JP2015040357A - Size fixing method - Google Patents
Size fixing method Download PDFInfo
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- JP2015040357A JP2015040357A JP2013171812A JP2013171812A JP2015040357A JP 2015040357 A JP2015040357 A JP 2015040357A JP 2013171812 A JP2013171812 A JP 2013171812A JP 2013171812 A JP2013171812 A JP 2013171812A JP 2015040357 A JP2015040357 A JP 2015040357A
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- raw material
- organic coagulant
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- papermaking
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- 238000000034 method Methods 0.000 title claims abstract description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 52
- 239000000701 coagulant Substances 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 40
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 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 claims abstract description 25
- 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 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 23
- 238000003860 storage Methods 0.000 claims abstract description 9
- 238000004513 sizing Methods 0.000 claims description 51
- 230000000694 effects Effects 0.000 abstract description 14
- 238000007792 addition Methods 0.000 description 38
- 239000000123 paper Substances 0.000 description 34
- 241000721671 Ludwigia Species 0.000 description 19
- 239000011295 pitch Substances 0.000 description 18
- 239000000178 monomer Substances 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 15
- 210000000038 chest Anatomy 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 12
- 125000002091 cationic group Chemical group 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229920000768 polyamine Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- -1 alkenyl succinic anhydride Chemical compound 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000011436 cob Substances 0.000 description 4
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical class C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011087 paperboard Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- 238000011143 downstream manufacturing Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical group C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-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
- 230000003287 optical effect Effects 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- ZVUAMUKZHFTJGR-UHFFFAOYSA-N 1-piperazin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCNCC1 ZVUAMUKZHFTJGR-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- FVPMLCUKLBYBSV-UHFFFAOYSA-M 2-hydroxypropyl-dimethyl-(prop-2-enoyloxymethyl)azanium;chloride Chemical compound [Cl-].CC(O)C[N+](C)(C)COC(=O)C=C FVPMLCUKLBYBSV-UHFFFAOYSA-M 0.000 description 1
- RIAVQNCBHNMYFJ-UHFFFAOYSA-M 2-hydroxypropyl-dimethyl-[phenyl(prop-2-enoyloxy)methyl]azanium;chloride Chemical compound [Cl-].CC(O)C[N+](C)(C)C(OC(=O)C=C)C1=CC=CC=C1 RIAVQNCBHNMYFJ-UHFFFAOYSA-M 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000012726 Water-in-Oil Emulsion Polymerization Methods 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001409 amidines Chemical group 0.000 description 1
- QBZPCMKUFMJWAN-UHFFFAOYSA-N benzyl-dimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C=CC(=O)NCCC[N+](C)(C)CC1=CC=CC=C1 QBZPCMKUFMJWAN-UHFFFAOYSA-N 0.000 description 1
- IUHDTQIYNQQIBP-UHFFFAOYSA-M benzyl-ethyl-dimethylazanium;chloride Chemical compound [Cl-].CC[N+](C)(C)CC1=CC=CC=C1 IUHDTQIYNQQIBP-UHFFFAOYSA-M 0.000 description 1
- 230000000740 bleeding effect Effects 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
Abstract
Description
本発明は、抄紙前の製紙工程において、有機系凝結剤を使用したサイズ定着方法に関するものであり、詳しくは、有機系凝結剤を特定の条件で特定の添加場所に添加するサイズ定着方法に関する。 The present invention relates to a size fixing method using an organic coagulant in a paper making process before paper making, and more particularly to a size fixing method in which an organic coagulant is added to a specific addition site under specific conditions.
製紙業界における紙の製造においては、中性抄造化に伴い抄造薬品もより適したものに移行している。水系のインクの滲みを防止、サイズ性を付与する目的で使用されるサイズ剤は、中性抄造においては、ロジン系サイズ剤の定着剤として使用されてきた硫酸バンドの添加率が減少、定着性が低下し高いサイズ効果が発現できない状況にあった。アルケニル無水コハク酸サイズ剤やアルキルケテンダイマーサイズ剤の様に、ロジン系サイズ剤は管理が煩雑ではなく、印刷適正に劣ることなく高いサイズ効果が得られるために中性抄造向けの中性ロジン系サイズ剤使用の要望が高くなっている。そこで、ロジン系サイズ剤の定着剤として従来、使用されてきた硫酸バンドの代用や併用として、カチオン性水溶性高分子の定着剤が種々考案されてきた（特許文献１〜３）。又、サイズ度を向上させるためにサイズ剤とサイズ定着剤の添加順序や方法が種々検討されている。例えば、特許文献４では、ジメチルジ（メタ）アリルアンモニウム塩の（共）重合体を添加するにあたり、ロジン系サイズ剤の添加に先立って添加し、剪断力を加えた後にロジン系サイズ剤を添加する方法、特許文献５では、カチオン性凝結剤を添加した後、硫酸バンド、サイズ剤の順番で連続添加するか、硫酸バンドとサイズ剤を同時に添加する方法等が提案されている。しかし、未だ中性ロジン系サイズ剤の満足な定着効果が得られていない場合が多く、サイズ度の向上を図るためには、サイズ剤の添加率を増加させる必要があり、未定着となったサイズ剤は製紙欠陥や汚れの発生等のピッチトラブルの要因となるため、更なる高いサイズ定着方法が求められおり、本発明の課題である。 In the manufacture of paper in the paper industry, papermaking chemicals are shifting to more suitable ones with the neutral papermaking. The sizing agent used for the purpose of preventing water-based ink bleeding and imparting sizing properties reduces the addition rate of the sulfuric acid band that has been used as a fixing agent for rosin sizing agents in neutral papermaking. As a result, the high size effect could not be realized. Like alkenyl succinic anhydride sizing agents and alkyl ketene dimer sizing agents, rosin sizing agents are not cumbersome to manage and neutral rosin for neutral papermaking because of high sizing effect without being inferior to printing There is a growing demand for sizing agents. Accordingly, various cationic water-soluble polymer fixing agents have been devised as substitutes or combinations of the sulfuric acid bands conventionally used as fixing agents for rosin sizing agents (Patent Documents 1 to 3). In order to improve the sizing degree, various addition orders and methods of the sizing agent and the size fixing agent have been studied. For example, in Patent Document 4, when adding the (co) polymer of dimethyldi (meth) allylammonium salt, it is added prior to the addition of the rosin sizing agent, and after adding the shearing force, the rosin sizing agent is added. In the method, Patent Document 5, a method is proposed in which a cationic coagulant is added, and then a sulfuric acid band and a sizing agent are continuously added in this order, or a sulfuric acid band and a sizing agent are added simultaneously. However, in many cases, the satisfactory fixing effect of the neutral rosin sizing agent has not yet been obtained, and in order to improve the sizing degree, it is necessary to increase the addition rate of the sizing agent, and it has not been fixed. Since the sizing agent causes pitch troubles such as papermaking defects and stains, a further high size fixing method is required, which is an object of the present invention.
本発明の課題は、製紙工程において有機系凝結剤を使用し、サイズ剤をパルプ繊維に定着させ優れたサイズ効果が得られ、安定な操業を図る方法を開発することである。 An object of the present invention is to develop a method of using an organic coagulant in a papermaking process, fixing a sizing agent to pulp fibers, obtaining an excellent size effect, and achieving stable operation.
上記課題を解決するため本発明者は、鋭意検討した結果、以下に述べる発明に達した。即ち、有機系凝結剤を特定の条件で特定の添加場所に添加するサイズ定着方法である。 In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, have reached the invention described below. That is, it is a size fixing method in which an organic coagulant is added to a specific addition place under specific conditions.
製紙工程において、パルプ乾燥固形分濃度が２．０質量％以上の製紙原料に硫酸バンドおよびロジン系サイズ剤を添加後、有機系凝結剤を添加することで、従来の添加方法に比べて優れたサイズ定着効果が得られると共にピッチ低減効果も得られ安定な操業が達成できる。 In the papermaking process, after adding a sulfuric acid band and a rosin sizing agent to a papermaking raw material having a pulp dry solid content concentration of 2.0% by mass or more, the organic coagulant is added, which is superior to conventional addition methods. A size fixing effect can be obtained and a pitch reduction effect can also be obtained, thereby achieving stable operation.
本発明の有機系凝結剤について説明する。本発明の有機系凝結剤として下記の数種が使用できる。（メタ）アクリル系カチオン性あるいは両性重合体を使用する。（メタ）アクリル系カチオン性あるいは両性重合体は、下記に挙げるカチオン性単量体の重合体、カチオン性単量体と非イオン性単量体との共重合体、あるいはカチオン性単量体とアニオン性単量体及び非イオン性単量体との共重合体である。カチオン性単量体としては、（メタ）アクリロイルオキシエチルトリメチルアンモニウム塩化物、（メタ）アクリロイルオキシ−２−ヒドロキシプロピルトリメチルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルトリメチルアンモニウム塩化物、（メタ）アクリロイルオキシエチルジメチルベンジルアンモニウム塩化物、（メタ）アクリロイルオキシ−２−ヒドロキシプロピルジメチルベンジルアンモニウム塩化物、（メタ）アクリロイルアミノプロピルジメチルベンジルアンモニウム塩化物等が挙げられる。これらのカチオン性単量体は１種を単独で用いることができ、２種以上を組み合わせて用いることもできる。 The organic coagulant of the present invention will be described. The following several kinds can be used as the organic coagulant of the present invention. A (meth) acrylic cationic or amphoteric polymer is used. The (meth) acrylic cationic or amphoteric polymer is a polymer of a cationic monomer listed below, a copolymer of a cationic monomer and a nonionic monomer, or a cationic monomer. It is a copolymer with an anionic monomer and a nonionic monomer. Cationic monomers include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxy-2-hydroxypropyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxy Examples thereof include ethyldimethylbenzylammonium chloride, (meth) acryloyloxy-2-hydroxypropyldimethylbenzylammonium chloride, (meth) acryloylaminopropyldimethylbenzylammonium chloride, and the like. These cationic monomers can be used individually by 1 type, and can also be used in combination of 2 or more type.
アニオン性単量体の例としては、（メタ）アクリル酸あるいはそのナトリウム塩等のアルカリ金属塩またはアンモニウム塩、マレイン酸やイタコン酸あるいはそのアルカリ金属塩、アクリルアミド−２−メチルプロパンスルホン酸等のアクリルアミドアルカンスルホン酸あるいはそのアルカリ金属塩またはアンモニウム塩等が挙げられる。これらのアニオン性単量体は１種を単独で用いることができ、２種以上を組み合わせて用いることもできる。 Examples of anionic monomers include alkali metal or ammonium salts such as (meth) acrylic acid or its sodium salt, maleic acid, itaconic acid or its alkali metal salt, and acrylamide such as acrylamide-2-methylpropanesulfonic acid. Examples thereof include alkanesulfonic acid or an alkali metal salt or ammonium salt thereof. These anionic monomers can be used individually by 1 type, and can also be used in combination of 2 or more type.
非イオン性単量体の例としては、（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、酢酸ビニル、アクリロニトリル、アクリル酸メチル、（メタ）アクリル酸２−ヒドロキシエチル、ジアセトンアクリルアミド、Ｎ−ビニルピロリドン、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミド、アクリロイルモルホリン、アクリロイルピペラジン等が挙げられる。これらのノニオン性単量体は１種を単独で用いることができ、２種以上を組み合わせて用いることもできる。 Examples of nonionic monomers include (meth) acrylamide, N, N-dimethylacrylamide, vinyl acetate, acrylonitrile, methyl acrylate, 2-hydroxyethyl (meth) acrylate, diacetone acrylamide, and N-vinyl pyrrolidone. N-vinylformamide, N-vinylacetamide, acryloylmorpholine, acryloylpiperazine, and the like. These nonionic monomers can be used individually by 1 type, and can also be used in combination of 2 or more type.
本発明の有機系凝結剤としては、ジアリルジメチルアンモニウム塩系重合体が使用できる。ジアリルジメチルアンモニウム塩系重合体は、ジアリルジメチルアンモニウム塩化物の重合体、ジアリルジメチルアンモニウム塩化物とアクリルアミドの共重合体である。 A diallyldimethylammonium salt polymer can be used as the organic coagulant of the present invention. The diallyldimethylammonium salt polymer is a diallyldimethylammonium chloride polymer or a diallyldimethylammonium chloride / acrylamide copolymer.
前記（メタ）アクリル系カチオン性あるいは両性重合体あるいはジアリルジメチルアンモニウム塩系重合体で使用されるカチオン性単量体のモル数は、１０〜１００モル％であり、アニオン性単量体のモル数は、０〜３０モル％であり、抄造条件や製紙原料に適正な組成を任意に適用する。又、重合体の重量平均分子量は１０万〜５００万の範囲である。（メタ）アクリル系カチオン性あるいは両性重合体あるいはジアリルジメチルアンモニウム塩系重合体は、抄造条件や製紙原料に適正な組成や分子量のものが得られるので本発明の有機系凝結剤として使用するには最も好ましい。 The number of moles of the cationic monomer used in the (meth) acrylic cationic or amphoteric polymer or diallyldimethylammonium salt-based polymer is 10 to 100% by mole, and the number of moles of the anionic monomer. Is 0 to 30 mol%, and an appropriate composition is arbitrarily applied to papermaking conditions and papermaking raw materials. The weight average molecular weight of the polymer is in the range of 100,000 to 5,000,000. The (meth) acrylic cationic or amphoteric polymer or diallyldimethylammonium salt-based polymer can be used as the organic coagulant of the present invention because it has a composition and molecular weight appropriate for papermaking conditions and papermaking raw materials. Most preferred.
本発明の有機系凝結剤として、重縮合系カチオン性物質を使用できる。重縮合系カチオン性物質は、アンモニア、脂肪族一価アミン及び脂肪族ポリアミンから選択された少なくとも一種以上の化合物とエピハロヒドリンとの重縮合物である。脂肪族一価アミンとしては、モノメチルアミン、モノエチルアミン、ジメチルアミン、ジエチルアミン、トリメチルアミン、トリエチルアミンなどである。脂肪族ポリアミンはエチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、ペンタエチレンヘキサミン、ヘキサメチレンジアミンなどである。これらアミン類のなかで特に好ましいものは、モノメチルアミン、ジメチルアミン、トリメチルアミン、エチレンジアミンあるいはペンタエチレンヘキサミンである。重縮合物は、これらアンモニア、脂肪族一価アミンあるいは脂肪族ポリアミンは、単独でも二種以上を混合しエピハロヒドリンと反応させたせた生成物でも良いし、また反応第一段階でまず脂肪族一価アミンとエピハロヒドリンとを反応し縮合物を生成させ、反応第ニ段階でアンモニアあるいは脂肪族ポリアミンと反応させ、分子量を増大した生成物でも良い。重縮合物の重量平均分子量としては、１万〜２００万である。また、本発明で使用する重縮合系カチオン性物質は、分子内に四級アンモニウム塩基を含有するほうがより好ましい。 A polycondensation cationic substance can be used as the organic coagulant of the present invention. The polycondensation cationic substance is a polycondensate of at least one compound selected from ammonia, an aliphatic monovalent amine and an aliphatic polyamine with an epihalohydrin. Examples of the aliphatic monovalent amine include monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, and triethylamine. Aliphatic polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, hexamethylenediamine and the like. Of these amines, monomethylamine, dimethylamine, trimethylamine, ethylenediamine or pentaethylenehexamine is particularly preferable. The polycondensate may be a product obtained by reacting these ammonia, aliphatic monovalent amine or aliphatic polyamine alone or in combination of two or more with an epihalohydrin. A product obtained by reacting an amine with epihalohydrin to produce a condensate and reacting with ammonia or an aliphatic polyamine in the second stage of the reaction to increase the molecular weight may be used. The weight average molecular weight of the polycondensate is 10,000 to 2,000,000. In addition, the polycondensation cationic substance used in the present invention more preferably contains a quaternary ammonium base in the molecule.
前記ポリアミン／エピハロヒドリン縮合物は、ポリアミン分子中アミノ基１モルに対し、エピハロヒドリン０．５モル〜３．０モルを反応し生成した縮合物であることが好ましい。このような比率で反応させることにより、一級、二級、三級あるいは四級アンモニウム塩基のうち複数の種類のアミノ基を有する縮合物を生成させることができる。また一級あるいは二級アミノ基による疎水性物質への吸着作用に効果があると推定される。従って縮合物中に活性水素が存在することが好ましく、エピハロヒドリンの比率を調節することによって原料アミンの水素原子を残しておくことが好ましい。従ってポリアミン分子中アミノ基１モルに対し、エピハロヒドリン０．５モル〜３．０モル、好ましくはポリアミン分子中アミノ基１モルに対し、エピハロヒドリン０．５モル〜１．５モルを反応し生成した縮合物であることが好ましい。 The polyamine / epihalohydrin condensate is preferably a condensate produced by reacting 0.5 mol to 3.0 mol of epihalohydrin with respect to 1 mol of amino group in the polyamine molecule. By reacting at such a ratio, a condensate having a plurality of types of amino groups among primary, secondary, tertiary or quaternary ammonium bases can be produced. In addition, it is presumed that the primary or secondary amino group is effective for the adsorption action to the hydrophobic substance. Therefore, it is preferable that active hydrogen is present in the condensate, and it is preferable to leave the hydrogen atom of the raw material amine by adjusting the ratio of epihalohydrin. Therefore, the condensation produced by reacting 0.5 mol to 1.5 mol of epihalohydrin with 1 mol of amino group in the polyamine molecule, preferably 0.5 mol to 1.5 mol of epihalohydrin with respect to 1 mol of amino group in the polyamine molecule. It is preferable that it is a thing.
本発明の有機系凝結剤として、ポリビニルアミンおよびポリビニルアミン繰り返し単位を有する水溶性共重合物を使用できる。ポリビニルアミン系水溶性高分子の製造法に関しては、特開平６−６５３２９号公報に開示されている。本発明で使用するポリビニルアミンおよびポリビニルアミン繰り返し単位を有する水溶性共重合物は、Ｎ−ビニルホルムアミド重合物あるいは共重合体を重合体中のホルミル基を変性することにより容易に得ることができる。すなわちＮ−ビニルホルムアミドと他の共重合可能な単量体とのモル比が、通常５０：５０〜１００：０の混合物、好ましくは、８０：２０〜１００：０の混合物をラジカル重合開始剤の存在下、重合することにより製造される。酸あるいはアルカリによりホルミル基を加水分解するため、共重合する単量体の一部も加水分解され、カルボキシル基が生成する場合が多い。そのためアクリロニトリルなどが共重合する場合便利である。その他アクリルアミド、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎプロピル、クリル酸−２−ヒドロキシエチル、メタクリル酸エチル、メタクリル酸ｎプロピル、メタクリル酸イソプロピル、メタクリル酸ｎブチル、メタクリル酸イソブチル、メタクリル酸−ｓｅｃブチル、メタクリル酸−２−ヒドロキシエチルなどが挙げられる。これら単量体は、アニオン性基が生成するので、共重合体中のモル比は、２０モル％未満であることが好ましい。 As the organic coagulant of the present invention, polyvinylamine and a water-soluble copolymer having a polyvinylamine repeating unit can be used. A method for producing a polyvinylamine water-soluble polymer is disclosed in JP-A-6-65329. The water-soluble copolymer having a polyvinylamine and a polyvinylamine repeating unit used in the present invention can be easily obtained by modifying a formyl group in the N-vinylformamide polymer or copolymer. That is, the molar ratio of N-vinylformamide to other copolymerizable monomer is usually a mixture of 50:50 to 100: 0, preferably 80:20 to 100: 0. It is produced by polymerizing in the presence. Since the formyl group is hydrolyzed with an acid or alkali, a part of the copolymerized monomer is also hydrolyzed to generate a carboxyl group in many cases. Therefore, it is convenient when acrylonitrile or the like is copolymerized. Other acrylamide, methyl acrylate, ethyl acrylate, npropyl acrylate, 2-hydroxyethyl acrylate, ethyl methacrylate, npropyl methacrylate, isopropyl methacrylate, nbutyl methacrylate, isobutyl methacrylate, methacrylic acid-sec Examples include butyl and 2-hydroxyethyl methacrylate. Since these monomers generate anionic groups, the molar ratio in the copolymer is preferably less than 20 mol%.
本発明の有機系凝結剤として、ポリビニルアミジンおよびビニルアミジン繰り返し単位を有する水溶性共重合物を使用できる。ポリビニルアミジンおよびビニルアミジン繰り返し単位を有する水溶性共重合物は、特開平５−１９２５１３号公報に記載されていて、以下のようなものである。Ｎ−ビニルホルムアミドとアクリロニトリル共重合体を酸により加水分解し、一級アミノ基を生成させ、そのご隣接するアクリロニトリルのシアノ基と反応することにより生成する。すなわちＮ−ビニルホルムアミドとアクリロニトリルのモル比が、通常５０：５０〜６０：４０の混合物をラジカル重合開始剤の存在下、重合する。重合体中のアミジン繰り返し単位は、２０〜１００モル％であり、好ましくは３０〜１００モル％であり、更に好ましくは５０〜１００モル％である。また分子量は重量平均分子量で１０万〜５００万であり、好ましくは２０万〜３００万である。 As the organic coagulant of the present invention, polyvinylamidine and a water-soluble copolymer having vinylamidine repeating units can be used. The water-soluble copolymer having polyvinylamidine and vinylamidine repeating units is described in JP-A-5-192513 and is as follows. N-vinylformamide and acrylonitrile copolymer are hydrolyzed with an acid to form a primary amino group, which is produced by reacting with the cyano group of the adjacent acrylonitrile. That is, a mixture having a molar ratio of N-vinylformamide and acrylonitrile of usually 50:50 to 60:40 is polymerized in the presence of a radical polymerization initiator. The amidine repeating unit in the polymer is 20 to 100 mol%, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. Moreover, molecular weight is 100,000-5 million in a weight average molecular weight, Preferably it is 200,000-3 million.
本発明の有機系凝結剤として、ポリエチレンイミンおよび四級アンモニウム塩基を含有するポリエチレンイミン変性物が使用できる。ポリエチレンイミンおよび四級アンモニウム塩基を含有するポリエチレンイミン変性物の合成法は、特開２００３−１９３３９６号公報に記載されている。ポリエチレンイミンは、重量平均分子量としては、５，０００以上あれば本発明の目的に使用できる。即ち、好ましくは５，０００〜５０万であり、更に好ましくは１０，０００〜５０万である。また四級アンモニウム塩基を含有するポリエチレンイミン変性物は、変性後の分子量が好ましくは５,０００〜５０万であり、更に好ましくは１０，０００〜５０万である。 As the organic coagulant of the present invention, a polyethyleneimine-modified product containing polyethyleneimine and a quaternary ammonium base can be used. A method for synthesizing a polyethyleneimine-modified product containing polyethyleneimine and a quaternary ammonium base is described in JP-A No. 2003-193396. Polyethyleneimine can be used for the purpose of the present invention if the weight average molecular weight is 5,000 or more. That is, it is preferably 5,000 to 500,000, and more preferably 10,000 to 500,000. The modified polyethylenimine containing a quaternary ammonium base preferably has a molecular weight after modification of 5,000 to 500,000, and more preferably 10,000 to 500,000.
本発明の有機系凝結剤は、水溶液重合、油中水型エマルジョン重合、油中水型分散重合、塩水中分散重合等によって重合した後、水溶液、油中水型エマルジョン、塩水中分散液あるいは粉末等任意の製品形態にすることができ、特に限定はない。 The organic coagulant of the present invention is polymerized by aqueous solution polymerization, water-in-oil emulsion polymerization, water-in-oil dispersion polymerization, salt water dispersion polymerization, etc., and then aqueous solution, water-in-oil emulsion, salt water dispersion or powder. Any product form can be used, and there is no particular limitation.
本発明の有機系凝結剤の添加率としては、パルプ乾燥固形分に対し０．００５〜０．１質量％、好ましくは０．０１〜０．０５質量％である。０．００５質量％より低いとサイズ剤定着効果が得られ難く、０．１質量％を超えると過剰添加でありサイズ剤以外の製紙薬剤やパルプ繊維と反応して過大なフロックが形成され成紙の地合いが不良となる場合がある。又、紙力増強剤、歩留向上剤、濾水性向上剤等の他の製紙用薬剤と併用しても差し支えない。 The addition rate of the organic coagulant of the present invention is 0.005 to 0.1 mass%, preferably 0.01 to 0.05 mass%, based on the dry pulp solid content. If the content is less than 0.005% by mass, it is difficult to obtain a sizing agent fixing effect. The texture may be poor. Further, it may be used in combination with other paper-making agents such as a paper strength enhancer, a yield improver, and a freeness improver.
中性ロジン系サイズ剤の場合、硫酸バンドの添加は必須であるが本発明の有機系凝結剤を使用することにより定着性が高まり、硫酸バンドの添加率を削減することができる。硫酸バンドは通常、対製紙原料当たり有姿として０．５〜３質量％添加され本発明もその範囲で適用される。サイズ剤の添加率は、対製紙原料当たり固形分０．０５〜５質量％の範囲である。 In the case of a neutral rosin-based sizing agent, the addition of a sulfuric acid band is indispensable, but the use of the organic coagulant of the present invention increases the fixability and can reduce the addition rate of the sulfuric acid band. The sulfuric acid band is usually added in an amount of 0.5 to 3% by mass as a solid per papermaking raw material, and the present invention is also applied within that range. The addition ratio of the sizing agent is in the range of 0.05 to 5% by mass of the solid content per papermaking raw material.
次に、ピッチトラブルについて説明する。古紙や塗工損紙、樹脂に由来するピッチ類あるいはアニオン性物質、濁度成分は、紙の汚れ、欠陥、断紙、抄紙機の汚れといった様々なピッチトラブルを引き起こす。未定着のサイズ剤もこのピッチトラブルを引き起こす要因になる。通常、これら、ピッチ成分や濁度成分を処理するのに凝結剤やピッチコントロール剤が使用されており、パルプ繊維と共にピッチ成分や濁度成分を凝結作用により処理している。本発明の有機系凝結剤の使用は、サイズ定着と同時にピッチ成分や濁度成分を処理し、ピッチトラブルの防止または抑制するための効果を併せ持つことになる。 Next, pitch trouble will be described. Waste paper, coating waste paper, pitches derived from resins, anionic substances, and turbidity components cause various pitch troubles such as paper stains, defects, paper breaks, and paper machine stains. Unfixed sizing agents also cause this pitch trouble. Usually, a coagulant and a pitch control agent are used to treat the pitch component and the turbidity component, and the pitch component and the turbidity component are treated together with the pulp fiber by the coagulation action. The use of the organic coagulant of the present invention treats the pitch component and turbidity component simultaneously with the size fixing, and also has the effect of preventing or suppressing pitch trouble.
サイズ定着剤の添加は、従来、リファイナー、原料配合チェスト、ミキシングチェスト、マシンチェスト、種箱等、パルプ乾燥固形分濃度が２．０質量％以上の様々な場所に添加されているが、一般的には硫酸バンドの効果を補う目的で硫酸バンドの前にサイズ定着剤を添加する方法が採用されていることが多い。本発明の有機系凝結剤の添加は、硫酸バンドとロジン系サイズ剤を添加した後に添加することが必須である。硫酸バンドを介在してパルプ繊維に定着したサイズ剤が下流工程で徐々に剥離するのを有機系凝結剤により再定着することにより優れたサイズ効果が発現することが推測される。そのため、有機系凝結剤の最も効果的な添加場所は製紙工程のパルプ乾燥固形分濃度が２．０質量％以上を有する製紙工程の最後の貯槽（チェスト）であり、通常、種箱と呼ばれる貯槽である。これは、種箱より上流の配合チェスト、マシンチェスト、ミキシングチェスト等では、抄紙機のワイヤーまでの距離が長くなり、有機系凝結剤を介在してパルプ繊維に定着したロジン系サイズ剤の剥離が徐々に進行し効果が得られないためと推測される。硫酸バンドとロジン系サイズ剤の添加は、有機系凝結剤の添加が硫酸バンドとロジン系サイズ剤よりも後であれば、添加場所は有機系凝結剤と同じ種箱であっても良いし種箱より上流のチェストでも良い。硫酸バンドとロジン系サイズ剤は同時であっても良いが、好ましくは、硫酸バンド、ロジン系サイズ剤の添加順序である。硫酸バンド、ロジン系サイズ剤の添加後に有機系凝結剤が添加されていれば、その後の下流工程において再度、硫酸バンドを添加しても差し支えない。
パルプ乾燥固形分濃度が２．０質量％以上を有する製紙工程の最後の貯槽（チェスト）を経た後、白水あるいは清水、工業用水等で希釈され２．０質量％より低い製紙原料にされ、通常の製紙工程では抄紙機の直前にはパルプ乾燥固形分濃度０．５〜１．５質量％に希釈されており、本発明もその範囲内で適用される。
Size fixers have been added to various places where the dry solid content of pulp is 2.0% by mass or more, such as refiners, raw material blending chests, mixing chests, machine chests, and seed boxes. In many cases, a method of adding a size fixing agent before the sulfuric acid band is employed for the purpose of supplementing the effect of the sulfuric acid band. It is essential to add the organic coagulant of the present invention after adding the sulfuric acid band and the rosin sizing agent. It is presumed that an excellent sizing effect is exhibited by re-fixing the sizing agent fixed on the pulp fiber through the sulfuric acid band from the gradual separation in the downstream process with the organic coagulant. Therefore, the most effective addition place of the organic coagulant is the last storage tank (chest) of the papermaking process having a pulp dry solid concentration of 2.0% by mass or more in the papermaking process, and is usually called a seed box. It is. This is because in the blending chest, machine chest, mixing chest, etc. upstream of the seed box, the distance to the wire of the paper machine becomes longer, and the rosin-based sizing agent fixed on the pulp fiber is peeled off via an organic coagulant. It is presumed that the effect progresses gradually and the effect cannot be obtained. The addition of the sulfuric acid band and rosin sizing agent may be in the same seed box as the organic coagulant as long as the organic coagulant is added after the sulfuric acid band and rosin sizing agent. A chest upstream of the box is also acceptable. The sulfuric acid band and the rosin sizing agent may be used at the same time, but the addition order of the sulfuric acid band and the rosin sizing agent is preferred. If the organic coagulant is added after the addition of the sulfuric acid band and rosin sizing agent, the sulfuric acid band may be added again in the subsequent downstream process.
After passing through the last storage tank (chest) of the papermaking process having a pulp dry solid content concentration of 2.0% by mass or more, it is diluted with white water or fresh water, industrial water, etc. to make a papermaking raw material lower than 2.0% by mass. In the papermaking process, the pulp is diluted to a pulp dry solid concentration of 0.5 to 1.5% by mass immediately before the paper machine, and the present invention is also applied within that range.
本発明の有機系凝結剤の好適な添加場所は、前記した様に製紙工程のパルプ乾燥固形分濃度が２．０質量％以上を有する製紙工程の最後の貯槽（チェスト）である種箱であるが、通常、種箱へ薬品を添加する場合、上方から滴下されている場合が多い。又、種箱には撹拌機能が備わっていない場合が多い。有機系凝結剤の添加は、種箱貯槽中の製紙原料に上方から添加しても良いが、効果的なのは種箱貯槽中の製紙原料内部に添加する方法である。具体的には、凝結剤用の配管やホース等を製紙原料内部に挿入して添加する方法である。種箱内の紙料送り設備や種箱への製紙原料送りポンプに添加しても効果的である。例えば、ロジン系サイズ剤を種箱に０．５５質量％添加（対製紙原料固形分）している某製紙会社のライナー板紙製造工程において、サイズ剤の添加場所より下流のマシンに近い側の種箱の製紙原料内部にホース配管を挿入し、その配管に有機系凝結剤として、アクリルアミド／アクリロイルオキシエチルトリメチルアンモニウムクロリド／アクリロイルオキシエチルジメチルベンジルアンモニウムクロリド（４／８０／１６モル％）共重合体（水溶液重合体、重量平均分子量４３万）を２００ｐｐｍ添加（対製紙原料固形分）した結果、その方法で添加しない場合に比べて、サイズ剤の添加率を０．４４質量％に減少させても０．５５質量％添加時と同等のサイズ度が得られた。これは、製紙原料との撹拌が効率的に行われ、ロジン系サイズ剤と有機系凝結剤の反応が効率的になされた結果であると考えられる。 A suitable addition place of the organic coagulant of the present invention is a seed box which is the last storage tank (chest) of the papermaking process having a pulp dry solid concentration of 2.0% by mass or more in the papermaking process as described above. However, usually, when a chemical is added to the seed box, it is often dropped from above. In many cases, the seed box does not have a stirring function. The organic coagulant may be added to the papermaking raw material in the seed box storage tank from above, but an effective method is to add it to the inside of the papermaking raw material in the seed box storage tank. Specifically, it is a method in which a coagulant pipe or hose is inserted into the papermaking raw material and added. It is also effective to add it to the paper feed feeding equipment in the seed box or the papermaking raw material feed pump to the seed box. For example, in a liner paperboard manufacturing process of a paper company that adds 0.55% by mass of a rosin sizing agent to the seed box (solid content of the papermaking raw material), the seed on the side closer to the machine downstream from the sizing agent addition site A hose pipe is inserted into the papermaking raw material of the box, and an acrylamide / acryloyloxyethyltrimethylammonium chloride / acryloyloxyethyldimethylbenzylammonium chloride (4/80/16 mol%) copolymer is used as an organic coagulant in the pipe ( As a result of adding 200 ppm of an aqueous solution polymer (weight average molecular weight 430,000) to the papermaking raw material solids, it is 0 even when the addition rate of the sizing agent is reduced to 0.44% by mass, compared with the case where it is not added by that method. A sizing degree equivalent to that when .55% by mass was added was obtained. This is considered to be a result of efficient stirring with the papermaking raw material and efficient reaction between the rosin sizing agent and the organic coagulant.
対象抄造製紙原料としては特に限定はなく、新聞用紙、上質紙、ＰＰＣ用紙、塗工原紙、微塗工紙、板紙等に適用できるが、サイズ性付与が最も求められる板紙原料において特に効果が顕著である。 There are no particular limitations on the target papermaking raw material, and it can be applied to newsprint, high-quality paper, PPC paper, coated base paper, fine coated paper, paperboard, etc., but the effect is particularly significant in paperboard raw materials that are most required to be sized. It is.
以下に実施例をあげて本発明を詳細に説明するが、本発明はこれら実施例により限定されるものではない。 EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
某製紙会社から入手したライナー板紙製造原料（表層、ｐＨ７．０、カチオン要求量ＢＴＧ社製ＰＣＤ０３型測定１１０μｅｑ／Ｌ、乾燥固形分濃度４．１１質量％）を対象にサイズ度効果試験を実施した。有機系凝結剤として、アクリルアミド／アクリロイルオキシエチルトリメチルアンモニウムクロリド／アクリロイルオキシエチルジメチルベンジルアンモニウムクロリド（４／８０／１６モル％））共重合体（水溶液重合体、重量平均分子量４３万）を用意し、純水で０．１質量％に溶解し試験に用いた。 A sizing effect test was carried out on linerboard production raw materials (surface layer, pH 7.0, PCD03 type measurement 110 μeq / L, manufactured by BTG Co., Ltd., dry solid content concentration 4.11% by mass) obtained from Sakai Paper Company. . As an organic coagulant, an acrylamide / acryloyloxyethyltrimethylammonium chloride / acryloyloxyethyldimethylbenzylammonium chloride (4/80/16 mol%) copolymer (aqueous polymer, weight average molecular weight 430,000) was prepared. It melt | dissolved in 0.1 mass% with the pure water, and used for the test.
（添加方法１）
板紙製造原料１００ｍＬをポリビーカーに採取し、硫酸バンドを２質量％添加（マシンチェスト添加想定）、２００ｒｐｍで４０秒攪拌、ロジン系サイズ剤を０．６５質量％添加（種箱添加想定）、１０秒攪拌、有機系凝結剤を２００ｐｐｍ添加（種箱添加想定）、３０秒撹拌した（添加は何れも対製紙原料固形分）。その後、ワットマン濾紙Ｎｏ．４１により濾過し、濾紙上の原料を清水５００ｍＬで希釈し、８００ｒｐｍ、６０秒撹拌後、ＴＡＰＰＩスタンダード抄紙機（６０メッシュワイヤー使用）で抄紙した。抄紙した湿紙を４．１ｋｇｆ／ｃｍ２で５分間、プレス機にてプレス脱水し、回転式ドラムドライヤーで１０５℃、３分間乾燥後、２５℃、ＲＨ６５％の条件で１８時間調湿し、坪量及びＣｏｂｂ吸水度を測定した。結果を表１に示す。
(Addition method 1)
100 mL of paperboard production raw material is collected in a poly beaker, 2% by mass of a sulfuric acid band is added (assuming machine chest is added), stirred at 200 rpm for 40 seconds, and 0.65% by mass of rosin sizing agent is added (assuming addition of seed box) Stirring for 2 seconds, 200 ppm of organic coagulant was added (assuming seed box addition), and stirring was performed for 30 seconds (both additions were solid content of the papermaking raw material). Then, Whatman filter paper No. After filtration through 41, the raw material on the filter paper was diluted with 500 mL of fresh water, stirred at 800 rpm for 60 seconds, and then paper-made with a TAPPI standard paper machine (using 60 mesh wire). The paper wetting paper was press dehydrated with a press at 4.1 kgf / cm 2 for 5 minutes, dried with a rotary drum dryer at 105 ° C. for 3 minutes, and then conditioned at 25 ° C. and RH 65% for 18 hours. Basis weight and Cobb water absorption were measured. The results are shown in Table 1.
（添加方法２）
実施例１と同様原料を対象に同様な有機系凝結剤を用いて試験を実施した。製紙原料１００ｍＬをポリビーカーに採取し、有機系凝結剤を対製紙原料固形分２００ｐｐｍ添加（リファイナー添加想定）、２００ｒｐｍで３０秒攪拌、硫酸バンドを２質量％添加（マシンチェスト添加想定）、４０秒攪拌、ロジン系サイズ剤を０．６５質量％添加（種箱添加想定）、４０秒攪拌した（添加は何れも対製紙原料固形分）。その後、ワットマン濾紙Ｎｏ．４１により濾過し、濾紙上の原料を清水５００ｍＬで希釈し、８００ｒｐｍ、６０秒撹拌後、ＴＡＰＰＩスタンダード抄紙機（６０メッシュワイヤー使用）で抄紙した。抄紙した湿紙を４．１ｋｇｆ／ｃｍ２で５分間、プレス機にてプレス脱水し、回転式ドラムドライヤーで１０５℃、３分間乾燥後、２５℃、ＲＨ６５％の条件で１８時間調湿し、坪量及びＣｏｂｂ吸水度を測定した。結果を表１に示す。
(Addition method 2)
A test was conducted using the same organic coagulant as the target for the raw materials as in Example 1. 100 mL of papermaking raw material is collected in a poly beaker, organic coagulant is added to the papermaking raw material at a solid content of 200 ppm (refiner addition assumed), stirred at 200 rpm for 30 seconds, 2% by mass of sulfuric acid band (assuming machine chest addition), 40 seconds Stirring, 0.65% by mass of rosin-based sizing agent (seed box addition assumed), and stirring for 40 seconds (both additions are solid content of papermaking raw material). Then, Whatman filter paper No. After filtration through 41, the raw material on the filter paper was diluted with 500 mL of fresh water, stirred at 800 rpm for 60 seconds, and then paper-made with a TAPPI standard paper machine (using 60 mesh wire). The paper wetting paper was press dehydrated with a press at 4.1 kgf / cm 2 for 5 minutes, dried with a rotary drum dryer at 105 ° C. for 3 minutes, and then conditioned at 25 ° C. and RH 65% for 18 hours. Basis weight and Cobb water absorption were measured. The results are shown in Table 1.
（添加方法３）
実施例１と同様原料を対象に同様な有機系凝結剤を用いて試験を実施した。製紙原料１００ｍＬをポリビーカーに採取し、硫酸バンドを対製紙原料固形分２質量％添加（マシンチェスト添加想定）、２００ｒｐｍで１０秒攪拌、有機系凝結剤を２００ｐｐｍ添加（マシンチェスト添加想定）、３０秒攪拌、ロジン系サイズ剤を０．６５質量％添加（種箱添加想定）、４０秒攪拌した（添加は何れも対製紙原料固形分）。その後、ワットマン濾紙Ｎｏ．４１により濾過し、濾紙上の原料を清水５００ｍＬで希釈し、８００ｒｐｍ、６０秒撹拌後、ＴＡＰＰＩスタンダード抄紙機（６０メッシュワイヤー使用）で抄紙した。抄紙した湿紙を４．１ｋｇｆ／ｃｍ２で５分間、プレス機にてプレス脱水し、回転式ドラムドライヤーで１０５℃、３分間乾燥後、２５℃、ＲＨ６５％の条件で１８時間調湿し、坪量及びＣｏｂｂ吸水度を測定した。結果を表１に示す。
(Addition method 3)
A test was conducted using the same organic coagulant as the target for the raw materials as in Example 1. 100 mL of papermaking raw material is collected in a poly beaker, 2% by mass of sulfuric acid band is added to the papermaking raw material solid content (assuming machine chest addition), stirred at 200 rpm for 10 seconds, 200 ppm of organic coagulant is added (assuming machine chest addition), 30 Stirring for 2 seconds, 0.65% by mass of a rosin sizing agent was added (assuming seed box addition), and stirring was performed for 40 seconds (both additions were solids for the papermaking raw material). Then, Whatman filter paper No. After filtration through 41, the raw material on the filter paper was diluted with 500 mL of fresh water, stirred at 800 rpm for 60 seconds, and then paper-made with a TAPPI standard paper machine (using 60 mesh wire). The paper wet paper was press dehydrated with a press at 4.1 kgf / cm 2 for 5 minutes, dried with a rotary drum dryer at 105 ° C. for 3 minutes, and then conditioned at 25 ° C. and RH 65% for 18 hours. Basis weight and Cobb water absorption were measured. The results are shown in Table 1.
（表１）
(Table 1)
実施例１における添加方法１の硫酸バンドとサイズ剤の添加の後に有機系凝結剤を添加した方法が、添加方法２、３に比べてＣｏｂｂ吸水度の値が小さくサイズ度が良好であることが分かった。これは、硫酸バンドを介在してサイズ剤がパルプ繊維に定着したものを有機系凝結剤により定着を補強した結果であると考えられる。 The method of adding organic coagulant after addition of sulfuric acid band and sizing agent in addition method 1 in Example 1 has a smaller Cobb water absorption value and better sizing degree than addition methods 2 and 3. I understood. This is considered to be the result of reinforcing the fixing with an organic coagulant in which the sizing agent was fixed to the pulp fiber via a sulfuric acid band.
実施例１の添加方法１において、ワットマン濾紙Ｎｏ．４１により濾過した濾液を厚さ０．２ｍｍのカウンティングチェンバー（ヘマサイトメーター）上に採取し、光学顕微鏡１２００倍で観察した。ピントを垂直方向にずらしていきながら静止画を複数枚撮影した。カウンティングチェンバー上の異なる５箇所以上で同様の操作を繰り返した。画像処理ソフト（Ｍｅｄｉａ Ｃｙｂｅｒｎｅｔｉｃｓ，ｉｎｃ． ＩＭＡＧＥ−ＰＲＯ ＰＬＵＳ Ｖｅｒ．５．０）を用い、顕微鏡画像の静止画を取込み、ＲＧＢ値のレンジ設定をＲ値（０−１９０）、Ｇ値（０−１３０）、Ｂ値（０−１５６）に調整することにより、目的とする粒子を抽出した。その抽出した粒子について、解析ソフトを用いてピッチ個数及びピッチ粒子面積を測定した。結果を表２に示す。 In addition method 1 of Example 1, Whatman filter paper No. The filtrate filtered through No. 41 was collected on a counting chamber (hemacytometer) having a thickness of 0.2 mm and observed with an optical microscope of 1200 times. I took several still images while shifting the focus vertically. The same operation was repeated at five or more different locations on the counting chamber. Using image processing software (Media Cybernetics, inc. IMAGE-PRO PLUS Ver. 5.0), a still image of a microscopic image is captured, and the RGB value range setting is set to R value (0-190), G value (0-130). ) And B value (0-156), the target particles were extracted. With respect to the extracted particles, the number of pitches and the pitch particle area were measured using analysis software. The results are shown in Table 2.
前記添加方法２、３において、ワットマン濾紙Ｎｏ．４１により濾過した濾液を厚さ０．２ｍｍのカウンティングチェンバー（ヘマサイトメーター）上に採取し、光学顕微鏡１２００倍で観察した。ピントを垂直方向にずらしていきながら静止画を複数枚撮影した。カウンティングチェンバー上の異なる５箇所以上で同様の操作を繰り返した。画像処理ソフト（Ｍｅｄｉａ Ｃｙｂｅｒｎｅｔｉｃｓ，ｉｎｃ． ＩＭＡＧＥ−ＰＲＯ ＰＬＵＳ Ｖｅｒ．５．０）を用い、顕微鏡画像の静止画を取込み、ＲＧＢ値のレンジ設定をＲ値（０−１９０）、Ｇ値（０−１３０）、Ｂ値（０−１５６）に調整することにより、目的とする粒子を抽出した。その抽出した粒子について、解析ソフトを用いてピッチ個数及びピッチ粒子面積を測定した。結果を表２に示す。 In the addition methods 2 and 3, Whatman filter paper No. The filtrate filtered through No. 41 was collected on a counting chamber (hemacytometer) having a thickness of 0.2 mm and observed with an optical microscope of 1200 times. I took several still images while shifting the focus vertically. The same operation was repeated at five or more different locations on the counting chamber. Using image processing software (Media Cybernetics, inc. IMAGE-PRO PLUS Ver. 5.0), a still image of a microscopic image is captured, and the RGB value range setting is set to R value (0-190), G value (0-130). ) And B value (0-156), the target particles were extracted. With respect to the extracted particles, the number of pitches and the pitch particle area were measured using analysis software. The results are shown in Table 2.
（表２）
(Table 2)
実施例２における添加方法１の硫酸バンドとサイズ剤の添加の後に有機系凝結剤を添加した方法が、添加方法２、３に比べてマイクロピッチ個数及びマイクロピッチ面積が小さい値を示した。これは、サイズ剤に起因するマイクロピッチの低下、及び製紙原料中のピッチ成分、濁度成分の処理効果が優れることを示すものである。
The method of adding an organic coagulant after the addition of the sulfuric acid band and the sizing agent in the addition method 1 in Example 2 showed smaller values for the number of micro pitches and the micro pitch area than the addition methods 2 and 3. This indicates that the micropitch is reduced due to the sizing agent, and the processing effect of the pitch component and turbidity component in the papermaking raw material is excellent.
Claims (3)
The size fixing method according to claim 2, wherein the organic coagulant is added to the inside of the papermaking raw material in the storage tank.
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|---|---|---|---|---|
| JPH06330496A (en) * | 1993-05-18 | 1994-11-29 | Seiko Kagaku Kogyo Co Ltd | Emulsion sizing agent for papermaking |
| JP2000080592A (en) * | 1998-09-08 | 2000-03-21 | Seiko Kagaku Kogyo Co Ltd | Sizing of paper |
| JP2003238631A (en) * | 2002-02-22 | 2003-08-27 | Seiko Pmc Corp | (meth)acrylamide polymer, its manufacturing method, agent for papermaking, and paper containing the same |
| JP2004044020A (en) * | 2002-07-12 | 2004-02-12 | Seiko Pmc Corp | Rosin emulsion sizing agent |
| JP2004269630A (en) * | 2003-03-06 | 2004-09-30 | Seiko Pmc Corp | Cationic polymer and paper |
| JP2007046180A (en) * | 2005-08-08 | 2007-02-22 | Kurita Water Ind Ltd | Paper-making method |
| JP2007092251A (en) * | 2005-09-29 | 2007-04-12 | Seiko Pmc Corp | Method and chemical for preventing soil |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06330496A (en) * | 1993-05-18 | 1994-11-29 | Seiko Kagaku Kogyo Co Ltd | Emulsion sizing agent for papermaking |
| JP2000080592A (en) * | 1998-09-08 | 2000-03-21 | Seiko Kagaku Kogyo Co Ltd | Sizing of paper |
| JP2003238631A (en) * | 2002-02-22 | 2003-08-27 | Seiko Pmc Corp | (meth)acrylamide polymer, its manufacturing method, agent for papermaking, and paper containing the same |
| JP2004044020A (en) * | 2002-07-12 | 2004-02-12 | Seiko Pmc Corp | Rosin emulsion sizing agent |
| JP2004269630A (en) * | 2003-03-06 | 2004-09-30 | Seiko Pmc Corp | Cationic polymer and paper |
| JP2007046180A (en) * | 2005-08-08 | 2007-02-22 | Kurita Water Ind Ltd | Paper-making method |
| JP2007092251A (en) * | 2005-09-29 | 2007-04-12 | Seiko Pmc Corp | Method and chemical for preventing soil |
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