JP4796282B2 - Low density printing paper - Google Patents
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- JP4796282B2 JP4796282B2 JP2004099184A JP2004099184A JP4796282B2 JP 4796282 B2 JP4796282 B2 JP 4796282B2 JP 2004099184 A JP2004099184 A JP 2004099184A JP 2004099184 A JP2004099184 A JP 2004099184A JP 4796282 B2 JP4796282 B2 JP 4796282B2
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Description
本発明は、低密度(嵩高)でながら、不透明度や印刷後不透明性に優れた低密度印刷用紙に関するものである。 The present invention relates to a low-density printing paper that is low in density (bulky) and excellent in opacity and opacity after printing.
近年の活字離れを反映して、書籍は重厚なものから内容的に軽いコミック本やペーパーバックが急激に普及してきている。一般に、これらの書籍は持ちやすく、軽い本であることが求められる。そのため、出版社等の用紙ユーザーが求める印刷用紙品質として、紙の軽量化がある。ここで、紙の軽量化とは、紙の厚さは維持した上での低密度化、すなわち嵩高化のことを指す。 Reflecting the recent divergence of type, books ranging from profound to light-weight comic books and paperbacks are rapidly spreading. In general, these books are required to be easy to hold and light. For this reason, the paper quality required by paper users such as publishers is a reduction in paper weight. Here, the weight reduction of paper refers to a reduction in density, that is, an increase in bulk while maintaining the thickness of the paper.
一方、紙ごみ発生に伴う環境汚染や、製紙用パルプ製造に用いられる森林資源の伐採問題など、紙を主体にした地球環境保護問題が注目されている。この地球環境保護気運の高まりに伴い、森林資源から得られる製紙用パルプを有効に活用することは、製紙業界にとって避けて通れない問題である。近年、この問題解決の手段として、製紙用パルプを有効に活用する方法が種々提案されているが、その一手法として、同一重量のパルプで広い面積の紙を得る嵩高化技術が注目されている。 On the other hand, global environmental protection issues based on paper, such as environmental pollution associated with the generation of paper waste, and the logging of forest resources used in the manufacture of pulp for papermaking, are attracting attention. With the increase in global environmental protection, effective utilization of paper pulp obtained from forest resources is an unavoidable problem for the paper industry. In recent years, various methods for effectively utilizing pulp for papermaking have been proposed as a means for solving this problem, and as one of the methods, a bulking technique for obtaining a large area of paper with the same weight of pulp has attracted attention. .
紙を嵩高にする従来の技術としては、パルプと疎水性繊維の混合物に架橋剤を反応させて得られる嵩高性パルプ組成物を使用する方法がある(特許文献１参照)。また、セルロースパルプ、特定形態のポリエステル複合繊維、および熱融着性バインダーとを混抄し、嵩高パルプシートを製造する方法がある(特許文献２参照)。しかし、架橋パルプや合成繊維等の使用は紙のリサイクルを不可能にしてしまうという問題がある。また特定樹種のパルプを用いて嵩高な書籍用紙を製造する方法についても提案されているが(特許文献３参照)、森林伐採に対する保護活動が活発に行われている現在、単一樹種よりパルプを製造することは難しい。 As a conventional technique for increasing the bulk of paper, there is a method of using a bulky pulp composition obtained by reacting a mixture of pulp and hydrophobic fibers with a crosslinking agent (see Patent Document 1). In addition, there is a method for producing a bulky pulp sheet by mixing cellulose pulp, a specific form of polyester composite fiber, and a heat-fusible binder (see Patent Document 2). However, the use of cross-linked pulp, synthetic fibers, etc. has the problem of making paper impossible to recycle. A method for producing bulky book paper using pulp of a specific tree species has also been proposed (see Patent Document 3). Currently, there is active protection activity against deforestation. It is difficult to manufacture.
一方、内添填料を利用した嵩高紙の製造方法についても多く検討されている。まず中空球状バテライト型炭酸カルシウムを充填して嵩高中性紙を製造する技術がある(特許文献４参照)が、特殊な填料であり、生産性を考慮した場合、実現は難しい。また、嵩比重0.3g/cm3以下の無定形シリカまたはシリケートを用いることで、嵩高な印刷用紙の製造方法について記載されている(特許文献５参照)。しかし、ホワイトカーボンのような比重の低い物質を填料として用いると、その用紙は嵩高となるが、紙の剛度およびサイズ度を低下させてしまう上、炭酸カルシウムなどと比較して不透明度発現性が低く、低密度印刷用紙に用いる場合、良好な印刷適性を得にくい。 On the other hand, many methods for producing bulky paper using an internal filler have been studied. First, there is a technique for producing a bulky neutral paper by filling hollow spherical vaterite-type calcium carbonate (see Patent Document 4), but it is a special filler and difficult to realize when considering productivity. Further, a method for producing bulky printing paper by using amorphous silica or silicate having a bulk specific gravity of 0.3 g / cm 3 or less is described (see Patent Document 5). However, when a low specific gravity material such as white carbon is used as a filler, the paper becomes bulky, but the stiffness and sizing of the paper are reduced, and the opacity is manifested in comparison with calcium carbonate and the like. When used for low and low density printing paper, it is difficult to obtain good printability.
また、オフセット印刷用紙として用いる場合、紙中へ水の浸透を押さえる特性(サイズ性)を用紙に付与することは印刷適性の観点から必要不可欠なことであるが、ホワイトカーボンを用いた紙は、サイズ性が激減し、印刷適性を維持することが難しい。一般にＢＥＴ比表面積の高い填料は、サイズ剤の効果を低下させやすい傾向が知られている。ホワイトカーボンは一次粒子が凝集した形態をとるため、他填料と比較して嵩高で吸油量も高いが、他填料より比表面積が著しく高くなる。これがホワイトカーボンを内添填料に用いた場合、サイズ剤効果を低減させ、紙のサイズ性が低くなる原因の一つと考えられる。 In addition, when used as offset printing paper, it is indispensable from the viewpoint of printability to give the paper the property (size) to suppress water penetration into the paper, but paper using white carbon is Size is drastically reduced and it is difficult to maintain printability. In general, a filler having a high BET specific surface area is known to tend to reduce the effect of the sizing agent. Since white carbon takes a form in which primary particles are aggregated, it is bulky and has a higher oil absorption than other fillers, but its specific surface area is significantly higher than other fillers. This is considered to be one of the causes that the sizing effect is reduced and the paper size is lowered when white carbon is used as the internal filler.
以上のように、紙の種類や、その製造に用いられるパルプ種類を問わず、嵩高かつ不透明度等の印刷適性が良好な印刷用紙が望まれており、これを可能にする高機能の填料の開発が望まれていた。 As described above, regardless of the type of paper and the type of pulp used in its production, a printing paper that is bulky and has good printability such as opacity is desired. Development was desired.
本発明が解決しようとする課題は、嵩高でありながら、不透明性や印刷後不透明性などの印刷適性に優れた低密度印刷用紙を提供することにある。 The problem to be solved by the present invention is to provide a low-density printing paper that is bulky and excellent in printability such as opacity and opacity after printing.
軽質炭酸カルシウムとケイ酸アルカリとの混合液のpHを7〜9まで中和して製造された、軽質炭酸カルシウム粒子の表面をシリカで被覆した軽質炭酸カルシウム−シリカ複合物を、紙中填料率として1〜25固形分重量%含有させることにより、低密度印刷用紙を得る。 The light calcium carbonate-silica composite produced by neutralizing the pH of the mixture of light calcium carbonate and alkali silicate to 7-9 and coated with silica on the surface of the light calcium carbonate particles was used as a filler in paper. As a result, a low density printing paper is obtained.
本発明の低密度印刷用紙は、嵩高でありながら、不透明性や印刷後不透明性に優れ、更にサイズ性にも優れるという効果を有する。 The low-density printing paper of the present invention is bulky, and has an effect of being excellent in opacity and post-printing opacity and also in size.
本発明の低密度印刷用紙に使用するパルプ原料の種類と配合は、上質紙、中質紙、下級紙などの紙のグレードにより決められ、特に限定はない。例えば、クラフトパルプ(KP)等の化学パルプ、ストーングランドパルプ(SGP)、加圧ストーングランドパルプ(PGP)、リファイナーグランドパルプ(RGP)、ケミグランドパルプ(CGP)、サーモグランドパルプ(TGP)、砕木パルプ(GP)、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)、リファイナーメカニカルパルプ(RMP)等の機械パルプ(MP)、更に、脱墨パルプ(DIP)等の古紙パルプから１種あるいは２種以上を適宜選択し、配合して使用することができる。 The types and blends of pulp raw materials used in the low density printing paper of the present invention are determined by the grade of paper such as high quality paper, medium quality paper, and lower grade paper, and are not particularly limited. For example, chemical pulp such as kraft pulp (KP), Stone Grand Pulp (SGP), Pressurized Stone Grand Pulp (PGP), Refiner Grand Pulp (RGP), Chemi Grand Pulp (CGP), Thermo Grand Pulp (TGP), Groundwood Pulp (GP), thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), refiner mechanical pulp (RMP) and other mechanical pulp (MP), and deinked pulp (DIP) and other waste paper pulp Two or more kinds can be appropriately selected and used in combination.
本発明の低密度印刷用紙では、後述する方法で製造される、軽質炭酸カルシウム粒子の表面をシリカで被覆した軽質炭酸カルシウム−シリカ複合粒子を、填料の全量または一部に使用する。この軽質炭酸カルシウム−シリカ複合粒子は、紙を低密度化する効果に優れ、吸油量が大きく、不透明度を向上させる効果に優れるという特性を有する粒子である。本発明の低密度印刷用紙においては、該軽質炭酸カルシウム−シリカ複合粒子を、紙中填料率として1〜25固形分重量%の割合で含有していることが好ましく、3〜25固形分重量%がより好ましく、5〜25固形分重量%が更に好ましい。紙中填料率が1固形分重量%未満では、印刷用紙の密度低下と不透明度の向上が不十分である。 In the low-density printing paper of the present invention, light calcium carbonate-silica composite particles produced by the method described later and having the surface of light calcium carbonate particles coated with silica are used for the total amount or a part of the filler. The light calcium carbonate-silica composite particles are particles having the characteristics of being excellent in the effect of reducing the density of paper, having a large oil absorption, and improving the opacity. In the low-density printing paper of the present invention, the light calcium carbonate-silica composite particles are preferably contained in a ratio of 1 to 25 solids by weight as a filler content in the paper, and 3 to 25 solids by weight. Is more preferable, and 5 to 25% by solid weight is more preferable. When the filler content in the paper is less than 1% by weight, the density of the printing paper is not lowered and the opacity is not sufficiently improved.
軽質炭酸カルシウム−シリカ複合粒子は内部に軽質炭酸カルシウムを含んでいるため、紙を酸性抄紙で抄造する場合には、その酸性によって粒子内部の軽質炭酸カルシウムが分解または溶解する可能性がある。従って、中性抄紙〜アルカリ性抄紙で紙を抄造することが好ましい。 Since the light calcium carbonate-silica composite particles contain light calcium carbonate, the light calcium carbonate inside the particles may be decomposed or dissolved by the acidity when paper is made by acidic papermaking. Therefore, it is preferable to make paper from neutral papermaking to alkaline papermaking.
また、本発明の低密度印刷用紙では、填料として軽質炭酸カルシウム−シリカ複合粒子の他に、本発明の効果である嵩高性、高不透明性、高サイズ性が損なわれない範囲内で、他の無機、有機填料を併用することも可能である。その種類については、中性抄紙やアルカリ性抄紙で通常使用されている填料であれば何ら制限はなく使用することができる。一例を挙げると炭酸マグネシウム、炭酸バリウム、水酸化アルミニウム、水酸化カルシウム、水酸化マグネシウム、水酸化亜鉛、クレー、焼成カオリン、デラミカオリン、二酸化チタン、酸化亜鉛、酸化珪素、非晶質シリカ等の無機填料や、尿素−ホルマリン樹脂、ポリスチレン樹脂、フェノール樹脂、微小中空粒子等から選ばれる１種類以上を併用することができる。軽質炭酸カルシウム−シリカ複合粒子と他の填料を併用する場合の紙中填料率は1.0固形分重量%を超え40固形分重量%以下が好ましく、3固形分重量%を超え40固形分重量%以下がより好ましく、5固形分重量%を超え40固形分重量以下が更に好ましい。40固形分重量%を超えると、紙力低下による断紙が多く操業が困難となり、また印刷時には紙粉の発生量が多くなる。 In addition, in the low density printing paper of the present invention, in addition to the light calcium carbonate-silica composite particles as fillers, other than the above, the bulkiness, high opacity, and high size properties that are the effects of the present invention are not impaired. Inorganic and organic fillers can be used in combination. As for the type, any filler that is usually used for neutral papermaking or alkaline papermaking can be used without any limitation. Examples include inorganics such as magnesium carbonate, barium carbonate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, clay, calcined kaolin, deramikaolin, titanium dioxide, zinc oxide, silicon oxide, amorphous silica, etc. One or more selected from fillers, urea-formalin resins, polystyrene resins, phenol resins, fine hollow particles and the like can be used in combination. When the light calcium carbonate-silica composite particles are used in combination with other fillers, the filler content in the paper is preferably more than 1.0 solids weight% and 40 solids weight% or less, more than 3 solids weight% and 40 solids weight% or less More preferably, it is more than 5% by weight and more preferably 40% by weight or less. If the solid content exceeds 40% by weight, paper breaks due to a decrease in paper strength make operation difficult, and the amount of paper dust generated during printing increases.
以上のパルプ原料と填料を混合した後、必要ならば紙力向上剤、歩留向上剤、湿潤紙力増強剤、染料、蛍光増白剤、消泡剤、ピッチコントロール剤、スライムコントロール剤などの製紙用補助薬品を加えても良い。さらにオフセット印刷適性向上のため、サイズ性付与剤も用いられる。中性抄紙〜アルカリ性抄紙の印刷用紙では、公知の内添中性サイズ剤である、アルキルケテンダイマー(AKD)系サイズ剤、アルケニル無水コハク酸(ASA)系サイズ剤、中性ロジン系サイズ剤等が挙げられるが、中性ロジンサイズ剤よりは、AKD、ASAが紙を低密度化しやすく、低密度印刷用紙を製造する場合には好適であると考えられる。これらのサイズ剤の添加量はパルプ絶乾重量に対して0.05〜5重量%が好ましく、0.1〜1重量%がより好ましい。 After mixing the above pulp materials and fillers, if necessary, paper strength improver, yield improver, wet paper strength enhancer, dye, fluorescent whitening agent, antifoaming agent, pitch control agent, slime control agent, etc. Auxiliary chemicals for papermaking may be added. Further, a size imparting agent is also used for improving the offset printability. For neutral paper to alkaline paper printing paper, known internally added neutral sizing agents, alkyl ketene dimer (AKD) sizing agents, alkenyl succinic anhydride (ASA) sizing agents, neutral rosin sizing agents, etc. However, it is considered that AKD and ASA tend to lower the density of the paper than the neutral rosin sizing agent, and are suitable for producing a low-density printing paper. The addition amount of these sizing agents is preferably 0.05 to 5% by weight, more preferably 0.1 to 1% by weight, based on the absolute dry weight of the pulp.
本発明の低密度印刷用紙の抄造に用いる抄紙機は公知の装置であれば良く、長網抄紙機、オントップツインワイヤー抄紙機、ギャップフォーマーなどが用いられる。 The paper machine used for making the low-density printing paper of the present invention may be any known apparatus, and a long net paper machine, an on-top twin wire paper machine, a gap former, and the like are used.
抄紙後、表面強度向上や耐水性付与、その他インク着肉性改良などを目的として、表面塗工を行っても良い。塗工装置については限定はない。表面処理剤の種類についても特に制限は無いが、一例を挙げると生澱粉や、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単独または併用できる。また、表面処理剤には前記の薬剤の他に、スチレンアクリル酸、スチレンマレイン酸、オレフィン系化合物、カチオン性サイズ剤などの表面サイズ剤を併用塗布することができる。 After papermaking, surface coating may be performed for the purpose of improving the surface strength, imparting water resistance, and improving ink deposition. There is no limitation on the coating apparatus. There are no particular restrictions on the type of surface treatment agent. For example, raw starch, modified starch such as oxidized starch, esterified starch, cationized starch, enzyme-modified starch, aldehyde-modified starch, and hydroxyethylated starch, carboxy Cellulose derivatives such as methylcellulose, hydroxyethylcellulose, methylcellulose, modified alcohols such as polyvinyl alcohol and carboxyl-modified polyvinyl alcohol, styrene butadiene copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, Polyacrylic acid ester, polyacrylamide and the like can be used alone or in combination. In addition to the above-mentioned agents, surface sizing agents such as styrene acrylic acid, styrene maleic acid, olefinic compounds, and cationic sizing agents can be applied to the surface treatment agent.
キャレンダーは通常の操業範囲内の線圧で用いられるが、低密度の紙を製造する観点からは、紙の平滑性を維持できる範囲でなるべく低線圧またはバイパスが好ましく、また、通常のキャレンダーよりもソフトキャレンダーが好ましい。 The calender is used at a linear pressure within the normal operating range. From the viewpoint of producing low density paper, the low linear pressure or bypass is preferable as long as the smoothness of the paper can be maintained. A soft calendar is preferred over a render.
以下に、本発明で填料として使用する軽質炭酸カルシウム−シリカ複合物の製造方法を説明する。
［軽質炭酸カルシウム−シリカ複合物の製造方法］
まず軽質炭酸カルシウムを水中に分散させる。この軽質炭酸カルシウムの結晶形態はカルサイト、アラゴナイトのいずれでも良く、また形状についても針状、柱状、紡錘状、球状、立方体状、ロゼッタ型のいずれでも良い。この中でも特にロゼッタ型のカルサイト系の軽質炭酸カルシウムを用いた場合に、特に優れた嵩高、不透明度改善効果が高い軽質炭酸カルシウム−シリカ複合物が得られる。なお、ロゼッタ型とは、紡錘状の軽質炭酸カルシウム一次粒子がいがくり状に凝集した形状を指し、他の軽質炭酸カルシウムより高い比表面積と吸油性を示す特徴がある。また、軽質炭酸カルシウムは粉砕処理を施して使用しても良い。
Below, the manufacturing method of the light calcium carbonate-silica composite used as a filler by this invention is demonstrated.
[Method for producing light calcium carbonate-silica composite]
First, light calcium carbonate is dispersed in water. The crystal form of the light calcium carbonate may be either calcite or aragonite, and the shape may be any of acicular, columnar, spindle, spherical, cubic, and rosetta types. Among these, in particular, when a rosetta-type calcite-type light calcium carbonate is used, a light calcium carbonate-silica composite having a particularly high bulk and high opacity improvement effect can be obtained. The rosetta type refers to a shape in which spindle-shaped light calcium carbonate primary particles are aggregated in a corrugated shape, and is characterized by a higher specific surface area and oil absorption than other light calcium carbonates. Light calcium carbonate may be used after being pulverized.
この軽質炭酸カルシウムの反応原液中濃度は、後述の軽質炭酸カルシウムとケイ酸の配合比率が重要であるため、ケイ酸濃度の影響も加味しなくてはならないが、1〜20固形分重量%が好ましい。1%未満の低濃度であると１バッチ当たりの生産量が少なく、生産性に問題がある。また、20%を超える高濃度とすると分散性が悪く、また軽質炭酸カルシウム量と比例して、反応に用いるケイ酸アルカリの濃度が高くなるため、反応時の粘度が上昇し、操業性に問題がある。 The concentration of the light calcium carbonate in the reaction stock solution is important for the ratio of light calcium carbonate and silicic acid, which will be described later, so the influence of the silicic acid concentration must be taken into account. preferable. When the concentration is less than 1%, the production amount per batch is small, and there is a problem in productivity. In addition, if the concentration exceeds 20%, dispersibility is poor, and the concentration of alkali silicate used in the reaction increases in proportion to the amount of light calcium carbonate. There is.
ついで、この軽質炭酸カルシウムのスラリーに、ナトリウム、カリウムのようなアルカリ溶液中に溶解した形のケイ酸を加える。一般的に工業用に用いられるものは、ケイ酸ソーダ(ナトリウム)もしくはケイ酸カリウムであるが、本発明である複合物を形成するためには、ケイ酸とアルカリのモル比はいずれでも良い。3号ケイ酸はSiO2：Na2O＝3〜3.4：1程度のモル比のものであるが、一般に入手しやすく、好適に使用される。軽質炭酸カルシウムとケイ酸アルカリとの仕込重量比は、生成する軽質炭酸カルシウム−シリカ複合物中の炭酸カルシウムとシリカの重量比が目標とする範囲に入るように仕込む。軽質炭酸カルシウム−シリカ複合物の炭酸カルシウムとシリカの重量比は、CaCO3/SiO2＝30/70〜70/30である。 Next, silicic acid dissolved in an alkaline solution such as sodium or potassium is added to the light calcium carbonate slurry. Generally used for industrial use is sodium silicate (sodium) or potassium silicate, but in order to form the composite according to the present invention, any molar ratio of silicic acid and alkali may be used. No. 3 silicic acid has a molar ratio of about SiO 2 : Na 2 O = 3 to 3.4: 1, but is generally easily available and is preferably used. The weight ratio of light calcium carbonate and alkali silicate is charged so that the weight ratio of calcium carbonate and silica in the resulting light calcium carbonate-silica composite falls within the target range. The weight ratio of calcium carbonate to silica in the light calcium carbonate-silica composite is CaCO 3 / SiO 2 = 30/70 to 70/30.
このスラリーをアジテータ、ホモミキサー、ミキサー等で攪拌、分散させるが、これは軽質炭酸カルシウムが水に十分に分散し、軽質炭酸カルシウムの粒子が極端に凝集してなければ問題なく、特に時間やアジテーションの強さ等の制限はない。 This slurry is stirred and dispersed with an agitator, homomixer, mixer, etc. This is fine as long as the light calcium carbonate is sufficiently dispersed in water and the light calcium carbonate particles are not extremely aggregated, especially time and agitation. There are no restrictions on the strength of
次に、酸を用いた中和反応を行う。この場合、酸は鉱酸ならいずれでも良く、さらには鉱酸中に硫酸バンドや硫酸マグネシウムのような酸性金属塩を含む酸でも使用できる。工業的には硫酸、塩酸等の比較的安価に購入できる酸が好ましい。高濃度の酸を用いた場合、酸による中和時の攪拌が不十分であると、高濃度の酸の添加により部分的にpHの低い部分ができ、軽質炭酸カルシウムが分解するため、酸添加口でホモミキサー等を用いた強攪拌を行う必要がある。一方、あまりに希薄な酸を用いると、酸添加により全体的な容量が極端に増えてしまうので好ましくない。この面からも、0.05N以上の濃度の酸を用いることが適当である。鉱酸または酸性金属塩水溶液の添加は、アルカリ性であるケイ酸金属塩水溶液と軽質炭酸カルシウムとの混合物の沸点以下の温度で行う。この中和処理によりケイ酸分を析出させ、非晶質ケイ酸を形成し、これが軽質炭酸カルシウム粒子の表面を被覆する。 Next, a neutralization reaction using an acid is performed. In this case, the acid may be any mineral acid, and further, an acid containing an acidic metal salt such as a sulfate band or magnesium sulfate in the mineral acid can be used. Industrially preferred are acids that can be purchased relatively inexpensively, such as sulfuric acid and hydrochloric acid. When a high concentration acid is used, if the stirring during neutralization with the acid is insufficient, the addition of the high concentration acid will result in a portion with a low pH, and light calcium carbonate will decompose, so acid addition It is necessary to perform strong stirring using a homomixer or the like at the mouth. On the other hand, if a too dilute acid is used, the overall capacity is extremely increased by the acid addition, which is not preferable. Also from this aspect, it is appropriate to use an acid having a concentration of 0.05 N or more. The mineral acid or acidic metal salt aqueous solution is added at a temperature not higher than the boiling point of the alkaline silicate metal salt aqueous solution and light calcium carbonate. By this neutralization treatment, silicic acid is deposited to form amorphous silicic acid, which covers the surface of the light calcium carbonate particles.
さらに、この酸添加は数回に分けて行っても良い。酸添加後、熟成を行っても良い。なお、熟成とは酸添加を一時中止し、攪拌のみを施し放置しておくことを指す。この熟成中に強攪拌や粉砕を行い、粒子の形態をコントロールすることも可能である。 Furthermore, this acid addition may be performed in several times. Aging may be performed after the acid addition. The aging means that the acid addition is temporarily stopped, only stirred and left to stand. It is also possible to control the morphology of the particles by vigorous stirring and pulverization during this aging.
次に、上記酸添加によるスラリーの中和はpH＝7〜9を目標に行う。析出してきたケイ酸分により軽質炭酸カルシウムが被覆されていくが、酸性側(pH7未満)にすると、軽質炭酸カルシウムが分解してしまう。一方、pHが高い(9.0超)状態で中和を終了すると、ケイ酸分の析出が十分に行われず、スラリー中に未反応のケイ酸分が残り、ケイ酸分のロスが多くなり、工業的に好ましくない。そのため、目標pHは7〜9で中和を終了させる。 Next, neutralization of the slurry by the above acid addition is carried out with the target of pH = 7-9. The light calcium carbonate is coated with the precipitated silicic acid component, but when it is on the acidic side (less than pH 7), the light calcium carbonate is decomposed. On the other hand, when neutralization is completed at a high pH (above 9.0), silicic acid is not sufficiently precipitated, unreacted silicic acid remains in the slurry, and the loss of silicic acid increases. Is not preferable. Therefore, neutralization is completed at a target pH of 7-9.
このようにして、製造された軽質炭酸カルシウム−ケイ酸の複合物は、軽質炭酸カルシウム粒子表面をシリカが被覆した懸濁液の状態となる。この懸濁液のまま抄紙工程等に使用しても良いが、生産規模が小規模の場合にはろ紙やメンブランフィルタ等のろ過設備、中規模以上の場合にはベルトフィルタやドラムフィルタ等を用いたろ過、または遠心分離機を用いた遠心分離を行うことによって固液分離を行い、中和反応で生成した余分な副生成物である塩を極力取り除いたほうが好ましい。これは、余分な塩が残存していると、抄紙工程においてこの塩が難溶性の金属塩(例えば、硫酸カルシウム)に変化し、これを原因としたスケーリングの問題を発生するおそれがあるためである。さらにこの固液分離を行った固形分濃度10〜50%のケーキ状複合物を、水またはエタノールにより再分散後、再び固液分離を行い、さらに余分なケイ酸や副生成物である塩を取り除いても良い。 Thus, the manufactured light calcium carbonate-silicic acid composite is in a suspension state in which the surface of the light calcium carbonate particles is coated with silica. This suspension may be used in the papermaking process, but if the production scale is small, filter equipment such as filter paper or membrane filter is used, and if it is medium or larger, a belt filter or drum filter is used. It is preferable to carry out solid-liquid separation by performing filtration or centrifugal separation using a centrifuge, and to remove as much as possible the salt which is an extra by-product generated by the neutralization reaction. This is because if excess salt remains, this salt may change into a poorly soluble metal salt (e.g., calcium sulfate) in the papermaking process, which may cause scaling problems. is there. Furthermore, after re-dispersing the cake-like composite having a solid content concentration of 10 to 50%, which has been subjected to the solid-liquid separation, with water or ethanol, the solid-liquid separation is performed again to further remove excess silicic acid and by-product salts. It may be removed.
得られた軽質炭酸カルシウム−ケイ酸の複合物は、目的粒子径より大きい粗粒物を取り除くため、振動篩やスクリーンを用いて、100μｍ以上の粒子を除去する。 The obtained light calcium carbonate-silicic acid composite removes particles of 100 μm or more using a vibrating sieve or a screen in order to remove coarse particles larger than the target particle size.
軽質炭酸カルシウム−ケイ酸の複合物の平均粒子径の調整は、前述のように、熟成中に強攪拌や粉砕を行うことにより粒子の形態をコントロールすることも可能であるが、中和反応終了後または反応終了後の固液分離したものを、湿式粉砕機を用いて、目的の平均粒子径に調整しても良い。また、この組み合わせにより平均粒子径を調整しても良い。 Adjustment of the average particle size of the light calcium carbonate-silicic acid composite can be controlled by intensive stirring and pulverization during aging as described above, but the neutralization reaction is completed. The solid or liquid separated after or after completion of the reaction may be adjusted to the target average particle size using a wet pulverizer. Further, the average particle diameter may be adjusted by this combination.
粗大粒子を除去した後、あるいは粗大粒子除去後さらに強撹拌や粉砕処理を施した軽質炭酸カルシウム−ケイ酸の複合物の平均粒子径は、その用途が紙用の填料である場合には、30μｍ以下が良く、20μｍ以下が好ましく、10μｍ以下が更に好ましい。 After removing the coarse particles, or after removing the coarse particles, the average particle size of the light calcium carbonate-silicic acid composite that has been further stirred and pulverized is 30 μm when the use is a filler for paper. The following is preferable, preferably 20 μm or less, and more preferably 10 μm or less.
以上のように軽質炭酸カルシウム−シリカ複合物を填料として用いることで、嵩高で不透明性に優れた低密度印刷用紙を得ることができる。またこの印刷用紙については、オフセット印刷用紙の他にも、凸版印刷用紙、感熱記録紙、感圧記録紙等や、インクジェット用の原紙などに使用することも可能である。 As described above, by using the light calcium carbonate-silica composite as a filler, it is possible to obtain a low-density printing paper that is bulky and excellent in opacity. In addition to offset printing paper, this printing paper can also be used for letterpress printing paper, heat-sensitive recording paper, pressure-sensitive recording paper, and ink jet base paper.
以下、実施例にて本発明を具体的に説明するが、本発明はこれ等の実施例に限定されるものではない。なお、実施例及び比較例中の%、部は各々重量%、重量部を表す。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In the examples and comparative examples, “%” and “part” represent “% by weight” and “part by weight”, respectively.
本発明における軽質炭酸カルシウム−シリカ複合物の各特性値と、これを填料として配合した紙の紙質の測定方法を下記に示した。
（1)吸油量：JIS K5101の方法による。
（2）粒度分布測定：軽質炭酸カルシウム−ケイ酸の複合物のスラリーを分散剤ヘキサメタリン酸ソーダ0.2重量%を添加した純水中に滴下混合して均一分散体とし、レーザー法粒度測定機(使用機器：マルバーン社製マスターサイザーＳ型)を使用して粒度測定し、平均粒子径を求めた。
（3）紙の不透明度、嵩高率、裂断長の測定：熊谷理機工業株式会社製の配向性抄紙機により、抄紙原料としてLBKP(ろ水度CSF370ml)スラリーを用い、軽質炭酸カルシウム−ケイ酸複合物のスラリーを填料として、その添加率を対パルプ5、10、15%として坪量60g/m2になるように抄造して、プレスにより脱水後、送風乾燥機にて乾燥し、各添加率のシートサンプルを作製した。このシートサンプルをJIS P8148、JIS P8149に準じ、色差計(村上色彩研究所製)を用い、白色度、不透明度を測定した。引張強度測定機(Lorentzen&Wettre社製、SE062/064)を用い、裂断長を測定した。
また嵩高率は、このシートサンプルの紙厚を測定し、下記の式に従い算出した。各シートサンプルを525℃にて焼成し灰分量を測定し、紙中填料率と白色度、紙中填料率と不透明度、紙中填料率と裂断長、紙中填料率と嵩高率の関係図を描いた。この図から、紙中填料率7%時の白色度、不透明度、裂断長および嵩高率を求めた。
嵩高率＝(1−サンプル密度/填料無添加品の密度)×100
Each characteristic value of the light calcium carbonate-silica composite in the present invention and a method for measuring the paper quality of the paper blended with this as a filler are shown below.
(1) Oil absorption: According to JIS K5101 method.
(2) Particle size distribution measurement: Light calcium carbonate-silicic acid composite slurry is dropped and mixed in pure water to which 0.2% by weight of sodium hexametaphosphate is added to form a uniform dispersion. The particle size was measured using an apparatus: Mastersizer S type manufactured by Malvern, and the average particle size was determined.
(3) Measurement of paper opacity, bulkiness ratio and tear length: Light calcium carbonate-silica using LBKP (freezing degree CSF 370 ml) slurry as a papermaking raw material with an orientation paper machine manufactured by Kumagai Riki Kogyo Co., Ltd. The slurry of the acid composite was used as a filler, and the addition ratio was 5, 10 and 15% for pulp, and the paper was made to have a basis weight of 60 g / m 2 , dehydrated with a press, dried with a blow dryer, An addition rate sheet sample was prepared. The sheet sample was measured for whiteness and opacity using a color difference meter (manufactured by Murakami Color Research Laboratory) according to JIS P8148 and JIS P8149. Using a tensile strength measuring device (SE062 / 064, manufactured by Lorentzen & Wettre), the breaking length was measured.
The bulkiness ratio was calculated according to the following formula by measuring the paper thickness of the sheet sample. Each sheet sample was baked at 525 ° C and the amount of ash was measured. Paper filler rate and whiteness, paper filler rate and opacity, paper filler rate and tear length, paper filler rate and bulkiness ratio I drew a figure. From this figure, the whiteness, opacity, tear length, and bulkiness ratio when the filler content in the paper was 7% were determined.
Bulkiness factor = (1−sample density / density of filler-free product) × 100
(1)(軽質炭酸カルシウム−シリカ複合物)Ａ
反応容器(12L)中に市販ロゼッタ型軽質炭酸カルシウム(商品名：アルバカー5970、Speciaty Minerals Inc.社製)262gを水に分散し、ここにSiO2濃度18.0wt/wt%、Na2O濃度6.1wt/wt%のケイ酸ソーダ溶液を3,400g加えた後、水を加え、全量を12Lとした。この混合スラリーをラボ用アジテータで十分に攪拌しながら加熱し、85℃とした。このスラリーに、10%硫酸溶液をロータリーポンプにより加えるが、この硫酸添加口付近が十分攪拌されるように、ホモミキサーの攪拌羽根直下とした。このように添加された硫酸が十分に分散される条件のもと、温度一定で、硫酸添加後の最終pHは8.0、全硫酸添加時間は240分間となるように、一定速度で硫酸を添加した。このスラリーは100メッシュ篩で粗粒分を分離した後、No.2のろ紙を用いて吸引ろ過し、さらに約10%に再分散し、平均粒子径、吸油量、手抄き分析用サンプルとした。平均粒子径、吸油量測定用サンプルは吸引ろ過後のサンプルをエタノール中に約10%となるよう再分散した後、ろ過、105℃の乾燥機にて乾燥をおこない、粉体サンプルとした。この軽質炭酸カルシウム/シリカ＝30/70の複合物の平均粒子径は7.3μｍ、吸油量は180ml/100gであった。なお、核に用いた市販ロゼッタ型軽質炭酸カルシウムの平均粒子径は3.0μｍ、吸油量121ml/100gである。
(2)(軽質炭酸カルシウム−シリカ複合物)Ｂ
上記(1)において、反応に使用した市販ロゼッタ型軽質炭酸カルシウム612gをとした以外は、同様にして製造した。この軽質炭酸カルシウム/シリカ＝50/50の複合物の平均粒子径は4.4μｍ、吸油量は160ml/100gであった。
(2)(軽質炭酸カルシウム−シリカ複合物)Ｃ
上記(1)において、反応に使用した市販ロゼッタ型軽質炭酸カルシウムを1,436gとした以外は、同様にして製造した。この軽質炭酸カルシウム/シリカ＝70/30の複合物の平均粒子径は3.6μｍ、吸油量は140ml/100gであった。
(1) (Light calcium carbonate-silica composite) A
Commercially available in a reaction vessel (12L) rosette type precipitated calcium carbonate (trade name: Arubaka 5970, Speciaty Minerals Inc. Co., Ltd.) 262g was dispersed in water, wherein the SiO 2 concentration 18.0wt / wt%, Na 2 O concentration 6.1 After adding 3,400 g of wt / wt% sodium silicate solution, water was added to make the total volume 12L. This mixed slurry was heated to 85 ° C. with sufficient stirring with a laboratory agitator. A 10% sulfuric acid solution was added to the slurry by a rotary pump, and the slurry was placed directly under the stirring blade of the homomixer so that the vicinity of the sulfuric acid addition port was sufficiently stirred. Under such conditions that the added sulfuric acid was sufficiently dispersed, sulfuric acid was added at a constant rate so that the temperature was constant, the final pH after addition of sulfuric acid was 8.0, and the total sulfuric acid addition time was 240 minutes. . This slurry is separated by coarse mesh with a 100 mesh sieve and suction filtered using No. 2 filter paper, and further re-dispersed to about 10%, with an average particle size, oil absorption, sample for handsheet analysis and did. The sample for measuring the average particle diameter and oil absorption amount was redispersed in ethanol so that the sample was about 10% after filtration, filtered, and dried in a dryer at 105 ° C. to obtain a powder sample. The composite of light calcium carbonate / silica = 30/70 had an average particle size of 7.3 μm and an oil absorption of 180 ml / 100 g. The average particle size of commercially available rosetta-type light calcium carbonate used for the core is 3.0 μm, and the oil absorption is 121 ml / 100 g.
(2) (Light calcium carbonate-silica composite) B
The same production as in (1) above except that 612 g of commercially available rosetta-type light calcium carbonate used in the reaction was used. The composite of light calcium carbonate / silica = 50/50 had an average particle size of 4.4 μm and an oil absorption of 160 ml / 100 g.
(2) (Light calcium carbonate-silica composite) C
Production was carried out in the same manner as in the above (1) except that 1,436 g of commercially available rosetta-type light calcium carbonate used in the reaction was used. The composite of light calcium carbonate / silica = 70/30 had an average particle size of 3.6 μm and an oil absorption of 140 ml / 100 g.
［実施例１］
填料として、(軽質炭酸カルシウム−シリカ複合物)Ａを使用し、上記の方法で紙を作成し、紙中填料7%時の白色度、不透明度、裂断長および嵩高率を表１に示した。
[Example 1]
Using (light calcium carbonate-silica composite) A as a filler, paper was prepared by the above method. Table 1 shows the whiteness, opacity, tear length and bulk ratio when the filler in the paper is 7%. It was.
［実施例２］
填料として、(軽質炭酸カルシウム−シリカ複合物)Ｂを使用し、上記の方法で紙を作成し、紙中填料7%時の白色度、不透明度、裂断長および嵩高率を表１に示した。
[Example 2]
Using (light calcium carbonate-silica composite) B as a filler, paper was prepared by the above method, and the whiteness, opacity, tearing length, and bulk ratio when the filler in the paper was 7% are shown in Table 1. It was.
［実施例３］
填料として、(軽質炭酸カルシウム−シリカ複合物)Ｃを使用し、上記の方法で紙を作成し、紙中填料7%時の白色度、不透明度、裂断長および嵩高率を表１に示した。
[Example 3]
Using (light calcium carbonate-silica composite) C as a filler, paper was prepared by the method described above, and the whiteness, opacity, tearing length and bulk ratio when the filler in the paper was 7% are shown in Table 1. It was.
［比較例１］
填料として、市販ロゼッタ型軽質炭酸カルシウム(商品名：アルバカー5970、Speciaty Minerals Inc.社製)を複合化せずそのまま用いた以外は、実施例１と同様にして紙を作成し、紙中填料7%時の白色度、不透明度、裂断長および嵩高率を表１に示した。
[Comparative Example 1]
A paper was prepared in the same manner as in Example 1 except that commercially available rosetta-type light calcium carbonate (trade name: Albuquer 5970, manufactured by Speciaty Minerals Inc.) was used as it was without being combined. Table 1 shows the whiteness, opacity, tear length, and bulk ratio at%.
［比較例２］
填料として、市販紡錘状軽質炭酸カルシウム(商品名：TP121、奥多摩工業株式会社社製)を複合化せずそのまま用いた以外は、実施例１と同様にして紙を作成し、紙中填料7%時の白色度、不透明度、裂断長および嵩高率を表１に示した。なお、TP121は紡錘状の一次粒子からなる軽質炭酸カルシウムであり、一次粒子が凝集して二次粒子を形成したものではない。
[Comparative Example 2]
A paper was prepared in the same manner as in Example 1 except that commercially available spindle-shaped light calcium carbonate (trade name: TP121, manufactured by Okutama Kogyo Co., Ltd.) was used as it was as a filler. Table 1 shows the whiteness, opacity, tear length, and bulkiness ratio. Note that TP121 is light calcium carbonate composed of spindle-shaped primary particles, and is not formed by aggregation of primary particles to form secondary particles.
［比較例３］
填料として、市販ホワイトカーボン(商品名：TIXOLEX17、Rhdia Silica Korea社製)を複合化せずそのまま用いた以外は、実施例１と同様にして紙を作成し、紙中填料7%時の白色度、不透明度、裂断長および嵩高率を表１に示した。
[Comparative Example 3]
A paper was prepared in the same manner as in Example 1 except that commercially available white carbon (trade name: TIXOLEX17, manufactured by Rhdia Silica Korea) was used as a filler as it was, and the whiteness when the filler in the paper was 7% was used. Table 1 shows the opacity, tear length, and bulk ratio.
［比較例４］
填料として、市販ホワイトカーボン(商品名：TIXOLEX17、Rhdia Silica Korea社製)と市販ロゼッタ型軽質炭酸カルシウム(商品名：アルバカー5970、Speciaty Minerals Inc.社製)を50：50で混合したものを複合化せずそのまま用いた以外は、実施例１と同様にして紙を作成し、紙中填料7%時の白色度、不透明度、裂断長および嵩高率を表１に示した。なお、TIXOLEX17/アルバカー5970＝50/50の混合填料の平均粒子径は3.8μｍ、吸油量は137ml/100gであった。
[Comparative Example 4]
As a filler, a mixture of commercial white carbon (trade name: TIXOLEX17, manufactured by Rhdia Silica Korea) and commercial rosetta-type light calcium carbonate (trade name: Albuquer 5970, manufactured by Speciaty Minerals Inc.) at 50:50 is combined. A paper was prepared in the same manner as in Example 1 except that the whiteness, opacity, tear length, and bulk ratio when the filler in the paper was 7% were shown in Table 1. The mixed filler of TIXOLEX17 / Albuquer 5970 = 50/50 had an average particle size of 3.8 μm and an oil absorption of 137 ml / 100 g.
［比較例５］
填料を用いない以外は、実施例１と同様にして紙を作成し、、紙中填料７％時の白色度、不透明度、裂断長および嵩高率を表１に示した。
[Comparative Example 5]
A paper was prepared in the same manner as in Example 1 except that no filler was used. Table 1 shows the whiteness, opacity, tear length, and bulk ratio when the filler in the paper is 7%.
表１の結果から、実施例１、２、３で示した軽質炭酸カルシウム−シリカ複合物を填料として用いた場合は、いずれも比較例１で示した軽質炭酸カルシウム−シリカ複合物の核として用いた軽質炭酸カルシウムを用いた場合より、同一紙中填料率でより高い嵩高効果が得られていることが分かる。次に紡錘状の一次粒子からなる軽質炭酸カルシウムを填料として用いた比較例２では、実施例１、２、３より不透明度、嵩高効果いずれの面でも劣る結果となった。また、填料自身が嵩高であるホワイトカーボンを填料として用いた比較例３との比較では、ホワイトカーボン系填料は紙を嵩高にする効果は高かったものの、不透明度向上効果が低いことが分かり、実施例のように嵩高性と不透明性を同時に達成することは出来なかった。一方、軽質炭酸カルシウムとシリカを混合して用いた比較例４では、嵩高効果が得られない。また填料無添加である比較例５は、嵩高性、不透明度の点で全ての実施例より劣る。このように軽質炭酸カルシウム−シリカ複合物を填料として使用することで、嵩高でありながら、不透明性や印刷後不透明性に優れた低密度印刷用紙を得ることができる。 From the results shown in Table 1, when the light calcium carbonate-silica composites shown in Examples 1, 2, and 3 were used as fillers, all were used as the core of the light calcium carbonate-silica composite shown in Comparative Example 1. It can be seen that a higher bulkiness effect is obtained with the same filler content in the paper than when light calcium carbonate is used. Next, in Comparative Example 2 in which light calcium carbonate composed of spindle-shaped primary particles was used as a filler, results were inferior to Examples 1, 2, and 3 in terms of opacity and bulkiness. In comparison with Comparative Example 3 using white carbon, which is bulky, as a filler, it was found that white carbon-based filler had a high effect of making paper bulky, but the effect of improving opacity was low. As in the examples, bulkiness and opacity could not be achieved at the same time. On the other hand, in Comparative Example 4 in which light calcium carbonate and silica are mixed and used, a bulky effect cannot be obtained. Further, Comparative Example 5 with no filler added is inferior to all Examples in terms of bulkiness and opacity. In this way, by using the light calcium carbonate-silica composite as a filler, it is possible to obtain a low-density printing paper that is bulky and excellent in opacity and opacity after printing.
Claims (1)
かつ、該軽質炭酸カルシウム−シリカ複合物は、平均粒子径が10μｍ以下であり、
サイズ剤の添加量パルプは絶乾重量に対して0.05〜5重量%であり、
下記の式によって求められる紙の嵩高率が7.3〜8.0%であること
を特徴とする低密度印刷用紙。
嵩高率＝(1−サンプル密度/填料無添加品の密度)×100 A light calcium carbonate-silica composite obtained by coating the surface of rosette-type calcite light calcium carbonate particles, in which spindle-shaped primary particles are agglomerated to form secondary particles, with silica as a filler content in paper is 1 to 25 The light calcium carbonate-silica composite is contained in a solid content by weight, and the light calcium carbonate / silica = 30/70 to 70/30 in terms of the solid content weight ratio.
And the light calcium carbonate-silica composite has an average particle size of 10 μm or less,
The amount of sizing agent added pulp is 0.05-5% by weight based on the absolute dry weight ,
Low-density printing paper bulk modulus of the paper that are determined by the following formula is characterized in that it is a 7.3 to 8.0%.
Bulkiness factor = (1−sample density / density of filler-free product) × 100
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| Application Number | Priority Date | Filing Date | Title |
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| JP2004099184A JP4796282B2 (en) | 2004-03-30 | 2004-03-30 | Low density printing paper |
| US10/599,135 US7611606B2 (en) | 2004-03-30 | 2005-03-15 | Low-density neutral paper |
| CN2005800090505A CN1954119B (en) | 2004-03-30 | 2005-03-15 | Low density printing paper |
| PCT/JP2005/004574 WO2005098132A1 (en) | 2004-03-30 | 2005-03-15 | Low-density neutral paper |
| KR1020067017859A KR20060134095A (en) | 2004-03-30 | 2005-03-15 | Low-density neutral paper |
| CA2561889A CA2561889C (en) | 2004-03-30 | 2005-03-15 | Bulky neutral paper |
| EP05720829A EP1736598A4 (en) | 2004-03-30 | 2005-03-15 | Low-density neutral paper |
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| JP2004099184A JP4796282B2 (en) | 2004-03-30 | 2004-03-30 | Low density printing paper |
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| JP4796282B2 true JP4796282B2 (en) | 2011-10-19 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007177374A (en) * | 2005-12-28 | 2007-07-12 | Nippon Paper Industries Co Ltd | Coated paper for printing |
| JP5003139B2 (en) * | 2006-01-19 | 2012-08-15 | 王子製紙株式会社 | Porous filler for paper, its production method and porous filler slurry for paper and paper |
| JP4652251B2 (en) * | 2006-02-27 | 2011-03-16 | 日本製紙株式会社 | Clear coated printing paper |
| JP4854341B2 (en) * | 2006-03-10 | 2012-01-18 | 日本製紙株式会社 | Coated paper for printing |
| JP2007239130A (en) * | 2006-03-07 | 2007-09-20 | Nippon Paper Industries Co Ltd | Clear-coated printing paper |
| JP2008057096A (en) * | 2006-08-01 | 2008-03-13 | Nippon Paper Industries Co Ltd | Information-recording paper |
| JP4540660B2 (en) * | 2006-12-22 | 2010-09-08 | 大王製紙株式会社 | Book paper and manufacturing method thereof |
| JP5222865B2 (en) * | 2010-02-22 | 2013-06-26 | 大王製紙株式会社 | Book paper and manufacturing method thereof |
| CN102051071A (en) * | 2010-11-04 | 2011-05-11 | 东北林业大学 | Method for preparing acid-proof calcium carbonate filler fit for making paper with old newspaper deinked pulp with high lignin content and filling paper thereof |
| FR2997421B1 (en) * | 2012-10-30 | 2015-04-17 | Munksjo Arches | DECORATIVE PAPER FOR LAMINATES. |
| PH12014000291A1 (en) | 2013-10-31 | 2016-05-02 | Glatz Julius Gmbh | Tobacco product wrapping material with controlled burning properties |
| CN103614949B (en) * | 2013-12-09 | 2015-12-09 | 淄博欧木特种纸业有限公司 | The goth black facing body paper of high osmosis |
| JP6447246B2 (en) * | 2015-03-04 | 2019-01-09 | 日本製紙株式会社 | Pressure sensitive copy paper |
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