JP2007291595A - Neutral newsprint for offset printing - Google Patents
Neutral newsprint for offset printing Download PDFInfo
- Publication number
- JP2007291595A JP2007291595A JP2007087279A JP2007087279A JP2007291595A JP 2007291595 A JP2007291595 A JP 2007291595A JP 2007087279 A JP2007087279 A JP 2007087279A JP 2007087279 A JP2007087279 A JP 2007087279A JP 2007291595 A JP2007291595 A JP 2007291595A
- Authority
- JP
- Japan
- Prior art keywords
- offset printing
- weight
- cationic
- polyethylene wax
- paper
- 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
- 238000007645 offset printing Methods 0.000 title claims abstract description 66
- 230000007935 neutral effect Effects 0.000 title claims abstract description 62
- -1 polyethylene Polymers 0.000 claims abstract description 122
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 107
- 238000004513 sizing Methods 0.000 claims abstract description 94
- 239000004698 Polyethylene Substances 0.000 claims abstract description 93
- 229920000573 polyethylene Polymers 0.000 claims abstract description 93
- 239000000839 emulsion Substances 0.000 claims abstract description 90
- 125000002091 cationic group Chemical group 0.000 claims abstract description 84
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 25
- 239000012875 nonionic emulsifier Substances 0.000 claims abstract description 23
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims description 40
- 239000012756 surface treatment agent Substances 0.000 claims description 36
- 229920001577 copolymer Polymers 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 23
- 239000012986 chain transfer agent Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- 230000003068 static effect Effects 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- 239000007869 azo polymerization initiator Substances 0.000 claims description 9
- 125000001302 tertiary amino group Chemical group 0.000 claims description 9
- 125000005907 alkyl ester group Chemical group 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 5
- 238000002296 dynamic light scattering Methods 0.000 claims description 4
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 4
- 150000003440 styrenes Chemical class 0.000 claims description 3
- 239000000123 paper Substances 0.000 abstract description 92
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 43
- 239000011248 coating agent Substances 0.000 abstract description 27
- 238000000576 coating method Methods 0.000 abstract description 27
- 238000010521 absorption reaction Methods 0.000 abstract description 24
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 22
- 239000000945 filler Substances 0.000 abstract description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- 229940048053 acrylate Drugs 0.000 description 27
- 238000000034 method Methods 0.000 description 26
- 229920002472 Starch Polymers 0.000 description 23
- 235000019698 starch Nutrition 0.000 description 23
- 239000008107 starch Substances 0.000 description 22
- 229920001131 Pulp (paper) Polymers 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 239000002585 base Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000007639 printing Methods 0.000 description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 10
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 10
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000005956 quaternization reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
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- 229920002401 polyacrylamide Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 5
- 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 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 238000004519 manufacturing process Methods 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
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000012874 anionic emulsifier Substances 0.000 description 4
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 229920006319 cationized starch Polymers 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000001254 oxidized starch Substances 0.000 description 3
- 235000013808 oxidized starch Nutrition 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000005476 size effect Effects 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 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 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
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- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
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- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
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- UMKKESOWESHQRE-UHFFFAOYSA-N 2-(aminomethyl)prop-2-enamide;prop-2-enamide Chemical compound NC(=O)C=C.NCC(=C)C(N)=O UMKKESOWESHQRE-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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Landscapes
- Paper (AREA)
Abstract
Description
本発明は、オフセット印刷用中性新聞用紙に関する。 The present invention relates to a neutral newsprint for offset printing.
近年、新聞用紙は、古紙由来の炭酸カルシウムの有効利用の点から、従来の酸性抄紙から中性抄紙に移行している。さらに填料として炭酸カルシウムを多く使用し、紙中灰分を増やすことで、該新聞用紙は、オフセット印刷した場合、高白色なためカラー印刷面が鮮やかである、不透明性に優れる、他填料と比較してブランケット紙粉のパイリングが少ないといった品質と作業性の面で優れた印刷適性を有している。しかしながらその用紙の物性の面をみてみると、紙中灰分が増加するに従い、紙の摩擦係数が上昇する傾向にあり、オフセット印刷時の剣先詰まりや皺の発生、印刷テンション増加による色ずれ等の発生要因となる。 In recent years, newsprint has shifted from conventional acidic papermaking to neutral papermaking in terms of effective utilization of calcium carbonate derived from used paper. In addition, by using a large amount of calcium carbonate as a filler and increasing the ash content in the paper, the newsprint paper has a high white color due to its high white color when offset printing is performed, and has excellent opacity compared to other fillers. It has excellent printability in terms of quality and workability such that there is little piling of blanket paper powder. However, looking at the physical properties of the paper, as the ash content in the paper increases, the friction coefficient of the paper tends to increase, such as clogging of the sword or offset during offset printing, color misregistration due to increased printing tension, etc. It becomes a generation factor.
さらに、中性新聞用紙では、従来の酸性新聞用の表面サイズ剤では十分な紙の吸水抵抗性（サイズ性）が得られないため、カチオン性表面サイズ剤（例えば、特許文献１、２参照）を塗布する方法があるが、一般的にこれらカチオン性表面サイズ剤は、紙表面に塗布することによって用紙の摩擦係数が上昇する。また、新聞用紙に表面処理剤として使用されるサイズ剤以外の澱粉、ポリアクリルアミド、ポリビニルアルコール等の水溶性高分子物質によっても、紙の摩擦係数が処理前に比べて上昇することがほとんどである。 Furthermore, with neutral newsprint paper, a conventional surface sizing agent for acidic newspapers does not provide sufficient water absorption resistance (size property) of the paper, so a cationic surface sizing agent (see, for example, Patent Documents 1 and 2). In general, these cationic surface sizing agents increase the coefficient of friction of the paper when applied to the paper surface. In addition, starch, polyacrylamide, polyvinyl alcohol, and other water-soluble polymer substances other than the sizing agent used as a surface treatment agent for newsprint papers almost always increase the coefficient of friction of paper compared to that before the treatment. .
新聞用紙は、印刷所毎に実に様々な印刷機機種、印刷条件で使用されているため、同じ摩擦係数でも一方の印刷所で問題ない場合でも、もう一方で摩擦係数に起因する印刷走行性の問題が発生する場合がある。このように新聞用紙は摩擦係数が高過ぎても、低過ぎても紙流れ等の問題が起きるため最適な範囲にある必要があり、かつ必要に応じて摩擦係数を細かく調整する技術が必要である。 Newspapers are used in a wide variety of printing press models and printing conditions at each printing station, so even if there is no problem with one printing station even with the same friction coefficient, there is a problem of printing runability due to the friction coefficient on the other side. May occur. In this way, newsprint paper needs to be in the optimum range because of problems such as paper flow even if the friction coefficient is too high or too low, and technology to finely adjust the friction coefficient as necessary is required. is there.
一般的な紙の摩擦係数を低下させる方法として、内添と外添の方法がある。内添の方法としては、抄造時にアルキルケテンダイマー（ＡＫＤ）やアルケニル琥珀酸無水物（ＡＳＡ）等の樹脂成分を含有する内添サイズ剤によりすべり性を付与する方法や填料としてタルクを添加して紙に抄き込む方法がある。しかしながら、内添サイズ剤による方法は、目標とする吸水抵抗性を得るために必要とされるサイズ剤量が決まるため、その時、必ずしも最適な摩擦係数が得られるわけではない。逆に摩擦係数の調節を優先してＡＫＤの添加量を決めると、最適な吸水抵抗性が得られない。さらにＡＫＤを内添した場合にはＡＫＤが紙巻取り内でマイグレーションすることにより、上巻きの摩擦係数が極端に低下するため、印刷時の紙流れを発生させる原因となる。タルク内添による方法は、相対的に炭酸カルシウムの添加量が減少するため、上述したような炭酸カルシウムの利点を損なうことや、炭酸カルシウムに比べて紙粉発生量が多くなる等の短所がある。 As a general method for reducing the friction coefficient of paper, there are an internal addition method and an external addition method. As an internal addition method, a talc is added as a filler or a method of imparting slipperiness with an internal sizing agent containing a resin component such as alkyl ketene dimer (AKD) or alkenyl succinic anhydride (ASA) at the time of papermaking. There is a method of making paper. However, the method using an internally added sizing agent determines the amount of sizing agent required to obtain the target water absorption resistance, and at that time, the optimum coefficient of friction is not always obtained. Conversely, if the amount of AKD added is determined with priority given to the adjustment of the friction coefficient, the optimum water absorption resistance cannot be obtained. Further, when AKD is internally added, the AKD migrates in the paper winding, and the friction coefficient of the upper winding is extremely reduced, which causes a paper flow during printing. The method based on talc addition has a disadvantage in that the amount of calcium carbonate added is relatively reduced, so that the advantages of calcium carbonate as described above are impaired and the amount of paper dust generated is larger than calcium carbonate. .
このため、表面処理剤を原紙表面に塗布する外添による方法が検討されている。内添サイズ剤であるＡＫＤやＡＳＡを適当な分散剤で処理したエマルジョンを表面サイズ剤として用いる場合があるが、表面処理剤の液中で加水分解を起こし、吸水抵抗性を損なう。しかも摩擦係数は少量で急激に低下するため、摩擦係数のコントロールが極めて困難である。例えば、吸水抵抗性と摩擦係数を最適な範囲にするためにサイズ剤としてアルケニルケテンダイマーを塗工する方法が提案されている（特許文献３参照）。 For this reason, a method by external addition in which a surface treatment agent is applied to the surface of the base paper has been studied. An emulsion obtained by treating an internal sizing agent, AKD or ASA, with a suitable dispersant may be used as a surface sizing agent. However, it causes hydrolysis in the liquid of the surface treating agent and impairs water absorption resistance. In addition, since the friction coefficient rapidly decreases with a small amount, it is very difficult to control the friction coefficient. For example, a method of applying an alkenyl ketene dimer as a sizing agent has been proposed in order to bring the water absorption resistance and the friction coefficient to the optimum ranges (see Patent Document 3).
また、ポリエチレンワックスを含有する表面処理剤を塗布する技術として、例えば、表面処理剤の主成分である共重合体ラテックスに離型剤としてポリエチレンワックスを含有する方法が提案されている（特許文献４参照）。この技術では、ポリエチレンワックスと、新聞用紙用として一般的に使用されている澱粉やポリビニルアルコールよりも摩擦係数の高いラテックスとを併用することで摩擦係数の低下を抑制している。また、顔料塗工用の滑剤として、ポリエチレンワックス系滑剤の方法が提案されている(特許文献５参照)。 In addition, as a technique for applying a surface treatment agent containing polyethylene wax, for example, a method of containing polyethylene wax as a release agent in a copolymer latex that is a main component of the surface treatment agent has been proposed (Patent Document 4). reference). In this technique, a decrease in the friction coefficient is suppressed by using polyethylene wax in combination with a latex having a higher friction coefficient than that of starch or polyvinyl alcohol generally used for newsprint. In addition, as a lubricant for pigment coating, a method of polyethylene wax lubricant has been proposed (see Patent Document 5).
上記特許文献３は、サイズ剤としてアルケニルケテンダイマーを塗工するものであるが、摩擦係数のコントロールにサイズ剤の塗布量を変えて調節するため、点滴吸水度も大きく変化してしまい、製品品質の安定性に欠けるという問題がある。
特許文献４は、表面処理剤の主成分である共重合体ラテックスに離型剤としてポリエチレンワックスを含有するものであるが、ネッパリ性と表面強度の改善について記載されているものの、積極的に摩擦係数をコントロールすることに主眼を置いてはおらず、吸水抵抗性や表面サイズ剤との併用に関しての記述もない。
また、特許文献５には、顔料塗工用の滑剤としてポリエチレンワックス系滑剤が記載されているが、顔料塗工では塗料のｐＨは通常７以上、中性新聞用紙では通常使用される澱粉とカチオン性サイズ剤を含む塗料ではｐＨは４．５〜６．５となる。そのため中性新聞用紙の表面処理剤に顔料塗工用の滑剤を添加すると表面処理剤液の分散安定性が低下し、塗布時に大きなシェアがかかると凝集物が発生し、操業上大きな問題となる。
以上のように、いずれの特許文献の方法においても、中性新聞用紙に表面処理剤を塗工して効果的な吸水抵抗性を付与し、かつ吸水抵抗性を目標とする程度に維持しながら摩擦係数を最適な範囲に調節するには不十分であり、これを可能とする表面処理剤の開発が望まれていた。
そこで、本発明は、吸水抵抗性を目標とする程度に維持しながら、摩擦係数の上昇が抑えられて最適な範囲に調節されたオフセット印刷用中性新聞用紙を提供することを課題とする。
In the above-mentioned Patent Document 3, an alkenyl ketene dimer is applied as a sizing agent. However, since the application amount of the sizing agent is changed to control the friction coefficient, the drip water absorption is greatly changed, resulting in product quality. There is a problem of lack of stability.
Patent Document 4 contains polyethylene wax as a mold release agent in a copolymer latex which is a main component of a surface treatment agent. There is no focus on controlling the coefficient, and there is no description of water absorption resistance and use in combination with surface sizing agents.
Patent Document 5 describes a polyethylene wax-based lubricant as a lubricant for pigment coating. The pH of the paint is usually 7 or more for pigment coating, and starch and cation that are usually used for neutral newsprint. The pH of the paint containing a natural sizing agent is 4.5 to 6.5. For this reason, if a pigment coating lubricant is added to the surface treatment agent of neutral newsprint paper, the dispersion stability of the surface treatment agent solution will decrease, and if a large share is applied during application, agglomerates will occur, which will be a major operational problem. .
As described above, in any of the methods disclosed in Patent Documents, a surface treatment agent is applied to neutral newsprint paper to impart effective water absorption resistance, while maintaining water absorption resistance at a target level. It is insufficient to adjust the coefficient of friction to an optimum range, and it has been desired to develop a surface treatment agent that enables this.
Accordingly, an object of the present invention is to provide a neutral newsprint for offset printing in which the increase in the coefficient of friction is suppressed and adjusted to an optimum range while maintaining water absorption resistance at a target level.
上記課題を解決するために、請求項１に記載の発明は、原紙上に、表面処理剤が塗工されたオフセット印刷用中性新聞用紙であって、前記表面処理剤が下記の（Ａ）、（Ｂ）及び（Ｃ）を含有することを特徴とする。
（Ａ）カチオン性表面サイズ剤、（Ｂ）ノニオン性乳化剤またはカチオン性乳化剤で乳化したポリエチレンワックスエマルジョン、（Ｃ）水溶性高分子物質。
請求項２に記載の発明は、（Ａ）カチオン性サイズ剤が、少なくとも成分ａ；３級アミノ基含有モノマー２０〜４０重量％と成分ｂ；（メタ）アクリル酸のＣ４〜Ｃ１８アルキルエステル１０〜８０重量％とをアゾ系重合開始剤を用い連鎖移動剤の存在下で重合して得られる共重合体を４級化したものであることを特徴とする。
請求項３に記載の発明は、前記アゾ系重合開始剤が、アゾビスメチルブチロニトリル、ジメチルアゾビスイソブチレート、またはアゾビスジメチルバレロニトリルの少なくとも１種であることを特徴とする。
請求項４に記載の発明は、（Ａ）カチオン性サイズ剤が、成分ａと成分ｂとに加えてさらに成分ｃ；スチレン類７０重量％以下を重合して得られる共重合体であることを特徴とする。
請求項５に記載の発明は、（Ｂ）ノニオン性乳化剤またはカチオン性乳化剤で乳化したポリエチレンワックスエマルジョンが、動的光散乱式粒度分布測定装置による平均粒子径が２０〜３００ｎｍの範囲であることを特徴とする。
請求項６に記載の発明は、（Ｂ）ノニオン性乳化剤またはカチオン性乳化剤で乳化したポリエチレンワックスエマルジョンの塗布量が、両面あたり０．００５〜０．０２５ｇ／ｍ２であることを特徴とする。
請求項７に記載の発明は、（Ａ）カチオン性表面サイズ剤と（Ｂ）ノニオン性乳化剤またはカチオン性乳化剤で乳化したポリエチレンワックスエマルジョンとの固形分重量比が、（Ａ）／（Ｂ）＝１００／５〜１００／３０であることを特徴とする。
請求項８に記載の発明は、原紙の紙中灰分が固形分比で１０〜２０重量％であることを特徴とする。
請求項９に記載の発明は、前記塗工層を設けたオフセット印刷用中性新聞用紙の静摩擦係数が０．５０〜０．７５かつ動摩擦係数が０．４０〜０．６０であることを特徴とする。
請求項１０に記載の発明は、前記共重合体の重量平均分子量が３万〜６万であることを特徴とする。
In order to solve the above-mentioned problem, the invention described in claim 1 is a neutral newsprint for offset printing in which a surface treatment agent is coated on a base paper, and the surface treatment agent is the following (A): , (B) and (C).
(A) a cationic surface sizing agent, (B) a polyethylene wax emulsion emulsified with a nonionic emulsifier or a cationic emulsifier, and (C) a water-soluble polymer substance.
The invention according to claim 2 is characterized in that (A) the cationic sizing agent is at least component a; tertiary amino group-containing monomer 20 to 40% by weight and component b; (meth) acrylic acid C4 to C18 alkyl ester 10 A copolymer obtained by polymerizing 80% by weight with an azo polymerization initiator in the presence of a chain transfer agent is quaternized.
The invention according to claim 3 is characterized in that the azo polymerization initiator is at least one of azobismethylbutyronitrile, dimethylazobisisobutyrate, or azobisdimethylvaleronitrile.
The invention according to claim 4 is that (A) the cationic sizing agent is a copolymer obtained by polymerizing component c; 70% by weight or less of styrene in addition to component a and component b. Features.
The invention according to claim 5 is that (B) the polyethylene wax emulsion emulsified with a nonionic emulsifier or a cationic emulsifier has an average particle diameter in the range of 20 to 300 nm by a dynamic light scattering particle size distribution analyzer. Features.
The invention according to claim 6 is characterized in that the coating amount of the polyethylene wax emulsion emulsified with (B) a nonionic emulsifier or a cationic emulsifier is 0.005 to 0.025 g / m 2 per both sides.
In the invention according to claim 7, the solid content weight ratio of (A) a cationic surface sizing agent to (B) a polyethylene wax emulsion emulsified with a nonionic emulsifier or a cationic emulsifier is (A) / (B) = 100/5 to 100/30.
The invention according to claim 8 is characterized in that the ash content of the base paper is 10 to 20% by weight in terms of solid content.
The invention according to claim 9 is characterized in that the static friction coefficient of the neutral newsprint paper for offset printing provided with the coating layer is 0.50 to 0.75 and the dynamic friction coefficient is 0.40 to 0.60. And
The invention according to claim 10 is characterized in that the copolymer has a weight average molecular weight of 30,000 to 60,000.
本発明によれば、オフセット印刷用中性新聞用紙において、カチオン性サイズ剤の高いサイズ性を維持したまま、摩擦係数を最適な範囲に調整できる。従って、摩擦係数に起因するオフセット印刷時の剣先詰まりや皺の発生、印刷テンション増加による色ずれ等の問題を改善することができる。
さらに、填料である炭酸カルシウムを紙中灰分として多く含有させても、紙の摩擦係数を過度に大きくすることがなく、白色度、不透明性の高いオフセット印刷用中性新聞用紙を得ることができる。
According to the present invention, in a neutral newsprint for offset printing, the friction coefficient can be adjusted to an optimum range while maintaining the high size of the cationic sizing agent. Therefore, problems such as clogging of the sword tip and occurrence of wrinkles during offset printing due to the friction coefficient, and color misregistration due to increased printing tension can be improved.
Furthermore, even if calcium carbonate as a filler is contained in a large amount as ash in the paper, neutral newspaper paper for offset printing with high whiteness and high opacity can be obtained without excessively increasing the friction coefficient of the paper. .
本発明のオフセット印刷用中性新聞用紙は、填料として炭酸カルシウムを主体とする原紙上に、下記の（Ａ）、（Ｂ）及び（Ｃ）を少なくとも含有する表面処理剤を塗工、乾燥してなる塗工層を設けることにより得ることができる。
（Ａ）カチオン性表面サイズ剤
（Ｂ）ノニオン性乳化剤またはカチオン性乳化剤で乳化したポリエチレンワックスエマルジョン
（Ｃ）水溶性高分子物質
The neutral newsprint for offset printing according to the present invention is coated with a surface treatment agent containing at least the following (A), (B) and (C) on a base paper mainly composed of calcium carbonate as a filler, and dried. It can obtain by providing the coating layer formed.
(A) Cationic surface sizing agent (B) Polyethylene wax emulsion emulsified with nonionic emulsifier or cationic emulsifier (C) Water-soluble polymer substance
＜カチオン性表面サイズ剤＞
本発明において、表面処理剤に含有される（Ａ）カチオン性表面サイズ剤としては、特に制限されるものではないが、少なくとも成分ａ；３級アミノ基含有モノマー２０〜４０重量％と成分ｂ；（メタ）アクリル酸のＣ４〜Ｃ１８アルキルエステル１０〜８０重量％とを、アゾ系重合開始剤を用いて連鎖移動剤の存在下で重合して得られる、重量平均分子量３万〜６万の共重合体を４級化したものが好ましく用いられる。このようなカチオン性表面サイズ剤は、（Ｂ）のポリエチレンワックスエマルジョンと混合したとき、増粘したり凝集することがなく好ましい。また、従来、表面サイズ剤を用いると、オフセット印刷時に表面サイズ剤が湿し水を介してＰＳ版上に転移し、ＰＳ版上の非画線部を感脂化して地汚れなどと呼ばれる版汚れを引き起こす弊害があるが、本発明で用いられるカチオン性表面サイズ剤は耐版汚れ性にも優れており好ましい。
<Cationic surface sizing agent>
In the present invention, the cationic surface sizing agent (A) contained in the surface treatment agent is not particularly limited, but at least component a; 20 to 40% by weight of a tertiary amino group-containing monomer and component b; A copolymer having a weight average molecular weight of 30,000 to 60,000 obtained by polymerizing 10 to 80% by weight of a C4-C18 alkyl ester of (meth) acrylic acid in the presence of a chain transfer agent using an azo polymerization initiator. A quaternized polymer is preferably used. Such a cationic surface sizing agent is preferable because it does not thicken or aggregate when mixed with the polyethylene wax emulsion (B). Conventionally, when a surface sizing agent is used, the surface sizing agent is transferred onto the PS plate via dampening water during offset printing, and a non-image area on the PS plate is sensitized so as to be called a background stain. The cationic surface sizing agent used in the present invention is preferable because it has excellent anti-stain resistance.
（ア．共重合成分）
本発明で使用するカチオン性表面サイズ剤の組成について、以下に詳細に説明する。
成分ａ；３級アミノ基含有モノマーとしては、ジアルキルアミノアルキル（メタ）アクリレート、ジアルキルアミノアルキル（メタ）アクリルアミドが適当である。
上記ジアルキルアミノアルキル（メタ）アクリレートは、ジメチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート、ジエチルアミノプロピル（メタ）アクリレートなどが代表であり、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレートが好ましい。
上記ジアルキルアミノアルキル（メタ）アクリルアミドは、ジメチルアミノエチル（メタ）アクリルアミド、ジエチルアミノエチル（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、ジエチルアミノプロピル（メタ）アクリルアミドなどが代表であり、ジメチルアミノエチル（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、ジエチルアミノプロピル（メタ）アクリルアミドが好ましい。
(A. Copolymerization component)
The composition of the cationic surface sizing agent used in the present invention will be described in detail below.
Component a: As the tertiary amino group-containing monomer, dialkylaminoalkyl (meth) acrylate and dialkylaminoalkyl (meth) acrylamide are suitable.
Representative examples of the dialkylaminoalkyl (meth) acrylate include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. And dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylate are preferred.
Examples of the dialkylaminoalkyl (meth) acrylamide include dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide. ) Acrylamide, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide are preferred.
成分ｂ；（メタ）アクリル酸のＣ４〜Ｃ１８アルキルエステルとしては、n-ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、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、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレートなどの環状又は非環状の炭化水素エステルが挙げられる。このように、成分ｂの（メタ）アクリル酸エステルは、Ｃ４〜Ｃ１８アルキル基を有するアルキル（メタ）アクリレートを初め、エステル部分に芳香族や脂環式の炭化水素基を含んだものでも良い。
また、成分ｂはメチルメタクリレート（ＭＭＡと略す）などの（メタ）アクリル酸のＣ１〜Ｃ３エステル（即ち、短鎖エステル）は含まれないが、下述のように、この共重合体を得る際に、成分ａからｃ以外のその他のモノマーとして、これらの（メタ）アクリル酸の短鎖エステルを使用しても良いことは言うまでもない。
成分ｂの好ましい例としては、エチルヘキシルメタクリレート、ラウリルメタクリレート、ステアリルメタクリレート、シクロヘキシルメタクリレート、ベンジルメタクリレートが挙げられる。
Component b: C4-C18 alkyl ester of (meth) acrylic acid includes n-butyl (meth) acrylate, isobutyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl Examples thereof include cyclic or acyclic hydrocarbon esters such as (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate. Thus, the (meth) acrylic acid ester of component b may contain an alkyl (meth) acrylate having a C4 to C18 alkyl group and an aromatic or alicyclic hydrocarbon group in the ester portion.
Component b does not include C1-C3 ester (that is, short chain ester) of (meth) acrylic acid such as methyl methacrylate (abbreviated as MMA), but when obtaining this copolymer as described below. Needless to say, short-chain esters of these (meth) acrylic acids may be used as other monomers other than components a to c.
Preferred examples of component b include ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate.
さらに、本発明では、成分ａ、ｂにさらに成分ｃ；スチレン類を加えて共重合体としてもよい。成分ｃとしては、スチレン、α-メチルスチレン、ビニルトルエン、エチルビニルトルエン、クロルメチルスチレンなどが挙げられる。 Furthermore, in the present invention, component c and styrene may be further added to components a and b to form a copolymer. Examples of component c include styrene, α-methyl styrene, vinyl toluene, ethyl vinyl toluene, chloromethyl styrene, and the like.
カチオン性表面サイズ剤を構成する共重合体の重合に際しては、上記成分ａ〜ｃ以外に、必要に応じて、その他の共重合性ビニルモノマーを使用することができる。
上記その他のモノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、n-プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレートなどのＣ１〜Ｃ３の短鎖アルキル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、2-ヒドロキシエチル（メタ）アクリレートなどの水酸基含有（メタ）アクリレート、（メタ）アクリルアミド、アクリロニトリルなどが挙げられる。
従って、例えば、成分ａ、あるいはさらに成分ｃを含み、（メタ）アクリル酸エステルとして、Ｃ４〜Ｃ１８の長鎖アルキルエステルとＣ３以下の短鎖アルキルエステルを併用した共重合体は、このカチオン性表面サイズ剤の共重合体に含まれるが、（メタ）アクリル酸エステルとしてＣ３以下の短鎖アルキル（メタ）アクリレートのみを使用し、Ｃ４〜Ｃ１８の長鎖アルキルエステルを使用しない場合は、この共重合体からは外れる。尚、（メタ）アクリル酸エステルにおいては、エステルの炭素数が増すほどサイズ剤の基本物性である撥水性への寄与が高まる。
In the polymerization of the copolymer constituting the cationic surface sizing agent, other copolymerizable vinyl monomers can be used as necessary in addition to the components a to c.
Examples of the other monomers include C1-C3 short chain alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate, hydroxypropyl (meth) ) Acrylate, 2-hydroxyethyl (meth) acrylate and other hydroxyl group-containing (meth) acrylate, (meth) acrylamide, acrylonitrile and the like.
Therefore, for example, a copolymer containing a component a or a component c and using a C4 to C18 long chain alkyl ester and a C3 or shorter short chain alkyl ester as a (meth) acrylic acid ester is a cationic surface. This copolymer is included in the copolymer of sizing agent, but only C3 or shorter short chain alkyl (meth) acrylate is used as (meth) acrylic acid ester and C4 to C18 long chain alkyl ester is not used. Depart from coalescence. In addition, in (meth) acrylic acid ester, the contribution to water repellency which is a basic physical property of a sizing agent increases as the carbon number of the ester increases.
本発明で使用するカチオン性表面サイズ剤の主成分である共重合体を構成する各モノマーの比率を述べると、まず、成分ａ；３級アミノ基含有モノマーは２０〜４０重量％であり、好ましくは２２〜３５重量％である。２０重量％よりも少ないと、水溶化するときの溶解度が退化し、４０重量％を超えると、疎水性が低下してサイズ効果が減少してしまう。
成分ｂ；（メタ）アクリル酸のＣ４〜Ｃ１８アルキルエステルの含有量は１０〜８０重量％であり、好ましくは１５〜７０重量％である。１０重量％より少ないと、疎水性が低下するとともに、溶液重合に際して溶解性が低下して共重合性が悪くなり、また、インキとの親和性が低下する。８０重量％を超えると、３級アミノ基含有モノマーの比率が低くなり過ぎる。即ち、インキとの親和性を良好に具備させるには、疎水性モノマーとして適正量の成分ｂが必要である。
また、成分ｃ；スチレン類の含有量は７０重量％以下であり、好ましくは６０重量％以下である。７０重量％を超えると、インキとの親和性が低下し、また、溶液重合に際して共重合性が悪くなる。共重合性が低下すると、溶液重合後に水溶化し、４級化する際に、表面サイズ剤の有効成分が凝集したミクロ粒子状となって紙表面に点在し、不均一な表面塗布しかできないため、サイズ効果が低減する恐れがある。従って、成分ｃは含有しないことが最も好ましい。但し、成分ｃ；スチレン類は、（メタ）アクリル酸エステルより疎水性に優れるため、本発明の所望の効果を阻害しない範囲で共重合体の適正量含有することは差し支えない。
更に、その他のモノマーは必要に応じて使用されるが、その含有量は３０重量％以下であり、好ましくは２０重量％以下である。
The ratio of each monomer constituting the copolymer which is the main component of the cationic surface sizing agent used in the present invention will be described. First, component a; the tertiary amino group-containing monomer is 20 to 40% by weight, preferably Is 22 to 35% by weight. If the amount is less than 20% by weight, the solubility when solubilized is degraded, and if it exceeds 40% by weight, the hydrophobicity is lowered and the size effect is reduced.
Component b; The content of the C4-C18 alkyl ester of (meth) acrylic acid is 10 to 80% by weight, preferably 15 to 70% by weight. When it is less than 10% by weight, the hydrophobicity is lowered, the solubility is lowered during solution polymerization, the copolymerizability is deteriorated, and the affinity with the ink is lowered. If it exceeds 80% by weight, the ratio of the tertiary amino group-containing monomer becomes too low. That is, an appropriate amount of the component b is required as a hydrophobic monomer in order to provide a good affinity with the ink.
The content of component c: styrenes is 70% by weight or less, preferably 60% by weight or less. When it exceeds 70% by weight, the affinity with the ink is lowered, and the copolymerizability is deteriorated during the solution polymerization. If the copolymerizability is reduced, the solution becomes water-soluble after solution polymerization, and when it is quaternized, the active component of the surface sizing agent becomes agglomerated microparticles that are scattered on the paper surface and can only be applied to a non-uniform surface. The size effect may be reduced. Therefore, it is most preferable not to contain the component c. However, since component c; styrenes are more hydrophobic than (meth) acrylic acid esters, they can be contained in an appropriate amount of the copolymer as long as the desired effects of the present invention are not impaired.
Further, other monomers are used as necessary, but their content is 30% by weight or less, preferably 20% by weight or less.
（イ．溶媒）
基本的に、この共重合体は成分ａ〜ｃを構成モノマーとして、有機溶媒中で溶液重合により製造される。上記有機溶媒としては、アルコール、ケトン等の酸素含有炭化水素類や、トルエン等の芳香族炭化水素類などが挙げられる。
溶媒としては、イソプロピルアルコール（ＩＰＡと略す）、n-ブタノール、イソブタノール、t-ブタノール、sec-ブタノール、メチルエチルケトン、メチル-n-プロピルケトン、3-メチル-2-ブタノール、ジエチルケトン、メチルイソプロピルケトン、メチルイソブチルケトン（ＭＩＢＫと略す）、ジイソプロピルケトン、エチルベンゼン、トルエンなどが挙げられる。
また、１５０℃以上の沸点で水への適度な溶解度（適度の親水性）を有する有機溶媒を使用すると、表面サイズ剤を塗布する際の臭気を抑制するのに有効である。具体的には、プロピレングリコール、プロピレングリコールジアセテート、ベンジルアルコール、1,3-ブチレングリコール、ヘキシレングリコールなどである。
有機溶媒の全モノマーに対する使用量は３０重量％以下が適量であり、好ましくは２０重量％以下である。
(A. Solvent)
Basically, this copolymer is produced by solution polymerization in an organic solvent using components a to c as constituent monomers. Examples of the organic solvent include oxygen-containing hydrocarbons such as alcohol and ketone, and aromatic hydrocarbons such as toluene.
Solvents include isopropyl alcohol (abbreviated as IPA), n-butanol, isobutanol, t-butanol, sec-butanol, methyl ethyl ketone, methyl-n-propyl ketone, 3-methyl-2-butanol, diethyl ketone, methyl isopropyl ketone. Methyl isobutyl ketone (abbreviated as MIBK), diisopropyl ketone, ethylbenzene, toluene and the like.
In addition, the use of an organic solvent having a boiling point of 150 ° C. or higher and appropriate solubility in water (appropriate hydrophilicity) is effective in suppressing odor when a surface sizing agent is applied. Specifically, propylene glycol, propylene glycol diacetate, benzyl alcohol, 1,3-butylene glycol, hexylene glycol and the like.
The amount of the organic solvent used relative to all monomers is an appropriate amount of 30% by weight or less, preferably 20% by weight or less.
（ウ．連鎖移動剤）
共重合体の溶液重合に際して粘度上昇を防止して重合反応を円滑に行う見地から、アゾ系重合開始剤を用いて連鎖移動剤の存在下で重合することが必要である。
上記連鎖移動剤は油溶性、水溶性の連鎖移動剤を任意に使用できるが、親油性の有機溶媒中で重合する場合には油溶性連鎖移動剤が、また、逆に親水性の有機溶媒を使用する場合には水溶性連鎖移動剤が相対的に好ましい。
上記油溶性連鎖移動剤としては、t-ドデシルメルカプタン、n-ドデシルメルカプタン、n-オクチルメルカプタン、メルカプトプロピオン酸ドデシルエステルなどのメルカプタン類の他、クメン、四塩化炭素、α-メチルスチレンダイマー、ターピノーレンなどが挙げられる。
上記水溶性連鎖移動剤としては、メルカプトエタノール、チオグリコール酸及びその塩などが挙げられる。
モノマーに対する連鎖移動剤の使用量は１〜５重量％程度が好ましいが、この範囲に制限されるものではない。
（エ．重合開始剤）
使用する重合開始剤はアゾ系重合開始剤であるが、水素引き抜きに起因した架橋化による分子量の増大や、枝分かれに伴う複雑な分子構造による溶解性の低下が著しく起こさない程度で有れば、過硫酸ベンゾイル、t-ブチルパーオキシベンゾエート、t-ブチルパーオキシイソプロピルモノカーボネート、t-ブチルパーオキシ-2-エチルヘキサノエート、クメンヒドロペルオキシドなどの過酸化物系重合開始剤を併用して使用しても良い。
上記アゾ系重合開始剤としては、アゾビスメチルブチロニトリル、ジメチルアゾビスイソブチレート、アゾビスジメチルバレロニトリル、アゾビスイソブチロニトリル（ＡＩＭＮと略す）などが挙げられる。なかでも、溶液重合に際して、溶剤並びに共重合体の構成モノマーへの溶解性を増す見地から、アゾ系重合開始剤のエタノールに対する溶解度（２５℃）は１５ｇ／１００ｇ以上が好ましい。当該エタノール溶解度を満たすアゾ系重合開始剤には、オゾビスメチルブチロニトリル、ジメチルアゾビスイソブチレート、オゾビスジメチルバレロニトリルなどがある。
上記過酸化物系重合開始剤は、過硫酸ベンゾイル、ｔ−ブチルパーオキシベンゾエート、ｔ−ブチルパーオキシイソプロピルモノカーボネート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、クメンヒドロペルオキシドなどが挙げられる。
このように、有機溶媒中にて連鎖移動剤並びにアゾ系開始剤の存在下で溶液重合を行うのであるが、当該溶液重合は公知の方式により行えば良く、特に制限されるものではない。
(C. Chain transfer agent)
From the standpoint of smoothing the polymerization reaction by preventing the viscosity increase during solution polymerization of the copolymer, it is necessary to perform polymerization in the presence of a chain transfer agent using an azo polymerization initiator.
As the chain transfer agent, an oil-soluble and water-soluble chain transfer agent can be arbitrarily used. However, when polymerizing in an oleophilic organic solvent, the oil-soluble chain transfer agent is used, and conversely, a hydrophilic organic solvent is used. When used, water-soluble chain transfer agents are relatively preferred.
Examples of the oil-soluble chain transfer agent include cumenes such as t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, mercaptopropionic acid dodecyl ester, cumene, carbon tetrachloride, α-methylstyrene dimer, terpinolene, etc. Is mentioned.
Examples of the water-soluble chain transfer agent include mercaptoethanol, thioglycolic acid and salts thereof.
The amount of the chain transfer agent used relative to the monomer is preferably about 1 to 5% by weight, but is not limited to this range.
(D. Polymerization initiator)
The polymerization initiator to be used is an azo polymerization initiator, but if it does not cause significant increase in molecular weight due to cross-linking due to hydrogen abstraction or a decrease in solubility due to complicated molecular structure due to branching, Used in combination with peroxide polymerization initiators such as benzoyl persulfate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexanoate, cumene hydroperoxide You may do it.
Examples of the azo polymerization initiator include azobismethylbutyronitrile, dimethylazobisisobutyrate, azobisdimethylvaleronitrile, azobisisobutyronitrile (abbreviated as AIMN), and the like. Among these, from the viewpoint of increasing the solubility of the solvent and copolymer in the constituent monomers during solution polymerization, the solubility (25 ° C.) of the azo polymerization initiator in ethanol is preferably 15 g / 100 g or more. Examples of the azo polymerization initiator that satisfies the ethanol solubility include ozobismethylbutyronitrile, dimethylazobisisobutyrate, and ozobisdimethylvaleronitrile.
Examples of the peroxide polymerization initiator include benzoyl persulfate, t-butylperoxybenzoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexanoate, cumene hydroperoxide, and the like. .
As described above, solution polymerization is performed in an organic solvent in the presence of a chain transfer agent and an azo initiator. However, the solution polymerization may be performed by a known method and is not particularly limited.
（オ．４級化）
構成モノマーとしては上記成分ａ〜ｃ以外、あるいは必要に応じて他の成分を溶液重合して得られた共重合体は、３級のまま使用しても同様な効果が得られるが、好ましくは４級化剤によりカチオン処理される。
上記４級化剤はジメチル硫酸、メチルクロライド、アリルクロライド、ベンジルクロライド、プロピレンオキシド、ブチレンオキシド、スチレンオキシド、エピクロルヒドリン、エピブロモヒドリン、エチレンクロルヒドリン、3-クロロー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などを単用又は併用できる。４級化剤の中では、エピクロルヒドリン、ベンジルクロライド、3-クロロー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が好ましい。
４級化に際しては、共重合体が有する３級アミノ基の５０〜１００モル％を４級化して、完全又は部分４級化することが好ましい。
共重合体を４級化することにより、中性、アルカリ側を含めた広いｐＨ領域で溶解性が増し、良好なサイズ効果を発揮することができる。
この４級化処理は、一般には、カチオン性共重合体を水溶化した後、溶剤を除去し、共重合体を４級化することにより行われるが、４級化した後に溶剤を除去しても差し支えない。
また、４級化処理は、溶液重合の円滑化の見地から、成分ａ；３級アミノ基含有モノマーを含む構成モノマーを共重合した後に、４級化剤でカチオン処理することが基本であるが、３級アミノ基含有モノマーを予め４級化し、得られた４級アンモニウム塩基含有モノマーを共重合することもできる。
この場合、４級モノマーの重合条件は、３級モノマーを重合する場合の処理条件と同様である。
(E. Grade 4)
As the constituent monomer, a copolymer obtained by solution polymerization of components other than the above-mentioned components a to c, or other components as necessary, can obtain the same effect even if it is used as tertiary, but preferably Cationic treatment with a quaternizing agent.
The above quaternizing agents are dimethyl sulfate, methyl chloride, allyl chloride, benzyl chloride, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, epibromohydrin, ethylene chlorohydrin, 3-chloro-2-hydroxypropyltrimethylammonium chloride, etc. Can be used alone or in combination. Of the quaternizing agents, epichlorohydrin, benzyl chloride, and 3-chloro-2-hydroxypropyltrimethylammonium chloride are preferable.
In the quaternization, it is preferable that 50 to 100 mol% of the tertiary amino group of the copolymer is quaternized and completely or partially quaternized.
By quaternizing the copolymer, the solubility increases in a wide pH range including neutrality and alkali side, and a good size effect can be exhibited.
This quaternization treatment is generally carried out by removing the solvent after water-solubilizing the cationic copolymer and quaternizing the copolymer. However, after quaternization, the solvent is removed. There is no problem.
The quaternization treatment is basically carried out from the viewpoint of facilitating solution polymerization by cation treatment with a quaternizing agent after copolymerization of component a; a constituent monomer containing a tertiary amino group-containing monomer. It is also possible to quaternize a tertiary amino group-containing monomer in advance and copolymerize the resulting quaternary ammonium base-containing monomer.
In this case, the polymerization conditions for the quaternary monomer are the same as the treatment conditions for the polymerization of the tertiary monomer.
（カ．分子量）
このような方法で合成した、カチオン性表面サイズ剤は一般的には分子量が大きい方がサイズ性が高いが、分子量が大きいと溶液の粘度が高く、製造作業性面、水溶性高分子との相溶性とサイズ性能のバランス面、オフセット印刷時の版汚れを避けるためにも３万〜６万の重量平均分子量が適当である。
(F. Molecular weight)
Cationic surface sizing agents synthesized by such a method generally have a higher molecular weight when the molecular weight is larger. However, when the molecular weight is large, the viscosity of the solution is high, so that the workability and the water-soluble polymer are high. A weight average molecular weight of 30,000 to 60,000 is appropriate in order to avoid compatibility between the compatibility and size performance and plate stains during offset printing.
＜ポリエチレンワックスエマルジョン＞
本発明では、表面処理剤に含有される（Ｂ）として、ノニオン性乳化剤またはカチオン性乳化剤で乳化したポリエチレンワックスエマルジョンが用いられる。ポリエチレンワックスエマルジョンが配合されることにより、カチオン性表面サイズ剤を含む表面処理剤にすべり性が付与されて、カチオン性表面サイズ剤の高いサイズ性を維持したまま、摩擦係数の上昇を抑えて最適な範囲に調整することができる。
本発明で使用するノニオン性乳化剤又はカチオン性乳化剤で乳化したポリエチレンワックスエマルジョンにおいて、原料ポリエチレンは公知の方法で製造されるものであり、例えばエチレンをラジカル触媒による高温高圧下で重合するか、あるいは、チーグラー触媒により低圧で重合して得られる。得られたポリエチレンワックス原体は、乳化剤を用いて乳化分散した水性エマルジョンの形態とする。該エマルジョンの製造方法は、水、ポリエチレンワックスおよび乳化剤を反応容器に入れ、ポリエチレンワックスの融点以上に加熱し撹拌により乳化分散後冷却する。あるいは、予め微粒子に粉砕したポリエチレンワックスを乳化剤を用いてそのまま水に分散させることによって得られる。
<Polyethylene wax emulsion>
In the present invention, a polyethylene wax emulsion emulsified with a nonionic emulsifier or a cationic emulsifier is used as (B) contained in the surface treatment agent. By blending polyethylene wax emulsion, the surface treatment agent including the cationic surface sizing agent is given slipperiness, while maintaining the high sizing property of the cationic surface sizing agent. Can be adjusted within a wide range.
In the polyethylene wax emulsion emulsified with the nonionic emulsifier or the cationic emulsifier used in the present invention, the raw material polyethylene is produced by a known method, for example, ethylene is polymerized under a high temperature and high pressure by a radical catalyst, or It is obtained by polymerization at low pressure with a Ziegler catalyst. The obtained polyethylene wax raw material is in the form of an aqueous emulsion emulsified and dispersed using an emulsifier. In the production method of the emulsion, water, polyethylene wax and an emulsifier are placed in a reaction vessel, heated to a temperature higher than the melting point of polyethylene wax, dispersed by emulsion and cooled after stirring. Alternatively, it can be obtained by dispersing polyethylene wax ground in advance into fine particles as it is using an emulsifier.
このときの乳化剤は、ノニオン性又はカチオン性である必要がある。これは、アニオン性乳化剤でエマルジョン化したポリエチレンワックスの場合、表面処理剤中のカチオン性表面サイズ剤との相溶性が悪く、凝集等を引き起こすことから、ノニオン性又はカチオン性乳化剤を用いる必要があるのである。
適するノニオン性乳化剤としては、公知のものを使用でき、具体的には、例えば、ソルビタンモノパルミテート、ソルビタンモノオレエート、ソルビタンモノステアレート等のソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノオレエート、ポリオキシエチレンソルビタンモノステアレート等のポリオキシアルキレン脂肪酸エステル類、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル等のポリオキシアルキレンエーテル類、ポリキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシアルキレンアルキルアリルエーテル類、ポリオキシエチレン・ポリオキシプロピレンブロック共重合体等が挙げられる。これらのノニオン性乳化剤は一種又は二種以上を組み合わせて用いても良い。
また、カチオン性乳化剤としては、公知のものを使用でき、具体的には、例えば、ジメチルアミノエチルアクリレート、ジメチルアミノエチルメタアクリレート、ジエチルアミノエチルアクリレート、ジメチルアミノスチレン、ジエチルアミノスチレン、メチルエチルアミノスチレン等が挙げられる。これらのカチオン性乳化剤は一種又は二種以上を組み合わせて用いても良い。
The emulsifier at this time needs to be nonionic or cationic. This is because in the case of polyethylene wax emulsified with an anionic emulsifier, it is necessary to use a nonionic or cationic emulsifier because it is poorly compatible with the cationic surface sizing agent in the surface treatment agent and causes aggregation. It is.
As the suitable nonionic emulsifier, known ones can be used. Specifically, for example, sorbitan fatty acid esters such as sorbitan monopalmitate, sorbitan monooleate, sorbitan monostearate, polyoxyethylene sorbitan monolaurate, Polyoxyalkylene fatty acid esters such as polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitan monostearate, polyoxyalkylene ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether and polyoxyethylene stearyl ether, poly Polyoxyalkylene alkyl allyl ethers such as xylethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether, polyoxyethylene polyoxyp Pyrene block copolymer and the like. These nonionic emulsifiers may be used singly or in combination of two or more.
As the cationic emulsifier, known ones can be used. Specifically, for example, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, dimethylaminostyrene, diethylaminostyrene, methylethylaminostyrene, and the like. Can be mentioned. These cationic emulsifiers may be used alone or in combination of two or more.
ノニオン性乳化剤又はカチオン性乳化剤の使用割合は、ポリエチレンワックス原体１００重量部に対して、０．３〜５０重量部、好ましくは０．５〜２０重量部、更に好ましくは０．５〜１０重量部である。０．３重量部未満であるとポリエチレンワックスの乳化が充分ではなくなり、得られるエマルジョンの平均粒子径が粗大となり、また平均粒子径分布もブロードとなるため、紙の摩擦係数を低下させる効果が小さくなるという問題がある。一方、５０重量部を超えるとポリエチレンワックスの乳化自体は良好であるが、得られるエマルジョン粒子の平均粒子径が小さくなり過ぎることがあり、この場合、紙の摩擦係数を低減する効果が小さくなり、更に表面処理剤が泡立ちやすく、抄紙上の問題となることがある。 The nonionic emulsifier or the cationic emulsifier is used in an amount of 0.3 to 50 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polyethylene wax raw material. Part. If it is less than 0.3 parts by weight, the emulsification of polyethylene wax will not be sufficient, the average particle size of the resulting emulsion will be coarse, and the average particle size distribution will also be broad, so the effect of reducing the friction coefficient of paper will be small There is a problem of becoming. On the other hand, if it exceeds 50 parts by weight, the emulsification of polyethylene wax itself is good, but the average particle diameter of the resulting emulsion particles may be too small, in this case, the effect of reducing the friction coefficient of the paper becomes small, Furthermore, the surface treatment agent tends to foam, which may cause problems in papermaking.
ポリエチレンワックスエマルジョンは、動的光散乱式粒度分布測定装置による平均粒子径で２０〜３００ｎｍが好ましく、１００〜３００ｎｍであることが更に好ましい。２０ｎｍ未満では新聞用紙の摩擦係数を低下させる効果が小さい。パルプ繊維が積層し絡み合って紙層が形成されているため、紙表面は多くの凹凸部が存在し、その紙表面にポリエチレンワックスエマルジョンを塗布した場合、ポリエチレンワックスの平均粒子径が小さ過ぎると紙表面の凹部にエマルジョン粒子が埋没するため、摩擦係数を低減させる効果が小さくなるものと考えている。一方、３００ｎｍを超えると紙表面の凹部にエマルジョン粒子が埋没することはないが、ポリエチレンワックスエマルジョンの塗布量が一定の場合、平均粒子径が大きいほど粒子数が少なく、紙表面にエマルジョン粒子がまばらにしか存在せず、これが原因で摩擦係数を低下させる効果が小さくなるものと考えている。 The average particle diameter of the polyethylene wax emulsion by a dynamic light scattering particle size distribution analyzer is preferably 20 to 300 nm, and more preferably 100 to 300 nm. If it is less than 20 nm, the effect of reducing the friction coefficient of newsprint is small. Since the paper layer is formed by the pulp fibers being laminated and intertwined, the paper surface has many irregularities, and when the polyethylene wax emulsion is applied to the paper surface, the paper will be damaged if the average particle diameter of the polyethylene wax is too small. Since the emulsion particles are buried in the recesses on the surface, the effect of reducing the friction coefficient is considered to be small. On the other hand, if it exceeds 300 nm, the emulsion particles will not be buried in the recesses on the paper surface. However, when the amount of polyethylene wax emulsion applied is constant, the larger the average particle diameter, the smaller the number of particles, and the smaller the emulsion particles on the paper surface. Therefore, it is considered that the effect of reducing the friction coefficient is reduced.
＜水溶性高分子物質＞
本発明では、表面処理剤に（Ｃ）水溶性高分子物質が含有される。水溶性高分子物質としては、例えば、澱粉、酵素変性澱粉、熱化学変性澱粉、酸化澱粉、エステル化澱粉、エーテル化澱粉（例えば、ヒドロキシエチル化澱粉等）、カチオン化澱粉等の澱粉類、ポリビニルアルコール、完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコール、カルボキシル変性ポリビニルアルコール、シラノール変性ポリビニルアルコール、カチオン変性ポリビニルアルコール、末端アルキル変性ポリビニルアルコール等のポリビニルアルコール類、ポリアクリルアミド、カチオン性ポリアクリルアミド、アニオン性ポリアクリルアミド、両性ポリアクリルアミド等のポリアクリルアミド類、カルボキシメチルセルロース、ヒドロキシエチルセルロース、メチルセルロース等のセルロース誘導体等が挙げられる。新聞用紙の表面強度を向上させ、オフセット印刷時の紙粉パイリング(ブランケトパイリング)、結束パルプ繊維に起因するヒッキー、ベッセルに起因する白ポチなどの発生を抑制する上で、これらの水溶性高分子物質の使用は重要である。中でも、表面強度の向上効果とネッパリ防止とのバランスから澱粉類が好ましく使用でき、その中でも、酸化澱粉、エステル化澱粉、エーテル化澱粉が最も好ましい。
＜表面処理剤の調整＞
<Water-soluble polymer material>
In the present invention, the surface treatment agent contains (C) a water-soluble polymer substance. Examples of water-soluble polymer substances include starch, enzyme-modified starch, thermochemically-modified starch, oxidized starch, esterified starch, etherified starch (for example, hydroxyethylated starch), starch such as cationized starch, polyvinyl Alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, polyvinyl alcohols such as terminal alkyl-modified polyvinyl alcohol, polyacrylamide, cationic polyacrylamide, anionic Examples include polyacrylamides such as polyacrylamide and amphoteric polyacrylamide, and cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, and methylcellulose. In order to improve the surface strength of newsprint paper and suppress the occurrence of paper dust piling (Blanketo piling) during offset printing, hickies caused by bundling pulp fibers, white spots caused by vessels, etc. The use of molecular materials is important. Among them, starches can be preferably used from the balance between the effect of improving the surface strength and the prevention of neppari, and among them, oxidized starch, esterified starch, and etherified starch are most preferable.
<Adjustment of surface treatment agent>
本発明においては、上述の方法で製造した（Ａ）のカチオン性表面サイズ剤に、（Ｂ）のポリエチレンワックスエマルジョンを添加混合した後、（Ｃ）の水溶性高分子物質を更に混合して表面処理剤を調製しても良い。この場合、カチオン性表面サイズ剤とポリエチレンワックスエマルジョンとの混合は、カチオン性表面サイズ剤の製造直後でも良いし、表面処理剤を調製する時点でカチオン性表面サイズ剤へポリエチレンワックスエマルジョンを添加混合する方法でも良い。また、表面処理剤の調製時に、カチオン性表面サイズ剤、ポリエチレンワックスエマルジョン、及び水溶性高分子物質をそれぞれ別々に添加して混合しても良い。
＜塗布量＞
In the present invention, the polyethylene wax emulsion (B) is added and mixed to the cationic surface sizing agent (A) produced by the above-described method, and then the water-soluble polymer substance (C) is further mixed to the surface. A treating agent may be prepared. In this case, the cationic surface sizing agent and the polyethylene wax emulsion may be mixed immediately after the production of the cationic surface sizing agent, or the polyethylene wax emulsion is added to and mixed with the cationic surface sizing agent when the surface treatment agent is prepared. The method is fine. Moreover, you may add and mix a cationic surface sizing agent, a polyethylene wax emulsion, and a water-soluble polymer substance separately at the time of preparation of a surface treating agent.
<Coating amount>
原紙へのカチオン性表面サイズ剤の塗布量は、要求される吸水抵抗性（言い換えれば、サイズ性）により適宜調整するが、一般的には両面当たりの塗布量（固形分重量）で０．０１〜０．５ｇ／ｍ２であり、０．０１ｇ／ｍ２未満では充分な吸水抵抗性が得られず、０．５ｇ／ｍ２を超えると吸水抵抗性は高く問題はないが、オフセット印刷時に用いる湿し水へ表面サイズ剤が溶出、蓄積し、印刷版を感脂化し、印刷面に地汚れが発生する場合がある。 The coating amount of the cationic surface sizing agent on the base paper is appropriately adjusted according to the required water absorption resistance (in other words, size property), but in general, the coating amount on both sides (solid content weight) is 0.01. was ~0.5g / m 2, 0.01g / m without sufficient water resistance is not obtained at less than 2, but is not high problem water resistance exceeds 0.5 g / m 2, at the time of offset printing In some cases, the surface sizing agent dissolves and accumulates in the fountain solution used, sensitizes the printing plate, and stains occur on the printing surface.
原紙へのポリエチレンワックスエマルジョンの塗布量は、本発明で規定する摩擦係数の範囲内に入るように適宜調整するが、両面当たりの塗布量（固形分重量）で０．００５〜０．０２５ｇ／ｍ２が好ましい。０．００５ｇ／ｍ２未満では摩擦係数低下の効果がほとんどなく、０．０２５ｇ／ｍ２を超えると静摩擦係数及び／又は動摩擦係数が過度に低下し、本発明で規定する摩擦係数の範囲外になるため紙流れ等の問題が発生する。
ポリエチレンワックスエマルジョンの添加方法は前述のように、（１）表面処理剤の調製時に、カチオン性表面サイズ剤、ポリエチレンワックスエマルジョン、及び水溶性高分子物質をそれぞれ別々に添加する方法、（２）カチオン性表面サイズ剤にポリエチレンワックスエマルジョンを添加混合する方法、がある。（１）の添加方法の場合には両面当たりの塗布量（固形分重量）が０．００５〜０．０２５ｇ／ｍ２となるように、表面処理剤液中にポリエチレンワックスエマルジョンを添加する。（２）の添加方法の場合、カチオン性表面サイズ剤の添加量は要求される吸水抵抗性により変わるので、この添加量の変動を考慮に入れ、しかもポリエチレンワックスエマルジョンの両面当たりの塗布量（固形分重量）が０．００５〜０．０２５ｇ／ｍ２となるように、カチオン性表面サイズ剤液中へポリエチレンワックスエマルジョンを添加する必要がある。カチオン性表面サイズ剤固形分に対しては、５〜３０固形分重量％添加することが好ましい。
The coating amount of the polyethylene wax emulsion on the base paper is appropriately adjusted so as to fall within the range of the coefficient of friction specified in the present invention, but 0.005 to 0.025 g / m in coating amount (solid content weight) per both sides. 2 is preferred. Little effect of lowering the friction coefficient is less than 0.005g / m 2, 0.025g / m 2 by weight, the static friction coefficient and / or dynamic friction coefficient is excessively reduced, the range of the friction coefficient defined by the present invention Therefore, problems such as paper flow occur.
As described above, the method for adding the polyethylene wax emulsion is as follows: (1) a method in which a cationic surface sizing agent, a polyethylene wax emulsion, and a water-soluble polymer substance are separately added at the time of preparation of the surface treatment agent; There is a method in which a polyethylene wax emulsion is added to and mixed with the surface sizing agent. In the case of the addition method (1), a polyethylene wax emulsion is added to the surface treating agent solution so that the coating amount (solid weight) per both sides is 0.005 to 0.025 g / m 2 . In the case of the addition method (2), the addition amount of the cationic surface sizing agent varies depending on the required water absorption resistance. Therefore, the variation of the addition amount is taken into consideration, and the coating amount (both solids) of the polyethylene wax emulsion is taken into account. It is necessary to add the polyethylene wax emulsion into the cationic surface sizing agent solution so that the (partial weight) is 0.005 to 0.025 g / m 2 . It is preferable to add 5 to 30% by weight of the solid content of the cationic surface sizing agent.
原紙への水溶性高分子物質の塗布量は、原料パルプの種類と配合、紙中灰分量、必要とされる表面強度等により適宜調整するが、一般的には両面当たりの塗布量（固形分重量）で、０．０５〜１．５ｇ／ｍ２である。各水溶性高分子物質の塗布量が、この範囲未満では充分な表面強度が得られず、この範囲を超えるとネッパリ強度が高くなるという問題がある。 The coating amount of the water-soluble polymer substance on the base paper is appropriately adjusted according to the type and composition of the raw pulp, the amount of ash in the paper, the required surface strength, etc. Weight) of 0.05 to 1.5 g / m 2 . If the coating amount of each water-soluble polymer substance is less than this range, sufficient surface strength cannot be obtained, and if it exceeds this range, there is a problem that Nepari strength increases.
＜塗工装置＞
表面処理剤を新聞用紙の原紙に塗布する塗工装置としては、特に限定されるものではなく、例えば、ゲートロールコーター、サイズプレス、ロッドメタリングサイズプレス、ブレードコーター、バーコーター、エアーナイフコーター、カーテンコーター等、一般に公知公用の塗工装置が適宜使用される。
<Coating device>
The coating apparatus for applying the surface treatment agent to newsprint base paper is not particularly limited. For example, a gate roll coater, a size press, a rod metering size press, a blade coater, a bar coater, an air knife coater, Generally known publicly used coating apparatuses such as curtain coaters are appropriately used.
＜原紙＞
本発明のオフセット印刷用中性新聞用紙に用いられる原紙は、填料として炭酸カルシウムを主体として含有するものが好ましく、紙面ｐＨ６〜９程度である。通常の中性抄紙では抄紙工程で紙料に硫酸バンドを添加しても炭酸カルシウムが相対的に多く存在することにより完全に中和され、特にｐＨ調整を行わない限り、紙料や白水のｐＨは安定的に中性領域となる。このようにして抄造された中性新聞用紙の紙面ｐＨは上記の範囲内となる。
本発明における原紙は、グランドパルプ（ＧＰ）、リファイナーグランドパルプ（ＲＧＰ）、サーモメカニカルパルプ（ＴＭＰ）、ケミカルサーモメカニカルパルプ（ＣＴＭＰ）、等のメカニカルパルプ（ＭＰ）、クラフトパルプ（ＫＰ）に代表されるケミカルパルプ（ＣＰ）、これらのパルプを含む古紙を脱墨して得られる脱墨パルプ（ＤＩＰ）、及び抄紙工程からの損紙を離解して得られる回収パルプ等を、単独あるいは任意の比率で混合し、一般に公知公用の抄紙機によって抄紙されたものである。全パルプ中のＤＩＰの配合率は、最近のＤＩＰの高配合化の流れからすると５０〜１００重量％の範囲が好ましい。
<Base paper>
The base paper used for the neutral newsprint for offset printing of the present invention preferably contains calcium carbonate as a main filler, and has a paper surface pH of about 6-9. In normal neutral papermaking, even if a sulfuric acid band is added to the paper stock in the paper making process, it is completely neutralized due to the relatively large amount of calcium carbonate. Becomes a neutral region stably. The paper surface pH of the neutral newsprint produced in this way falls within the above range.
The base paper in the present invention is represented by mechanical pulp (MP) such as ground pulp (GP), refiner ground pulp (RGP), thermomechanical pulp (TMP), chemical thermomechanical pulp (CTMP), and kraft pulp (KP). Chemical pulp (CP), deinked pulp (DIP) obtained by deinking waste paper containing these pulps, and recovered pulp obtained by disaggregating damaged paper from the papermaking process, alone or in any ratio And are generally made by a publicly known paper machine. The blending ratio of DIP in the whole pulp is preferably in the range of 50 to 100% by weight based on the recent trend toward high blending of DIP.
本発明における原紙は、絶乾重量に対する灰分が３重量％以上であることが好ましく、１０〜２０重量％の範囲であることがより好ましい。灰分が１０重量％以上であると、紙の不透明性が高く、オフセット印刷した場合のインキ裏抜けが目立たない。また灰分が高すぎると紙の強度や吸水抵抗性が低下し、断紙や紙粉パイリング等の問題が生じやすいため、２０重量％以下程度が好適である。さらに灰重量に対する炭酸カルシウムの割合が６０重量％以上であることが好ましい。通常ＤＩＰの灰成分の中では炭酸カルシウムの割合が多くを占める場合が多いが、ＤＩＰには炭酸カルシウム以外の灰成分も多く含まれ、その割合は新聞古紙、雑誌古紙等の古紙種類や回収状況等により異なるため、品質変動の要因になる。また灰成分はトナーや異物を含有し、紙面ダートや紙面欠陥の原因となる場合もある。そのためＤＩＰの灰分を填料として利用することも行うが、ＤＩＰ中の灰成分を洗浄工程である程度洗い出し、新たにフレッシュな填料として炭酸カルシウムを添加する。
填料として炭酸カルシウムを添加し、紙中の炭酸カルシウムを増やすほど紙の摩擦係数が上昇する。このため、オフセット印刷用中性新聞用紙の中でも、紙中の炭酸カルシウムが多いほど、本発明で使用するポリエチレンを構成成分として含有するカチオン性表面サイズ剤を塗布することによる紙の摩擦係数の低減効果が大きくなる。このようにして、得られるオフセット印刷用中性新聞用紙の摩擦係数を過度に上昇させることなく、填料として炭酸カルシウムを高配合できるため、紙の白色度、不透明度を向上させることができる。
The base paper in the present invention preferably has an ash content of 3% by weight or more, more preferably in the range of 10 to 20% by weight based on the absolute dry weight. When the ash content is 10% by weight or more, the paper has high opacity, and ink see-through is not noticeable when offset printing is performed. On the other hand, if the ash content is too high, the strength and water absorption resistance of the paper are lowered, and problems such as paper breakage and paper dust piling are likely to occur. Furthermore, the ratio of calcium carbonate to the ash weight is preferably 60% by weight or more. Usually, the proportion of calcium carbonate in the ash component of DIP is large, but DIP also contains a lot of ash components other than calcium carbonate. Because of this, it becomes a factor of quality fluctuation. Further, the ash component contains toner and foreign matters, and may cause paper surface darts and paper surface defects. Therefore, the ash content of DIP is also used as a filler, but the ash component in DIP is washed out to some extent in the washing step, and calcium carbonate is newly added as a fresh filler.
The coefficient of friction of the paper increases as calcium carbonate is added as a filler and the amount of calcium carbonate in the paper is increased. For this reason, among neutral newsprint paper for offset printing, the more calcium carbonate in the paper, the lower the friction coefficient of the paper by applying a cationic surface sizing agent containing polyethylene as a constituent component used in the present invention. The effect is increased. Thus, since the calcium carbonate can be highly blended as a filler without excessively increasing the friction coefficient of the obtained neutral newsprint for offset printing, the whiteness and opacity of the paper can be improved.
本発明における原紙の抄造時、必要に応じて、一般に公知公用の製紙用填料、抄紙用薬品を適宜使用することができる。填料としては、炭酸カルシウム以外に、ホワイトカーボン、クレー、シリカ、タルク、酸化チタン、合成樹脂填料（塩化ビニル樹脂、ポリスチレン樹脂、尿素ホルマリン樹脂、メラミン系樹脂、スチレン／ブタジエン系共重合体樹脂等）等を使用しても良い。また、抄紙用内添薬品としては、ポリアクリルアミド系高分子、ポリビニルアルコール系高分子、カチオン化澱粉、尿素−ホルマリン系樹脂、メラミン−ホルマリン系樹脂等の紙力増強剤、アクリルアミド−アミノメチルアクリルアミド共重合体の塩、カチオン化澱粉、ポリエチレンイミン、ポリエチレンオキサイド、アクリルアミド−アクリル酸ナトリウム共重合体等の濾水性及び／又は歩留まり向上剤、ロジンサイズ剤、エマルジョンサイズ剤、アルキルケテンダイマー（ＡＫＤ）、アルケニル琥珀酸無水物（ＡＳＡ）等の内添サイズ剤、硫酸アルミニウム(硫酸バンド)、紫外線防止剤、退色防止剤、消泡剤等の助剤等を含有してもよい。また、原紙の坪量としては特に限定されるものではないが、３４〜５０ｇ／ｍ２の範囲である。この新聞原紙の物性に関しては、オフセット印刷で印刷可能である必要があり、通常の新聞用紙程度の引張り強度、引裂き強度、伸び等の物性を有するものであればよい。 When making the base paper in the present invention, generally known and publicly available papermaking fillers and papermaking chemicals can be appropriately used as necessary. In addition to calcium carbonate, fillers include white carbon, clay, silica, talc, titanium oxide, synthetic resin filler (vinyl chloride resin, polystyrene resin, urea formalin resin, melamine resin, styrene / butadiene copolymer resin, etc.) Etc. may be used. Examples of internal chemicals for papermaking include polyacrylamide polymers, polyvinyl alcohol polymers, cationized starch, urea-formalin resins, melamine-formalin resins and other paper strength enhancers, and acrylamide-aminomethylacrylamide. Polymer salt, cationized starch, polyethyleneimine, polyethylene oxide, acrylamide-sodium acrylate copolymer drainage and / or yield improver, rosin sizing agent, emulsion sizing agent, alkyl ketene dimer (AKD), alkenyl An auxiliary additive such as an internal sizing agent such as succinic anhydride (ASA), aluminum sulfate (sulfuric acid band), an ultraviolet ray inhibitor, a fading inhibitor, and an antifoaming agent may be contained. The basis weight of the base paper is not particularly limited, but is in the range of 34 to 50 g / m 2 . Regarding the physical properties of this newspaper base paper, it is necessary to be able to print by offset printing, and any material having physical properties such as tensile strength, tear strength, and elongation equivalent to those of ordinary newsprint paper may be used.
＜摩擦係数＞
本発明におけるオフセット印刷用中性新聞用紙の適切な摩擦係数の範囲とは、静摩擦係数０．５０〜０．７５、動摩擦係数０．４０〜０．６０の範囲であり、この範囲にあることにより、摩擦係数が高いことに起因するオフセット印刷時の剣先詰まりや皺の発生、印刷テンション増加による色ずれ等の問題を改善することができる。好ましくは静摩擦係数０．５５〜０．７０、動摩擦係数０．４５〜０．５５の範囲である。
<Friction coefficient>
The appropriate friction coefficient range of the neutral newsprint for offset printing in the present invention is a range of a static friction coefficient of 0.50 to 0.75 and a dynamic friction coefficient of 0.40 to 0.60. In addition, problems such as clogging of a sword tip and occurrence of wrinkles during offset printing due to a high friction coefficient, and color misregistration due to increased printing tension can be improved. Preferably, the static friction coefficient is 0.55 to 0.70 and the dynamic friction coefficient is 0.45 to 0.55.
（実施例）
以下、実施例にて本発明を具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、実施例及び比較例の中の％、部は特に断らない限り、それぞれ重量％、重量部を示す。
(Example)
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a following example. In addition, unless otherwise indicated,% and a part in an Example and a comparative example show weight% and a weight part, respectively.
［カチオン性表面サイズ剤の製造方法］
（合成例１）
スチレン５０部、2-エチルヘキシルメタクリレート２０部と、ジメチルアミノプロピルアクリルアミド３０部と、連鎖移動剤のn-ドデシルメルカプタン２部と、イソプロピルアルコール４２．７部とを４つ口フラスコに入れ、８５℃まで加熱して、開始剤として2,2-アゾビス-2-メチルブチロニトリル（２５℃のエタノールへの溶解度７５ｇ／１００ｇ）２．５部を加え、９０℃で３時間重合した。このとき、サンプリングしてshodexGPCシステム-21H（カラムGF-7M、GF-310、溶媒ＤＭＦでポリスチレン換算値)で分子量を測定したところ、重量平均分子量は４３,０００であった。次いで、水３４０部と９０％酢酸１２．８部を加えて水溶化した後、加熱蒸留してイソプロピルアルコールを留去した。その後、８５℃でエピクロルヒドリン１７．７部を加えて３時間反応し、冷却し、水で希釈して、固形分２０％、淡黄微濁液の表面サイズ剤を得た。（４級化率１００％）
[Method for producing cationic surface sizing agent]
(Synthesis Example 1)
50 parts of styrene, 20 parts of 2-ethylhexyl methacrylate, 30 parts of dimethylaminopropyl acrylamide, 2 parts of chain transfer agent n-dodecyl mercaptan and 42.7 parts of isopropyl alcohol are placed in a four-necked flask up to 85 ° C. Upon heating, 2.5 parts of 2,2-azobis-2-methylbutyronitrile (solubility of 75 g / 100 g in ethanol at 25 ° C.) was added as an initiator, and polymerization was carried out at 90 ° C. for 3 hours. At this time, the molecular weight was sampled and measured with shodexGPC system-21H (column GF-7M, GF-310, solvent DMF in terms of polystyrene), and the weight average molecular weight was 43,000. Subsequently, 340 parts of water and 12.8 parts of 90% acetic acid were added to make it water-soluble, and then distilled by heating to distill off isopropyl alcohol. Thereafter, 17.7 parts of epichlorohydrin was added at 85 ° C., reacted for 3 hours, cooled, and diluted with water to obtain a surface sizing agent having a solid content of 20% and a pale yellow turbid liquid. (Quaternization rate 100%)
（合成例２）
スチレン６０部と、n-ブチルメタクリレート１５部と、ジメチルアミノエチルメタクリレート２５部と、連鎖移動剤のt-ドデシルメルカプタン２部と、トルエン４２．７部とを４つ口フラスコに入れ、１０５℃まで加熱して、開始剤としてジメチル-2,2-アゾビスイソブチレート（２５℃のエタノールへの溶解度１３０ｇ以上／１００ｇエタノール）２部を加え、１１０℃で３時間重合した。このときの共重合物の重量平均分子量は３５,０００であった。次いで、水３５０部と９０％%酢酸１０．６部を加えて水溶化した後、加熱蒸留してトルエンを留去し、水で希釈して、固形分２０％、淡黄微濁液の表面サイズ剤を得た。（４級化率６０％）
(Synthesis Example 2)
60 parts of styrene, 15 parts of n-butyl methacrylate, 25 parts of dimethylaminoethyl methacrylate, 2 parts of t-dodecyl mercaptan as a chain transfer agent, and 42.7 parts of toluene are placed in a four-necked flask and heated to 105 ° C. After heating, 2 parts of dimethyl-2,2-azobisisobutyrate (solubility of 130 g or more in ethanol at 25 ° C./100 g ethanol) was added as an initiator, and polymerization was carried out at 110 ° C. for 3 hours. The weight average molecular weight of the copolymer at this time was 35,000. Next, 350 parts of water and 10.6 parts of 90% acetic acid were added to make it water-soluble, and then distilled by heating to distill off toluene and diluted with water to obtain a solid content of 20% and the surface of a pale yellow turbid liquid. A sizing agent was obtained. (Quaternization rate 60%)
（合成例３）
n-ブチルメタクリレート５０部と、ラウリルメタクリレート２０部と、ジメチルアミノエチルメタクリレート３０部と、連鎖移動剤のt-ドデシルメルカプタン２部と、イソプロピルアルコール３２．５部とを４つ口フラスコに入れ、８５℃まで加熱し、開始剤として2,2-アゾビス-2,4-ジメチルバレロニトリル（２５℃のエタノールへの溶解度２０ｇ／１００ｇエタノール）２部を加え、９０℃で３時間重合した。このときの共重合物の重量平均分子量は４８,０００であった。次いで、水３３５部と、酢酸１２．７部を加えて水溶化した後、溶媒蒸留せずに８５℃でエピクロルヒドリン１７．７部を加えて３時間反応し、冷却し、水で希釈して、固形分２０％、淡黄微濁液の表面サイズ剤を得た。（４級化率１００％）
(Synthesis Example 3)
50 parts of n-butyl methacrylate, 20 parts of lauryl methacrylate, 30 parts of dimethylaminoethyl methacrylate, 2 parts of chain transfer agent t-dodecyl mercaptan and 32.5 parts of isopropyl alcohol are placed in a four-necked flask. Then, 2 parts of 2,2-azobis-2,4-dimethylvaleronitrile (20 g / 100 g ethanol in 25 ° C. ethanol) was added as an initiator, and polymerization was carried out at 90 ° C. for 3 hours. The weight average molecular weight of the copolymer at this time was 48,000. Next, 335 parts of water and 12.7 parts of acetic acid were added to make it water-soluble, and then 17.7 parts of epichlorohydrin was added at 85 ° C. without solvent distillation and reacted for 3 hours, cooled, diluted with water, A surface sizing agent having a solid content of 20% and a pale yellow cloudy liquid was obtained. (Quaternization rate 100%)
（合成例４）
スチレン３０部と、イソブチルメタクリレート４８部と、ジエチルアミノエチルアクリレート２２部と、連鎖移動剤のn-ドデシルメルカプタン２部と、イソプロピルアルコール４７．５部とを４つ口フラスコに入れ、９０℃まで加熱し、開始剤として2,2-アゾビス-2-メチルブチロニトリル（２５℃のエタノールへの溶解度７５ｇ／１００ｇエタノール）２部を加え、９０℃で３時間重合した。このときの共重合物の重量平均分子量は３７,０００であった。次いで、水３３０部と９０％酢酸９．３部を加えて水溶化した後、加熱蒸留してイソプロピルアルコールを留去した。その後、８５℃で塩化ベンジル１５．９部を加えて４時間反応し、冷却し、水で希釈して、固形分２０％、淡黄微濁液の表面サイズ剤を得た。（４級化率９０％）
(Synthesis Example 4)
30 parts of styrene, 48 parts of isobutyl methacrylate, 22 parts of diethylaminoethyl acrylate, 2 parts of chain transfer agent n-dodecyl mercaptan and 47.5 parts of isopropyl alcohol are placed in a four-necked flask and heated to 90 ° C. Then, 2 parts of 2,2-azobis-2-methylbutyronitrile (solubility of 75 g / 100 g ethanol in ethanol at 25 ° C.) was added as an initiator and polymerized at 90 ° C. for 3 hours. The weight average molecular weight of the copolymer at this time was 37,000. Next, 330 parts of water and 9.3 parts of 90% acetic acid were added to make it water-soluble, and then distilled by heating to distill off isopropyl alcohol. Thereafter, 15.9 parts of benzyl chloride was added at 85 ° C., reacted for 4 hours, cooled, and diluted with water to obtain a surface sizing agent having a solid content of 20% and a pale yellow turbid liquid. (Quarterization rate 90%)
（合成例５）
スチレン５０部と、2-エチルヘキシルメタクリレート１５部と、ジメチルアミノエチルメタクリレート３５部と、連鎖移動剤のt-ドデシルメルカプタン２部と、イソプロピルアルコール４７．５部とを４つ口フラスコに入れ、８５℃まで加熱し、開始剤としてアゾビスイソブチロニトリル（２５℃のエタノールへの溶解度２．７ｇ／１００ｇエタノール）２部を加え、９０℃で３時間重合した。このときの共重合物の重量平均分子量は６０,０００であった。次いで、水３５０部と９０％酢酸１４．８部を加えて水溶化した後、加熱蒸留してイソプロピルアルコールを留去した、その後、８５℃でエピクロルヒドリン２０．７部を加えて３時間反応し、冷却し、水で希釈して、固形分２０％、微白濁液の表面サイズ剤を得た。（４級化率１００％）
(Synthesis Example 5)
50 parts of styrene, 15 parts of 2-ethylhexyl methacrylate, 35 parts of dimethylaminoethyl methacrylate, 2 parts of t-dodecyl mercaptan as a chain transfer agent, and 47.5 parts of isopropyl alcohol are placed in a four-necked flask and heated to 85 ° C. 2 parts of azobisisobutyronitrile (solubility of 2.7 g / 100 g ethanol in ethanol at 25 ° C.) was added as an initiator and polymerized at 90 ° C. for 3 hours. The weight average molecular weight of the copolymer at this time was 60,000. Next, 350 parts of water and 14.8 parts of 90% acetic acid were added to make it water-soluble, and then distilled by heating to distill off isopropyl alcohol. Then, 20.7 parts of epichlorohydrin was added at 85 ° C. and reacted for 3 hours. It was cooled and diluted with water to obtain a surface sizing agent having a solid content of 20% and a slightly cloudy liquid. (Quaternization rate 100%)
（合成例６）
スチレン５５部と、n-ブチルメタクリレート１５部と、ジメチルアミノエチルメタクリレート３０部と、連鎖移動剤のt-ドデシルメルカプタン１．８部と、イソプロピルアルコール４５部とを４つ口フラスコに入れ、８５℃まで加熱して、開始剤としてジメチル-2,2-アゾビスイソブチレート（２５℃のエタノールへの溶解度１３０ｇ以上／１００ｇエタノール）１．５部とt-ブチルパ-オキシ-2-エチルヘキサノエート０．５部を加え、９０℃で３時間重合した。このときの共重合物の重量平均分子量は４１,０００であった。次いで、水３５０部と酢酸１２．７部を加えて水溶化した後、加熱蒸留してイソプロピルアルコールを留去した。その後、８０℃で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２５．１部を加えて３時間反応し、冷却し、水で希釈して、固形分２０％、淡黄微濁液の表面サイズ剤を得た。（４級化率７０％）
(Synthesis Example 6)
55 parts of styrene, 15 parts of n-butyl methacrylate, 30 parts of dimethylaminoethyl methacrylate, 1.8 parts of t-dodecyl mercaptan as a chain transfer agent, and 45 parts of isopropyl alcohol are placed in a four-necked flask at 85 ° C. To 1.5 parts of dimethyl-2,2-azobisisobutyrate (solubility of 130 g or more in ethanol at 25 ° C./100 g ethanol) as an initiator and t-butyl peroxy-2-ethylhexanoate 0.5 part was added and polymerization was performed at 90 ° C. for 3 hours. The weight average molecular weight of the copolymer at this time was 41,000. Next, 350 parts of water and 12.7 parts of acetic acid were added to make it water-soluble, and then distilled by heating to distill off isopropyl alcohol. Thereafter, 25.1 parts of 3-chloro-2-hydroxypropyltrimethylammonium chloride was added at 80 ° C., reacted for 3 hours, cooled, diluted with water, solid content 20%, surface size of pale yellow turbid liquid An agent was obtained. (Quarterization rate 70%)
［ポリエチレンワックスエマルジョン］
使用したポリエチレンワックスエマルジョンの調製時に添加した乳化剤の商品名、成分、イオン性、及び該エマルジョンの動的光散乱式粒度分布測定装置による平均粒子径を表１に示した。
[Polyethylene wax emulsion]
Table 1 shows the trade name, components, ionicity of the emulsifier added during the preparation of the polyethylene wax emulsion used, and the average particle size of the emulsion measured by a dynamic light scattering particle size distribution analyzer.
［実施例１］
ＴＭＰ２０部、ＤＩＰ７５部、ＮＢＫＰ５部から成る混合パルプスラリーを調製し、この混合パルプ１００部(固形分重量)に対して硫酸バンドを１．３部、炭酸カルシウム２０部（商品名：オプチカルＨＦ、イメリス社製、平均粒子径１．５μｍ)を添加し、ツインワイヤー型抄紙機にて、坪量４３ｇ／ｍ２、厚さ７０μｍ、灰分１８％の中性新聞用紙の原紙を得た。
次にヒドロキシエチル化澱粉（商品名：ETHYLEX-2025、STAYLEY社製）を蒸煮したものを濃度７％に調製し、澱粉固形分重量に対し、上記の合成例１のカチオン性表面サイズ剤を１５固形分重量％添加し、更にポリエチレンワックスエマルジョンＡ（商品名：WAX-E1、ハリマ化成株式会社製、平均粒子径１１０ｎｍ、ノニオン性乳化剤）を３固形分重量％添加（カチオン性表面サイズ剤固形分重量に対し２０固形分重量％になる）して、表面処理剤を調製した。
次にゲートロールコーターにて塗工速度１２００ｍ／分で上記の原紙に表面処理剤を澱粉塗布量が両面で０．５ｇ／ｍ２になるように塗工し乾燥後、８０℃のホットソフトニップカレンダーで１ニップ処理し、オフセット印刷用中性新聞用紙を得た。
[Example 1]
A mixed pulp slurry comprising 20 parts of TMP, 75 parts of DIP, and 5 parts of NBKP was prepared, and 1.3 parts of a sulfuric acid band and 20 parts of calcium carbonate (trade names: Optical HF, Imeris) with respect to 100 parts (solid content weight) of this mixed pulp. A neutral newsprint base paper having a basis weight of 43 g / m 2 , a thickness of 70 μm, and an ash content of 18% was obtained using a twin wire type paper machine.
Next, steamed hydroxyethylated starch (trade name: ETHYLEX-2025, manufactured by STAYLEY) was prepared to a concentration of 7%, and the cationic surface sizing agent of Synthesis Example 1 above was added to the starch solid content weight by 15%. Solid weight% added, and further polyethylene wax emulsion A (trade name: WAX-E1, manufactured by Harima Kasei Co., Ltd., average particle size 110 nm, nonionic emulsifier) added 3% solid weight% (cationic surface sizing agent solid content The surface treatment agent was prepared with a solid content of 20% by weight.
Next, a surface treatment agent was applied to the above base paper with a gate roll coater at a coating speed of 1200 m / min so that the starch coating amount was 0.5 g / m 2 on both sides, dried, and then a hot soft nip at 80 ° C. One nip treatment was performed with a calendar to obtain neutral newsprint for offset printing.
［実施例２］
ポリエチレンワックスエマルジョンＡの澱粉固形分重量に対する添加量を１．５固形分重量％（カチオン性表面サイズ剤固形分重量に対し１０固形分重量％になる）に変更した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 2]
The same as Example 1 except that the addition amount of the polyethylene wax emulsion A with respect to the starch solid weight was changed to 1.5 solid weight% (10 solid weight% with respect to the cationic surface sizing agent solid weight). Thus, neutral newsprint for offset printing was obtained.
［実施例３］
ポリエチレンワックスエマルジョンＡの代わりにポリエチレンワックスエマルジョンＢ（商品名：WAX-E3、ハリマ化成株式会社製、粒径４０ｎｍ、カチオン性乳化剤）を使用した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 3]
For offset printing in the same manner as in Example 1 except that polyethylene wax emulsion B (trade name: WAX-E3, manufactured by Harima Kasei Co., Ltd., particle size 40 nm, cationic emulsifier) was used instead of polyethylene wax emulsion A. I got sex newspaper.
［実施例４］
ポリエチレンワックスエマルジョンＡの代わりにポリエチレンワックスエマルジョンＣ（商品名：MYE-3510、丸芳化成品株式会社製、粒径９０ｎｍ、ノニオン性乳化剤）を使用した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 4]
Offset printing was performed in the same manner as in Example 1 except that polyethylene wax emulsion C (trade name: MYE-3510, manufactured by Maruyoshi Kasei Co., Ltd., particle size 90 nm, nonionic emulsifier) was used instead of polyethylene wax emulsion A. A neutral newspaper was obtained.
［実施例５］
ポリエチレンワックスエマルジョンＡの代わりにポリエチレンワックスエマルジョンＤ（商品名：ポリエチレンエマルジョン、ユサ・テクニカ・ジャパン株式会社製、粒径５０ｎｍ、ノニオン性乳化剤）を使用した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 5]
Offset printing was performed in the same manner as in Example 1 except that polyethylene wax emulsion D (trade name: polyethylene emulsion, manufactured by Yusa Technica Japan Co., Ltd., particle size 50 nm, nonionic emulsifier) was used instead of polyethylene wax emulsion A. A neutral newspaper was obtained.
［実施例６］
ポリエチレンワックスエマルジョンＡの代わりにポリエチレンワックスエマルジョンＥ（商品名：メイカテックスHP-70、明成化学工業株式会社製、粒径７０ｎｍ、ノニオン性乳化剤）を使用した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 6]
Offsetting was carried out in the same manner as in Example 1 except that polyethylene wax emulsion E (trade name: Meikax HP-70, manufactured by Meisei Chemical Industry Co., Ltd., particle size 70 nm, nonionic emulsifier) was used instead of polyethylene wax emulsion A. A neutral newspaper for printing was obtained.
［実施例７］
ポリエチレンワックスエマルジョンＡの代わりにポリエチレンワックスＦ（商品名：パーマリン PN、三洋化成株式会社製、粒径１９０ｎｍ、ノニオン性乳化剤）を使用した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 7]
Neutral newspaper for offset printing in the same manner as in Example 1 except that polyethylene wax F (trade name: Permarin PN, manufactured by Sanyo Chemical Co., Ltd., particle size 190 nm, nonionic emulsifier) was used instead of polyethylene wax emulsion A. Got the paper.
［実施例８］
合成例１のカチオン性表面サイズ剤を、合成例２のカチオン性表面サイズ剤へ変更した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 8]
Neutral newsprint paper for offset printing was obtained in the same manner as in Example 1 except that the cationic surface sizing agent of Synthesis Example 1 was changed to the cationic surface sizing agent of Synthesis Example 2.
［実施例９］
合成例１のカチオン性表面サイズ剤を、合成例３のカチオン性表面サイズ剤へ変更した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 9]
Neutral newsprint paper for offset printing was obtained in the same manner as in Example 1 except that the cationic surface sizing agent of Synthesis Example 1 was changed to the cationic surface sizing agent of Synthesis Example 3.
［実施例１０］
合成例１のカチオン性表面サイズ剤を、合成例４のカチオン性表面サイズ剤へ変更した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 10]
Neutral newsprint paper for offset printing was obtained in the same manner as in Example 1 except that the cationic surface sizing agent of Synthesis Example 1 was changed to the cationic surface sizing agent of Synthesis Example 4.
［実施例１１］
合成例１のカチオン性表面サイズ剤を、合成例５のカチオン性表面サイズ剤へ変更した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 11]
Neutral newsprint paper for offset printing was obtained in the same manner as in Example 1 except that the cationic surface sizing agent of Synthesis Example 1 was changed to the cationic surface sizing agent of Synthesis Example 5.
［実施例１２］
合成例１のカチオン性表面サイズ剤を、合成例６のカチオン性表面サイズ剤へ変更した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 12]
Neutral newsprint paper for offset printing was obtained in the same manner as in Example 1 except that the cationic surface sizing agent of Synthesis Example 1 was changed to the cationic surface sizing agent of Synthesis Example 6.
［実施例１３］
原紙の製造に際して、炭酸カルシウムを１２部添加し、紙中灰分を１５％にした以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 13]
Neutral newsprint for offset printing was obtained in the same manner as in Example 1 except that 12 parts of calcium carbonate was added and the ash content in the paper was changed to 15% in the production of the base paper.
［実施例１４］
ヒドロキシエチル化澱粉の変わりに酸化澱粉（商品名：SK-20、日本コーンスターチ株式会社製）を使用した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 14]
Neutral newspaper for offset printing was obtained in the same manner as in Example 1 except that oxidized starch (trade name: SK-20, manufactured by Nippon Corn Starch Co., Ltd.) was used instead of hydroxyethylated starch.
［比較例１］
ポリエチレンワックスエマルジョンＡの代わりにポリエチレンワックスエマルジョンＧ（商品名：ノプコマル MS-40、サンノプコ株式会社製、粒径６３０ｎｍ、アニオン性乳化剤）を使用した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Comparative Example 1]
For offset printing in the same manner as in Example 1 except that polyethylene wax emulsion G (trade name: Nopcomal MS-40, manufactured by San Nopco, particle size 630 nm, anionic emulsifier) was used instead of polyethylene wax emulsion A. I got sex newspaper.
［比較例２］
ポリエチレンワックスエマルジョンＡを添加しないこと以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Comparative Example 2]
A neutral newsprint for offset printing was obtained in the same manner as in Example 1 except that the polyethylene wax emulsion A was not added.
［比較例３］
ポリエチレンワックスエマルジョンＡを添加しないこと以外は、実施例１３と同様にしてオフセット印刷用中性新聞用紙を得た。
[Comparative Example 3]
A neutral newsprint for offset printing was obtained in the same manner as in Example 13 except that the polyethylene wax emulsion A was not added.
［比較例４］
ポリエチレンワックスエマルジョンＡの代わりにポリエチレンワックスエマルジョンＨ（商品名：PEM-17、サンノプコ株式会社製、アニオン性乳化剤）を使用し、澱粉固形分重量に対する添加量を４．５固形分重量％（カチオン性表面サイズ剤固形分重量に対し３０固形分重量％になる）に変更した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Comparative Example 4]
Polyethylene wax emulsion H (trade name: PEM-17, manufactured by San Nopco Co., Ltd., anionic emulsifier) is used instead of polyethylene wax emulsion A, and the amount added is 4.5 solids weight% (cationic) A neutral newsprint for offset printing was obtained in the same manner as in Example 1 except that the solid sizing agent was changed to 30% by weight based on the solid weight of the surface sizing agent.
［比較例５］
ポリエチレンワックスエマルジョンＡの代わりにＡＫＤエマルジョン（商品名：SE2362、ノニオン性乳化剤）を使用し、澱粉固形分重量に対する添加量を４．５固形分重量％（カチオン性表面サイズ剤固形分重量に対し３０固形分重量％になる）に変更した以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Comparative Example 5]
An AKD emulsion (trade name: SE2362, nonionic emulsifier) is used in place of the polyethylene wax emulsion A, and the added amount with respect to the starch solid content is 4.5% by weight (30% with respect to the cationic surface sizing agent solid content). A neutral newsprint for offset printing was obtained in the same manner as in Example 1 except that the solid content was changed to weight%.
［比較例６］
カチオン性サイズ剤の代わりにＡＫＤエマルジョン（商品名：SE2362、ノニオン性乳化剤）を使用し、ポリエチレンワックスエマルジョンＡを添加しないこと以外は、実施例１と同様にしてオフセット印刷用中性新聞用紙を得た。
[Comparative Example 6]
Neutral newsprint for offset printing is obtained in the same manner as in Example 1 except that AKD emulsion (trade name: SE2362, nonionic emulsifier) is used instead of the cationic sizing agent, and polyethylene wax emulsion A is not added. It was.
［実施例１５］
ＴＭＰ２０部、ＤＩＰ７５部、ＮＢＫＰ５部から成る混合パルプスラリーを調製し、この混合パルプ１００部（固形分重量）に対して硫酸バンドを１．３部、炭酸カルシウム９部（商品名：オプチカルHF、イメリス社製、平均粒子径１．５μｍ）を部添加し、ツインワイヤー型抄紙機にて、坪量４３ｇ／ｍ２、厚さ７０μｍ、灰分１２％の中性新聞用紙の原紙を得た。
次にヒドロキシエチル化澱粉（商品名：ETHYLEX-2025、STAYLEY社製）を蒸煮したものを濃度７％に調製した。予め、合成例１のカチオン性表面サイズ剤にポリエチレンワックスエマルジョンＡをサイズ剤固形分重量に対し２０固形分重量％添加して、カチオン性表面サイズ剤とポリエチレンワックスエマルジョンとの混合液を調製した。この混合液を、カチオン性表面サイズ剤の添加量が澱粉固形分重量に対し１５固形分重量％となるように、濃度７％に調製した澱粉糊液へ添加して表面処理剤を調製した。
次にゲートロールコーターにて塗工速度１２００ｍ／分で上記の原紙に表面処理剤を澱粉塗布量が両面あたり０．５ｇ／ｍ２になるように塗工し乾燥後、８０℃のホットソフトニップカレンダーで１ニップ処理し、オフセット印刷用中性新聞用紙を得た。
[Example 15]
A mixed pulp slurry consisting of 20 parts of TMP, 75 parts of DIP and 5 parts of NBKP was prepared, and 1.3 parts of a sulfuric acid band and 9 parts of calcium carbonate (trade names: Optical HF, Imelis) with respect to 100 parts (solid weight) of this mixed pulp. A neutral newspaper paper having a basis weight of 43 g / m 2 , a thickness of 70 μm and an ash content of 12% was obtained using a twin wire type paper machine.
Next, steamed hydroxyethylated starch (trade name: ETHYLEX-2025, manufactured by STAYLEY) was prepared to a concentration of 7%. In advance, a polyethylene wax emulsion A was added to the cationic surface sizing agent of Synthesis Example 1 in an amount of 20% by solid weight based on the solid weight of the sizing agent to prepare a mixture of the cationic surface sizing agent and the polyethylene wax emulsion. This mixed solution was added to the starch paste solution prepared to a concentration of 7% so that the addition amount of the cationic surface sizing agent was 15% by weight based on the weight of the starch solids to prepare a surface treating agent.
Next, the surface treatment agent was applied to the above base paper with a gate roll coater at a coating speed of 1200 m / min so that the starch coating amount was 0.5 g / m 2 per both sides, dried, and then a hot soft nip at 80 ° C. One nip treatment was performed with a calendar to obtain neutral newsprint for offset printing.
［実施例１６］
ポリエチレンワックスエマルジョンＡのサイズ剤固形分に対する配合率を１０重量％添加に変更した以外は、実施例１５と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 16]
Neutral newsprint for offset printing was obtained in the same manner as in Example 15 except that the blending ratio of the polyethylene wax emulsion A with respect to the solid content of the sizing agent was changed to 10% by weight.
［実施例１７］
ポリエチレンワックスエマルジョンＡの代わりにポリエチレンワックスエマルジョンＢを使用した以外は、実施例１５と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 17]
Neutral newsprint for offset printing was obtained in the same manner as in Example 15 except that polyethylene wax emulsion B was used instead of polyethylene wax emulsion A.
［実施例１８］
ポリエチレンワックスエマルジョンＡの代わりにポリエチレンワックスエマルジョンＣを使用した以外は、実施例１５と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 18]
Neutral newsprint for offset printing was obtained in the same manner as in Example 15 except that polyethylene wax emulsion C was used instead of polyethylene wax emulsion A.
［実施例１９］
ポリエチレンワックスエマルジョンＡの代わりにポリエチレンワックスエマルジョンＤを使用した以外は、実施例１５と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 19]
Neutral newsprint for offset printing was obtained in the same manner as in Example 15 except that polyethylene wax emulsion D was used instead of polyethylene wax emulsion A.
［実施例２０］
ポリエチレンワックスエマルジョンＡの代わりにポリエチレンワックスエマルジョンＥを使用した以外は、実施例１５と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 20]
Neutral newsprint for offset printing was obtained in the same manner as in Example 15 except that polyethylene wax emulsion E was used instead of polyethylene wax emulsion A.
［実施例２１］
ポリエチレンワックスエマルジョンＡの代わりにポリエチレンワックスエマルジョンＦを使用した以外は、実施例１５と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 21]
Neutral newsprint for offset printing was obtained in the same manner as in Example 15 except that polyethylene wax emulsion F was used instead of polyethylene wax emulsion A.
［実施例２２］
ポリエチレンワックスエマルジョンＡの澱粉固形分重量に対する添加量を０．７固形分重量％（カチオン性表面サイズ剤固形分重量に対し４．７固形分重量％になる）に変更した以外は、実施例１３と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 22]
Example 13 except that the amount of polyethylene wax emulsion A added to the solid weight of the starch was changed to 0.7% by weight (4.7% by weight with respect to the cationic surface sizing agent solids). In the same manner, neutral newsprint for offset printing was obtained.
［実施例２３］
ポリエチレンワックスエマルジョンＡの澱粉固形分重量に対する添加量を５．２固形分重量％（カチオン性表面サイズ剤固形分重量に対し３４．７固形分重量％になる）に変更した以外は、実施例１３と同様にしてオフセット印刷用中性新聞用紙を得た。
[Example 23]
Example 13 with the exception that the amount of polyethylene wax emulsion A added to the starch solids weight was changed to 5.2% by weight (34.7% by weight with respect to the cationic surface sizing agent solids). In the same manner, neutral newsprint for offset printing was obtained.
実施例、比較例で得られたオフセット印刷用中性新聞用紙について、摩擦係数と点滴吸水度を測定し、以下のように評価を行い、結果を表２に示した。
＜摩擦係数の範囲＞
ＩＳＯ １５３５９に準拠し測定した。測定装置はAmontons II（Mu Mesurements Inc.社製）を用いた。この方法では、静摩擦係数と動摩擦係数を同じサンプルを使用して３回測定する。ＩＳＯでは静摩擦係数は１回目と３回目、動摩擦係数は３回目の数値と規定しているが、本発明では静摩擦係数と動摩擦係数はいずれも１回目の数値を採用し、次のように評価した。
○：静摩擦係数０．５５〜０．７５、動摩擦係数０．４５〜０．６０
×：静摩擦係数０．５５未満または０．７５超、動摩擦係数０．４５未満または０．６０超
＜摩擦係数の低下＞
摩擦係数低減の効果をポリエチレンワックスエマルジョンを入れない場合と比較し、その低下値により以下のように評価した。灰分が１２％のものについては、比較例２を基準とし、１５％のものについては比較例３を基準として比較した。なお、動摩擦係数の方が印刷機トラブルなどの原因と相関が高いため、動摩擦係数に重点を置いた。
◎：静摩擦係数０．０５以上低下かつ動摩擦係数０．０３以上低下
○：静摩擦係数０．０５未満低下かつ動摩擦係数０．０３以上低下
×：静摩擦係数０．０５未満低下かつ動摩擦係数０．０３未満低下
The neutral newspapers for offset printing obtained in the examples and comparative examples were measured for friction coefficient and drip water absorption, evaluated as follows, and the results are shown in Table 2.
<Range of friction coefficient>
Measured according to ISO 15359. Amontons II (Mu Mesurements Inc.) was used as a measuring device. In this method, the static friction coefficient and the dynamic friction coefficient are measured three times using the same sample. In ISO, the static friction coefficient is defined as the first and third times, and the dynamic friction coefficient is defined as the third value. In the present invention, both the static friction coefficient and the dynamic friction coefficient are employed as the first value and evaluated as follows. .
○: Static friction coefficient 0.55 to 0.75, dynamic friction coefficient 0.45 to 0.60
X: Static friction coefficient less than 0.55 or more than 0.75, dynamic friction coefficient less than 0.45 or more than 0.60 <decrease in friction coefficient>
The effect of reducing the friction coefficient was compared with the case where no polyethylene wax emulsion was added, and the reduction value was evaluated as follows. For those having an ash content of 12%, Comparative Example 2 was used as a reference, and for those having an ash content of 15%, Comparative Example 3 was used as a reference. Since the dynamic friction coefficient is more correlated with the causes of printer troubles, the dynamic friction coefficient was emphasized.
◎: Static friction coefficient decreased by 0.05 or more and dynamic friction coefficient decreased by 0.03 or more ○: Static friction coefficient decreased by less than 0.05 and dynamic friction coefficient decreased by 0.03 or more ×: Static friction coefficient decreased by less than 0.05 and dynamic friction coefficient less than 0.03 Decline
＜点滴吸水度の範囲＞
Ｊａｐａｎ ＴＡＰＰＩ No.３３に準拠して、紙面に水１μｌを滴下し、水滴が紙に吸収され、紙面に見えなくなるまでの時間を測定した。評価は次のように行った。
○：点滴吸水度が１５秒以上
×：点滴吸水度が１５秒未満
＜点滴吸水度への影響＞
ポリエチレンワックスエマルジョンを入れない場合と比較し、以下のように評価した。灰分が１２％のものについては比較例２を基準とし、１５％のものについては比較例３を基準として比較した。
◎：点滴吸水度が大きくなる、あるいは低下値が１０秒未満の場合
○：点滴吸水度の低下値が１０秒以上１５秒未満の場合
×：点滴吸水度の低下値が１５秒以上の場合
＜紙中灰分（重量％）＞
ＪＩＳ Ｐ ８２５１（対応ＩＳＯ１７６２）に準拠して測定し、灰化は５２５℃、２時間で行った。
<Drip water absorption range>
In accordance with Japan TAPPI No. 33, 1 μl of water was dropped on the paper surface, and the time until the water droplet was absorbed by the paper and disappeared from the paper surface was measured. Evaluation was performed as follows.
○: Drip water absorption is 15 seconds or more ×: Drip water absorption is less than 15 seconds <Influence on drip water absorption>
In comparison with the case where no polyethylene wax emulsion was added, the evaluation was as follows. Comparison was made based on Comparative Example 2 for the ash content of 12%, and Comparative Example 3 for the ash content of 15%.
◎: When the drip water absorption increases or when the drop value is less than 10 seconds. ○: When the drop water absorption value falls between 10 seconds and less than 15 seconds. Ash content in paper (wt%)>
Measured according to JIS P 8251 (corresponding ISO 1762), ashing was performed at 525 ° C. for 2 hours.
＜相溶性と塗料安定性＞
各実施例および比較例の表面処理剤を調製する場合において、カチオン性サイズ剤とポリエチレンワックスエマルジョンを混合するときの相溶性と、ゲートロール塗工後の表面処理剤の安定性を次のように評価し、表３に示した。
○：混合時に増粘や凝集物が発生しない、かつ塗工時の表面処理剤に凝集物が発生しない
×：混合時に増粘あるいは凝集する、または塗工時の表面処理剤に凝集物が発生する
<Compatibility and paint stability>
When preparing the surface treatment agent of each Example and Comparative Example, the compatibility when mixing the cationic sizing agent and the polyethylene wax emulsion and the stability of the surface treatment agent after gate roll coating are as follows: The results are shown in Table 3.
○: No thickening or agglomeration occurs during mixing, and no agglomeration occurs in the surface treatment agent during coating. ×: Aggregation occurs in the surface treatment agent during coating, or thickening or aggregation occurs during mixing. Do
表３の結果から、次のことがいえる。
カチオン性表面サイズ剤、ノニオン性乳化剤又はカチオン性乳化剤で乳化したポリエチレンワックスエマルジョン、及び水溶性高分子物質とからなる表面処理剤は、その調製混合時に相溶性が良く、かつ塗工時の安定性も良好であることがわかる。
これに対し、アニオン性乳化剤で乳化したポリエチレンワックスエマルジョンを使用した比較例１、４や、ＡＫＤエマルジョンを使用した比較例５では、相溶性や表面処理剤の安定性が悪く、十分な摩擦係数の低下の効果が得られず、塗工操業性にも懸念がある。
From the results in Table 3, the following can be said.
A surface treatment agent comprising a cationic surface sizing agent, a polyethylene wax emulsion emulsified with a nonionic emulsifier or a cationic emulsifier, and a water-soluble polymer substance has good compatibility during preparation and mixing, and stability during coating. It turns out that it is also favorable.
On the other hand, in Comparative Examples 1 and 4 using a polyethylene wax emulsion emulsified with an anionic emulsifier and Comparative Example 5 using an AKD emulsion, the compatibility and the stability of the surface treatment agent are poor, and a sufficient friction coefficient is obtained. Decreasing effect cannot be obtained, and there is concern about coating operability.
表２の結果から、次のことがいえる。
（１）カチオン性表面サイズ剤、ノニオン性乳化剤又はカチオン性乳化剤で乳化したポリエチレンワックスエマルジョン、及び水溶性高分子物質をそれぞれ表面処理剤調製時に添加混合して、これを塗布した実施例１〜１４のオフセット印刷用新聞用紙は、摩擦係数の低下の効果が大きく、かつ摩擦係数は適切な範囲となり、さらにポリエチレンワックスによる点滴吸水度の低下がないことがわかる。
（２）さらに、実施例１と１５、実施例２と１６、実施例３と１７、実施例４と１８、実施例５と１９、実施例６と２０、実施例７と２１の各比較から、ポリエチレンワックスエマルジョンは表面処理剤の調製時に添加しても、予めカチオン性表面サイズ剤へ添加して混合液を作製し表面処理剤を調整しても、同程度の効果が得られることがわかる。
（３）一方、表面サイズ剤としてＡＫＤエマルジョンを用いた比較例６では、摩擦係数の低下が大き過ぎ、かつ十分な吸水度が得られなかった。ＡＫＤエマルジョンの添加量を摩擦係数を最適な範囲とするために減量したとしても、点滴吸水度が低下し、十分なサイズ性は得られない。
（４）また、実施例１と２２、２３との比較から、ポリエチレンワックスエマルジョンの塗布量が少な目な場合（実施例２２）は、十分な摩擦係数の低下の効果が得られにくく、逆に多目な場合（比較例５）は摩擦係数が下がりすぎるため、実施例１の方が摩擦係数のコントロールに優れていることがわかる。
From the results in Table 2, the following can be said.
(1) Examples 1 to 14 in which a cationic surface sizing agent, a polyethylene wax emulsion emulsified with a nonionic emulsifier or a cationic emulsifier, and a water-soluble polymer substance were added and mixed at the time of preparation of the surface treatment agent and applied thereto. It can be seen that the newsprint for offset printing has a great effect of lowering the coefficient of friction, the coefficient of friction is in an appropriate range, and there is no decrease in drip water absorption due to polyethylene wax.
(2) Further, each comparison between Examples 1 and 15, Examples 2 and 16, Examples 3 and 17, Examples 4 and 18, Examples 5 and 19, Examples 6 and 20, and Examples 7 and 21 It can be seen that the same effect can be obtained by adding the polyethylene wax emulsion at the time of preparation of the surface treatment agent or by adding it to the cationic surface sizing agent in advance to prepare a mixed solution and adjusting the surface treatment agent. .
(3) On the other hand, in Comparative Example 6 using the AKD emulsion as the surface sizing agent, the friction coefficient was too low and sufficient water absorption was not obtained. Even if the amount of AKD emulsion added is reduced to bring the coefficient of friction within the optimum range, the drip water absorption decreases and sufficient size characteristics cannot be obtained.
(4) From the comparison between Examples 1 and 22 and 23, when the amount of the polyethylene wax emulsion applied is small (Example 22), it is difficult to obtain a sufficient effect of reducing the friction coefficient. In an obvious case (Comparative Example 5), since the friction coefficient is too low, it can be seen that Example 1 is superior in controlling the friction coefficient.
Claims (10)
（Ａ）カチオン性表面サイズ剤
（Ｂ）ノニオン性乳化剤またはカチオン性乳化剤で乳化したポリエチレンワックスエマルジョン
（Ｃ）水溶性高分子物質 Neutral newsprint for offset printing in which a surface treatment agent is coated on a base paper, wherein the surface treatment agent contains at least the following (A), (B) and (C): Neutral newsprint for offset printing.
(A) Cationic surface sizing agent (B) Polyethylene wax emulsion emulsified with nonionic emulsifier or cationic emulsifier (C) Water-soluble polymer substance
The newspaper for offset printing according to any one of claims 2 to 9, wherein the copolymer has a weight average molecular weight of 30,000 to 60,000.
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| JP2009235597A (en) * | 2008-03-26 | 2009-10-15 | Seiko Pmc Corp | Surface-sizing agent and paper coated with the same |
| JP2011529142A (en) * | 2008-07-24 | 2011-12-01 | ハーキュリーズ・インコーポレーテッド | Improved surface sizing of paper |
| JP2012214744A (en) * | 2011-03-30 | 2012-11-08 | Mitsui Chemicals Inc | Under-coating agent for release substrate |
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| JP2009235597A (en) * | 2008-03-26 | 2009-10-15 | Seiko Pmc Corp | Surface-sizing agent and paper coated with the same |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |