JP4233478B2 - Neutral newspaper printing paper - Google Patents
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- JP4233478B2 JP4233478B2 JP2004100698A JP2004100698A JP4233478B2 JP 4233478 B2 JP4233478 B2 JP 4233478B2 JP 2004100698 A JP2004100698 A JP 2004100698A JP 2004100698 A JP2004100698 A JP 2004100698A JP 4233478 B2 JP4233478 B2 JP 4233478B2
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本発明は、白色度が高く、不透明性に優れ、かつ印刷時の裏抜け改善効果が高い中性新聞用紙に関するものである。 The present invention relates to neutral newsprint with high whiteness, excellent opacity, and high effect of improving the see-through during printing.
近年、印刷技術は、オフセット印刷化、カラー印刷化、高速大量印刷化、自動化など大きな進歩を遂げてきている。新聞用紙の印刷においても、オフセット印刷化、カラー印刷化、高速大量印刷化が急速に進んでおり、それに付随して印刷媒体となる新聞印刷用紙に対しても、より優れたカラー印刷適性や印刷作業性が求められている。特に印刷時に印刷された文字や画像が反対面から透けて見える現象、いわゆる裏抜けについては年々その改善要求レベルが高くなっている。また、印刷作業性の効率化や新聞用紙の輸送コスト低減を目的として、新聞印刷用紙の軽量化が進んでいる。新聞印刷用紙の軽量化に際しては、用紙に裏抜け改善の対策を施すことが必須となっている。 In recent years, printing technology has made great progress such as offset printing, color printing, high-speed mass printing, and automation. In newspaper printing, offset printing, color printing, and high-speed mass printing are rapidly progressing, and it is accompanied by superior color printing aptitude and printing on newspaper printing paper that becomes the printing medium. Workability is required. In particular, with respect to a phenomenon in which characters and images printed during printing can be seen through from the opposite side, so-called back-through, the level of improvement is increasing year by year. In addition, the weight of newspaper printing paper has been reduced for the purpose of improving the efficiency of printing work and reducing the transportation cost of newspaper. In order to reduce the weight of newspaper printing paper, it is indispensable to take measures to improve the show-through.
新聞印刷用紙の裏抜けを少なくするためには、用紙の不透明度及び吸油度を上げることが最も効果的であることが知られている。不透明度を上げるには、比散乱係数の大きい二酸化チタンを配合すると効果的であるが、二酸化チタンは高価であり、多く配合することは経済的ではない。酸性新聞印刷用紙の裏抜けを抑える方法としては、吸油度が高い填料を配合することが有効であり、ホワイトカーボンが広く使用されて来た。 It is known that increasing the opacity and oil absorption of the paper is the most effective way to reduce the show-through of newspaper printing paper. In order to increase the opacity, it is effective to mix titanium dioxide having a large specific scattering coefficient. However, titanium dioxide is expensive and it is not economical to mix a large amount. As a method for suppressing the slip-through of acidic newspaper printing paper, it is effective to blend a filler having a high oil absorption, and white carbon has been widely used.
最近の新聞印刷用紙に関する新技術として、新聞印刷用紙の中性抄造がある。酸性新聞印刷用紙と同等以上の強度、不透明度、樹脂歩留、耐オフセット印刷版摩耗性を有する中性新聞印刷用紙の提供を課題として、5〜15重量%の炭酸カルシウムを填料として含有する中性新聞印刷用紙とその製造方法が開示されている（特許文献１参照）。 As a new technology related to recent newspaper printing paper, there is neutral papermaking of newspaper printing paper. In order to provide neutral newspaper printing paper with strength, opacity, resin yield, and anti-offset printing plate wear resistance equal to or higher than that of acid newspaper printing paper, it contains 5-15% calcium carbonate as filler. Sexual newspaper printing paper and its manufacturing method are disclosed (refer patent document 1).
また、中性新聞印刷用紙における填料の配合に関しては、次のような技術がある。例えば、吸油量が250〜350ml/100gであり、全細孔容積が4.0〜6.0cc/gで、平均細孔半径が200〜400オングストロームの範囲であり、平均粒子径がレーザー法で3.0〜15μｍである粒子特性を満足する水和珪酸と、軽質炭酸カルシウムまたは重質炭酸カルシウムとを填料とした紙(新聞印刷用紙を含む)の製造方法が記載されている(特許文献２参照)。また、填料がホワイトカーボンと炭酸カルシウムとを主体とし、これらをJIS P 8128に規定の550℃の灰分の原子吸光分析におけるSiO2とCaOとの割合が9：1〜5：5となるように含有する新聞印刷用紙が開示されている(特許文献３参照)が、不透明度や印刷裏抜けが不十分である。また、二酸化チタン−炭酸カルシウム複合体を含有する坪量45g/m2以下のオフセット印刷用中性新聞用紙が開示されている(特許文献４参照)が、高価な二酸化チタンを使用するという問題がある。 There are the following techniques for blending fillers in neutral newspaper printing paper. For example, the oil absorption is 250 to 350 ml / 100 g, the total pore volume is 4.0 to 6.0 cc / g, the average pore radius is in the range of 200 to 400 angstroms, and the average particle size is 3.0 to 15 μm by the laser method. A method for producing paper (including newspaper printing paper) using hydrated silicic acid satisfying the above particle characteristics and light calcium carbonate or heavy calcium carbonate as a filler is described (see Patent Document 2). Also, the filler is mainly white carbon and calcium carbonate, and these are included so that the ratio of SiO2 and CaO in the atomic absorption analysis of ash at 550 ° C specified in JIS P 8128 is 9: 1 to 5: 5 Newspaper printing paper is disclosed (see Patent Document 3), but the opacity and print back-through are insufficient. Further, a neutral newsprint for offset printing having a basis weight of 45 g / m 2 or less containing a titanium dioxide-calcium carbonate composite is disclosed (see Patent Document 4), but there is a problem that expensive titanium dioxide is used. .
本発明の課題は、白色度が高く、不透明性に優れ、かつ印刷時の裏抜け改善効果が高い中性新聞印刷用紙を提供することある。 An object of the present invention is to provide a neutral newspaper printing paper having high whiteness, excellent opacity, and a high effect of improving back-through during printing.
軽質炭酸カルシウムとシリカとの固形分重量比が、軽質炭酸カルシウム/シリカ＝30/70〜70/30であり、紡錘状の一次粒子が凝集して二次粒子を形成しているロゼッタ型カルサイト系であ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−シリカ複合物を、紙中填料率として１〜25固形分重量%の範囲で含有させた紙料を抄紙し、中性新聞印刷用紙を得る。
Rosetta-type calcite in which the solid weight ratio of light calcium carbonate and silica is light calcium carbonate / silica = 30/70 to 70/30, and spindle-shaped primary particles aggregate to form secondary particles Paper made from a light calcium carbonate-silica composite with light calcium carbonate-silica composite coated with silica in a range of 1 to 25% solids by weight as a filler content in paper. Get printing paper.
軽質炭酸カルシウムとシリカとの固形分重量比が、軽質炭酸カルシウム/シリカ＝30/70〜70/30である、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−シリカ複合物を、填料として含有させた紙料を抄紙することにより、白色度が高く、不透明性に優れ、かつ印刷時の裏抜け改善効果が高い中性新聞印刷用紙を製造することができる。 A light calcium carbonate-silica composite in which the surface of light calcium carbonate particles is coated with silica, and the solid weight ratio of light calcium carbonate to silica is light calcium carbonate / silica = 30/70 to 70/30. As a result, the neutral newspaper printing paper having high whiteness, excellent opacity, and high effect of improving the through-through at the time of printing can be produced.
本発明の中性新聞印刷用紙の原料パルプは、新聞印刷用紙に通常使用されているパルプであれば良く、特に限定はない。例えば、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)等の機械パルプや、脱墨パルプ(DIP)等の古紙パルプから、１種あるいは数種を適宜選択して使用することができる。また、必要によっては、クラフトパルプ(KP)等の化学パルプ(CP)も使用することができる。 The raw material pulp of the neutral newsprint paper of the present invention is not particularly limited as long as it is a pulp normally used for newsprint paper. For example, Stone Grand Pulp (SGP), Pressurized Stone Grand Pulp (PGP), Refiner Grand Pulp (RGP), Chemi Grand Pulp (CGP), Thermo Grand Pulp (TGP), Ground Pulp (GP), Thermomechanical Pulp (TMP) ), Chemi-thermo-mechanical pulp (CTMP), refiner mechanical pulp (RMP) and other mechanical pulp, and used paper pulp such as deinked pulp (DIP) can be used by appropriately selecting one or several kinds. If necessary, chemical pulp (CP) such as kraft pulp (KP) can also be used.
本発明の中性新聞印刷用紙では、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、吸油量が大きく、不透明度向上効果、裏抜け改善効果に優れるという特性を有する粒子である。本発明の中性新聞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い。紙中填料率が1固形分重量%未満では、印刷用紙の不透明度向上効果と印刷裏抜け改善効果が不十分である。
In the neutral newspaper printing paper of the present invention, light calcium carbonate-silica composite particles produced by a method described later and having the surface of light calcium carbonate particles coated with silica are used for the entire amount or a part of the filler. The light calcium carbonate-silica composite particles are particles having a large oil absorption amount and excellent properties in improving opacity and through-holes. In neutral newsprint paper of the invention, said light calcium carbonate - silica composite particles, preferred that are contained in a proportion of 1 to 25% solids by weight as the paper filler content arbitrary. When the filler content in the paper is less than 1% by weight, the effect of improving the opacity of printing paper and the effect of improving print back-through are insufficient.
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、抄紙pH=6〜9の中性抄紙で紙を抄造することが好ましい。pHが9を超えるアルカリ条件では、原料パルプの白色度が低下し、これにより、中性新聞印刷用紙の白色度が低下してしまうという問題がある。 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 with neutral paper making pH = 6-9. Under alkaline conditions where the pH exceeds 9, there is a problem that the whiteness of the raw material pulp is lowered, and thus the whiteness of the neutral newsprint paper is lowered.
また、本発明の中性新聞印刷用紙では、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高不透明性など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両填料の紙中填料率の合計は、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。 Further, in the neutral newspaper printing paper of the present invention, in addition to the light calcium carbonate-silica composite particles as fillers, other inorganic and organic fillers may be used within a range not damaging the high opacity which is the effect of the present invention. It can also be used in combination. As for the type, any filler that is usually used in neutral papermaking can be used without any limitation. For example, inorganic 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 total filler content in the paper of both fillers is preferably more than 1.0 solids weight% and less than 40 solids weight%, more than 3 solids weight% More preferably, the solid content is 40% by weight or less, more preferably 5% by solid content and 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.
パルプ原料と、軽質炭酸カルシウム−シリカ複合物および／または他の填料とを混合した後、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。中性抄紙における公知の内添中性サイズ剤としては、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、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 pulp raw material with the light calcium carbonate-silica composite and / or other fillers, if necessary, a paper strength improver, a yield improver, a wet strength enhancer, a dye, a fluorescent whitening agent, You may add auxiliary chemicals for papermaking, such as a foaming agent, a pitch control agent, and a slime control agent. Further, a size imparting agent is also used for improving the offset printability. Known neutral sizing agents for neutral papermaking include alkyl ketene dimer (AKD) sizing agents, alkenyl succinic anhydride (ASA) sizing agents, and neutral rosin sizing agents. The addition amount of the sizing agent 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.
本発明の中性新聞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 neutral newsprint 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.
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、不透明度向上効果と裏抜け改善効果に優れる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, a light calcium carbonate-silica composite excellent in opacity improvement effect and back-through improvement effect can be obtained particularly when rosetta-type calcite light calcium carbonate is used. 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 CaCO3 / SiO2 = 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 the water and the light calcium carbonate particles are not extremely agglomerated, especially time and agitation. There is no limit on the strength of the.
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 precipitated 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 if 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 silicic acid loss 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、30μｍ以下が良く、20μｍ以下が好ましく、10μｍ以下が更に好ましい。 The average particle size of the light calcium carbonate-silicic acid composite after removing coarse particles or after coarse particle removal and further subjected to strong stirring and pulverization is preferably 30 μm or less, preferably 20 μm or less, and more preferably 10 μm or less. preferable.
以下に実施例及び比較例を示し、本発明をより具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、例中の%は全て固形分重量%を示す。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples. In addition, all% in an example shows solid content weight%.
本発明で使用する軽質炭酸カルシウムーシリカ複合物と、比較例で使用する填料の各特性値と、抄紙方法、及び填料配合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)抄紙方法：熊谷理機工業株式会社製の配向性抄紙機により、抄紙原料として填料配合無しの新聞離解原料(NBKP/MP/DIP＝20/50/30、持込み灰分４%)を用い、原料パルプに填料を添加し、坪量40g/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、各添加率の紙サンプルを作製した。
(4)紙の白色度、不透明度、裏抜け値の測定：JIS P8148、JIS P8149に準じ、色差計(村上色彩研究所製)を用い、この紙サンプルの白色度、不透明度を測定した。
(5)裏抜け値：紙サンプルに、ＲＩ印刷機を用いて、キーレスオフセット用新聞インキ(東洋インキ株式会社製、New King VANTEAN墨)を使用して片面印刷を施した。20℃、65%RHの雰囲気に24時間放置後、マクベス反射濃度計で、印刷裏面の反射率を測定し、次式により裏抜け値(印刷後不透明度)を算出した。
裏抜け値(%)＝(印刷裏面の反射率/未印刷の裏面の反射率)×100
The light calcium carbonate-silica composite used in the present invention, the characteristic values of the filler used in the comparative examples, the paper making method, and the method for measuring the paper quality of the filler-mixed paper 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) Papermaking method: Using an orientation paper machine manufactured by Kumagai Riki Kogyo Co., Ltd., using newspaper disaggregation raw material (NBKP / MP / DIP = 20/50/30, brought-in ash content 4%) as a papermaking raw material. Then, a filler was added to the raw material pulp, the paper was made so as to have a basis weight of 40 g / m 2 , dehydrated by a press, and then dried by a blow dryer to prepare paper samples of each addition rate.
(4) Measurement of whiteness, opacity, and see-through value of paper: According to JIS P8148 and JIS P8149, a color difference meter (manufactured by Murakami Color Research Laboratory) was used to measure the whiteness and opacity of this paper sample.
(5) Back-through value: A single-sided printing was performed on a paper sample using a keyless offset newspaper ink (New King VANTEAN ink, manufactured by Toyo Ink Co., Ltd.) using an RI printer. After being left in an atmosphere of 20 ° C. and 65% RH for 24 hours, the reflectance of the printed back surface was measured with a Macbeth reflection densitometer, and the back-through value (opacity after printing) was calculated by the following formula.
Strike through value (%) = (Reflectance of printed back side / Reflectance of unprinted back side) × 100
実施例で填料として添加した軽質炭酸カルシウム−シリカ複合物の製造方法を次に示す。
(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。
A method for producing a light calcium carbonate-silica composite added as a filler in the examples is shown below.
(1) (Light calcium carbonate-silica composite) A
In a reaction vessel (12 L), 262 g of commercially available rosetta-type light calcium carbonate (trade name: Albuquer 5970, manufactured by Speciaty Minerals Inc.) was dispersed in water, where the SiO 2 concentration was 18.0 wt / wt% and the Na 2 O concentration was 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、上記の方法で紙中填料率7%の紙を作成し、白色度、不透明度、裏抜け値を表１に示した。
[Example 1]
(Light calcium carbonate-silica composite) A was used as a filler, and a paper with a filler content of 7% was prepared by the above-described method. The whiteness, opacity, and strikethrough values are shown in Table 1.
［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、上記の方法で紙中填料率7%の紙を作成し、白色度、不透明度、裏抜け値を表１に示した。
[Example 2]
(Light calcium carbonate-silica composite) B was used as a filler, and a paper with a filler content of 7% was prepared by the above-described method. Table 1 shows the whiteness, opacity, and strikethrough value.
［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、上記の方法で紙中填料率7%の紙を作成し、白色度、不透明度、裏抜け値を表１に示した。
[Example 3]
Using (light calcium carbonate-silica composite) C as a filler, paper with a filler content of 7% was prepared by the above method, and the whiteness, opacity, and back-through values are shown in Table 1.
［実施例４］
填料として、(軽質炭酸カルシウム−シリカ複合物)Ｂを紙中填料率1%、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)を紙中填料率7%になるようにした以外は、実施例１と同様にして紙を作成し、白色度、不透明度、裏抜け値を表１に示した。
[Example 4]
As a filler, (light calcium carbonate-silica composite) B is 1% in paper, and commercially available rosetta-type light calcium carbonate (trade name: Albuquer 5970, manufactured by Speciaty Minerals Inc.) is 7% in paper. Except for the above, paper was prepared in the same manner as in Example 1, and the whiteness, opacity, and strikethrough values are shown in Table 1.
［比較例１］
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、填料として、そのまま用いた以外は、実施例１と同様にして紙中填料率7%の紙を作成し、白色度、不透明度、裏抜け値を表１に示した。
[Comparative Example 1]
A paper with a 7% filler content in the same manner as in Example 1 except that commercially available rosetta-type light calcium carbonate (trade name: Albuquer 5970, Speciaty Minerals Inc.) was not combined and used as a filler. Table 1 shows the whiteness, opacity, and strikethrough values.
［比較例２］
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、填料として、そのまま用いた以外は、実施例１と同様にして紙中填料率7%の紙を作成し、白色度、不透明度、裏抜け値を表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]
Commercially available spindle-shaped light calcium carbonate (trade name: TP121, manufactured by Okutama Kogyo Co., Ltd.) was used in the same manner as in Example 1 except that it was used as it was as a filler. Table 1 shows the whiteness, opacity, and strikethrough values. 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］
市販角状軽質炭酸カルシウムを複合化せず、填料として、そのまま用いた以外は、実施例１と同様にして紙中填料率7%の紙を作成し、白色度、不透明度、裏抜け値を表１に示した。なお、この軽質炭酸カルシウムは角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 3]
A paper with a filler content of 7% was prepared in the same manner as in Example 1 except that the commercial square light calcium carbonate was not used as a filler and was used as it was, and the whiteness, opacity, and strikethrough values were determined. It is shown in Table 1. The light calcium carbonate is light calcium carbonate composed of angular primary particles, and the primary particles are not aggregated to form secondary particles.
［比較例４］
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)の紙中填料率が3.5%、市販ホワイトカーボン(商品名：TIXOLEX17、Rhdia Silica Korea社製)の紙中填料率が3.5%となるように紙を作成し、白色度、不透明度、裏抜け値を表１に示した。
[Comparative Example 4]
Commercial rosette-type light calcium carbonate (trade name: Albuquer 5970, Speciaty Minerals Inc.) has a paper filling rate of 3.5%, and commercial white carbon (trade name: TIXOLEX17, Rhdia Silica Korea) has a paper filling rate. Paper was prepared so as to be 3.5%, and the whiteness, opacity, and strikethrough values are shown in Table 1.
［比較例５］
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)の紙中填料率が4.9%、市販ホワイトカーボン(商品名：TIXOLEX17、Rhdia Silica Korea社製)の紙中填料率が2.1%となるように紙を作成し、白色度、不透明度、裏抜け値を表１に示した。
[Comparative Example 5]
Commercial rosette-type light calcium carbonate (trade name: Albuquer 5970, Speciaty Minerals Inc.) has a paper filling rate of 4.9%, and commercial white carbon (trade name: TIXOLEX17, Rhdia Silica Korea) has a paper filling rate. Paper was prepared so as to be 2.1%, and the whiteness, opacity, and strikethrough values are shown in Table 1.
［比較例６］
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)の紙中填料率が7.0%、市販ホワイトカーボン(商品名：TIXOLEX17、Rhdia Silica Korea社製)の紙中填料率が1.0%となるように紙を作成し、白色度、不透明度、裏抜け値を表１に示した。
[Comparative Example 6]
Commercial rosette-type light calcium carbonate (trade name: Albuquer 5970, Speciaty Minerals Inc.) has a paper filling rate of 7.0%, and commercial white carbon (trade name: TIXOLEX17, Rhdia Silica Korea) has a paper filling rate. Paper was prepared so as to be 1.0%, and Table 1 shows the whiteness, opacity, and strikethrough value.
［比較例７］
市販ホワイトカーボン(商品名：TIXOLEX17、Rhdia Silica Korea社製)の紙中填料率が2.0%となるように紙を作成し、白色度、不透明度、裏抜け値を表１に示した。
[Comparative Example 7]
Paper was prepared so that the filler content in the paper of commercial white carbon (trade name: TIXOLEX17, manufactured by Rhdia Silica Korea) was 2.0%, and the whiteness, opacity, and back-through values are shown in Table 1.
軽質炭酸カルシウム−シリカ複合物を填料として使用した実施例１、２、３は、各種軽質炭酸カルシウムを使用した比較例１〜３よりも、また、軽質炭酸カルシウムとホワイトカーボンを填料として併用した比較例４、５よりも、白色度、不透明度、裏抜け値のすべてにおいて優れていることがわかる。また、軽質炭酸カルシウム填料に、軽質炭酸カルシウム−シリカ複合物を少量併用した実施例４は、軽質炭酸カルシウム填料にホワイトカーボンを少量併用した比較例６よりも、高い白色度、不透明度、裏抜け値を得ることができる。比較例７はホワイトカーボン単独であるが、ホワイトカーボンは高配合すると強度低下や粉落ちの問題が発生するため、通常、紙中填料率を2%以上とすることは難しい。実施例１〜４は、ホワイトカーボンとしては高配合である比較例７と比べても、白色度、不透明度、裏抜け値のすべてにおいて優れている。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使用することによって、高白色度で、高不透明度、かつ印刷時の裏抜けが少ない優れた中性新聞印刷用紙を得ることができる。
Examples 1, 2, and 3 using a light calcium carbonate-silica composite as a filler are more than Comparative Examples 1 to 3 using various light calcium carbonates, and comparison using light calcium carbonate and white carbon as fillers. It turns out that it is excellent in all of whiteness, opacity, and strike-through value than Examples 4 and 5. In addition, Example 4 in which a small amount of light calcium carbonate-silica composite is used in combination with a light calcium carbonate filler is higher in whiteness, opacity, and strikethrough than Comparative Example 6 in which a small amount of white carbon is used in combination with a light calcium carbonate filler. A value can be obtained. In Comparative Example 7, white carbon is used alone. However, when white carbon is blended in a high amount, problems such as a decrease in strength and powder falling occur, so it is usually difficult to make the filler content in paper 2% or more. Examples 1-4 are excellent in all of whiteness, opacity, and strike-through value as compared with Comparative Example 7, which is a high blend of white carbon. As described above, by using a light calcium carbonate-silica composite as a filler, it is possible to obtain an excellent neutral newspaper printing paper having high whiteness, high opacity, and little show-through during printing.
Claims (1)
Rosetta-type calcite in which the solid weight ratio of light calcium carbonate and silica is light calcium carbonate / silica = 30/70 to 70/30, and spindle-shaped primary particles aggregate to form secondary particles A light calcium carbonate-silica composite having an average particle diameter of 10 μm or less , coated with silica on the surface of light calcium carbonate particles as a system, is contained in a range of 1 to 25% by weight as a filler content in paper. Neutral newspaper printing paper.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004100698A JP4233478B2 (en) | 2004-03-30 | 2004-03-30 | Neutral newspaper printing paper |
| PCT/JP2005/004574 WO2005098132A1 (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 |
| CN2005800090505A CN1954119B (en) | 2004-03-30 | 2005-03-15 | Low density printing paper |
| US10/599,135 US7611606B2 (en) | 2004-03-30 | 2005-03-15 | Low-density neutral paper |
| KR1020067017859A KR20060134095A (en) | 2004-03-30 | 2005-03-15 | Low-density neutral paper |
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| JP2004100698A JP4233478B2 (en) | 2004-03-30 | 2004-03-30 | Neutral newspaper printing paper |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006063501A (en) * | 2004-08-30 | 2006-03-09 | Daio Paper Corp | Paper for newspaper |
| JP4796409B2 (en) * | 2006-03-07 | 2011-10-19 | 日本製紙株式会社 | Neutral newsprint for offset printing |
| JP4725393B2 (en) * | 2006-03-31 | 2011-07-13 | 王子製紙株式会社 | Offset newspaper printing paper |
| JP2007270377A (en) * | 2006-03-31 | 2007-10-18 | Nippon Paper Industries Co Ltd | Lightweight coated paper for printing |
| JP4742988B2 (en) * | 2006-05-25 | 2011-08-10 | 王子製紙株式会社 | Newspaper for cold offset printing |
| JP5047667B2 (en) * | 2007-03-30 | 2012-10-10 | 日本製紙株式会社 | Offset printing paper |
| JP4958677B2 (en) * | 2007-08-03 | 2012-06-20 | 大王製紙株式会社 | Newspaper and production method thereof |
| JP5230135B2 (en) * | 2007-08-06 | 2013-07-10 | 株式会社トクヤマ | Calcium carbonate-silica composite material and method for producing the same |
| JP5265900B2 (en) * | 2007-09-28 | 2013-08-14 | 日本製紙株式会社 | Offset printing paper |
| JP5268611B2 (en) * | 2008-12-10 | 2013-08-21 | 株式会社トクヤマ | Method for producing calcium carbonate-silica composite |
| JP5762050B2 (en) * | 2011-02-28 | 2015-08-12 | 大王製紙株式会社 | Printing paper |
| JP7076864B1 (en) * | 2021-10-27 | 2022-05-30 | 株式会社白石中央研究所 | Calcium carbonate manufacturing method |
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