JP2000034692A - Mechanical pulp-containing paper and its production - Google Patents
Mechanical pulp-containing paper and its productionInfo
- Publication number
- JP2000034692A JP2000034692A JP10218663A JP21866398A JP2000034692A JP 2000034692 A JP2000034692 A JP 2000034692A JP 10218663 A JP10218663 A JP 10218663A JP 21866398 A JP21866398 A JP 21866398A JP 2000034692 A JP2000034692 A JP 2000034692A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- mechanical pulp
- paper
- weight
- sizing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001131 Pulp (paper) Polymers 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000004513 sizing Methods 0.000 claims abstract description 117
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 92
- 239000000178 monomer Substances 0.000 claims abstract description 80
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 70
- 230000007935 neutral effect Effects 0.000 claims abstract description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000654 additive Substances 0.000 claims abstract description 25
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims abstract description 13
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 125000002091 cationic group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 21
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 17
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 claims description 16
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 claims description 16
- 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 description 13
- 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 description 13
- 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 description 13
- 150000003972 cyclic carboxylic anhydrides Chemical class 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229920006163 vinyl copolymer Polymers 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 229940125782 compound 2 Drugs 0.000 claims 1
- 229940125898 compound 5 Drugs 0.000 claims 1
- 150000003865 secondary ammonium salts Chemical class 0.000 claims 1
- 229920003169 water-soluble polymer Polymers 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 9
- 239000000470 constituent Substances 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 63
- -1 alkenyl succinic anhydride Chemical compound 0.000 description 28
- 239000007788 liquid Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- 238000007792 addition Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000013055 pulp slurry Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229920003118 cationic copolymer Polymers 0.000 description 5
- 229940014800 succinic anhydride Drugs 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011121 hardwood Substances 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005956 quaternization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002023 wood Substances 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
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- JNDVNJWCRZQGFQ-UHFFFAOYSA-N 2-methyl-N,N-bis(methylamino)hex-2-enamide Chemical compound CCCC=C(C)C(=O)N(NC)NC JNDVNJWCRZQGFQ-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- AJTFTYHGFWNENF-UHFFFAOYSA-N azanium;hydroxy sulfate Chemical compound [NH4+].OOS([O-])(=O)=O AJTFTYHGFWNENF-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- ABBZJHFBQXYTLU-UHFFFAOYSA-N but-3-enamide Chemical compound NC(=O)CC=C ABBZJHFBQXYTLU-UHFFFAOYSA-N 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000002761 deinking Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- JOXWSDNHLSQKCC-UHFFFAOYSA-N ethenesulfonamide Chemical group NS(=O)(=O)C=C JOXWSDNHLSQKCC-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ketene group Chemical group C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-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
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical group C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 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
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paper (AREA)
Abstract
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、機械パルプ含有紙及び
その製造方法に係わり、さらに詳しくは、機械パルプを
使用した抄紙工程に伴うピッチによる障害を抑制すると
共に、紙に優れたサイズ性を与えることができる機械パ
ルプ含有紙及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mechanical pulp-containing paper and a method for producing the same. The present invention relates to a mechanical pulp-containing paper that can be provided and a method for producing the same.
【０００２】[0002]
【従来の技術】機械パルプは、機械的に木材を繊維化し
て製造したパルプであり、ピッチと言われる樹脂分等の
有機物を主体とした水難溶性の粘着性物質を比較的多く
含んでいる。それ故、機械パルプを使用した中性サイズ
剤による抄紙では、抄紙装置のフェルトやプレスロー
ル、スムーザーロール、キャンバスストレッチロール等
の抄紙用具にピッチが付着し、湿紙がこれらに接触しな
がらできあがる製品としての紙は、このピッチの付着物
により汚されるという、いわゆるピッチ障害を起こし易
い。殊に、ケテンダイマー系サイズ剤やアルケニルコハ
ク酸無水物のような置換環式ジカルボン酸無水物系サイ
ズ剤、中性抄紙用ロジン系サイズ剤等の中性サイズ剤を
使用して中性サイジングを行う場合には、ピッチ障害が
より起り易くなる場合がある。いわゆる反応型のケテン
ダイマーあるいは置換環式ジカルボン酸無水物は加水分
解し易いため、パルプ繊維に定着してサイズ性を発現す
るに到る前に、その一部が抄紙系水中で加水分解物とな
って、凝集物を形成することがある。抄紙温度付近にお
いて、それらの凝集物が粘着性を帯びていると、その粘
着物がフェルトやロールの表面に付着したときに、比較
的疎水的な粘着物の成分に、機械パルプの疎水性のピッ
チがその親和性や粘着性によりさらに付着し、その結
果、フェルトやロール表面に汚れが堆積し、これに接触
する湿紙も汚され易いからである。また、中性抄紙用ロ
ジン系サイズ剤を使用する場合には、ケテンダイマー系
サイズ剤や置換環式ジカルボン酸無水物系サイズ剤と同
程度のサイズレベルを得るには、比較的に添加率を高く
する必要があり、その結果、パルプ繊維に定着しない部
分も多くなり易く、いわゆる歩留りが悪くなって、その
定着されない固形分の成分が上記の場合と同様にフェル
トやロールの表面に付着し、これらを汚し、湿紙も汚さ
れ易い。このようなピッチ障害は、できあがった製品で
ある紙の商品価値を低下させ、これを回避しようとすれ
ば、フェルトやロール等に付着したピッチを除去する作
業が必要になり、抄紙工程の操業性を低下させる深刻な
問題となる。2. Description of the Related Art Mechanical pulp is a pulp manufactured by mechanically converting wood into fibers, and contains a relatively large amount of a hardly water-soluble adhesive substance mainly composed of organic substances such as resin called pitch. Therefore, in papermaking with a neutral sizing agent using mechanical pulp, pitch is attached to papermaking tools such as felt, press rolls, smoother rolls, and canvas stretch rolls of papermaking equipment, and products that are formed while wet paper comes in contact with these. The paper as described above is liable to cause a so-called pitch disturbance that is soiled by the deposits of the pitch. In particular, neutral sizing using a neutral sizing agent such as a ketene dimer sizing agent or a substituted cyclic dicarboxylic anhydride sizing agent such as alkenyl succinic anhydride, or a rosin sizing agent for neutral papermaking. If so, pitch disturbance may be more likely to occur. Since the so-called reactive ketene dimer or substituted cyclic dicarboxylic anhydride is easily hydrolyzed, a part of the ketene dimer or the substituted cyclic dicarboxylic anhydride is converted into a hydrolyzate in papermaking water before fixing to the pulp fiber and developing the size. To form aggregates. If the aggregates are sticky at around the papermaking temperature, when the stickies adhere to the surface of felt or rolls, the relatively hydrophobic sticky components become hydrophobic components of the mechanical pulp. This is because the pitch further adheres due to its affinity and tackiness, and as a result, dirt accumulates on the felt or roll surface, and the wet paper web that comes into contact therewith is also easily stained. Also, when using a rosin-based sizing agent for neutral papermaking, to obtain a size level comparable to that of a ketene dimer-based sizing agent or a substituted cyclic dicarboxylic anhydride-based sizing agent, the addition rate should be relatively high. It is necessary to increase, as a result, the portion that does not settle on the pulp fiber tends to increase, so-called yield deteriorates, and the solid component that is not fixed adheres to the surface of the felt or the roll as in the above case, These are stained, and wet paper is also easily stained. Such a pitch hindrance reduces the commercial value of the finished product, paper, and if it is to be avoided, it will be necessary to remove the pitch attached to felt, rolls, etc. Degrading becomes a serious problem.
【０００３】[0003]
【発明が解決しようとする課題】ピッチ障害を抑制する
方法としては、特定の両性界面活性剤と水溶性カチオン
性ポリマーを有効成分とするピッチコントロール剤を使
用する方法が特開平７−１２６９９６号公報に開示され
ているが、界面活性剤の使用は紙のサイズ性等、紙質に
悪影響を及ぼし易く、満足な方法とは言えない。また、
特開昭５８−２２０８８９号公報には、抄紙系の添加物
等のイオンバランスに悪影響を及ぼさないタイプとして
ノニオン性親水性単量体である（メタ）アクリルアミド
とスチレン等の疎水性単量体との共重合体を製紙用ピッ
チ付着防止剤として使用する方法が開示されているが、
ノニオン性のものはパルプ繊維に定着し難く、抄紙系に
おいて発泡を起こしたり、その他の障害の原因になり易
いという問題がある。さらに特開昭５３−４１５０７号
公報には、下記〔化１〕で表される重合単位からなる単
独重合体、あるいは他のエチレン系不飽和単量体と共重
合させた水溶性直鎖状カチオン重合体を含むピッチ付着
防止用組成物を使用する方法が開示されているが、その
ピッチ障害を抑制する効果は満足のいくものではなかっ
た。As a method for suppressing pitch disturbance, a method using a pitch control agent containing a specific amphoteric surfactant and a water-soluble cationic polymer as active ingredients is disclosed in Japanese Patent Application Laid-Open No. Hei 7-126996. However, the use of a surfactant tends to have an adverse effect on the paper quality, such as paper sizing properties, and is not a satisfactory method. Also,
JP-A-58-220889 discloses a nonionic hydrophilic monomer (meth) acrylamide and a hydrophobic monomer such as styrene, which do not adversely affect the ion balance of papermaking additives and the like. A method of using a copolymer as a papermaking pitch adhesion inhibitor has been disclosed,
Nonionic materials have a problem that they hardly settle on pulp fibers and easily cause foaming or other obstacles in papermaking systems. Further, JP-A-53-41507 discloses a water-soluble linear cation copolymerized with a homopolymer comprising a polymerized unit represented by the following chemical formula 1 or another ethylenically unsaturated monomer. Although a method using a pitch adhesion preventing composition containing a polymer is disclosed, the effect of suppressing pitch disturbance was not satisfactory.
【０００４】[0004]
【化１】 （式中、Ａは炭素数２又は３のアルキレン基、ＲはＨ又
はＣＨ3 、Ｒ1 はヒドロキシエチル基又はヒドロキシプ
ロピル基、Ｒ2 およびＲ3 は炭素数１〜４のアルキル
基、Ｘは陰イオンを表す。）Embedded image (Where A is an alkylene group having 2 or 3 carbon atoms, R is H or CH 3 , R 1 is a hydroxyethyl group or hydroxypropyl group, R 2 and R 3 are alkyl groups having 1 to 4 carbon atoms, X is Represents an anion.)
【０００５】近年、森林保護の観点や、低コスト化の観
点から、原料パルプ中に原料使用効率の良い機械パルプ
を配合して使用する紙の生産が増加しており、一方、抄
紙系の中性化の進行に伴い、ケテンダイマー系サイズ剤
や置換環式ジカルボン酸無水物系サイズ剤、中性抄紙用
ロジン系サイズ剤等の中性サイズ剤が比較的広く使用さ
れるようになってきており、機械パルプを配合したパル
プ原料を使用し、中性サイズ剤でサイジングを行う抄紙
系において、ピッチ障害を抑制するとともに、得られた
紙のサイズ性に優れる紙の製造方法が切に望まれてい
る。本発明の第１の目的は、ピッチ障害を抑制できる機
械パルプ含有紙及びその製造方法を提供することにあ
る。本発明の第２の目的は、サイズ性の優れた機械パル
プ含有紙及びその製造方法を提供することにある。本発
明の第３の目的は、中性サイズ剤の歩留まりを向上させ
ることができる機械パルプ含有紙及びその製造方法を提
供することにある。[0005] In recent years, from the viewpoint of forest protection and cost reduction, the production of paper using mechanical pulp having a high raw material use efficiency in raw pulp has been increasing. With the progress of sintering, neutral sizing agents such as ketene dimer sizing agents, substituted cyclic dicarboxylic anhydride sizing agents, and rosin sizing agents for neutral papermaking have become relatively widely used. In a papermaking system using a pulp material blended with mechanical pulp and sizing with a neutral sizing agent, a method for producing a paper that suppresses pitch disturbance and has excellent sizing properties of the obtained paper is urgently desired. ing. A first object of the present invention is to provide a mechanical pulp-containing paper capable of suppressing pitch disturbance and a method for producing the same. A second object of the present invention is to provide a mechanical pulp-containing paper excellent in size and a method for producing the same. A third object of the present invention is to provide a mechanical pulp-containing paper capable of improving the yield of a neutral sizing agent and a method for producing the same.
【０００６】[0006]
【問題を解決するための手段】本願発明者らは、上記目
的を達成するために鋭意検討した結果、（１）、乾燥重
量基準で機械パルプを少なくとも５重量％含有する製紙
用パルプを用いて中性サイズ剤によりサイジングした機
械パルプ含有紙において、下記（Ａ）５０〜９５重量％
及び下記（Ｂ）５〜５０重量％の各単量体に対応する構
成単位の結合体を有し、かつ４級アンモニウム塩を有す
るビニル系共重合体であるカチオン性ポリマーを添加物
として上記機械パルプの乾燥重量に対して０．０３〜１
重量％含有する機械パルプ含有紙を提供するものであ
る。 （Ａ）スチレン系単量体及びアルキル（メタ）アクリレ
ートからなる群より選択された少なくとも１種の疎水性
単量体 （Ｂ）ジアルキルアミノアルキル（メタ）アクリルアミ
ド及びジアルキルアミノアルキル（メタ）アクリレート
からなる３級アミノ基を有する単量体並びにそれぞれの
４級化物からなる４級アンモニウム塩を有する単量体の
群より選ばれた少なくとも１種のカチオン性単量体 また、本発明は、（２）、上記（Ｂ）成分の一部に上記
（Ａ）及び（Ｂ）成分以外のその他のビニル系単量体を
用いる上記（１）の機械パルプ含有紙、（３）、中性サ
イズ剤がケテンダイマー系サイズ剤、置換環式ジカルボ
ン酸無水物系サイズ剤及び中性抄紙用ロジン系サイズ剤
からなる群から選ばれる少なくとも１種である上記
（１）又は（２）の機械パルプ含有紙、（４）、乾燥重
量基準で機械パルプを少なくとも５重量％含有する製紙
用パルプを原料とし、ｐＨ６〜９で中性サイズ剤を使用
してサイジングする抄紙工程を有する機械パルプ含有紙
の製造方法において、下記（Ａ）５０〜９５重量％及び
下記（Ｂ）５〜５０重量％含有する単量体から得られる
ビニル系共重合体であって、下記（Ｂ）成分として３級
アミノ基を有する単量体を使用する場合は該ビニル系共
重合体の重合過程及び重合後の少なくとも一方において
４級化することがある４級アンモニウム塩を有するカチ
オン性ポリマーを含有する添加剤を上記抄紙工程におい
て使用し、かつ該カチオン性ポリマーを上記機械パルプ
の乾燥重量に対して０．０３〜１重量％使用する機械パ
ルプ含有紙の製造方法、 （Ａ）スチレン系単量体及びアルキル（メタ）アクリレ
ートからなる群より選択された少なくとも１種の疎水性
単量体 （Ｂ）ジアルキルアミノアルキル（メタ）アクリルアミ
ド及びジアルキルアミノアルキル（メタ）アクリレート
からなる３級アミノ基を有する単量体並びにそれぞれの
４級化物からなる４級アンモニウム塩を有する単量体の
群より選ばれた少なくとも１種のカチオン性単量体 （５）、上記（Ｂ）成分の一部に上記（Ａ）及び（Ｂ）
成分以外のその他のビニル系単量体を用いる上記（４）
の機械パルプ含有紙の製造方法を提供するものである。Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object. As a result, (1) using paper pulp containing at least 5% by weight of mechanical pulp on a dry weight basis. In a paper containing mechanical pulp sized with a neutral sizing agent, the following (A) 50 to 95% by weight
And (B) a cationic polymer which is a vinyl-based copolymer having a conjugate of a structural unit corresponding to 5 to 50% by weight of each monomer and having a quaternary ammonium salt as an additive, 0.03-1 to dry weight of pulp
The present invention provides a paper containing mechanical pulp containing 0.1% by weight. (A) at least one hydrophobic monomer selected from the group consisting of styrene monomers and alkyl (meth) acrylates (B) consisting of dialkylaminoalkyl (meth) acrylamide and dialkylaminoalkyl (meth) acrylate At least one cationic monomer selected from the group consisting of a monomer having a tertiary amino group and a monomer having a quaternary ammonium salt composed of each quaternary compound. The paper containing mechanical pulp according to the above (1), in which a vinyl monomer other than the above components (A) and (B) is used as a part of the component (B), (3), and the neutralizing agent is ketene (1) or (2) above, which is at least one selected from the group consisting of a dimer sizing agent, a substituted cyclic dicarboxylic anhydride sizing agent and a rosin sizing agent for neutral papermaking. Mechanical pulp-containing paper, (4) containing mechanical pulp having a papermaking process of sizing using a neutral sizing agent at pH 6 to 9 using paper pulp containing at least 5% by weight of mechanical pulp on a dry weight basis In the paper production method, a vinyl copolymer obtained from a monomer containing 50 to 95% by weight of the following (A) and 5 to 50% by weight of the following (B). When a monomer having an amino group is used, an additive containing a cationic polymer having a quaternary ammonium salt that may be quaternized in at least one of the polymerization process and the polymerization after the polymerization of the vinyl copolymer is used. A process for producing mechanical pulp-containing paper, wherein the cationic polymer is used in the above-mentioned paper making step and the cationic polymer is used in an amount of 0.03 to 1% by weight based on the dry weight of the mechanical pulp; (B) Tertiary amino comprising dialkylaminoalkyl (meth) acrylamide and dialkylaminoalkyl (meth) acrylate, at least one hydrophobic monomer selected from the group consisting of alkyl monomer and alkyl (meth) acrylate At least one cationic monomer selected from the group consisting of a monomer having a group and a monomer having a quaternary ammonium salt comprising each quaternary compound (5), and a part of the component (B) The above (A) and (B)
(4) above using other vinyl monomers other than the component
And a method for producing paper containing mechanical pulp.
【０００７】次に本発明を詳細に説明する。本発明にお
いて、機械パルプとは、機械的に木材を繊維化して製造
したパルプであり、砕木パルプ、リファイナー砕木パル
プ、加圧砕木パルプ、サーモメカニカルパルプのような
高収率パルプや、これらの高収率パルプを原料とした紙
を離解脱墨した脱墨パルプ等をいう。Next, the present invention will be described in detail. In the present invention, mechanical pulp is pulp produced by mechanically fiberizing wood, and high-yield pulp such as groundwood pulp, refined groundwood pulp, pressurized groundwood pulp, and thermomechanical pulp, It refers to deinked pulp or the like obtained by disintegrating and deinking paper made from pulp with a high yield.
【０００８】また、中性サイズ剤とは、中性域の抄紙系
で使用されるサイズ剤であり、ケテンダイマー系サイズ
剤、置換環式ジカルボン酸無水物系サイズ剤、中性抄紙
用ロジン系サイズ剤等が挙げられ、これらは１種又は少
なくとも２種混合して使用でき、公知一般の市販品は使
用できる。ケテンダイマー系サイズ剤及び／または置換
環式ジカルボン酸無水物系サイズ剤のパルプスラリーに
対する添加率は、乾燥パルプに対し０．０１〜１％が好
ましく、より好ましくは０．０２〜０．５％である。ケ
テンダイマー系サイズ剤及び／または置換環式ジカルボ
ン酸無水物系サイズ剤の添加率が、０．０１％より少な
いとサイズ効果が十分でない場合があり、１％より多く
なるとコスト高や、抄紙系の汚れの原因となる場合があ
る。[0008] The neutral sizing agent is a sizing agent used in a papermaking system in a neutral region, and includes a ketene dimer sizing agent, a substituted cyclic dicarboxylic anhydride sizing agent, and a rosin-based sizing agent for neutral papermaking. Sizing agents and the like can be mentioned, and these can be used singly or as a mixture of at least two types, and known general commercial products can be used. The addition ratio of the ketene dimer-based sizing agent and / or the substituted cyclic dicarboxylic anhydride-based sizing agent to the pulp slurry is preferably 0.01 to 1%, more preferably 0.02 to 0.5%, based on the dry pulp. It is. If the addition ratio of the ketene dimer-based sizing agent and / or the substituted cyclic dicarboxylic anhydride-based sizing agent is less than 0.01%, the sizing effect may not be sufficient. It may cause stains.
【０００９】中性抄紙用ロジン系サイズ剤としては、特
願平９−６１７６２号に記載されているようなロジンの
一部を例えば疎水化する変性をしたタイプのものは使用
できる。中性抄紙用ロジン系サイズ剤のパルプスラリー
に対する添加率は、乾燥パルプに対し０．０１〜２％が
好ましく、より好ましくは０．０５〜１％である。添加
率が、０．０１％より少ないとサイズ効果が十分でない
場合があり、２％より多くなるとコスト高や、抄紙系の
汚れの原因となる場合がある。ケテンダイマー系サイズ
剤、置換環式ジカルボン酸無水物系サイズ剤及び中性抄
紙用ロジン系サイズ剤の中では、ケテンダイマー系サイ
ズ剤を使用することが、本発明に用いるカチオン性ポリ
マーを含有する添加剤と併用する場合に、ピッチ障害の
抑制効果、サイズ性の向上効果の点においてより好まし
い。As the rosin-based sizing agent for neutral papermaking, a rosin-modified sizing agent described in Japanese Patent Application No. 9-61762 can be used, which is obtained by modifying a part of rosin, for example, to make it hydrophobic. The rate of addition of the rosin-based sizing agent for neutral papermaking to the pulp slurry is preferably 0.01 to 2%, more preferably 0.05 to 1%, based on the dry pulp. If the addition ratio is less than 0.01%, the sizing effect may not be sufficient, and if it is more than 2%, the cost may increase and the papermaking system may be stained. Among ketene dimer sizing agents, substituted cyclic dicarboxylic anhydride sizing agents and rosin sizing agents for neutral papermaking, the use of ketene dimer sizing agents contains the cationic polymer used in the present invention. When used in combination with an additive, it is more preferable in terms of the effect of suppressing pitch disturbance and the effect of improving size.
【００１０】本発明に用いるカチオン性ポリマーは、上
記（Ａ）成分５０〜９５重量％及び上記（Ｂ）成分５〜
５０重量％の各単量体に対応する構成単位の結合を有
し、かつ４級アンモニウム塩を有するビニル系共重合体
であるが、上記（Ａ）成分５０〜９５重量％及び上記
（Ｂ）成分５〜５０重量％含有する単量体組成から得ら
れるビニル系共重合体であるカチオン性共重合体であっ
て、この（Ｂ）成分として３級アミノ基を有する単量体
を使用する場合には、このカチオン性共重合体の重合過
程及び重合後の少なくとも一方で４級化剤で４級化する
ことがある。上記（Ｂ）成分として３級アミノ基を有す
る単量体を使用した場合でも、その４級化した単量体を
使用した場合には、カチオン性共重合体の重合過程及び
重合後の少なくとも一方で４級化剤で４級化しなくても
よい場合がある。上記（Ａ）成分のスチレン系単量体と
しては、スチレン、ビニルトルエン、α−メチルスチレ
ン、ジビニルベンゼン等を挙げることができ、これらは
１種又は少なくとも２種用いることができる。また、上
記（Ａ）成分のアルキル（メタ）アクリレート（アルキ
ルアクリレート及びアルキルメタクリレートの少なくと
も１種を示し、以下、（メタ）の付加された化合物はこ
れを準用する。）としては、メチル（メタ）アクリレー
ト、エチル（メタ）アクリレート、ブチル（メタ）アク
リレート、シクロヘキシル（メタ）アクリレート、２−
エチルヘキシル（メタ）アクリレート、ラウリル（メ
タ）アクリレート、ステアリル（メタ）アクリレート等
の低級アルキル基、高級アルキル基又はシクロアルキル
基を有する単量体が挙げられ、これらは１種又は少なく
とも２種用いることができる。The cationic polymer used in the present invention comprises 50 to 95% by weight of the component (A) and 5 to 95% by weight of the component (B).
50% by weight of a vinyl copolymer having a bond of a structural unit corresponding to each monomer and having a quaternary ammonium salt, wherein 50% to 95% by weight of the component (A) and 50% by weight of the above (B) When a cationic copolymer which is a vinyl copolymer obtained from a monomer composition containing 5 to 50% by weight of a component and a monomer having a tertiary amino group is used as the component (B) In some cases, the cationic copolymer may be quaternized with a quaternizing agent in at least one of a polymerization step and after the polymerization. Even when a monomer having a tertiary amino group is used as the component (B), when the quaternized monomer is used, at least one of the polymerization process of the cationic copolymer and after the polymerization is performed. In some cases, it is not necessary to quaternize with a quaternizing agent. Examples of the styrene monomer as the component (A) include styrene, vinyl toluene, α-methylstyrene, divinylbenzene, and the like, and one or at least two of these can be used. The alkyl (meth) acrylate of the component (A) (which represents at least one of an alkyl acrylate and an alkyl methacrylate, and hereinafter the compound to which (meth) is added mutatis mutandis) is methyl (meth). Acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-
Monomers having a lower alkyl group, a higher alkyl group or a cycloalkyl group, such as ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate, may be used alone or in combination of at least two. it can.
【００１１】上記（Ｂ）成分の３級アミノ基を有する単
量体としてのジアルキルアミノアルキル（メタ）アクリ
ルアミドとしてはN,N-ジメチルアミノプロピル（メタ）
アクリルアミド等が挙げられる。また、ジアルキルアミ
ノアルキル（メタ）アクリレートとしてはN,N-ジメチル
アミノエチル（メタ）アクリレート等が挙げられる。上
記（Ｂ）成分の４級アンモニウム塩を有する単量体とし
ては、上記の３級アミノ基を有する単量体を、アルキル
ハライド、ベンジルハライド、アルキルトシレート、ア
ルキルメシレート、ジアルキルカーボネート、ジメチル
硫酸、エピハロヒドリン等の４級化剤との反応で４級ア
ンモニウム塩とする方法や、３−クロロ−２−ヒドロキ
シプロピルトリメチルアンモニウムクロライド等の４級
化剤との反応でビス４級アンモニウム塩とする方法等を
挙げることができる。これらの単量体は１種又は少なく
とも２種用いることができる。本発明のカチオン性ポリ
マーを得るには、上述したように、上記（Ｂ）成分のジ
アルキルアミノアルキル（メタ）アクリルアミド及び／
又はジアルキルアミノアルキル（メタ）アクリレートの
３級アミノ基を有する単量体を４級化物とした後、上記
（Ａ）成分の疎水性単量体と共重合する方法、上記
（Ｂ）成分の３級アミノ基を有する単量体と上記（Ａ）
成分の疎水性単量体を共重合する途中で４級化反応を行
う方法、あるいはその共重合後に４級化反応を行う方法
の何れでもよいが、カチオン性ポリマーを構成する全単
量体に対する上記（Ａ）成分の疎水性単量体の割合は５
０〜９５重量％であり、好ましくは５５〜９０重量％で
ある。疎水性単量体の割合が、５０重量％より少ない場
合、あるいは、９５重量％より多い場合はピッチ障害の
抑制の効果が得られ難く、紙のサイズ性も向上し難い。
上記（Ｂ）成分の３級アミノ基を有する単量体及び／又
はその４級化単量体の割合は５〜５０重量％で、好まし
くは１０〜４５重量％である。これらの割合が、５重量
％より少ない場合、あるいは、５０重量％より多い場合
はピッチ障害の抑制の効果が得られ難く、紙のサイズ性
も向上し難い。また、ジアルキルアミノアルキル（メ
タ）アクリルアミド４級化物を共重合単位に有する共重
合体の方が、ジアルキルアミノアルキル（メタ）アクリ
レート４級化物を共重合単位に有する共重合体に比べて
好ましく、耐加水分解性も良い。The dialkylaminoalkyl (meth) acrylamide as the monomer having a tertiary amino group of the component (B) is N, N-dimethylaminopropyl (meth).
Acrylamide and the like can be mentioned. Further, examples of the dialkylaminoalkyl (meth) acrylate include N, N-dimethylaminoethyl (meth) acrylate. As the monomer having a quaternary ammonium salt of the component (B), the above-mentioned monomer having a tertiary amino group may be an alkyl halide, benzyl halide, alkyl tosylate, alkyl mesylate, dialkyl carbonate, dimethyl sulfate. , Quaternary ammonium salts by reaction with a quaternizing agent such as epihalohydrin or bis-quaternary ammonium salts by reaction with a quaternizing agent such as 3-chloro-2-hydroxypropyltrimethylammonium chloride And the like. One or at least two of these monomers can be used. In order to obtain the cationic polymer of the present invention, as described above, the dialkylaminoalkyl (meth) acrylamide of component (B) and / or
Or a method in which a monomer having a tertiary amino group of dialkylaminoalkyl (meth) acrylate is converted into a quaternized product, and then copolymerized with the hydrophobic monomer of the component (A). Monomer having a secondary amino group and the above (A)
Either a method of performing a quaternization reaction in the course of copolymerizing the hydrophobic monomer of the component or a method of performing a quaternization reaction after the copolymerization may be used, but the method is based on all monomers constituting the cationic polymer. The ratio of the hydrophobic monomer of the component (A) is 5
It is 0 to 95% by weight, preferably 55 to 90% by weight. When the proportion of the hydrophobic monomer is less than 50% by weight or more than 95% by weight, it is difficult to obtain the effect of suppressing the pitch disturbance, and it is difficult to improve the sizing of the paper.
The proportion of the monomer having a tertiary amino group and / or the quaternary monomer of the component (B) is 5 to 50% by weight, preferably 10 to 45% by weight. When these proportions are less than 5% by weight or more than 50% by weight, it is difficult to obtain the effect of suppressing the pitch disturbance, and it is difficult to improve the sizing properties of the paper. Further, a copolymer having a quaternized dialkylaminoalkyl (meth) acrylamide in the copolymerized unit is more preferable than a copolymer having a quaternized dialkylaminoalkyl (meth) acrylate in the copolymerized unit. Good hydrolysis.
【００１２】本発明においては、上記の単量体の他に、
所望により、ジアルキルアミノアルキル（メタ）アクリ
ルアミド４級化物及び／又はジアルキルアミノアルキル
（メタ）アクリレート４級化物の一部を置き換える方法
で（メタ）アクリルアミド、（メタ）アクリロニトリ
ル、オレフィン、ビニルエーテル、アリルエステル、ビ
ニルケトン、ビニルスルホンアミド、N-ビニル-2-ピロ
リドン、（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-アルキル（メタ）アクリル
アミド、メチレンビスアクリルアミド、アリルアミン、
ジアリルアミン、ビニルピリジン、ビニルホルムアミ
ド、ビニルアセトアミド、ビニルアミン誘導体等のビニ
ル系単量体を併用することができる。これらは１種又は
少なくとも２種併用することができる。In the present invention, in addition to the above monomers,
If desired, (meth) acrylamide, (meth) acrylonitrile, olefin, vinyl ether, allyl ester, a method of substituting a part of dialkylaminoalkyl (meth) acrylamide quaternary and / or part of dialkylaminoalkyl (meth) acrylate quaternary Vinyl ketone, vinyl sulfonamide, N-vinyl-2-pyrrolidone, 2-hydroxyethyl (meth) acrylate, diacetone acrylamide, N-alkyl (meth) acrylamide, methylenebisacrylamide, allylamine,
Vinyl monomers such as diallylamine, vinylpyridine, vinylformamide, vinylacetamide, and vinylamine derivatives can be used in combination. These can be used alone or in combination of at least two kinds.
【００１３】共重合体の重合方法としては、上記単量体
をラジカル重合開始剤の存在下で溶液重合法あるいは塊
状重合法、乳化重合法、分散重合法等を用いて重合反応
を行う。必要に応じて溶剤を留去し、所定の固形分濃度
に調整することによりカチオン性ポリマー水性液を得る
ことができる。これをそのまま添加剤としてもよいが、
さらに他の添加物を加えたものを添加剤としてもよい。
カチオン性ポリマーは、パルプ原料中に配合された機械
パルプの乾燥重量に対して０．０３〜１重量％の割合で
パルプ原料に添加する。カチオン性ポリマーの添加率
が、機械パルプの乾燥重量に対して０．０３％より少な
いとピッチ障害の抑制効果や紙へのサイズ性の付与が十
分でなく、１％より多くなるとコスト高となる。As a method for polymerizing the copolymer, the above monomers are subjected to a polymerization reaction in the presence of a radical polymerization initiator using a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, a dispersion polymerization method or the like. The cationic polymer aqueous liquid can be obtained by removing the solvent as necessary and adjusting the solid content to a predetermined concentration. This may be used as it is as an additive,
What added another additive may be used as an additive.
The cationic polymer is added to the pulp raw material at a ratio of 0.03 to 1% by weight based on the dry weight of the mechanical pulp blended in the pulp raw material. If the addition ratio of the cationic polymer is less than 0.03% with respect to the dry weight of the mechanical pulp, the effect of suppressing the pitch obstacle and the sizing property to the paper are not sufficient, and if it exceeds 1%, the cost increases. .
【００１４】本発明に用いるカチオン性ポリマーを含有
する添加剤及び中性サイズ剤の抄紙工程における添加場
所については制限されることはないが、パルプスラリー
中でそれらが十分分散されることが望ましい。添加順序
についても制限はなく、添加剤が先で、次いで中性サイ
ズ剤の順に加えても良く、この逆でも良く、また、これ
らを同時に加えても良く、さらにこれらの混合液を加え
ても良い。また、填料、乾燥紙力増強剤、歩留り向上
剤、濾水性向上剤等の添加剤も、各々の紙種の要求され
る物性を発揮するために必要に応じて使用しても良い。
また、本発明における抄紙ｐＨは６〜９の範囲である。
ｐＨが６より低いとケテンダイマー系サイズ剤や置換環
式ジカルボン酸無水物系サイズ剤のサイズ効果が低下す
る。ｐＨが９より高い場合においても、中性サイズ剤の
サイズ効果が低下し、さらに、機械パルプの黄変等の問
題が有り、実用的でない。The location of the cationic polymer-containing additive and the neutral sizing agent used in the present invention in the papermaking process is not limited, but it is desirable that they are sufficiently dispersed in the pulp slurry. There is no limitation on the order of addition, the additives may be added first, then the neutral sizing agent may be added in that order, vice versa, or they may be added at the same time. good. Additives such as a filler, a dry paper strength enhancer, a retention improver, and a drainage improver may also be used as needed to exhibit the required physical properties of each paper type.
The papermaking pH in the present invention is in the range of 6-9.
If the pH is lower than 6, the sizing effect of the ketene dimer sizing agent or the substituted cyclic dicarboxylic anhydride sizing agent is reduced. Even when the pH is higher than 9, the sizing effect of the neutral sizing agent is reduced, and furthermore, there are problems such as yellowing of mechanical pulp, which is not practical.
【００１５】[0015]
【発明の実施の形態】疎水性単量体としてスチレン、
2-エチルヘキシル（メタ）アクリレート、メチルメタク
リレート、３級アミノ基を有する単量体として N,N-
ジメチルアミノプロピル（メタ）アクリルアミド、N,N-
ジメチルアミノエチル（メタ）アクリレートを使用し、
これらの少なくとも１種及びの少なくとも１種、好
ましくはのスチレン及びの N,N- ジメチルアミノプ
ロピルアクリルアミドを含有する単量体を共重合させ、
その共重合体をエピハロヒドリンで４級化したカチオン
性ポリマー水溶液を調製する。これらについて、共重合
割合を、（ａ）の単量体を５０〜８５重量％、の単
量体をエピハロヒドリンで４級化した単量体として１５
〜５０重量％としたカチオン性ポリマー、また、（ｂ）
上記の少なくとも１種、好ましくはスチレンを含有す
る単量体５５〜６０重量％、の4 級アンモニウム塩を
有する単量体の少なくとも１種としてアルキルハライド
で4 級化したN,N-ジメチルアミノプロピルメタクリルア
ミドを４０〜４５重量％共重合させたカチオン性ポリマ
ー、（ｃ）上記の少なくとも１種、好ましくはスチレ
ンを含有する単量体５５〜６０重量％、の少なくとも
１種、好ましくはアルキルハライドで4 級化したN,N-ジ
メチルアミノプロピルメタクリルアミド３９〜４１重量
％、（メタ）アクリアミド１〜４重量％を共重合させた
カチオン性ポリマーをそれぞれ含有するカチオン性ポリ
マー水性液からなる添加剤を調製する。乾燥重量基準で
機械パルプの含有率１０〜９０重量％とした原料パルプ
を用い、ケテンダイマー系サイズ剤の添加量を０．１〜
０．２重量％（対乾燥パルプ）とし、上記添加剤を上記
（ａ）〜（ｃ）のカチオン性ポリマー分として０．０２
〜０．０８重量％（対機械パルプ）添加し、抄紙する。
また、ケテンダイマー系サイズ剤の代わりに、アルケニ
ルコハク酸無水物系サイズ剤を０．１〜０．２重量％
（対乾燥パルプ）用い、機械パルプの含有率を８〜１２
重量％とし、上記添加剤を上記（ａ）〜（ｃ）のカチオ
ン性ポリマー分として０．５〜０．９重量％（対機械パ
ルプ）添加し、抄紙する。また、アルケニルコハク酸無
水物系サイズ剤の代わりに、中性抄紙用ロジン系サイズ
剤を０．２〜０．４重量％（対乾燥パルプ）用い、機械
パルプの含有率を２０〜４０重量％とし、上記添加剤を
上記（ａ）〜（ｃ）のカチオン性ポリマー分として０．
２５〜０．４５重量％（対機械パルプ）添加し、抄紙す
る。このようにすると、サイズ剤定着量が多く、ロール
等の汚れが少ないとともに、得られた紙はサイズ度が良
くなるが、その理由は、上記（ａ）〜（ｃ）のカチオン
性ポリマーを含有する添加剤の使用により、機械パルプ
に付随するピッチや中性サイズ剤が紙料中に保持され易
く、したがってフェルトやロール等の抄紙用具に付着し
難くなるためと解される。これは、上記（ａ）〜（ｃ）
のカチオン性ポリマーが疎水性単量体に対応する構成単
位からなる疎水性部分と、カチオン性単量体に対応する
構成単位からなる親水性部分をバランス良く有してお
り、その疎水性部分とピッチや中性サイズ剤の疎水性部
分との親和性が良く、その親水性部分は水との親和性が
良いためと考えられるが、この考え方に限られるもので
はない。DETAILED DESCRIPTION OF THE INVENTION Styrene as a hydrophobic monomer,
2-Ethylhexyl (meth) acrylate, methyl methacrylate, N, N-
Dimethylaminopropyl (meth) acrylamide, N, N-
Using dimethylaminoethyl (meth) acrylate,
Copolymerizing a monomer containing at least one of these and at least one, preferably styrene, and N, N-dimethylaminopropylacrylamide,
A cationic polymer aqueous solution obtained by quaternizing the copolymer with epihalohydrin is prepared. For these, the copolymerization ratio was 15 to 85% by weight of the monomer (a) and 15% as the monomer obtained by quaternizing the monomer with epihalohydrin.
(B) a cationic polymer having a concentration of about 50% by weight;
N, N-dimethylaminopropyl quaternized with an alkyl halide as at least one of the monomers having a quaternary ammonium salt of at least one of the above, preferably 55 to 60% by weight of a monomer containing styrene. A cationic polymer obtained by copolymerizing 40 to 45% by weight of methacrylamide, and (c) at least one of the above-mentioned at least one, preferably 55 to 60% by weight of a monomer containing styrene, preferably an alkyl halide. An additive consisting of a cationic polymer aqueous liquid containing a cationic polymer obtained by copolymerizing 39 to 41% by weight of quaternized N, N-dimethylaminopropyl methacrylamide and 1 to 4% by weight of (meth) acrylamide is used. Prepare. Using raw pulp having a mechanical pulp content of 10 to 90% by weight on a dry weight basis, the addition amount of the ketene dimer sizing agent is 0.1 to
0.2% by weight (based on dry pulp), and the additive was 0.02% as the cationic polymer component of (a) to (c).
0.08% by weight (based on mechanical pulp) is added, and paper is made.
Also, instead of the ketene dimer sizing agent, an alkenyl succinic anhydride sizing agent is used in an amount of 0.1 to 0.2% by weight.
(Vs. dry pulp), using 8 to 12 mechanical pulp
% By weight, and the above additives are added in the amount of 0.5 to 0.9% by weight (based on mechanical pulp) as the cationic polymer of (a) to (c), and papermaking is performed. Further, instead of the alkenyl succinic anhydride sizing agent, a rosin sizing agent for neutral papermaking is used in an amount of 0.2 to 0.4% by weight (based on dry pulp), and the content of the mechanical pulp is adjusted to 20 to 40% by weight. And the above additives are added in an amount of 0.1 as the cationic polymer component of (a) to (c).
25 to 0.45% by weight (based on mechanical pulp) is added and the paper is made. By doing so, the fixing amount of the sizing agent is large, the dirt on the rolls and the like is small, and the degree of sizing of the obtained paper is improved. This is because the cationic polymer of (a) to (c) It is understood that the use of such additives makes it easy for the pitch and the neutral sizing agent attached to the mechanical pulp to be retained in the stock, and hence to be less likely to adhere to papermaking tools such as felts and rolls. This corresponds to the above (a) to (c)
The cationic polymer has a hydrophobic portion composed of structural units corresponding to a hydrophobic monomer, and a hydrophilic portion composed of structural units corresponding to a cationic monomer in a well-balanced manner. It is considered that the affinity with the hydrophobic portion of the pitch or neutral sizing agent is good, and the hydrophilic portion has a good affinity with water, but the present invention is not limited to this concept.
【００１６】[0016]
【実施例】以下本発明の実施例を挙げて具体的に説明す
るが、本発明はこれら実施例のみに限定されるものでは
ない。なお、以下の実施例、比較例において、％とある
ものは特に断わりの無い限り、固形分重量％を意味す
る。EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “%” means “% by weight of solid content” unless otherwise specified.
【００１７】実施例用カチオン性ポリマー水性液（添加
剤）の製造例１ 攪拌機、温度計、冷却管を備え付けた１リットルの４つ
口フラスコに、スチレン７２．９ｇ、２−エチルヘキシ
ルアクリレート９．２ｇ、N-エチル-N,N- ジメチル−３
−（メタクリロイルアミノプロピル）アンモニウムブロ
マイド５７．６ｇ、５０％アクリルアミド水溶液７．１
ｇ、イソプロピルアルコール１５０ｇ、アゾビスイソブ
チロニトリル２ｇを加え、窒素気流中、８０℃で５時間
反応した。次に水４２２ｇを加え、よく攪拌して水に分
散させ、冷却し、カチオン性ポリマー水性液Ａを７００
ｇ得た。その固形分は２０％であった。全単量体に対す
る各単量体の重量百分率は、スチレン５０．９％、２−
エチルヘキシルアクリレート６．４％、N-エチル-N,N-
ジメチル−３−（メタクリロイルアミノプロピル）アン
モニウムブロマイド４０．２％、アクリルアミド２．５
％であり、スチレンと２−エチルヘキシルアクリレート
を合わせた疎水性単量体の合計は５７．３％である。使
用した単量体の重量組成を表１に示した。Production Example 1 of Cationic Polymer Aqueous Liquid (Additive) for Examples 12.9 g of styrene and 9.2 g of 2-ethylhexyl acrylate were placed in a 1-liter four-necked flask equipped with a stirrer, a thermometer and a condenser. , N-ethyl-N, N-dimethyl-3
-(Methacryloylaminopropyl) ammonium bromide 57.6 g, 50% acrylamide aqueous solution 7.1
g, 150 g of isopropyl alcohol and 2 g of azobisisobutyronitrile, and reacted at 80 ° C. for 5 hours in a nitrogen stream. Next, 422 g of water was added, and the mixture was stirred well to be dispersed in water, and cooled, and the cationic polymer aqueous liquid A was mixed with 700 g of water.
g was obtained. Its solids content was 20%. The weight percentage of each monomer with respect to all the monomers was 50.9% of styrene, 2-
Ethylhexyl acrylate 6.4%, N-ethyl-N, N-
Dimethyl-3- (methacryloylaminopropyl) ammonium bromide 40.2%, acrylamide 2.5
%, And the total amount of hydrophobic monomers obtained by combining styrene and 2-ethylhexyl acrylate is 57.3%. Table 1 shows the weight composition of the monomers used.
【００１８】実施例用カチオン性ポリマー水性液（添加
剤）の製造例２ 攪拌機、温度計、冷却管を備え付けた１リットルの４つ
口フラスコに、スチレン８３．３ｇ、N,N-ジメチルアミ
ノプロピルアクリルアミド３１．２ｇ、ベンゼン１１７
ｇ、アゾビスイソブチロニトリル２ｇを入れ、窒素気流
中、８０℃で５時間反応した。次に３％酢酸溶液４２３
ｇを加え、９７℃まで加熱しベンゼンを留去した。留去
後、留去した分の水を加え、エピクロルヒドリン１８．
５ｇを加え、８０℃で３時間４級化反応を行った後、冷
却しカチオン性ポリマー水性液Ｂを６７０ｇ得た。その
固形分は２０％であった。使用した単量体の重量組成を
表１に示した。Production Example 2 of Cationic Polymer Aqueous Liquid (Additive) for Examples In a 1-liter four-necked flask equipped with a stirrer, a thermometer and a condenser, 83.3 g of styrene and N, N-dimethylaminopropyl were added. Acrylamide 31.2 g, benzene 117
g, 2 g of azobisisobutyronitrile, and reacted at 80 ° C. for 5 hours in a nitrogen stream. Next, a 3% acetic acid solution 423
g was added and heated to 97 ° C. to distill off benzene. After the distillation, the distilled water is added, and epichlorohydrin.
After adding 5 g and performing a quaternization reaction at 80 ° C. for 3 hours, the mixture was cooled to obtain 670 g of an aqueous cationic polymer solution B. Its solids content was 20%. Table 1 shows the weight composition of the monomers used.
【００１９】実施例用カチオン性ポリマー水性液（添加
剤）の製造例３〜６ 表１に示す単量体の種類及び重量組成を変える以外は、
実施例用カチオン性共重合体の製造例２と同様にしてカ
チオン性ポリマー水性液Ｃ、Ｄ、Ｅ、Ｆを製造した。共
重合体の固形分濃度は２０％になるように調整した。使
用した単量体の重量組成を表１に示した。Preparation Examples of Cationic Polymer Aqueous Liquids (Additives) for Examples 3 to 6 Except for changing the type and weight composition of the monomers shown in Table 1,
Cationic polymer aqueous liquids C, D, E, and F were produced in the same manner as in Production Example 2 of the cationic copolymer for the example. The solid content concentration of the copolymer was adjusted to 20%. Table 1 shows the weight composition of the monomers used.
【００２０】比較例用カチオン性ポリマー水性液（添加
剤）の製造例１ 特開昭５３−４１５０７号公報の実施例１に従い、次の
様にしてN,N-ジメチル-N-(β- ヒドロキシエチル)-N-(
β- メタクリルオキシエチル) アンモニウムアセテート
のホモポリマーを製造した。１９．３部の氷酢酸、６
０．５部の脱イオン水及び２８．６部の０．１５％Ｆｅ
ＳＯ4 ・Ｈ2 Ｏ水溶液を加圧釜に入れた。窒素で釜内容
物から酸素を除き、６０℃に加熱し、ジメチルアミノエ
チルメタクリレート４７．８部、ペルオキソ硫酸アンモ
ニウム９．８部を脱イオン水１１６．２部で溶解した水
溶液及び二亜硫酸ナトリウム９．８部を脱イオン水１１
６．２部で溶解した水溶液を３時間後に加えた。６０℃
で更に３０分間保ち、次いで４０℃に下げ、その温度で
エチレンオキサイド１４０．７部を徐々に添加し、カチ
オン性ポリマー水性液Ｇを得た。使用した単量体の重量
組成を表１に示した。Preparation Example 1 of Cationic Polymer Aqueous Liquid (Additive) for Comparative Example According to Example 1 of JP-A-53-41507, N, N-dimethyl-N- (β-hydroxy) was prepared as follows. (Ethyl) -N- (
A homopolymer of β-methacryloxyethyl) ammonium acetate was prepared. 19.3 parts of glacial acetic acid, 6
0.5 parts deionized water and 28.6 parts 0.15% Fe
The aqueous solution of SO 4 · H 2 O was put into a pressure cooker. The contents of the kettle were deoxygenated with nitrogen, heated to 60 ° C., and an aqueous solution in which 47.8 parts of dimethylaminoethyl methacrylate and 9.8 parts of ammonium peroxosulfate were dissolved in 116.2 parts of deionized water, and 9.8 parts of sodium disulfite. Deionized water 11
The aqueous solution dissolved in 6.2 parts was added after 3 hours. 60 ° C
, And then lowered to 40 ° C., and at that temperature, 140.7 parts of ethylene oxide were gradually added to obtain a cationic polymer aqueous liquid G. Table 1 shows the weight composition of the monomers used.
【００２１】比較例用カチオン性ポリマー水性液（添加
剤）の製造例２、３ 表１に示す単量体の種類及び重量組成に変える以外は、
上記比較例用カチオン性重合体の製造例１の手順で、カ
チオン性ポリマー水性液Ｈ、Ｉの重合体を得た。Preparation Examples 2 and 3 of Comparative Cationic Polymer Aqueous Liquids (Additives) Except for changing the type and weight composition of the monomers shown in Table 1,
According to the procedure of Production Example 1 of the cationic polymer for the comparative example, polymers of the aqueous cationic polymer liquids H and I were obtained.
【００２２】比較例用カチオン性ポリマー水性液（添加
剤）の製造例４ 表１に示す単量体の種類及び重量組成に変える以外は、
実施例用カチオン性共重合体の製造例２と同様にして比
較例用カチオン性ポリマー水性液Ｊを製造した。共重合
体の固形分濃度は２０％になるように調整した。Preparation Example 4 of Cationic Polymer Aqueous Liquid (Additive) for Comparative Example Except for changing the type and weight composition of the monomers shown in Table 1,
A cationic polymer aqueous liquid J for a comparative example was produced in the same manner as in Production Example 2 for the cationic copolymer for the example. The solid content concentration of the copolymer was adjusted to 20%.
【００２３】[0023]
【表１】 [Table 1]
【００２４】実施例１ 砕木パルプ、サーモメカニカルパルプ、漂白広葉樹クラ
フトパルプを乾燥重量基準で５／５／９０の比率（機械
パルプ１０％）で混合したパルプの２．５％パルプスラ
リー（カナディアン スタンダード フリーネス ３８
０ｍｌ）を調製し、これに軽質炭酸カルシウム（タマパ
ール１２１Ｓ、奥多摩工業株式会社製）を対乾燥パルプ
１５％添加し、２分間攪拌後、硫酸バンドを対乾燥パル
プ０．５％、両性澱粉（Ｃａｔｏ３２１０、日本ＮＳＣ
株式会社製）を対乾燥パルプ０．６％、アルキルケテン
ダイマー系サイズ剤（ＡＳ２６３、日本ＰＭＣ株式会社
製）を対乾燥パルプ０．１％、それぞれ攪拌しながらこ
の順で添加した。添加の間隔は１分間とした。その後カ
チオン性ポリマー水性液Ａをカチオン性ポリマー分とし
て対乾燥パルプ０．００５％（対機械パルプ０．０５
％）添加し、１分間攪拌した。さらに、得られた紙料を
ｐＨ８の希釈用水で０．２５％に希釈し、歩留り向上剤
（ＮＲ１２ＭＬＳ、ハイモロック株式会社製）を対乾燥
パルプ０．０２％添加し、３０秒間攪拌した。ここでの
抄紙ｐＨは７．８であった。 ノーブルアンドウッド社
製手抄き装置を使用し、得られた紙料から湿紙を作成し
た。抄紙温度は４５℃とした。湿紙をプレス後、１００
℃のドラムドライヤーで80秒間乾燥し、目的とする手抄
紙とした。坪量は７０ｇ／ｍ2 に調整した。Example 1 A 2.5% pulp slurry (Canadian Standard Freeness) of pulp obtained by mixing groundwood pulp, thermomechanical pulp, and bleached hardwood kraft pulp in a ratio of 5/5/90 (mechanical pulp 10%) on a dry weight basis 38
0 ml), light calcium carbonate (Tamapearl 121S, manufactured by Okutama Kogyo Co., Ltd.) was added to the dried pulp at 15%, and the mixture was stirred for 2 minutes. Then, the sulfate band was added to the dried pulp at 0.5% and amphoteric starch (Cato3210). , NSC Japan
0.6% of dry pulp and 0.1% of alkyl ketene dimer-based sizing agent (AS263, manufactured by Nippon PMC Co., Ltd.) were added in this order with stirring. The interval between additions was 1 minute. Thereafter, the cationic polymer aqueous liquid A was used as a cationic polymer component in an amount of 0.005% to dry pulp (0.05 to mechanical pulp).
%) And stirred for 1 minute. Further, the obtained paper stock was diluted to 0.25% with water for dilution at pH 8, and a retention aid (NR12MLS, manufactured by Himoloc Co., Ltd.) was added to 0.02% of the dry pulp, followed by stirring for 30 seconds. The papermaking pH here was 7.8. A wet paper was prepared from the obtained stock using a hand-making apparatus manufactured by Noble & Wood. The papermaking temperature was 45 ° C. After pressing the wet paper, 100
It was dried for 80 seconds with a drum dryer at ℃ to obtain the desired hand-made paper. The basis weight was adjusted to 70 g / m 2 .
【００２５】作成した手抄紙につき、ＪＩＳ Ｐ−８１
２２に準じ、抄紙直後および調湿１日後のステキヒトサ
イズ度を測定した。調湿条件は６５％ＲＨ、２０℃とし
た。また、熱分解ガスクロマトグラフにより、紙中アル
キルケテンダイマー量を測定した。それらの結果を表２
に示す。According to the hand-made paper made, JIS P-81
According to No. 22, the degree of Stigecht sizing immediately after papermaking and one day after humidity control was measured. Humidity control conditions were 65% RH and 20 ° C. Further, the amount of alkyl ketene dimer in the paper was measured by pyrolysis gas chromatography. Table 2 shows the results.
Shown in
【００２６】また、抄紙機のプレスロールが汚れる現象
を模した次の試験を行い、ピッチ障害の抑制効果を調べ
た。すなわち、上記手抄き実験においてＡＳ２６３を２
倍の０．２％とする。また、希釈用水による希釈濃度を
０．７％とする以外は同様にして紙料を調製した。得ら
れた紙料をロール汚れ試験機（抄紙装置の汚れを試験す
る試験装置であり、第１図に概略説明図を示す）に供給
して２時間後及び５時間後のプレスロールの汚れ具合を
調べた。汚れの評価は目視で行い、プレスロールの汚れ
が最も著しいものを「１０」、汚れ無しを「０」とする
指数を用いた段階評価で表示した。その結果を表２に示
す。なお、上記ＡＳ２６３の添加率を２倍にしたのは、
効果の差を際立たせるためであり、これらの通常の添加
量の抄紙系における抄紙を長時間続けた場合とは相関関
係がある。Further, the following test was conducted to simulate the phenomenon that the press roll of a paper machine becomes dirty, and the effect of suppressing pitch disturbance was examined. That is, in the above hand-making experiment, AS263 was added by 2
Double the value to 0.2%. Also, a stock was prepared in the same manner except that the concentration of the diluted water was 0.7%. The obtained paper stock is supplied to a roll dirt tester (a test device for testing dirt of a paper making apparatus, and a schematic explanatory diagram is shown in FIG. 1). Was examined. The evaluation of the stain was visually performed, and the result was indicated by a grade using an index of “10” when the stain on the press roll was most remarkable and “0” when there was no stain on the press roll. Table 2 shows the results. The reason why the addition ratio of AS263 was doubled was that
This is in order to highlight the difference in the effects, and there is a correlation with the case where the papermaking is continued for a long time in the papermaking system with the usual addition amount.
【００２７】なお、第１図は、紙料投入口１から紙料を
ワイヤー装置２に順次供給し、重力脱水した後、第１ロ
ール３と主ロール４でプレスし、さらに主ロール４と第
２ロール５でプレスして脱水した湿紙６を得る装置を示
すもので、その具体的構造は以下の通りである。 主ロール：直径約２５ｃｍ、幅約４０ｃｍ 第１ロール：直径約１４．５ｃｍ、幅約４０ｃｍ 第２ロール：直径約１０ｃｍ、幅約４０ｃｍ ワイヤー：幅約３５ｃｍ この装置において、第１ロール、第２ロールの主ロール
に対する圧はそれぞれのロールの自重によるもので、第
２ロール通過後の湿紙の水分率は６０％である。試験条
件は、抄速１．５ｍ／分、紙料温度４５℃、ロール温度
３４〜３６℃、抄幅１５ｃｍとした。第２ロールに対す
る汚れを目視により調べた。FIG. 1 shows that the stock is sequentially supplied to the wire device 2 from the stock inlet 1 and dewatered by gravity, then pressed by the first roll 3 and the main roll 4, and further This shows an apparatus for obtaining dewatered wet paper 6 by pressing with two rolls 5, and its specific structure is as follows. Main roll: about 25 cm in diameter, about 40 cm in width First roll: about 14.5 cm in diameter, about 40 cm in width Second roll: about 10 cm in diameter, about 40 cm in width Wire: about 35 cm in width In this device, the first roll and the second roll Is based on the weight of each roll, and the moisture content of the wet paper web after passing through the second roll is 60%. The test conditions were as follows: papermaking speed 1.5 m / min, stock temperature 45 ° C, roll temperature 34 to 36 ° C, papermaking width 15 cm. The dirt on the second roll was visually inspected.
【００２８】実施例２ 砕木パルプ、サーモメカニカルパルプ、漂白広葉樹クラ
フトパルプを乾燥重量基準で１５／１５／７０の比率
（機械パルプ３０％）で混合したパルプの２．５％パル
プスラリー（カナディアン スタンダード フリーネス
２８０ｍｌ）を使用し、カチオン性ポリマー水性液Ａ
の添加率をカチオン性ポリマー分として対乾燥パルプ
０．０２％（対機械パルプ ０．０６７％）とした以外
は実施例１と同様にして手抄紙を作成し、サイズ度の測
定を行い、サイズ剤の定着量を求めた。また、実施例１
と同様にしてロール汚れ試験を行った。それらの結果を
表２に示す。Example 2 A 2.5% pulp slurry (Canadian Standard Freeness) of pulp obtained by mixing groundwood pulp, thermomechanical pulp, and bleached hardwood kraft pulp in a ratio of 15/15/70 (mechanical pulp 30%) on a dry weight basis 280 ml) of the cationic polymer aqueous liquid A
Hand paper was prepared in the same manner as in Example 1 except that the addition rate of the cationic polymer was 0.02% to dry pulp (0.067% to mechanical pulp), and the sizing degree was measured. The fixing amount of the agent was determined. Example 1
A roll dirt test was performed in the same manner as described above. Table 2 shows the results.
【００２９】実施例３〜７ カチオン性ポリマー水性液Ａに代えて、各々カチオン性
ポリマー水性液Ｂ、Ｃ、Ｄ、Ｅ、Ｆを使用したこと以外
は実施例２と同様にして手抄紙を作成し、実施例２と同
様にサイズ度の測定を行い、サイズ剤の定着量を求め
た。また、実施例２と同様にロール汚れ試験を行った。
それらの結果を表２に示す。Examples 3 to 7 Hand papers were prepared in the same manner as in Example 2 except that the aqueous cationic polymer solutions B, C, D, E and F were used in place of the aqueous cationic polymer solution A, respectively. Then, the sizing degree was measured in the same manner as in Example 2, and the fixing amount of the sizing agent was determined. Further, a roll dirt test was performed in the same manner as in Example 2.
Table 2 shows the results.
【００３０】実施例８ 砕木パルプ、サーモメカニカルパルプ、高収率パルプを
原料とした紙の脱墨パルプ、漂白広葉樹クラフトパルプ
を乾燥重量基準で３０／３０／３０／１０の比率（機械
パルプ９０％）で混合したパルプの２．５％パルプスラ
リー（カナディアン スタンダード フリーネス １９
０ｍｌ）を使用し、上記ＡＳ２６３を対乾燥パルプ０．
２％、カチオン性ポリマー水性液Ａのカチオン性ポリマ
ー分としての添加率を対乾燥パルプ０．０３％（対機械
パルプ０．０３３％）としたこと以外は実施例１と同様
にして手抄紙を作成し、実施例１と同様にしてサイズ度
の測定を行い、サイズ剤の定着量を求めた。また、実施
例１と同様にロール汚れ試験を行った。それらの結果を
表２に示す。Example 8 Groundwood pulp, thermomechanical pulp, paper deinked pulp made of high yield pulp, and bleached hardwood kraft pulp at a ratio of 30/30/30/10 by dry weight (mechanical pulp 90%) 2.5% pulp slurry (Canadian Standard Freeness 19)
0 ml) and the AS263 to dry pulp 0.
Hand paper was prepared in the same manner as in Example 1 except that the addition ratio of the cationic polymer aqueous liquid A was 2% and the cationic polymer content was 0.03% based on dry pulp (0.033% based on mechanical pulp). The sizing degree was measured in the same manner as in Example 1 to determine the fixing amount of the sizing agent. Further, a roll dirt test was performed in the same manner as in Example 1. Table 2 shows the results.
【００３１】比較例１〜４ カチオン性ポリマー水性液Ａに代えて、各々カチオン性
ポリマー水性液Ｇ、Ｈ、Ｉ、Ｊを使用したこと以外は実
施例２と同様にして手抄紙を作成し、実施例２と同様に
サイズ度の測定を行い、サイズ剤の定着量を求めた。ま
た、実施例２と同様にロール汚れ試験を行った。それら
の結果を表２に示す。Comparative Examples 1 to 4 Hand papers were prepared in the same manner as in Example 2 except that the aqueous cationic polymer solutions G, H, I and J were used in place of the aqueous cationic polymer solution A, respectively. The sizing degree was measured in the same manner as in Example 2 to determine the fixing amount of the sizing agent. Further, a roll dirt test was performed in the same manner as in Example 2. Table 2 shows the results.
【００３２】比較例５ カチオン性ポリマー水性液Ａのカチオン性ポリマー分と
しての添加率を対乾燥パルプ０．００５％（対機械パル
プ０．０１７％）としたこと以外は実施例２と同様にし
て手抄紙を作成し、実施例２と同様にサイズ度の測定を
行い、サイズ剤の定着量を求めた。また、実施例２と同
様にロール汚れ試験を行った。それらの結果を表２に示
す。Comparative Example 5 The same procedure as in Example 2 was carried out except that the addition ratio of the cationic polymer aqueous liquid A as the cationic polymer component was 0.005% to dry pulp (0.017% to mechanical pulp). Hand paper was prepared and the sizing degree was measured in the same manner as in Example 2 to determine the fixing amount of the sizing agent. Further, a roll dirt test was performed in the same manner as in Example 2. Table 2 shows the results.
【００３３】比較例６ カチオン性ポリマー水性液Ａのカチオン性ポリマー分と
しての添加率を対乾燥パルプ０．０２％（対機械パルプ
０．０２２％）としたこと以外は実施例８と同様にして
手抄紙を作成し、実施例８と同様にサイズ度の測定を行
い、サイズ剤の定着量を求めた。また、実施例８と同様
にロール汚れ試験を行った。それらの結果を表２に示
す。なお、ロール汚れ試験の評価は「１０」であった
が、比較例１よりもその程度は劣っていたので「１０
（以上）」とした。Comparative Example 6 The same procedure as in Example 8 was carried out except that the addition ratio of the cationic polymer aqueous liquid A as the cationic polymer component was 0.02% to dry pulp (0.022% to mechanical pulp). Hand paper was prepared and the sizing degree was measured in the same manner as in Example 8 to determine the fixing amount of the sizing agent. Further, a roll dirt test was performed in the same manner as in Example 8. Table 2 shows the results. The evaluation of the roll dirt test was “10”, which was inferior to Comparative Example 1.
(Or more). "
【００３４】[0034]
【表２】 [Table 2]
【００３５】実施例１０ アルキルケテンダイマー系サイズ剤に代えて、アルケニ
ルコハク酸無水物系サイズ剤（ＡＳ２９０、日本ＰＭＣ
株式会社製）を対乾燥パルプ０．１％使用し、カチオン
性ポリマー水性液Ａの添加率を対乾燥パルプ０．０７％
（対機械パルプ０．２３％）としたこと以外は実施例２
と同様にして手抄紙を作成し、実施例２と同様にサイズ
度の測定を行った。抄紙ｐＨは７．８であった。熱分解
ガスクロマトグラフにより、得られた紙の中のアルケニ
ルコハク酸無水物量を測定し、ケテンダイマー系サイズ
剤を使用した上記実施例の場合と同様にして、サイズ剤
の定着量を求めた。また、アルキルケテンダイマー系サ
イズ剤に代えて、上記ＡＳ２９０を対乾燥パルプ０．２
％使用したこと以外は上記実施例１と同様にして、ロー
ル汚れ試験を行った。その評価方法は実施例１に準じて
行った。それらの結果を表３に示す。Example 10 An alkenyl succinic anhydride sizing agent (AS290, Nippon PMC) was used in place of the alkyl ketene dimer sizing agent.
Co., Ltd.) was used in an amount of 0.1% with respect to the dry pulp.
(Example 2) except that (with respect to mechanical pulp 0.23%)
A hand paper was prepared in the same manner as described above, and the sizing degree was measured in the same manner as in Example 2. The papermaking pH was 7.8. The amount of alkenyl succinic anhydride in the obtained paper was measured by pyrolysis gas chromatography, and the fixing amount of the sizing agent was determined in the same manner as in the above example using a ketene dimer sizing agent. Also, instead of the alkyl ketene dimer-based sizing agent, the above-mentioned AS290 was added to dry pulp 0.2%.
A roll stain test was performed in the same manner as in Example 1 except that% was used. The evaluation method was performed according to Example 1. Table 3 shows the results.
【００３６】実施例１１〜１５ カチオン性ポリマー水性液Ａに代えて、各々カチオン性
ポリマー水性液Ｂ、Ｃ、Ｄ、Ｅ、Ｆを使用したこと以外
は実施例１０と同様にして手抄紙を作成し、実施例１０
と同様にサイズ度の測定を行い、サイズ剤の定着量を求
めた。また、実施例１０と同様にロール汚れ試験を行っ
た。それらの結果を表３に示す。Examples 11 to 15 Hand-made paper was prepared in the same manner as in Example 10, except that the aqueous cationic polymer solutions B, C, D, E and F were used in place of the aqueous cationic polymer solution A, respectively. And Example 10
The sizing degree was measured in the same manner as in Example 1 to determine the fixing amount of the sizing agent. Further, a roll contamination test was performed in the same manner as in Example 10. Table 3 shows the results.
【００３７】比較例７〜１０ カチオン性ポリマー水性液Ａに代えて、各々カチオン性
ポリマー水性液Ｇ、Ｈ、Ｉ、Ｊを使用したこと以外は実
施例１０と同様にして手抄紙を作成し、実施例１０と同
様にサイズ度の測定を行い、サイズ剤の定着量を求め
た。また、実施例１０と同様にロール汚れ試験を行っ
た。それらの結果を表３に示す。Comparative Examples 7 to 10 Hand papers were prepared in the same manner as in Example 10 except that the aqueous cationic polymer solutions G, H, I and J were used instead of the aqueous cationic polymer solution A, respectively. The sizing degree was measured in the same manner as in Example 10, and the fixing amount of the sizing agent was determined. Further, a roll contamination test was performed in the same manner as in Example 10. Table 3 shows the results.
【００３８】[0038]
【表３】 [Table 3]
【００３９】実施例１６ 硫酸アルミニウムの添加率を１．５％とし、アルキルケ
テンダイマー系サイズ剤に代えて中性抄紙用ロジン系サ
イズ剤（ＣＣ１６７、日本ＰＭＣ株式会社製）を対乾燥
パルプ０．３％使用し、カチオン性ポリマー水性液Ａの
添加率をカチオン性ポリマー分として対乾燥パルプ０．
１％（対機械パルプ０．３３％）としたこと以外は実施
例２と同様にして手抄紙を作成し、実施例２と同様にサ
イズ度の測定を行った。抄紙ｐＨは７．６であった。手
抄紙を酸性条件下でほぐし、エーテル抽出を行い、ゲル
浸透クロマトグラフで有機相中のロジン成分量を測定
し、ケテンダイマー系サイズ剤を使用した上記実施例１
の場合と同様にして、サイズ剤の定着量を求めた。ま
た、アルキルケテンダイマー系サイズ剤に代えて上記Ｃ
Ｃ１６７を対乾燥パルプ０．５％使用したこと以外は上
記実施例１と同様にして、ロール汚れ試験を行った。そ
の評価方法は実施例１に準じて行った。それらの結果を
表４に示す。Example 16 A rosin-based sizing agent for neutral papermaking (CC167, manufactured by Nippon PMC Co., Ltd.) was used in place of an alkyl ketene dimer-based sizing agent with an addition ratio of aluminum sulfate of 1.5%. 3%, and the addition ratio of the cationic polymer aqueous liquid A to the dry pulp was 0.1% based on the cationic polymer content.
A hand-made paper was prepared in the same manner as in Example 2 except that 1% (vs. mechanical pulp 0.33%), and the sizing degree was measured in the same manner as in Example 2. The papermaking pH was 7.6. Hand paper was loosened under acidic conditions, extracted with ether, the amount of rosin component in the organic phase was measured by gel permeation chromatography, and the above Example 1 using a ketene dimer sizing agent was performed.
In the same manner as in the above case, the fixing amount of the sizing agent was determined. Further, instead of the alkyl ketene dimer sizing agent, the above C
A roll dirt test was performed in the same manner as in Example 1 except that C167 was used in an amount of 0.5% to dry pulp. The evaluation method was performed according to Example 1. Table 4 shows the results.
【００４０】実施例１７〜２１ カチオン性ポリマー水性液Ａに代えて、各々カチオン性
ポリマー水性液Ｂ、Ｃ、Ｄ、Ｅ、Ｆを使用したこと以外
は実施例１６と同様にして手抄紙を作成し、実施例１６
と同様にサイズ度の測定を行い、サイズ剤の定着量を求
めた。また、実施例１６と同様にロール汚れ試験を行っ
た。それらの結果を表４に示す。Examples 17 to 21 Hand paper was prepared in the same manner as in Example 16 except that the aqueous cationic polymer solutions B, C, D, E and F were used in place of the aqueous cationic polymer solution A, respectively. Example 16
The sizing degree was measured in the same manner as in Example 1 to determine the fixing amount of the sizing agent. Further, a roll dirt test was performed in the same manner as in Example 16. Table 4 shows the results.
【００４１】比較例１１〜１４ カチオン性ポリマー水性液Ａに代えて、各々カチオン性
ポリマー水性液Ｇ、Ｈ、Ｉ、Ｊを使用したこと以外は実
施例１６と同様にして手抄紙を作成し、実施例１６と同
様にサイズ度の測定を行い、サイズ剤の定着量を求め
た。また、実施例１６と同様にロール汚れ試験を行っ
た。それらの結果を表４に示す。Comparative Examples 11 to 14 Hand papers were prepared in the same manner as in Example 16 except that the aqueous cationic polymer solutions G, H, I and J were used in place of the aqueous cationic polymer solution A, respectively. The sizing degree was measured in the same manner as in Example 16 to determine the fixing amount of the sizing agent. Further, a roll dirt test was performed in the same manner as in Example 16. Table 4 shows the results.
【００４２】[0042]
【表４】 [Table 4]
【００４３】以上の結果より、機械パルプを含有する原
料パルプを用いた抄紙系において、実施例のものは比較
例のものよりもピッチ抑制効果及び得られた紙のサイズ
性が共に優れていることが分かる。即ち、機械パルプを
配合した原料を使用し、中性サイズ剤でサイジングする
場合、本発明に係わるカチオン性ポリマーを使用して抄
造することにより、ピッチ障害の抑制や成紙のサイズ性
の向上を図ることができる。実施例１と比較例５、実施
例２と比較例６のデータの対比から分かるように、配合
する機械パルプの割合が高い場合、それに応じて、本発
明に係わるカチオン性ポリマーの添加率も高くする必要
がある。その作用機構は定かではないが、本発明に係わ
るカチオン性ポリマーは機械パルプ中のピッチ成分の凝
集防止作用を有していると考えられる。サイズ剤定着量
をみると実施例の方が、比較例のものよりも高い。この
ことはサイズ剤の歩留りが高くなることによって、ピッ
チ障害の一因となる可能性がある抄紙系中に滞留するサ
イズ剤やその加水分解物が減少すると共に、紙のサイズ
度が向上しているためと考えられる。本発明に係わるカ
チオン性ポリマーは、一定量以上の疎水性部を有してい
る点で、比較例のカチオン性ポリマーと異なるが、この
一定量以上の疎水性部が、機械パルプを含有した抄紙系
で中性サイズ剤を使用する条件下で、効果的に作用して
いるといえる。即ち、一定量以上の疎水性部を導入した
本発明に係わるカチオン性ポリマーによって、従来では
なし得なかったレベルのピッチ障害の抑制ができると共
に、成紙のサイズ度も向上させることができる。From the above results, in the papermaking system using the raw pulp containing the mechanical pulp, those of Examples are superior to those of Comparative Examples in both the pitch suppressing effect and the size of the obtained paper. I understand. That is, when using a raw material blended with mechanical pulp and sizing with a neutral sizing agent, by using the cationic polymer according to the present invention to form a paper, it is possible to suppress pitch disturbance and improve the size of formed paper. Can be planned. As can be seen from the comparison of the data of Example 1 and Comparative Example 5 and the data of Example 2 and Comparative Example 6, when the ratio of the mechanical pulp to be blended is high, the addition ratio of the cationic polymer according to the present invention is correspondingly high. There is a need to. Although the mechanism of action is unclear, it is considered that the cationic polymer according to the present invention has an action of preventing aggregation of pitch components in mechanical pulp. The sizing agent fixing amount is higher in the example than in the comparative example. This means that by increasing the yield of the sizing agent, the sizing agent and its hydrolyzate that remain in the papermaking system, which may contribute to pitch disturbance, are reduced, and the sizing degree of the paper is improved. It is thought that there is. The cationic polymer according to the present invention differs from the cationic polymer of the comparative example in that it has a certain amount or more of hydrophobic parts, but the certain part or more of the hydrophobic part contains mechanical pulp. It can be said that it works effectively under the condition that a neutral sizing agent is used in the system. That is, the cationic polymer according to the present invention into which a certain amount or more of the hydrophobic portion is introduced can suppress pitch disturbance at a level that could not be achieved conventionally, and can also improve the sizing degree of the formed paper.
【００４４】[0044]
【発明の効果】本発明によれば、機械パルプを配合した
パルプ原料を使用して中性サイズ剤でサイジングする際
にピッチ障害を抑制できるとともに、中性サイズ剤の歩
留まりを向上し、サイズ性の優れた機械パルプ含有紙及
びその製造方法を提供することができる。According to the present invention, pitch disturbance can be suppressed when sizing with a neutral sizing agent using a pulp material containing mechanical pulp, and the yield of the neutral sizing agent is improved, And a method for producing the same.
【図１】抄紙装置のロールの汚れを試験する試験装置で
ある。FIG. 1 is a test apparatus for testing a roll of a papermaking apparatus for dirt.
フロントページの続き Ｆターム(参考） 4L055 AC01 AG40 AG41 AG50 AG63 AG71 AG72 AG73 AH12 AH22 AH50 BD10 EA04 EA31 EA32 FA17 FA20 FA30 Continued on the front page F term (reference) 4L055 AC01 AG40 AG41 AG50 AG63 AG71 AG72 AG73 AH12 AH22 AH50 BD10 EA04 EA31 EA32 FA17 FA20 FA30
Claims (5)
重量％含有する製紙用パルプを用いて中性サイズ剤によ
りサイジングした機械パルプ含有紙において、下記
（Ａ）５０〜９５重量％及び下記（Ｂ）５〜５０重量％
の各単量体に対応する構成単位の結合体を有し、かつ４
級アンモニウム塩を有するビニル系共重合体であるカチ
オン性ポリマーを添加物として上記機械パルプの乾燥重
量に対して０．０３〜１重量％含有する機械パルプ含有
紙。 （Ａ）スチレン系単量体及びアルキル（メタ）アクリレ
ートからなる群より選択された少なくとも１種の疎水性
単量体 （Ｂ）ジアルキルアミノアルキル（メタ）アクリルアミ
ド及びジアルキルアミノアルキル（メタ）アクリレート
からなる３級アミノ基を有する単量体並びにそれぞれの
４級化物からなる４級アンモニウム塩を有する単量体の
群より選ばれた少なくとも１種のカチオン性単量体1. The method of claim 1 wherein the mechanical pulp is at least 5 parts on a dry weight basis.
In a mechanical pulp-containing paper sized with a neutral sizing agent using a paper pulp containing 5% by weight, the following (A) 50 to 95% by weight and the following (B) 5 to 50% by weight
Having a conjugate of a structural unit corresponding to each monomer of
A mechanical pulp-containing paper containing, as an additive, a cationic polymer which is a vinyl copolymer having a secondary ammonium salt in an amount of 0.03 to 1% by weight based on the dry weight of the mechanical pulp. (A) at least one hydrophobic monomer selected from the group consisting of styrene monomers and alkyl (meth) acrylates (B) consisting of dialkylaminoalkyl (meth) acrylamide and dialkylaminoalkyl (meth) acrylate At least one cationic monomer selected from the group consisting of a monomer having a tertiary amino group and a monomer having a quaternary ammonium salt composed of each quaternized compound
（Ｂ）成分以外のその他のビニル系単量体を用いる請求
項１記載の機械パルプ含有紙。2. The mechanical pulp-containing paper according to claim 1, wherein a vinyl monomer other than the components (A) and (B) is used as a part of the component (B).
剤、置換環式ジカルボン酸無水物系サイズ剤及び中性抄
紙用ロジン系サイズ剤からなる群から選ばれる少なくと
も１種である請求項１又は２記載の機械パルプ含有紙。3. The method according to claim 1, wherein the neutral sizing agent is at least one selected from the group consisting of a ketene dimer sizing agent, a substituted cyclic dicarboxylic anhydride sizing agent, and a rosin sizing agent for neutral papermaking. 2. The paper containing mechanical pulp according to 2.
重量％含有する製紙用パルプを原料とし、ｐＨ６〜９で
中性サイズ剤を使用してサイジングする抄紙工程を有す
る機械パルプ含有紙の製造方法において、下記（Ａ）５
０〜９５重量％及び下記（Ｂ）５〜５０重量％含有する
単量体から得られるビニル系共重合体であって、下記
（Ｂ）成分として３級アミノ基を有する単量体を使用す
る場合は該ビニル系共重合体の重合過程及び重合後の少
なくとも一方において４級化することがある４級アンモ
ニウム塩を有するカチオン性ポリマーを含有する添加剤
を上記抄紙工程において使用し、かつ該カチオン性ポリ
マーを上記機械パルプの乾燥重量に対して０．０３〜１
重量％使用する機械パルプ含有紙の製造方法。 （Ａ）スチレン系単量体及びアルキル（メタ）アクリレ
ートからなる群より選択された少なくとも１種の疎水性
単量体 （Ｂ）ジアルキルアミノアルキル（メタ）アクリルアミ
ド及びジアルキルアミノアルキル（メタ）アクリレート
からなる３級アミノ基を有する単量体並びにそれぞれの
４級化物からなる４級アンモニウム塩を有する単量体の
群より選ばれた少なくとも１種のカチオン性単量体4. The method of claim 1, wherein the mechanical pulp is at least 5 parts on a dry weight basis.
In a method for producing a mechanical pulp-containing paper having a papermaking step of sizing using a neutral sizing agent at pH 6 to 9 using a paper pulp containing 5% by weight as a raw material, the following (A) 5
A vinyl copolymer obtained from a monomer containing 0 to 95% by weight and the following (B) 5 to 50% by weight, wherein a monomer having a tertiary amino group is used as the following component (B). In such a case, an additive containing a cationic polymer having a quaternary ammonium salt which may be quaternized in at least one of the polymerization step and the polymerization step of the vinyl copolymer is used in the papermaking step, and Water-soluble polymer in an amount of 0.03 to 1 based on the dry weight of the mechanical pulp.
A method for producing paper containing mechanical pulp to be used by weight. (A) at least one hydrophobic monomer selected from the group consisting of styrene monomers and alkyl (meth) acrylates (B) consisting of dialkylaminoalkyl (meth) acrylamide and dialkylaminoalkyl (meth) acrylate At least one cationic monomer selected from the group consisting of a monomer having a tertiary amino group and a monomer having a quaternary ammonium salt composed of each quaternized compound
（Ｂ）成分以外のその他のビニル系単量体を用いる請求
項４記載の機械パルプ含有紙の製造方法。5. The method for producing paper containing mechanical pulp according to claim 4, wherein a vinyl monomer other than the components (A) and (B) is used as a part of the component (B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21866398A JP4048612B2 (en) | 1998-07-17 | 1998-07-17 | Mechanical pulp-containing paper and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21866398A JP4048612B2 (en) | 1998-07-17 | 1998-07-17 | Mechanical pulp-containing paper and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000034692A true JP2000034692A (en) | 2000-02-02 |
| JP4048612B2 JP4048612B2 (en) | 2008-02-20 |
Family
ID=16723482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21866398A Expired - Fee Related JP4048612B2 (en) | 1998-07-17 | 1998-07-17 | Mechanical pulp-containing paper and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4048612B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003055895A (en) * | 2001-08-10 | 2003-02-26 | Hymo Corp | Method for treating paper-making raw material |
| JP2006265759A (en) * | 2005-03-23 | 2006-10-05 | Kurita Water Ind Ltd | Method for preventing papermaking machine from soiling and soil-preventing agent |
| JP2007186822A (en) * | 2006-01-13 | 2007-07-26 | Seiko Pmc Corp | Method for producing paperboard and paperboard |
| JP2008144312A (en) * | 2006-12-11 | 2008-06-26 | Seiko Pmc Corp | Method for producing paperboard |
| JP2010236125A (en) * | 2009-03-31 | 2010-10-21 | Somar Corp | Method for producing paper, and paper using the same |
| JP2011521114A (en) * | 2008-05-15 | 2011-07-21 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing paper, board and cardboard with high dry strength |
-
1998
- 1998-07-17 JP JP21866398A patent/JP4048612B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003055895A (en) * | 2001-08-10 | 2003-02-26 | Hymo Corp | Method for treating paper-making raw material |
| JP2006265759A (en) * | 2005-03-23 | 2006-10-05 | Kurita Water Ind Ltd | Method for preventing papermaking machine from soiling and soil-preventing agent |
| JP2007186822A (en) * | 2006-01-13 | 2007-07-26 | Seiko Pmc Corp | Method for producing paperboard and paperboard |
| JP2008144312A (en) * | 2006-12-11 | 2008-06-26 | Seiko Pmc Corp | Method for producing paperboard |
| JP2011521114A (en) * | 2008-05-15 | 2011-07-21 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing paper, board and cardboard with high dry strength |
| JP2010236125A (en) * | 2009-03-31 | 2010-10-21 | Somar Corp | Method for producing paper, and paper using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4048612B2 (en) | 2008-02-20 |
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