JP2007297511A - Method for producing aqueous solution of cationic thermosetting resin - Google Patents
Method for producing aqueous solution of cationic thermosetting resin Download PDFInfo
- Publication number
- JP2007297511A JP2007297511A JP2006126399A JP2006126399A JP2007297511A JP 2007297511 A JP2007297511 A JP 2007297511A JP 2006126399 A JP2006126399 A JP 2006126399A JP 2006126399 A JP2006126399 A JP 2006126399A JP 2007297511 A JP2007297511 A JP 2007297511A
- Authority
- JP
- Japan
- Prior art keywords
- thermosetting resin
- polyamide polyamine
- acid
- paper
- cationic thermosetting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 94
- 239000011347 resin Substances 0.000 title claims abstract description 94
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 54
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 title description 17
- 239000000126 substance Substances 0.000 claims abstract description 34
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920002396 Polyurea Polymers 0.000 claims abstract description 25
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 4
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 239000013055 pulp slurry Substances 0.000 claims description 10
- 239000013054 paper strength agent Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 abstract description 77
- 239000004952 Polyamide Substances 0.000 abstract description 61
- 229920002647 polyamide Polymers 0.000 abstract description 61
- 238000000034 method Methods 0.000 abstract description 31
- 239000007787 solid Substances 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 15
- 150000008282 halocarbons Chemical class 0.000 abstract 2
- 238000004321 preservation Methods 0.000 abstract 2
- 229940079826 hydrogen sulfite Drugs 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 89
- 238000006243 chemical reaction Methods 0.000 description 51
- 150000001735 carboxylic acids Chemical class 0.000 description 29
- 239000000243 solution Substances 0.000 description 27
- 229920001281 polyalkylene Polymers 0.000 description 26
- 125000003277 amino group Chemical group 0.000 description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 239000000543 intermediate Substances 0.000 description 20
- 239000003623 enhancer Substances 0.000 description 17
- 238000003860 storage Methods 0.000 description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 16
- 235000013877 carbamide Nutrition 0.000 description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- 238000004513 sizing Methods 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 230000002708 enhancing effect Effects 0.000 description 9
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 9
- 150000003672 ureas Chemical class 0.000 description 9
- -1 wool Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 7
- 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 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 238000011534 incubation Methods 0.000 description 6
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 150000002896 organic halogen compounds Chemical class 0.000 description 4
- 239000010893 paper waste Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 206010037660 Pyrexia Diseases 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000011087 paperboard Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 3
- 229940001584 sodium metabisulfite Drugs 0.000 description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 description 2
- XYUINKARGUCCQJ-UHFFFAOYSA-N 3-imino-n-propylpropan-1-amine Chemical compound CCCNCCC=N XYUINKARGUCCQJ-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
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- 238000005187 foaming Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- 230000007935 neutral effect Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
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- 230000035484 reaction time Effects 0.000 description 2
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
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- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
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- 125000005265 dialkylamine group Chemical group 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- UPCIBFUJJLCOQG-UHFFFAOYSA-L ethyl-[2-[2-[ethyl(dimethyl)azaniumyl]ethyl-methylamino]ethyl]-dimethylazanium;dibromide Chemical compound [Br-].[Br-].CC[N+](C)(C)CCN(C)CC[N+](C)(C)CC UPCIBFUJJLCOQG-UHFFFAOYSA-L 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229940117803 phenethylamine Drugs 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 229940043349 potassium metabisulfite Drugs 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Paper (AREA)
- Polyamides (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、陽イオン性熱硬化性樹脂の製造方法、湿潤紙力剤又はクレープ剤助剤、前記陽イオン性熱硬化性樹脂の製造方法によって得られた樹脂を含有する紙、及びその紙の製造方法に関する。 The present invention relates to a method for producing a cationic thermosetting resin, a wet paper strength agent or a crepe agent auxiliary, a paper containing a resin obtained by the method for producing a cationic thermosetting resin, and the paper It relates to a manufacturing method.
陽イオン性熱硬化性樹脂、例えば、ポリアミドポリアミン−エピハロヒドリン樹脂やポリアミドポリアミンポリ尿素−エピハロヒドリン樹脂などが、有用な湿潤紙力増強剤として一般に使用されており、その製造方法は、公知である（例えば、特許文献１参照、特許文献２参照）。 Cationic thermosetting resins such as polyamide polyamine-epihalohydrin resins and polyamide polyamine polyurea-epihalohydrin resins are generally used as useful wet strength agents, and their production methods are known (eg, , See Patent Document 1 and Patent Document 2).
近年、発癌性の疑いの持たれている吸着性有機ハロゲン化合物（以下、ＡＯＸと略すことがある）の含有量が少なく、さらに高固形分においても保存安定性に優れるような陽イオン性熱硬化性樹脂、特に、湿潤紙力増強剤用の陽イオン性熱硬化性樹脂に対する高度の要求を満たす樹脂の製造方法が求められている。ここでＡＯＸとは、例えば、エピハロヒドリン、エピハロヒドリンから誘導されるジハロゲノプロパノールやモノハロゲノプロパンジオールなどの低分子有機ハロゲン化合物、さらにオリゴマーのような低分子量の重合体骨格に結合している有機ハロゲンなどが挙げられる。 Cationic thermosetting that has a low content of adsorptive organohalogen compounds (hereinafter sometimes abbreviated as AOX) that are suspected of carcinogenicity and has excellent storage stability even at high solids. There is a need for a process for producing a resin that satisfies the high demands on a cationic resin, in particular, a cationic thermosetting resin for a wet paper strength enhancer. Here, AOX is, for example, epihalohydrin, low-molecular organic halogen compounds such as dihalogenopropanol and monohalogenopropanediol derived from epihalohydrin, and organic halogen bonded to a low molecular weight polymer skeleton such as oligomer. Is mentioned.
その中でも、湿潤紙力増強用の熱硬化性樹脂に含まれるＡＯＸの代表的な成分として、１，３−ジクロロ−２−プロパノール［以下においてＤＣＰと称することがある］やエピクロロヒドリン［以下においてＥｐｉと称することがある］を挙げることができる。欧州や米国を中心に、ＤＣＰやＥｐｉが湿潤紙力増強用熱硬化性樹脂中に１０００ｐｐｍ以上含まれる場合には、環境や健康に悪影響を及ぼすとの認識が広がっている。 Among them, as a typical component of AOX contained in the thermosetting resin for enhancing wet paper strength, 1,3-dichloro-2-propanol [hereinafter sometimes referred to as DCP] or epichlorohydrin [hereinafter referred to as DCP]. May be referred to as Epi]. In Europe and the United States, when DCP or Epi is contained in a thermosetting resin for enhancing wet paper strength in an amount of 1000 ppm or more, there is a growing recognition that it adversely affects the environment and health.
前記課題を克服するため、ポリアミドポリアミン−エピハロヒドリン樹脂製造時に塩基性物質や求核性物質を反応させてＡＯＸに由来する有機ハロゲン化合物を低減させる方法は、公知である（例えば、特許文献３、特許文献４参照）。また、ポリアミドポリアミン−エピハロヒドリン樹脂に比べ保存安定性に優れ、ＡＯＸの含有量が著しく少ないことを特徴とするポリアミドポリアミンポリ尿素−エピハロヒドリン樹脂の製造方法は公知である（例えば、特許文献５参照）。しかしながら、本発明の如く、硫黄原子を含む求核性物質（Ｄ）と窒素原子を含む求核性物質（Ｅ）を反応させることにより優れた湿潤紙力効果を保ったまま、ＡＯＸ含量が低く、高固形分で且つ保存安定性に優れた具体的な湿潤紙力剤の製造方法は記載されていない。 In order to overcome the above-mentioned problems, a method of reducing an organic halogen compound derived from AOX by reacting a basic substance or a nucleophilic substance during production of a polyamide polyamine-epihalohydrin resin is known (for example, Patent Document 3, Patent Reference 4). In addition, a method for producing a polyamide polyamine polyurea-epihalohydrin resin, which is superior in storage stability and has a significantly lower AOX content than a polyamide polyamine-epihalohydrin resin, is known (see, for example, Patent Document 5). However, as in the present invention, by reacting a nucleophilic substance (D) containing a sulfur atom with a nucleophilic substance (E) containing a nitrogen atom, the AOX content is low while maintaining an excellent wet paper strength effect. No specific method for producing a wet paper strength agent having a high solid content and excellent storage stability is described.
さらには、ポリアミドポリアミン−エピハロヒドリン製造後、酵素的にポリアミドポリアミン中のＡＯＸを分解したり（例えば特許文献６参照）するという方法が公知であるが、生物学的な方法を加えることによりＡＯＸを分解する時間がかかるため、作業効率が下がる問題があった。
本発明の課題は、化学的な手法によりＡＯＸ含量が低く、高固形分で且つ保存安定性に優れた、優れた湿潤紙力効果を持つ陽イオン性熱硬化性樹脂の製造方法、その製造方法によって得られた樹脂を含有する紙及びその紙の製造方法を提供することにある。 An object of the present invention is to provide a method for producing a cationic thermosetting resin having an excellent wet paper strength effect, which has a low AOX content by a chemical method, a high solid content and excellent storage stability, and a method for producing the same. It is to provide a paper containing a resin obtained by the above and a method for producing the paper.
本発明者らは、前記課題を解決すべく鋭意検討を重ねた結果、ポリアミドポリアミンやポリアミドポリアミンポリ尿素［以下においてポリアミドポリアミンとポリアミドポリアミンポリ尿素の両者を総称して中間体と称することがある。］にエピハロヒドリンと特定の２種類の求核性物質を同時又は順次反応させることにより、ＡＯＸ含量が低く、高固形分で保存安定性に優れた湿潤紙力効果に優れる樹脂を得ることができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have made a polyamide polyamine or a polyamide polyamine polyurea [hereinafter, both the polyamide polyamine and the polyamide polyamine polyurea may be collectively referred to as an intermediate. ], By reacting epihalohydrin and two specific nucleophilic substances simultaneously or sequentially, a resin having a low AOX content, a high solid content and excellent storage stability can be obtained. The headline and the present invention were completed.
すなわち、本発明は、（１）ポリアミドポリアミン（Ａ）及び／又はポリアミドポリアミンポリ尿素（Ｂ）にエピハロヒドリン類（Ｃ）と硫黄原子を含む求核性物質（Ｄ）及び窒素原子を含む求核性物質（Ｅ）を反応させることを特徴とする陽イオン性熱硬化性樹脂の製造方法であり、好ましい態様として（２）硫黄原子を含む求核性物質（Ｄ）が亜硫酸水素塩又はメタ重亜硫酸塩であることを特徴とする上記（１）の陽イオン性熱硬化性樹脂の製造方法であり、（３）窒素原子を含む求核性物質（Ｅ）がアンモニアであることを特徴とする上記（１）又は（２）に記載の陽イオン性熱硬化性樹脂の製造方法である陽イオン性熱硬化性樹脂の製造方法である。
別の態様としては
（４）上記（１）〜（３）のいずれかの製造方法によって得られる陽イオン性熱硬化性樹脂を含有する湿潤紙力剤又はクレープ剤助剤であり
また別の態様としては、
（５）上記（１）〜（３）のいずれかの製造方法により得られた陽イオン性熱硬化性樹脂を含有する紙であり、
さらに別の態様としては
（６）上記（１）〜（３）のいずれかの製造方法により得られた陽イオン性熱硬化性樹脂を含有する液を表面塗工又はパルプスラリーに添加することを特徴とする紙の製造方法である。
That is, the present invention provides (1) polyamide polyamine (A) and / or polyamide polyamine polyurea (B) with an epihalohydrin (C), a nucleophilic substance containing a sulfur atom (D), and a nucleophilicity containing a nitrogen atom. A method for producing a cationic thermosetting resin characterized by reacting a substance (E), wherein (2) a nucleophilic substance (D) containing a sulfur atom is bisulfite or metabisulfite as a preferred embodiment (1) The method for producing a cationic thermosetting resin according to (1) above, wherein (3) the nucleophilic substance (E) containing a nitrogen atom is ammonia. (1) It is a manufacturing method of the cationic thermosetting resin which is a manufacturing method of the cationic thermosetting resin as described in (2).
Another embodiment is (4) a wet paper strength agent or crepe agent auxiliary containing a cationic thermosetting resin obtained by the production method of any one of (1) to (3) above. as,
(5) A paper containing a cationic thermosetting resin obtained by the production method of any one of (1) to (3) above,
As another aspect, (6) adding a liquid containing a cationic thermosetting resin obtained by any one of the production methods (1) to (3) to the surface coating or pulp slurry. This is a characteristic paper manufacturing method.
本発明の方法にしたがって得られた陽イオン性熱硬化性樹脂水溶液は、公知の方法で製造されたポリアミドポリアミン−エピクロロヒドリン樹脂またはポリアミドポリアミンポリ尿素−エピクロロヒドリン樹脂と同等もしくはそれ以上の優れた湿潤紙力増強効果を付与し、しかも、樹脂中に含まれる低分子有機ハロゲン化合物の含有量が著しく少なく、固形分が高いにもかかわらず卓越した保存安定性を有するという極めて優れた性質を有している。 The aqueous cationic thermosetting resin solution obtained according to the method of the present invention is equivalent to or more than the polyamide polyamine-epichlorohydrin resin or polyamide polyamine polyurea-epichlorohydrin resin produced by a known method. The excellent wet paper strength-enhancing effect of the resin, and the content of the low-molecular-weight organic halogen compound contained in the resin is remarkably low, and it has excellent storage stability despite its high solid content. It has properties.
また、本発明の方法により得られる樹脂水溶液は、紙の湿潤紙力増強剤、クレープ剤助剤、抄紙工程で使用される濾水性向上剤あるいは、填料・サイズ剤などの歩留り向上剤として有用であるばかりでなく、工場の排水処理における凝集沈殿剤、あるいは、セルロース材料の耐水化剤、ポリビニルアルコール等の耐水化剤、羊毛などの天然繊維処理剤、合成繊維処理剤としても使用することが出来る。 In addition, the aqueous resin solution obtained by the method of the present invention is useful as a paper wet strength enhancer, a crepe aid, a freeness improver used in the paper making process, or a yield improver such as a filler / size agent. Not only can it be used as an agglomerating and precipitating agent in factory wastewater treatment, or as a water resistant agent for cellulose materials, a water resistant agent such as polyvinyl alcohol, a natural fiber treating agent such as wool, and a synthetic fiber treating agent. .
本発明に係る陽イオン性熱硬化性樹脂水溶液は、ポリアミドポリアミン（Ａ）及び／又はポリアミドポリアミンポリ尿素（Ｂ）にエピハロヒドリン類（Ｃ）と硫黄原子を含む求核性物質（Ｄ）及び窒素原子を含む求核性物質（Ｅ）を反応させることを特徴とする陽イオン性熱硬化性樹脂の製造方法により得られる。 The cationic thermosetting resin aqueous solution according to the present invention includes a polyamide polyamine (A) and / or a polyamide polyamine polyurea (B), a nucleophilic substance (D) containing an epihalohydrin (C) and a sulfur atom, and a nitrogen atom. It is obtained by a method for producing a cationic thermosetting resin characterized by reacting a nucleophilic substance (E) containing
ポリアミドポリアミン（Ａ）は、ポリアルキレンポリアミン類（ａ）［以下において、（ａ）成分又は単なる（ａ）と称することがある。］と二塩基性カルボン酸類（ｂ）［以下において、（ｂ）成分又は単なる（ｂ）と称することがある。］とを反応させることにより得ることができ、ポリアミドポリアミンポリ尿素（Ｂ）は、ポリアルキレンポリアミン類（ａ）［以下において、（ａ）成分又は単なる（ａ）と称することがある。］と二塩基性カルボン酸類（ｂ）［以下において、（ｂ）成分又は単なる（ｂ）と称することがある。］と尿素類（ｃ）［以下において、（ｃ）成分又は単なる（ｃ）と称することがある。］とを反応させることにより得ることができる。なお、（ａ）成分の一部にモノアミン類（ｇ）［以下において、（ｇ）成分、又は（ｇ）と称することがある。］を用いることができ、（ｂ）成分に一塩基性カルボン酸類（ｈ）［以下において、（ｈ）成分、又は（ｈ）と称することがある。］を用いることができる。 Polyamide polyamine (A) may be referred to as polyalkylene polyamines (a) [hereinafter referred to as component (a) or simply (a). ] And a dibasic carboxylic acid (b) [In the following, it may be referred to as component (b) or simply (b). The polyamide polyamine polyurea (B) may be referred to as polyalkylene polyamines (a) [hereinafter referred to as component (a) or simply (a). ] And a dibasic carboxylic acid (b) [In the following, it may be referred to as component (b) or simply (b). ] And ureas (c) [in the following, they may be referred to as component (c) or simply (c). ] Can be obtained. In addition, a part of (a) component may be monoamines (g) [hereinafter referred to as (g) component or (g). In the component (b), a monobasic carboxylic acid (h) [hereinafter referred to as the component (h) or (h) may be used. ] Can be used.
本発明に使用される中間体を得るために用いられるポリアルキレンポリアミン類（ａ）としては２個以上の第１級アミノ基を有していればよく、例えば、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、イミノビスプロピルアミンなどを挙げることができ、工業的には、ジエチレントリアミンが好ましい。これら１種又は２種以上を使用することができる。また、ポリアルキレンポリアミン類（ａ）の一部としてポリアルキレンポリアミン類（ａ）に代えて、エチレンジアミン、プロピレンジアミン又はヘキサメチレンジアミン等のアルキレンジアミンを使用することもできる。 The polyalkylene polyamines (a) used for obtaining the intermediate used in the present invention may have at least two primary amino groups, such as diethylenetriamine, triethylenetetramine, tetraethylene. Examples thereof include pentamine and iminobispropylamine. Industrially, diethylenetriamine is preferable. These 1 type (s) or 2 or more types can be used. Moreover, it can replace with polyalkylene polyamine (a) as a part of polyalkylene polyamine (a), and can also use alkylenediamine, such as ethylenediamine, propylenediamine, or hexamethylenediamine.
本発明に使用される中間体を得るために用いられる二塩基性カルボン酸類（ｂ）は、分子中に２個のカルボン酸及び／又はその誘導体を有していればよい。その誘導体とは、例えば、それら二塩基性カルボン酸のモノ又はジエステル、或いは酸無水物を挙げることができる。二塩基性カルボン酸としては、例えば、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ブラシル酸、ドデカン二酸などが挙げられ、工業的には炭素数５〜１０の二塩基性カルボン酸が好ましい。又、二塩基性カルボン酸のモノ又はジエステルとしては、好ましくは炭素数１〜５、特に好ましくは炭素数１〜３の低級アルコール（メチル、エチル、プロピル）エステルを挙げることができる。酸無水物としては、遊離酸の分子内脱水縮合物のほか、低級カルボン酸、好ましくは炭素数１〜５の低級カルボン酸との縮合物などが挙げられる。二塩基性カルボン酸類で工業的に特に好ましいものとしては、アジピン酸、グルタル酸ジメチルエステル、アジピン酸ジメチルエステルが挙げられる。上記の二塩基性カルボン酸類は１種又は２種以上を併用して使用することができる。また、二塩基性カルボン酸類の一部として、クエン酸など、分子中に３個以上のカルボン酸及び／又はそのカルボン酸エステル、或いはその酸無水物を有する誘導体を使用することもできるが、中間体の粘度が急激に上昇し、ゲル化することがある。 The dibasic carboxylic acid (b) used for obtaining the intermediate used in the present invention may have two carboxylic acids and / or derivatives thereof in the molecule. Examples of the derivative include mono- or diesters of these dibasic carboxylic acids, or acid anhydrides. Examples of the dibasic carboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, dodecanedioic acid and the like. A dibasic carboxylic acid having a number of 5 to 10 is preferred. Moreover, as mono- or diester of dibasic carboxylic acid, Preferably it is C1-C5, Most preferably, C1-C3 lower alcohol (methyl, ethyl, propyl) ester can be mentioned. Examples of acid anhydrides include intramolecular dehydration condensates of free acids and condensates of lower carboxylic acids, preferably lower carboxylic acids having 1 to 5 carbon atoms. Particularly preferred industrially preferred dibasic carboxylic acids include adipic acid, glutaric acid dimethyl ester, and adipic acid dimethyl ester. The above dibasic carboxylic acids can be used alone or in combination of two or more. Further, as a part of the dibasic carboxylic acids, it is possible to use a derivative having three or more carboxylic acids and / or carboxylic acid esters or acid anhydrides in the molecule such as citric acid. The viscosity of the body may rise rapidly and gel.
本発明に使用されるポリアミドポリアミンポリ尿素（Ｂ）を得るために用いられる尿素類（ｃ）は、尿素、チオ尿素、グアニル尿素、フェニル尿素、メチル尿素、ジメチル尿素などを挙げることができる。この中でも尿素が特に工業的に好ましい。これら尿素類（ｃ）の一部として尿素類に代えて、アミノ基とアミド交換反応し得るＮ無置換アミド基を１個以上有する化合物、例えば、アセトアミド、プロピオンアミドなどの脂肪族アミド類、或いはベンズアミド、フェニル酢酸アミドなどの芳香族アミド類なども使用することもできる。 Examples of ureas (c) used for obtaining the polyamide polyamine polyurea (B) used in the present invention include urea, thiourea, guanylurea, phenylurea, methylurea, and dimethylurea. Of these, urea is particularly preferred industrially. As a part of these ureas (c), instead of ureas, compounds having one or more N unsubstituted amide groups capable of undergoing an amide exchange reaction with amino groups, for example, aliphatic amides such as acetamide and propionamide, or Aromatic amides such as benzamide and phenylacetamide can also be used.
前記モノアミン類（ｇ）は、１級アミノ基を分子中１個有する化合物であればよく、さらに他の官能基を有するものであっても良い。モノアミン類（ｇ）の代表的なものとしては、ブチルアミン、モノエタノールアミン、シクロヘキシルアミン、ジエチルアミノエチルアミン、ラウリルアミン、ステアリルアミン、イソプロピルアミン若しくはＮ−アミノエチルピペラジンなどの脂肪族アミン類、又はベンジルアミン若しくはフェニチルアミンなどの芳香族アミン類などを挙げることができる。さらに他の官能基を有するものとして、ε−アミノカプロン酸などの炭素数１〜６のアミノカルボン酸、該アミノカルボン酸の炭素数１〜５、特に炭素数１〜３の低級アルコール（メチル、エチル、プロピル）エステル、さらにε−カプロラクタムのような該アミノカルボン酸のラクタムが挙げられる。これらは１種又は２種以上を使用することができる。 The monoamines (g) may be compounds having one primary amino group in the molecule, and may further have other functional groups. Representative examples of monoamines (g) include butylamine, monoethanolamine, cyclohexylamine, diethylaminoethylamine, laurylamine, stearylamine, isopropylamine or aliphatic amines such as N-aminoethylpiperazine, or benzylamine or Aromatic amines such as phenethylamine can be exemplified. Further, those having other functional groups include aminocarboxylic acids having 1 to 6 carbon atoms such as ε-aminocaproic acid, lower alcohols having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms (methyl, ethyl, etc.). , Propyl) esters, and also lactams of the aminocarboxylic acid such as ε-caprolactam. These can use 1 type (s) or 2 or more types.
前記一塩基性カルボン酸類（ｈ）は、分子中に少なくともカルボン酸又はその誘導体を１個有する化合物であればよい。例えば、カプロン酸、ステアリン酸、ラウリン酸、ミリスチン酸、オレイン酸等の脂肪族モノカルボン酸、又は上記各酸の炭素数１〜５、特に炭素数１〜３の低級アルコール（メチル、エチル、プロピル）エステルなどを挙げることができる。これらは１種又は２種以上を使用することができる。 The monobasic carboxylic acid (h) may be a compound having at least one carboxylic acid or derivative thereof in the molecule. For example, an aliphatic monocarboxylic acid such as caproic acid, stearic acid, lauric acid, myristic acid, oleic acid or the like, or a lower alcohol having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms (methyl, ethyl, propyl). ) Esters can be mentioned. These can use 1 type (s) or 2 or more types.
本発明におけるポリアミドポリアミンは、ポリアルキレンポリアミン類（ａ）と二塩基性カルボン酸類（ｂ）を任意の順序または同時に反応することで得られる。また、本発明におけるポリアミドポリアミンポリ尿素は、ポリアルキレンポリアミン類（ａ）と二塩基性カルボン酸類（ｂ）と尿素類（ｃ）を任意の順序で又は同時に反応することができる。例えば、ポリアルキレンポリアミン類（ａ）と尿素類（ｃ）とを反応させてポリアルキレンポリアミンポリ尿素を得、次いで、該ポリアルキレンポリアミンポリ尿素と二塩基性カルボン酸類（ｂ）を反応させること又は該ポリアルキレンポリアミンポリ尿素と二塩基性カルボン酸類（ｂ）を反応させた後にさらに尿素類（ｃ）を反応させることができる。また、ポリアルキレンポリアミン類（ａ）と二塩基性カルボン酸類（ｂ）とを反応させてポリアミドポリアミンを得、該ポリアミドポリアミンと尿素類（ｃ）とを反応させることもできる。 The polyamide polyamine in the present invention can be obtained by reacting the polyalkylene polyamine (a) and the dibasic carboxylic acid (b) in any order or simultaneously. The polyamide polyamine polyurea in the present invention can react polyalkylene polyamines (a), dibasic carboxylic acids (b) and ureas (c) in any order or simultaneously. For example, a polyalkylene polyamine (a) and a urea (c) are reacted to obtain a polyalkylene polyamine polyurea, and then the polyalkylene polyamine polyurea and a dibasic carboxylic acid (b) are reacted, or After reacting the polyalkylene polyamine polyurea with the dibasic carboxylic acid (b), the urea (c) can be further reacted. Alternatively, a polyalkylene polyamine (a) and a dibasic carboxylic acid (b) can be reacted to obtain a polyamide polyamine, and the polyamide polyamine and urea (c) can be reacted.
上記ポリアミドポリアミン（Ａ）を得る際のポリアルキレンポリアミン類（ａ）、二塩基性カルボン酸類（ｂ）の反応比は、ポリアルキレンポリアミン類（ａ）と二塩基性カルボン酸類（ｂ）のモル比が０．８〜１．４：１、特に０．８〜１．２：１の範囲とすることで、保存安定性に優れ、有用な湿潤紙力増強効果を示す陽イオン性熱硬化性樹脂が得られやすいので好ましく、上記のモル比が０．８より小さい場合は、得られる陽イオン性熱硬化性樹脂の十分な保存安定性が得られない場合がある。上記のモル比が１．４より大きい場合は、ポリアルキレンポリアミン類（ａ）と二塩基性カルボン酸類（ｂ）の重合度が上がりにくいため、ポリアミドポリアミンが所定の粘度に達するまで長時間を要するか又は所定の粘度に達しないため、得られる陽イオン性熱硬化性樹脂の湿潤紙力増強効果が十分得られない場合がある。 The reaction ratio of the polyalkylene polyamines (a) and the dibasic carboxylic acids (b) in obtaining the polyamide polyamine (A) is the molar ratio of the polyalkylene polyamines (a) and the dibasic carboxylic acids (b). Is in the range of 0.8 to 1.4: 1, in particular 0.8 to 1.2: 1, it is excellent in storage stability and exhibits a useful wet paper strength enhancing effect. Is preferable, and when the molar ratio is less than 0.8, sufficient storage stability of the obtained cationic thermosetting resin may not be obtained. When the above molar ratio is larger than 1.4, the degree of polymerization of the polyalkylene polyamines (a) and the dibasic carboxylic acids (b) is difficult to increase, so it takes a long time for the polyamide polyamine to reach a predetermined viscosity. Alternatively, since the predetermined viscosity is not reached, there is a case where the effect of enhancing the wet paper strength of the obtained cationic thermosetting resin cannot be obtained sufficiently.
また、上記ポリアミドポリアミンポリ尿素（Ｂ）を得る際のポリアルキレンポリアミン類（ａ）、二塩基性カルボン酸類（ｂ）及び尿素類（ｃ）の反応比は、ポリアルキレンポリアミン類（ａ）と二塩基性カルボン酸類（ｂ）のモル比が０．８〜１．４：１、特に０．８〜１．２：１の範囲とすることで、保存安定性に優れ、有用な湿潤紙力増強効果を示す陽イオン性熱硬化性樹脂が得られやすいので好ましく、上記のモル比が０．８より小さい場合は、得られる陽イオン性熱硬化性樹脂の十分な保存安定性が得られない場合がある。上記のモル比が１．４より大きい場合は、ポリアルキレンポリアミン類（ａ）と二塩基性カルボン酸類（ｂ）の重合度が上がりにくいため、ポリアミドポリアミンポリ尿素が所定の粘度に達するまで長時間を要するか又は所定の粘度に達しないため、得られる陽イオン性熱硬化性樹脂の湿潤紙力増強効果が十分得られない場合がある。一方、尿素類（ｃ）は、ポリアルキレンポリアミン類（ａ）のアミノ基１モルに対して０．００５〜０．９、特に０．０１〜０．６：１の範囲とすることで、安定化効果と湿潤紙力増強効果に優れた陽イオン性熱硬化性樹脂が得られやすいので好ましく、尿素類（ｃ）が０．００５よりも小さい場合は、得られる陽イオン性熱硬化性樹脂の十分な安定化効果が得られない場合があり、０．９よりも大きい場合は、得られる陽イオン性熱硬化性樹脂の湿潤紙力増強効果が十分得られない場合がある。 The reaction ratio of the polyalkylene polyamines (a), the dibasic carboxylic acids (b) and the ureas (c) in obtaining the polyamide polyamine polyurea (B) is the same as that of the polyalkylene polyamines (a). When the molar ratio of the basic carboxylic acids (b) is in the range of 0.8 to 1.4: 1, particularly 0.8 to 1.2: 1, the storage stability is excellent and the useful wet paper strength is enhanced. It is preferable because a cationic thermosetting resin having an effect is easily obtained. When the above molar ratio is less than 0.8, sufficient storage stability of the obtained cationic thermosetting resin cannot be obtained. There is. When the above molar ratio is larger than 1.4, the degree of polymerization of the polyalkylene polyamines (a) and the dibasic carboxylic acids (b) is difficult to increase, so it takes a long time for the polyamide polyamine polyurea to reach a predetermined viscosity. Or does not reach a predetermined viscosity, the resulting cationic thermosetting resin may not sufficiently achieve the wet paper strength enhancing effect. On the other hand, the urea (c) is stable by adjusting the amount to 0.005 to 0.9, particularly 0.01 to 0.6: 1 with respect to 1 mol of the amino group of the polyalkylene polyamine (a). It is preferable because a cationic thermosetting resin excellent in the effect of increasing the wet strength and wet paper strength can be easily obtained. When ureas (c) are smaller than 0.005, the obtained cationic thermosetting resin In some cases, a sufficient stabilizing effect cannot be obtained, and in the case where it is greater than 0.9, the wet paper strength enhancing effect of the obtained cationic thermosetting resin may not be sufficiently obtained.
また、上記（ａ）成分と（ｂ）成分の反応時、又は上記（ａ）成分と（ｂ）成分と（ｃ）成分の反応時に前記（ｇ）成分及び／又は（ｈ）成分を適宜加えて反応させることができる。モノアミン類（ｇ）、一塩基性カルボン酸類（ｈ）を反応させることで、ポリアミドポリアミン又はポリアミドポリアミンポリ尿素にモノアミン類及び／又は一塩基性カルボン酸類を脱水及び／又は脱アルコール縮合反応によって導入することができる。モノアミン類及び／又は一塩基性カルボン酸類を導入することによって、樹脂の末端アミノ基或いはカルボン酸基が封鎖され、得られる陽イオン性熱硬化性樹脂の保存安定性が向上することがある。このような末端封鎖基としてのモノアミン類とポリアルキレンポリアミン類及び／又は一塩基性カルボン酸類と二塩基性カルボン酸類の反応モル比は０．００１〜０．１：１の範囲であることが好ましい。 In addition, during the reaction of the component (a) and the component (b), or during the reaction of the component (a), the component (b), and the component (c), the component (g) and / or the component (h) are appropriately added. Can be reacted. Monoamines and / or monobasic carboxylic acids are introduced into polyamide polyamine or polyamide polyamine polyurea by dehydration and / or dealcoholization condensation reaction by reacting monoamines (g) and monobasic carboxylic acids (h). be able to. By introducing monoamines and / or monobasic carboxylic acids, the terminal amino group or carboxylic acid group of the resin is blocked, and the storage stability of the resulting cationic thermosetting resin may be improved. The reaction molar ratio of monoamines and polyalkylene polyamines and / or monobasic carboxylic acids and dibasic carboxylic acids as such end-capping groups is preferably in the range of 0.001 to 0.1: 1. .
ポリアルキレンポリアミン類（ａ）と二塩基性カルボン酸類（ｂ）との反応、又はポリアルキレンポリアミン類（ａ）と二塩基性カルボン酸類（ｂ）と尿素類（ｃ）との反応は、生成するポリアミドポリアミン、又はポリアミドポリアミンポリ尿素の５０％水溶液の２５℃における５０％水溶液の粘度が２００〜１，０００ｍＰａ・ｓとなるまで続けることにより、湿潤紙力増強効果、保存安定性に優れた陽イオン性熱硬化性樹脂が得られやすいので好ましい。 Reaction of polyalkylene polyamines (a) and dibasic carboxylic acids (b) or reaction of polyalkylene polyamines (a), dibasic carboxylic acids (b) and ureas (c) is produced. Cation excellent in wet paper strength enhancement effect and storage stability by continuing until the viscosity of a 50% aqueous solution of polyamide polyamine or polyamide polyamine polyurea at 25 ° C. reaches a viscosity of 200 to 1,000 mPa · s. This is preferable because a heat-curable thermosetting resin is easily obtained.
ポリアルキレンポリアミン類（ａ）、ポリアルキレンポリアミンポリ尿素、モノアミン類（ｇ）が有するアミノ基と、二塩基性カルボン酸類（ｂ）、一塩基性カルボン酸類（ｈ）が有するカルボン酸及び／その誘導体とを反応させるときは、原料仕込み時に発生する反応熱を利用するか、外部より加熱して脱水及び／又は脱アルコール反応を行い、その反応温度は１１０℃〜２５０℃、特に１２０℃〜１８０℃であることが好ましい。反応温度条件は出発原料の二塩基性カルボン酸類（ｂ）又は一塩基性カルボン酸類（ｈ）がカルボン酸であるのか、その誘導体であるのかによって適宜変更する。この際、重合反応の触媒として、硫酸、ベンゼンスルホン酸、パラトルエンスルホン酸などのスルホン酸類を使用することもできる。その使用量は、ポリアルキレンポリアミン１モルに対して０．００５〜０．１モル、特に０．０１〜０．０５モルが好ましい。 Polyalkylene polyamines (a), polyalkylene polyamine polyureas, amino groups of monoamines (g), dibasic carboxylic acids (b), carboxylic acids of monobasic carboxylic acids (h) and / or their derivatives Is reacted using the reaction heat generated during raw material charging or heated from the outside to perform dehydration and / or dealcoholization reaction, and the reaction temperature is 110 ° C to 250 ° C, particularly 120 ° C to 180 ° C. It is preferable that The reaction temperature conditions are appropriately changed depending on whether the starting dibasic carboxylic acid (b) or monobasic carboxylic acid (h) is a carboxylic acid or a derivative thereof. In this case, sulfonic acids such as sulfuric acid, benzenesulfonic acid, and paratoluenesulfonic acid can be used as a catalyst for the polymerization reaction. The amount used is preferably 0.005 to 0.1 mol, particularly preferably 0.01 to 0.05 mol, per 1 mol of the polyalkylene polyamine.
例えば、ポリアルキレンポリアミン、ポリアミドポリアミンが有するアミノ基と尿素類（ｃ）を反応させる場合、発生するアンモニアを系外に除去しながらアミド交換反応を行う。このときの反応温度は８０〜１８０℃、特に９０℃〜１６０℃とすることが、急激な粘度の上昇が伴いにくく、適度に反応が進行しやすくなるので好ましい。また、反応時間は反応温度に依存するものの、通常３０分〜１０時間である。 For example, when the amino group of polyalkylene polyamine or polyamide polyamine is reacted with ureas (c), an amide exchange reaction is performed while removing the generated ammonia out of the system. The reaction temperature at this time is preferably 80 to 180 ° C., particularly 90 ° C. to 160 ° C., since it is difficult for the viscosity to increase rapidly and the reaction proceeds moderately. Moreover, although reaction time is dependent on reaction temperature, it is 30 minutes-10 hours normally.
中間体のアミノ基の量は、下記の式によって中間体１ｇ中に含まれるアミンを中和するのに必要な塩酸量を測定することによって求めることができる。
アミノ基の量（ミリモル／ｇ）＝Ｖ×Ｆ×０．５／Ｓ
Ｖ：１／２規定の塩酸液の滴定量
Ｆ：１／２規定の塩酸液の力価
Ｓ：採取した試料の固形分量（ｇ）
The amount of the amino group of the intermediate can be determined by measuring the amount of hydrochloric acid necessary to neutralize the amine contained in 1 g of the intermediate according to the following formula.
Amino group content (mmol / g) = V × F × 0.5 / S
V: titration amount of 1/2 N hydrochloric acid solution F: titer of 1/2 N hydrochloric acid solution S: solid content (g) of sample collected
本発明に係る陽イオン性熱硬化性樹脂水溶液の製造方法は、前記のようにして得ることができる中間体に以下の態様を含む工程を有する。 The method for producing a cationic thermosetting resin aqueous solution according to the present invention includes a step including the following aspects in the intermediate that can be obtained as described above.
即ち、中間体にエピハロヒドリン類（Ｃ）成分と硫黄原子を含む求核性物質（Ｄ）成分及び窒素原子を含む求核性物質（Ｅ）を反応させる態様がある。 That is, there is an embodiment in which an epihalohydrin (C) component, a nucleophilic substance (D) component containing a sulfur atom, and a nucleophilic substance (E) containing a nitrogen atom are reacted with the intermediate.
本発明に使用されるエピハロヒドリン類（Ｃ）は、エピハロヒドリンのことであり、例えば、エピハロヒドリンとしては、エピクロロヒドリン、エピブロムヒドリンなどが挙げられるが、工業的にはエピクロロヒドリンが好ましい。 The epihalohydrins (C) used in the present invention are epihalohydrins. For example, epihalohydrins include epichlorohydrin, epibromohydrin, etc., but industrially epichlorohydrin is preferred. .
本発明に使用される硫黄原子を含む求核性物質（Ｄ）としては、硫黄原子を分子中に有し、求核性を有している化合物であればよく、亜硫酸ナトリウム、亜硫酸カリウム等の亜硫酸塩、亜硫酸水素ナトリウム、亜硫酸水素カリウム等の亜硫酸水素塩、チオ硫酸ナトリウム、チオ硫酸カリウム等のチオ硫酸塩、硫化ナトリウム、硫化カリウム等のアルカリ金属硫化物、水硫化ナトリウム、水硫化カリウム等のアルカリ金属水硫化物、チオシアン酸アンモニウム、チオシアン酸カリウム、チオシアン酸ナトリウム等のチオシアン酸塩及びメタ重亜硫酸ナトリウム、メタ重亜硫酸カリウム等のメタ重亜硫酸塩等の無機化合物、ならびに、２−メルカプトベンゾチアゾールまたはそのナトリウム塩、２−メルカプトベンゾイミダゾールまたはそのナトリウム塩、２−メルカプトチアゾールまたはそのナトリウム塩、２−メルカプトイミダゾールまたはそのナトリウム塩、アルキルチオールまたはそのナトリウム塩、ベンゼンチオールまたはそのナトリウム塩、チオ尿素等の有機化合物またはそのアルカリ金属塩等が挙げられ、これらの中から１種または２種以上使用できる。これらの中でも亜硫酸塩、亜硫酸水素塩、メタ重亜硫酸塩が好ましく、具体的には、亜硫酸水素ナトリウム、メタ重亜硫酸ナトリウムが好ましい。 The nucleophilic substance (D) containing a sulfur atom used in the present invention may be a compound having a sulfur atom in the molecule and having nucleophilicity, such as sodium sulfite and potassium sulfite. Bisulfites such as sulfites, sodium bisulfite, potassium bisulfite, thiosulfates such as sodium thiosulfate and potassium thiosulfate, alkali metal sulfides such as sodium sulfide and potassium sulfide, sodium hydrosulfide, potassium hydrosulfide, etc. Inorganic compounds such as alkali metal hydrosulfides, thiocyanates such as ammonium thiocyanate, potassium thiocyanate, sodium thiocyanate, and metabisulfites such as sodium metabisulfite and potassium metabisulfite, and 2-mercaptobenzothiazole Or its sodium salt, 2-mercaptobenzimidazole or its sodium Um salt, 2-mercaptothiazole or sodium salt thereof, 2-mercaptoimidazole or sodium salt thereof, alkylthiol or sodium salt thereof, benzenethiol or sodium salt thereof, organic compounds such as thiourea or alkali metal salts thereof , One or more of these can be used. Among these, sulfite, bisulfite, and metabisulfite are preferable, and specifically, sodium hydrogensulfite and sodium metabisulfite are preferable.
本発明に使用される窒素原子を含む求核性物質無機塩基性物質（Ｅ）としては、メチルアミン、エチルアミン、モノエタノールアミンなどのモノアルキルアミン、ジメチルアミン、ジエチルアミン、ジエタノールアミンなどのジアルキルアミン、トリメチルアミン、トリエチルアミン、トリエタノールアミンなどのトリアルキルアミン、アンモニア、或いは、エチレンジアミン、ジエチレントリアミン、テトラエチレンペンタミン、イミノビスプロピルアミンなどのポリアルキレンポリアミンやポリビニルアミンなどが挙げられ、これらの中から１種または２種以上使用できる。これらの中でもアンモニアが好ましい。 Examples of the nucleophilic substance inorganic basic substance (E) containing a nitrogen atom used in the present invention include monoalkylamines such as methylamine, ethylamine and monoethanolamine, dialkylamines such as dimethylamine, diethylamine and diethanolamine, and trimethylamine , Trialkylamines such as triethylamine and triethanolamine, ammonia, and polyalkylenepolyamines such as ethylenediamine, diethylenetriamine, tetraethylenepentamine, iminobispropylamine, and polyvinylamine. More than seeds can be used. Among these, ammonia is preferable.
エピハロヒドリン類（Ｃ）の量は、中間体のアミノ基１モルに対して、０．７〜２モル、特に０．８〜１．５モルとすることで、高固形分で保存安定性及び湿潤紙力増強効果に優れ、ＡＯＸ含有量の少ない陽イオン性熱硬化性樹脂が得られやすいので好ましい。 The amount of the epihalohydrins (C) is 0.7 to 2 mol, particularly 0.8 to 1.5 mol, based on 1 mol of the amino group of the intermediate, so that the storage stability and wetness are high at a high solid content. A cationic thermosetting resin having an excellent paper strength enhancing effect and a low AOX content is easily obtained, which is preferable.
硫黄原子を含む求核性物質（Ｄ）の量は中間体のアミノ基１モルに対して０．００１〜０．３モル、特に０．００５〜０．２モル使用することが好ましい。０．００１より少ない場合にはAOXを低減する効果が不十分であり、０．３より多い場合には湿潤紙力効果に悪影響を及ぼす場合がある。 The amount of the nucleophilic substance (D) containing a sulfur atom is preferably 0.001 to 0.3 mol, particularly 0.005 to 0.2 mol, relative to 1 mol of the amino group of the intermediate. When it is less than 0.001, the effect of reducing AOX is insufficient, and when it is more than 0.3, the wet paper strength effect may be adversely affected.
窒素原子を含む求核性物質（Ｅ）の量は中間体のアミノ基１モルに対して０．００１〜０．３モル、特に０．００５〜０．２モル使用することが好ましい。０．００１より少ない場合にはAOXを低減する効果が不十分であり、０．３より多い場合には湿潤紙力効果に悪影響を及ぼす場合がある。 The amount of the nucleophilic substance (E) containing a nitrogen atom is preferably 0.001 to 0.3 mol, particularly preferably 0.005 to 0.2 mol, per mol of the amino group of the intermediate. When it is less than 0.001, the effect of reducing AOX is insufficient, and when it is more than 0.3, the wet paper strength effect may be adversely affected.
中間体とエピハロヒドリン類（Ｃ）との反応は反応液の濃度が１０〜８０質量％、反応温度は反応濃度に依存するものの５〜９０℃で行うことが好ましい。 The reaction between the intermediate and the epihalohydrins (C) is preferably carried out at a reaction solution concentration of 10 to 80% by mass and a reaction temperature of 5 to 90 ° C., although it depends on the reaction concentration.
特に、中間体とエピハロヒドリン類（Ｃ）との反応は、中間体にエピハロヒドリン類（Ｃ）を付加させる工程（１次工程と称することがある）と、さらに架橋反応により粘度を増加させる工程（２次工程と称することがある）を経ることが好ましく、硫黄原子を含む求核性物質（Ｄ）及び窒素原子を含む求核性物質（Ｅ）は１次工程、２次工程のいずれか又は複数の箇所において中間体とエピハロヒドリンの反応物にさらに反応させることができる。 In particular, the reaction between the intermediate and the epihalohydrin (C) includes a step of adding the epihalohydrin (C) to the intermediate (sometimes referred to as a primary step) and a step of further increasing the viscosity by a crosslinking reaction (2 The nucleophilic substance (D) containing a sulfur atom and the nucleophilic substance (E) containing a nitrogen atom may be either a primary process or a secondary process. The intermediate can be further reacted with the reaction product of the intermediate and epihalohydrin.
前記１次工程における中間体とエピハロヒドリン類（Ｃ）との反応は、中間体の濃度が３０〜８０質量％、特に４０〜７０質量％の水溶液で行われることが、樹脂水溶液の急激な粘度上昇を伴わずに適度に反応が進行しやすいので好ましい。この１次工程における反応温度は急激な粘度の上昇を伴わないように、また中間体とエピハロヒドリン類（Ｃ）との付加の効率が低下しないようにすることが好ましく、反応温度が５〜５０℃、特に１０〜４５℃、さらに好ましくは１５〜３５℃の範囲で反応を進めることが好ましい。また、反応時間は１〜１０時間とすることが好ましい。 The reaction between the intermediate and the epihalohydrin (C) in the primary step is carried out in an aqueous solution having an intermediate concentration of 30 to 80% by mass, particularly 40 to 70% by mass. It is preferable because the reaction easily proceeds moderately without accompanying. It is preferable that the reaction temperature in this primary step is not accompanied by a sudden increase in viscosity and that the efficiency of addition of the intermediate and the epihalohydrin (C) is not lowered, and the reaction temperature is 5 to 50 ° C. In particular, it is preferable to proceed the reaction in the range of 10 to 45 ° C, more preferably 15 to 35 ° C. The reaction time is preferably 1 to 10 hours.
前記２次工程として、反応液を希釈して、又は希釈することなく、反応温度を３０〜９０℃、特に５０〜７５℃に加熱し、反応を続けることが好ましい。通常、２次工程の際に加熱温度が高くなると反応混合物の粘度が急激に上昇して反応の制御が困難になることがあるので、２次工程において、反応水溶液の濃度を１０〜７０％に、特に１０〜５０％に希釈するのが好ましい。更に、硫酸、硝酸、及びリン酸などの無機酸、ギ酸、及び酢酸などの有機酸、好ましくは特にハロゲンを含まない無機酸、並びに有機酸などの一種以上の酸を中間体とエピハロヒドリン類（Ｃ）との反応物の反応制御を容易にするために、中間体のアミノ基に対し０．０１〜０．７当量、特に０．０２〜０．３５当量加えることが好ましい。 As the secondary step, it is preferable to continue the reaction by diluting the reaction solution or heating the reaction solution to 30 to 90 ° C., particularly 50 to 75 ° C. without diluting. Usually, when the heating temperature is increased during the secondary process, the viscosity of the reaction mixture may increase rapidly, making it difficult to control the reaction. Therefore, in the secondary process, the concentration of the aqueous reaction solution is adjusted to 10 to 70%. In particular, it is preferable to dilute to 10 to 50%. Further, an inorganic acid such as sulfuric acid, nitric acid, and phosphoric acid, an organic acid such as formic acid, and acetic acid, preferably an inorganic acid that does not contain halogen, and one or more acids such as an organic acid as intermediates and epihalohydrins (C In order to facilitate the reaction control of the reaction product with), it is preferable to add 0.01 to 0.7 equivalent, particularly 0.02 to 0.35 equivalent, relative to the amino group of the intermediate.
前記２次工程の反応は、生成物の固形分が２５質量％水溶液の２５℃における粘度が３００ｍＰａ・ｓ以下、特に５０〜２５０ｍＰａ・ｓに達するまで反応を続けることで、保存安定性に優れた陽イオン性熱硬化性樹脂水溶液が得られやすく、また、抄紙工程においてパルプスラリーに添加すると、著しい発泡を伴わないので、抄紙作業を容易にし、抄造される紙の地合いが良好になりやすいので好ましい。 The reaction in the secondary step is excellent in storage stability by continuing the reaction until the solid content of the product reaches a viscosity of 300 mPa · s or less, particularly 50 to 250 mPa · s, at 25 ° C. in a 25 mass% aqueous solution. It is easy to obtain a cationic thermosetting resin aqueous solution, and when added to the pulp slurry in the paper making process, it is not accompanied by significant foaming, so that the paper making work is facilitated and the texture of the paper to be made is likely to be good. .
反応生成物に水を加えて反応を停止させ、冷却すると同時に固形分を１０〜５０％に調節することが好ましい。更に、塩酸、硫酸、硝酸、及びリン酸などの無機酸、ギ酸、及び酢酸などの有機酸、特にハロゲンを含まない無機酸、並びに有機酸などの一種以上の酸を加えて、好ましくはｐＨを１〜６、特にｐＨ２〜５に調整することで、得られる陽イオン性熱硬化性樹脂水溶液の保存安定性を向上させることが好ましい。 It is preferable that water is added to the reaction product to stop the reaction, and the solid content is adjusted to 10 to 50% while cooling. Further, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, an organic acid such as formic acid and acetic acid, particularly an inorganic acid not containing halogen, and one or more acids such as organic acid are preferably added to adjust the pH. It is preferable to improve the storage stability of the aqueous cationic thermosetting resin solution obtained by adjusting the pH to 1 to 6, particularly 2 to 5.
反応液の２５％水溶液の２５℃の粘度が５０ｃｐｓ未満であると、陽イオン性熱硬化性樹脂を湿潤紙力増強剤として用いたときの性能が十分でない場合があり、また、３００ｃｐｓを越えると、陽イオン性熱硬化性樹脂の水溶液の保存安定性が悪くなるばかりでなく、抄紙工程においてパルプスラリーに添加すると、発泡が生じ、抄紙作業を困難になる場合がある。反応液の粘度が前記の粘度範囲に到達したら、必要に応じて水を加えて固形分を２０〜４０％に調節し、さらに、ハロゲンを含まない酸、例えば硫酸、硝酸、リン酸などの無機酸、あるいはギ酸、酢酸などの有機酸などのうち１種以上の酸を加えてｐＨを２．５〜３．５に調整し陽イオン性熱硬化性樹脂の水溶液を得る。 When the viscosity at 25 ° C. of a 25% aqueous solution of the reaction solution is less than 50 cps, the performance when the cationic thermosetting resin is used as a wet paper strength enhancer may not be sufficient, and when the viscosity exceeds 300 cps. Further, not only the storage stability of the aqueous solution of the cationic thermosetting resin is deteriorated, but if it is added to the pulp slurry in the paper making process, foaming may occur and the paper making operation may be difficult. When the viscosity of the reaction solution reaches the above viscosity range, water is added as necessary to adjust the solid content to 20 to 40%, and further, an acid containing no halogen, for example, inorganic such as sulfuric acid, nitric acid, phosphoric acid, etc. One or more acids among acids or organic acids such as formic acid and acetic acid are added to adjust the pH to 2.5 to 3.5 to obtain an aqueous solution of a cationic thermosetting resin.
このようにしてポリアミドポリアミン（Ａ）及び／又はポリアミドポリアミンポリ尿素（Ｂ）にエピハロヒドリン類（Ｃ）と硫黄原子と含む求核性物質（Ｄ）及び窒素原子を含む求核性物質（Ｅ）を反応させることによりポリアミドポリアミン−エピハロヒドリン樹脂またはポリアミドポリアミンポリ尿素−エピハロヒドリン樹脂が得られる。この陽イオン性熱硬化性樹脂は、従来のポリアミドポリアミン−エピハロヒドリン樹脂またはポリアミドポリアミンポリ尿素−エピハロヒドリン樹脂に比べ高固形分にもかかわらず粘度安定性に優れ、従来のポリアミドポリアミン−エピハロヒドリン樹脂又はポリアミドポリアミン尿素−エピハロヒドリン樹脂よりも樹脂中のＡＯＸ含有量が著しく少なく優れた湿潤紙力効果を示すという極めて優れた性質を有している。 In this way, the polyamidopolyamine (A) and / or the polyamidopolyamine polyurea (B) are converted to the nucleophilic substance (E) containing epihalohydrins (C) and sulfur atoms and the nucleophilic substance (E) containing nitrogen atoms. By reacting, a polyamide polyamine-epihalohydrin resin or a polyamide polyamine polyurea-epihalohydrin resin is obtained. This cationic thermosetting resin is superior in viscosity stability to the conventional polyamide polyamine-epihalohydrin resin or polyamide polyamine polyurea-epihalohydrin resin in spite of its high solid content, and has a conventional polyamide polyamine-epihalohydrin resin or polyamide polyamine. Compared to urea-epihalohydrin resin, the resin has an extremely excellent property that the AOX content in the resin is remarkably low and an excellent wet paper strength effect is exhibited.
本発明の製造方法によって得られる陽イオン性熱硬化性樹脂は、湿潤紙力増強剤やクレープ剤助剤として使用することができる。 The cationic thermosetting resin obtained by the production method of the present invention can be used as a wet paper strength enhancer or a crepe agent auxiliary.
本発明の製造方法によって得られる陽イオン性熱硬化性樹脂を湿潤紙力増強剤として使用することにより、紙に有用な湿潤紙力増強効果を与えることができる。湿潤紙力増強剤としての使用方法は、例えば、湿潤紙力増強剤をパルプスラリーに添加する方法、抄紙された紙にサイズプレス、ゲートロールコーター等を用いて湿潤紙力増強剤を表面塗工あるいは含浸加工する方法などが挙げられ、中でも湿潤紙力増強剤をパルプスラリーに添加する方法（内添）が好適である。 By using the cationic thermosetting resin obtained by the production method of the present invention as a wet paper strength enhancer, it is possible to give a useful wet paper strength enhancement effect to paper. The method of using the wet paper strength enhancer includes, for example, a method of adding a wet paper strength enhancer to the pulp slurry, and applying a wet paper strength enhancer to the paper-made paper using a size press, a gate roll coater, or the like. Alternatively, a method of impregnating and the like can be mentioned, and among them, a method of adding a wet paper strength enhancer to the pulp slurry (internal addition) is preferable.
湿潤紙力増強剤として内添して使用する場合は、パルプの水性分散液に又はファンポンプ部の白水中にパルプの乾燥質量当たり通常０．０１〜５固形分質量％、好ましくは０．０５〜３固形分質量％を添加して使用することができる。添加する際の陽イオン性熱硬化性樹脂は１〜２００倍に希釈して適宜使用されることが好ましい。 When used internally as a wet paper strength enhancer, it is usually 0.01 to 5% by mass, preferably 0.05, per dry mass of the pulp in the aqueous dispersion of the pulp or in the white water of the fan pump part. It can be used by adding ~ 3% solids by weight. It is preferable that the cationic thermosetting resin at the time of addition is appropriately used after being diluted 1 to 200 times.
また、本発明の製造方法によって得られる陽イオン性熱硬化性樹脂をクレープ剤助剤として使用することにより、例えば、ティシュペーパー等の家庭紙の製造工程で、すなわちヤンキードライヤー表面に接着した紙匹をヤンキードライヤー表面からドクターブレードで剥離させることで優れたクレープを付与することができる。クレープ剤助剤としての使用方法としては、パルプスラリーに添加する方法、ヤンキードライヤーの前方で湿紙にスプレーする方法、ヤンキードライヤーの表面に直接スプレーする方法、及びこれら前記方法を組み合わせて行う方法がある。 Further, by using the cationic thermosetting resin obtained by the production method of the present invention as a crepe agent auxiliary agent, for example, in the production process of household paper such as tissue paper, that is, a paper sheet adhered to the surface of the Yankee dryer. An excellent crepe can be imparted by separating the surface from the surface of the Yankee dryer with a doctor blade. As a method of using as a crepe aid, there are a method of adding to a pulp slurry, a method of spraying wet paper in front of a Yankee dryer, a method of spraying directly on the surface of a Yankee dryer, and a method of combining these methods. is there.
クレープ剤助剤として使用する場合は、パルプの乾燥質量当たり通常０．００１〜５固形分質量％、好ましくは０．０１〜３固形分質量％を添加して使用することができる。 When used as a crepe agent auxiliary, it can be used usually by adding 0.001 to 5 solids mass%, preferably 0.01 to 3 solids mass% per dry mass of the pulp.
本発明の紙は、硫酸アルミニウムを用いる酸性系、または、硫酸アルミニウムを全く用いないかあるいは少量用いる中性系のいずれのパイプスラリーを用いても良い。また、パルプスラリーに対して、酸性ロジン系サイズ剤、中性ロジン系サイズ剤、アルキルケテンダイマー系サイズ剤、アルケニルもしくはアルキルコハク酸無水物系サイズ剤などを添加しても良い。サイズ剤の添加方法としては、例えば、パルプスラリーにサイズ剤を添加した後、湿潤紙力増強剤を添加する方法、湿潤紙力増強剤を添加した後、サイズ剤を添加する方法、サイズ剤に湿潤紙力増強剤を希釈して予め混合した後、添加する方法などが挙げられる。また、他に、パルプスラリーにサイズ定着剤、乾燥紙力増強剤、消泡剤、クレー、カオリン、炭酸カルシウム、硫酸バリウム、酸化チタン等の充填剤、ｐＨ調整剤、染料、蛍光増白剤等を適宜含有せしめてもよい。また、製造される紙は、通常、坪量が１０〜４００ｇ／ｍ２程度である。 The paper of the present invention may use any pipe slurry of an acidic type using aluminum sulfate or a neutral type using no or a small amount of aluminum sulfate. Further, an acidic rosin sizing agent, a neutral rosin sizing agent, an alkyl ketene dimer sizing agent, an alkenyl or alkyl succinic anhydride sizing agent, and the like may be added to the pulp slurry. Examples of the method of adding the sizing agent include a method of adding a sizing agent after adding a sizing agent to a pulp slurry, a method of adding a sizing agent after adding a wet paper strength enhancing agent, and a sizing agent. Examples include a method of adding a wet paper strength enhancer after diluting and mixing in advance. In addition, size fixers, dry paper strength enhancers, antifoaming agents, clay, kaolin, calcium carbonate, barium sulfate, titanium oxide and other fillers, pH adjusters, dyes, fluorescent whitening agents, etc. May be included as appropriate. Moreover, the paper to be manufactured usually has a basis weight of about 10 to 400 g / m 2 .
本発明の製造方法によって得られる陽イオン性熱硬化性樹脂を湿潤紙力増強剤やクレープ剤助剤として使用する場合のパルプ原料としては、クラフトパルプ、及びサルファイトパルプの晒並びに未晒化学パルプ、砕木パルプ、機械パルプ、及びサーモメカニカルパルプ等の晒並びに未晒高収率パルプ、新聞古紙、雑誌古紙、段ボール古紙及び脱墨古紙等の古紙パルプを挙げることができ、これらの１種又は２種以上を使用することができる。 As a pulp raw material when the cationic thermosetting resin obtained by the production method of the present invention is used as a wet paper strength enhancer or a crepe agent auxiliary, kraft pulp, bleached sulfite pulp and unbleached chemical pulp And recycled paper pulp such as bleached and unbleached high-yield pulp such as groundwood pulp, mechanical pulp, and thermomechanical pulp, newspaper waste paper, magazine waste paper, corrugated waste paper, and deinked waste paper. More than seeds can be used.
また、前記原料パルプからなるパルプスラリーに、填料、染料、乾燥紙力増強剤、歩留り向上剤、及びサイズ剤等の添加剤も必要に応じて使用しても良い。更にサイズプレス、ゲートロールコーター、ビルブレードコーター、及びキャレンダー等で、澱粉、ポリビニルアルコール、アクリルアミド系ポリマー等の表面紙力増強剤、表面サイズ剤、染料、コーティングカラー及び防滑剤等を必要に応じて塗布しても良い。 Moreover, you may use additives, such as a filler, a dye, a dry paper strength enhancer, a yield improving agent, and a sizing agent, in the pulp slurry which consists of the said raw material pulp as needed. Furthermore, with a size press, gate roll coater, bill blade coater, calendar, etc., surface paper strength enhancer such as starch, polyvinyl alcohol, acrylamide polymer, surface sizing agent, dye, coating color and anti-slip agent, etc., as required May be applied.
本発明の製造方法によって得られる陽イオン性熱硬化性樹脂を湿潤紙力増強剤として用いて製造される紙としては、ＰＰＣ用紙・感光紙原紙・感熱紙原紙のような情報用紙、ティシュペーパー・タオルペーパー・ナプキン原紙のような衛生用紙、化粧板原紙・壁紙原紙・印画紙用紙・積層板原紙・食品容器原紙のような加工原紙、重袋用両更クラフト紙・片艶クラフト紙などの包装用紙、電気絶縁紙、耐水ライナー、耐水中芯、新聞用紙、紙器用板紙等が該当し、何れの抄紙工程においても、抄造された紙に有用な湿潤紙力増強効果を与える。本発明の陽イオン性熱硬化性樹脂を湿潤紙力増強剤として使用すると紙中に残存する無機ハロゲン分が少ない特徴があることから、無機ハロゲン分を特に低減する必要がある紙に使用することが好ましい。紙中の無機ハロゲン分を特に低減する必要がある紙としては、電気絶縁紙、積層板原紙等が挙げられる。なお、本発明でいう紙には板紙も含まれる。 Paper produced using the cationic thermosetting resin obtained by the production method of the present invention as a wet paper strength enhancer includes information paper such as PPC paper, photosensitive paper base, and thermal paper base, tissue paper, Sanitary paper such as towel paper and napkin base paper, decorative base paper, wallpaper base paper, photographic paper paper, laminated base paper, processed base paper such as food container base paper, packaging of double kraft paper for heavy bags, single gloss craft paper, etc. Paper, electrical insulating paper, water-resistant liner, water-resistant core, newsprint paper, paperboard paperboard, and the like are applicable, and in any papermaking process, a useful wet paper strength enhancing effect is given to the papermaking. When the cationic thermosetting resin of the present invention is used as a wet paper strength enhancer, it has a feature that there is little inorganic halogen remaining in the paper. Is preferred. Examples of paper that needs to particularly reduce the inorganic halogen content in the paper include electrically insulating paper and laminated base paper. The paper referred to in the present invention includes paperboard.
さらには、本発明の製造方法によって得られる陽イオン性熱硬化性樹脂を、酵素やイオン交換樹脂によってＡＯＸを分解することにより、さらにＡＯＸを低減することができるため好ましい。 Furthermore, the cationic thermosetting resin obtained by the production method of the present invention is preferable because AOX can be further reduced by decomposing AOX with an enzyme or an ion exchange resin.
以下、本発明の実施例および比較例を挙げて具体的に説明するが、本発明はこれらの例に限定されるものではない。なお、各例中、％は特記しない限りすべて重量％である。 Hereinafter, although an example and a comparative example of the present invention are given and explained concretely, the present invention is not limited to these examples. In each example, “%” means “% by weight” unless otherwise specified.
合成例１＜ポリアミドポリアミンの合成＞
温度計、冷却器、撹拌機、窒素導入管を備えた５リットル四つ口丸底フラスコに、ジエチレントリアミン８３２ｇ（８．０８モル）を仕込み、撹拌しながらアジピン酸１１６９ｇ（８モル）を加え、窒素気流下、生成する水を系外に除去しながら昇温し、１７５℃で３時間反応させた後、水１５００ｇを徐々に加えてポリアミドポリアミンの水溶液を得た。このポリアミドポリアミンの水溶液は固形分５０．７％であり、その固形分５０％の粘度は５２８ｍＰａ・ｓ（２５℃）であった。固形分中のアミノ基の量は５．０４ミリモル／ｇであった。
Synthesis Example 1 <Synthesis of polyamide polyamine>
A 5 liter four-necked round bottom flask equipped with a thermometer, a condenser, a stirrer, and a nitrogen inlet tube was charged with 832 g (8.08 mol) of diethylenetriamine, and 1169 g (8 mol) of adipic acid was added with stirring. The temperature was raised while removing the generated water out of the system under an air stream, and the mixture was reacted at 175 ° C. for 3 hours. Then, 1500 g of water was gradually added to obtain an aqueous solution of polyamidepolyamine. This polyamide polyamine aqueous solution had a solid content of 50.7%, and the viscosity of the solid content of 50% was 528 mPa · s (25 ° C.). The amount of amino groups in the solid content was 5.04 mmol / g.
合成例２＜ポリアミドポリアミンポリ尿素の合成＞
実施例１と同様の反応装置にジエチレントリアミン１０８ｇ（１．０５モル）を仕込み、攪拌しながらアジピン酸１４６ｇ（１．０モル）を加え、窒素気流下、生成する水を系外に除去しながら昇温し、１７０℃で５時間反応を行った。次いで反応液を１２０℃まで冷却し、尿素６ｇ（０．１モル）を加えて同温度で１．５時間脱アンモニア反応を行った後、水を徐々に加えてポリアミドポリアミンポリ尿素の水溶液を得た。このポリアミドポリアミンポリ尿素の水溶液は固形分５１．３％であり、その固形分５０％の粘度は５４５ｍＰａ・ｓ（２５℃）であった。固形分中のアミノ基の量は４．７９ミリモル／ｇであった。
Synthesis Example 2 <Synthesis of polyamide polyamine polyurea>
In a reactor similar to Example 1, 108 g (1.05 mol) of diethylenetriamine was added, and 146 g (1.0 mol) of adipic acid was added with stirring. The reaction was carried out at 170 ° C. for 5 hours. Next, the reaction solution was cooled to 120 ° C., 6 g (0.1 mol) of urea was added and a deammonia reaction was performed at the same temperature for 1.5 hours, and then water was gradually added to obtain an aqueous solution of polyamide polyamine polyurea. It was. The polyamide polyamine polyurea aqueous solution had a solid content of 51.3%, and the viscosity of the solid content of 50% was 545 mPa · s (25 ° C.). The amount of amino groups in the solid content was 4.79 mmol / g.
実施例1
温度計、還流冷却器、撹拌機、滴下ロートを備えた５００ｍｌ四つ口フラスコに、合成例１で得られたポリアミドポリアミン水溶液１１７．４ｇ（ポリアミドポリアミン中のアミノ基の量として０．３モル）を仕込み、水を加え固形分４０％に希釈した。２０℃でエピクロルヒドリン３１．９ｇ（０．３４５モル）を滴下した。３０℃に昇温して１．５時間同温度で保持した後（１次保温）。次いで、亜硫酸水素ナトリウム３．６ｇ（ポリアミドポリアミンのアミノ基に対し０．１０当量）、アンモニア０．５ｇ（ポリアミドポリアミンのアミノ基に対し０．１０当量）を加え、３０℃でさらに２時間保温した。次いで、水１２８．６ｇを加えて固形分を３０％とした後、３０％硫酸７．３ｇを加え、６５℃まで昇温してこの温度を保持し、反応液の粘度が３００ｍＰａ・ｓに到達した時点で、さらに水７０．２ｇ、３０％硫酸３．９ｇおよび８８％ギ酸２．０ｇ加えて冷却した。得られた樹脂水溶液の性状及びＤＣＰ含有量を表２に示した。なお、ＤＣＰの含有量は樹脂水溶液当たりの値で定量はガスクロマトグラフィーにより行ったものをいう（以下、同様）。
Example 1
In a 500 ml four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, 117.4 g of the polyamide polyamine aqueous solution obtained in Synthesis Example 1 (0.3 mol as the amount of amino groups in the polyamide polyamine) Was added and diluted with water to a solid content of 40%. Epichlorohydrin 31.9g (0.345mol) was dripped at 20 degreeC. The temperature was raised to 30 ° C. and held at the same temperature for 1.5 hours (primary heat retention). Next, 3.6 g of sodium hydrogen sulfite (0.10 equivalent to the amino group of the polyamide polyamine) and 0.5 g of ammonia (0.10 equivalent to the amino group of the polyamide polyamine) were added, and the mixture was further kept at 30 ° C. for 2 hours. . Next, 128.6 g of water was added to make the solid content 30%, then 7.3 g of 30% sulfuric acid was added, the temperature was raised to 65 ° C. and this temperature was maintained, and the viscosity of the reaction solution reached 300 mPa · s. At that time, 70.2 g of water, 3.9 g of 30% sulfuric acid and 2.0 g of 88% formic acid were further added and cooled. Table 2 shows the properties of the aqueous resin solution and the DCP content. The content of DCP is a value per aqueous resin solution, and quantification is performed by gas chromatography (hereinafter the same).
実施例２
実施例１と同様の装置に、合成例２で得られたポリアミドポリアミンポリ尿素水溶液１２２．１ｇ（ポリアミドポリアミンポリ尿素中のアミノ基の量として０．３モル）を仕込み、水を加え固形分４０％に希釈した。２０℃でエピクロルヒドリン３１．９ｇ（０．３４５モル）を滴下した。３０℃に昇温して１．５時間同温度で保持した後（１次保温）。次いで、亜硫酸水素ナトリウム３．６ｇ（ポリアミドポリアミンポリ尿素のアミノ基に対し０．１０当量）、アンモニア０．５ｇ（ポリアミドポリアミンポリ尿素のアミノ基に対し０．１０当量）を加え、３０℃でさらに２時間保温した。次いで、水１３１．２ｇを加えて固形分を３０％とした後、３０％硫酸７．２ｇを加え、６５℃まで昇温してこの温度を保持し、反応液の粘度が３００ｍＰａ・ｓに到達した時点で、さらに水７２．２ｇ、３０％硫酸３．９ｇおよび８８％ギ酸２．０ｇ加えて冷却した。得られた樹脂水溶液の性状及びＤＣＰ含有量を表２に示した。
Example 2
In the same apparatus as in Example 1, 122.1 g of the polyamide polyamine polyurea aqueous solution obtained in Synthesis Example 2 (0.3 mol as the amount of amino groups in the polyamide polyamine polyurea) was charged, water was added, and the solid content was 40. Diluted to%. Epichlorohydrin 31.9g (0.345mol) was dripped at 20 degreeC. The temperature was raised to 30 ° C. and held at the same temperature for 1.5 hours (primary heat retention). Next, 3.6 g of sodium hydrogen sulfite (0.10 equivalent to the amino group of the polyamide polyamine polyurea) and 0.5 g of ammonia (0.10 equivalent to the amino group of the polyamide polyamine polyurea) were added, and further at 30 ° C. Incubated for 2 hours. Next, 131.2 g of water was added to adjust the solid content to 30%, then 7.2 g of 30% sulfuric acid was added, the temperature was raised to 65 ° C. and this temperature was maintained, and the viscosity of the reaction solution reached 300 mPa · s. At that time, 72.2 g of water, 3.9 g of 30% sulfuric acid and 2.0 g of 88% formic acid were added and cooled. Table 2 shows the properties of the aqueous resin solution and the DCP content.
実施例３
実施例１において、亜硫酸水素ナトリウム３．６ｇ（ポリアミドポリアミンのアミノ基に対し０．１０当量）に代えて、メタ重亜硫酸ナトリウム２．８ｇ（ポリアミドポリアミンのアミノ基に対し０．１０当量）、アンモニア０．５ｇ（ポリアミドポリアミンのアミノ基に対し０．１０当量）を加えた後、３０℃でさらに２時間保温した。次いで、水１２８．６ｇを加えて固形分を３０％とした後、３０％硫酸７．３ｇを加え、６５℃まで昇温してこの温度を保持し、反応液の粘度が３００ｍＰａ・ｓに到達した時点で、さらに水７０．２ｇ、３０％硫酸３．９ｇおよび８８％ギ酸２．０ｇ加えて冷却した。得られた樹脂水溶液の性状及びＤＣＰ含有量を表２に示した。
Example 3
In Example 1, instead of 3.6 g of sodium hydrogen sulfite (0.10 equivalent to the amino group of polyamide polyamine), 2.8 g of sodium metabisulfite (0.10 equivalent to the amino group of polyamide polyamine), ammonia After adding 0.5 g (0.10 equivalent with respect to the amino group of the polyamide polyamine), the mixture was further kept at 30 ° C. for 2 hours. Next, 128.6 g of water was added to make the solid content 30%, then 7.3 g of 30% sulfuric acid was added, the temperature was raised to 65 ° C. and this temperature was maintained, and the viscosity of the reaction solution reached 300 mPa · s. At that time, 70.2 g of water, 3.9 g of 30% sulfuric acid and 2.0 g of 88% formic acid were further added and cooled. Table 2 shows the properties of the aqueous resin solution and the DCP content.
実施例４〜７
実施例１において、１次保温後に加える硫黄原子を含む求核性物質の種類、窒素原子を含む求核性物質の種類、それぞれの使用量および、６５℃への昇温前に加える硫酸量を表１に示すように変えた以外は、実施例３と同様に反応を行った。得られた樹脂水溶液の性状及びＤＣＰ含有量を表２に示した。
Examples 4-7
In Example 1, the kind of nucleophilic substance containing sulfur atoms added after the primary heat retention, the kind of nucleophilic substance containing nitrogen atoms, the amount of each used, and the amount of sulfuric acid added before raising the temperature to 65 ° C. The reaction was performed in the same manner as in Example 3 except that the conditions were changed as shown in Table 1. Table 2 shows the properties of the aqueous resin solution and the DCP content.
比較例１
実施例１において、１次保温後に亜硫酸水素ナトリウム及びアンモニアを加えなかった以外は実施例１と同様に反応を行った。得られた樹脂水溶液の性状及びＤＣＰ含有量を表２に示した。
Comparative Example 1
In Example 1, the reaction was carried out in the same manner as in Example 1 except that sodium hydrogen sulfite and ammonia were not added after the primary incubation. Table 2 shows the properties of the aqueous resin solution and the DCP content.
比較例２
実施例２において、１次保温後に亜硫酸水素ナトリウム及びアンモニアを加えなかった以外は実施例３と同様に反応を行った。得られた樹脂水溶液の性状及びＤＣＰ含有量を表２に示した。
Comparative Example 2
In Example 2, the reaction was performed in the same manner as in Example 3 except that sodium hydrogen sulfite and ammonia were not added after the primary incubation. Table 2 shows the properties of the aqueous resin solution and the DCP content.
比較例３
実施例１において、１次保温後に亜硫酸水素ナトリウムを加えなかった以外は実施例１と同様に反応を行った。得られた樹脂水溶液の性状及びＤＣＰ含有量を表２に示した。
Comparative Example 3
In Example 1, the reaction was carried out in the same manner as in Example 1 except that sodium bisulfite was not added after the primary incubation. Table 2 shows the properties of the aqueous resin solution and the DCP content.
比較例４
実施例１において、１次保温後に加える亜硫酸ナトリウムを加えず、アンモニア１．０ｇ（ポリアミドポリアミンのアミノ基に対し０．２０当量）を加えた以外は実施例１と同様に反応を行った。得られた樹脂水溶液の性状及びＤＣＰ含有量を表２に示した。
Comparative Example 4
In Example 1, the reaction was carried out in the same manner as in Example 1 except that 1.0 g of ammonia (0.20 equivalents relative to the amino group of the polyamide polyamine) was added without adding sodium sulfite added after the primary incubation. Table 2 shows the properties of the aqueous resin solution and the DCP content.
比較例５
実施例１において、１次保温後にアンモニアを加えなかった以外は実施例１と同様に反応を行った。得られた樹脂水溶液の性状及びＤＣＰ含有量を表２に示した。
Comparative Example 5
In Example 1, the reaction was performed in the same manner as in Example 1 except that ammonia was not added after the primary incubation. Table 2 shows the properties of the aqueous resin solution and the DCP content.
比較例６
実施例１において、１次保温後に加えるアンモニアを加えず、亜硫酸水素ナトリウム７．２ｇ（ポリアミドポリアミンのアミノ基に対し０．２０当量）を加えた以外は実施例１と同様に反応を行った。得られた樹脂水溶液の性状及びＤＣＰ量を表２に示した。
Comparative Example 6
In Example 1, the reaction was performed in the same manner as in Example 1 except that 7.2 g of sodium bisulfite (0.20 equivalents relative to the amino group of the polyamide polyamine) was added without adding the ammonia added after the primary incubation. Table 2 shows the properties and DCP amount of the obtained aqueous resin solution.
なお、実施例１〜７、比較例１〜６で得られた樹脂水溶液を４０℃で３５日間保存してもゲル化しなったため、保存安定性は十分あることがわかる。 In addition, since the resin aqueous solution obtained in Examples 1-7 and Comparative Examples 1-6 was gelatinized even if it preserve | saved for 35 days at 40 degreeC, it turns out that storage stability is enough.
応用実施例１
実施例１〜７および比較例１〜６で得られたそれぞれの樹脂水溶液を、ノーブルアンドウッド式手抄き抄紙機を使用した抄紙試験に供した。得られた紙の湿潤時の紙力強度をＪＩＳ−Ｐ−８１１３に準拠して測定した。結果を表３に示した。
抄紙条件
使用パルプ：晒クラフトパルプ（針葉樹／広葉樹＝１／１）
叩解度（ＣＳＦ）４２２ｍｌ
樹脂添加率：０．３％（対パルプ固形分）
抄紙坪量：６５ｇ／ｍ2
乾燥条件：１００℃×１２０ｓｅｃ（ドラムドライヤー）
Application Example 1
The respective aqueous resin solutions obtained in Examples 1 to 7 and Comparative Examples 1 to 6 were subjected to a papermaking test using a Noble and Wood handmade paper machine. The paper strength when the obtained paper was wet was measured according to JIS-P-8113. The results are shown in Table 3.
Pulp used under papermaking conditions: Bleached kraft pulp (conifer / hardwood = 1/1)
Degree of beating (CSF) 422ml
Resin addition rate: 0.3% (vs. pulp solids)
Papermaking basis weight: 65 g / m 2
Drying conditions: 100 ° C x 120 sec (drum dryer)
応用実施例２
＜接着強度の評価方法＞
実施例１〜７で得られた熱硬化性樹脂それぞれ０．１％と鉱物油タイプの離型剤「ＣＲ６１０４」（星光ＰＭＣ株式会社製）０．０２％を含むサンプル液を噴霧器でアルミ箔（３×１１ｃｍ）に０．１ｇスプレーし、ホットプレート上で加熱乾燥させた。サンプルが乾燥したアルミ箔の面に湿紙（３×１２ｃｍ）を貼り合わせ、１２０℃、３分−１００ｋｇｆ／ｃｍ２で熱プレスし、湿紙の余分な水分を取り除くと同時にアルミ箔と紙を接着させた。アルミ箔から紙を剥離するときの剥離強度をＪ．ＴＡＰＰＩ−１９−（２）−Ｂ法に準拠して測定した。剥離強度が強いほど、接着強度に優れたクレーピング用接着剤である。
Application Example 2
<Evaluation method of adhesive strength>
A sample solution containing 0.1% of each of the thermosetting resins obtained in Examples 1 to 7 and 0.02% of a mineral oil type release agent “CR6104” (manufactured by Seiko PMC Co., Ltd.) was sprayed with an aluminum foil ( (3 × 11 cm) was sprayed in an amount of 0.1 g, and dried by heating on a hot plate. Adhere wet paper (3 x 12 cm) to the surface of the aluminum foil where the sample is dried, and heat-press at 120 ° C for 3 minutes to 100 kgf / cm2 to remove excess moisture from the wet paper and simultaneously bond the aluminum foil and paper. I let you. The peel strength when peeling paper from an aluminum foil It measured based on TAPPI-19- (2) -B method. The stronger the peel strength, the better the adhesive strength for creping.
剥離強度は１００ｍＮ／３ｃｍを越えることが好ましい。 The peel strength is preferably over 100 mN / 3 cm.
表４に示す結果から明らかな通り、本発明の実施例１〜７は、接着強度が約２６０〜３５０ｍＮ／３ｃｍと十分に強く、クレーピング用接着剤として適している。
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