to 140 ° C., and after completion of the addition, the mixture was further stirred at an internal temperature of 140 to 155 ° C. for 1 hour. 160.7 parts (0.43 mol, amount of substance as a free carboxyl group of 0.86 mol) having a free carboxyl group was obtained. This is designated as resin composition 1-1.
＜（重合物（Ａ）と（ｃ）成分と（ｇ）成分の生成物の製造例１：樹脂１−２の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂組成物１−１を１６０．７部（０．４３モル、遊離カルボキシル基としての物質量０．８６モル）添加し、８５％ε−カプロラクタム４．０部（０．０３０モル、ポリアミンに対して０．０２８モル比）を滴下した後、内温を１１０℃まで昇温させたのち、トリエチレンテトラミン１５７．４部（１．０８モル、遊離カルボキシル基の酸価に対する物質量比１．２５）を１００〜１３０℃でゆっくりと滴下した。次いで、生成する水を留去しながら内温を１５０℃まで昇温させ、発生する水を留去しながら、さらに内温１５０〜１５５℃で４時間反応させた。このとき、留去した水の重量は６．４部であった。その後、水１２７．５部を加えて固形分濃度７０％のポリエステルポリアミド樹脂組成物水溶液４４０．６部（０．４３モル、ポリアミン類（ｃ）に由来する構造単位１．０８モル）を得た。これを樹脂組成物１−２とする。
<Production Example 1: Product of Polymer (A), (c) Component, and (g) Component 1: Synthesis of Resin 1-2>
To a reactor equipped with a thermometer, a reflux condenser, and a stirring rod, 160.7 parts (0.43 mol, amount of substance as a free carboxyl group) of resin composition 1-1 was added, and 85% After 4.0 parts of ε-caprolactam (0.030 mole, 0.028 mole ratio with respect to polyamine) was added dropwise, the internal temperature was raised to 110 ° C., and then 157.4 parts of triethylenetetramine (1. 08 mol, the amount ratio of the free carboxyl group to the acid value of 1.25) was slowly added dropwise at 100 to 130 ° C. Next, the internal temperature was raised to 150 ° C. while distilling off the generated water, and the reaction was further performed at an internal temperature of 150 to 155 ° C. for 4 hours while distilling off the generated water. At this time, the weight of distilled water was 6.4 parts. Thereafter, 127.5 parts of water was added to obtain 440.6 parts of an aqueous polyester polyamide resin composition solution having a solid content concentration of 70% (0.43 mole, structural unit 1.08 mole derived from polyamines (c)). . This is designated as resin composition 1-2.
＜重合物（Ａ）と（ｃ）成分と（ｇ）成分と（ｅ）成分との生成物の製造例１：樹脂１−３の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂組成物１−２を４２９．６部（０．４２モル、ポリアミン類（ｃ）に由来する構造単位１．０５モル）と水１１０．５部を添加し、６５〜７５℃に内温を保持しながら、エピクロルヒドリン５８．３部（０．６３モル、ポリアミン類（ｃ）に対する物質量比０．６）を４時間かけて滴下し、さらに内温６５〜７５℃で２時間攪拌した。その後、室温に冷却し、固形分濃度６０％のエピクロルヒドリン変性ポリエステルポリアミド樹脂組成物水溶液５９７．８部（０．４２モル、１級および２級アミノ基の物質量合計３．３６モル）を得た。これを樹脂組成物１−３とする。
<Production Example 1: Product of Polymer (A), (c) Component, (g) Component, and (e) Component 1: Synthesis of Resin 1-3>
In a reactor equipped with a thermometer, a reflux condenser, and a stirring rod, 429.6 parts of resin composition 1-2 (0.42 mol, structural unit derived from polyamines (c) 1.05 mol) and water 110.5 parts were added, and 58.3 parts of epichlorohydrin (0.63 mol, a mass ratio of 0.6 to polyamines (c)) was dropped over 4 hours while maintaining the internal temperature at 65 to 75 ° C. The mixture was further stirred at an internal temperature of 65 to 75 ° C. for 2 hours. Thereafter, the mixture was cooled to room temperature to obtain 597.8 parts of epichlorohydrin-modified polyester polyamide resin composition aqueous solution having a solid content concentration of 60% (0.42 mol, total amount of primary and secondary amino group substances: 3.36 mol). . This is designated as resin composition 1-3.
＜重合物（Ｂ）の製造例１：樹脂１−４の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂１−３を５９７．８部（０．４２モル、１級および２級アミノ基の物質量合計３．３６モル）添加し、９０℃まで内温を昇温させた。次に、尿素１５１．３部（２．５２モル、アミノ基に対して０．７５モル比）を添加した後、内温を９０℃まで昇温させた。続いて、発生するアンモニアを系外に留去しながら、内温１０４℃まで２時間かけて昇温させ、さらに、発生するアンモニアを反応器から留去しながら、内温１０４〜１０６℃で８時間反応させた。その後、水５９．５部を徐々に加えながら冷却して、固形分６１．０％、ｐＨ７．７６、粘度２０７ｍＰａ・ｓの水溶液７９０．１部を得た。これを樹脂組成物１−４とする。
<Production Example 1 of Polymer (B) 1: Synthesis of Resin 1-4>
To a reactor equipped with a thermometer, a reflux condenser and a stir bar, 597.8 parts of resin 1-3 (0.42 mol, total amount of primary and secondary amino group substances 3.36 mol) was added, The internal temperature was raised to 90 ° C. Next, after adding 151.3 parts of urea (2.52 mol, 0.75 mol ratio with respect to amino groups), the internal temperature was raised to 90 ° C. Subsequently, while the generated ammonia is distilled out of the system, the temperature is raised to an internal temperature of 104 ° C. over 2 hours, and further, the generated ammonia is distilled from the reactor at an internal temperature of 104 to 106 ° C. for 8 hours. Reacted for hours. Thereafter, the mixture was cooled while gradually adding 59.5 parts of water to obtain 790.1 parts of an aqueous solution having a solid content of 61.0%, a pH of 7.76, and a viscosity of 207 mPa · s. This is designated as resin composition 1-4.
＜製造例２＞
＜重合物（Ａ）の製造例２：樹脂２−１の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、３−メチルテトラヒドロ無水フタル酸および４−メチルテトラヒドロ無水フタル酸の混合物３９．４部（０．２４モル、ＨＮ−２０００ 日立化成工業（株）製）及びテトラヒドロ無水フタル酸９５．０部（０．６２モル）を仕込み（合計０．８６モル）、内温を１２０℃に昇温した。次に、内温１２０〜１４０℃に保温しながら、エチレングリコール２６．７部（０．４３モル）をゆっくりと滴下し、滴下終了後、内温１４０〜１５５℃でさらに１時間攪拌し、末端に遊離カルボキシル基を有する反応生成物１６１．１部（０．４３モル、遊離カルボキシル基としての物質量０．８６モル）を得た。これを樹脂組成物２−１とする。
<Production Example 2>
<Production Example 2 of Polymer (A): Synthesis of Resin 2-1>
A reactor equipped with a thermometer, a reflux condenser and a stir bar was charged with 39.4 parts of a mixture of 3-methyltetrahydrophthalic anhydride and 4-methyltetrahydrophthalic anhydride (0.24 mol, HN-2000 Hitachi Chemical) Co., Ltd.) and 95.0 parts (0.62 mol) of tetrahydrophthalic anhydride were charged (total 0.86 mol), and the internal temperature was raised to 120 ° C. Next, 26.7 parts (0.43 mol) of ethylene glycol was slowly added dropwise while keeping the internal temperature at 120 to 140 ° C., and after completion of the addition, the mixture was further stirred at an internal temperature of 140 to 155 ° C. for 1 hour. 161.1 parts (0.43 mol, amount of substance as a free carboxyl group of 0.86 mol) having a free carboxyl group was obtained. This is designated as resin composition 2-1.
＜（重合物（Ａ）と（ｃ）成分の生成物の製造例２：樹脂２−２の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂組成物２−１を１６１．１部（０．４３モル、遊離カルボキシル基としての物質量０．８６モル）添加し、内温を１１０℃まで昇温させたのち、トリエチレンテトラミン１５７．４部（１．０８モル、遊離カルボキシル基の酸価に対する物質量比１．２５）を１００〜１３０℃でゆっくりと滴下した。次いで、生成する水を留去しながら内温を１５０℃まで昇温させ、発生する水を留去しながら、さらに内温１５０〜１５５℃で４時間反応させた。このとき、留去した水の重量は５．６部であった。その後、水１２６．６部を加えて固形分濃度７０％のポリエステルポリアミド樹脂組成物水溶液４３９．５部（０．４３モル、ポリアミン類（ｃ）に由来する構造単位１．０８モル）を得た。これを樹脂組成物２−２とする。
<Production Example 2 of Polymer (A) and (c) Component Product: Synthesis of Resin 2-2>
To a reactor equipped with a thermometer, a reflux condenser, and a stirring rod, 161.1 parts of resin composition 2-1 (0.43 mol, substance amount as free carboxyl group 0.86 mol) was added, and the internal temperature Was heated to 110 ° C., and then 157.4 parts of triethylenetetramine (1.08 mol, a mass ratio of the free carboxyl group to the acid value of 1.25) was slowly added dropwise at 100 to 130 ° C. Next, the internal temperature was raised to 150 ° C. while distilling off the generated water, and the reaction was further performed at an internal temperature of 150 to 155 ° C. for 4 hours while distilling off the generated water. At this time, the weight of distilled water was 5.6 parts. Thereafter, 126.6 parts of water was added to obtain 439.5 parts of an aqueous polyester polyamide resin composition solution having a solid content concentration of 70% (0.43 mol, 1.08 mol of a structural unit derived from polyamines (c)). . This is designated as resin composition 2-2.
＜重合物（Ａ）と（ｃ）成分と（ｅ）成分との生成物の製造例２：樹脂２−３の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂組成物２−２を４３９．５部（０．４３モル、ポリアミン類（ｃ）に由来する構造単位１．０８モル）と水１１３．１部を添加し、６５〜７５℃に内温を保持しながら、エピクロルヒドリン５９．８部（０．６５モル、ポリアミン類（ｃ）に対する物質量比０．６）を４時間かけて滴下し、さらに内温６５〜７５℃で２時間攪拌した。その後、室温に冷却し、固形分濃度６０％のエピクロルヒドリン変性ポリエステルポリアミド樹脂組成物水溶液６１２．４部（０．４３モル、１級および２級アミノ基の物質量合計３．４６モル）を得た。これを樹脂組成物２−３とする。
<Production Example 2 of Product of Polymer (A), (c) Component, and (e) Component: Synthesis of Resin 2-3>
In a reactor equipped with a thermometer, a reflux condenser, and a stirring rod, 439.5 parts (0.43 mol, structural unit derived from polyamines (c), 1.08 mol) of resin composition 2-2 and water 113.1 parts were added, and 59.8 parts of epichlorohydrin (0.65 mol, substance amount ratio to polyamines (c) of 0.6) was added dropwise over 4 hours while maintaining the internal temperature at 65 to 75 ° C. The mixture was further stirred at an internal temperature of 65 to 75 ° C. for 2 hours. Thereafter, the mixture was cooled to room temperature to obtain 612.4 parts of an aqueous solution of an epichlorohydrin-modified polyester polyamide resin composition having a solid content concentration of 60% (0.43 mol, total amount of primary and secondary amino group substances: 3.46 mol). . This is designated as resin composition 2-3.
＜重合物（Ｂ）の製造例２：樹脂２−４の合成＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂２−３を６１２．４部（０．４３モル、１級および２級アミノ基の物質量合計３．４６モル）添加し、９０℃まで内温を昇温させた。次に、尿素１５５．２部（２．５８モル、アミノ基に対して０．７５モル比）を添加した後、内温を９０℃まで昇温させた。続いて、発生するアンモニアを系外に留去しながら、内温１０４℃まで２時間かけて昇温させ、さらに、発生するアンモニアを反応器から留去しながら、内温１０４〜１０６℃で８時間反応させた。その後、水６１．０部を徐々に加えながら冷却して、固形分６１．０％、ｐＨ７．８２、粘度２０４ｍＰａ・ｓの水溶液８０９．６部を得た。これを樹脂組成物２−４とする。
<Production Example 2 of Polymer (B): Synthesis of Resin 2-4>
To a reactor equipped with a thermometer, a reflux condenser and a stir bar, 612.4 parts of resin 2-3 (0.43 mol, total amount of primary and secondary amino group substances 3.46 mol) was added, The internal temperature was raised to 90 ° C. Next, after adding 155.2 parts of urea (2.58 mol, 0.75 mol ratio with respect to amino groups), the internal temperature was raised to 90 ° C. Subsequently, while the generated ammonia is distilled out of the system, the temperature is raised to an internal temperature of 104 ° C. over 2 hours, and further, the generated ammonia is distilled from the reactor at an internal temperature of 104 to 106 ° C. for 8 hours. Reacted for hours. Thereafter, the mixture was cooled while gradually adding 61.0 parts of water to obtain 809.6 parts of an aqueous solution having a solid content of 61.0%, a pH of 7.82, and a viscosity of 204 mPa · s. This is designated as resin composition 2-4.
＜合成例１＞
＜紙塗工用樹脂組成物の製造例１：紙塗工用樹脂組成物１の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂１−４を１００部仕込み、続いて尿素１．５部（重合物（Ｂ）の固形分に対する重量比２．５％）、水１．０部を添加した。内温４０℃まで昇温して１時間攪拌し、尿素を溶解させた。固形分６０．９％、ｐＨ７．７５、粘度２０２ｍＰａ・ｓの水溶液１０２．５部を得た。これを紙塗工用樹脂組成物１とする。
<Synthesis Example 1>
<Production Example 1 of Resin Composition for Paper Coating 1: Preparation of Resin Composition 1 for Paper Coating>
A reactor equipped with a thermometer, a reflux condenser and a stir bar is charged with 100 parts of resin 1-4, followed by 1.5 parts of urea (2.5% by weight with respect to the solid content of the polymer (B)), 1.0 part of water was added. The temperature was raised to an internal temperature of 40 ° C. and stirred for 1 hour to dissolve urea. 102.5 parts of an aqueous solution having a solid content of 60.9%, pH of 7.75, and a viscosity of 202 mPa · s were obtained. This is designated as a resin composition 1 for paper coating.
＜合成例２＞
＜紙塗工用樹脂組成物の製造例２：紙塗工用樹脂組成物２の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂１−４を１００部仕込み、続いて尿素３．０部（重合物（Ｂ）の固形分に対する重量比５．０％）、水１．９部を添加した。内温４０℃まで昇温して１時間攪拌し、尿素を溶解させた。固形分６１．１％、ｐＨ７．７３、粘度１８９ｍＰａ・ｓの水溶液１０４．９部を得た。これを紙塗工用樹脂組成物２とする。
<Synthesis Example 2>
<Production Example 2 of Paper Coating Resin Composition: Adjustment of Paper Coating Resin Composition 2>
A reactor equipped with a thermometer, a reflux condenser and a stir bar is charged with 100 parts of resin 1-4, followed by 3.0 parts of urea (5.0% by weight with respect to the solid content of the polymer (B)), 1.9 parts of water was added. The temperature was raised to an internal temperature of 40 ° C. and stirred for 1 hour to dissolve urea. 104.9 parts of an aqueous solution having a solid content of 61.1%, a pH of 7.73, and a viscosity of 189 mPa · s were obtained. This is designated as a resin composition 2 for paper coating.
＜合成例３＞
＜紙塗工用樹脂組成物の製造例３：紙塗工用樹脂組成物３の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂１−４を１００部仕込み、続いて尿素４．６部（重合物（Ｂ）の固形分に対する重量比７．５％）、水２．９部を添加した。内温４０℃まで昇温して１時間攪拌し、尿素を溶解させた。固形分６１．３％、ｐＨ７．６９、粘度１７１ｍＰａ・ｓの水溶液１０７．６部を得た。これを紙塗工用樹脂組成物３とする。
<Synthesis Example 3>
<Production Example 3 of Paper Coating Resin Composition: Adjustment of Paper Coating Resin Composition 3>
A reactor equipped with a thermometer, a reflux condenser and a stir bar was charged with 100 parts of resin 1-4, followed by 4.6 parts of urea (7.5% by weight with respect to the solid content of the polymer (B)), 2.9 parts of water were added. The temperature was raised to an internal temperature of 40 ° C. and stirred for 1 hour to dissolve urea. 107.6 parts of an aqueous solution having a solid content of 61.3%, pH of 7.69, and a viscosity of 171 mPa · s were obtained. This is designated as a resin composition 3 for paper coating.
＜合成例４＞
＜紙塗工用樹脂組成物の製造例４：紙塗工用樹脂組成物４の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂１−４を１００部仕込み、続いて尿素６．１部（重合物（Ｂ）の固形分に対する重量比１０％）、水３．９部を添加した。内温４０℃まで昇温して１時間攪拌し、尿素を溶解させた。固形分６１．０％、ｐＨ７．５１、粘度１５３ｍＰａ・ｓの水溶液１１０．１部を得た。これを紙塗工用樹脂組成物４とする。
<Synthesis Example 4>
<Production Example 4 of Paper Coating Resin Composition: Adjustment of Paper Coating Resin Composition 4>
A reactor equipped with a thermometer, a reflux condenser and a stir bar is charged with 100 parts of resin 1-4, followed by 6.1 parts of urea (10% by weight with respect to the solid content of the polymer (B)), water 3 .9 parts were added. The temperature was raised to an internal temperature of 40 ° C. and stirred for 1 hour to dissolve urea. 110.1 parts of an aqueous solution having a solid content of 61.0%, a pH of 7.51, and a viscosity of 153 mPa · s were obtained. This is designated as a resin composition 4 for paper coating.
＜合成例５＞
＜紙塗工用樹脂組成物の製造例５：紙塗工用樹脂組成物５の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂１−４を１００部仕込み、続いて尿素１２．２部（重合物（Ｂ）の固形分に対する重量比２０％）、水７．８部を添加した。内温４０℃まで昇温して１時間攪拌し、尿素を溶解させた。固形分６１．２％、ｐＨ７．３６、粘度１２１ｍＰａ・ｓの水溶液１２０．０部を得た。これを紙塗工用樹脂組成物５とする。
<Synthesis Example 5>
<Production Example 5 of Paper Coating Resin Composition: Preparation of Paper Coating Resin Composition 5>
A reactor equipped with a thermometer, a reflux condenser, and a stirring rod was charged with 100 parts of resin 1-4, followed by 12.2 parts of urea (20% by weight with respect to the solid content of the polymer (B)), water 7 8 parts were added. The temperature was raised to an internal temperature of 40 ° C. and stirred for 1 hour to dissolve urea. 120.0 parts of an aqueous solution having a solid content of 61.2%, a pH of 7.36, and a viscosity of 121 mPa · s were obtained. This is designated as a resin composition 5 for paper coating.
＜合成例６＞
＜紙塗工用樹脂組成物の製造例６：紙塗工用樹脂組成物６の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂１−４を１００部仕込み、続いて尿素１８．３部（重合物（Ｂ）の固形分に対する重量比３０％）、水１１．７部を添加した。内温４０℃まで昇温して１時間攪拌し、尿素を溶解させた。固形分６０．９％、ｐＨ７．３７、粘度１０９ｍＰａ・ｓの水溶液１３０．１部を得た。これを紙塗工用樹脂組成物６とする。
<Synthesis Example 6>
<Production Example 6 of Paper Coating Resin Composition: Adjustment of Paper Coating Resin Composition 6>
A reactor equipped with a thermometer, a reflux condenser and a stir bar was charged with 100 parts of resin 1-4, followed by 18.3 parts of urea (30% by weight relative to the solid content of the polymer (B)), water 11 7 parts were added. The temperature was raised to an internal temperature of 40 ° C. and stirred for 1 hour to dissolve urea. 130.1 parts of an aqueous solution having a solid content of 60.9%, a pH of 7.37, and a viscosity of 109 mPa · s were obtained. This is designated as a resin composition 6 for paper coating.
＜合成例７＞
＜紙塗工用樹脂組成物の製造例７：紙塗工用樹脂組成物７の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂２−４を１００部仕込み、続いて尿素３．０部（重合物（Ｂ）の固形分に対する重量比５．０％）、水１．９部を添加した。内温４０℃まで昇温して１時間攪拌し、尿素を溶解させた。固形分６１．０％、ｐＨ７．７５、粘度１８４ｍＰａ・ｓの水溶液１０４．９部を得た。これを紙塗工用樹脂組成物７とする。
<Synthesis Example 7>
<Production Example 7 of Paper Coating Resin Composition: Adjustment of Paper Coating Resin Composition 7>
A reactor equipped with a thermometer, a reflux condenser and a stir bar is charged with 100 parts of resin 2-4, followed by 3.0 parts of urea (5.0% by weight with respect to the solid content of the polymer (B)), 1.9 parts of water was added. The temperature was raised to an internal temperature of 40 ° C. and stirred for 1 hour to dissolve urea. 104.9 parts of an aqueous solution having a solid content of 61.0%, a pH of 7.75, and a viscosity of 184 mPa · s were obtained. This is designated as a resin composition 7 for paper coating.
＜合成例８＞
＜紙塗工用樹脂組成物の製造例８：紙塗工用樹脂組成物８の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂２−４を１００部仕込み、続いて尿素６．１部（重合物（Ｂ）の固形分に対する重量比１０％）、水３．９部を添加した。内温４０℃まで昇温して１時間攪拌し、尿素を溶解させた。固形分６１．１％、ｐＨ７．４９、粘度１５２ｍＰａ・ｓの水溶液１１０．０部を得た。これを紙塗工用樹脂組成物８とする。
<Synthesis Example 8>
<Production Example 8 of Paper Coating Resin Composition: Adjustment of Paper Coating Resin Composition 8>
A reactor equipped with a thermometer, a reflux condenser and a stir bar is charged with 100 parts of resin 2-4, followed by 6.1 parts of urea (10% by weight with respect to the solid content of the polymer (B)), water 3 .9 parts were added. The temperature was raised to an internal temperature of 40 ° C. and stirred for 1 hour to dissolve urea. 110.0 parts of an aqueous solution having a solid content of 61.1%, a pH of 7.49, and a viscosity of 152 mPa · s were obtained. This is designated as a resin composition 8 for paper coating.
＜合成例９＞
＜紙塗工用樹脂組成物の製造例９：紙塗工用樹脂組成物９の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂２−４を１００部仕込み、続いて尿素１２．２部（重合物（Ｂ）の固形分に対する重量比２０％）、水７．８部を添加した。内温４０℃まで昇温して１時間攪拌し、尿素を溶解させた。固形分６０．９％、ｐＨ７．３１、粘度１１８ｍＰａ・ｓの水溶液１２０．１部を得た。これを紙塗工用樹脂組成物９とする。
<Synthesis Example 9>
<Production Example 9 of Paper Coating Resin Composition: Preparation of Paper Coating Resin Composition 9>
A reactor equipped with a thermometer, a reflux condenser and a stir bar is charged with 100 parts of resin 2-4, followed by 12.2 parts of urea (20% by weight with respect to the solid content of the polymer (B)), water 7 8 parts were added. The temperature was raised to an internal temperature of 40 ° C. and stirred for 1 hour to dissolve urea. 120.1 parts of an aqueous solution having a solid content of 60.9%, a pH of 7.31, and a viscosity of 118 mPa · s were obtained. This is designated as a resin composition 9 for paper coating.
＜比較合成例１＞
＜紙塗工用樹脂組成物の製造例１０：紙塗工用樹脂組成物１０の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂１−４を１００部仕込み、続いて合成例１の尿素を用いる代わりに水１．５部（重合物（Ｂ）の固形分に対する重量比２．５％）、さらに水１．０部を添加した。内温４０℃まで昇温して１時間攪拌した固形分５９．６％、ｐＨ７．７７、粘度１９９ｍＰａ・ｓの水溶液１０２．５部を得た。これを紙塗工用樹脂組成物１０とする。
<Comparative Synthesis Example 1>
<Production Example 10 of Paper Coating Resin Composition: Adjustment of Paper Coating Resin Composition 10>
A reactor equipped with a thermometer, a reflux condenser, and a stirring rod was charged with 100 parts of resin 1-4, and instead of using urea of Synthesis Example 1, 1.5 parts of water (the solid content of the polymer (B)) And 2.5 parts by weight of water were added. The temperature was raised to 40 ° C. and stirred for 1 hour to obtain 102.5 parts of an aqueous solution having a solid content of 59.6%, a pH of 7.77, and a viscosity of 199 mPa · s. This is designated as a resin composition 10 for paper coating.
＜比較合成例２＞
＜紙塗工用樹脂組成物の製造例１１：紙塗工用樹脂組成物１１の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂１−４を１００部仕込み、続いて合成例２の尿素を用いる代わりに水３．０部（重合物（Ｂ）の固形分に対する重量比５．０％）、さらに水１．９部を添加した。内温４０℃まで昇温して１時間攪拌した。固形分５７．９％、ｐＨ７．７５、粘度１８３ｍＰａ・ｓの水溶液１０４．９部を得た。これを紙塗工用樹脂組成物１１とする。
<Comparative Synthesis Example 2>
<Production Example 11 of Paper Coating Resin Composition: Adjustment of Paper Coating Resin Composition 11>
A reactor equipped with a thermometer, a reflux condenser, and a stirring rod was charged with 100 parts of resin 1-4, and then 3.0 parts of water (polymer (B) solid content instead of using the urea of Synthesis Example 2). And 1.9 parts of water was further added. The temperature was raised to 40 ° C. and stirred for 1 hour. 104.9 parts of an aqueous solution having a solid content of 57.9%, a pH of 7.75, and a viscosity of 183 mPa · s were obtained. This is designated as a resin composition 11 for paper coating.
＜比較合成例３＞
＜紙塗工用樹脂組成物の製造例１２：紙塗工用樹脂組成物１２の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂１−４を１００部仕込み、続いて合成例３の尿素を用いる代わりに水４．６部（重合物（Ｂ）の固形分に対する重量比７．５％）、さらに水２．９部を添加した。内温４０℃まで昇温して１時間攪拌した。固形分５６．５％、ｐＨ７．６９、粘度１７２ｍＰａ・ｓの水溶液１０７．５部を得た。これを紙塗工用樹脂組成物１２とする。
<Comparative Synthesis Example 3>
<Production Example 12 of Paper Coating Resin Composition: Adjustment of Paper Coating Resin Composition 12>
A reactor equipped with a thermometer, a reflux condenser, and a stirring rod was charged with 100 parts of resin 1-4, and then 4.6 parts of water (the solid content of the polymer (B) was used instead of the urea of Synthesis Example 3. And 2.9 parts of water was added. The temperature was raised to 40 ° C. and stirred for 1 hour. 107.5 parts of an aqueous solution having a solid content of 56.5%, a pH of 7.69, and a viscosity of 172 mPa · s were obtained. This is designated as a resin composition 12 for paper coating.
＜比較合成例４＞
＜紙塗工用樹脂組成物の製造例１３：紙塗工用樹脂組成物１３の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂１−４を１００部仕込み、続いて合成例４の尿素を用いる代わりに水６．１部（重合物（Ｂ）の固形分に対する重量比１０％）、さらに水３．９部を添加した。内温４０℃まで昇温して１時間攪拌した。固形分５５．３％、ｐＨ７．６３、粘度１４５ｍＰａ・ｓの水溶液１０９．９部を得た。これを紙塗工用樹脂組成物１３とする。
<Comparative Synthesis Example 4>
<Production Example 13 of Paper Coating Resin Composition: Adjustment of Paper Coating Resin Composition 13>
A reactor equipped with a thermometer, a reflux condenser, and a stirring rod was charged with 100 parts of resin 1-4, and then 6.1 parts of water (polymer (B) solid content instead of using the urea of Synthesis Example 4). And 3.9 parts of water was added. The temperature was raised to 40 ° C. and stirred for 1 hour. 109.9 parts of an aqueous solution having a solid content of 55.3%, pH of 7.63, and a viscosity of 145 mPa · s were obtained. This is designated as a resin composition 13 for paper coating.
＜比較合成例５＞
＜紙塗工用樹脂組成物の製造例１４：紙塗工用樹脂組成物１４の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂１−４を１００部仕込み、続いて合成例５の尿素を用いる代わりに水１２．２部（重合物（Ｂ）の固形分に対する重量比２０％）、さらに水７．８部を添加した。内温４０℃まで昇温して１時間攪拌した。固形分５０．６％、ｐＨ７．５９、粘度１２４ｍＰａ・ｓの水溶液１２０．６部を得た。これを紙塗工用樹脂組成物１４とする。
<Comparative Synthesis Example 5>
<Manufacture example 14 of resin composition for paper coatings: Preparation of resin composition 14 for paper coatings>
A reactor equipped with a thermometer, a reflux condenser and a stir bar was charged with 100 parts of resin 1-4, and then 12.2 parts of water (polymer (B) solid content instead of using the urea of Synthesis Example 5) And 7.8 parts of water was added. The temperature was raised to 40 ° C. and stirred for 1 hour. 120.6 parts of an aqueous solution having a solid content of 50.6%, a pH of 7.59, and a viscosity of 124 mPa · s were obtained. This is designated as a resin composition 14 for paper coating.
＜比較合成例６＞
＜紙塗工用樹脂組成物の製造例１５：紙塗工用樹脂組成物１５の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂１−４を１００部仕込み、続いて合成例６の尿素を用いる代わりに水１８．３部（重合物（Ｂ）の固形分に対する重量比３０％）、さらに水１１．７部を添加した。内温４０℃まで昇温して１時間攪拌した。固形分４６．９％、ｐＨ７．３３、粘度１０６ｍＰａ・ｓの水溶液１３０．０部を得た。これを紙塗工用樹脂組成物１５とする。
<Comparative Synthesis Example 6>
<Production Example 15 of Paper Coating Resin Composition: Preparation of Paper Coating Resin Composition 15>
A reactor equipped with a thermometer, a reflux condenser, and a stir bar was charged with 100 parts of resin 1-4, and then 18.3 parts of water (polymer (B) solid content instead of using urea of Synthesis Example 6). And 11.7 parts of water were added. The temperature was raised to 40 ° C. and stirred for 1 hour. 130.0 parts of an aqueous solution having a solid content of 46.9%, a pH of 7.33, and a viscosity of 106 mPa · s were obtained. This is designated as a resin composition 15 for paper coating.
＜比較合成例７＞
＜紙塗工用樹脂組成物の製造例１６：紙塗工用樹脂組成物１６の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂１−４を１００部仕込み、続いて尿素２４．４部（重合物（Ｂ）の固形分に対する重量比４０％）、水１５．６部を添加した。内温５０℃まで昇温して１時間攪拌し、尿素を溶解させた。固形分６１．０％、ｐＨ７．３１、粘度８９ｍＰａ・ｓの水溶液１４０．０部を得た。これを紙塗工用樹脂組成物１６とする。
<Comparative Synthesis Example 7>
<Manufacture example 16 of resin composition for paper coatings: Preparation of resin composition 16 for paper coatings>
A reactor equipped with a thermometer, a reflux condenser and a stir bar is charged with 100 parts of resin 1-4, followed by 24.4 parts of urea (40% by weight with respect to the solid content of the polymer (B)), water 15 .6 parts were added. The temperature was raised to an internal temperature of 50 ° C. and stirred for 1 hour to dissolve urea. 140.0 parts of an aqueous solution having a solid content of 61.0%, a pH of 7.31, and a viscosity of 89 mPa · s were obtained. This is designated as a resin composition 16 for paper coating.
＜比較合成例８＞
＜紙塗工用樹脂組成物の製造例１７：紙塗工用樹脂組成物１７の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂２−４を１００部仕込み、続いて合成例７の尿素を用いる代わりに水３．０部（重合物（Ｂ）の固形分に対する重量比５．０％）、さらに水１．９部を添加した。内温４０℃まで昇温して１時間攪拌した。固形分５８．１％、ｐＨ７．７２、粘度１８１ｍＰａ・ｓの水溶液１０４．９部を得た。これを紙塗工用樹脂組成物１７とする。
<Comparative Synthesis Example 8>
<Production Example 17 of Paper Coating Resin Composition: Preparation of Paper Coating Resin Composition 17>
A reactor equipped with a thermometer, a reflux condenser, and a stirring rod was charged with 100 parts of resin 2-4, followed by 3.0 parts of water (the solid content of the polymer (B) instead of using urea of Synthesis Example 7). And 1.9 parts of water was further added. The temperature was raised to 40 ° C. and stirred for 1 hour. 104.9 parts of an aqueous solution having a solid content of 58.1%, a pH of 7.72, and a viscosity of 181 mPa · s were obtained. This is designated as a resin composition 17 for paper coating.
＜比較合成例９＞
＜紙塗工用樹脂組成物の製造例１８：紙塗工用樹脂組成物１８の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂２−４を１００部仕込み、続いて合成例８の尿素を用いる代わりに水６．１部（重合物（Ｂ）の固形分に対する重量比１０％）、水３．９部を添加した。内温４０℃まで昇温して１時間攪拌した。固形分５５．４％、ｐＨ７．５０、粘度１４９ｍＰａ・ｓの水溶液１１０．０部を得た。これを紙塗工用樹脂組成物１８とする。
<Comparative Synthesis Example 9>
<Production Example 18 of Paper Coating Resin Composition: Preparation of Resin Composition 18 for Paper Coating>
A reactor equipped with a thermometer, a reflux condenser, and a stir bar was charged with 100 parts of resin 2-4, and then 6.1 parts of water (polymer (B) solid content instead of using urea of Synthesis Example 8). And 3.9 parts of water was added. The temperature was raised to 40 ° C. and stirred for 1 hour. 110.0 parts of an aqueous solution having a solid content of 55.4%, a pH of 7.50, and a viscosity of 149 mPa · s were obtained. This is designated as a resin composition 18 for paper coating.
＜比較合成例１０＞
＜紙塗工用樹脂組成物の製造例１９：紙塗工用樹脂組成物１９の調整＞
温度計、還流冷却器及び攪拌棒を備えた反応器に、樹脂２−４を１００部仕込み、続いて合成例９の尿素を用いる代わりに水１２．２部（重合物（Ｂ）の固形分に対する重量比２０％）、水７．８部を添加した。内温４０℃まで昇温して１時間攪拌した。固形分５０．８％、ｐＨ７．３３、粘度１２０ｍＰａ・ｓの水溶液１１９．９部を得た。これを紙塗工用樹脂組成物１９とする。
<Comparative Synthesis Example 10>
<Manufacture example 19 of resin composition for paper coatings: Preparation of resin composition 19 for paper coatings>
A reactor equipped with a thermometer, a reflux condenser and a stirring rod was charged with 100 parts of resin 2-4, and then 12.2 parts of water (polymer (B) solid content instead of using the urea of Synthesis Example 9) 7.8 parts of water was added. The temperature was raised to 40 ° C. and stirred for 1 hour. 119.9 parts of an aqueous solution having a solid content of 50.8%, a pH of 7.33, and a viscosity of 120 mPa · s were obtained. This is designated as a resin composition 19 for paper coating.
＜塗工組成物の製造例＞
ウルトラホワイト９０（顔料、米国エンゲルハードミネラルズ社製のクレー）６０重量部、カービタル９０（顔料、富士カオリン（株）製の炭酸カルシウム）４０重量部、ポリアクリル酸系顔料分散剤０．２重量部、スチレン−ブタジエン系ラテックス（水性バインダー）８重量部及び市販の酸化でんぷん３重量部を混合し、水を加えて、固形分６４．５％となるようにマスターカラーを調製した。続いて、マスターカラーの顔料１００重量部に＜紙塗工用樹脂組成物の製造例１＞で得られた紙塗工用樹脂組成物１の固形分が０．６重量部となる割合で添加し、固形分を６４％に調整した。
得られた塗工組成物のｐＨは９．２、粘度は１６５０ｍＰａ・ｓであった。
<Production example of coating composition>
Ultra white 90 (pigment, clay manufactured by Engelhard Minerals, USA) 60 parts by weight Carbital 90 (pigment, calcium carbonate manufactured by Fuji Kaolin Co., Ltd.) 40 parts by weight, polyacrylic acid pigment dispersant 0.2 weight Parts, 8 parts by weight of styrene-butadiene latex (aqueous binder) and 3 parts by weight of commercially available oxidized starch were mixed, and water was added to prepare a master color so that the solid content was 64.5%. Subsequently, the solid content of the resin composition 1 for paper coating obtained in <Preparation Example 1 for Resin Composition for Paper Coating> is added to 100 parts by weight of the pigment of the master color at a ratio of 0.6 parts by weight. The solid content was adjusted to 64%.
The obtained coating composition had a pH of 9.2 and a viscosity of 1650 mPa · s.
＜塗工紙の製造例＞
塗工組成物を、米坪量８０ｇ／m2の上質紙の片面に、ワイヤーロッドを用いて塗工量が１５ｇ／m2となるように塗布した。塗布後ただちに、１１５℃にて２０秒間熱風乾燥し、次いで温度２３℃、相対湿度５０％にて１６時間調湿し、さらに温度６０℃、線圧６０kN／mの条件で２回スーパーカレンダー処理を施して、塗工紙を得た。こうして得た塗工紙を耐水性及びインキ受理性の試験に供し、試験結果を表１に示した。なお、試験方法は以下のとおりである。
<Examples of coated paper production>
The coating composition was applied to one side of a high-quality paper having a basis weight of 80 g / m 2 using a wire rod so that the coating amount was 15 g / m 2. Immediately after the application, it was dried with hot air at 115 ° C. for 20 seconds, then conditioned for 16 hours at a temperature of 23 ° C. and a relative humidity of 50%, and further subjected to supercalender treatment twice under the conditions of a temperature of 60 ° C. and a linear pressure of 60 kN / m And coated paper was obtained. The coated paper thus obtained was subjected to water resistance and ink acceptability tests, and the test results are shown in Table 1. The test method is as follows.
＜耐水性：ウェットピック法（ＷＰ法）＞
ＲＩ試験機（明製作所製）を使用し、塗工面を給水ロールで湿潤させた後に印刷し、紙むけ状態を肉眼で観察して判定した。判定基準は次のように行った。
耐水性 （劣）１〜５（優）
<Water resistance: Wet pick method (WP method)>
Using an RI testing machine (manufactured by Meisei Seisakusho), the coated surface was wetted with a water supply roll and then printed, and the peeled state was visually observed and judged. The judgment criteria were as follows.
Water resistance (poor) 1-5 (excellent)
＜インキ受理性：Ａ法＞
ＲＩ試験機（明製作所製）を使用し、塗工面を給水ロールで湿潤させた後に印刷し、インキの受理性を肉眼で観察して判定した。判定基準は次のように行った。
インキ受理性 （劣）１〜５（優）
<Ink acceptability: Method A>
Using an RI tester (manufactured by Meisei Seisakusho), the coated surface was wetted with a water supply roll and then printed, and the acceptability of the ink was visually observed and judged. The judgment criteria were as follows.
Ink acceptability (poor) 1 to 5 (excellent)
＜インキ受理性：Ｂ法＞
ＲＩ試験機（明製作所製）を使用し、金属ロールとゴムロールの間にわずかな間隙をあけ、その間隙に水を注いだ後速やかに印刷し、インキの受理性を肉眼で観察して判定した。判定基準は次のように行った。
インキ受理性 （劣）１〜５（優）
<Ink acceptability: Method B>
Using a RI tester (Meiji Seisakusho), a slight gap was made between the metal roll and the rubber roll, water was poured into the gap and then printed immediately, and the acceptability of the ink was visually observed and judged. . The judgment criteria were as follows.
Ink acceptability (poor) 1 to 5 (excellent)
＜冷蔵貯蔵安定性＞
紙塗工用樹脂組成物を５℃の冷蔵ショーケースで１週間保管し、その状態を肉眼で観察して判定した。判定基準は次のように行った。
冷蔵貯蔵安定性 ○：澄明であり外観に問題が見られない。
×：固体が析出している。
<Refrigerated storage stability>
The resin composition for paper coating was stored in a refrigerated showcase at 5 ° C. for 1 week, and the state was determined by visual observation. The judgment criteria were as follows.
Refrigerated storage stability ○: Clear and no problem in appearance.
X: A solid is precipitated.
（実施例２〜９、比較例１〜１０）
表１〜４に記載の紙塗工用樹脂を用いる以外は実施例１と同様にして、塗工組成物及び塗工紙を製造し、紙塗工用樹脂組成物の物性及び塗工紙の物性を測定した。実施例１の結果とともに、結果を表１〜４に示した。
(Examples 2-9, Comparative Examples 1-10)
A coating composition and coated paper were produced in the same manner as in Example 1 except that the paper coating resins listed in Tables 1 to 4 were used. The physical properties of the paper coating resin composition and the coated paper Physical properties were measured. Along with the results of Example 1, the results are shown in Tables 1 to 4.
（比較例１１）
＜重合物（Ｂ）の製造例：樹脂１−４の合成＞で得られた樹脂１−４を尿素や水を添加することなく紙塗工用樹脂組成物として用いる以外は実施例１と同様にして、塗工組成物及び塗工紙を製造し、紙塗工用樹脂組成物の物性及び塗工紙の物性を測定した。結果を表５に示した。
(Comparative Example 11)
<Example of production of polymer (B): synthesis of resin 1-4> Similar to Example 1 except that resin 1-4 obtained as a resin composition for paper coating is used without adding urea or water. Thus, a coating composition and coated paper were produced, and the physical properties of the resin composition for paper coating and the physical properties of the coated paper were measured. The results are shown in Table 5.
（比較例１２）
＜重合物（Ｂ）の製造例：樹脂２−４の合成＞で得られた樹脂２−４を尿素や水を添加することなく紙塗工用樹脂組成物として用いる以外は実施例１と同様にして、塗工組成物及び塗工紙を製造し、紙塗工用樹脂組成物の物性及び塗工紙の物性を測定した。結果を表５に示した。
(Comparative Example 12)
<Since Example of Production of Polymer (B): Synthesis of Resin 2-4> Resin 2-4 obtained in the same manner as in Example 1 except that it is used as a resin composition for paper coating without adding urea or water. Thus, a coating composition and coated paper were produced, and the physical properties of the resin composition for paper coating and the physical properties of the coated paper were measured. The results are shown in Table 5.
（比較例１３）
紙塗工用樹脂を用いない以外は実施例１と同様にして、塗工組成物及び塗工紙を製造し、紙塗工用樹脂組成物の物性及び塗工紙の物性を測定した。結果を表５に示した。
(Comparative Example 13)
A coating composition and coated paper were produced in the same manner as in Example 1 except that the paper coating resin was not used, and the physical properties of the paper coating resin composition and the coated paper were measured. The results are shown in Table 5.
Claims (5)
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