JPH07310296A - Production of finely fibrillated cellulose - Google Patents
Production of finely fibrillated celluloseInfo
- Publication number
- JPH07310296A JPH07310296A JP6102755A JP10275594A JPH07310296A JP H07310296 A JPH07310296 A JP H07310296A JP 6102755 A JP6102755 A JP 6102755A JP 10275594 A JP10275594 A JP 10275594A JP H07310296 A JPH07310296 A JP H07310296A
- Authority
- JP
- Japan
- Prior art keywords
- fibrillated cellulose
- pulp
- pulp slurry
- abrasive
- fine
- 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
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、紙を製造する際に製紙
用パルプに添加することによって、紙力を増加させた
り、紙の透気度を高めることができる微細フィブリル化
セルロースを効率よく製造するための方法に関するもの
である。FIELD OF THE INVENTION The present invention efficiently adds fine fibrillated cellulose capable of increasing paper strength and increasing air permeability of paper by adding it to pulp for paper making at the time of producing paper. It relates to a method for manufacturing.
【０００２】[0002]
【従来の技術】木材パルプ等のセルロース繊維を微細化
すると、細胞膜を形成している構成単位であるフィブリ
ルへの分割が進むため、繊維形態を保持した状態で枝分
かれしながら微細化が進行し、微細フィブリル化セルロ
ースが得られる。このような微細フィブリル化セルロー
スを製紙用パルプに添加して紙を抄造すると、数々のお
もしろい特性を有する紙が得られることが知られてい
る。例えば、微細フィブリル化セルロースのバインダー
的性質を利用して、紙の引張り強さや破裂強さを向上さ
せることができる。また、微細フィブリル化セルロース
は繊維状であるため緻密なネットワークを形成し、紙の
透気度を上昇させる。2. Description of the Related Art When cellulose fibers such as wood pulp are miniaturized, they are divided into fibrils, which are the structural units forming the cell membrane, and therefore the miniaturization proceeds while branching while maintaining the fiber morphology. A fine fibrillated cellulose is obtained. It is known that when such fine fibrillated cellulose is added to papermaking pulp to make a paper, a paper having various interesting properties can be obtained. For example, the binder properties of finely fibrillated cellulose can be used to improve the tensile strength and burst strength of paper. Further, since fine fibrillated cellulose is fibrous, it forms a dense network and increases the air permeability of the paper.
【０００３】このような微細フィブリル化セルロースの
特性を利用して、プリント配線基板等に使用する含浸加
工原紙の紙力を増強させる技術が提案されている（特公
昭６２ー０３３３６０号）。また、微細フィブリル化セ
ルロースの水懸濁液が適度な粘性を有しかつ分散性が良
好であることを利用して、この水懸濁液を紙の表面に塗
工することにより紙の強度を増し、印刷適性を向上させ
る技術も提案されている（特開平０４−１９４０９７
号）。A technique has been proposed (Japanese Patent Publication No. 62-033360) for enhancing the paper strength of impregnated base paper used for printed wiring boards and the like by utilizing the characteristics of such fine fibrillated cellulose. Further, by utilizing the fact that the aqueous suspension of fine fibrillated cellulose has an appropriate viscosity and good dispersibility, the strength of the paper can be improved by applying this aqueous suspension to the surface of the paper. And a technique for improving printability has been proposed (Japanese Patent Laid-Open No. 04-194097).
issue).
【０００４】微細フィブリル化セルロースは、製紙用パ
ルプ等のセルロース繊維に強力な機械的せん断力を与え
ることにより得られることは、従来から良く知られてお
り、その製造方法も数多く提案されている。例えば特公
昭６０−１９９２１号では、繊維状セルロースの懸濁液
を小径のオリフィスを通過させて、その懸濁液に少なく
とも３０００ｐｓｉの圧力差で高速度を与え、次にこれ
を衝突させて急速に減速させることにより切断作用を行
わせる工程と、この工程を繰返して前記セルロース懸濁
液が実質的に安定な懸濁液となるようにする工程とから
なる微小繊維状セルロースの製造方法を提案している。It is well known in the past that fine fibrillated cellulose can be obtained by applying a strong mechanical shearing force to cellulose fibers such as pulp for papermaking, and many manufacturing methods have been proposed. For example, in Japanese Examined Patent Publication No. 60-19921, a suspension of fibrous cellulose is passed through a small-diameter orifice to give the suspension a high velocity with a pressure difference of at least 3000 psi, which is then collided to rapidly. Proposed is a method for producing microfibrous cellulose, which comprises a step of performing a cutting action by decelerating and a step of repeating this step so that the cellulose suspension becomes a substantially stable suspension. ing.
【０００５】特開平４−８２９０７号では、乾燥状態で
天然セルロース繊維の短繊維を解砕させることによりフ
ィブリル化天然セルロースを製造する方法を提案してい
る。さらに特開平０６−１０２８６号では、ガラス、ア
ルミナ、ジルコニア、ジルコン、スチール、チタニア等
の材質のビーズまたはボールを粉砕媒体として用いた振
動ミル粉砕装置によって、繊維状セルロースの懸濁液に
湿式粉砕処理を施す微細繊維状セルロースの製造方法が
開示されている。Japanese Patent Laid-Open No. 4-82907 proposes a method for producing fibrillated natural cellulose by crushing short fibers of natural cellulose fiber in a dry state. Further, in Japanese Patent Laid-Open No. 06-10286, a suspension of fibrous cellulose is wet pulverized by a vibrating mill pulverizer using beads or balls made of glass, alumina, zirconia, zircon, steel, titania or the like as a pulverizing medium. A method for producing fine fibrous cellulose is disclosed.
【０００６】[0006]
【発明が解決しようとする課題】上記した特公昭６０−
１９９２１号で提案されている方法においては、パルプ
のような繊維状物質の懸濁液を高圧で小径オリフィスに
通過させる必要があり、固形分濃度が１重量％より高い
懸濁液を小径オリフィスに通過させるとオリフィスに詰
まりが発生する傾向があるため、処理する懸濁液の固形
分濃度は１重量％以下の低濃度としなければならず、処
理効率の点で問題がある。また処理後の固形分濃度の低
い懸濁液を濃縮して高濃度の微細フィブリル化セルロー
スを得るためには、濃縮作業に大きな労力が必要とな
る。このような処理効率および作業効率の悪さは、すべ
て製造される微細フィブリル化セルロースのコストに反
映するため、かような方法で製造されるコスト高の微細
フィブリル化セルロースは、紙のように安く大量に生産
される製品には利用できない。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
In the method proposed in No. 19921, it is necessary to pass a suspension of a fibrous substance such as pulp through a small diameter orifice under high pressure, and a suspension having a solid content concentration of more than 1% by weight is passed through the small diameter orifice. Since the orifice tends to be clogged when it is passed, the solid content concentration of the suspension to be treated must be a low concentration of 1% by weight or less, which causes a problem in treatment efficiency. Further, in order to concentrate the suspension having a low solid content concentration after the treatment to obtain a high concentration of fine fibrillated cellulose, a great labor is required for the concentration work. Such poor processing efficiency and work efficiency are reflected in the cost of all the fine fibrillated cellulose produced. Therefore, the high cost fine fibrillated cellulose produced by such a method is cheap and large like paper. Not available for products produced in.
【０００７】また上記した特開平４−８２９０７号で提
案されているような乾燥状態での微細化方法は、湿式で
微細化するのと異なりセルロース繊維のフィブリル化が
余り起こらないため、保水力の小さいフレーク状の微細
化セルロースしか得られない。Further, the method of micronizing in a dry state as proposed in Japanese Patent Laid-Open No. 4-82907 described above does not cause fibrillation of cellulose fibers unlike the micronization in a wet state. Only small flaky micronized cellulose is obtained.
【０００８】さらに特開平０６−１０２８６号で提案さ
れている振動ミル粉砕装置を用る湿式粉砕処理方法にお
いては、針葉樹材や非木材繊維のような長繊維を微細化
する場合には非常に長時間の処理が必要とされ、広葉樹
材のような短繊維の場合にも、調製された微細フィブリ
ル化セルロースが粘着性を有するため、粉砕媒体である
ビーズやボールからの分離が困難となり、処理効率の点
で問題がある。Further, in the wet pulverization treatment method using the vibration mill pulverizer proposed in Japanese Patent Laid-Open No. 06-10286, when the long fibers such as softwood and non-wood fibers are made fine, it is very long. It requires time treatment, and even in the case of short fibers such as hardwood, the prepared fine fibrillated cellulose has adhesiveness, which makes it difficult to separate it from the grinding media such as beads or balls, resulting in processing efficiency. There is a problem with.
【０００９】そこで本発明は、上述した従来技術におけ
る問題点を解消し、微細化処理に供するパルプスラリー
の固形分濃度を比較的高くした場合でも効率よく微細化
処理できるとともに、高い保水能力を有ししかも繊維長
分布も均一な微細フィブリル化セルロースが得られる、
新規かつ改良された微細フィブリル化セルロースの製造
方法を提供することを目的としてなされたものである。Therefore, the present invention solves the above-mentioned problems in the prior art and enables efficient fine refining treatment even when the solid concentration of the pulp slurry to be subjected to the fine refining treatment is relatively high, and has a high water retention capacity. Moreover, fine fibrillated cellulose having a uniform fiber length distribution can be obtained.
The object of the present invention is to provide a new and improved method for producing fine fibrillated cellulose.
【００１０】[0010]
【課題を解決するための手段】すなわち本発明による微
細フィブリル化セルロースの製造方法は、粒度が１６〜
１２０番の砥粒からなる砥粒板を複数枚擦り合わせ配置
した砥粒板擦り合せ装置を使用し、この装置の擦り合わ
せ部に、予め叩解処理したパルプスラリーを通過させて
パルプを微細化することにより、繊維の数平均繊維長が
０．０５〜０．３ｍｍ、保水値が２５０％以上、全本数
に対する積算本数の９５％以上が０．５ｍｍ以下の微細
フィブリル化セルロースを得ることを特徴とするもので
ある。That is, the method for producing fine fibrillated cellulose according to the present invention has a particle size of 16 to
An abrasive grain plate rubbing device in which a plurality of abrasive grain plates made of abrasive grains No. 120 are arranged by rubbing is used, and the pulp slurry that has been beaten in advance is passed through the rubbing portion of this device to refine the pulp. By this, the number average fiber length of the fibers is 0.05 to 0.3 mm, the water retention value is 250% or more, and 95% or more of the cumulative number of fibers to the total number is 0.5 mm or less. To do.
【００１１】本発明で使用するような砥粒板擦り合せ装
置を用いても、予め叩解処理を施していない長繊維のパ
ルプスラリーを砥粒板擦り合せ装置に導入して微細化処
理を行なった場合には、繊維の水保持性が悪いため、砥
粒板の擦り合わせ部で脱水が最初に起こり、排出される
微細化物は、導入されたパルプスラリーの濃度より非常
に薄くなってしまい、処理効率が悪くなる。しかしなが
ら、パルプスラリーに予め叩解処理を施した後に、砥粒
板擦り合せ装置に導入して微細化処理を施すことによ
り、パルプスラリーの固形分濃度を高い状態に維持しな
がら微細化処理を行なうことができるとともに、保水値
が高くしかも繊維長分布の均一な目的とする微細フィブ
リル化セルロースが能率的に比較的短時間で得られるの
である。Even if the abrasive plate rubbing apparatus used in the present invention is used, the long-fiber pulp slurry which has not been beaten in advance is introduced into the abrasive plate rubbing apparatus to carry out the refining treatment. In this case, since the water-retaining property of the fiber is poor, dehydration first occurs at the rubbing part of the abrasive plate, and the finely-divided product discharged becomes extremely thinner than the concentration of the pulp slurry introduced, It becomes less efficient. However, after the pulp slurry is subjected to a beating process in advance, the pulp slurry is introduced into an abrasive plate rubbing device and subjected to a refining process, thereby performing a refining process while maintaining a high solid content concentration of the pulp slurry. In addition, the desired fine fibrillated cellulose having a high water retention value and a uniform fiber length distribution can be efficiently obtained in a relatively short time.
【００１２】予備叩解処理における叩解の程度は、原料
として用いるパルプの種類によって２種類の叩解の程度
に分類できる。１つは、数平均繊維長が０．８ｍｍ以上
の長繊維のパルプであり、この場合にはフリーネスを４
００ｍｌＣＳＦ以下になるように予備叩解した後、砥粒
板擦り合せ装置へ導入する。このようなパルプとして
は、国産のエゾマツ、トドマツ、アカマツ、カラマツ
等、外国産のブラックスプルース、ホワイトスプルー
ス、ダグラスファー、ウェスターンヘムロック、サウザ
ーンパイン、ジャックパイン等に代表される針葉樹材か
ら機械的方法や化学的方法で繊維を抽出したものが含ま
れる。これ以外に、非木材繊維から抽出したパルプも含
まれる。非木材繊維としては、コットンパルプ、麻、バ
ガス、ケナフ、エスパルト、楮、三椏、雁皮等が代表的
なものである。また、レーヨン、テンセル、ポリノジッ
ク繊維などの再生セルロースも非木材繊維に含まれる。The degree of beating in the preliminary beating process can be classified into two types of beating depending on the type of pulp used as a raw material. One is pulp of long fibers having a number average fiber length of 0.8 mm or more, and in this case, the freeness is 4
After preliminarily beating so as to be less than 00 ml CSF, it is introduced into the abrasive plate rubbing device. As such pulp, domestically produced spruce, Todo pine, red pine, larch, etc., foreign black spruce, white spruce, Douglas fir, western hemlock, southern pine, jack pine, etc. Included are fibers extracted by chemical or chemical methods. In addition to this, pulp extracted from non-wood fibers is also included. Typical examples of non-wood fibers are cotton pulp, hemp, bagasse, kenaf, esparto, mulberry, san tsubaki, and goose bark. Regenerated cellulose such as rayon, tencel, and polynosic fiber are also included in the non-wood fiber.
【００１３】もう１つは、数平均繊維長が０．８ｍｍ未
満である短繊維のパルプであり、この場合にはフリーネ
スを６００ｍｌＣＳＦ以下になるように予備叩解する。
このようなパルプとしては、国産のドノノキ、シナノ
キ、セン、ポプラ、カバ等、外国産のアスペン、コット
ンウッド、ブラックウィロー、イエローポプラー、イエ
ローバーチ、ユーカリ等に代表される広葉樹材から機械
的方法や化学的方法で繊維を抽出したものが含まれる。
その他、非木材繊維の１部、再生セルロースで機械的方
法で繊維長を短くしたものが含まれる。The other is a short fiber pulp having a number average fiber length of less than 0.8 mm, and in this case, it is pre-beaten to have a freeness of 600 ml CSF or less.
Examples of such a pulp include a domestic hardwood, linden, linden, sen, poplar, hippopotamus, etc., aspen, cottonwood, black willow, yellow poplar, yellow birch, eucalyptus, etc. Fibers extracted by chemical methods are included.
In addition, a part of non-wood fibers, regenerated cellulose whose fiber length is shortened by a mechanical method are included.
【００１４】本発明において原料として使用できるパル
プは、その製造方法に制限はなく、あらゆる方法で得ら
れたパルプが使用できる。機械的方法で得られたパルプ
としては、ＧＰ、ＰＧＷ、ＲＧＰ、ＴＭＰ、ＣＴＭＰ、
ＳＣＰ、ＣＧＰ等、化学的方法で得られたパルプとして
はＫＰ、ＳＰ等が使用できる。また、アントラキノン蒸
解やアルカペール法、爆砕法、バイオメカニカルパルプ
化法、オルガノソルブパルプ化法、ハイドロトロピック
パルプ化法などの特殊なパルプ化法によって得られるパ
ルプも使用できる。The pulp which can be used as a raw material in the present invention is not limited in its production method, and pulp obtained by any method can be used. The pulp obtained by the mechanical method includes GP, PGW, RGP, TMP, CTMP,
KP, SP and the like can be used as pulp obtained by a chemical method such as SCP and CGP. In addition, pulp obtained by a special pulping method such as anthraquinone digestion, an alkapel method, an explosion method, a biomechanical pulping method, an organosolv pulping method, or a hydrotropic pulping method can also be used.
【００１５】前処理としての予備叩解を行なうに際して
は、製紙用で従来から慣用されている一般的な叩解機が
使用でき、例えば、ビーター、ジョルダン、コニカルリ
ファイナー、シングルディスクリファイナー、ダブルデ
ィスクリファイナー等のいずれの叩解機も使用できる。For pre-beating as a pretreatment, a general beater conventionally used for papermaking can be used. For example, beater, Jordan, conical refiner, single disc refiner, double disc refiner, etc. You can also use the beater.
【００１６】上記したごときパルプ叩解機の処理効率は
非常に高いため、かような叩解機を使用する予備叩解処
理においてはフリーネスをできるだけ小さくしておくこ
とが好ましく、長繊維パルプ、短繊維パルプいずれの場
合もフリーネスを２００ｍｌＣＳＦ以下にしておくこと
が好ましい。Since the processing efficiency of the pulp beating machine as described above is very high, it is preferable to keep the freeness as small as possible in the pre-beating processing using such a beating machine. For both long fiber pulp and short fiber pulp. Also in this case, the freeness is preferably 200 ml CSF or less.
【００１７】本発明で使用する砥粒板擦り合せ装置の一
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底部は摩砕室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１
１が摩砕室３のほぼ中央に配置されている。An example of the abrasive plate rubbing apparatus used in the present invention 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 notching 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 installed above the central opening 5 of the fixed abrasive plate 1, and the bottom 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. The support bar 10 extending upward from the sealing plate 7 of the rotary abrasive plate 2 causes the umbrella-shaped current plate 1 to move.
1 is arranged in the center of the grinding chamber 3.
【００１８】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。FIG. 3 is a view of the fixed abrasive plate 1 seen from the inner surface side. 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, and the rubbing portion is formed. The feed groove 12 is not formed in the flat surface 4a near the outer peripheral edge. The form and number of the feed grooves are not necessarily limited to those shown in the figure.
【００１９】この装置による微細化処理は以下のように
して行なわれる。予め叩解処理を施したパルプスラリー
をホッパー６へ供給すると（図２の矢印Ａ）、このパル
プ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の回転による遠心力と砕
室３内面の送り溝１２の作用によって砥粒板１，２の擦
り合せ部４へ送られ、ここで上下の砥粒板の擦り合せ作
用によってパルプの微細化がなされる。かくして生成さ
れた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）。流出する微細フィブリル化セルロースのスラリー
はホッパー６へ再循環し、所望の微細フィブリル化セル
ロースが得られるまで微細化処理を施こすことができ
る。The miniaturization process by this apparatus is performed as follows. When the pulp slurry that has been beaten in advance is supplied to the hopper 6 (arrow A in FIG. 2), the pulp slurry flows down, is dispersed radially by the straightening plate 11 and is uniformly supplied into the grinding chamber 3. . The pulp slurry in the grinding chamber 3 is sent to the rubbing section 4 of the abrasive plates 1 and 2 by the centrifugal force generated by the rotation of the rotary abrasive plate 2 and the action of the feed groove 12 on the inner surface of the grinding chamber 3, where it is moved up and down. The pulp is refined by the rubbing action of the abrasive grain plate. The slurry of finely 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 fine fibrillated cellulose that flows out can be recycled to the hopper 6 and subjected to a fine treatment until the desired fine fibrillated cellulose is obtained.
【００２０】砥粒板擦り合せ装置の砥粒板は、研磨材の
粒子である砥粒を結合材で固めて成形したものであり、
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
して多孔性の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 device is formed by solidifying abrasive grains, which are abrasive grains, with a binder.
As the material of the abrasive grains, those conventionally used, for example, natural products such as diamond, corundum, and emery,
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.
【００２１】特に本発明で用いる砥粒板擦り合せ装置の
砥粒板としては、砥粒の粒度がＪＩＳ Ｒ ６００１に
規定されている粒度で１６番〜１２０番のものを使用す
ることが必要である。本発明者らは、パルプスラリーの
微細化効果について粒度が５番から２４０番までの砥粒
を順次検討した結果、粒度が１６番より粗い砥粒の場合
は、微細化処理を長時間施しても所望の微細化、均一化
が進行せず、一方、粒度が１２０番より細かい砥粒の場
合には、砥粒板の擦り合せ部で詰まりが発生しやすくな
り微細化されたパルプ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１６番〜１２０番、
好ましくは２４番〜８０番とする。In particular, as the abrasive grain plate of the abrasive grain plate rubbing apparatus used in the present invention, it is necessary to use the abrasive grain plates having a grain size of 16 to 120 in accordance with JIS R 6001. is there. As a result of sequentially examining the abrasive grains having a grain size of No. 5 to No. 240 with respect to the refining effect of the pulp slurry, the inventors of the present invention have conducted the grain refining treatment for a long time in the case of abrasive grains having a grain size coarser than No. 16. Even if the desired fineness and homogenization do not proceed, on the other hand, when the grain size is finer than 120, clogging is likely to occur at the rubbed portion of the grain plate, and the finely divided pulp slurry is discharged. Turned out to be difficult. Therefore, the grain size of the abrasive grains is 16 to 120,
The number is preferably 24 to 80.
【００２２】砥粒板の擦り合せによるパルプの微細化が
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、砥粒板擦り合せ面にミクロな突出部が形成され非常
に凸凹であることが大きく関係している。かような砥粒
の突出部でパルプ繊維が強力なせん断力を受けることに
よって微細化が進行するのであるが、突出部が砥粒板擦
り合せ面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されるこ
とになる。このようなパルプ繊維の微細化機構であるか
ら、砥粒板が擦り合せ配置された装置であればどんな構
造のものでも使用でき、必ずしも図示したような装置に
限定されない。さらに砥粒板擦り合せ部にパルプスラリ
ーを供給する方式としても、図示したような構造以外に
も、遠心力、重力、圧送ポンプ等による種々の方式を採
用することができる。また砥粒板は２枚だけでなく３枚
以上の砥粒板を擦り合せ配置した装置でも使用できる。It is effective to make the pulp fine by rubbing the abrasive grain plates because the fine abrasive grains forming the abrasive grain plates form microscopic protrusions on the abrading surface of the abrasive grain plates, resulting in very unevenness. It has a lot to do with. The miniaturization proceeds by receiving a strong shearing force on the pulp fibers at the protrusions of such abrasive grains, but since the protrusions are present everywhere on the abrading surface of the abrasive grain plate, the cell walls of the pulp fibers are Each fibril will be efficiently divided. Since such a pulp fiber refining mechanism is used, any device having an abrasive grain plate arranged by rubbing can be used, and the device is not necessarily limited to that shown in the drawings. Further, as the method of supplying the pulp slurry to the abrading portion of the abrasive grain plate, various methods such as centrifugal force, gravity, a pressure pump, etc. can be adopted in addition to the structure shown in the drawing. Further, not only two abrasive grain plates but also an apparatus in which three or more abrasive grain plates are rubbed and arranged can be used.
【００２３】本発明においては、砥粒板擦り合せ装置に
供給するパルプスラリーの固形分濃度も微細化効率に影
響する。固形分濃度が高過ぎると砥粒板擦り合せ装置の
運転負荷がかかり過ぎ、砥粒板擦り合せ部をパルプが通
過しにくくなり、最終的には擦り合せ部で発生する熱に
よってパルプが焦げてしまう現象も生じるため好ましく
ない。本発明によれば、砥粒板擦り合せ装置に供給する
パルプスラリーは予め叩解処理を施してあるため、パル
プスラリーの固形分濃度を６重量％程度としても擦り合
せ部の通過は支障なくなされるが、４重量％前後の固形
分濃度が最適である。小径オリフィスを通過させる従来
の高圧ホモジナイザーを利用した微細化処理において
は、小径オリフィスを詰まらせないで通過させ得るパル
プスラリーの固形分濃度が１重量％程度であったのに比
べて、上記した本発明におけるパルプスラリー固形分濃
度はかなり高濃度であるということができ、その結果、
能率のよい微細化処理が可能となる。In the present invention, the solid content concentration of the pulp slurry fed to the abrasive plate rubbing device also affects the refining efficiency. If the solid content concentration is too high, the operating load of the abrasive plate rubbing device will be too high, and it will be difficult for the pulp to pass through the abrasive plate rubbing part, and eventually the heat generated in the rubbing part will burn the pulp. This is not preferable because a phenomenon that occurs occurs. According to the present invention, since the pulp slurry supplied to the abrasive plate rubbing device has been subjected to a beating process in advance, even if the solid concentration of the pulp slurry is set to about 6% by weight, passage through the rubbing portion is not hindered. However, a solid content concentration of around 4% by weight is optimum. In the refinement treatment using a conventional high-pressure homogenizer that passes through a small-diameter orifice, the solid content concentration of the pulp slurry that can be passed without blocking the small-diameter orifice is about 1% by weight. It can be said that the pulp slurry solids concentration in the invention is considerably high, and as a result,
A highly efficient miniaturization process is possible.
【００２４】本発明で規定している数平均繊維長は、Ｋ
ＡＪＡＡＮＩ社（フィンランド）製造の繊維長測定機
（ＦＳ−２００型）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。積算本数の割合は、同
様の繊維長分布測定機で測定して得たものである。通常
の紙の原料であるＬＢＫＰおよびＮＢＫＰは数平均繊維
長でそれぞれ０．５ｍｍおよび１ｍｍ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０．３５ｍｍ程度の長さであ
る。これに対し、本発明で製造される微細フィブリル化
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 specified in the present invention is K
Among the data measured by the fiber length measuring machine (FS-200 type) manufactured by AJANI (Finland), the total length of the fibers existing in a certain pulp suspension is integrated, and then the value is divided by the number. The ratio of the cumulative number is obtained by measuring with the same fiber length distribution measuring machine. LBKP and NBKP, which are the raw materials for ordinary paper, have number average fiber lengths of about 0.5 mm and 1 mm, respectively, and even fibrillated fibers generated by beating further have a number average fiber length of at least 0. The length is about 35 mm. On the other hand, the number average fiber length of the fine fibrillated cellulose produced in the present invention is 0.05 to 0.3 mm, which is extremely fine.
【００２５】また、保水値はパルプの膨潤度の指標であ
り、膨潤繊維中に取り込まれて保持された水分と繊維内
および繊維間に存在する自由水とを、適当な遠心力によ
り区別しうるという考えに基づき測定される値である。
本発明で規定している保水値も同様の概念に基づき、Ｊ
ＡＰＡＮ ＴＡＰＰＩ Ｎｏ．２６に指示されている方
法で測定した値である。すなわち、規定のフィルターに
一定量の試料のマットを予め形成しておき、遠心分離機
を用いて３０００Ｇの遠心力で１５分間脱水した後、保
持されていた水の量を絶乾パルプ量で割ったときの値を
示している。通常の未叩解のパルプでは９０％前後、叩
解したパルプでも２００％程度の保水値しか示さない。
これに対し、本発明で製造される微細フィブリル化セル
ロースの保水値は、２５０％以上であり、極めて高い保
水値を示すものである。The water retention value is an index of the degree of swelling of pulp, and the water retained in the swollen fibers and retained can be distinguished from the free water existing in and between the fibers by an appropriate centrifugal force. It is a value measured based on the idea.
The water retention value specified in the present invention is based on the same concept as J
APAN TAPPI No. 26 is a value measured by the method specified by No. 26. That is, a predetermined amount of a sample mat is formed in advance on a specified filter, and after dehydrating for 15 minutes with a centrifugal force of 3000 G using a centrifuge, the retained water amount is divided by the absolute dry pulp amount. It shows the value at the time. Normal unbeaten pulp shows a water retention value of about 90%, and beaten pulp shows a water retention value of about 200%.
On the other hand, the fine fibrillated cellulose produced by the present invention has a water retention value of 250% or more, which is an extremely high water retention value.
【００２６】本発明で叩解の程度を規定しているフリー
ネスは、ＪＩＳ Ｐ ８１２１で規格されているカナダ
標準型ろ水度試験器によって測定した値を示している。The freeness which defines the degree of beating in the present invention is a value measured by a Canadian standard freeness tester specified by JIS P8121.
【００２７】[0027]
【実施例】以下に実施例および比較例を挙げて本発明を
具体的に説明する。実施例および比較例に示した重量％
は、いずれも絶乾重量を基準とするものである。EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. Weight% shown in Examples and Comparative Examples
Are based on absolute dry weight.
【００２８】実施例１ フリーネス７２０ｍｌＣＳＦの未叩解のＮＢＫＰをリフ
ァイナーを用いてフリーネス３００ｍｌＣＳＦまで予め
叩解したＮＢＫＰパルプスラリー（固形分濃度４重量
％）を、図１〜図３に図示したような砥粒板擦り合せ装
置（商品名「スーパーグラインデル」、増幸産業（株）
製造。砥粒の粒度：４６番。回転砥粒板の回転数：１８
００ｒｐｍ。ホッパー容量：３０リットル）を用いて微
細化処理を施した。砥粒板擦り合せ部から排出される処
理済パルプスラリーは、連続的にホッパーへ再循環し、
微細化処理時間を合計３０分間として微細フィブリル化
セルロースを得た。得られた微細フィブリル化セルロー
スを、未叩解のＬＢＫＰに対して対パルプ重量で５％添
加し、常法により１００ｇ／ｍ2 の手抄シートを得た。 Example 1 NBKP pulp slurry (solid content concentration 4% by weight), in which unbroken NBKP having a freeness of 720 ml CSF was beaten in advance to a freeness of 300 ml CSF by using a refiner, an abrasive grain plate as shown in FIGS. Rubbing device (brand name "Super Grindel", Masuyuki Sangyo Co., Ltd.)
Manufacturing. Abrasive grain size: No. 46. Rotational speed of rotating abrasive plate: 18
00 rpm. The pulverization treatment was performed using a hopper capacity: 30 liters. The treated pulp slurry discharged from the abrasive plate rubbing section is continuously recirculated to the hopper,
Fine fibrillated cellulose was obtained with a total fine treatment time of 30 minutes. The fine fibrillated cellulose thus obtained was added to the unbeaten LBKP in an amount of 5% based on the weight of pulp, and a 100 g / m 2 hand-made sheet was obtained by a conventional method.
【００２９】実施例２ フリーネス１００ｍｌＣＳＦまで予め叩解したＮＢＫＰ
パルプスラリーを微細化処理した以外は、実施例１と同
様にして微細フィブリル化セルロースを製造し、さらに
この微細フィブリル化セルロースを含有した手抄シート
を製造した。 Example 2 Freeness NBKP beaten up to 100 ml CSF in advance
Fine fibrillated cellulose was produced in the same manner as in Example 1 except that the pulp slurry was subjected to a fine treatment, and a handmade sheet containing the fine fibrillated cellulose was produced.
【００３０】比較例１ フリーネス７２０ｍｌＣＳＦの未叩解のＮＢＫＰからな
るパルプスラリー（固形分濃度４重量％）を予備叩解せ
ずに砥粒板擦り合せ装置を用いて微細化処理した以外
は、実施例１と同様にして微細フィブリル化セルロース
を製造し、さらにこの微細フィブリル化セルロースを含
有した手抄シートを製造した。 Comparative Example 1 Example 1 was repeated except that the pulp slurry (solid concentration 4% by weight) made of unbeaten NBKP having a freeness of 720 ml CSF was refined by using an abrasive plate rubbing device without prebeating. Fine fibrillated cellulose was produced in the same manner as in, and a handmade sheet containing the fine fibrillated cellulose was further produced.
【００３１】実施例３ フリーネス６８０ｍｌＣＳＦの未叩解のＬＢＫＰをリフ
ァイナーを用いてフリーネス５００ｍｌＣＳＦまで予め
叩解したＬＢＫＰパルプスラリー（固形分濃度４重量
％）を、図１〜図３に図示したような砥粒板擦り合せ装
置（商品名「スーパーグラインデル」、増幸産業（株）
製造。砥粒の粒度：４６番。回転砥粒板の回転数：１８
００ｒｐｍ。ホッパー容量：３０リットル）を用いて微
細化処理を施した。砥粒板擦り合せ部から排出される処
理済パルプスラリーは、連続的にホッパーへ再循環し、
微細化処理時間を合計３０分間として微細フィブリル化
セルロースを得た。得られた微細フィブリル化セルロー
スを、未叩解のＬＢＫＰに対して対パルプ重量で５％添
加し、常法により１００ｇ／ｍ2 の手抄シートを得た。 Example 3 LBKP pulp slurry (solid content concentration 4% by weight) in which unrefined LBKP having a freeness of 680 ml CSF was beaten in advance to a freeness of 500 ml CSF by using a refiner, an abrasive grain plate as shown in FIGS. Rubbing device (brand name "Super Grindel", Masuyuki Sangyo Co., Ltd.)
Manufacturing. Abrasive grain size: No. 46. Rotational speed of rotating abrasive plate: 18
00 rpm. The pulverization treatment was performed using a hopper capacity: 30 liters. The treated pulp slurry discharged from the abrasive plate rubbing section is continuously recirculated to the hopper,
Fine fibrillated cellulose was obtained with a total fine treatment time of 30 minutes. The fine fibrillated cellulose thus obtained was added to the unbeaten LBKP in an amount of 5% based on the weight of pulp, and a 100 g / m 2 hand-made sheet was obtained by a conventional method.
【００３２】実施例４ フリーネス２００ｍｌＣＳＦまで予め叩解したＬＢＫＰ
パルプスラリーを微細化処理した以外は、実施例３と同
様にして微細フィブリル化セルロースを製造し、さらに
この微細フィブリル化セルロースを含有した手抄シート
を製造した。 Example 4 Freeness LBKP beaten to 200 ml CSF in advance
Fine fibrillated cellulose was produced in the same manner as in Example 3 except that the pulp slurry was subjected to a fine treatment, and further a handmade sheet containing the fine fibrillated cellulose was produced.
【００３３】比較例２ フリーネス６８０ｍｌＣＳＦの未叩解のＬＢＫＰからな
るパルプスラリー（固形分濃度４重量％）を予備叩解せ
ずに砥粒板擦り合せ装置を用いて微細化処理した以外
は、実施例３と同様にして微細フィブリル化セルロース
を製造し、さらにこの微細フィブリル化セルロースを含
有した手抄シートを製造した。 Comparative Example 2 Example 3 was repeated except that a pulp slurry (solid concentration 4% by weight) made of unbeaten LBKP having a freeness of 680 ml CSF was subjected to a fine treatment using an abrasive plate rubbing device without prebeating. Fine fibrillated cellulose was produced in the same manner as in, and a handmade sheet containing the fine fibrillated cellulose was further produced.
【００３４】上記の実施例および比較例で得られた微細
フィブリル化セルロースとこの微細フィブリル化セルロ
ースを含有した手抄シートの特性を測定した結果を表１
に示す。なお、手抄シートの物性はそれぞれ下記のＪＩ
Ｓに規定される方法により測定した。 坪量： ＪＩＳ Ｐ ８１２４ 厚みと密度：ＪＩＳ Ｐ ８１１８ 列断長： ＪＩＳ Ｐ ８１１３ 比破裂強さ：ＪＩＳ Ｐ ８１１２ 透気度： ＪＩＳ Ｐ ８１１７The results of measuring the characteristics of the fine fibrillated cellulose obtained in the above Examples and Comparative Examples and the handmade sheet containing this fine fibrillated cellulose are shown in Table 1.
Shown in. In addition, the physical properties of the handmade sheet are as follows.
It was measured by the method specified in S. Basis weight: JIS P 8124 Thickness and density: JIS P 8118 Row breaking length: JIS P 8113 Specific burst strength: JIS P 8112 Air permeability: JIS P 8117
【００３５】 [0035]
【００３６】表１からわかるように、砥粒板擦り合せ装
置による微細化処理に先立って予備叩解を施した場合に
は、同一処理時間で比較すると、予備叩解を施さない場
合に比べて、微細で保水値が高く、しかも繊維長分布の
均一な微細フィブリル化セルロースが得られている。ま
た、予備叩解を行なうことによって、微細化処理後の微
細フィブリル化セルローススラリーの固形分濃度は、微
細化処理に供するパルプスラリーの固形分濃度と同程度
の高い濃度の状態が維持できることから、効率よく微細
フィブリル化セルロースが得られることがわかる。As can be seen from Table 1, when pre-beating was performed prior to the refining treatment by the abrasive plate rubbing device, when compared at the same treatment time, it was finer than that without pre-beating. As a result, fine fibrillated cellulose having a high water retention value and a uniform fiber length distribution was obtained. Further, by performing the preliminary beating, the solid content concentration of the fine fibrillated cellulose slurry after the refining treatment, since it can be maintained in a state of high concentration as high as the solid concentration of the pulp slurry to be subjected to the refining treatment, efficiency It can be seen that fine fibrillated cellulose can be obtained well.
【００３７】さらに、微細フィブリル化セルロースを含
有するシートの特性も、予備叩解を施した後に微細化処
理して得られた微細フィブリル化セルロースを含有した
シートの方が、予備叩解せずに得られた微細フィブリル
化セルロースを含有したシートに比べて、引張り強さ、
破裂強さ、透気度でより大きな値を示すことがわかる。Further, regarding the characteristics of the sheet containing fine fibrillated cellulose, the sheet containing fine fibrillated cellulose obtained by subjecting it to a refinement treatment after pre-beating is obtained without pre-beating. Compared to the sheet containing fine fibrillated cellulose, tensile strength,
It can be seen that the burst strength and air permeability show larger values.
【００３８】またＮ材とＬ材のパルプ原料の相違は認め
られず、両方とも同様の結果が得られている。しかし、
Ｎ材に比べてＬ材の方が未叩解パルプの平均繊維長が短
いため、予備叩解の程度を５００ｍｌＣＳＦ（実施例
１）とあまり高くしなくても、砥粒板擦り合せ装置によ
る微細化処理を効率的に行なうことができる。No difference was found between the pulp raw materials of N material and L material, and the same results were obtained for both. But,
Since the average fiber length of the unbeaten pulp is shorter in the L material than in the N material, even if the degree of preliminary beating is not so high as 500 ml CSF (Example 1), it is possible to perform a finer treatment by the abrasive plate rubbing device. Can be done efficiently.
【００３９】[0039]
【発明の効果】以上説明したところからわかるように、
本発明よれば、予めパルプスラリーを予備叩解した後、
特定の粒度の砥粒板からなる砥粒板擦り合せ装置を用い
てパルプスラリーを微細化処理することによって、非常
に微細で保水値が高く、しかも繊維長分布の均一な微細
フィブリル化セルロースを得ることができる。As can be seen from the above description,
According to the present invention, after preliminarily beating the pulp slurry,
By finely treating the pulp slurry using an abrasive plate rubbing device consisting of abrasive particles of a specific particle size, it is possible to obtain very fine and highly water-retaining values, and even fine fibrillated cellulose with a uniform fiber length distribution. be able to.
【００４０】また、砥粒板擦り合せ装置に供給するパル
プスラリーは、予備叩解がされているため固形分濃度を
６重量％程度の比較的高い濃度としても、効果的な微細
化処理を行なうことができる。さらに、微細化処理後の
微細フィブリル化セルローススラリーの固形分濃度も、
砥粒板擦り合せ装置に供給するパルプスラリーの固形分
濃度と同程度の高い濃度が維持できるため、効率のよい
微細化処理が可能となる。Further, since the pulp slurry supplied to the abrasive plate rubbing device is pre-beaten, effective fine refining treatment should be carried out even if the solid content concentration is relatively high such as about 6% by weight. You can Furthermore, the solid content concentration of the fine fibrillated cellulose slurry after the fine processing is also
Since it is possible to maintain the concentration as high as the solid content concentration of the pulp slurry supplied to the abrasive grain plate rubbing device, it is possible to perform an efficient micronization treatment.
【００４１】さらに、微細フィブリル化セルロースを含
有するシートの特性も、予備叩解を施した後に微細化処
理して得られた微細フィブリル化セルロースを含有した
シートの方が、予備叩解せずに得られた微細フィブリル
化セルロースを含有したシートに比べて、引張り強さ、
破裂強さ、透気度でより大きな値を示すことがわかる。Further, regarding the characteristics of the sheet containing fine fibrillated cellulose, the sheet containing fine fibrillated cellulose obtained by subjecting it to a refinement treatment after pre-beating is obtained without pre-beating. Compared to the sheet containing fine fibrillated cellulose, tensile strength,
It can be seen that the burst strength and air permeability show larger values.
【００４２】本発明により得られる非常に微細で保水値
が高く繊維長分布も均一な微細フィブリル化セルロース
は、例えば製紙用パルプに添加して抄紙した場合には、
紙中に均一に保持され、母体となるパルプのネットワー
クで形成される穴の部分でミクロなネットワークを形成
するため、紙力の増強や透気度の増加をもたらすことが
できる。The fine fibrillated cellulose obtained according to the present invention, which is very fine and has a high water retention value and a uniform fiber length distribution, is added to, for example, pulp for papermaking to produce paper.
Since it is held uniformly in the paper and a micro network is formed in the hole portion formed by the network of pulp as the matrix, it is possible to enhance the paper strength and increase the air permeability.
【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)
粒板を複数枚擦り合わせ配置した砥粒板擦り合せ装置を
使用し、この装置の擦り合せ部に、予め叩解処理したパ
ルプスラリーを通過させてパルプを微細化することによ
り、繊維の数平均繊維長が０．０５〜０．３ｍｍ、保水
値が２５０％以上、全本数に対する積算本数の９５％以
上が０．５ｍｍ以下の微細フィブリル化セルロースを得
ることを特徴とする微細フィブリル化セルロースの製造
方法。1. A pulp slurry, which is preliminarily beaten at a rubbing portion of an abrasive grain plate rubbing device in which a plurality of abrasive grain plates made of abrasive grains having a grain size of 16 to 120 are rubbed and arranged. The number average fiber length of the fibers is 0.05 to 0.3 mm, the water retention value is 250% or more, and 95% or more of the total number of fibers is 0.5 mm or less by finely dividing the pulp by passing through A method for producing fine fibrillated cellulose, which comprises obtaining fibrillated cellulose.
長が０．８ｍｍ以上であるパルプのフリーネスを４００
ｍｌＣＳＦ以下になるように予め叩解処理したパルプス
ラリーを使用することを特徴とする請求項１記載の微細
フィブリル化セルロースの製造方法。2. The pulp slurry having a number average fiber length of 0.8 mm or more has a freeness of 400 as the pulp slurry.
The method for producing finely fibrillated cellulose according to claim 1, wherein a pulp slurry that has been beaten in advance so as to have a mlCSF or less is used.
長が０．８ｍｍ未満であるパルプのフリーネスを６００
ｍｌＣＳＦ以下になるように予め叩解処理したパルプス
ラリーを使用することを特徴とする請求項１記載の微細
フィブリル化セルロースの製造方法。3. The pulp slurry having a number average fiber length of less than 0.8 mm has a freeness of 600 as the pulp slurry.
The method for producing finely fibrillated cellulose according to claim 1, wherein a pulp slurry that has been beaten in advance so as to have a mlCSF or less is used.
通過させるパルプスラリーの固形分濃度を６重量％以下
とすることを特徴とする請求項１、２または３記載の微
細フィブリル化セルロースの製造方法。4. The fine fibrillated cellulose according to claim 1, wherein the solid content concentration of the pulp slurry to be passed through the rubbing section of the abrasive plate rubbing device is 6% by weight or less. Manufacturing method.
粒板と回転砥粒板とを上下に擦り合せ配置した装置を使
用すること特徴とする請求項１、２、３または４記載の
微細フィブリル化セルロースの製造方法。5. An apparatus in which a fixed abrasive plate and a rotary abrasive plate are rubbed and arranged in a vertical direction is used as the abrasive plate abrading device, according to claim 1, 2, 3 or 4. A method for producing fine fibrillated cellulose.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6102755A JP3036354B2 (en) | 1994-05-17 | 1994-05-17 | Method for producing fine fibrillated cellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6102755A JP3036354B2 (en) | 1994-05-17 | 1994-05-17 | Method for producing fine fibrillated cellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07310296A true JPH07310296A (en) | 1995-11-28 |
| JP3036354B2 JP3036354B2 (en) | 2000-04-24 |
Family
ID=14336028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6102755A Expired - Lifetime JP3036354B2 (en) | 1994-05-17 | 1994-05-17 | Method for producing fine fibrillated cellulose |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3036354B2 (en) |
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| JP2000017592A (en) * | 1998-06-23 | 2000-01-18 | Daicel Chem Ind Ltd | Fibrillar cellulose and its production |
| US6183596B1 (en) | 1995-04-07 | 2001-02-06 | Tokushu Paper Mfg. Co., Ltd. | Super microfibrillated cellulose, process for producing the same, and coated paper and tinted paper using the same |
| CN1075514C (en) * | 1997-10-13 | 2001-11-28 | 徐旗开 | Method for producing microcrystalline cellulose by sulfating waste cotton velvet |
| WO2004009902A1 (en) * | 2002-07-18 | 2004-01-29 | Japan Absorbent Technology Institute | Method and apparatus for producing microfibrillated cellulose |
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| JP2008544112A (en) * | 2005-06-28 | 2008-12-04 | アクゾ ノーベル エヌ．ブイ． | Method for preparing microfibrillar polysaccharide |
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