JP4957265B2 - Bulky paper manufacturing method and bulky paper - Google Patents
Bulky paper manufacturing method and bulky paper Download PDFInfo
- Publication number
- JP4957265B2 JP4957265B2 JP2007014030A JP2007014030A JP4957265B2 JP 4957265 B2 JP4957265 B2 JP 4957265B2 JP 2007014030 A JP2007014030 A JP 2007014030A JP 2007014030 A JP2007014030 A JP 2007014030A JP 4957265 B2 JP4957265 B2 JP 4957265B2
- Authority
- JP
- Japan
- Prior art keywords
- paper
- component
- mol
- strength enhancer
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- 239000003623 enhancer Substances 0.000 claims description 61
- -1 monocarboxylic acid compound Chemical class 0.000 claims description 51
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 25
- 239000004067 bulking agent Substances 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 21
- 229920002401 polyacrylamide Polymers 0.000 claims description 18
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 15
- 125000003142 tertiary amide group Chemical group 0.000 claims description 15
- 229920000768 polyamine Polymers 0.000 claims description 14
- 150000001408 amides Chemical class 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920001281 polyalkylene Polymers 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 238000012360 testing method Methods 0.000 description 29
- 230000000694 effects Effects 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000243 solution Substances 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000003995 emulsifying agent Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 9
- 125000002091 cationic group Chemical group 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 238000004945 emulsification Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 7
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 229920001131 Pulp (paper) Polymers 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000013055 pulp slurry Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 101001046633 Homo sapiens Junctional adhesion molecule A Proteins 0.000 description 4
- 102100022304 Junctional adhesion molecule A Human genes 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000007112 amidation reaction Methods 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 125000001302 tertiary amino group Chemical group 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 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 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000003368 amide group Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-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
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- ZFINIPDNRKJWGK-UHFFFAOYSA-N 1-N,2-N-bis(2-methylpropyl)propane-1,2-diamine Chemical compound CC(C)CNCC(C)NCC(C)C ZFINIPDNRKJWGK-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N 1-butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- FUJUAXDOMMJSRK-UHFFFAOYSA-N 1-n,2-n-di(propan-2-yl)propane-1,2-diamine Chemical compound CC(C)NCC(C)NC(C)C FUJUAXDOMMJSRK-UHFFFAOYSA-N 0.000 description 1
- VECZPMZNUKYYOJ-UHFFFAOYSA-N 1-n,2-n-diethylpropane-1,2-diamine Chemical compound CCNCC(C)NCC VECZPMZNUKYYOJ-UHFFFAOYSA-N 0.000 description 1
- RDHNFSNXWLWMIX-UHFFFAOYSA-N 1-n,2-n-dimethylpropane-1,2-diamine Chemical compound CNCC(C)NC RDHNFSNXWLWMIX-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-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
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021353 Lignoceric acid Nutrition 0.000 description 1
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- TXXHDPDFNKHHGW-CCAGOZQPSA-N Muconic acid Natural products OC(=O)\C=C/C=C\C(O)=O TXXHDPDFNKHHGW-CCAGOZQPSA-N 0.000 description 1
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 description 1
- 241001181114 Neta Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 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 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 125000005131 dialkylammonium group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 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
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LTUMISDAHGVYGU-UHFFFAOYSA-N n,n'-bis(2-methylpropyl)ethane-1,2-diamine Chemical compound CC(C)CNCCNCC(C)C LTUMISDAHGVYGU-UHFFFAOYSA-N 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- VATUKUMHBXZSCD-UHFFFAOYSA-N n,n'-dipropylethane-1,2-diamine Chemical compound CCCNCCNCCC VATUKUMHBXZSCD-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Chemical compound CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 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 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000001374 small-angle light scattering Methods 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- UNWZKBKTIYBBRV-UHFFFAOYSA-N tetraazanium;tetrachloride Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Cl-].[Cl-].[Cl-].[Cl-] UNWZKBKTIYBBRV-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paper (AREA)
Description
本発明は嵩高紙の製造方法および、当該製造方法で得られる嵩高紙に関する。 The present invention relates to a method for producing a bulky paper and a bulky paper obtained by the production method.
嵩高紙とは、紙の厚みを維持しつつ低密度化した(以下、嵩高効果ということがある)軽量紙のことをいい、紙の単位体積あたりのパルプ量が少ないことから、省資源に寄与する紙として、近年その需要が著しく伸びている。 Bulky paper refers to lightweight paper that has been reduced in density while maintaining the thickness of the paper (hereinafter sometimes referred to as “bulky effect”), and contributes to resource conservation because the amount of pulp per unit volume of paper is small. In recent years, the demand for paper has increased significantly.
嵩高紙の製造方法は種々あるが、抄紙時に、有機系または無機系の添加剤(嵩高剤)を紙料に添加する方法によれば、嵩高効果に加えて他の要求性能を紙に付与しやすく、また特殊な装置を用いる必要もないなど利点が多い(特許文献1、2等参照)。 There are various methods for producing bulky paper, but the method of adding an organic or inorganic additive (bulkiening agent) to the stock during papermaking gives the paper other required performance in addition to the bulky effect. There are many advantages such as being easy and not requiring the use of a special device (see Patent Documents 1 and 2).
ところで従来の製造方法で得られる嵩高紙は、表面強度や特に内部強度(紙内部のパルプ結合の強さ)が小さいなど、紙力効果の点で十分でない場合が多く、印刷時に膨れやエッジ捲れ、ピッキング等の問題が発生することが懸念されている。これはおそらく、嵩高紙は前記したように低密度化されているため、パルプ繊維間の相互作用(例えば、繊維の絡み合いや、セルロース分子間の水素結合等)が小さくなっていることが要因であると考えられている。
本発明は、嵩高効果を維持しつつ、嵩高紙の紙力効果(特に内部強度)を向上させることができる、嵩高紙の製造方法を提供することを課題とする。
また、本発明は、嵩高効果を保ちつつ、かつ、紙力効果(特に内部強度)に優れる嵩高紙を提供することを更なる課題とする。
This invention makes it a subject to provide the manufacturing method of bulky paper which can improve the paper strength effect (especially internal strength) of bulky paper, maintaining a bulky effect.
Moreover, this invention makes it the further subject to provide the bulky paper which is excellent in paper strength effect (especially internal strength), maintaining a bulky effect.
本発明者は、特定の脂肪酸変性アミド樹脂系の嵩高剤を紙料に添加した後で抄紙を行う嵩高紙の製造方法において、当該嵩高剤と、パルプを一定の程度で凝集させる両性ポリアクリルアミド系の紙力増強剤とを併用することによって、前記課題を解決できることを見出した。即ち、本発明は、 The present inventor is an amphoteric polyacrylamide system for agglomerating the bulking agent and pulp to a certain degree in a bulky paper manufacturing method in which papermaking is performed after adding a specific fatty acid-modified amide resin bulking agent to the stock. It has been found that the above-mentioned problems can be solved by using the paper strength enhancer together. That is, the present invention
1.第2級アミノ基含有ポリアミン化合物(a1)、モノカルボン酸化合物(a2)およびグリシジル基含有化合物(a3)を反応成分とする第3級アミド基含有脂肪酸変性アミド樹脂(A)を含む嵩高剤(1)と、両性ポリアクリルアミド(B)を含む紙力増強剤(2)を、紙料(3)に添加した後で、抄紙を行う嵩高紙の製造方法において、
前記第3級アミド基含有脂肪酸変性アミド樹脂(A)における(第3級アミド基含有脂肪酸変性アミド樹脂(A)が有する第3級アミド基の個数)/(第2級アミノ基含有ポリアミン化合物(a1)が有する第2級アミノ基の個数)の値が0.2〜0.7であり、
かつ、前記両性ポリアクリルアミド(B)が(メタ)アクリルアミド(b1)57〜99.78モル%、カチオン性ビニルモノマー(b2)0.1〜15モル%、アニオン性ビニルモノマー(b3)0.1〜15モル%、N−置換(メタ)アクリルアミド(b4)0.01〜2モル%、(メタ)アリル基含有ビニルモノマー(b5)0.01〜10モル%を共重合させてなるものであり、
かつ、当該紙力増強剤(2)が、〔紙力増強剤(2)を含有する紙料(3)のカナダ標準ろ水度(ml)〕と〔紙力増強剤(2)を含有しない紙料(3)のカナダ標準ろ水度(ml)〕との差として50ml以下の値を与えるものであることを特徴とする、嵩高紙の製造方法、
1. A bulking agent comprising a tertiary amide group-containing fatty acid-modified amide resin (A) having a secondary amino group-containing polyamine compound (a1), a monocarboxylic acid compound (a2) and a glycidyl group-containing compound (a3) as reaction components ( 1) and a paper strength enhancer (2) containing amphoteric polyacrylamide (B), after adding to paper stock (3), in the method for producing bulk paper,
In the tertiary amide group-containing fatty acid-modified amide resin (A) (number of tertiary amide groups of the tertiary amide group-containing fatty acid-modified amide resin (A)) / (secondary amino group-containing polyamine compound ( the number of secondary amino groups a1) has is 0.2 to 0.7,
And said amphoteric polyacrylamide (B) is (meth) acrylamide (b1) 57-99.78 mol%, cationic vinyl monomer (b2) 0.1-15 mol%, anionic vinyl monomer (b3) 0.1 ~ 15 mol%, N-substituted (meth) acrylamide (b4) 0.01-2 mol%, (meth) allyl group-containing vinyl monomer (b5) 0.01-10 mol% are copolymerized. ,
And, the paper strength enhancer (2) does not contain [the Canadian standard freeness (ml) of the paper stock (3) containing the paper strength enhancer (2)] and [the paper strength enhancer (2). A method for producing bulky paper, characterized in that it gives a value of 50 ml or less as a difference from Canadian Standard Freeness (ml) of the stock (3),
2.前記第2級アミノ基含有ポリアミン化合物(a1)が、一般式(I):H2N−[−(CH2)xNH−]y−H(式中、xは1〜3の整数を、またyは2〜6の整数を表す。)で表されるポリアルキレンポリアミンである、前記1に記載の製造方法、 2 . The secondary amino group-containing polyamine compound (a1) has the general formula (I): H 2 N — [— (CH 2 ) x NH—] y —H (wherein x represents an integer of 1 to 3, Moreover, y represents the integer of 2-6.) The manufacturing method of said 1 which is a polyalkylene polyamine represented by these,
3.前記紙力増強剤(2)の固形分濃度1.0重量%の溶液状態における濁度単位(NTU)が500未満である、前記1.または2.に記載の製造方法。 3 . 1. The turbidity unit (NTU) in a solution state of the paper strength enhancer (2) having a solid content concentration of 1.0% by weight is less than 500. Or 2. The manufacturing method as described in.
4.前記両性ポリアクリルアミド(B)の重量平均分子量が100万以上である、前記1.〜3.のいずれかに記載の製造方法。 4 . The amphoteric polyacrylamide (B) has a weight average molecular weight of 1 million or more. ~ 3. The manufacturing method in any one of.
5.前記紙料(3)のパルプ濃度が0.1〜4重量%である、前記1.〜4.のいずれかに記載の製造方法、 5 . 1. The pulp concentration of the stock (3) is 0.1 to 4% by weight. ~ 4. The production method according to any one of
6.前記嵩高剤(1)を紙料(3)に添加した後に、前記紙力増強剤(2)を更に添加して抄紙を行う、前記1.〜5.のいずれかに記載の製造方法、 6 . After adding the bulking agent (1) to the stock (3), the paper strength enhancer (2) is further added to perform papermaking. ~ 5. The production method according to any one of
7.前記1.〜6.のいずれかの製造方法で得られる嵩高紙、に関する。 7 . 1 above. ~ 6. This relates to a bulky paper obtained by any one of the production methods.
本発明の製造方法により、嵩高効果を維持しつつ、紙力効果(特に内部強度)に優れる嵩高紙を提供することができる。また、当該嵩高紙は、低密度でありながら紙力効果に優れるほか、サイズ効果や地合いが良好であるため、各種印刷用紙(例えば、書籍用紙、印刷・情報用紙、新聞用紙、包装用紙、塗工紙、インクジェット記録用紙等)として有用である。 By the production method of the present invention, it is possible to provide a bulky paper excellent in paper strength effect (particularly internal strength) while maintaining the bulky effect. In addition, the bulky paper has a low density and excellent paper strength effect, and also has a good size effect and texture, so various printing paper (for example, book paper, printing / information paper, newsprint paper, wrapping paper, coating paper, etc.) Useful as industrial paper, inkjet recording paper, etc.).
本発明で用いられる嵩高剤(1)は、第3級アミド基含有脂肪酸変性アミド樹脂(A)(以下、(A)成分と略す)を含むものであり、当該(A)成分は、例えば、第2級アミノ基含有ポリアミン化合物(a1)(以下、(a1)成分という)、モノカルボン酸化合物(a2)(以下、(a2)成分という)およびグリシジル基含有化合物(a3)(以下、(a3)成分という)を反応させることにより得られる。 The bulking agent (1) used in the present invention contains a tertiary amide group-containing fatty acid-modified amide resin (A) (hereinafter abbreviated as (A) component), and the (A) component is, for example, Secondary amino group-containing polyamine compound (a1) (hereinafter referred to as component (a1)), monocarboxylic acid compound (a2) (hereinafter referred to as component (a2)) and glycidyl group-containing compound (a3) (hereinafter referred to as (a3) ) Component)).
前記(a1)成分としては、分子内に第2級アミノ基を1個以上有するポリアミン化合物であれば、各種公知のものを特に制限なく用いることができる。なお、(a1)成分を構成する炭化水素基は直鎖状、環状、分岐状のいずれかであればよく、また、当該炭化水素基には炭素−炭素不飽和二重結合が存在していてもよい。また、(a1)成分には第2級アミノ基の他に、第1級アミノ基や第3級アミノ基が存在していてもよい。 As the component (a1), various known compounds can be used without particular limitation as long as they are polyamine compounds having one or more secondary amino groups in the molecule. The hydrocarbon group constituting the component (a1) may be linear, cyclic, or branched, and the hydrocarbon group has a carbon-carbon unsaturated double bond. Also good. In addition to the secondary amino group, the component (a1) may contain a primary amino group or a tertiary amino group.
(a1)成分の具体例としては、例えば、一般式(I):H2N−[−(CH2)xNH−]y−H(式中、xは1〜3の整数を、またyは2〜6の整数を表す。)で表されるポリアルキレンポリアミン〔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、ジプロピレントリアミン等〕、一般式(II):HRN(CH2)zNRH(式中、Rは炭素数が1〜3のアルキル基を、zは1〜6の整数を表す)で表されるN,N’−ジアルキルアルキレンジアミン〔N,N’−ジメチルエチレンジアミン、N,N’−ジエチルエチレンジアミン、N,N’−ジメチルプロピレンジアミン、N,N’−ジエチルプロピレンジアミン、N,N’−ジイソブチルエチレンジアミン、N,N’−ジイソプロピルエチレンジアミン、N,N’−ジイソブチルプロピレンジアミン、N,N’−ジイソプロピルプロピレンジアミン、N,N’−ジ−n−プロピルエチレンジアミン等〕などが挙げられ、これらは1種を単独で、あるいは2種以上を組み合わせて用いることができる。これらの中でも、(a2)成分との反応性が良好であり前記(A)成分中に第3級アミド基を導入しやすいことや、(A)成分のエマルジョンが安定になること、常温で低粘度なのでハンドリング性が良好であること、入手が容易であること等の理由から、前記一般式(I)で表されるポリアルキレンポリアミンが、特に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から選ばれる少なくとも1種が好ましい。 Specific examples of the component (a1) include, for example, general formula (I): H 2 N — [— (CH 2 ) x NH—] y —H (wherein x represents an integer of 1 to 3, Represents an integer of 2 to 6.) Polyalkylene polyamine represented by (diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, etc.), general formula (II): HRN (CH 2 ) z NRH (wherein R represents an alkyl group having 1 to 3 carbon atoms, and z represents an integer of 1 to 6) N, N′-dialkylalkylenediamine [N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-dimethylpropylenediamine, N, N′-diethylpropylenediamine, N, N′-diisobutylethylenediamine, N, N′-diisopropylethylene Amine, N, N′-diisobutylpropylenediamine, N, N′-diisopropylpropylenediamine, N, N′-di-n-propylethylenediamine, etc.), and these are used alone or in combination of two or more. Can be used in combination. Among these, the reactivity with the component (a2) is good, the tertiary amide group is easily introduced into the component (A), the emulsion of the component (A) becomes stable, and it is low at room temperature. The polyalkylene polyamine represented by the general formula (I) is particularly selected from diethylenetriamine, triethylenetetramine, and tetraethylenepentamine for reasons such as good handling properties due to viscosity, and easy availability. At least one is preferred.
前記(a2)成分としては、分子内にカルボキシル基を1個有するモノカルボン酸化合物であれば、各種公知のものを特に制限なく用いることができる。なお、(a2)成分を構成する炭化水素基は直鎖状、環状、分岐状のいずれかであればよく、また、当該炭化水素基には炭素−炭素不飽和二重結合が存在していてもよい。 As the component (a2), various known compounds can be used without particular limitation as long as they are monocarboxylic acid compounds having one carboxyl group in the molecule. The hydrocarbon group constituting the component (a2) may be linear, cyclic, or branched, and the hydrocarbon group has a carbon-carbon unsaturated double bond. Also good.
(a2)成分の具体例としては、例えば、酢酸、飽和脂肪酸〔酪酸、プロピオン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、アラキン酸、ベヘン酸、リグノセリン酸、セロチン酸、モンタン酸、メリシン酸等〕、不飽和脂肪酸〔パルミトレイン酸、オレイン酸、エルカ酸、リノール酸、リノレン酸等〕、植物油脂ないし動物油脂〔ひまし油脂肪酸、ヤシ油脂肪酸、パーム油脂肪酸、牛脂脂肪酸、大豆油脂肪酸、なたね油脂肪酸、トール油脂肪酸等〕などが挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。特に(a2)成分を2種以上組み合わせて用いる場合には、複数種の炭化水素基を前記(A)成分中に組み込めるなど、構造制御が可能になる。これらの中でも、後述するアミド化反応における反応性や、前記嵩高効果や粘度安定性が良好になる等の理由から、炭素数が12〜22程度の直鎖状アルキル基を有するモノカルボン酸化合物、特にステアリン酸、パルミチン酸、デカン酸、ベヘン酸、カプロン酸から選ばれる少なくとも1種が好ましい。 Specific examples of the component (a2) include, for example, acetic acid, saturated fatty acids [butyric acid, propionic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and serothin. Acid, montanic acid, melicic acid, etc.), unsaturated fatty acids (palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, etc.), vegetable oils and animal fats (castor oil fatty acid, coconut oil fatty acid, palm oil fatty acid, beef tallow fatty acid) , Soybean oil fatty acid, rapeseed oil fatty acid, tall oil fatty acid and the like], and the like can be used alone or in combination of two or more. In particular, when two or more types of component (a2) are used in combination, structural control becomes possible, such as incorporating a plurality of types of hydrocarbon groups into component (A). Among these, a monocarboxylic acid compound having a linear alkyl group having about 12 to 22 carbon atoms, for reasons such as reactivity in an amidation reaction described later, and the above-described bulky effect and viscosity stability are good, In particular, at least one selected from stearic acid, palmitic acid, decanoic acid, behenic acid, and caproic acid is preferable.
前記(a3)成分としては、分子内にグリシジル基を1個有する化合物であれば、各種公知のものを特に制限なく用いることができる。なお、(a3)成分を用いることにより(A)成分にカチオン性基や、分岐構造・架橋構造が導入される。(a3)成分の具体例としては、例えば、エピハロヒドリン類〔エピクロロヒドリン、エピブロモヒドリン、エピヨードヒドリン等〕、グリシドール類〔2,3−エポキシ−1−プロパノール、3,4−エポキシ−1−ブタノール等〕などが挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。これらの中でも、前記(a2)成分との反応性が高いため前記カチオン性基・分岐構造・架橋構造を導入しやすいことや、得られる嵩高紙のサイズ効果が良好になること、安価であること等の理由から、前記エピハロヒドリン類、特にエピクロロヒドリンが好ましい。 As the component (a3), various known compounds can be used without particular limitation as long as they are compounds having one glycidyl group in the molecule. In addition, by using the component (a3), a cationic group or a branched structure / crosslinked structure is introduced into the component (A). Specific examples of the component (a3) include epihalohydrins [epichlorohydrin, epibromohydrin, epiiohydrin, etc.], glycidols [2,3-epoxy-1-propanol, 3,4-epoxy, for example. -1-butanol and the like], and the like can be used alone or in combination of two or more. Among these, since the reactivity with the component (a2) is high, it is easy to introduce the cationic group / branched structure / crosslinked structure, the size effect of the resulting bulky paper is good, and it is inexpensive. For these reasons, the epihalohydrins, particularly epichlorohydrin, are preferred.
(A)成分における、前記(a1)成分、前記(a2)成分および前記(a3)成分の各使用量は特に限定されないが、通常は、前記(a1)成分の1級アミノ基をM個とし、またその第2級アミノ基をN個とした場合において、(a1)成分1モル(即ち、1級アミノ基がMモル、第2級アミノ基がNモル)に対し、(a2)成分が通常(M+0.05N)モル〜(M+0.9N)モル程度(好ましくは(M+0.2N)モル〜(M+0.7N)モルとなる範囲とし、また、(a3)成分が通常0.1Nモル〜1.5Nモル程度(好ましくは0.3Nモル〜0.75Nモル)となる範囲とすればよい。 In the component (A), the amount of each of the component (a1), the component (a2) and the component (a3) used is not particularly limited. Usually, the number of primary amino groups in the component (a1) is M. In addition, when the number of secondary amino groups is N, (a1) component (a1) with respect to 1 mol of component (that is, primary amino group is M mol and secondary amino group is N mol) Usually in the range of (M + 0.05N) to about (M + 0.9N) mol (preferably (M + 0.2N) mol to (M + 0.7N) mol, and (a3) component is usually 0.1N mol to 1 The range may be about 5 Nmol (preferably 0.3 Nmol to 0.75 Nmol).
なお、(a2)成分の使用量が(M+0.05N)モル未満の場合には、(A)成分に導入される分岐構造や架橋構造の量が少なくなり、嵩高効果を維持し難くなる傾向にある。一方、その使用量が(M+0.9N)モルを超える場合には、残存する(a2)成分と(a3)成分との副反応の影響により前記粘度安定性や、得られる嵩高紙の各種性能が悪化する傾向にある。 In addition, when the usage-amount of (a2) component is less than (M + 0.05N) mol, the quantity of the branched structure and bridge | crosslinking structure introduce | transduced into (A) component decreases, and it tends to become difficult to maintain a bulky effect. is there. On the other hand, when the amount used exceeds (M + 0.9N) mol, the viscosity stability and various performances of the resulting bulky paper are affected by the side reaction between the remaining component (a2) and component (a3). It tends to get worse.
また、(a3)成分の使用量が0.1Nモル未満の場合には、(A)成分に導入されるカチオン性基の量が少なくなるため、(A)成分がパルプへ定着しにくくなり、嵩高効果を維持し難くなる傾向にある。一方、その使用量が1.5Nモルを超える場合には、(A)成分に導入される架橋構造やカチオン性基の量が少なくなる傾向にある。 In addition, when the amount of the component (a3) used is less than 0.1 N mol, the amount of the cationic group introduced into the component (A) decreases, so that the component (A) becomes difficult to fix to the pulp, It tends to be difficult to maintain the bulky effect. On the other hand, when the amount used exceeds 1.5 Nmol, the amount of the crosslinked structure or cationic group introduced into the component (A) tends to be small.
なお、(a1)成分を2種以上組み合わせて用いる場合には、前記MとNの値はそれぞれ平均値とする必要がある。例えば、(a1)成分1モルが、ジエチレントリアミン(M=2、N=3)0.2モルとペンタエチレンヘキサミン(M=3、N=2)0.8モルとの混合物であった場合には、M≒2.8およびN≒2.2となる。 In addition, when using 2 or more types of (a1) component combining, it is necessary to make the value of said M and N into an average value, respectively. For example, when 1 mol of component (a1) is a mixture of 0.2 mol of diethylenetriamine (M = 2, N = 3) and 0.8 mol of pentaethylenehexamine (M = 3, N = 2) , M≈2.8 and N≈2.2.
(A)成分の製造方法は特に限定されず、各種公知のアミド化反応および付加反応を採用できる。なお、(A)成分の構造が制御しやすくなることから、(a1)成分と(a2)成分とをアミド化反応(脱水縮合反応)させて第3級アミド基含有化合物(A’)(以下、(A’)成分という)を一旦製造し、次いで、当該(A’)成分と前記(a3)成分とを付加反応させる方法が好ましい。 The manufacturing method of (A) component is not specifically limited, Various well-known amidation reaction and addition reaction are employable. Since the structure of the component (A) can be easily controlled, the (a1) component and the (a2) component are subjected to an amidation reaction (dehydration condensation reaction) to produce a tertiary amide group-containing compound (A ′) (hereinafter referred to as “a”). , (A ′) component) is once produced, and then the (A ′) component and the (a3) component are subjected to an addition reaction.
前記アミド化反応は特に限定されず、各種公知の方法を採用できる。具体的には、溶媒や触媒の存在下または不存在下において、通常、150℃〜200℃程度の温度において、2〜8時間程度、反応生成水を除去しながら、(a1)成分と前記モル範囲の(a2)成分を脱水縮合反応させればよい。 The amidation reaction is not particularly limited, and various known methods can be employed. Specifically, in the presence or absence of a solvent or a catalyst, the reaction product water is removed for about 2 to 8 hours at a temperature of about 150 ° C. to 200 ° C. The component (a2) in the range may be subjected to a dehydration condensation reaction.
なお、前記溶媒としては、各種公知のものを特に制限なく用いることができる。具体的には、例えば、芳香族炭化水素類〔ベンゼン、トルエン、キシレン、クロルベンゼン等〕、ピリジン類〔N−メチル−2−ピロリドン等〕などが挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。なお、これらの中でも、反応生成水とともに共沸しやすいもの(トルエン等)が好ましい。また、該溶媒の使用量は、反応系の固形分濃度が通常50〜100重量%程度となる範囲であればよい。 In addition, as said solvent, various well-known things can be especially used without a restriction | limiting. Specifically, for example, aromatic hydrocarbons [benzene, toluene, xylene, chlorobenzene, etc.], pyridines [N-methyl-2-pyrrolidone, etc.] and the like can be mentioned. A combination of more than one species can be used. Of these, those that readily azeotrope with the reaction product water (such as toluene) are preferred. Moreover, the usage-amount of this solvent should just be a range from which the solid content concentration of a reaction system will be about 50 to 100 weight% normally.
また、前記触媒としては、各種公知のものを特に制限なく用いることができる。具体的には、例えば、酸触媒〔アルキルスルホン酸、p−トルエンスルホン酸、ベンゼンスルホン酸、硫酸、亜リン酸等〕、塩基性触媒〔ピリジン、トリメチルアミン、トリエチルアミン等〕などが挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。なお、該触媒の使用量は、(a1)成分と(a2)成分の合計重量に対して、通常3重量%以下程度となる範囲であればよい。 As the catalyst, various known catalysts can be used without particular limitation. Specific examples include acid catalysts [alkyl sulfonic acid, p-toluene sulfonic acid, benzene sulfonic acid, sulfuric acid, phosphorous acid, etc.], basic catalysts [pyridine, trimethylamine, triethylamine, etc.], etc. These can be used singly or in combination of two or more. In addition, the usage-amount of this catalyst should just be the range used as about 3 weight% or less normally with respect to the total weight of (a1) component and (a2) component.
前記付加反応は特に限定されず、各種公知の方法を採用できる。具体的には、通常は水の存在下において、通常、50〜100℃程度において、2〜6時間程度、前記(A’)成分と前記(a3)成分とを反応させればよい。 The addition reaction is not particularly limited, and various known methods can be employed. Specifically, the component (A ′) and the component (a3) may be reacted usually in the presence of water at about 50 to 100 ° C. for about 2 to 6 hours.
こうして得られる(A)成分は、分子中に第3級アミド基を有することを特徴とする。なお、第3級アミド基の含有量は、(該(A)成分が有する第3級アミド基の個数)/(前記(a1)成分が有する第2級アミノ基の個数)の値が0.2〜0.7となる範囲である。当該数値範囲内であることにより、前記嵩高効果が特に良好となる。 The component (A) thus obtained is characterized by having a tertiary amide group in the molecule. The content of the tertiary amide group is such that the value of (number of tertiary amide groups of the component (A)) / (number of secondary amino groups of the component (a1)) is 0. It is the range which becomes 2-0.7 . By being in the numerical range, the bulky effect is particularly good.
なお、該第3級アミド基とは、(a1)成分の第2級アミノ基と(a2)成分のカルボキシル基とから形成されるN,N−置換アミド基またはN,N’−置換アミド基をいう。例えば、(a1)成分が前記一般式(I)で表されるポリアルキレンポリアミンである場合には、前記N,N−置換アミド基はR1R1N−CO−R2と表現できる(なお、該構造式中、R1は当該ポリアルキレンポリアミンのアルキレン基(−(CH2)x−)に、また、R2は前記(a2)成分の炭化水素残基に、それぞれ由来する。)。また、(a1)成分が前記一般式(II)で表されるN,N’−ジアルキルアルキレンジアミンである場合には、前記N,N’−置換アミド基はR3R4N−CO−R3と表現できる(該構造式中、R3とR4は、いずれか一方が当該N,N’−ジアルキルアルキレンジアミンのアルキレン基(―(CH2)z―)に、また他方がそのアルキル基(R)にそれぞれ由来する。また、R2は前記(a2)成分の炭化水素残基に由来する。) The tertiary amide group is an N, N-substituted amide group or an N, N′-substituted amide group formed from the secondary amino group of the component (a1) and the carboxyl group of the component (a2). Say. For example, when the component (a1) is a polyalkylene polyamine represented by the general formula (I), the N, N-substituted amide group can be expressed as R 1 R 1 N—CO—R 2 (note that In the structural formula, R 1 is derived from the alkylene group (— (CH 2 ) x —) of the polyalkylene polyamine, and R 2 is derived from the hydrocarbon residue of the component (a2). When the component (a1) is N, N′-dialkylalkylenediamine represented by the general formula (II), the N, N′-substituted amide group is R 3 R 4 N—CO—R. 3 and can be expressed (the structural formula, R 3 and R 4, either one the N, N'-dialkyl alkylenediamine alkylene group (- (CH 2) z - ) in and the other is the alkyl group (R) is derived from (R), and R 2 is derived from the hydrocarbon residue of component (a2).)
当該(A)成分は、そのままでも嵩高剤(1)として用いうるが、紙料(3)が水系であることを考慮すると、これを水および乳化剤(界面活性剤)、ならびに必要に応じて保護コロイドの存在下で乳化または水分散させることにより、エマルジョンとして用いるのが好ましい。 The component (A) can be used as a bulking agent (1) as it is, but considering that the paper (3) is water-based, protect it with water and an emulsifier (surfactant), and if necessary. It is preferably used as an emulsion by emulsification or water dispersion in the presence of a colloid.
該乳化剤としては、各種公知の非反応性乳化剤ないし反応性乳化剤を特に制限なく用いることができる。なお、該乳化剤の使用量は、前記(A)成分(固形分)に対して通常1〜10重量%程度の範囲とするのがよい。 As the emulsifier, various known non-reactive emulsifiers or reactive emulsifiers can be used without particular limitation. In addition, the usage-amount of this emulsifier is good to set it as the range of about 1 to 10 weight% normally with respect to the said (A) component (solid content).
該非反応性乳化剤としては、具体的には、例えば、カチオン性乳化剤〔テトラアルキルアンモニウムクロライド、モノアルキルアンモニウムクロライド、ジアルキルアンモニウムクロライド、トリアルキルアンモニウムクロライド、テトラアンモニウムクロライドトリアルキルベンジルアンモニウムクロライドオキシエチレンアルキルアミンの酢酸塩または塩酸塩、ポリオキシエチレンアルキルアミンの酢酸塩または塩酸塩等〕、ノニオン性乳化剤〔ポリオキシエチレンラウリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ソルビタンモノラウレート、ソルビタントリオレエート、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンモノラウレート、ポリオキシエチレンモノオレエート、オレイン酸モノグリセライド、ステアリン酸モノグリセライド、ポリオキシエチレン・ポリオキシプロピレン・ブロックコポリマー等〕、アニオン性乳化剤〔ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ドデシル硫酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、ジアルキルスルホコハク酸ナトリウム、アルキルリン酸カリウム、ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルフェニルエーテル硫酸ナトリウム、ポリオキシエチレントリデシルエーテル硫酸ナトリウム等〕などが挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。 Specific examples of the non-reactive emulsifier include cationic emulsifiers [tetraalkylammonium chloride, monoalkylammonium chloride, dialkylammonium chloride, trialkylammonium chloride, tetraammonium chloride trialkylbenzylammonium chloride oxyethylene alkylamine. Acetate or hydrochloride, acetate or hydrochloride of polyoxyethylene alkylamine, etc.), nonionic emulsifier (polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene styryl phenyl ether, Sorbitan monolaurate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxy Ethylene monolaurate, polyoxyethylene monooleate, oleic acid monoglyceride, stearic acid monoglyceride, polyoxyethylene / polyoxypropylene / block copolymer, etc.), anionic emulsifier (sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl sulfate, dodecylbenzene) Sodium sulfonate, sodium dialkylsulfosuccinate, potassium alkyl phosphate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, etc.). It can be used alone or in combination of two or more.
また、該反応性乳化剤としては、分子中に炭素−炭素二重結合〔(メタ)アリル基、1−プロペニル基、2−メチル−1−プロペニル基、ビニル基、イソプロペニル基、(メタ)アクリロイル基等〕、親水基および疎水基を有する乳化剤を用いうる。具体的には、例えば、該炭素−炭素二重結合を分子中に少なくとも一つ有するポリオキシアルキレンアルキルエーテル類やそのスルホコハク酸エステル塩類、硫酸エステル塩類;該炭素−炭素二重結合を分子中に少なくとも一つ有するポリオキシアルキレンフェニルエーテル類やそのスルホコハク酸エステル塩類、硫酸エステル塩類;該炭素−炭素二重結合を分子中に少なくとも一つ有するポリオキシアルキレンアルキルフェニルエーテル類やそのスルホコハク酸エステル塩類、硫酸エステル塩類;該炭素−炭素二重結合を分子中に少なくとも一つ有するポリオキシアルキレンアラルキルフェニルエーテル類やそのスルホコハク酸エステル塩類、硫酸エステル塩類;該炭素−炭素二重結合を分子中に少なくとも一つ有するポリオキシアルキレンアルキルフェニルエーテルの脂肪族や、該炭素−炭素二重結合を分子中に少なくとも一つ有する芳香族カルボン酸塩類;ロジングリシジルエステルアクリレートの酸無水物変性物(特開平4−256429号参照);酸性リン酸(メタ)アクリル酸エステル系乳化剤;その他公知の反応性乳化剤(特開昭63−23725号公報、特開昭63−240931号公報、特開昭62−104802号公報、特開平4−50204号公報、特開平4−53802号公報等参照)が挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。なお、前記「オキシアルキレン」には、オキシエチレン、オキシプロピレン、オキシエチレン・オキシプロピレンなどが含まれる。 The reactive emulsifier includes carbon-carbon double bonds [(meth) allyl group, 1-propenyl group, 2-methyl-1-propenyl group, vinyl group, isopropenyl group, (meth) acryloyl in the molecule. Group, etc.], emulsifiers having a hydrophilic group and a hydrophobic group may be used. Specifically, for example, polyoxyalkylene alkyl ethers having at least one carbon-carbon double bond in the molecule, sulfosuccinic acid ester salts, sulfate ester salts thereof; the carbon-carbon double bond in the molecule. Polyoxyalkylene phenyl ethers having at least one thereof, sulfosuccinic acid ester salts thereof, sulfate ester salts; polyoxyalkylene alkyl phenyl ethers having at least one carbon-carbon double bond in the molecule, and sulfosuccinic acid ester salts thereof, Sulfate ester salts; polyoxyalkylene aralkyl phenyl ethers having at least one carbon-carbon double bond in the molecule, sulfosuccinate salts thereof, sulfate ester salts; at least one carbon-carbon double bond in the molecule Polyoxyalkylene Aliphatic alkyl phenyl ethers and aromatic carboxylates having at least one carbon-carbon double bond in the molecule; acid anhydride modified product of rosin glycidyl ester acrylate (see JP-A-4-256429); acidic Phosphoric acid (meth) acrylate ester emulsifier; other known reactive emulsifiers (Japanese Unexamined Patent Publication Nos. 63-23725, 63-240931, 62-104802, 4-50204) No. 4, JP-A-4-53802, etc.), and these can be used alone or in combination of two or more. The “oxyalkylene” includes oxyethylene, oxypropylene, oxyethylene / oxypropylene, and the like.
前記保護コロイドとしては、各種公知のものを特に制限なく用いることができる。具体的には、例えば、ポリアクリル酸のアルカリ金属塩、スチレン−マレイン酸共重合体のアルカリ金属塩、イソブチレン−マレイン酸共重合体のアルカリ金属塩、p−スルホン酸スチレン重合体のアルカリ金属塩、スルホン酸変性アミノ樹脂のアルカリ金属塩、ポリビニルアルコール等の酢酸ビニル重合体のケン化物が挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。なお、該保護コロイドの使用量は特に制限されないが、前記(A)成分(固形分)に対して、通常1〜10重量%程度の範囲とするのがよい。 As the protective colloid, various known ones can be used without particular limitation. Specifically, for example, alkali metal salt of polyacrylic acid, alkali metal salt of styrene-maleic acid copolymer, alkali metal salt of isobutylene-maleic acid copolymer, alkali metal salt of p-sulfonic acid styrene polymer And saponified products of vinyl acetate polymers such as alkali metal salts of sulfonic acid-modified amino resins and polyvinyl alcohol, which can be used alone or in combination of two or more. In addition, although the usage-amount of this protective colloid is not restrict | limited especially, it is good to set it as the range of about 1 to 10 weight% normally with respect to the said (A) component (solid content).
乳化方法としては、各種公知の乳化方法を特に制限なく利用できる。具体的には、例えば、前記(A)成分と水を強制的に乳化させる機械的乳化法、前記(A)成分の溶融物に水を徐々に加えてゆき油相と水相を反転させる反転乳化法、前記(A)成分と水を高圧下で乳化する高圧乳化法などを採用することができる。なお、該機械的乳化法に用いる乳化機は特に限定されず、例えば、ホモミキサーや高圧ホモジナイザー(マントン−ガウリン社製)などを用いうる。 As the emulsification method, various known emulsification methods can be used without particular limitation. Specifically, for example, a mechanical emulsification method for forcibly emulsifying the component (A) and water, and a reversal in which the oil phase and the aqueous phase are reversed by gradually adding water to the melt of the component (A). An emulsification method, a high-pressure emulsification method in which the component (A) and water are emulsified under high pressure can be employed. In addition, the emulsifier used for this mechanical emulsification method is not specifically limited, For example, a homomixer, a high-pressure homogenizer (made by Manton-Gaurin) etc. can be used.
こうして得られたエマルジョンの物性は特に限定されないが、作業性等を考慮して固形分濃度が通常0.1〜50重量%程度であり、また前記(A)成分のパルプへの定着等を考慮してゼータ電位が通常+10〜+60mV程度であり、また前記(A)成分の紙料(3)への分散性等を考慮して、粒子径が通常0.2〜10μm程度であるのが好ましい。また、pHは通常4〜7程度であり、外観は通常、白色ないし黄白色である。 The physical properties of the emulsion thus obtained are not particularly limited, but considering the workability and the like, the solid content concentration is usually about 0.1 to 50% by weight, and the fixing of the component (A) to the pulp is considered. The zeta potential is usually about +10 to +60 mV, and the particle size is preferably about 0.2 to 10 μm in consideration of the dispersibility of the component (A) in the stock (3). . The pH is usually about 4 to 7, and the appearance is usually white to yellowish white.
なお、当該エマルジョンには、pH調整剤などの添加剤を必要に応じて含有させることができる。該pH調整剤としては、例えば、アルカリ金属化合物〔水酸化ナトリウム、水酸化カリウム等〕、鉱酸〔リン酸、硫酸、塩酸等〕、有機酸〔蟻酸、酢酸等〕アンモニアが挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。 The emulsion can contain an additive such as a pH adjuster as necessary. Examples of the pH adjuster include alkali metal compounds [sodium hydroxide, potassium hydroxide, etc.], mineral acids [phosphoric acid, sulfuric acid, hydrochloric acid, etc.], and organic acids [formic acid, acetic acid, etc.] ammonia. These can be used singly or in combination of two or more.
本発明では、紙力増強剤(2)として、〔紙力増強剤(2)を含有する紙料(3)のカナダ標準ろ水度(ml)〕と〔紙力増強剤(2)を含有しない紙料(3)のカナダ標準ろ水度(ml)〕との差として50ml以下の値を与えるものを用いる点に特徴がある。なお、当該カナダ標準ろ水度(以下、フリーネス値という)とは、JIS P 8121に規定される、パルプの水切れの程度(ml)を表す指標である。また、前記差(以下、フリーネス差という)とは、当該紙力増強剤(2)によるパルプの凝集程度を表す指標である。 In the present invention, the paper strength enhancer (2) contains [Canadian standard freeness (ml) of paper stock (3) containing paper strength enhancer (2)] and [paper strength enhancer (2). It is characterized in that a material that gives a value of 50 ml or less as a difference from the Canadian standard freeness (ml) of the paper material (3) that is not used is used. The Canadian standard freeness (hereinafter referred to as “freeness value”) is an index representing the degree of drainage (ml) of pulp as defined in JIS P 8121. The difference (hereinafter referred to as freeness difference) is an index representing the degree of pulp aggregation by the paper strength enhancer (2).
該紙力増強剤(2)により本発明の効果が得られる理由は定かではないが、おそらく、該フリーネス差が50ml以下であることにより当該紙力増強剤(2)のパルプへの定着率が向上し、且つ、嵩高紙における地合乱れが抑制されるためではないかと考えられる。 Although the reason why the effect of the present invention can be obtained by the paper strength enhancer (2) is not clear, the fixing rate of the paper strength enhancer (2) to the pulp is probably due to the difference in freeness being 50 ml or less. This is thought to be due to the improvement and suppression of formation disturbance in bulky paper.
当該「紙力増強剤(2)を含有する紙料(3)」(以下、試験紙料と略す)は、後述する紙料(3)に紙力増強剤(2)を含めたものと同一であってよい。また、当該「紙力増強剤(2)を含有しない紙料(3)」(以下、ブランク紙料と略す)は、後述する紙料(3)と同一であってよい。(換言すれば、紙力増強剤(2)を含まない以外は前記試験紙料と同一であってよい。) The “paper (3) containing the paper strength enhancer (2)” (hereinafter abbreviated as test paper) is the same as the paper (3) described later including the paper strength enhancer (2). It may be. The “paper material (3) not containing the paper strength enhancer (2)” (hereinafter abbreviated as blank paper material) may be the same as the paper material (3) described later. (In other words, it may be the same as the test strip except that it does not contain the paper strength enhancer (2).)
なお、フリーネス値の測定の際、該試験紙料と該ブランク紙料のパルプ種は問わないが、両紙料間で同一とする必要がある。また、両紙料におけるパルプの叩解度は、いずれにおいてもフリーネス値が通常200〜500ml程度の範囲とする必要がある。また、該試験紙料と該ブランク紙料は、嵩向上剤(1)を通常0.01〜5重量%程度となる範囲で含んでいてもよい。 In the measurement of the freeness value, the pulp types of the test paper stock and the blank stock material are not limited, but it is necessary to make the paper stock the same. Further, the pulp beating degree in both paper stocks is required to have a freeness value in a range of about 200 to 500 ml in any case. Further, the test paper stock and the blank stock material may contain the bulk improver (1) in a range of usually about 0.01 to 5% by weight.
また当該紙力増強剤(2)としては、特に、固形分濃度1.0重量%の溶液状態における濁度単位(NTU)が通常500未満であるもの、特に、50〜400程度であるものが好ましい。ここに、濁度単位(NTU)とは、当該紙力増強剤(2)中の両性ポリアクリルアミド(B)(以下、(B)成分という)が所謂ポリイオンコンプレックスをどの程度形成しているかを示す指標であり、これが500を超えると、当該両性ポリアクリルアミド(B)のパルプを凝集させる力が強くなりすぎ、目的とする嵩高紙が得難くなる傾向にある。 Further, as the paper strength enhancer (2), in particular, a turbidity unit (NTU) in a solution state having a solid content concentration of 1.0% by weight is usually less than 500, in particular, about 50 to 400. preferable. Here, the turbidity unit (NTU) indicates how much the so-called polyion complex is formed by the amphoteric polyacrylamide (B) (hereinafter referred to as component (B)) in the paper strength enhancer (2). If it exceeds 500, the force of aggregating the amphoteric polyacrylamide (B) pulp tends to be too strong, and the intended bulky paper tends to be difficult to obtain.
なお、当該濁度単位(NTU)は、具体的には、ANALITE濁度計「NEP-160 Portable
Turbidity Meter」(MacVan社製)を用い、900nmの赤外光における180度の散乱光を測定することにより得られる、標準物質(ホルマジン標準液(400NTU)、和光純薬工業(株)製)に対する相対的な値である。
The turbidity unit (NTU) is specifically determined by ANALITE turbidimeter “NEP-160 Portable
For a standard substance (formazine standard solution (400 NTU), manufactured by Wako Pure Chemical Industries, Ltd.) obtained by measuring 180 degree scattered light in 900 nm infrared light using “Turbidity Meter” (manufactured by MacVan). It is a relative value.
前記(B)成分としては、各種公知のものから、前記フリーネス差や好ましくは前記濁度単位(NTU)を与えるものを適宜選択して用いることができる。 As the component (B), those that give the difference in freeness or preferably the turbidity unit (NTU) can be appropriately selected from various known ones.
該(B)成分は、(メタ)アクリルアミド(b1)(以下、(b1)成分という)、カチオン性(メタ)アクリル系モノマー(b2)(以下、(b2)成分という)、アニオン性(メタ)アクリル系モノマー(b3)(以下、(b3)成分という)、N−置換(メタ)アクリルアミド(b4)(以下、(b4)成分という)、(メタ)アリル基含有ビニルモノマー(b5)(以下、(b5)成分という)、および必要に応じて(b1)〜(b5)以外のビニルモノマー(b6)(以下、(b6)成分という)を共重合させてなるポリマーを含む組成物である。(なお、以下、「(メタ)アクリル」とは、「アクリル」または「メタクリル」の意味である。) The component (B) includes: (meth) acrylamide (b1) (hereinafter referred to as (b1) component), cationic (meth) acrylic monomer (b2) (hereinafter referred to as (b2) component), anionic (meth) Acrylic monomer (b3) (hereinafter referred to as component (b3)), N-substituted (meth) acrylamide (b4) (hereinafter referred to as component (b4)), (meth) allyl group-containing vinyl monomer (b5) (hereinafter referred to as component) (B5) component) and, if necessary, a composition comprising a polymer obtained by copolymerizing a vinyl monomer (b6) other than (b1) to (b5) (hereinafter referred to as component (b6)). (Hereinafter, “(meth) acryl” means “acryl” or “methacryl”.)
前記(b1)成分としては、アクリルアミドやメタクリルアミドが挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。 Examples of the component (b1) include acrylamide and methacrylamide, and these can be used alone or in combination of two or more.
前記(b2)成分としては、分子内に(メタ)アクリロイル基とカチオン性官能基を少なくとも1つずつ有する化合物であれば、各種公知のものを特に制限なく用いることができる。具体的には、例えば、第3級アミノ基含有(メタ)アクリル系モノマー〔N,N−ジメチルアミノエチル(メタ)アクリレート、N,N−ジエチルアミノエチル(メタ)アクリレート、N,N−ジメチルアミノプロピル(メタ)アクリルアミド、N,N−ジエチルアミノプロピル(メタ)アクリルアミド等〕、当該第3級アミノ基含有(メタ)アクリル系モノマーの塩〔塩酸塩、硫酸塩、酢酸塩等〕、該第3級アミノ基含有(メタ)アクリル系モノマーと四級化剤(メチルクロライド、ベンジルクロライド、ジメチル硫酸、エピクロルヒドリン等)が反応してなる、第4級アンモニウム塩含有(メタ)アクリル系モノマーなどが挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。 As the component (b2), various known compounds can be used without particular limitation as long as the compound has at least one (meth) acryloyl group and one cationic functional group in the molecule. Specifically, for example, tertiary amino group-containing (meth) acrylic monomers [N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (Meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, etc.], salt of the tertiary amino group-containing (meth) acrylic monomer [hydrochloride, sulfate, acetate, etc.], the tertiary amino Examples include quaternary ammonium salt-containing (meth) acrylic monomers formed by the reaction of group-containing (meth) acrylic monomers and quaternizing agents (methyl chloride, benzyl chloride, dimethyl sulfate, epichlorohydrin, etc.). Can be used singly or in combination of two or more.
前記(b3)成分としては、分子内に(メタ)アクリロイル基とアニオン性官能基を少なくとも1つずつ有する化合物であれば、各種公知のものを特に制限なく用いることができる。具体的には、例えば、α、β−不飽和モノカルボン酸類〔アクリル酸、メタクリル酸、クロトン酸等〕、α、β−不飽和ジカルボン酸〔マレイン酸、(無水)マレイン酸、フマル酸、イタコン酸、ムコン酸、シトラコン酸等〕、α、β−不飽和スルホン酸〔スチレンスルホン酸、2−アクリルアミド−2−メチルプロパンスルホン酸等〕、これらの塩類〔ナトリウム塩、カリウム塩、アンモニウム塩等〕などが挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。 As the component (b3), various known compounds can be used without particular limitation as long as they are compounds having at least one (meth) acryloyl group and an anionic functional group in the molecule. Specifically, for example, α, β-unsaturated monocarboxylic acids [acrylic acid, methacrylic acid, crotonic acid, etc.], α, β-unsaturated dicarboxylic acid [maleic acid, (anhydrous) maleic acid, fumaric acid, itacon Acid, muconic acid, citraconic acid, etc.], α, β-unsaturated sulfonic acid (styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, etc.), and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) These may be used alone or in combination of two or more.
前記(b4)成分としては、前記(b2)成分以外のN−置換(メタ)アクリルアミドであれば、各種公知のものを特に制限なく用いることができる。具体的には、例えば、N,N−ジメチル(メタ)アクリルアミド、N,N−ジエチル(メタ)アクリルアミド、N,N−ジイソプロピル(メタ)アクリルアミド、N−メチル(ネタ)アクリルアミド、N−エチル(メタ)アクリルアミド、N−イソプロピル(メタ)アクリルアミド、N−t−ブチル(メタ)アクリルアミド等が挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。 As the component (b4), various known compounds can be used without particular limitation as long as they are N-substituted (meth) acrylamides other than the component (b2). Specifically, for example, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N-methyl (neta) acrylamide, N-ethyl (meta) ) Acrylamide, N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, and the like. These may be used alone or in combination of two or more.
前記(b5)成分としては、分子内に(メタ)アリル基を1つ有する化合物であれば、各種公知のものを特に制限なく用いることができる。具体的には、例えば、(メタ)アリルスルホン酸ナトリウムおよびその中和塩、アリルアルコール、アリルアミンが等が挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。なお、当該中和塩としては、例えば、アルカリ金属塩(ナトリウム塩、カリウム塩等)や、アンモニウム塩等が挙げられる。(b5)成分の中でも、両性ポリアクリルアミド(B)が高分子量化し、前記紙力向上効果が得られやすいことから、(メタ)アリルスルホン酸ナトリウムおよびその中和塩が、特にそれ自体の安定性をも考慮してメタリルスルホン酸ナトリウムおよびその中和塩が好ましい。 As the component (b5), various known compounds can be used without particular limitation as long as they are compounds having one (meth) allyl group in the molecule. Specific examples include sodium (meth) allylsulfonate and neutralized salts thereof, allyl alcohol, and allylamine. These can be used alone or in combination of two or more. Examples of the neutralized salt include alkali metal salts (sodium salt, potassium salt, etc.), ammonium salts, and the like. Among the components (b5), the amphoteric polyacrylamide (B) has a high molecular weight, and the effect of improving the paper strength can be easily obtained. Therefore, sodium (meth) allylsulfonate and its neutralized salt are particularly stable in themselves. In view of the above, sodium methallylsulfonate and neutralized salts thereof are preferred.
なお、本発明では、必要に応じて、前記(b1)〜(b5)以外のビニルモノマー(以下、(b6)成分という)を用いることができる。(b6)成分の具体例としては、例えば、前記α、β−不飽和モノカルボン酸類のアルキルエステル類〔(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸デシル、(メタ)アクリル酸ミリスチル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸イソステアリルアルコール等〕、多官能ビニルモノマー〔メチレンビス(メタ)アクリルアミド、エチレンビス(メタ)アクリルアミド、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、ジビニルベンゼン、1、3、5−トリアクロイルヘキサヒドロ−S−トリアジン、トリアリルイソシアヌレート、トリアリルアミン、テトラメチロールメタンテトラアクリレート等〕などが挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。これらの中でも、該多官能ビニルモノマーを用いると、(B)成分が高分子量化することにより前記紙力効果が向上するため好ましい。 In the present invention, vinyl monomers other than the above (b1) to (b5) (hereinafter referred to as (b6) component) can be used as necessary. Specific examples of the component (b6) include alkyl esters of the α, β-unsaturated monocarboxylic acids [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth ) Octyl acrylate, decyl (meth) acrylate, myristyl (meth) acrylate, stearyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) acrylic acid isostearyl alcohol, etc.], polyfunctional vinyl monomers [methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, divinylbenzene, 1, 3, 5-triacroyl hexahydride -S-triazine, triallyl isocyanurate, triallylamine, tetramethylol methane tetraacrylate, etc.] and the like. These can be used alone or in combination of two or more. Among these, it is preferable to use the polyfunctional vinyl monomer because the paper strength effect is improved by increasing the molecular weight of the component (B).
前記(b1)成分〜(b6)成分の使用量は特に限定されないが、一般的には、(b1)成分が57〜99.78モル%程度(好ましくは63〜97.8モル%)の範囲、(b2)成分が0.1〜15モル%程度(好ましくは1〜15モル%)の範囲、(b3)成分が0.1〜15モル%程度(好ましくは1〜15モル%)の範囲、(b4)成分が0.01〜2モル%程度(好ましくは0.1〜1モル%)の範囲、(b5)成分が0.01〜10モル%程度(好ましくは0.1〜5モル%)の範囲、(b6)成分が1モル%未満の範囲とするのがよい。 The amount of the (b1) component to (b6) component used is not particularly limited, but in general, the component (b1) is in the range of about 57 to 99.78 mol% (preferably 63 to 97.8 mol%). The component (b2) is in the range of about 0.1 to 15 mol% (preferably 1 to 15 mol%), and the component (b3) is in the range of about 0.1 to 15 mol% (preferably 1 to 15 mol%). The component (b4) is in the range of about 0.01 to 2 mol% (preferably 0.1 to 1 mol%), and the component (b5) is in the range of about 0.01 to 10 mol% (preferably 0.1 to 5 mol%). %), And the component (b6) is preferably less than 1 mol%.
なお、(b2)成分と(b3)成分のいずれか或いは双方が0.1モル%未満の場合には、(B)成分がパルプに定着し難くなって、紙力効果が得難くなる傾向にあり、一方、両成分のいずれか或いは双方が15モル%を越える場合には、(B)成分中のアクリルアミド分が減少するため、やはり紙力効果が得難くなる傾向にある。また、(b4)成分が0.01モル%未満の場合には、(B)成分が高分子量化し難くなり、一方、2.0モル%を超える場合には、(B)成分を製造する際にゲル化が生ずる傾向にある。また、(b5)成分が0.01モル%未満の場合には、その連鎖移動効果が弱くなって、(B)成分に分岐構造が十分に導入されなくなる傾向にあり、一方、10モル%超える場合には、逆に連鎖移動効果が強くなりすぎて、(B)成分の高分子量化が困難になる傾向にある。 In addition, when either (b2) component and (b3) component or both are less than 0.1 mol%, (B) component becomes difficult to fix to a pulp, and it is difficult to obtain a paper strength effect. On the other hand, when either or both of the components exceed 15 mol%, the acrylamide content in the component (B) is decreased, so that the paper strength effect tends to be difficult to obtain. Further, when the component (b4) is less than 0.01 mol%, the component (B) is difficult to increase in molecular weight, whereas when it exceeds 2.0 mol%, the component (B) is produced. Gelation tends to occur. Further, when the component (b5) is less than 0.01 mol%, the chain transfer effect is weakened, and the branched structure tends not to be sufficiently introduced into the component (B), whereas it exceeds 10 mol%. In some cases, the chain transfer effect is too strong, and it tends to be difficult to increase the molecular weight of component (B).
(B)成分の製造方法は特に限定されず、各種公知の方法を採用することができる。具体的には、例えば、前記(b1)成分〜(b5)成分(必要に応じてさらに(b6)成分)を反応容器中に滴下しながら重合反応させる方法や、各成分を反応容器に一括で仕込んで重合反応させる方法が挙げられる。なお、各重合方法は、各種公知のラジカル重合開始剤および水の存在下、および必要に応じて連鎖移動剤の存在下において、通常20〜140℃程度、2〜12時間程度行えばよい。 The manufacturing method of (B) component is not specifically limited, Various well-known methods are employable. Specifically, for example, a method in which the components (b1) to (b5) (and further (b6) as necessary) are added dropwise to the reaction vessel while the polymerization reaction is performed, or each component is collectively added to the reaction vessel. A method of charging and polymerization reaction is exemplified. In addition, what is necessary is just to perform each superposition | polymerization method normally at about 20-140 degreeC and about 2 to 12 hours in presence of various well-known radical polymerization initiators and water, and presence of a chain transfer agent as needed.
前記重合開始剤としては、各種公知のものを特に限定なく使用することができる。具体的には、例えば、有機過酸化物〔ベンゾイルパーオキサイド、ジクミルパーオキサイド、ラウリルパーオキサイド等〕、無機過酸化物〔過酸化水素、過硫酸アンモニウム、過硫酸カリウム等〕、アゾ系化合物〔2、2’−アゾビスイソブチロニトリル、ジメチル−2、2’−アゾビスイソブチレイト等〕などが挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。なお、該重合開始剤の使用量は、通常、前記(b1)成分〜(b6)成分の総重量に対して0.01〜5重量%程度の範囲とすればよい。 As the polymerization initiator, various known ones can be used without particular limitation. Specifically, for example, organic peroxides [benzoyl peroxide, dicumyl peroxide, lauryl peroxide, etc.], inorganic peroxides [hydrogen peroxide, ammonium persulfate, potassium persulfate, etc.], azo compounds [2 2′-azobisisobutyronitrile, dimethyl-2, 2′-azobisisobutyrate, etc.] and the like. These may be used alone or in combination of two or more. In addition, what is necessary is just to make the usage-amount of this polymerization initiator into the range of about 0.01-5 weight% normally with respect to the total weight of said (b1) component-(b6) component.
前記連鎖移動剤は、(B)成分の分子量や粘度を調整することを目的として必要に応じて用いることができる。具体例としては、例えば、エチルアルコール、メチルアルコール、イソプロピルアルコール等のアルコール系連鎖移動剤が挙げられる。また、該連鎖移動剤の使用量は、通常、前記(b1)成分〜(b6)成分の総重量に対して0〜5重量%程度の範囲とすればよい。なお、該連鎖移動剤は溶媒としても作用する。 The chain transfer agent can be used as necessary for the purpose of adjusting the molecular weight and viscosity of the component (B). Specific examples include alcohol chain transfer agents such as ethyl alcohol, methyl alcohol, and isopropyl alcohol. Moreover, what is necessary is just to make the usage-amount of this chain transfer agent into the range of about 0-5 weight% normally with respect to the total weight of said (b1) component-(b6) component. The chain transfer agent also acts as a solvent.
なお、本発明では、(B)成分として、上記方法で得られた(B)成分を各種公知の方法でホフマン分解ないしマンニッヒ変性したもの(以下、(B’)成分という)を用いることもできる。 In the present invention, the component (B) obtained by the above method can be Hoffman-decomposed or Mannich-modified (hereinafter referred to as component (B ')) by various known methods. .
前記ホフマン分解による(B’)成分の調製法は特に限定されず、各種公知の方法を採用すればよい。具体的には、例えば、前記(B)成分の水溶液に次亜ハロゲン酸塩とアルカリ触媒とを添加することにより、アルカリ性領域においてアクリルアミド系ポリマーと次亜ハロゲン酸とを反応させた後に、酸を添加して反応系を通常pH3.5〜5.5程度に調整すればよい。当該(B’)成分におけるアクリルアミド系ポリマーは、一般的には、カチオン性単量体単位を通常5〜50モル%程度、アクリルアミド単位を通常60〜95モル%程度含有したものであり、また重量平均分子量が通常5〜300万程度であるのが好ましい。 The method for preparing the component (B ′) by the Hofmann decomposition is not particularly limited, and various known methods may be employed. Specifically, for example, by adding a hypohalite and an alkali catalyst to the aqueous solution of the component (B), the acrylamide polymer and the hypohalous acid are reacted in the alkaline region, and then the acid is added. The reaction system is usually adjusted to about pH 3.5 to 5.5 by adding. The acrylamide polymer in the component (B ′) generally contains about 5 to 50 mol% of a cationic monomer unit and usually about 60 to 95 mol% of an acrylamide unit, and has a weight. The average molecular weight is preferably about 5 to 3 million.
また、本発明では、当該(B’)成分のほかにも、次に例示するホフマン分解物を用いることができる。具体的には、塩化コリンの存在下にポリアクリルアミド系ポリマーをホフマン分解して調製したカチオン変性物(特開昭53-109594号)、ホフマン分解反応において、水酸基を有する第3級アミンと、塩化ベンジルあるいはその誘導体との4級か反応物を添加して調製したカチオン変性物(特公昭58-8682号)、ホフマン分解反応において安定剤として有機多価アミンを添加して調製したカチオン変性物(特公昭60-17322号)、またホフマン分解反応において安定剤として特定のカチオン性化合物を添加して調製したカチオン変性物(特公昭62-45884号)等が挙げられる。 In the present invention, in addition to the component (B ′), Hofmann degradation products exemplified below can be used. Specifically, a cation-modified product prepared by decomposing a polyacrylamide polymer in the presence of choline chloride (Japanese Patent Laid-Open No. 53-109594), a tertiary amine having a hydroxyl group in the Hofmann decomposition reaction, A cation modified product prepared by adding a quaternary or a reaction product with benzyl or a derivative thereof (Japanese Patent Publication No. 58-8682), a cation modified product prepared by adding an organic polyvalent amine as a stabilizer in the Hofmann decomposition reaction ( JP-B-60-17322) and cation-modified products prepared by adding a specific cationic compound as a stabilizer in the Hofmann decomposition reaction (JP-B-62-45884).
前記マンニッヒ反応による(B’)成分の調製法は特に限定されず、各種公知の方法を採用すればよい。具体的には、例えば、前記(B)成分の水溶液に、ホルマリン及び第2級アミン(ジメチルアミン等)を添加し、通常、40〜60℃程度、1〜5時間程度反応させればよい。なお、当該(B’)成分におけるアクリルアミド系ポリマーは、一般的には、カチオン性単量体単位を通常10〜60モル%程度、アクリルアミド単位を通常40〜90モル%程度含有するものである。 The method for preparing the component (B ′) by the Mannich reaction is not particularly limited, and various known methods may be employed. Specifically, for example, formalin and a secondary amine (dimethylamine or the like) are added to the aqueous solution of the component (B), and the reaction is usually performed at about 40 to 60 ° C. for about 1 to 5 hours. In addition, the acrylamide polymer in the component (B ′) generally contains about 10 to 60 mol% of the cationic monomer unit and usually about 40 to 90 mol% of the acrylamide unit.
(B)成分(または(B’)成分)の物性は特に限定されないが、例えば、重量平均分子量が通常100万以上、具体的には、100万〜1000万であるのが好ましい。重量平均分子量が100万以上であることにより、十分な紙力効果が得やすくなる傾向にある。これはおそらく、当該紙力増強剤(2)のパルプへの定着率が特に向上し、また、嵩高紙の地合乱れが抑制されるためではないかと考えられる。 Although the physical property of (B) component (or (B ') component) is not specifically limited, For example, it is preferable that a weight average molecular weight is 1 million or more normally, Specifically, it is 1 million to 10 million. When the weight average molecular weight is 1,000,000 or more, a sufficient paper strength effect tends to be easily obtained. This is probably because the fixing rate of the paper strength enhancer (2) to the pulp is particularly improved, and the formation disturbance of the bulky paper is suppressed.
なお、該重量平均分子量は、GPC−LALLS法やGPC−RALLS法によるポリエチレンオキシド換算値をいう。また、測定条件はいずれの方法においても、0.5mol/l酢酸緩衝液(0.5mol/l酢酸+0.5mol/l酢酸ナトリウム水溶液、pH約4.2)を溶媒(溶離液)として、ポリマー濃度が0.025%、溶液温度が40℃、光散乱角が5°あるいは90°である。 In addition, this weight average molecular weight says the polyethylene oxide conversion value by GPC-LALLS method or GPC-RALLS method. In either method, the measurement conditions were 0.5 mol / l acetate buffer (0.5 mol / l acetic acid + 0.5 mol / l sodium acetate aqueous solution, pH about 4.2) as a solvent (eluent), polymer The concentration is 0.025%, the solution temperature is 40 ° C., and the light scattering angle is 5 ° or 90 °.
また、(B)成分は、粘度が通常、2万mPa・sec/25℃以下、具体的には10〜5000mPa・sec/25℃程度であるのが好ましい。粘度を2万mPa・sec/25℃以下とすることにより、得られる嵩高紙の紙力効果や地合いが良好になる傾向にある。なお、該粘度は、B型粘度計を用い、固形分濃度5%、温度25℃で測定した値をいう。 The component (B) preferably has a viscosity of usually 20,000 mPa · sec / 25 ° C. or less, specifically about 10 to 5000 mPa · sec / 25 ° C. By setting the viscosity to 20,000 mPa · sec / 25 ° C. or less, the paper strength effect and texture of the resulting bulky paper tend to be good. The viscosity is a value measured using a B-type viscometer at a solid content concentration of 5% and a temperature of 25 ° C.
本発明で用いられる抄紙を行う際に用いる紙料(3)とは、具体的には、パルプ、水、および必要に応じて各種添加剤(定着剤、填料、前記pH調整剤等)を含むパルプスラリーをいう。但し、ここでいう紙料(3)は、嵩高剤(1)と紙力増強剤(2)をいずれも含まない。 Specifically, the stock (3) used in the paper making used in the present invention includes pulp, water, and various additives (fixing agent, filler, pH adjusting agent, etc.) as necessary. This refers to pulp slurry. However, the paper material (3) here does not contain either the bulking agent (1) or the paper strength enhancing agent (2).
前記パルプとしては、各種公知のものを特に制限なく用いることができる。具体的には、例えば、砕木パルプ(BKP)、加圧砕木パルプ(P−BKP)、広葉樹さらしパルプ(L−BKP)、サーモメカニカルパルプ(TMP)、ケミサーモメカニカルパルプ(CTMP)、セミケミカルパルプ(SCP)、化学パルプ(AP,KP)、脱墨パルプ(DIP)から選ばれる1種を単独で、あるいは2種以上を組み合わせて用いることができる。なお、当該パルプの叩解度は特に限定されないが、通常は、JIS P 8121で測定されるカナダ標準ろ水度(以下、フリーネス値ということがある)が通常200〜500程度の範囲となるものが用いられる。 As the pulp, various known ones can be used without particular limitation. Specifically, for example, groundwood pulp (BKP), pressurized groundwood pulp (P-BKP), hardwood bleached pulp (L-BKP), thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), semichemical pulp One type selected from (SCP), chemical pulp (AP, KP), and deinked pulp (DIP) can be used alone, or two or more types can be used in combination. In addition, although the beating degree of the said pulp is not specifically limited, Usually, what has a Canadian standard freeness measured by JIS P 8121 (hereinafter sometimes referred to as freeness value) is usually in the range of about 200 to 500. Used.
また、紙料(3)における該パルプの含有量は特に限定されないが、嵩高剤(1)および紙力増強剤(2)の分散性を考慮して、通常0.1〜4重量%程度、好ましくは0.3〜3.5重量%の範囲とするのがよい。 In addition, the content of the pulp in the stock (3) is not particularly limited, but considering the dispersibility of the bulking agent (1) and the paper strength enhancer (2), usually about 0.1 to 4% by weight, Preferably it is 0.3 to 3.5 weight%.
前記定着剤としては、各種公知のアルミニウム化合物を用いることができる。具体的には、例えば、ポリ塩化アルミニウム、アルミナゾル、ポリ硫酸アルミニウム、ポリ硫酸ケイ酸アルミニウム、塩化アルミニウム、硫酸アルミニウム、ミョウバンが挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。なお、紙料(3)における当該定着剤の含有量は特に限定されないが、パルプに対して、通常0〜10重量%の範囲とすればよい。 Various known aluminum compounds can be used as the fixing agent. Specifically, for example, polyaluminum chloride, alumina sol, polyaluminum sulfate, polyaluminum sulfate silicate, aluminum chloride, aluminum sulfate, alum can be used, and these can be used alone or in combination of two or more. Can do. In addition, although content of the said fixing agent in paper stock (3) is not specifically limited, What is necessary is just to set it as the range of 0 to 10 weight% normally with respect to a pulp.
前記填料としては、例えば、クレー、タルク、カオリン、炭酸カルシウム、酸化チタンが挙げられ、これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。なお、紙料(3)における当該填料の含有量は特に限定されないが、パルプに対して通常、0〜100重量%程度の範囲とすればよい。 Examples of the filler include clay, talc, kaolin, calcium carbonate, and titanium oxide, and these can be used alone or in combination of two or more. In addition, although content of the said filler in paper stock (3) is not specifically limited, What is necessary is just to set it as the range of about 0 to 100 weight% normally with respect to a pulp.
その他、本発明では、前記添加剤のほかにも、サイズ剤、デンプン、ピッチコントロール剤、スライムコントロール剤、歩留向上剤、消泡剤、顔料、染料等の添加剤を、1種を単独で、あるいは2種以上を組み合わせて用いることができる。 In addition, in the present invention, in addition to the above additives, additives such as a sizing agent, starch, pitch control agent, slime control agent, yield improver, antifoaming agent, pigment, dye, etc. can be used alone. Alternatively, two or more types can be used in combination.
なお、該紙料(3)の水温は特に限定されず、通常10〜60℃程度である。また、そのpHも特に限定されず、通常4〜9程度である。 In addition, the water temperature of this stock (3) is not specifically limited, Usually, about 10-60 degreeC. Moreover, the pH is not specifically limited, Usually, it is about 4-9.
嵩高剤(1)と紙力増強剤(2)を紙料(3)に添加する際、その添加順序は特に限定されないが、本発明の効果を良好なものとするためには、嵩高剤(1)を紙料(3)に添加した後に、紙力増強剤(2)を更に添加してから、抄紙を行うのが好ましい。なお、両者の添加は、通常、強い攪拌下に行う。 When adding the bulking agent (1) and the paper strength enhancer (2) to the stock (3), the order of addition is not particularly limited, but in order to improve the effect of the present invention, the bulking agent ( After adding 1) to the stock (3), it is preferable to add the paper strength enhancer (2) before paper making. In addition, both addition is normally performed under strong stirring.
また、抄紙系における嵩高剤(1)と紙力増強剤(2)の各使用量は特に限定されないが、前記嵩高効果と紙力効果を考慮して、通常、嵩高剤(1)は0.01〜5重量%程度(好ましくは0.01〜2重量%)、紙力増強剤(2)は0.01〜2重量%程度(好ましくは0.05〜1重量%)の範囲とするのがよい。 In addition, the amount of each of the bulking agent (1) and the paper strength enhancing agent (2) used in the papermaking system is not particularly limited, but the bulking agent (1) is usually 0. About 01 to 5% by weight (preferably 0.01 to 2% by weight), and paper strength enhancer (2) is in the range of about 0.01 to 2% by weight (preferably 0.05 to 1% by weight). Is good.
また、紙の製造ラインにおいて、嵩高剤(1)と紙力増強剤(2)を紙料(3)に添加する地点は特に限定されず、例えば、パルプ調製工程におけるミキシングチェスト、マシンチェスト、原料移送ポンプ等のいずれの地点であってもよい。 In addition, the point at which the bulking agent (1) and the paper strength enhancer (2) are added to the paper stock (3) in the paper production line is not particularly limited. For example, the mixing chest, machine chest, raw material in the pulp preparation process It may be any point such as a transfer pump.
また、抄紙機については、インレット、ワイヤーパート、プレスパート、ドライヤーパート、表面塗布装置、キャレンダーパート等の、形式や形態は特に限定されない。 Moreover, about a paper machine, a form and form, such as an inlet, a wire part, a press part, a dryer part, a surface coating apparatus, a calendar part, are not specifically limited.
以下に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
製造例1
(嵩高剤の調製)
攪拌機、脱水管、冷却管、温度計及び窒素ガス導入管を備えた反応容器にステアリン酸1095.2gを仕込んで加熱溶融した後に、トリエチレンテトラミン(M=2、N=2)166.6gを加えて窒素雰囲気下に反応系を180℃まで昇温した。(なお、トリエチレンテトラミン1モルに対し、ステアリン酸は(M+0.69N)モルである。)次いで、反応生成水を除去しながら反応系を180℃〜200℃に保持し、反応生成水の発生が認められなくなったことを確認してから加熱を停止して、反応系を室温まで冷却することにより、第3級アミド化合物を得た。
Production Example 1
(Preparation of bulking agent)
After charging 1095.2 g of stearic acid into a reaction vessel equipped with a stirrer, dehydration tube, cooling tube, thermometer and nitrogen gas introduction tube and heating and melting, 166.6 g of triethylenetetramine (M = 2, N = 2) was added. In addition, the reaction system was heated to 180 ° C. in a nitrogen atmosphere. (Note that stearic acid is (M + 0.69N) moles per mole of triethylenetetramine.) Next, the reaction system is maintained at 180 ° C. to 200 ° C. while removing the reaction product water, and the reaction product water is generated. After confirming that no more was observed, the heating was stopped and the reaction system was cooled to room temperature to obtain a tertiary amide compound.
次いで、第3級アミド化合物100重量部を採取して同様の反応容器に仕込み、さらに20重量部のイソプロピルアルコールを加えて、反応系を80℃〜90℃に保持した。次いで、80℃のイオン交換水1247gを加え、反応系を激しく攪拌することにより、懸濁状の溶液を調製した。次いで、エピクロロヒドリン52.7gを加え、反応系を80℃〜85℃で約4時間保持することにより、脂肪酸変性アミド樹脂を得た。なお、当該脂肪酸変性アミド樹脂の、ASTM D 2074に準拠して測定した第2級アミン価は約25mgKOH/g、また第3級アミン価は約77mgKOH/gであった。 Next, 100 parts by weight of a tertiary amide compound was collected and charged into the same reaction vessel, and further 20 parts by weight of isopropyl alcohol was added to maintain the reaction system at 80 ° C. to 90 ° C. Next, 1247 g of ion exchange water at 80 ° C. was added, and the reaction system was vigorously stirred to prepare a suspension solution. Next, 52.7 g of epichlorohydrin was added, and the reaction system was kept at 80 ° C. to 85 ° C. for about 4 hours to obtain a fatty acid-modified amide resin. The fatty acid-modified amide resin had a secondary amine value measured in accordance with ASTM D 2074 of about 25 mg KOH / g and a tertiary amine value of about 77 mg KOH / g.
次いで、同じ反応系にノニオン性界面活性剤(商品名:エパン720、第一工業製薬(株)製)24.0gを加えて良く攪拌し、得られた溶液を高圧乳化機(model 15MR、APV GAULIN社製)を用いてさらに乳化することにより、前記脂肪酸変性アミド樹脂のエマルジョンを得た。 Next, 24.0 g of a nonionic surfactant (trade name: Epan 720, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to the same reaction system and stirred well, and the resulting solution was mixed with a high-pressure emulsifier (model 15MR, APV The emulsion of fatty acid-modified amide resin was obtained by further emulsification using GAULIN).
なお、当該エマルジョンの粒子径は、レーザー回折式粒度分布測定装置(装置名:SALD2000、島津製作所(株)製)を用いた測定した測定値として、約1.8μmであった。当該エマルジョンは、嵩高剤(1−1)として用いる。 The particle diameter of the emulsion was about 1.8 μm as a measured value using a laser diffraction particle size distribution measuring device (device name: SALD2000, manufactured by Shimadzu Corporation). The emulsion is used as a bulking agent (1-1).
製造例2(紙力増強剤の調製)
撹拌機、温度計、還流冷却管、窒素ガス導入管および2つの滴下ロートを備えた反応装置にイオン交換水350部を仕込んだ。次いで、一の滴下ロートには、pHを3に調整したモノマー溶液(アクリルアミド179部、62.5%硫酸11部、80%のアクリル酸水溶液12.8部、メタアリルスルホン酸ナトリウム2.3部、ジメチルアミノエチルメタクリレ−ト22.4部、ジメチルアクリルアミド2.8部およびイオン交換水340部)を、また他の滴下ロートには、重合開始剤溶液(過硫酸アンモニウム0.3部、イオン交換水100部)を仕込んだ。次いで、窒素ガス導入管を通じて反応系内の酸素を除去した後、反応系を90℃まで加熱し、前記各滴下ロートからモノマー溶液および重合開始剤溶液をそれぞれ約3時間かけて、反応系に滴下した。滴下終了後、前記他の滴下ロートから更に重合開始剤溶液(過硫酸アンモニウム0.45部、イオン交換水10部)を仕込み、反応系を1時間保温することにより重合反応を完結させた。次いで、イオン交換水80部を加えることにより、固形分濃度が20.2重量%、粘度が6000mPa・s重量平均分子量が2,500,000の両性ポリアクリルアミド(以下、PAM−1という)の水溶液を得た。当該水溶液は、紙力増強剤(2−1)として用いる。また、PAM−1の組成とその使用割合、物性を表1に示す。なお、PAM−1の重量平均分子量は、以下の条件で求めた(以下、同様にして求める)。
Production Example 2 (Preparation of paper strength enhancer)
350 parts of ion-exchanged water was charged into a reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and two dropping funnels. Then, in one dropping funnel, a monomer solution adjusted to pH 3 (179 parts of acrylamide, 11 parts of 62.5% sulfuric acid, 12.8 parts of 80% aqueous acrylic acid solution, 2.3 parts of sodium methallylsulfonate) 22.4 parts of dimethylaminoethyl methacrylate, 2.8 parts of dimethylacrylamide and 340 parts of ion-exchanged water), and other dropping funnels were used as a polymerization initiator solution (0.3 parts of ammonium persulfate, ion exchange). 100 parts of water) was charged. Next, after removing oxygen in the reaction system through a nitrogen gas introduction tube, the reaction system is heated to 90 ° C., and the monomer solution and the polymerization initiator solution are dropped into the reaction system from the dropping funnels over about 3 hours. did. After completion of the dropping, a polymerization initiator solution (0.45 parts of ammonium persulfate, 10 parts of ion-exchanged water) was further charged from the other dropping funnel, and the polymerization reaction was completed by keeping the reaction system for 1 hour. Next, an aqueous solution of amphoteric polyacrylamide (hereinafter referred to as PAM-1) having a solid content concentration of 20.2% by weight and a viscosity of 6000 mPa · s weight average molecular weight of 2,500,000 by adding 80 parts of ion-exchanged water. Got. The aqueous solution is used as a paper strength enhancer (2-1). In addition, Table 1 shows the composition of PAM-1, its use ratio, and physical properties. The weight average molecular weight of PAM-1 was determined under the following conditions (hereinafter determined in the same manner).
GPC本体:東ソー(株)製
カラム:東ソー(株)製ガードカラムPWXL1本およびGMPWXL2本(温度40℃)
溶離液:0.5mol/l酢酸緩衝液(0.5mol/l酢酸(和光純薬工業(株)製)+0.5mol/l酢酸ナトリウム(キシタ゛化学(株)製)水溶液、pH約4.2)
流速:0.8ml/分
検出器:ビスコテック社製TDA MODEL301(濃度検出器および90°光散乱検出器および粘度検出器(温度40℃))(GC−RALLS法)
GPC body: Tosoh Co., Ltd. column: Tosoh Co., Ltd. guard column PWXL 1 and GMPWXL 2 (temperature 40 ° C.)
Eluent: 0.5 mol / l acetic acid buffer (0.5 mol / l acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) + 0.5 mol / l sodium acetate (manufactured by Kishida Chemical Co., Ltd.), pH approximately 4.2 )
Flow rate: 0.8 ml / min Detector: TDA MODEL301 (concentration detector and 90 ° light scattering detector and viscosity detector (temperature: 40 ° C.)) manufactured by Viscotech (GC-RALLS method)
製造例3〜4(紙力増強剤の調製)
製造例2において、両性ポリアクリルアミドの組成とその使用割合を表1のように変えたほかは同様にして、PAM−2およびPAM−3の各水溶液を得た。それぞれ紙力増強剤(2−2)、紙力増強剤(2−3)として用いる。また、PAM−1とPAM−3の各物性を表1に示す。
Production Examples 3 to 4 (Preparation of paper strength enhancer)
In Production Example 2, aqueous solutions of PAM-2 and PAM-3 were obtained in the same manner except that the composition of amphoteric polyacrylamide and the use ratio thereof were changed as shown in Table 1. They are used as a paper strength enhancer (2-2) and a paper strength enhancer (2-3), respectively. Table 1 shows the physical properties of PAM-1 and PAM-3.
製造例5(紙力増強剤の調製)
製造例2と同様の反応装置に、アクリルアミド135.2部、62.5%硫酸4.0部、ジメチルアミノエチルメタクリレ−ト8.1部、60%ジメチルアミノエチルメタクリレ−トの4級化物水溶液24.4部、イタコン酸6.7部、メタアリルスルホン酸ナトリウム0.8部、メチレンビスアクリルアミド0.06部及びイオン交換水660部を仕込み、窒素ガス導入管を通じて反応系の酸素を除去した。次いで、反応系を55℃に昇温して、攪拌下に重合開始剤溶液(過硫酸アンモニウム0.23部、イオン交換水10部)を加えた。次いで、反応系を90℃まで昇温した後30分保温し、更に重合開始剤溶液(過硫酸アンモニウム0.34部、イオン交換水10部)を加えて1時間保温することにより重合反応を完結させた。次いで、イオン交換水260部を加えることにより、両性ポリアクリルアミド(以下、PAM−4という)の水溶液を得た。当該水溶液は、紙力増強剤(2−4)として用いる。また、PAM−4の組成とその使用割合、物性を表1に示す。
Production Example 5 (Preparation of paper strength enhancer)
In a reaction apparatus similar to Production Example 2, quaternary acrylamide 135.2 parts, 62.5% sulfuric acid 4.0 parts, dimethylaminoethyl methacrylate 8.1 parts, 60% dimethylaminoethyl methacrylate quaternary. 24.4 parts of an aqueous solution of chemicals, 6.7 parts of itaconic acid, 0.8 part of sodium methallyl sulfonate, 0.06 part of methylenebisacrylamide and 660 parts of ion-exchanged water are charged, and oxygen in the reaction system is introduced through a nitrogen gas inlet tube. Removed. Next, the temperature of the reaction system was raised to 55 ° C., and a polymerization initiator solution (ammonium persulfate 0.23 parts, ion-exchanged water 10 parts) was added with stirring. Next, the temperature of the reaction system was raised to 90 ° C., and then kept for 30 minutes, and a polymerization initiator solution (ammonium persulfate 0.34 parts, ion-exchanged water 10 parts) was further added and kept for 1 hour to complete the polymerization reaction. It was. Subsequently, 260 parts of ion-exchanged water was added to obtain an aqueous solution of amphoteric polyacrylamide (hereinafter referred to as PAM-4). The aqueous solution is used as a paper strength enhancer (2-4). In addition, Table 1 shows the composition of PAM-4, its use ratio, and physical properties.
製造例6(紙力増強剤の調製)
製造例2と同様の反応装置に、アクリルアミド75.1部、62.5%硫酸4.5部、ジメチルアミノエチルメタクリレ−ト9.1部、イタコン酸1.9部、80%アクリル酸水溶液2.6部、トリアリルイソシアヌレート0.04部及びイオン交換水470部を仕込み、窒素ガス導入管を通じて反応系の酸素を除去した。次いで、反応系を55℃に昇温して、攪拌下に重合開始剤溶液(過硫酸アンモニウム0.12部、イオン交換水10部)を加えた。次いで、反応系を90℃まで昇温した後30分保温し、更に重合開始剤溶液(過硫酸アンモニウム0.18部、イオン交換水10部)を加えて1時間保温することにより重合反応を完結させた。次いで、イオン交換水530部を加えることにより、両性ポリアクリルアミド(以下、PAM−5という)の水溶液を得た。当該水溶液は、紙力増強剤(2−5)として用いる。また、PAM−5の組成とその使用割合、物性を表1に示す。
Production Example 6 (Preparation of paper strength enhancer)
In the same reactor as in Production Example 2, acrylamide 75.1 parts, 62.5% sulfuric acid 4.5 parts, dimethylaminoethyl methacrylate 9.1 parts, itaconic acid 1.9 parts, 80% aqueous acrylic acid solution 2.6 parts, 0.04 part of triallyl isocyanurate and 470 parts of ion-exchanged water were charged, and oxygen in the reaction system was removed through a nitrogen gas introduction tube. Next, the temperature of the reaction system was raised to 55 ° C., and a polymerization initiator solution (ammonium persulfate 0.12 parts, ion-exchanged water 10 parts) was added with stirring. Next, the temperature of the reaction system was raised to 90 ° C., and then kept for 30 minutes. Further, a polymerization initiator solution (0.18 part of ammonium persulfate, 10 parts of ion-exchanged water) was added and kept for 1 hour to complete the polymerization reaction. It was. Subsequently, 530 parts of ion-exchanged water was added to obtain an aqueous solution of amphoteric polyacrylamide (hereinafter referred to as PAM-5). The aqueous solution is used as a paper strength enhancer (2-5). In addition, Table 1 shows the composition of PAM-5, its use ratio, and physical properties.
(濁度単位(NTU)の測定)
製造例2で得た水溶液に水を加えて固形分濃度1.0重量%の溶液とし、これの濁度単位を、ANALITE濁度計「NEP-160 Portable Turbidity Meter」(MacVan社製)を用いて測定した。なお、測定値は、標準物質(ホルマジン標準液(400NTU)、和光純薬工業(株)製)に対する相対的な値である。
また、製造例3〜6で得た水溶液についても同様にして濁度単位を測定した。結果を表1に示す。
(Measurement of turbidity unit (NTU))
Water is added to the aqueous solution obtained in Production Example 2 to obtain a solution having a solid concentration of 1.0% by weight, and the turbidity unit thereof is an ANALITE turbidity meter “NEP-160 Portable Turbidity Meter” (manufactured by MacVan). Measured. The measured value is a relative value with respect to a standard substance (formazine standard solution (400 NTU), manufactured by Wako Pure Chemical Industries, Ltd.).
Moreover, the turbidity unit was similarly measured about the aqueous solution obtained by manufacture example 3-6. The results are shown in Table 1.
表1中、
AA:アクリル酸
SMAS:メタアリルスルホン酸ナトリウム
IA:イタコン酸
DM:ジメチルアミノエチルメタクリレート
DML:ジメチルアミノエチルメタクリレートのベンジルクロライド4級化物
AM:アクリルアミド
DMAA:N,N−ジメチルアクリルアミド
MBAA:メチレンビスアクリルアミド
TAIC:トリアリルイソシアヌレート
In Table 1,
AA: acrylic acid SMAS: sodium methallylsulfonate IA: itaconic acid DM: dimethylaminoethyl methacrylate DML: benzyl chloride quaternary product of dimethylaminoethyl methacrylate AM: acrylamide DMAA: N, N-dimethylacrylamide MBAA: methylenebisacrylamide TAIC : Triallyl isocyanurate
(フリーネス値の測定)
フリーネス値の測定試験条件は、以下の通りである。
・試験器具:熊谷理機工業(株)販売「カナディアンフリーネステスター No.2580-A」
・試験回数:2回
・紙料水温:20.0±0.5℃
・紙料におけるパルプ濃度:約0.3%
・紙料におけるパルプの種類:上質古紙の再生パルプとナイアガラビーターで叩解したL−BKPを重量比で7:3の割合で含むパルプ。
・紙料におけるパルプの種類の叩解度:フリーネス値が420ml
・実測値の補正:実測値をJIS P 8121の補正表により補正し、補正値を前記試験回数で割った値を測定値とする。
(Measurement of freeness value)
The test conditions for measuring the freeness value are as follows.
・ Testing equipment: “Canadian Freeness Tester No.2580-A” sold by Kumagai Rikyu Kogyo Co., Ltd.
・ Number of tests: 2 times ・ Paper water temperature: 20.0 ± 0.5 ° C.
・ Pulp concentration in paper: About 0.3%
Pulp type in paper stock: Pulp containing recycled pulp of high-quality waste paper and L-BKP beaten with Niagara Beater in a ratio of 7: 3 by weight.
・ Pulpability of pulp type in paper stock: Freeness value is 420ml
-Correction of actual measurement value: The actual measurement value is corrected according to the correction table of JIS P 8121, and the value obtained by dividing the correction value by the number of tests is taken as the measurement value.
実施例1
前記パルプと水とを混合し、パルプ濃度が2%含の紙料を調製した。次いで、当該紙料に、嵩高剤(1−1)(対パルプ0.8重量%)、紙力増強剤(2−1)(対パルプ0.3重量%)、硫酸アルミニウム(対パルプ0.7重量%)、軽質炭酸カルシウム(対パルプ20重量%)を添加し、攪拌下に良く分散させて、試験試料1を調製した。次いで、当該試験紙料1についてフリーネス値を測定した。結果を表2に示す。
Example 1
The pulp and water were mixed to prepare a paper stock containing a pulp concentration of 2%. Subsequently, the bulking agent (1-1) (0.8% by weight with respect to pulp), the paper strength enhancer (2-1) (0.3% by weight with respect to pulp), and aluminum sulfate (with respect to pulp 0.3%) were added to the stock. 7 wt%) and light calcium carbonate (20 wt% of pulp) were added and dispersed well with stirring to prepare Test Sample 1. Next, the freeness value of the test paper stock 1 was measured. The results are shown in Table 2.
次に、前記試験試料1から、80g/m2の手抄き紙(シート)を作成できる量を採取し、これを1重量%となるまで水で希釈した。次いで、当該希釈液を丸型抄紙機(タッピ・スタンダード・シートマシン)にて抄紙し、湿潤シートを得た。そして、当該湿潤シートを自動プレス機(343kPa)で2分間脱水し、その後回転ドライヤー(105℃、1分間)で乾燥させ、紙(ア)を得た。 Next, an amount capable of producing a hand-made paper (sheet) of 80 g / m 2 was collected from the test sample 1 and diluted with water to 1 wt%. Next, the diluted solution was subjected to paper making with a round paper machine (Tappi Standard Sheet Machine) to obtain a wet sheet. Then, the wet sheet was dehydrated with an automatic press machine (343 kPa) for 2 minutes and then dried with a rotary dryer (105 ° C., 1 minute) to obtain paper (A).
実施例2
前記実施例1において、紙力増強剤(2−1)に換えて紙力増強剤(2−2)を用いたほかは同様にして試験紙料2を調製し、同様にフリーネス値を測定した。結果を表2に示す。
Example 2
In Example 1, except that the paper strength enhancer (2-2) was used instead of the paper strength enhancer (2-1), the test paper stock 2 was prepared in the same manner, and the freeness value was measured in the same manner. . The results are shown in Table 2.
実施例3
前記実施例1において、紙力増強剤(2−1)に換えて紙力増強剤(2−3)を用いたほかは同様にして試験紙料3を調製し、同様にフリーネス値を測定した。結果を表2に示す。
Example 3
In Example 1, except that the paper strength enhancer (2-3) was used instead of the paper strength enhancer (2-1), the test paper stock 3 was prepared in the same manner, and the freeness value was measured in the same manner. . The results are shown in Table 2.
比較例1
前記実施例1において、紙力増強剤(2−1)に換えて紙力増強剤(2−4)を用いたほかは同様にして試験紙料4を調製し、同様にフリーネス値を測定した。結果を表2に示す。
Comparative Example 1
In Example 1, except that the paper strength enhancer (2-4) was used instead of the paper strength enhancer (2-1), the test paper stock 4 was prepared in the same manner, and the freeness value was measured in the same manner. . The results are shown in Table 2.
比較例2
前記実施例1において、紙力増強剤(2−1)に換えて紙力増強剤(2−5)を用いたほかは同様にして試験紙料5を調製し、同様にフリーネス値を測定した。結果を表2に示す。
Comparative Example 2
In Example 1, except that the paper strength enhancer (2-5) was used instead of the paper strength enhancer (2-1), the test paper stock 5 was prepared in the same manner, and the freeness value was measured in the same manner. . The results are shown in Table 2.
比較例3
前記パルプと水とを混合し、パルプ濃度が2%含のパルプスラリーを調製した。次いで、当該パルプスラリーから、80g/m2の手抄き紙(シート)を作成できる量を採取し、これに、紙力増強剤(2−1)(対パルプ0.3重量%)、硫酸アルミニウム(対パルプ0.7重量%)、軽質炭酸カルシウム(対パルプ20重量%)を添加し、攪拌下に良く分散させて試験試料4を調製した。次いで、当該試験紙料6についてフリーネス値を測定した。結果を表2に示す。
Comparative Example 3
The pulp and water were mixed to prepare a pulp slurry containing 2% pulp concentration. Next, an amount capable of producing a hand-made paper (sheet) of 80 g / m 2 was collected from the pulp slurry, and a paper strength enhancer (2-1) (0.3% by weight of pulp), sulfuric acid was added thereto. Test sample 4 was prepared by adding aluminum (0.7% by weight to pulp) and light calcium carbonate (20% by weight to pulp) and dispersing well with stirring. Next, the freeness value of the test paper stock 6 was measured. The results are shown in Table 2.
比較例4
前記比較例3において、紙力増強剤(2−1)に換えて紙力増強剤(2−2)を用いたほかは同様にして試験紙料7を調製し、同様にフリーネス値を測定した。結果を表2に示す。
Comparative Example 4
In Comparative Example 3, a test paper stock 7 was prepared in the same manner except that the paper strength enhancer (2-2) was used instead of the paper strength enhancer (2-1), and the freeness value was measured in the same manner. . The results are shown in Table 2.
比較例5
前記比較例3において、紙力増強剤(2−1)に換えて紙力増強剤(2−3)を用いたほかは同様にして試験紙料8を調製し、同様にフリーネス値を測定した。結果を表2に示す。
Comparative Example 5
In Comparative Example 3, a test paper 8 was prepared in the same manner except that the paper strength enhancer (2-3) was used instead of the paper strength enhancer (2-1), and the freeness value was measured in the same manner. . The results are shown in Table 2.
比較例6
前記比較例3において、紙力増強剤(2−1)に換えて紙力増強剤(2−4)を用いたほかは同様にして試験紙料9を調製し、同様にフリーネス値を測定した。結果を表2に示す。
Comparative Example 6
In Comparative Example 3, a test paper stock 9 was prepared in the same manner except that the paper strength enhancer (2-4) was used instead of the paper strength enhancer (2-1), and the freeness value was measured in the same manner. . The results are shown in Table 2.
比較例7
前記比較例3において、紙力増強剤(2−1)に換えて紙力増強剤(2−5)を用いたほかは同様にして試験紙料10を調製し、同様にフリーネス値を測定した。結果を表2に示す。
Comparative Example 7
In Comparative Example 3, the test stock 10 was prepared in the same manner except that the paper strength enhancer (2-5) was used instead of the paper strength enhancer (2-1), and the freeness value was measured in the same manner. . The results are shown in Table 2.
比較例8
前記比較例3において、紙力増強剤(2−1)(対パルプ0.3重量%)に換えて嵩高剤(1−1)(対パルプ0.8重量%)を用いたほかは同様にしてブランク紙料1を調製し、同様にフリーネス値を測定した。結果を表2に示す。
Comparative Example 8
In Comparative Example 3, the bulking agent (1-1) (0.8% by weight of pulp) was used instead of the paper strength enhancer (2-1) (0.3% by weight of pulp). A blank stock 1 was prepared and the freeness value was measured in the same manner. The results are shown in Table 2.
参照例
前記パルプと水とを混合し、パルプ濃度が2%含のパルプスラリーを調製した。次いで、当該パルプスラリーから、80g/m2の手抄き紙(シート)を作成できる量を採取し、これに、硫酸アルミニウム(対パルプ0.7重量%)、軽質炭酸カルシウム(対パルプ20重量%)を添加し、攪拌下に良く分散させて紙料1を調製した。次いで、当該紙料1についてフリーネス値を測定した。結果を表2に示す。
Reference Example The pulp and water were mixed to prepare a pulp slurry containing a pulp concentration of 2%. Next, an amount capable of producing a hand-made paper (sheet) of 80 g / m 2 was collected from the pulp slurry, and aluminum sulfate (0.7% by weight with respect to pulp) and light calcium carbonate (with respect to 20% by weight of pulp) were collected. %) Was added and dispersed well with stirring to prepare stock 1. Next, the freeness value of the stock 1 was measured. The results are shown in Table 2.
(フリーネス差の計算)
なお、表2における実施例1についてのフリーネス差は、〔実施例1における試験試料1のフリーネス値(397ml)〕と、〔比較例8におけるブランク紙料1のフリーネス値(376ml)〕の差として求めた値(21ml)である。
実施例2、3および比較例1、2のそれぞれについてのフリーネス差も同様にして求めた値である。
(Calculation of freeness difference)
The difference in freeness for Example 1 in Table 2 is the difference between [Freeness value of test sample 1 in Example 1 (397 ml)] and [Freeness value of blank stock 1 in Comparative Example 8 (376 ml)]. This is the calculated value (21 ml).
The freeness difference for each of Examples 2 and 3 and Comparative Examples 1 and 2 is a value obtained in the same manner.
また、表2における、比較例3についてのフリーネス差は、〔比較例3における試験紙料試験紙料6のフリーネス値(482ml)〕と、〔参照例における紙料1のフリーネス値(387ml)〕の差として求めた値(17ml)である。
比較例4〜7のそれぞれについてのフリーネス差も同様にして求めた値である。
In Table 2, the difference in freeness for Comparative Example 3 is [freeness value of test paper 6 in Comparative Example 3 (482 ml)] and [freeness value of paper 1 in Reference Example (387 ml)]. (17 ml) obtained as the difference between
The difference in freeness for each of Comparative Examples 4 to 7 is a value obtained in the same manner.
(嵩高紙の作成)
前記実施例1における試験試料1から、80g/m2の手抄き紙(シート)を作成できる量を採取し、これを1重量%となるまで水で希釈した。次いで、当該希釈液を丸型抄紙機(タッピ・スタンダード・シートマシン)にて抄紙し、湿潤シートを得た。そして、当該湿潤シートを自動プレス機(343kPa)で2分間脱水し、その後回転ドライヤー(105℃、1分間)で乾燥させ、紙(ア)を得た。
(Creation of bulky paper)
An amount capable of producing a hand-made paper (sheet) of 80 g / m 2 was collected from the test sample 1 in Example 1, and diluted with water to 1% by weight. Next, the diluted solution was subjected to paper making with a round paper machine (Tappi Standard Sheet Machine) to obtain a wet sheet. Then, the wet sheet was dehydrated with an automatic press machine (343 kPa) for 2 minutes and then dried with a rotary dryer (105 ° C., 1 minute) to obtain paper (A).
次いで、当該紙(ア)を温度23℃湿度50%の恒湿室で24時間調湿し、試験用シートとした。その後、以下の項目に基づき、該試験用シートを評価した。 Next, the paper (A) was conditioned for 24 hours in a constant humidity chamber at a temperature of 23 ° C. and a humidity of 50% to obtain a test sheet. Thereafter, the test sheet was evaluated based on the following items.
(1)密度
JIS P 8118(紙及び板紙−厚さ及び密度の試験方法)に準じ、各試験用シートの密度を測定した。結果を表2に示す。
(2)内部強度
JAPAN TAPPI紙パルプ試験法No.54-93の試験方法に準じ、各試験用シートの内部強度を測定した。結果を表2に示す。
(1) Density
The density of each test sheet was measured in accordance with JIS P 8118 (paper and paperboard-thickness and density test method). The results are shown in Table 2.
(2) Internal strength
The internal strength of each test sheet was measured according to the test method of JAPAN TAPPI paper pulp test method No.54-93. The results are shown in Table 2.
前記実施例2、3および比較例1〜8、ならびに参照例についても、各紙料について前記同様にして、紙(イ)〜(シ)を作成した。そして、各紙を前記同様に試験用シートとし、前記同様に評価した。結果を表2に示す。 For Examples 2 and 3 and Comparative Examples 1 to 8 and Reference Example, papers (i) to (shi) were prepared in the same manner as described above for each paper stock. Each paper was used as a test sheet in the same manner as described above, and evaluated in the same manner as described above. The results are shown in Table 2.
まず、比較例8と参照例との対比により、嵩高剤(1−1)を用いることで紙が低密度化されている(嵩高効果が得られる)が、紙の内部強度も小さくなる(紙力効果が失われる)ことがわかる。
また、実施例1〜3と比較例8との対比により、嵩高剤(1−1)とともに、フリーネス差が50ml以下となる紙力増強剤((2−1)〜(2−3))とを用いることで、紙の密度をほぼ維持したまま、紙の内部強度を向上できることがわかる。
一方、実施例1〜3と比較例1〜2との対比より、嵩高剤(1−1)と、フリーネス差が50mlより大きくなる紙力増強剤((2−4)〜(2−5))とを併用した場合には、紙の密度を維持することができず、また、紙の内部強度も小さくなることがわかる。
なお、実施例1〜3および比較例1〜2と、比較例3〜7との対比により、嵩高剤(1−1)を用いない場合には紙を低密度化できないことがわかる。
First, by comparing the comparative example 8 with the reference example, the paper is reduced in density by using the bulking agent (1-1) (a bulking effect is obtained), but the internal strength of the paper is also reduced (paper) It can be seen that the force effect is lost.
Moreover, by contrast with Examples 1-3 and the comparative example 8, paper strength enhancer ((2-1)-(2-3)) from which a freeness difference will be 50 ml or less with a bulking agent (1-1) and. It can be seen that the internal strength of the paper can be improved while maintaining the paper density substantially.
On the other hand, as compared with Examples 1-3 and Comparative Examples 1-2, the bulking agent (1-1) and the paper strength enhancer ((2-4) to (2-5) in which the difference in freeness is greater than 50 ml). ) In combination, the density of the paper cannot be maintained, and the internal strength of the paper is also reduced.
In addition, by contrast with Examples 1-3 and Comparative Examples 1-2, and Comparative Examples 3-7, when a bulking agent (1-1) is not used, it turns out that a paper cannot be reduced in density.
Claims (7)
前記第3級アミド基含有脂肪酸変性アミド樹脂(A)における(第3級アミド基含有脂肪酸変性アミド樹脂(A)が有する第3級アミド基の個数)/(第2級アミノ基含有ポリアミン化合物(a1)が有する第2級アミノ基の個数)の値が0.2〜0.7であり、
かつ、前記両性ポリアクリルアミド(B)が(メタ)アクリルアミド(b1)57〜99.78モル%、カチオン性ビニルモノマー(b2)0.1〜15モル%、アニオン性ビニルモノマー(b3)0.1〜15モル%、N−置換(メタ)アクリルアミド(b4)0.01〜2モル%、(メタ)アリル基含有ビニルモノマー(b5)0.01〜10モル%を共重合させてなるものであり、
かつ、当該紙力増強剤(2)が、〔紙力増強剤(2)を含有する紙料(3)のカナダ標準ろ水度(ml)〕と〔紙力増強剤(2)を含有しない紙料(3)のカナダ標準ろ水度(ml)〕との差として50ml以下の値を与えるものであることを特徴とする、嵩高紙の製造方法。 A bulking agent comprising a tertiary amide group-containing fatty acid-modified amide resin (A) having a secondary amino group-containing polyamine compound (a1), a monocarboxylic acid compound (a2) and a glycidyl group-containing compound (a3) as reaction components ( 1) and a paper strength enhancer (2) containing amphoteric polyacrylamide (B), after adding to paper stock (3), in the method for producing bulk paper,
In the tertiary amide group-containing fatty acid-modified amide resin (A) (number of tertiary amide groups of the tertiary amide group-containing fatty acid-modified amide resin (A)) / (secondary amino group-containing polyamine compound ( the number of secondary amino groups a1) has is 0.2 to 0.7,
And said amphoteric polyacrylamide (B) is (meth) acrylamide (b1) 57-99.78 mol%, cationic vinyl monomer (b2) 0.1-15 mol%, anionic vinyl monomer (b3) 0.1 ~ 15 mol%, N-substituted (meth) acrylamide (b4) 0.01-2 mol%, (meth) allyl group-containing vinyl monomer (b5) 0.01-10 mol% are copolymerized. ,
And, the paper strength enhancer (2) does not contain [the Canadian standard freeness (ml) of the paper stock (3) containing the paper strength enhancer (2)] and [the paper strength enhancer (2). A method for producing a bulky paper, characterized in that a value of 50 ml or less is given as a difference from the Canadian standard freeness (ml) of the stock (3).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007014030A JP4957265B2 (en) | 2007-01-24 | 2007-01-24 | Bulky paper manufacturing method and bulky paper |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007014030A JP4957265B2 (en) | 2007-01-24 | 2007-01-24 | Bulky paper manufacturing method and bulky paper |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2008179910A JP2008179910A (en) | 2008-08-07 |
JP4957265B2 true JP4957265B2 (en) | 2012-06-20 |
Family
ID=39724016
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2007014030A Expired - Fee Related JP4957265B2 (en) | 2007-01-24 | 2007-01-24 | Bulky paper manufacturing method and bulky paper |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4957265B2 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5240500B2 (en) * | 2007-03-12 | 2013-07-17 | 荒川化学工業株式会社 | Bulky paper manufacturing method and bulky paper |
JP6354417B2 (en) * | 2013-08-08 | 2018-07-11 | 荒川化学工業株式会社 | Paper strength enhancer, paper obtained thereby, and method for producing paper |
JP6268519B2 (en) * | 2013-12-12 | 2018-01-31 | 荒川化学工業株式会社 | Surface paper strength enhancer for papermaking and surface coated paper |
CA2937050C (en) | 2014-12-08 | 2023-01-17 | Harima Chemicals, Incorporated | Acrylamide-based polymer, paper strength agent, and paper |
JP6943047B2 (en) * | 2016-07-12 | 2021-09-29 | 荒川化学工業株式会社 | A method for producing a paper strength enhancer and a method for producing paper |
EP3647492B1 (en) | 2017-06-28 | 2022-10-19 | Harima Chemicals, Incorporated | Method for producing (meth)acrylamide-based polymer papermaking additive and (meth)acrylamide-based polymer papermaking additive |
JP7036073B2 (en) * | 2018-03-28 | 2022-03-15 | 荒川化学工業株式会社 | Surface paper strength enhancer, coating liquid, paper manufacturing method |
CN110407974B (en) * | 2019-08-15 | 2021-09-21 | 浙江传化华洋化工有限公司 | Preparation method of crosslinkable amphoteric polyacrylamide polymer |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3575018B2 (en) * | 1996-07-24 | 2004-10-06 | 荒川化学工業株式会社 | Papermaking additives |
JP3944823B2 (en) * | 2001-11-06 | 2007-07-18 | 星光Pmc株式会社 | Paper additive and paper containing the same |
-
2007
- 2007-01-24 JP JP2007014030A patent/JP4957265B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP2008179910A (en) | 2008-08-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4957265B2 (en) | Bulky paper manufacturing method and bulky paper | |
JP6354417B2 (en) | Paper strength enhancer, paper obtained thereby, and method for producing paper | |
KR20160052734A (en) | Paper-making aid composition and process for increasing ash retention of finished paper | |
CN107604755B (en) | Paper strength agent, method for producing paper strength agent, and method for producing paper and paper | |
KR20170086642A (en) | Paper-making aid composition and process for increasing tensile strength of paper | |
JP6525397B2 (en) | Rosin-based emulsion sizing agent and paper obtained using the sizing agent | |
JP6897227B2 (en) | Paper strength enhancer, paper manufacturing method, and paper | |
JP5240500B2 (en) | Bulky paper manufacturing method and bulky paper | |
JP2017040021A (en) | Rosin-based emulsion sizing agent and paper | |
WO2014123087A1 (en) | Method for manufacturing composite filler for manufacturing paper, and method for manufacturing filler-containing paper | |
US9303359B2 (en) | Method for manufacturing paper using a cationic polymer obtained by hofmann degradation | |
CN112601860A (en) | Additive for papermaking, paper and method for producing paper | |
TWI791577B (en) | Hydrophobic vinylamine-containing polymer compositions and their use in papermaking applications | |
JP4868277B2 (en) | Paperboard manufacturing method | |
JP2011168948A (en) | Water-soluble polymer dispersion, paper strengthening agent, freeness enhancement agent for papermaking, and yield enhancement agent for papermaking | |
JP5467485B2 (en) | Bulking agent for papermaking | |
JP5273352B2 (en) | Bulky paper manufacturing method and bulky paper | |
US20170362776A1 (en) | Production of paper and board | |
JP2020147888A (en) | Dispersion for paper manufacturing agent, paper strengthening agent including the dispersion for paper manufacturing agent, freeness improver, and yield improver | |
WO2014115192A1 (en) | Method for manufacturing paperboard | |
JP6057091B2 (en) | Emulsion sizing agent for papermaking | |
US20170233950A1 (en) | Solidifying composition for paper and cardboard | |
EP2971349A1 (en) | Method of using aldehyde-functionalized polymers to increase papermachine performance and enhance sizing | |
JP6764136B2 (en) | Paper manufacturing method | |
JP4784857B2 (en) | Paper manufacturing method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100107 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20111028 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111104 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120104 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120221 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120305 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150330 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 4957265 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |