JPH0881896A - Production of powder-containing paper - Google Patents
Production of powder-containing paperInfo
- Publication number
- JPH0881896A JPH0881896A JP6240588A JP24058894A JPH0881896A JP H0881896 A JPH0881896 A JP H0881896A JP 6240588 A JP6240588 A JP 6240588A JP 24058894 A JP24058894 A JP 24058894A JP H0881896 A JPH0881896 A JP H0881896A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- pulp
- fibrillated cellulose
- paper
- slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Paper (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、従来法に比較して紙力
低下が少なく、粉体の歩留りを向上させ、抄紙時の濾水
性に問題なく、安定した状態で抄造できる粉体含有紙の
製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a powder-containing paper which has less deterioration in paper strength as compared with the conventional method, improves the yield of powder, has no problem in drainage during papermaking, and can be produced in a stable state. The present invention relates to a manufacturing method of.
【０００２】[0002]
【従来の技術】印刷適性、平滑度の向上や不透明度、白
色度などの光学特性の改良のために、紙にカオリン、炭
酸カルシウム、二酸化チタン、クレー、タルクなどの粉
体を充填することは広く行われている。粉体を効率よく
紙中に歩留まらせる方法の１つとして、紙料調成の際に
硫酸バンド（硫酸アルミニウム）等の多価金属イオンや
ポリアクリルアマイド、カチオン澱粉、ジアルデヒド澱
粉、ポリアミンポリアミドエピクロルヒドリンなどの有
機高分子化合物等の各種薬品を添加することが行われて
いる。2. Description of the Related Art To improve printability, smoothness, and optical properties such as opacity and whiteness, it is not possible to fill paper with powder such as kaolin, calcium carbonate, titanium dioxide, clay and talc. It is widely practiced. As one of the methods for efficiently retaining the powder in the paper, polyvalent metal ions such as sulfuric acid band (aluminum sulfate), polyacrylic amide, cationic starch, dialdehyde starch, polyamine polyamide during preparation of the stock material. Various chemicals such as organic polymer compounds such as epichlorohydrin are added.
【０００３】一方、最近では抄紙機の高速大型化と中性
抄紙の進展に伴って、粉体の歩留まり向上の要求がます
ます高まり、種々のデュアルシステムが提案されてい
る。デュアルシステムは２種類以上の凝集剤を組み合わ
せて、セルロース繊維と粉体の強固なフロックを形成さ
せて粉体歩留まりを向上させる抄造方法である。例えば
特開昭５７−５１９００号、特開昭６２−１５３９１号
などに提案されているようなカチオン性澱粉とコロイド
状ケイ酸の組み合わせ、グアーガムとコロイド状ケイ酸
の組み合わせ、カチオン性ポリアクリルアミドとコロイ
ド状ケイ酸の組み合わせ、特開昭６２−１９１５９８号
に提案されているようなカチオン性ポリアクリルアミド
と変性ベントナイトの組み合わせ、両性ポリアクリルア
ミドとアルミ化合物の組み合わせ、ポリエチレンオキサ
イドと特殊フェノール樹脂の組み合わせ、ポリエチレン
オキサイドとベントナイトの組み合わせ、アニオン性ポ
リアクリルアミドの組み合わせ、ベントナイトとポリエ
チレンイミンとポリアクリルアミドの組み合わせ等が知
られている。On the other hand, recently, with the increase in the size of paper machines at high speed and the progress of neutral papermaking, the demand for improving the yield of powder has been increasing, and various dual systems have been proposed. The dual system is a papermaking method in which two or more types of flocculants are combined to form strong flocs of cellulose fibers and powders to improve the powder yield. For example, the combination of cationic starch and colloidal silicic acid, the combination of guar gum and colloidal silicic acid, the combination of cationic polyacrylamide and colloid as proposed in JP-A-57-51900 and JP-A-62-15391. Combination of crystalline silicic acid, combination of cationic polyacrylamide and modified bentonite as proposed in JP-A-62-191598, combination of amphoteric polyacrylamide and aluminum compound, combination of polyethylene oxide and special phenol resin, polyethylene oxide And a bentonite, an anionic polyacrylamide, a bentonite, a polyethyleneimine, and a polyacrylamide are known.
【０００４】薬品を添加する方法の他に、粉体の歩留り
を向上させる方法として、抄造する製紙用パルプの叩解
を進め、繊維をフィブリル化させる方法がある。これ
は、パルプ繊維の比表面積を増やし、粉体との接触面積
を多くし、粉体歩留まりを向上させる方法である。ま
た、抄紙時にフィブリルが形成するネットワークによっ
ても、粉体が捕捉される。叩解を進める方法の中で、最
近、叩解を極端に進めた微細フィブリル化セルロースの
持つ特性が注目されている。微細フィブリル化セルロー
スは製紙用パルプに機械的せん断力を与え、繊維幅１μ
ｍ以下、繊維長数十〜数百μｍにまで極度に叩解したも
のであり、その比表面積は未叩解パルプ繊維の数百倍に
もなっている。この微細フィブリル化セルロースを製紙
用パルプに数％添加することにより、粉体含有紙を抄紙
する場合に歩留まり向上剤として優れた効果を示した例
が、特開昭６０−８１３９８、特開昭６０−８１３９
９、特開昭６０−８８１９９等に提案されている。In addition to the method of adding a chemical, there is a method of improving the yield of powder by smashing the pulp for papermaking to make the fibers into fibrils. This is a method of increasing the specific surface area of pulp fibers, increasing the contact area with the powder, and improving the powder yield. The powder is also captured by the network formed by fibrils during papermaking. Among the methods of promoting beating, attention has recently been paid to the properties of finely fibrillated cellulose that has been extremely advanced. The fine fibrillated cellulose gives mechanical pulp shear force to the pulp for paper making, and the fiber width is 1 μm.
It is an extremely beaten fiber having a fiber length of m or less and a fiber length of several tens to several hundreds μm, and its specific surface area is several hundred times that of an unbeaten pulp fiber. Japanese Patent Application Laid-Open No. 60-81398 and Japanese Patent Application Laid-Open No. 60-81398 show examples in which the fine fibrillated cellulose is added to a pulp for papermaking in an amount of several% to exhibit an excellent effect as a yield improving agent in the case of making powder-containing paper. -8139
9 and JP-A-60-88199.
【０００５】[0005]
【発明が解決しようとする課題】上記した方法が粉体歩
留まりを向上させる方法として従来行われてきたが、数
々の問題点もでている。種々の薬品を添加する方法で
は、使用量を多くすると分散系全体の電荷平衡が破れ、
過度の凝集を引き起こすことがある。強い凝集によって
粉体歩留まり（ワンパスリテンション）は向上するもの
の、地合が悪く、あるいは紙質が堅くなってしまい、紙
本来の風合いが損なわれる問題点がある。薬品によって
粉体の歩留りを向上させても、粉体の充填割合が増加す
るに従って、添加された粉体が繊維間結合の形成を阻害
するため、強度、特に引張り強さが著しく減少するとい
う問題点もある。The above-mentioned method has hitherto been carried out as a method for improving the powder yield, but there are also a number of problems. In the method of adding various chemicals, if the amount used is increased, the charge balance of the entire dispersion system is broken,
May cause excessive aggregation. Although the powder yield (one-pass retention) is improved by the strong aggregation, there is a problem that the texture is poor or the paper quality is stiff, and the original texture of the paper is impaired. Even if the yield of powder is improved by chemicals, as the filling ratio of powder increases, the added powder inhibits the formation of interfiber bonds, resulting in a significant decrease in strength, especially tensile strength. There are also points.
【０００６】また、微細フィブリル化セルロースを添加
する方法では、微細フィブリル化セルロースの添加量が
増加するに従い濾水性が悪くなり、抄紙機のワイヤーパ
ートでの水切れが悪化し、紙切れなどの問題を起こすこ
とが判っている。本発明は、従来法と比較して、紙力低
下が少なく、紙の地合い等の風合いを乱すことなく、粉
体の歩留まりを向上させ、抄紙時の濾水性が良く、安定
して抄造できる粉体含有紙の製造方法を新たに提供する
ものである。In addition, in the method of adding fine fibrillated cellulose, the drainage becomes worse as the amount of fine fibrillated cellulose added increases, and water drainage in the wire part of the paper machine worsens, causing problems such as paper breakage. I know that. Compared with the conventional method, the present invention has less paper strength reduction, does not disturb the texture of the paper, etc., improves the yield of powder, has good drainage at the time of papermaking, and can be stably produced. The present invention newly provides a method for producing body-containing paper.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、微細フィ
ブリル化セルロースの粉体歩留り向上効果に注目し、鋭
意検討していたところ、粉体とパルプを混合したスラリ
ーに機械的せん断力を与えることによって得られる粉体
と微細フィブリル化セルロースの複合体（以下本発明で
は、粉体複合化微細フィブリル化セルロースと言う）を
製紙用パルプスラリーに添加することにより、従来法と
比較して、地合い等の風合いを乱すことなく粉体の歩留
まりを向上させ、紙力の低下が少なく、また、微細フィ
ブリル化セルロースを抄紙工程で利用する際に最も大き
な問題となる、濾水性の悪化を防ぐという効果を見いだ
し本発明を完成させた。即ち本発明の要旨とするところ
は、粉体とパルプを混合したスラリーに強力な機械的せ
ん断力を与えることによって得られる粉体と微細フィブ
リル化セルロースの複合体（粉体複合化微細フィブリル
化セルロース）を製紙用パルプスラリーに添加した後、
抄紙することを特徴とする粉体含有紙の製造方法であ
る。Means for Solving the Problems The present inventors have paid attention to the powder yield improvement effect of finely fibrillated cellulose and have made diligent studies. As a result, the mechanical shearing force was applied to a slurry in which powder and pulp are mixed. By adding a composite of powder and fine fibrillated cellulose obtained by giving (hereinafter referred to as powder complex fine fibrillated cellulose in the present invention) to a pulp pulp for papermaking, as compared with the conventional method, To improve the yield of powder without disturbing the texture such as texture, to reduce the decrease in paper strength, and to prevent deterioration of drainage, which is the biggest problem when using fine fibrillated cellulose in the papermaking process The effect was found and the present invention was completed. That is, the gist of the present invention is that a composite of powder and fine fibrillated cellulose obtained by applying a strong mechanical shearing force to a slurry in which powder and pulp are mixed (powder-composited fine fibrillated cellulose). ) To the pulp pulp for papermaking,
It is a method for producing powder-containing paper, which is characterized by making paper.
【０００８】本発明者らは、粉体とパルプを混合したス
ラリーに機械的せん断力を与えることによって得られる
粉体複合化微細フィブリル化セルロースが、上記のよう
な効果を示すのは、顕微鏡観察によって以下に述べる理
由によるものと推定した。粉体とパルプスラリーの混合
物に強力な機械的せん断力を与えることで、パルプを構
成するセルロース繊維が微細化され、微細フィブリル化
セルロースを生成する。この生成過程で、粉体が微細フ
ィブリル化セルロースのネットワークに包み込まれ、あ
るいは吸着され、微細フィブリル化セルロースが粉体を
保持しているような房状の凝集体である粉体複合化微細
フィブリル化セルロースを形成する。微細化する装置の
種類や、粉体の組成によっても異なるが、粉体自身もこ
の過程で微細化される場合がある。The present inventors have found that the powder-composite fine fibrillated cellulose obtained by applying mechanical shearing force to a slurry in which powder and pulp are mixed exhibits the above-mentioned effects by microscopic observation. It is assumed that the reason is as follows. By imparting a strong mechanical shearing force to the mixture of powder and pulp slurry, the cellulose fibers constituting the pulp are micronized, and fine fibrillated cellulose is produced. During this generation process, the powder is wrapped in or adsorbed in the network of fine fibrillated cellulose, and the fine fibrillated cellulose is a tuft-like aggregate that holds the powder. Form cellulose. The powder itself may be miniaturized in this process, although it depends on the type of device to be miniaturized and the composition of the powder.
【０００９】粉体複合化微細フィブリル化セルロースは
粉体の粒径よりも大きく、また、上記したように粉体が
微細フィブリル化セルロースに包み込まれている房状の
凝集体の形状をしているので、これをパルプスラリーに
添加した場合は、パルプ繊維との結合力も大きく、紙中
への歩留まりが高くなる。また、粉体複合化微細フィブ
リル化セルロースは、パルプスラリーに添加してもパル
プの凝集は起こさないので、地合の悪化を起こさずに抄
紙できる利点もある。粉体と微細フィブリル化セルロー
スが凝集した形態は、微細フィブリル化セルロースを単
独で添加したときに起こる濾水性の悪化を防ぎ、また、
粉体を添加したときに起こるパルプ繊維間結合の阻害を
防止している。また、微細化されたパルプ繊維は比表面
積が増加し、紙力の向上につながることが知られてい
て、粉体の含有量が増加しても、紙力低下を起こさず逆
に強固になる。The powder-composited fine fibrillated cellulose is larger than the particle size of the powder, and as described above, the powder is in the form of tuft-like aggregates encased in the fine fibrillated cellulose. Therefore, when this is added to the pulp slurry, the binding force with the pulp fiber is large and the yield in the paper is high. Further, the powder-composited finely fibrillated cellulose does not cause aggregation of the pulp even when it is added to the pulp slurry, so that there is an advantage that the paper can be made without causing deterioration of the formation. The morphology in which the powder and the fine fibrillated cellulose are aggregated prevents the deterioration of drainage that occurs when the fine fibrillated cellulose is added alone,
It prevents the inhibition of pulp fiber-fiber bonding that occurs when powder is added. Further, it is known that the refined pulp fiber has an increased specific surface area, which leads to an improvement in paper strength. Even if the content of the powder is increased, the paper strength is not lowered and the strength is increased. .
【００１０】粉体複合化微細フィブリル化セルロースを
得るための機械的処理の方法としては、微細フィブリル
化セルロースを製造できるあらゆる装置を利用できる。
例えば、高圧ホモジナイザー、媒体攪拌ミル、メディア
撹拌式湿式粉砕装置、振動ミル、ボールミル、遊星ミ
ル、砥粒板擦り合わせ装置等が使用できるが、その中で
も砥粒板擦り合わせ装置を用いて粉体複合化微細フィブ
リル化セルロースを製造する方法が効率よく、また、そ
の効果も大きいことが判った。As a mechanical treatment method for obtaining powder-composited fine fibrillated cellulose, any apparatus capable of producing fine fibrillated cellulose can be used.
For example, a high-pressure homogenizer, a medium agitating mill, a media agitating wet pulverizing device, a vibration mill, a ball mill, a planetary mill, an abrasive grain plate rubbing device, and the like can be used. Among them, an abrasive grain plate rubbing device is used to form a powder composite. It was found that the method for producing pulverized fine fibrillated cellulose is efficient and has a great effect.
【００１１】砥粒板の擦り合わせによるパルプの微細化
と粉体との複合化が効率的であるのは、砥粒板を構成す
る細かい砥粒によって、砥粒板擦り合わせ面にミクロな
突出部が形成され、非常に凹凸であることが大きく関係
してる。このような砥粒の突出部でパルプ繊維と粉体が
強力な機械的せん断力を受けることによって微細化と複
合化が進行するのであるが、突出部が砥粒板のいたると
ころで存在するため、パルプ繊維の細胞壁を１本１本の
フィブリルに効率的に分割し、さらに擦り合わされるこ
とによって粉体との複合化も効率的に進むと考えられ
る。また、粉体が存在することによってパルプのフィブ
リル化がさらに効率的に進むことを確認し、粉体を混合
しないときと比較して処理時間が大幅に短縮できるとい
う副次的な効果があることがわかった。The refinement of the pulp by the rubbing of the abrasive grain plate and the compounding with the powder are effective because the fine abrasive grains constituting the abrasive grain plate cause microscopic protrusions on the abrading surface of the abrasive grain plate. It is greatly related that the part is formed and is very uneven. In such protrusions of the abrasive grains pulp fiber and powder undergoes a strong mechanical shearing force, so that fineness and compounding progress, but since protrusions are present everywhere in the abrasive grain plate, It is considered that the cell wall of the pulp fiber is efficiently divided into individual fibrils and further rubbed together to effectively form a composite with the powder. Also, it was confirmed that the presence of the powder promotes the fibrillation of the pulp more efficiently, and that there is a secondary effect that the processing time can be significantly shortened compared to when the powder is not mixed. I understood.
【００１２】以上のように説明した砥粒板擦り合わせ装
置の一例を模式的に図１および図２に示す。図示の装置
は、上方の固定砥粒板１と下方の回転砥粒板２とを擦り
合わせ配置して構成されており、２枚の砥粒板の対向す
る内面はその中心に向けてテーパー状に切欠されて摩砕
室３となる空間を形成し、２枚の砥粒板の外周縁近傍の
フラット面４ａは互いに接触して擦り合わせ部４を形成
する。固定砥粒板１の中央開孔５の上方にはホッパー６
が設置され、ホッパー６低部は摩砕室３と連通してい
る。回転砥粒板２の中央開孔は封止板７で塞がれてお
り、回転砥粒板２はその下面から下方に伸びるシャフト
８を介して駆動モーター９により回転される。回転砥粒
板２の封止板７から上方に伸びる支持棒１０により、傘
状の整流板１１が摩砕室３のほぼ中央に配置されてい
る。図３は固定砥粒板１を内面側からみた図であり、摩
砕室３を形成するテーパー面には中央開孔５からほぼ放
射方向に送り溝１２が形成され、擦り合わせ部となる外
周縁近傍のフラット面４ａには送り溝１２は形成されて
いない。なお、送り溝の形態や本数は必ずしも図示のも
のに限定されない。An example of the abrasive plate rubbing apparatus described above is schematically shown in FIGS. 1 and 2. The illustrated apparatus is configured by arranging an upper fixed abrasive plate 1 and a lower rotating abrasive plate 2 by rubbing each other, and the inner surfaces of the two abrasive plates facing each other are tapered toward the center thereof. A space to be the grinding chamber 3 is formed by cutting out the flat surfaces 4a in the vicinity of the outer peripheral edges of the two abrasive grain plates to contact with each other to form the rubbing portion 4. A hopper 6 is provided above the central opening 5 of the fixed abrasive plate 1.
Is installed, and the lower part of the hopper 6 communicates with the grinding chamber 3. A central hole of the rotary abrasive grain plate 2 is closed by a sealing plate 7, and the rotary abrasive grain plate 2 is rotated by a drive motor 9 via a shaft 8 extending downward from the lower surface thereof. A support rod 10 extending upward from the sealing plate 7 of the rotary abrasive grain plate 2 arranges an umbrella-shaped flow straightening plate 11 substantially at the center of the grinding chamber 3. FIG. 3 is a view of the fixed abrasive plate 1 as seen from the inner surface side, and a feed groove 12 is formed in the taper surface forming the grinding chamber 3 from the central opening 5 in a substantially radial direction to serve as a friction portion. The feed groove 12 is not formed in the flat surface 4a near the periphery. The form and number of the feed grooves are not necessarily limited to those shown in the figure.
【００１３】この装置による微細化および複合化処理は
以下のようにして行われる。パルプと粉体を混合したス
ラリーをホッパー６へ供給すると（図２の矢印Ａ）、こ
の混合スラリーは流下して整流板１１により放射方向へ
分散されて摩砕室３内に均一に供給される。摩砕室３内
のパルプスラリーは、回転砥粒板２の遠心力と摩砕室３
内面の送り溝１２の作用によって砥粒板１、２の擦り合
わせ部４へ送られ、ここで上下の砥粒板の擦り合わせ作
用によってパルプの微細化と粉体との複合化がなされ
る。かくして生成された粉体複合化微細フィブリル化セ
ルロースのスラリーは砥粒板１、２の外周縁から遠心力
により流出する（図２の矢印Ｂ）。流出する粉体複合化
微細フィブリル化セルロースのスラリーはホッパー６に
再循環し、所望の粉体複合化微細フィブリル化セルロー
スが得られるまでこの処理を施すことができる。The miniaturization and composite processing by this apparatus is performed as follows. When the slurry in which the pulp and the powder are mixed is supplied to the hopper 6 (arrow A in FIG. 2), the mixed slurry flows down, is dispersed radially by the straightening vanes 11 and is uniformly supplied into the grinding chamber 3. . The pulp slurry in the grinding chamber 3 is caused by the centrifugal force of the rotary abrasive plate 2 and the grinding chamber 3
By the action of the feed groove 12 on the inner surface, it is sent to the rubbing portion 4 of the abrasive grain plates 1 and 2, where the rubbing action of the upper and lower abrasive grain plates makes the pulp fine and combines it with the powder. The slurry of the powder-composited fine fibrillated cellulose thus produced flows out from the outer peripheral edges of the abrasive grain plates 1 and 2 by a centrifugal force (arrow B in FIG. 2). The slurry of the powder-composited fine fibrillated cellulose that flows out is recycled to the hopper 6 and can be subjected to this treatment until the desired powder-composited fine fibrillated cellulose is obtained.
【００１４】砥粒板擦り合わせ装置の砥粒板は、研磨材
の粒子である砥粒を結合材で固めて形成したものであ
り、砥粒の材質としては従来から慣用されているもの、
例えばダイヤモンド、コランダム、エメリー等の天然品
や、合成ダイヤ、立方晶窒化ホウ素、アルミナ、炭化ケ
イ素、炭化ホウ素等の人造品が使用できる。砥粒の材質
として多孔性セラミックスを使用する場合には、微細化
されたセルロースがセラミックスの細孔内部に進入し、
細菌が発生する可能性があるため、セラミックスの細孔
を合成樹脂等で予め埋めておくことが望ましい。The abrasive grain plate of the abrasive grain plate rubbing apparatus is formed by solidifying abrasive grains, which are particles of the abrasive, with a binder, and the conventionally used material for the abrasive grains,
For example, natural products such as diamond, corundum, and emery, and artificial products such as synthetic diamond, cubic boron nitride, alumina, silicon carbide, and boron carbide can be used. When using porous ceramics as the material of the abrasive grains, the finely divided cellulose enters inside the pores of the ceramics,
Since bacteria may be generated, it is desirable to fill the pores of the ceramic with synthetic resin or the like in advance.
【００１５】特に本発明で用いる砥粒板擦り合わせ装置
の砥粒板としては、砥粒の粒度がＪＩＳ Ｐ ６００１
に規定されている粒度で２４番〜８０番のものを使用す
ることが必要である。本発明者らは、パルプの微細化効
果および粉体との複合化効果について粒度が５番〜２４
０番までの粒度を順次検討した結果、粒度が２４番より
粗い粒度の場合は、摩砕処理を長時間施しても所望の微
細化、複合化が進行せず、一方、粒度が８０番より細か
い粒度の場合には、砥粒板の擦り合わせ部で詰まりが発
生しやすくなり微細化および複合化されたスラリーの排
出が困難になることが判明した。従って砥粒の粒度は２
４〜８０番である必要がある。Particularly, as the abrasive grain plate of the abrasive grain plate rubbing apparatus used in the present invention, the grain size of the abrasive grain is JIS P 6001.
It is necessary to use the particles of No. 24 to No. 80 with the grain size specified in. The present inventors have found that the grain size is 5 to 24 for the pulp refining effect and the composite effect with the powder.
As a result of sequentially examining the particle sizes up to No. 0, when the particle size is coarser than No. 24, even if the grinding treatment is performed for a long time, desired miniaturization and compounding do not proceed, while the particle size is more than 80 It has been found that when the particle size is fine, clogging easily occurs at the rubbing part of the abrasive grain plate, and it becomes difficult to discharge the finely pulverized and composited slurry. Therefore, the grain size of the abrasive is 2
Must be numbered 4-80.
【００１６】本発明者ら種々検討した結果では、粉体複
合化微細フィブリル化セルロースを構成する微細フィブ
リル化セルロースは、数平均繊維長が０．０５〜０．３
ｍｍであることが好ましいことが判った。この長さより
長いと粉体を包み込む効果が少なくなり、また同時に比
表面積も小さくなってしまうため、繊維間結合を補強す
るバインダー効果も小さくなり、紙力増強効果が少なく
なる。また、０．０５ｍｍよりも短くなると抄紙時のワ
イヤー上での脱水時にワイヤーの間隙から粉体複合化微
細フィブリル化セルロースが抜ける傾向が大きくなるた
め、歩留りが良好でなくなる。As a result of various studies by the present inventors, the fine fibrillated cellulose constituting the powder-composited fine fibrillated cellulose has a number average fiber length of 0.05 to 0.3.
It has been found that mm is preferred. If the length is longer than this length, the effect of wrapping the powder is reduced, and at the same time, the specific surface area is also reduced, so that the binder effect for reinforcing the interfiber bond is reduced and the paper strength increasing effect is reduced. On the other hand, if the length is shorter than 0.05 mm, the powder composite fine fibrillated cellulose tends to come out from the gap between the wires during dehydration on the wires during paper making, resulting in poor yield.
【００１７】本発明の数平均繊維長はＫＡＪＡＡＮＩ社
（フィンランド）製の繊維長分布測定器（ＦＳ−２０
０）で測定したデータのうち、一定のパルプサスペンシ
ョン中に存在する繊維の全長を積算した後、その本数で
割った値を示す。通常の紙の原料であるＬＢＫＰ、ＮＢ
ＫＰは数平均繊維長でそれぞれ０．５ｍｍ，および１ｍ
ｍ程度の長さであり、叩解を進めることで発生するフィ
ブリル化した繊維ですら数平均繊維長は最小０．３５ｍ
ｍ程度の長さである。これに対し、本発明で製造される
粉体複合化微細フィブリル化セルロースの数平均繊維長
は０．０５〜０．３ｍｍであり、極めて微細なものであ
る。The number average fiber length of the present invention is a fiber length distribution measuring device (FS-20 manufactured by KAJAANI (Finland).
Of the data measured in 0), the total length of the fibers present in a given pulp suspension is integrated and then divided by the number. LBKP and NB, which are the raw materials for ordinary paper
KP is a number average fiber length of 0.5 mm and 1 m, respectively.
It has a length of about m, and the number average fiber length is 0.35m at the minimum even for fibrillated fibers generated by the beating process.
The length is about m. On the other hand, the number average fiber length of the powder-composited fine fibrillated cellulose produced in the present invention is 0.05 to 0.3 mm, which is extremely fine.
【００１８】この粉体複合化微細フィブリル化セルロー
スを製造する際のパルプと粉体の割合は、どのような割
合でも効果を示すが、乾燥重量比で１：１〜１：１０の
範囲で効果が著しいことが判った。この範囲以外ではパ
ルプ繊維と粉体のどちらかが過剰な状態であり、製造効
率が悪くなり、製紙用パルプに添加したときの効果も小
さくなる傾向があることを確認した。また、実機での濾
水性、粉体の添加量、微細フィブリル化セルロースの使
用量などを考慮すると、１：５の割合が好ましい。The ratio of the pulp to the powder in producing the powder-composited fine fibrillated cellulose is effective at any ratio, but the dry weight ratio is in the range of 1: 1 to 1:10. Was found to be remarkable. It has been confirmed that if the content is outside this range, either pulp fiber or powder is in an excessive state, the production efficiency is deteriorated, and the effect when added to the pulp for papermaking tends to be small. A ratio of 1: 5 is preferable in consideration of the drainage in an actual machine, the amount of powder added, the amount of fine fibrillated cellulose used, and the like.
【００１９】粉体複合化微細フィブリル化セルロースを
製造する際の粉体とパルプを混合したスラリーの固形分
濃度は１〜１０％が好ましい。固形分濃度が１％未満だ
と処理時間が長くかかり、また粉体と繊維との距離が大
きくなるため、うまく粉体を保持しない場合がある。ま
たパルプを微細化するに従い粘度が著しく増加してしま
うため、１０％を越える濃度ではスムーズに処理できな
くなる。The solid content concentration of the slurry in which the powder and the pulp are mixed at the time of producing the powder composite fine fibrillated cellulose is preferably 1 to 10%. When the solid content concentration is less than 1%, it takes a long treatment time and the distance between the powder and the fiber becomes large, so that the powder may not be held properly. Further, since the viscosity increases remarkably as the pulp is made finer, it becomes impossible to smoothly process it at a concentration exceeding 10%.
【００２０】粉体複合化微細フィブリル化セルロースを
製造する際に使用するパルプとしてはあらゆるものが使
用できる。例えば広葉樹晒しクラフトパルプ（ＬＢＫ
Ｐ）、針葉樹晒しクラフトパルプ（ＮＢＫＰ）、針葉樹
晒しサルファイトパルプ（ＮＢＳＰ）、等の化学パル
プ、砕木パルプ（ＧＰ），サーモメカニカルパルプ（Ｔ
ＭＰ）等の機械パルプ等の木材パルプや、コットンパル
プや、麻、雁皮、三椏繊維パルプ等の非木材パルプ、再
生セルロース繊維が用いられる。粉体を複合化するため
にはよりフィブリル化しやすい繊維の方が適するため、
木材パルプでは仮導管を主成分とするＮＢＫＰを使用す
ることが好ましい。As the pulp used for producing the powder-composited fine fibrillated cellulose, any pulp can be used. For example, hardwood bleached kraft pulp (LBK
P), chemical pulp such as softwood bleached kraft pulp (NBKP), softwood bleached sulfite pulp (NBSP), groundwood pulp (GP), thermomechanical pulp (T
Wood pulp such as mechanical pulp such as MP), cotton pulp, non-wood pulp such as hemp, goose bark, and San camellia fiber pulp, and regenerated cellulose fiber are used. Fibers that are easier to fibrillate are more suitable for compounding powders,
In wood pulp, it is preferable to use NBKP containing a temporary conduit as a main component.
【００２１】粉体複合化微細フィブリル化セルロースを
製造する際に使用する粉体としてはあらゆるものが使用
できる。具体的に述べるとクレー、炭酸カルシウム、タ
ルク、二酸化チタン、水酸化アルミニウム、水酸化マグ
ネシウム、水酸化カルシウム、アルミン酸カルシウム、
ゼオライト、セピオライト、硫化亜鉛、石こう、珪藻
土、沈降性硫酸バリウム、プラスチックピグメントなど
が使用できる。また、紙を着色する目的で使用するモリ
ブデンオレンジ、酸化鉄、ウルトラマリーン等の無機顔
料や、ナフタノール顔料、燐モリブデン酸顔料、フタロ
シアニン系顔料、キナクリドン系顔料、シアン化鉄等の
有機顔料が使用できる。As the powder used in the production of the powder-composited fine fibrillated cellulose, any powder can be used. Specifically, clay, calcium carbonate, talc, titanium dioxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, calcium aluminate,
Zeolites, sepiolite, zinc sulfide, gypsum, diatomaceous earth, precipitated barium sulfate, plastic pigments and the like can be used. Further, it is possible to use inorganic pigments such as molybdenum orange, iron oxide, and ultramarine used for coloring paper, and naphthalanol pigments, phosphomolybdic acid pigments, phthalocyanine pigments, quinacridone pigments, and organic pigments such as iron cyanide. .
【００２２】本発明の粉体含有紙を製造する方法は、通
常濃度４重量％程度の製紙用パルプスラリーに粉体複合
化微細フィブリル化セルロースを粉体比に換算して製紙
用パルプに対して１〜２０重量％添加する。この際必要
に応じて染料、顔料等の着色剤、サイズ剤、乾燥紙力増
強剤、湿潤紙力増強剤、歩留り向上剤等を添加すること
もできる。粉体複合化微細フィブリル化セルロースの添
加場所は、その歩留りを考慮し、よりヘッドボックスに
近い位置の方が好ましい。The method for producing the powder-containing paper of the present invention is as follows. The powder-composite fine fibrillated cellulose is converted into a powder ratio in a papermaking pulp slurry having a normal concentration of about 4% by weight, and the paper-making pulp is used. Add 1 to 20% by weight. At this time, a colorant such as a dye or a pigment, a sizing agent, a dry paper strength enhancer, a wet paper strength enhancer, a yield improving agent and the like can be added as required. The powder composite microfibrillated cellulose is preferably added at a position closer to the head box in consideration of the yield.
【００２３】歩留り向上剤としては、硫酸バンド（硫酸
アルミニウム）等の無機化合物やポリエチレンイミン、
ポリアクリルアミド、ポリアミドポリアミンエピクロル
ヒドリン等の有機高分子化合物を用いることが可能で、
カチオン性のポリアクリルアミドとアニオン性のポリア
クリルアミドを併用する等の前記したようなデュアルシ
ステムの方法なども可能である。本発明の粉体含有紙は
円網抄紙機、長網抄紙機、傾斜型抄紙機、ツインワイヤ
ー抄紙機等を使用して常法に従い抄紙する。As the yield improver, an inorganic compound such as a sulfuric acid band (aluminum sulfate) or polyethyleneimine,
It is possible to use organic polymer compounds such as polyacrylamide and polyamide polyamine epichlorohydrin,
The dual system method as described above, such as the combined use of cationic polyacrylamide and anionic polyacrylamide, is also possible. The powder-containing paper of the present invention is prepared by a conventional method using a cylinder paper machine, a fourdrinier paper machine, an inclined paper machine, a twin wire paper machine, or the like.
【００２４】以下実施例により本発明を具体的に説明す
る。重量部、重量％はいずれも乾燥重量部、乾燥重量％
を示す。実施例１ ＮＢＫＰとクレー（白土一級、白石工業（株）製造）を
乾燥重量比１：５に混合し、固形分濃度６重量％のスラ
リーを調製した。このスラリーをスーパーグラインデル
（増幸産業（株）製造）で１５分間処理し、粉体複合化
微細フィブリル化セルロースを得た。微細フィブリル化
セルロースの数平均繊維長を測定したところ０．２８ｍ
ｍであった。ついでフリーネス５００ｍｌＣＳＦに調製
したＮＢＫＰからなる製紙用パルプ８８重量部に、先に
調製した粉体複合微細フィブリル化セルロースを１２重
量部添加した。これにより全製紙原料（製紙用パルプ＋
微細フィブリル化セルロース）に対する微細フィブリル
化セルロースおよびクレーの含有量は、それぞれ２重量
％、１０重量％になる。粉体複合微細フィブリル化セル
ロースを均一に分散するため１０分間攪拌した後、定着
剤として硫酸アルミニウムを使用し、スラリーのｐＨが
４．５になるように添加した。ついで長網抄紙機を使用
して常法に従い坪量８０ｇ／ｍ2の粉体含有紙を抄造し
た。The present invention will be specifically described below with reference to examples. Both parts by weight and% by weight are dry parts by weight and dry weight%
Indicates. Example 1 NBKP and clay (white clay first grade, manufactured by Shiraishi Industry Co., Ltd.) were mixed at a dry weight ratio of 1: 5 to prepare a slurry having a solid content concentration of 6% by weight. This slurry was treated with Super Grindel (manufactured by Masuyuki Sangyo Co., Ltd.) for 15 minutes to obtain a powder-composited fine fibrillated cellulose. When the number average fiber length of fine fibrillated cellulose was measured, it was 0.28 m.
It was m. Then, 12 parts by weight of the powder-composite fine fibrillated cellulose prepared above was added to 88 parts by weight of the paper-making pulp made of NBKP prepared to have a freeness of 500 ml CSF. As a result, all papermaking raw materials (papermaking pulp +
The contents of fine fibrillated cellulose and clay with respect to fine fibrillated cellulose) are 2% by weight and 10% by weight, respectively. The powder composite fine fibrillated cellulose was stirred for 10 minutes in order to be uniformly dispersed, and then aluminum sulfate was used as a fixing agent and added so that the pH of the slurry became 4.5. Then, using a Fourdrinier paper machine, a powder-containing paper having a basis weight of 80 g / m 2 was produced by a conventional method.
【００２５】実施例２ ＮＢＫＰ（同上）とクレー（同上）を乾燥重量比１：１
０に混合し、固形分濃度６重量％のスラリーを調製し
た。このスラリーをスーパーグラインデル（同上）で１
５分間処理し、粉体複合化微細フィブリル化セルロース
を得た。微細フィブリル化セルロースの数平均繊維長を
測定したところ０．１８ｍｍであった。ついでフリーネ
ス５００ｍｌＣＳＦに調製したＮＢＫＰからなる製紙用
パルプ４５重量部に、先に調製した粉体複合微細フィブ
リル化セルロースを５５重量部添加した。これにより全
製紙原料に対する微細フィブリル化セルロースおよびク
レーの含有量は、それぞれ５重量％、５０重量％にな
る。粉体複合微細フィブリル化セルロースを均一に分散
するため１０分間攪拌した後、定着剤として硫酸アルミ
ニウムを使用し、スラリーのｐＨが４．５になるように
添加した。ついで長網抄紙機を使用して常法に従い坪量
８０ｇ／ｍ2の粉体含有紙を抄造した。 Example 2 NBKP (same as above) and clay (same as above) in a dry weight ratio of 1: 1.
0 to prepare a slurry having a solid content concentration of 6% by weight. 1 this slurry with Super Grindell (same as above)
The mixture was treated for 5 minutes to obtain a powder-composited fine fibrillated cellulose. The number average fiber length of the fine fibrillated cellulose was measured and found to be 0.18 mm. Next, 55 parts by weight of the powder composite fine fibrillated cellulose prepared above was added to 45 parts by weight of the papermaking pulp made of NBKP prepared to have a freeness of 500 ml CSF. As a result, the contents of fine fibrillated cellulose and clay with respect to the total amount of the papermaking raw materials are 5% by weight and 50% by weight, respectively. The powder composite fine fibrillated cellulose was stirred for 10 minutes in order to be uniformly dispersed, and then aluminum sulfate was used as a fixing agent and added so that the pH of the slurry became 4.5. Then, using a Fourdrinier paper machine, a powder-containing paper having a basis weight of 80 g / m 2 was produced by a conventional method.
【００２６】比較例１ フリーネス５００ｍｌＣＳＦに調製したＮＢＫＰ（同
上）９０重量部にクレー（同上）を１０重量部添加し
た。全製紙原料に対するクレーの含有量は、１０重量％
になる。クレーを均一に分散するため１０分間攪拌した
後、定着剤として硫酸アルミニウムを使用し、スラリー
のｐＨが４．５になるように添加した。ついでポリエチ
レンイミン（商品名「ポリミンＳＮ」、ＢＡＳＦ（株）
製造）を１重量部添加し、長網抄紙機を使用して常法に
従い坪量８０ｇ／ｍ2の粉体含有紙を抄造した。 Comparative Example 1 10 parts by weight of clay (same as above) was added to 90 parts by weight of NBKP (same as above) prepared to have a freeness of 500 ml CSF. Clay content is 10% by weight with respect to all papermaking raw materials
become. After stirring for 10 minutes to uniformly disperse the clay, aluminum sulfate was used as a fixing agent and added so that the pH of the slurry became 4.5. Then polyethyleneimine (trade name "Polymin SN", BASF Corporation)
(Manufacturing) was added in an amount of 1 part by weight, and a powder-containing paper having a basis weight of 80 g / m 2 was produced by a conventional method using a Fourdrinier paper machine.
【００２７】比較例２ フリーネス５００ｍｌＣＳＦに調製したＮＢＫＰ（同
上）８８重量部に対し、スーパーグラインデル（同上）
によって数平均繊維長０．２８ｍｍに調製した微細フィ
ブリル化セルロースを２重量部添加し、均一に分散し
た。このスラリーにクレー（同上）を１０重量部添加し
た。これにより全製紙原料に対する微細フィブリル化セ
ルロースおよびクレーの含有量は、それぞれ２重量％、
１０重量％になる。クレーを均一に分散するため１０分
間攪拌した後、定着剤として硫酸アルミニウムを使用
し、スラリーのｐＨが４．５になるように添加した。長
網抄紙機を使用して常法に従い坪量８０ｇ／ｍ2の粉体
含有紙を抄造した。 Comparative Example 2 Freeness 500 ml CSF NBKP (same as above) 88 parts by weight, Super Grindell (same as above)
2 parts by weight of fine fibrillated cellulose prepared by the method to have a number average fiber length of 0.28 mm was added and uniformly dispersed. 10 parts by weight of clay (same as above) was added to this slurry. As a result, the content of fine fibrillated cellulose and clay with respect to the total amount of papermaking raw materials was 2% by weight,
It becomes 10% by weight. After stirring for 10 minutes to uniformly disperse the clay, aluminum sulfate was used as a fixing agent and added so that the pH of the slurry became 4.5. Using a Fourdrinier paper machine, a powder-containing paper having a basis weight of 80 g / m 2 was produced by a conventional method.
【００２８】比較例３ フリーネス５００ｍｌＣＳＦに調製したＮＢＫＰ（同
上）９０重量部にクレー（同上）を５０重量部添加し
た。これにより全製紙原料に対するクレーの含有量は、
５０重量％になる。クレーを均一に分散するため１０分
間攪拌した後、定着剤として硫酸アルミニウムを使用
し、スラリーのｐＨが４．５になるように添加し、つい
でポリエチレンイミン（同上）を１重量部添加し、長網
抄紙機を使用して常法に従い坪量８０ｇ／ｍ2の粉体含
有紙を抄造した。 Comparative Example 3 50 parts by weight of clay (same as above) was added to 90 parts by weight of NBKP (same as above) prepared to have a freeness of 500 ml CSF. As a result, the content of clay relative to all papermaking raw materials is
50% by weight. After stirring for 10 minutes to uniformly disperse the clay, aluminum sulfate was used as a fixing agent and added so that the pH of the slurry was 4.5, and then 1 part by weight of polyethyleneimine (same as above) was added to Using a net paper machine, a powder-containing paper having a basis weight of 80 g / m 2 was produced by a conventional method.
【００２９】比較例４ フリーネス５００ｍｌＣＳＦに調製したＮＢＫＰ（同
上）４５重量部に対し、スーパーグラインデル（同上）
によって数平均繊維長０．１８ｍｍに調製した微細フィ
ブリル化セルロースを５重量部添加し、均一に分散し
た。このスラリーにクレー（同上）を４５重量部添加し
た。これにより全製紙原料に対する微細フィブリル化セ
ルロースおよびクレーの含有量は、それぞれ５重量％、
５０重量％になる。クレーを均一に分散するため１０分
間攪拌した後、定着剤として硫酸アルミニウムをｐＨ
４．５になるように添加した。長網抄紙機を使用して常
法に従い坪量８０ｇ／ｍ2の粉体含有紙を抄造した。 Comparative Example 4 Freeness: NBKP prepared in 500 ml CSF (same as above) to 45 parts by weight, SuperGrindel (same as above)
5 parts by weight of fine fibrillated cellulose adjusted to have a number average fiber length of 0.18 mm was added and uniformly dispersed. To this slurry, 45 parts by weight of clay (same as above) was added. As a result, the content of fine fibrillated cellulose and clay relative to the total amount of papermaking raw materials was 5% by weight,
50% by weight. After stirring for 10 minutes to evenly disperse the clay, use aluminum sulfate as a fixing agent to adjust the pH.
It was added so that it might be 4.5. Using a Fourdrinier paper machine, a powder-containing paper having a basis weight of 80 g / m 2 was produced by a conventional method.
【００３０】実施例及び比較例で得られた粉体含有紙の
物性評価を行った。各物性測定方法及び評価は下記によ
った。 １）濾水性：抄紙網上で水切れの程度を目視により観察
した。○は濾水性が良好なことを、△は実用上問題の無
いことを、×は濾水性が悪く実用上問題のあることをを
示す。 ２）灰分：ＪＩＳ Ｐ８１２８に規定する方法で測定し
た。 ３）粉体歩留り：（灰分／理論灰分値）×１００から求
めた。 ４）裂断長：ＪＩＳ Ｐ８１１３に規定する方法で測定
した。同一の坪量の紙においては、裂断長が大きいほう
が引張り強さも大きなことを示す。 ５）地合：透過光で観察した紙のシートフォーメーショ
ンが均一な状態を○、ややフロックが形成されている状
態を△、大きなフロックが形成され不均一な状態を×で
示す。 評価結果を表１に示す。The physical properties of the powder-containing papers obtained in the examples and comparative examples were evaluated. Each physical property measuring method and evaluation were as follows. 1) Drainage: The degree of drainage was visually observed on a paper making net. O indicates that the drainage is good, Δ indicates that there is no problem in practical use, and X indicates that the drainage is poor and there is a problem in practice. 2) Ash content: Measured by the method specified in JIS P8128. 3) Powder yield: determined from (ash content / theoretical ash value) × 100. 4) Breaking length: measured by the method specified in JIS P8113. For papers of the same basis weight, the larger the breaking length, the greater the tensile strength. 5) Formation: The sheet formation of the paper observed with transmitted light is indicated by ◯, the state where a little floc is formed is indicated by Δ, and the large floc is indicated by x. The evaluation results are shown in Table 1.
【００３１】[0031]
【表１】 [Table 1]
【００３２】実施例１と２は粉体複合化微細フィブリル
化セルロースをスラリーに添加した例で、比較例１と３
はデュアルポリマーシステムを使用した例で、比較例２
と４は微細フィブリル化セルロースと粉体を別個にスラ
リーに添加使用した例である。表１から以下のことが判
る。 １）実施例１と比較例１を比べると繊維（パルプ＋微細
フィブリル化セルロース）に対しての粉体添加量が同一
であるにも関わらず、粉体複合化微細フィブリル化セル
ロースを使用した実施例１のほうが、比較例１のデュア
ルポリマーシステムより、粉体歩留り、引張り強さ、地
合が優れていることが判る。 ２）実施例１と比較例２を比べるとパルプ、微細フィブ
リル化セルロース、クレーの比率が同一であるのにもか
かわらず、粉体複合化微細フィブリル化セルロースを使
用した実施例１のほうが濾水性、粉体歩留り、引張り強
さ、地合がいずれも比較例２より優れていることが判
る。 ３）粉体の添加量を多くした実施例２と比較例３を比べ
ると、デュアルポリマーシステム（比較例３）では、濾
水性は良好であるが、引張り強さが弱く、フロック地合
になってしまうことが判る。これに対して実施例２で
は、濾水性も良好で、引張り強さ、粉体歩留り、地合の
いずれも比較例３より良好のことが判る。 ４）粉体の添加量を多くした実施例２と比較例４を比べ
ると、パルプ、微細フィブリル化セルロース、クレーの
比率が同一であるのにもかかわらず、粉体複合化微細フ
ィブリル化セルロースを使用した実施例２のほうが、微
細フィブリル化セルロースと粉体を別個に添加した実施
例４より、濾水性、粉体歩留り、引張り強さ、地合がい
ずれも良好なことが判る。Examples 1 and 2 are examples in which powder-composited fine fibrillated cellulose was added to the slurry, and Comparative Examples 1 and 3
Is an example using a dual polymer system, Comparative Example 2
And 4 are examples in which the fine fibrillated cellulose and the powder were separately added to the slurry and used. The following can be seen from Table 1. 1) Comparison between Example 1 and Comparative Example 1 using the powder-combined fine fibrillated cellulose, even though the amount of powder added to the fiber (pulp + fine fibrillated cellulose) was the same. It can be seen that Example 1 is superior to the dual polymer system of Comparative Example 1 in powder yield, tensile strength and formation. 2) Comparing Example 1 and Comparative Example 2, although the ratios of pulp, fine fibrillated cellulose and clay were the same, Example 1 using powder-composited fine fibrillated cellulose was more draining. It can be seen that the powder yield, the tensile strength and the formation are all superior to those of Comparative Example 2. 3) Comparing Example 2 in which the amount of powder added is large with Comparative Example 3, the dual polymer system (Comparative Example 3) has good drainage but weak tensile strength, resulting in flock formation. It turns out that it will end up. On the other hand, in Example 2, the drainage is also good, and it is understood that the tensile strength, the powder retention, and the formation are all better than those of Comparative Example 3. 4) Comparing Example 2 and Comparative Example 4 in which the amount of powder added was large, powder-composited fine fibrillated cellulose was obtained even though the ratios of pulp, fine fibrillated cellulose and clay were the same. It can be seen that the used Example 2 has better drainage, powder retention, tensile strength and formation than Example 4 in which the fine fibrillated cellulose and the powder were added separately.
【００３３】上記実施例及び比較例では粉体としてクレ
ーの例を挙げたが、前述したような他の粉体においても
同様の結果が得られることを本発明者らは確認した。In the above Examples and Comparative Examples, an example of clay was given as the powder, but the present inventors have confirmed that similar results can be obtained with other powders as described above.
【００３４】[0034]
【発明の効果】本発明の粉体含有紙の製造方法は下記に
述べるような顕著な効果を有する。 １）粉体の歩留りが最も良いと言われてきたデュアルポ
リマーシステムをも凌ぐ粉体歩留りを実現出来るにもか
かわらず、紙の地合を崩さずに抄紙することができる。 ２）粉体と微細フィブリル化セルロースを別々に添加す
る従来の方法の問題点であった濾水性の悪化を本発明で
は改善でき、抄造が容易になる。 ３）粉体含有紙を抄造するにあたって、従来、粉体の定
着量の増加に伴う紙の強度の低下が言われていたが、本
発明では粉体の定着量が増加しても紙力の低下を防ぐこ
とができる。 ４）以上の特性を利用して、本発明はクレー、タルク、
カオリン、炭酸カルシウム、二酸化チタン等の粉体を内
添した上質紙等の印刷用紙や水酸化アルミニウム、水酸
化マグネシウム、カルシウムアルミネート、水酸化カル
シウム、アルミン酸カルシウム等の粉体を内添した難燃
紙、不燃紙やシリカゲル、アルミノシリケート、ゼオラ
イト、活性炭、活性アルミナ等の粉体を内添したガス吸
着紙等々の製造に好適に利用できる。The method for producing powder-containing paper according to the present invention has the following remarkable effects. 1) Although it is possible to realize a powder yield surpassing the dual polymer system, which has been said to have the best powder yield, it is possible to make paper without breaking the texture of the paper. 2) The deterioration of drainage, which was a problem of the conventional method of separately adding powder and fine fibrillated cellulose, can be improved in the present invention, and papermaking becomes easy. 3) In papermaking of powder-containing paper, it has been conventionally said that the strength of the paper decreases with an increase in the fixing amount of the powder. However, in the present invention, even if the fixing amount of the powder increases, the paper strength is increased. You can prevent the decline. 4) Utilizing the above characteristics, the present invention provides clay, talc,
Printing paper such as high-quality paper containing powders such as kaolin, calcium carbonate, titanium dioxide, etc. and powder containing aluminum hydroxide, magnesium hydroxide, calcium aluminate, calcium hydroxide, calcium aluminate, etc. It can be suitably used for the production of combustible paper, non-combustible paper, silica gel, aluminosilicate, zeolite, activated carbon, gas-adsorbed paper internally added with powder such as activated alumina, and the like.
【図１】本発明で使用する砥粒板擦り合わせ装置の一例
を示す斜視図。FIG. 1 is a perspective view showing an example of an abrasive grain plate rubbing apparatus used in the present invention.
【図２】図１の装置の断面図。2 is a cross-sectional view of the device of FIG.
【図３】図１の装置に使用される砥粒板の一例を示す平
面図。FIG. 3 is a plan view showing an example of an abrasive grain plate used in the apparatus of FIG.
１：固定砥粒板 ２：回転砥粒板 ３：摩砕室 ４：擦り合わせ部 ６：ホッパー ９：駆動モーター １２：送り溝 1: Fixed abrasive grain plate 2: Rotating abrasive grain plate 3: Grinding chamber 4: Rubbing part 6: Hopper 9: Drive motor 12: Feed groove
Claims (5)
な機械的せん断力を与えることによって得られる粉体と
微細フィブリル化セルロースの複合体（粉体複合化微細
フィブリル化セルロース）を製紙用パルプスラリーに添
加した後、抄紙することを特徴とする粉体含有紙の製造
方法。1. A pulp for papermaking comprising a composite of powder and fine fibrillated cellulose (powder-combined fine fibrillated cellulose) obtained by applying a strong mechanical shearing force to a slurry obtained by mixing powder and pulp. A method for producing a powder-containing paper, which comprises adding paper to a slurry and then making a paper.
度が２４〜８０番の砥粒からなる砥粒板を複数枚擦り合
わせ配置した砥粒板擦り合わせ装置を使用し、この装置
の擦り合わせ部に粉体とパルプを混合したスラリーを通
過させて製造した粉体複合化微細フィブリル化セルロー
スを使用することを特徴とする請求項１記載の粉体含有
紙の製造方法。2. An abrasive grain plate rubbing device in which a plurality of abrasive grain plates made of abrasive grains having a grain size of 24 to 80 are rubbed and arranged as a device for giving a mechanical shearing force, and the rubbing of this device is performed. The method for producing a powder-containing paper according to claim 1, characterized in that powder-composited fine fibrillated cellulose produced by passing a slurry in which powder and pulp are mixed is used.
維長が０．０５〜０．３ｍｍであることを特徴とする請
求項１記載の粉体含有紙の製造方法。3. The method for producing a powder-containing paper according to claim 1, wherein the number average fiber length of the fine fibrillated cellulose is 0.05 to 0.3 mm.
を製造する際のパルプと粉体の割合が、乾燥重量比で
１：１〜１：１０であることを特徴とする請求項１及び
３に記載の粉体含有紙の製造方法。4. The dry weight ratio of the pulp to the powder in the production of the powder-composited fine fibrillated cellulose is 1: 1 to 1:10, and the ratio is in the range of 1 to 3. A method for producing the powder-containing paper described.
を製造する際のスラリーの固形分濃度が１〜１０重量％
であることを特徴とする請求項１及び３及び４に記載の
粉体含有紙の製造方法。5. The solid content concentration of the slurry when producing the powder-composited fine fibrillated cellulose is 1 to 10% by weight.
The method for producing the powder-containing paper according to claim 1, 2, or 3, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24058894A JP3421446B2 (en) | 1994-09-08 | 1994-09-08 | Method for producing powder-containing paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24058894A JP3421446B2 (en) | 1994-09-08 | 1994-09-08 | Method for producing powder-containing paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0881896A true JPH0881896A (en) | 1996-03-26 |
| JP3421446B2 JP3421446B2 (en) | 2003-06-30 |
Family
ID=17061749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24058894A Expired - Fee Related JP3421446B2 (en) | 1994-09-08 | 1994-09-08 | Method for producing powder-containing paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3421446B2 (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6375794B2 (en) | 1995-06-29 | 2002-04-23 | Metsa-Serla | Filler for use in paper manufacture and procedure for producing a filler |
| JP2011038031A (en) * | 2009-08-17 | 2011-02-24 | Toppan Printing Co Ltd | Method for producing molded product and molded product |
| JP2012007247A (en) * | 2010-06-22 | 2012-01-12 | Oji Paper Co Ltd | Composite sheet of fine fibrous cellulose and inorganic compound nanoparticles |
| JP2012514137A (en) * | 2009-05-15 | 2012-06-21 | イメリーズ ミネラルズ リミテッド | Paper filler composition |
| JP2013527333A (en) * | 2010-04-27 | 2013-06-27 | オムヤ・デイベロツプメント・アー・ゲー | Method for fabricating structured materials using nanofibril cellulose gel |
| KR20130096755A (en) * | 2010-11-15 | 2013-08-30 | 이메리즈 미네랄즈 리미티드 | Compositions |
| JP2013534976A (en) * | 2010-05-12 | 2013-09-09 | ストラ エンソ オーワイジェイ | Method and composition for producing a composition comprising fibrillated cellulose |
| JP2014530946A (en) * | 2011-10-26 | 2014-11-20 | ストラ エンソ オサケ ユキチュアユルキネンＳｔｏｒａ Ｅｎｓｏ Ｏｙｊ | Method for producing dispersion containing nanoparticles and dispersion produced by said method |
| JP2015121010A (en) * | 2009-03-30 | 2015-07-02 | オムヤ インターナショナル アーゲー | Method for producing nano-fibrillar cellulose suspensions |
| AU2014227494B2 (en) * | 2010-04-27 | 2016-02-04 | Omya International Ag | Process for the manufacture of structured materials using nano-fibrillar cellulose gels |
| EP2569468B1 (en) | 2010-05-11 | 2017-01-25 | FPInnovations | Cellulose nanofilaments and method to produce same |
| JP2018065988A (en) * | 2010-04-27 | 2018-04-26 | ファイバーリーン テクノロジーズ リミテッド | Method for manufacturing composite material based on gel |
| JP2018530685A (en) * | 2015-10-12 | 2018-10-18 | ソレニス テクノロジーズ、エル．ピー． | Method for enhancing drainage performance of pulp slurry during the manufacture of paper products and products produced from the method |
| US10214859B2 (en) | 2016-04-05 | 2019-02-26 | Fiberlean Technologies Limited | Paper and paperboard products |
| JP2019058855A (en) * | 2017-09-26 | 2019-04-18 | レンゴー株式会社 | Moisture adsorbing/desorbing sheet and production method thereof |
| US10294371B2 (en) | 2009-03-30 | 2019-05-21 | Fiberlean Technologies Limited | Process for the production of nano-fibrillar cellulose gels |
| US10577469B2 (en) | 2015-10-14 | 2020-03-03 | Fiberlean Technologies Limited | 3D-formable sheet material |
| US10794006B2 (en) | 2016-04-22 | 2020-10-06 | Fiberlean Technologies Limited | Compositions comprising microfibrilated cellulose and polymers and methods of manufacturing fibres and nonwoven materials therefrom |
| US11846072B2 (en) | 2016-04-05 | 2023-12-19 | Fiberlean Technologies Limited | Process of making paper and paperboard products |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57112489A (en) * | 1980-12-27 | 1982-07-13 | Sanyo Kokusaku Pulp Co | Friction grinding of papermaking stock material |
-
1994
- 1994-09-08 JP JP24058894A patent/JP3421446B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57112489A (en) * | 1980-12-27 | 1982-07-13 | Sanyo Kokusaku Pulp Co | Friction grinding of papermaking stock material |
Cited By (64)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6375794B2 (en) | 1995-06-29 | 2002-04-23 | Metsa-Serla | Filler for use in paper manufacture and procedure for producing a filler |
| US6599391B2 (en) | 1995-06-29 | 2003-07-29 | M-Real Corporation | Filler for use in paper manufacture and procedure for producing a filler |
| JP2017106151A (en) * | 2009-03-30 | 2017-06-15 | オムヤ インターナショナル アーゲー | Process for production of nano-fibrillar cellulose suspension |
| KR20180125048A (en) * | 2009-03-30 | 2018-11-21 | 파이버린 테크놀로지스 리미티드 | Process for the production of nano-fibrillar cellulose suspensions |
| JP2015121010A (en) * | 2009-03-30 | 2015-07-02 | オムヤ インターナショナル アーゲー | Method for producing nano-fibrillar cellulose suspensions |
| EP2236664B1 (en) | 2009-03-30 | 2015-12-16 | Omya International AG | Process for the production of nano-fibrillar cellulose suspensions |
| JP2019007127A (en) * | 2009-03-30 | 2019-01-17 | ファイバーリーン テクノロジーズ リミテッド | Method for producing nanofibril cellulose suspension |
| US10294371B2 (en) | 2009-03-30 | 2019-05-21 | Fiberlean Technologies Limited | Process for the production of nano-fibrillar cellulose gels |
| US10301774B2 (en) | 2009-03-30 | 2019-05-28 | Fiberlean Technologies Limited | Process for the production of nano-fibrillar cellulose suspensions |
| US10982387B2 (en) | 2009-03-30 | 2021-04-20 | Fiberlean Technologies Limited | Process for the production of nano-fibrillar cellulose suspensions |
| US10975242B2 (en) | 2009-03-30 | 2021-04-13 | Fiberlean Technologies Limited | Process for the production of nano-fibrillar cellulose gels |
| US11162219B2 (en) | 2009-05-15 | 2021-11-02 | Fiberlean Technologies Limited | Paper filler composition |
| US11377791B2 (en) | 2009-05-15 | 2022-07-05 | Fiberlean Technologies Limited | Paper filler composition |
| EP3715528A1 (en) * | 2009-05-15 | 2020-09-30 | FiberLean Technologies Limited | Paper filler composition |
| KR101378720B1 (en) * | 2009-05-15 | 2014-03-27 | 이메리즈 미네랄즈 리미티드 | Paper filler composition |
| AU2010247184B2 (en) * | 2009-05-15 | 2013-01-10 | Fiberlean Technologies Limited | Paper filler composition |
| JP2020079476A (en) * | 2009-05-15 | 2020-05-28 | ファイバーリーン テクノロジーズ リミテッド | Paper filler composition |
| JP2017048497A (en) * | 2009-05-15 | 2017-03-09 | イメリーズ ミネラルズ リミテッド | Paper filler composition |
| US10100464B2 (en) | 2009-05-15 | 2018-10-16 | Fiberlean Technologies Limited | Paper filler composition |
| US11970817B2 (en) | 2009-05-15 | 2024-04-30 | Fiberlean Technologies Limited | Paper filler composition |
| JP2017166118A (en) * | 2009-05-15 | 2017-09-21 | ファイバーリーン テクノロジーズ リミテッド | Paper filler composition |
| JP2012514137A (en) * | 2009-05-15 | 2012-06-21 | イメリーズ ミネラルズ リミテッド | Paper filler composition |
| US11732411B2 (en) | 2009-05-15 | 2023-08-22 | Fiberlean Technologies Limited | Paper filler composition |
| JP2018188793A (en) * | 2009-05-15 | 2018-11-29 | ファイバーリーン テクノロジーズ リミテッド | Paper filler composition |
| JP2011038031A (en) * | 2009-08-17 | 2011-02-24 | Toppan Printing Co Ltd | Method for producing molded product and molded product |
| JP2016216884A (en) * | 2010-04-27 | 2016-12-22 | オムヤ インターナショナル アーゲー | Method for producing structured materials using nano-fibrillar cellulose gels |
| JP2022000550A (en) * | 2010-04-27 | 2022-01-04 | ファイバーリーン テクノロジーズ リミテッド | Process for manufacture of structured materials using nano-fibrillar cellulose gels |
| US10633796B2 (en) | 2010-04-27 | 2020-04-28 | Fiberlean Technologies Limited | Process for the manufacture of structured materials using nano-fibrillar cellulose gels |
| US10053817B2 (en) | 2010-04-27 | 2018-08-21 | Fiberlean Technologies Limited | Process for the manufacture of structured materials using nano-fibrillar cellulose gels |
| JP2018065988A (en) * | 2010-04-27 | 2018-04-26 | ファイバーリーン テクノロジーズ リミテッド | Method for manufacturing composite material based on gel |
| JP2018031105A (en) * | 2010-04-27 | 2018-03-01 | ファイバーリーン テクノロジーズ リミテッド | Method for producing structured materials using nano-fibrillar cellulose gels |
| JP2013527333A (en) * | 2010-04-27 | 2013-06-27 | オムヤ・デイベロツプメント・アー・ゲー | Method for fabricating structured materials using nanofibril cellulose gel |
| JP2020109176A (en) * | 2010-04-27 | 2020-07-16 | ファイバーリーン テクノロジーズ リミテッド | Process for production of gel-based composite materials |
| JP2019196580A (en) * | 2010-04-27 | 2019-11-14 | ファイバーリーン テクノロジーズ リミテッド | Method for producing structured material using nanofibril cellulose gell |
| US11155697B2 (en) | 2010-04-27 | 2021-10-26 | Fiberlean Technologies Limited | Process for the production of gel-based composite materials |
| US10100467B2 (en) | 2010-04-27 | 2018-10-16 | Fiberlean Technologies Limited | Process for the manufacture of structured materials using nano-fibrillar cellulose gels |
| AU2014227494B2 (en) * | 2010-04-27 | 2016-02-04 | Omya International Ag | Process for the manufacture of structured materials using nano-fibrillar cellulose gels |
| EP2569468B1 (en) | 2010-05-11 | 2017-01-25 | FPInnovations | Cellulose nanofilaments and method to produce same |
| JP2013534976A (en) * | 2010-05-12 | 2013-09-09 | ストラ エンソ オーワイジェイ | Method and composition for producing a composition comprising fibrillated cellulose |
| JP2012007247A (en) * | 2010-06-22 | 2012-01-12 | Oji Paper Co Ltd | Composite sheet of fine fibrous cellulose and inorganic compound nanoparticles |
| JP2017203243A (en) * | 2010-11-15 | 2017-11-16 | ファイバーリーン テクノロジーズ リミテッド | Compositions |
| KR20130096755A (en) * | 2010-11-15 | 2013-08-30 | 이메리즈 미네랄즈 리미티드 | Compositions |
| KR20200087280A (en) * | 2010-11-15 | 2020-07-20 | 파이버린 테크놀로지스 리미티드 | Compositions |
| EP2640893B1 (en) | 2010-11-15 | 2017-08-23 | FiberLean Technologies Limited | Compositions |
| US11655594B2 (en) | 2010-11-15 | 2023-05-23 | Fiberlean Technologies Limited | Compositions |
| KR20220053050A (en) * | 2010-11-15 | 2022-04-28 | 파이버린 테크놀로지스 리미티드 | Compositions |
| JP2020169434A (en) * | 2010-11-15 | 2020-10-15 | ファイバーリーン テクノロジーズ リミテッド | Compositions |
| KR20190025748A (en) * | 2010-11-15 | 2019-03-11 | 파이버린 테크놀로지스 리미티드 | Compositions |
| JP2014503696A (en) * | 2010-11-15 | 2014-02-13 | イメリーズ ミネラルズ リミテッド | Composition |
| KR20210090747A (en) * | 2010-11-15 | 2021-07-20 | 파이버린 테크놀로지스 리미티드 | Compositions |
| US11136721B2 (en) | 2010-11-15 | 2021-10-05 | Fiberlean Technologies Limited | Compositions |
| US10253457B2 (en) | 2010-11-15 | 2019-04-09 | Fiberlean Technologies Limited | Compositions |
| JP2014530946A (en) * | 2011-10-26 | 2014-11-20 | ストラ エンソ オサケ ユキチュアユルキネンＳｔｏｒａ Ｅｎｓｏ Ｏｙｊ | Method for producing dispersion containing nanoparticles and dispersion produced by said method |
| JP2018530685A (en) * | 2015-10-12 | 2018-10-18 | ソレニス テクノロジーズ、エル．ピー． | Method for enhancing drainage performance of pulp slurry during the manufacture of paper products and products produced from the method |
| US10577469B2 (en) | 2015-10-14 | 2020-03-03 | Fiberlean Technologies Limited | 3D-formable sheet material |
| US11384210B2 (en) | 2015-10-14 | 2022-07-12 | Fiberlean Technologies Limited | 3-D formable sheet material |
| US11274399B2 (en) | 2016-04-05 | 2022-03-15 | Fiberlean Technologies Limited | Paper and paperboard products |
| US10801162B2 (en) | 2016-04-05 | 2020-10-13 | Fiberlean Technologies Limited | Paper and paperboard products |
| US10214859B2 (en) | 2016-04-05 | 2019-02-26 | Fiberlean Technologies Limited | Paper and paperboard products |
| US11732421B2 (en) | 2016-04-05 | 2023-08-22 | Fiberlean Technologies Limited | Method of making paper or board products |
| US11846072B2 (en) | 2016-04-05 | 2023-12-19 | Fiberlean Technologies Limited | Process of making paper and paperboard products |
| US11572659B2 (en) | 2016-04-22 | 2023-02-07 | Fiberlean Technologies Limited | Compositions comprising microfibrillated cellulose and polymers and methods of manufacturing fibres and nonwoven materials therefrom |
| US10794006B2 (en) | 2016-04-22 | 2020-10-06 | Fiberlean Technologies Limited | Compositions comprising microfibrilated cellulose and polymers and methods of manufacturing fibres and nonwoven materials therefrom |
| JP2019058855A (en) * | 2017-09-26 | 2019-04-18 | レンゴー株式会社 | Moisture adsorbing/desorbing sheet and production method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3421446B2 (en) | 2003-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3421446B2 (en) | Method for producing powder-containing paper | |
| US10982387B2 (en) | Process for the production of nano-fibrillar cellulose suspensions | |
| US12018433B2 (en) | Process for treating microfibrillated cellulose | |
| JP2967804B2 (en) | Ultrafine fibrillated cellulose, method for producing the same, method for producing coated paper using ultrafine fibrillated cellulose, and method for producing dyed paper | |
| US6214163B1 (en) | Super microfibrillated cellulose, process for producing the same, and coated paper and tinted paper using the same | |
| KR101178394B1 (en) | Process for producing fibrillated fibers | |
| FI68283B (en) | FOERFARANDE FOER PAPPERSTILLVERKNING | |
| JP3036354B2 (en) | Method for producing fine fibrillated cellulose | |
| JP2005517100A (en) | Method for preparing fibers contained in pulp suspension | |
| JPH073691A (en) | Filled paper | |
| JPH09170197A (en) | Production of fluorescent-brightened paper | |
| JPH08188981A (en) | Production of finely fibrillated pulp sheet | |
| CN117926614A (en) | Recycled paper pulp preparation method, recycled paper pulp and paper preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |