JP5064953B2 - Bulky medium printing paper - Google Patents
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- JP5064953B2 JP5064953B2 JP2007252156A JP2007252156A JP5064953B2 JP 5064953 B2 JP5064953 B2 JP 5064953B2 JP 2007252156 A JP2007252156 A JP 2007252156A JP 2007252156 A JP2007252156 A JP 2007252156A JP 5064953 B2 JP5064953 B2 JP 5064953B2
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- 238000007639 printing Methods 0.000 title claims description 31
- 239000000123 paper Substances 0.000 claims description 82
- 239000004067 bulking agent Substances 0.000 claims description 47
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 238000004513 sizing Methods 0.000 claims description 27
- 125000002091 cationic group Chemical group 0.000 claims description 24
- 229920001131 Pulp (paper) Polymers 0.000 claims description 18
- 239000012756 surface treatment agent Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 9
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 9
- 239000004368 Modified starch Substances 0.000 claims description 6
- 229920000881 Modified starch Polymers 0.000 claims description 6
- 235000019426 modified starch Nutrition 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 10
- -1 fatty acid ester compounds Chemical class 0.000 description 10
- 229920002472 Starch Polymers 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 239000008107 starch Substances 0.000 description 9
- 235000019698 starch Nutrition 0.000 description 9
- 230000000740 bleeding effect Effects 0.000 description 8
- 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 7
- 230000000694 effects Effects 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 150000001875 compounds Chemical group 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000002655 kraft paper Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000013054 paper strength agent Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- DLYIADMTZNYBSL-UHFFFAOYSA-N N1C=NCC1.C(CCCCCCCC=C/CCCCCCCC)(=O)N Chemical class N1C=NCC1.C(CCCCCCCC=C/CCCCCCCC)(=O)N DLYIADMTZNYBSL-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
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- Paper (AREA)
Description
本発明は、低密度で柔軟(剛度が低い)であり、しかも印刷適性に優れてインキのブリードを抑制する嵩高中質印刷用紙に関する。 The present invention relates to a bulky medium-sized printing paper that has low density and flexibility (low rigidity), and has excellent printability and suppresses ink bleeding.
昨今、紙製品に求められる重要な品質の一つとして嵩高性(低密度)が挙げられる。近年の環境保護気運の高まりにともない、森林資源から製造される製紙用パルプを有効に活用する上で、紙の厚さを維持しつつ軽量化、すなわち低密度化した嵩高の紙製品がユーザーから求められている。 One of the important qualities demanded for paper products in recent years is bulkiness (low density). Along with the recent increase in environmental protection, users have been able to reduce the weight of paper while maintaining the thickness of paper and effectively reduce the density of paper. It has been demanded.
従来、紙の低密度化(嵩高化)の方法の一つとして、嵩高のパルプの使用がある。製紙用パルプとしては、一般に木材パルプが汎用されるが、化学薬品により木材繊維中の補強材料であるリグニンを抽出した化学パルプよりも、グラインダーで木材を磨り潰す砕木パルプやリファイナーで木材を精砕するリファイナーメカニカルパルプ、又はサーモメカニカルパルプ等のような機械パルプの方が繊維は剛直であり、紙の低密度化には効果的であることが知られている。しかし、機械パルプを配合して抄造した紙は、剛度が高いことから、印刷・製本した書籍のめくりやすさが不良となる問題があり、印刷用紙の曲げ剛さを低下させる、いわゆる柔軟化の向上が課題となっていた。 Conventionally, as one method for reducing the density (bulking) of paper, there is the use of bulky pulp. Wood pulp is generally used as a pulp for papermaking. However, compared with chemical pulp extracted from lignin, which is a reinforcing material in wood fibers, using chemicals, the wood is refined using ground pulp or refiner that grinds the wood with a grinder. It is known that mechanical fibers such as refiner mechanical pulp, thermomechanical pulp, and the like have more rigid fibers and are effective in reducing the density of paper. However, paper made by blending mechanical pulp has high rigidity, so there is a problem that the printed and bound books are not easily turned. Improvement was an issue.
紙の低密度化のもう一つの手法として嵩高剤の使用によることも知られている。公知の嵩高剤として、例えば、特定のアルコール及び/又はそのポリオキシアルキレン付加物を含有する紙用嵩高剤(特許文献1参照)、非イオン界面活性剤(特許文献2参照)、多価アルコールと脂肪酸のエステル化合物からなる紙用嵩高剤(特許文献3参照)が知られており、これらの紙用嵩高剤を板紙に応用した技術も開示されている(特許文献4参照)。 It is also known to use a bulking agent as another method for reducing the density of paper. Known bulking agents include, for example, paper bulking agents containing a specific alcohol and / or polyoxyalkylene adduct thereof (see Patent Document 1), nonionic surfactants (see Patent Document 2), polyhydric alcohols and the like. Paper bulking agents comprising fatty acid ester compounds (see Patent Document 3) are known, and a technique in which these paper bulking agents are applied to paperboard is also disclosed (see Patent Document 4).
このうち非界面活性剤系の嵩高剤として、特定構造のカチオン性化合物、アミン、アミンの酸塩及び両性化合物から選ばれた少なくとも1種以上の化合物を含有する紙用嵩高剤が開示されている(特許文献5参照)。また、脂肪酸ポリアミドポリアミン型の嵩高剤もある。また、離水度が4%以上となる化合物であって、嵩、白色度、不透明度のいずれか2つ以上の紙質向上効果を有する化合物が記載されている(特許文献6参照)。さらに、離水度が4%以上となる化合物であって、嵩、白色度、不透明度のいずれか1つ以上の紙質向上効果を有する化合物を使用するパルプシートの製造方法が開示されている(特許文献7参照)。 Among these, as a non-surfactant bulking agent, a paper bulking agent containing at least one compound selected from a cationic compound having a specific structure, an amine, an acid salt of an amine and an amphoteric compound is disclosed. (See Patent Document 5). There are also fatty acid polyamide polyamine type bulking agents. Further, a compound having a water separation degree of 4% or more and a compound having an effect of improving paper quality of any two of bulk, whiteness, and opacity is described (see Patent Document 6). Furthermore, a pulp sheet manufacturing method using a compound having a water separation degree of 4% or more and having a paper quality improving effect of any one of bulk, whiteness and opacity is disclosed (patent) Reference 7).
しかしながら、低密度の紙が得られても低密度化した紙のみの特性では、インキを用いてオフセット印刷した場合に、経時的にインキが印刷裏面に滲み出す、いわゆるインキのブリード(「以下、「ブリード」という。)が発生し、これが印刷トラブルの一因となって、紙の低密度化にともなう大きな問題となっている。また、近年はブリードがより発生し易いインキが使用される場合もあり、今まで問題のなかった用紙でもブリードの発生することが起きている。 However, even if a low-density paper is obtained, the characteristics of only the low-density paper are so-called ink bleed (hereinafter referred to as “the ink bleed”). "Bleed") occurs, which contributes to printing troubles and is a major problem associated with the reduction in paper density. In recent years, ink that is more likely to bleed may be used, and bleed occurs even on paper that has not been problematic until now.
以上のような背景から、本発明は、低密度、柔軟(剛度が低い)で、しかも印刷適性に優れ、ブリード(印刷滲み)が発生しない嵩高中質印刷用紙を提供することを課題とする。 In view of the above background, it is an object of the present invention to provide a bulky medium-sized printing paper that has low density, flexibility (low rigidity), excellent printability, and no bleeding (print bleeding).
上記課題を解決するために、請求項1に係る発明の嵩高中質印刷用紙は、嵩高剤を含有する原紙の上に表面処理剤が塗布されている嵩高中質印刷用紙であって、
前記原紙が機械パルプをパルプ重量当たり30重量%以上含有され、前記嵩高剤として不飽和脂肪酸アミド系嵩高剤が含有され、その含有量が全パルプ絶乾重量基準で0.1〜2.0%含有されており、前記表面処理剤として少なくともカチオン性表面サイズ剤が塗布され、上記表面処理剤の塗布量が紙片面当たり0.3〜3.0g/m 2 であり、上記表面処理剤中に上記カチオン性表面サイズ剤が5〜10重量%であり、且つ上記カチオン性表面サイズ剤の塗布量が紙片面当たり0.05〜1.0g/m 2 であることを特徴とする。
請求項2に係る発明の嵩高中質印刷用紙は、前記表面処理剤として、前記カチオン性表面サイズ剤と変性澱粉を併用して塗布されていることを特徴とする。
In order to solve the above problems, the bulky medium-sized printing paper of the invention according to claim 1 is a bulky medium-sized printing paper in which a surface treatment agent is applied on a base paper containing a bulking agent,
The base paper contains 30% by weight or more of mechanical pulp per pulp weight, and an unsaturated fatty acid amide bulking agent is contained as the bulking agent, and the content is 0.1 to 2.0% based on the total dry weight of the pulp. And at least a cationic surface sizing agent is applied as the surface treatment agent, and the coating amount of the surface treatment agent is 0.3 to 3.0 g / m 2 per one side of the paper , an upper Symbol cationic surface sizing agent is 5-10 wt%, and the coating amount of the cationic surface sizing agent is characterized in that it is a 0.05 to 1.0 g / m 2 per paper face.
The bulky medium-sized printing paper of the invention according to claim 2 is coated with the cationic surface sizing agent and modified starch as the surface treatment agent.
本発明により、低密度であってもインキのブリード現象が抑制でき、柔軟で印刷適性にも優れる嵩高中質印刷用紙を得ることができる。 According to the present invention, it is possible to obtain a bulky medium-size printing paper that can suppress the ink bleeding phenomenon even at low density, and is flexible and excellent in printability.
本発明の中質印刷用紙では、原料パルプとして化学パルプ(針葉樹の晒クラフトパルプ(NBKP)又は未晒クラフトパルプ(NUKP)、広葉樹の晒クラフトパルプ(LBKP)又は未晒クラフトパルプ(LUKP)等)、針葉樹、広葉樹の機械パルプ(グラウンドウッドパルプ(GP)、リファイナーメカニカルパルプ(RGP)、サーモメカニカルパルプ(TMP)、ケミサーモメカニカルパルプ(CTMP)等)又は脱墨パルプ(DIP)を単独もしくは任意の割合で混合して使用することができる。本発明においては、機械パルプをパルプ重量当たり30重量%以上で、より嵩高でありながら柔軟性の効果を有するものである。 In the medium-quality printing paper of the present invention, chemical pulp (such as bleached kraft pulp (NBKP) or unbleached kraft pulp (NUKP), bleached kraft pulp (LBKP) or unbleached kraft pulp (LUKP) of hardwood) as raw material pulp , Softwood, hardwood mechanical pulp (groundwood pulp (GP), refiner mechanical pulp (RGP), thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), etc.) or deinked pulp (DIP) alone or in any It can be used by mixing at a ratio. In the present invention, the mechanical pulp is 30% by weight or more per pulp weight, and has a softness effect while being bulky.
本発明で使用する嵩高剤は不飽和脂肪酸アミド系である。機械パルプを配合した中質紙を抄造する場合、不飽和脂肪酸アミド系嵩高剤は、他の嵩高剤、例えば飽和脂肪酸アミド系、脂肪酸エステル系、高級アルコールアルキレンオキサイド系、アミン系など、と比較して嵩高効果が高い。 The bulking agent used in the present invention is an unsaturated fatty acid amide system. In the case of making medium paper containing mechanical pulp, unsaturated fatty acid amide bulking agents are compared with other bulking agents such as saturated fatty acid amides, fatty acid esters, higher alcohol alkylene oxides, amines, etc. High bulky effect.
不飽和脂肪酸アミド系嵩高剤としては、オレイン酸アミドアミン系、リノール酸アミドアミン系、オレイン酸アミドイミダゾリン系、リノール酸アミドイミダゾリン系などが挙げられる。 Examples of the unsaturated fatty acid amide bulking agent include oleic acid amide amines, linoleic acid amide amines, oleic acid amide imidazolines, linoleic acid amide imidazolines.
全パルプへの嵩高剤の添加量は、全パルプ絶乾重量基準で0.1〜2.0%が好ましく、より好ましくは0.1〜1.2%であり、0.5〜1.2%が更に好ましい。0.1%未満では、嵩高効果がほとんど無く、2.0%を越えて添加しても、嵩はそれ以上高くならない。 The amount of the bulking agent added to the total pulp is preferably 0.1 to 2.0%, more preferably 0.1 to 1.2%, and more preferably 0.5 to 1.2, based on the total dry weight of the pulp. % Is more preferable. If it is less than 0.1%, there is almost no bulky effect, and even if added over 2.0%, the bulk does not increase any more.
本発明の嵩高中質印刷用紙は、填料を含有してもよい。填料としては、ホワイトカーボン、タルク、カオリン、クレー、重質炭酸カルシウム、軽質炭酸カルシウム、酸化チタン又は合成樹脂填料等の公知の填料を使用することができる。填料の含有量は、紙重量当たり3〜20重量%が好ましい。 The bulky medium-size printing paper of the present invention may contain a filler. As the filler, known fillers such as white carbon, talc, kaolin, clay, heavy calcium carbonate, light calcium carbonate, titanium oxide, or synthetic resin filler can be used. The filler content is preferably 3 to 20% by weight per paper weight.
また、本発明の嵩高中質印刷用紙は、硫酸バンドや各種のアニオン性、カチオン性、ノニオン性又は両性の歩留まり向上剤、濾水性向上剤、紙力増強剤や内添サイズ剤等の抄紙用内添助剤を必要に応じて使用することができる。
さらに、染料、蛍光増白剤、pH調整剤、消泡剤、ピッチコントロール剤又はスライムコントロール剤等も必要に応じて添加しても何ら問題はない。
Further, the bulky medium-sized printing paper of the present invention is used for papermaking such as sulfate bands, various anionic, cationic, nonionic or amphoteric yield improvers, drainage improvers, paper strength enhancers, and internal sizing agents. An internal additive can be used as required.
Furthermore, there is no problem even if a dye, a fluorescent brightening agent, a pH adjuster, an antifoaming agent, a pitch control agent, a slime control agent, or the like is added as necessary.
本発明の嵩高中質印刷用紙の抄造は、長網抄紙機、ギャップフォーマ又はハイブリッドフォーマ(オントップフォーマ)等の公知の抄紙機にて行うことができる。中質紙の嵩高性の観点から、抄紙機におけるプレス線圧は、操業に支障を来さない範囲内でなるべく低いことが望ましく、また、カレンダー線圧は嵩高中質印刷用紙の平滑性が損なわれない範囲内でなるべく低いことが望ましい。また、抄紙の際、表面処理剤を塗布することが必要である。 Paper making of the bulky medium-sized printing paper of the present invention can be performed by a known paper machine such as a long paper machine, a gap former, or a hybrid former (on-top former). From the viewpoint of bulkiness of medium quality paper, it is desirable that the press linear pressure in the paper machine is as low as possible within the range that does not hinder the operation, and the calendar linear pressure is impaired in smoothness of bulky medium quality printing paper. As low as possible within the range. In addition, it is necessary to apply a surface treatment agent during papermaking.
本発明においては、嵩高剤として不飽和脂肪酸アミド系を、そして、表面処理剤としてカチオン性表面サイズ剤を用いている。該不飽和脂肪酸アミド系嵩高剤は、中質紙を嵩高にして柔軟性を有する効果には優れるが、ブリードが発生しやすい傾向があり、澱粉系表面紙力剤を0.3〜3.0g/m2、好ましくは0.5〜2.0g/m2塗布することにより防止対策を行ってきが、近年、ブリードの発生し易いインキの使用により上記の対策では不十分となってきたので、前記カチオン性表面サイズ剤の表面処理剤が塗布されることによりブリードの発生が抑制できる。このブリードの発生を抑制するために、カチオン性表面サイズ剤の塗布量は、抄紙した紙に対して、片面当たり0.05〜1.0g/m2が好ましい。 In the present invention, an unsaturated fatty acid amide system is used as a bulking agent, and a cationic surface sizing agent is used as a surface treatment agent. The unsaturated fatty acid amide bulking agent is excellent in the effect of making the medium paper bulky and flexible, but tends to cause bleeding, and the starch-based surface paper strength agent is 0.3 to 3.0 g. / M 2 , preferably 0.5 to 2.0 g / m 2, to prevent this, but in recent years, the above measures have become insufficient due to the use of ink that tends to bleed. The occurrence of bleeding can be suppressed by applying the surface treatment agent of the cationic surface sizing agent. In order to suppress the occurrence of this bleed, the coating amount of the cationic surface sizing agent is preferably 0.05 to 1.0 g / m 2 per side with respect to the paper made.
本発明のカチオン性表面サイズ剤とは、疎水モノマーとカチオン性の官能基を有した親水モノマーの共重合体であれば良いが、具体的にはスチレン系、スチレンアクリレート系、アクリレート系のカチオン性サイズ剤である。疎水モノマーとしてはスチレン、アクリル酸エステルが、親水モノマーとしては(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸ジメチルアミノプロピル、(メタ)アクリル酸ジエチルアミノエチル、(メタ)アクリル酸ジエチルアミノプロピルなどが挙げられる。 The cationic surface sizing agent of the present invention may be a copolymer of a hydrophobic monomer and a hydrophilic monomer having a cationic functional group. Specifically, the cationic surface sizing agent is a styrenic, styrene acrylate, or acrylate cationic. It is a sizing agent. Hydrophobic monomers include styrene and acrylic acid esters, and hydrophilic monomers include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and the like. Can be mentioned.
本発明では、ブリードを発生させないために、カチオン性表面サイズ剤が必要であるが、表面強度やサイズ性向上の目的で、例えば、生澱粉や、酸化澱粉、エステル化澱粉、カチオン化澱粉、酵素変性澱粉、アルデヒド化澱粉、ヒドロキシエチル化澱粉などの変性澱粉、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、メチルセルロースなどのセルロース誘導体、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などの変性アルコール、スチレンブタジエン共重合体、ポリ酢酸ビニル、塩化ビニル−酢酸ビニル共重合体、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリアクリル酸エステル、ポリアクリルアミドなどを1種類以上併用することができる。その中でも表面強度やサイズ性向上効果のためには、変性澱粉を併用して塗布することが好ましく、ヒドロキシエチル化澱粉の塗布が最も好ましい。表面強度とブリードの抑制効果とのバランスをとるために、表面処理剤の塗布量は、抄紙した紙に対して、片面当たり0.3〜3.0g/m2が好ましく、より好ましくは0.5〜2.0g/m2である。また、飽和脂肪酸ポリアミドポリアミンエピクロロヒドリン重縮合物を表面処理剤中に1〜10重量%が好ましい。 In the present invention, a cationic surface sizing agent is necessary so as not to generate bleed. For the purpose of improving surface strength and size, for example, raw starch, oxidized starch, esterified starch, cationized starch, enzyme Modified starch such as modified starch, aldehyde-modified starch, hydroxyethylated starch, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, modified alcohols such as polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, styrene-butadiene copolymer, polyvinyl acetate, One or more kinds of vinyl chloride-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid ester, polyacrylamide and the like can be used in combination. Among them, in order to improve the surface strength and size, it is preferable to apply a modified starch in combination, and the application of hydroxyethylated starch is most preferable. In order to balance the surface strength and the bleed suppressing effect, the coating amount of the surface treatment agent is preferably 0.3 to 3.0 g / m 2 per side, more preferably 0. 5 to 2.0 g / m 2 . Moreover, 1 to 10 weight% of saturated fatty acid polyamide polyamine epichlorohydrin polycondensate is preferable in a surface treating agent.
表面処理剤を塗布する装置の種類は、特に限定はなく、2ロールサイズプレスコーター、ゲートロールコーター、ブレードメタリングコーター又はロッドメタリングコーター等の塗工機によって塗布することができる。他の抄造条件は、特に規定されるものではなく、抄紙時のpHは、酸性、中性又はアルカリ性のいずれでもよい。
また、紙の表面を平滑にする目的で、マシンキャレンダー、ソフトニップカレンダー、高温ソフトニップカレンダーなどの公知のカレンダー装置を用いて処理を行っても良い。
The kind of apparatus which apply | coats a surface treating agent does not have limitation in particular, It can apply | coat with coating machines, such as a 2 roll size press coater, a gate roll coater, a blade metalling coater, or a rod metalling coater. Other papermaking conditions are not particularly defined, and the pH during papermaking may be acidic, neutral or alkaline.
Further, for the purpose of smoothing the surface of the paper, the processing may be performed using a known calendar device such as a machine calendar, a soft nip calender, or a high temperature soft nip calender.
以上のように、本発明では、不飽和脂肪酸アミド系嵩高剤を添加した紙料を抄造して得られた紙にカチオン性表面サイズ剤を塗布することにより、低密度で、柔軟(剛度が低い)であり、しかも印刷適性に優れ、ブリードが発生しない嵩高中質印刷用紙を製造できる。
本発明の嵩高中質印刷用紙は、書籍用紙、オフセット印刷用紙又は凸版印刷用紙、グラビア印刷用紙等、及びそれらの塗工原紙として好適に使用することができる。
As described above, in the present invention, a cationic surface sizing agent is applied to paper obtained by making a paper stock to which an unsaturated fatty acid amide-based bulking agent is added, thereby providing low density and flexibility (low rigidity). In addition, it is possible to produce a bulky medium-sized printing paper that is excellent in printability and does not generate bleed.
The bulky medium-size printing paper of the present invention can be suitably used as book paper, offset printing paper or letterpress printing paper, gravure printing paper, and their coating base paper.
以下に実施例を示すが、この実施例は本発明の範囲を限定するものではない。
なお、説明中%は固形分重量%である。
供試した機械パルプ、嵩高剤、表面紙力剤を下記に示した。
また、紙質測定方法は下記の通りである。
(1)供試嵩高剤
・嵩高剤A:オレイン酸アミドアミン系
・嵩高剤B:オレイン酸アミドイミダゾリン系
・嵩高剤C:ステアリン酸アミドアミン系
・嵩高剤D:ステアリン酸エステル系
・嵩高剤E:ラウリルアルコールエーテル系
Examples are shown below, but these examples do not limit the scope of the present invention.
In the description, “%” is solid content weight%.
The tested mechanical pulp, bulking agent and surface paper strength agent are shown below.
The paper quality measurement method is as follows.
(1) Sample bulking agent / bulking agent A: oleic acid amidoamine-based bulking agent B: oleic acid amidoimidazoline-based / bulky bulking agent C: stearic acid amidoamine-based / bulky bulking agent D: stearic acid ester-based bulking agent E: lauryl Alcohol ether
(2)紙質測定方法
・坪量:JIS P 8124に準じて測定した。
・紙厚、密度:JIS P 8118に準じて測定した。
・ブリード試験:ローランドR202印刷機で、湿し水はエッチ液(東京インキ(製)・H液No.8、大日本印刷で使用)1%添加のものを使用し、インキはインクテック(製)の藍にコンパウンドを10%添加したものを使用して印刷した後、30日間暗所保存し、インキの裏面への滲み(ブリード)の抑制程度を目視評価した。
前記目視評価は、次の4段階とした。
◎:非常に良好。
○:良好。
△:やや不良。
×:不良。
(2) Paper quality measuring method / basis weight: Measured according to JIS P 8124.
-Paper thickness and density: Measured according to JIS P 8118.
・ Bleed test: Roland R202 printing machine, dampening solution with 1% added etchant (Tokyo Ink (manufactured), H liquid No. 8, used in Dai Nippon Printing), ink used with Inktec (manufactured) ) Was added using 10% compound added to indigo, and was stored in the dark for 30 days, and the degree of suppression of bleeding (bleed) on the back surface of the ink was visually evaluated.
The visual evaluation was performed in the following four stages.
A: Very good.
○: Good.
Δ: Slightly poor
X: Defect.
・柔軟性試験(剛度):ベンディングテスター(Lorentzen& Wettre)を用いて、MD方向の剛度を測定し、紙厚の影響を避けるために、次の計算式で求めた値を剛度とした。
剛度=105×ベンディングテスター剛度測定値/(紙厚)3
ここで、純曲げ剛度測定値の単位はμN・m2/m、紙厚の単位はμmである。
[実施例1]
針葉樹TMP(CSF110ml)のパルプスラリーに、硫酸バンド1.5%、嵩高剤Aを1.0%添加し、炭酸カルシウム3.0%、歩留り剤(DR−3600、ハイモ株式会社製)200ppmを添加し、ベルベIV型抄紙機にて1000m/分の速度で抄紙し、ヒドロキシエチル化澱粉とスチレンとメタクリル酸ジメチルアミノエチルの共重合体であるスチレン系カチオン性サイズ剤の重量配合比率が20/1のサイズプレス液をゲートロールコーターで2g/m2の塗布量で塗布し、10kgfのニップ圧カレンダー処理し、嵩高中質印刷用紙を得た。
-Flexibility test (rigidity): Using a bending tester (Lorentzen & Wettre), the stiffness in the MD direction was measured, and the value obtained by the following calculation formula was taken as the stiffness in order to avoid the influence of the paper thickness.
Stiffness = 10 5 x Bending tester stiffness measurement / (paper thickness) 3
Here, the unit of the measured value of pure bending stiffness is μN · m 2 / m, and the unit of paper thickness is μm.
[Example 1]
To a pulp slurry of conifer TMP (CSF 110 ml), 1.5% sulfuric acid band and 1.0% bulking agent A are added, 3.0% calcium carbonate, 200 ppm yield agent (DR-3600, manufactured by Hymo Co., Ltd.), Paper is made with a Velve IV paper machine at a speed of 1000 m / min, and the weight ratio of the styrene cationic sizing agent, which is a copolymer of hydroxyethylated starch, styrene and dimethylaminoethyl methacrylate, is 20/1. The press liquid was applied at a coating amount of 2 g / m 2 with a gate roll coater and subjected to a nip pressure calendar treatment of 10 kgf to obtain a bulky medium-sized printing paper.
[実施例2]
実施例1のカチオン性サイズ剤がスチレンとメタクリル酸ジメチルアミノエチルの共重合体の代りにスチレンと2−エチルヘキシルメタクリレートとメタクリル酸ジメチルアミノエチルの共重合体であるスチレンアクリレート系カチオン性サイズ剤を使用したこと以外は実施例1と同様に嵩高中質印刷用紙を得た。
[実施例3]
実施例1のカチオン性サイズ剤がスチレンとメタクリル酸ジメチルアミノエチルの共重合体の代りにn−ブチルメタクリレートとラウリルメタクリレートとメタクリル酸ジメチルアミノエチルの共重合体であるアクリレート系カチオン性サイズ剤を使用したこと以外は実施例1と同様に嵩高中質印刷用紙を得た。
[実施例4]
実施例1の嵩高剤Aの代りに嵩高剤Bを使用したこと以外は実施例1と同様に嵩高中質印刷用紙を得た。
[Example 2]
The cationic sizing agent of Example 1 is a styrene acrylate cationic sizing agent which is a copolymer of styrene, 2-ethylhexyl methacrylate and dimethylaminoethyl methacrylate instead of the copolymer of styrene and dimethylaminoethyl methacrylate. Except that, a bulky medium-sized printing paper was obtained in the same manner as in Example 1.
[Example 3]
The cationic sizing agent in which the cationic sizing agent of Example 1 is a copolymer of n-butyl methacrylate, lauryl methacrylate, and dimethylaminoethyl methacrylate is used instead of the copolymer of styrene and dimethylaminoethyl methacrylate. Except that, a bulky medium-sized printing paper was obtained in the same manner as in Example 1.
[Example 4]
A bulky medium-sized printing paper was obtained in the same manner as in Example 1 except that the bulking agent B was used in place of the bulking agent A of Example 1.
[実施例5]
実施例1において、ヒドロキシエチル化澱粉とスチレンとメタクリル酸ジメチルアミノエチルの共重合体であるカチオン性サイズ剤の重量配合比率を10/1にしたこと以外は実施例1と同様に嵩高中質印刷用紙を得た。
[実施例6]
実施例1において、ヒドロキシエチル化澱粉とスチレンとメタクリル酸ジメチルアミノエチルの共重合体であるカチオン性サイズ剤の重量配合比率を20/0.1にしたこと以外は実施例1と同様に嵩高中質印刷用紙を得た。
[比較例1]
実施例1の嵩高剤Aの代りに嵩高剤Cを使用したこと以外は実施例1と同様に嵩高中質印刷用紙を得た。
[比較例2]
実施例1の嵩高剤Aの代りに嵩高剤Dを使用したこと以外は実施例1と同様に嵩高中質印刷用紙を得た。
[Example 5]
Bulky and medium-quality printing in the same manner as in Example 1 except that the weight blending ratio of the cationic sizing agent which is a copolymer of hydroxyethylated starch, styrene and dimethylaminoethyl methacrylate was changed to 10/1. Got the paper.
[Example 6]
In Example 1, bulky as in Example 1, except that the weight blending ratio of the cationic sizing agent, which is a copolymer of hydroxyethylated starch, styrene, and dimethylaminoethyl methacrylate, was 20 / 0.1. Quality printing paper was obtained.
[Comparative Example 1]
A bulky medium-quality printing paper was obtained in the same manner as in Example 1 except that the bulking agent C was used instead of the bulking agent A of Example 1.
[Comparative Example 2]
A bulky medium-sized printing paper was obtained in the same manner as in Example 1 except that the bulking agent D was used in place of the bulking agent A of Example 1.
[比較例3]
実施例1の嵩高剤Aの代りに嵩高剤Eを使用したこと以外は実施例1と同様に嵩高中質印刷用紙を得た。
[比較例4]
実施例1のカチオン性サイズ剤の代りにスチレンとアクリル酸の共重合体であるアニオン性サイズ剤を使用したこと以外は実施例1と同様に嵩高中質印刷用紙を得た。
[比較例5]
ヒドロキシエチル化澱粉のみを塗布したこと以外は実施例1と同様に嵩高中質印刷用紙を得た。
[Comparative Example 3]
A bulky medium-sized printing paper was obtained in the same manner as in Example 1 except that the bulking agent E was used in place of the bulking agent A of Example 1.
[Comparative Example 4]
A bulky medium-sized printing paper was obtained in the same manner as in Example 1 except that an anionic sizing agent, which is a copolymer of styrene and acrylic acid, was used instead of the cationic sizing agent of Example 1.
[Comparative Example 5]
A bulky medium printing paper was obtained in the same manner as in Example 1 except that only hydroxyethylated starch was applied.
上記の実施例1〜6及び比較例1〜4の条件と、密度、ブリード試験及び柔軟性試験(剛度)の結果を表1に示す。
表1に示した結果から次のことがわかる。
嵩高剤A、Bを含有する実施例1〜6及び比較例4、5の原紙の密度は、他のタイプの嵩高剤を含有する比較例1〜3のそれより小さいことから、不飽和脂肪酸アミド系の嵩高剤は他のタイプの嵩高剤と比較して低密度にできることがわかる。
また、嵩高剤A、Bを含有する実施例1〜6及び比較例4、5の原紙の剛度は、他のタイプの嵩高剤を含有する比較例1〜3のそれより小さいことから、不飽和脂肪酸アミド系の嵩高剤は他のタイプの嵩高剤と比較して柔軟にできることがわかる。
嵩高剤A、Bを含有している実施例1〜6の原紙は、上記したように低密度及び柔軟であると共に、カチオン性表面サイズ剤がその表面に塗布されることにより、インキブリードの抑制ができることがわかる。
From the results shown in Table 1, the following can be understood.
Since the density of the base papers of Examples 1 to 6 and Comparative Examples 4 and 5 containing the bulking agents A and B is smaller than that of Comparative Examples 1 to 3 containing other types of bulking agents, the unsaturated fatty acid amide It can be seen that the bulking agent of the system can have a lower density than other types of bulking agents.
Further, the stiffness of the base papers of Examples 1 to 6 and Comparative Examples 4 and 5 containing the bulking agents A and B is smaller than that of Comparative Examples 1 to 3 containing other types of bulking agents. It can be seen that the fatty acid amide-based bulking agent can be made more flexible than other types of bulking agents.
The base papers of Examples 1 to 6 containing the bulking agents A and B are low density and flexible as described above, and the cationic surface sizing agent is applied to the surface, thereby suppressing ink bleeding. You can see that
Claims (2)
前記原紙が機械パルプをパルプ重量当たり30重量%以上含有され、前記嵩高剤として不飽和脂肪酸アミド系嵩高剤が含有され、その含有量が全パルプ絶乾重量基準で0.1〜2.0%含有されており、前記表面処理剤として少なくともカチオン性表面サイズ剤が塗布され、上記表面処理剤の塗布量が紙片面当たり0.3〜3.0g/m2であり、上記表面処理剤中に上記カチオン性表面サイズ剤が5〜10重量%であり、且つ上記カチオン性表面サイズ剤の塗布量が紙片面当たり0.05〜1.0g/m 2 であることを特徴とする嵩高中質印刷用紙。 A bulky medium-sized printing paper in which a surface treatment agent is applied on a base paper containing a bulking agent,
The base paper contains 30% by weight or more of mechanical pulp per pulp weight , and an unsaturated fatty acid amide bulking agent is contained as the bulking agent, and the content is 0.1 to 2.0% based on the total dry weight of the pulp. And at least a cationic surface sizing agent is applied as the surface treatment agent, and the coating amount of the surface treatment agent is 0.3 to 3.0 g / m 2 per one side of the paper , an upper Symbol cationic surface sizing agent is 5-10 wt%, and bulky coating amount of the cationic surface sizing agent is characterized in that it is a 0.05 to 1.0 g / m 2 per paper face wood containing Printing paper.
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| JPWO2005003457A1 (en) * | 2003-07-07 | 2006-08-17 | 日本製紙株式会社 | Newspaper sized with a cationic surface sizing agent |
| JP4266747B2 (en) * | 2003-08-25 | 2009-05-20 | 日本製紙株式会社 | Bulky medium paper |
| JP2005163253A (en) * | 2003-11-14 | 2005-06-23 | Nippon Paper Industries Co Ltd | High-bulk, wood-containing printing paper |
| JP4744105B2 (en) * | 2004-06-30 | 2011-08-10 | 日本製紙株式会社 | Printability improver and paper coated with the same |
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| JP4690084B2 (en) * | 2005-03-23 | 2011-06-01 | 日本製紙株式会社 | Bulky high-quality printing paper |
| JP4688603B2 (en) * | 2005-08-01 | 2011-05-25 | 日本製紙株式会社 | Surface sizing agent, surface sizing method and paper |
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