JPH09216950A - Transparent plate material made of cellulose and its production - Google Patents
Transparent plate material made of cellulose and its productionInfo
- Publication number
- JPH09216950A JPH09216950A JP5991096A JP5991096A JPH09216950A JP H09216950 A JPH09216950 A JP H09216950A JP 5991096 A JP5991096 A JP 5991096A JP 5991096 A JP5991096 A JP 5991096A JP H09216950 A JPH09216950 A JP H09216950A
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- fine particles
- pressure
- microparticles
- transparent plate
- 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.)
- Pending
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はセルロースからなる透明
板状素材、及びその製造法を提供するものである。この
透明板状素材は化学修飾していないセルロース微粒子を
原料とし、微粒子内部及び微粒子間での光の乱反射が起
こらないほど十分な結合を生じさせることによって得ら
れる。本透明板状素材はセルロース微粒子から、特殊な
溶剤等を用いることなく、ホットプレス等の簡単な手段
によって製造でき、また、セルロースは古紙等の状態で
多量に存在しているため、工業的に大量生産が可能であ
り、セルロースからの新規なプラスチック素材として種
々の産業分野で利用できる。FIELD OF THE INVENTION The present invention provides a transparent plate material made of cellulose and a method for producing the same. This transparent plate-shaped material is obtained by using cellulose fine particles that have not been chemically modified as a raw material, and by forming a sufficient bond so that diffuse reflection of light does not occur inside and between the fine particles. This transparent plate-shaped material can be produced from cellulose fine particles by a simple means such as hot pressing without using a special solvent or the like, and since cellulose is present in a large amount in the state of waste paper, it is industrially used. It can be mass-produced and can be used in various industrial fields as a new plastic material made of cellulose.
【０００２】[0002]
【従来の技術】天然及び再生セルロースは本質的に熱可
塑性が無く、合成高分子のように融解して繊維やフィル
ム、板等を製造することは不可能である。そのため直接
に原料として用いて製造することができるものとして
は、紙等に限定されていた。2. Description of the Related Art Natural and regenerated cellulose are essentially non-thermoplastic, and it is impossible to produce fibers, films, plates and the like by melting like synthetic polymers. Therefore, the materials that can be directly used as raw materials have been limited to paper and the like.
【０００３】セルロースに熱可塑性を付与するために、
ニトロセルロースやアセチルセルロースなどのように化
学修飾等によって誘導体化し、繊維やフィルム、板等が
製造されているが、化学修飾によってセルロースは全く
別の物質になっており、セルロースが本来持っている生
分解性などの特性は大きく低下あるいは失なわれてい
る。In order to impart thermoplasticity to cellulose,
Fibers, films, boards, etc. are manufactured by derivatization such as nitrocellulose and acetylcellulose by chemical modification, etc., but the chemical modification makes cellulose a completely different substance, and it is a raw material that cellulose originally possesses. Properties such as degradability have been greatly reduced or lost.
【０００４】セルロースを溶解して繊維やフィルム等を
製造する方法では、セルロースが一般的溶剤には溶けに
くいため、溶剤は特殊なものに限定されている。その特
殊溶剤であるアミン−二硫化炭素、銅アンモニア、アミ
ンオキシド等に溶解して湿式凝固させることにより再生
セルロース繊維やフィルムを製造することはよく知られ
ている技術である。しかし、溶解することなく固体状態
で、透明性を有する板状素材を得ることは、従来、不可
能な技術であった。In the method of dissolving cellulose to produce fibers, films, etc., it is difficult for cellulose to be dissolved in a general solvent, so that the solvent is limited to a special solvent. It is a well-known technique to manufacture regenerated cellulose fibers and films by dissolving them in a special solvent such as amine-carbon disulfide, copper ammonia, amine oxide and wet coagulating. However, it has heretofore been impossible to obtain a transparent plate-like material in a solid state without being dissolved.
【０００５】[0005]
【発明が解決しようとする課題】上記のように溶解する
ことなく透明性を有するセルロース板を得る手段は今ま
でになかった。セルロースを溶剤で溶解して成型する方
法では、セロハンやレーヨンに代表されるような再生セ
ルロースのフイルムや繊維しか得られず、しかも厚い板
状の素材を得ることはできなかった。また、セルロース
を化学修飾して熱可塑性物質にして透明性を有する厚板
を得る方法はあるが、原料はセルロースとは別の物質に
なっており、セルロースが本来持っている生分解性など
の特性は失われている。そこで、透明性を有する木板と
でも言える新規な成形板を、いかにしてセルロースを溶
解することなく、また、化学修飾することなく、直接的
に得るかが本発明の課題であった。As described above, there has been no means for obtaining a transparent cellulose plate without melting as described above. The method of dissolving and molding cellulose in a solvent can only obtain a regenerated cellulose film or fiber typified by cellophane or rayon, and cannot obtain a thick plate-shaped material. There is also a method of chemically modifying cellulose to form a thermoplastic slab that has transparency, but the raw material is a different substance from cellulose, and the biodegradability inherent in cellulose is The property is lost. Therefore, it was an object of the present invention to directly obtain a new molded plate which can be called a transparent wooden plate without dissolving cellulose and without chemically modifying it.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、微粒子化した
セルロースの吸着水分量を適切に調整し、適切にホット
プレスで加熱加圧すれば、セルロース微粒子内及び微粒
子間に結合が生じ、透明性を有するセルロースの板が得
られることを見いだし、この知見に基づいて本発明を完
成するに至った。Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have appropriately adjusted the adsorbed water content of finely divided cellulose and heated it with a hot press. It was found that when pressure is applied, bonds are formed within and between the cellulose fine particles, and a transparent cellulose plate is obtained, and the present invention has been completed based on this finding.
【０００７】すなわち、本発明では、透明性を有するセ
ルロース板を得るために、セルロース微粒子内及び微粒
子間に、いかに多くの化学結合を生じさせることができ
るかということが重要である。セルロースに不可逆の化
学変化を起こさせず、セルロース本来の特性を失うこと
なくセルロース分子鎖間に生じさせ得る化学結合として
は、水素結合が最適のものである。ファンデルワールス
分子間力の利用も考えられるが、これは分子間の相互作
用が小さく、また安定性も低い。水素結合であれば結合
力も強く、また結合が破壊されても、元の状態のセルロ
ースに戻るだけである。That is, in the present invention, in order to obtain a transparent cellulose plate, it is important how many chemical bonds can be generated in and between the cellulose fine particles. Hydrogen bond is the most suitable chemical bond that can be generated between cellulose molecular chains without causing irreversible chemical change in cellulose and without losing the original properties of cellulose. The use of van der Waals intermolecular forces is also conceivable, but they have low intermolecular interactions and low stability. If it is a hydrogen bond, it has a strong bonding force, and even if the bond is broken, it only returns to the original state of cellulose.
【０００８】この水素結合の形成により透明性を有する
板状素材を得るためには、セルロース分子鎖同士が十分
に接近し、両分子鎖の水酸基に互いに水素結合を形成さ
せ、さらに、その結合は、分子鎖間の接近が保持できる
よう多量に生じていることが必要条件である。このよう
な条件を満足させるためには、セルロース分子鎖が十分
に接近できるよう、加圧し、原料セルロースも密着しや
すい形状であることが重要である。また、水素結合の形
成を促進するために微量の水分と加熱も必要となる。In order to obtain a transparent plate-like material by the formation of this hydrogen bond, the cellulose molecular chains are sufficiently close to each other to form a hydrogen bond with the hydroxyl groups of both molecular chains. , It is a necessary condition that a large amount is generated so that the closeness between the molecular chains can be maintained. In order to satisfy such a condition, it is important that the raw material cellulose is in a shape in which pressure is applied so that the cellulose molecular chains are sufficiently close to each other and the raw material cellulose is easily adhered. Also, a small amount of water and heating are required to promote the formation of hydrogen bonds.
【０００９】本発明者らは、既に特許出願した方法（出
願番号：特開平７−４１５０２）等を用いてセルロース
を微粉砕することによって得られた、平均粒径２０ミク
ロン以下、結晶化度０〜２０％のセルロース微粒子の吸
着水分量を３〜６重量％の範囲に調節して、１００〜１
８０℃の温度、５００〜３０００キログラム／平方セン
チメートルの圧力、で加熱加圧することにより、上記の
条件を満たして透明性を有する板状成形物が得られるこ
とを初めて見いだした。セルロースに関して、このよう
な透明性を有する板状成形物はいまだかつて得られてい
ない。The present inventors have obtained an average particle size of 20 μm or less and a crystallinity of 0 by finely pulverizing cellulose using the method already filed for patent (application number: JP-A-7-41502). The amount of adsorbed water of cellulose fine particles of ˜20% is adjusted to the range of 3 to 6% by weight, and 100 to 1
It was found for the first time that a transparent plate-shaped molded product was obtained that satisfied the above-mentioned conditions by heating and pressurizing at a temperature of 80 ° C. and a pressure of 500 to 3000 kg / square centimeter. With regard to cellulose, plate-like moldings having such transparency have never been obtained.
【０００１０】なお、当該発明において請求項２はセル
ロース微粒子の吸着水分量を適切に調製し、加熱加圧す
ることによって水素結合を形成させ、これにより請求項
１の透明性を有する新規なセルロース板を生産できるこ
とを基本としているが、セルロースに水分と共に生産を
容易にするために水分以外にも添加剤等を加えることを
否定しているものではない。According to a second aspect of the present invention, the adsorbed water content of the cellulose fine particles is appropriately adjusted, and a hydrogen bond is formed by heating and pressurizing, whereby the novel cellulose plate having transparency according to the first aspect is obtained. Although it is based on the fact that it can be produced, it does not mean that addition of an additive other than water to cellulose is added to facilitate production together with water.
【０００１１】[00011]
【発明の効果】本発明による透明性を有するセルロース
板及び製造法は、天然高分子からの新しいプラスチック
素材、及びプラスチック化技術として発展する可能性が
あり、これまで、主に再生紙等にしか再利用されていな
かった古紙からの新規プラスチック素材の製造や、これ
まで材料化が困難であった物質からの新規素材の製造な
ど広範囲な産業分野での利用が期待できる。INDUSTRIAL APPLICABILITY The transparent cellulose plate and the method for producing the same according to the present invention have the possibility of developing as a new plastic material from a natural polymer and a plasticization technique, and so far, it has been mainly used only for recycled paper and the like. It can be expected to be used in a wide range of industrial fields such as the production of new plastic materials from recycled paper that has not been reused, and the production of new materials from substances that have been difficult to materialize.
【００１２】[0012]
【実施例】次に、実施例により本発明をさらに詳細に説
明するが、本発明はこれらの例によってなんら限定され
るものではない。The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.
【００１３】実施例１ セルロース原料として綿花リンター由来の高純度セルロ
ース繊維を、振動ボールミルをもちいて乾式微粉砕し、
平均粒径２０ミクロン以下、結晶化度０〜２０％のセル
ロース微粒子を得た。この微粒子の吸着水分量を１〜１
５重量％に調節し、この水分量調節試料を直径５センチ
メートルの円形金型に詰め、ホットプレスを用いて１５
０℃の温度をかけながら５分間プレスを行った。プレス
圧力は試料単位面積に対して５００キログラム／平方セ
ンチメートルとした。その結果、吸着水分量３〜６重量
％付近の試料において、得られたセルロース成形物は透
明性を有していた。Example 1 High-purity cellulose fibers derived from cotton linter as a cellulose raw material were dry finely pulverized by using a vibrating ball mill,
Cellulose fine particles having an average particle size of 20 microns or less and a crystallinity of 0 to 20% were obtained. The amount of adsorbed water of the fine particles is 1 to 1
After adjusting to 5% by weight, the water content adjusting sample was packed in a circular mold having a diameter of 5 cm, and hot-pressed for 15 minutes.
Pressing was carried out for 5 minutes while applying a temperature of 0 ° C. The pressing pressure was 500 kilograms / square centimeter per unit area of the sample. As a result, in the sample having an adsorbed water content of about 3 to 6% by weight, the obtained cellulose molded product had transparency.
【００１４】表−１に得られたセルロース成形物の性状
について示す。吸着水分量１重量％では、成形物は簡単
に元の微粒子に崩れ、微粒子内及び間にほとんど結合は
生じていなかった。また、１０重量％では粒子には崩れ
ず、微粒子内及び間に形成された水素結合によって形状
は保っていたが、逆に加水分解等が進行して、透明には
ならず褐色になった。１５重量％では更に褐色になり収
縮等によるひび割れが発生し形状を保つことができる成
形物は得られなかった。吸着水分量が３〜６重量％付近
の場合においてのみ、加水分解等があまり起こらず、微
粒子内及び間に水素結合が形成され、透明性を有するセ
ルロース成形物が得られた。これらの結果は、水素結合
形成により透明性セルロース成形物を得るためには適切
な吸着水分量に調節することが重要であることを示して
いる。Table 1 shows the properties of the obtained cellulose molded product. When the amount of adsorbed water was 1% by weight, the molded product easily collapsed into the original fine particles, and almost no binding occurred in or between the fine particles. Further, at 10% by weight, the particles did not disintegrate and the shape was maintained by the hydrogen bonds formed in and between the particles, but conversely hydrolysis proceeded, and the particles did not become transparent but turned brown. When the content was 15% by weight, the product was further browned and cracked due to shrinkage and the like, and a molded product capable of maintaining its shape was not obtained. Only when the amount of adsorbed water was about 3 to 6% by weight, hydrolysis and the like did not occur so much, hydrogen bonds were formed in and between the fine particles, and a transparent cellulose molded product was obtained. These results indicate that it is important to adjust the amount of adsorbed water appropriately in order to obtain a transparent cellulose molded product by hydrogen bond formation.
【表−１】 [Table-1]
【００１５】実施例２ 成形原料として実施例１と同じセルロース微粒子を用い
て、吸着水分量を５重量％に調節し、圧力は５００キロ
グラム／平方センチメートルとして、温度が２５〜２０
０℃の範囲で、５分間ホットプレス成形を行った。表−
２に得られたセルロース成形物の性状について示す。１
８０℃を超えると、加水分解等が進行して褐色になり、
ひび割れが生じた。特に吸着水分量が多い場合にはその
程度は大きくなった。一方、１００℃より低い温度で
は、吸着水分量によらず、白色のままで、微粒子内及び
間に結合が十分に形成されずに、元の粒子に崩れやす
く、透明にもならなかった。Example 2 The same cellulose fine particles as in Example 1 were used as a molding raw material, the adsorbed water content was adjusted to 5% by weight, the pressure was 500 kg / cm 2, and the temperature was 25 to 20.
Hot press molding was performed for 5 minutes in the range of 0 ° C. Table-
2 shows the properties of the obtained cellulose molded product. 1
If it exceeds 80 ° C, hydrolysis etc. will progress and turn brown,
A crack occurred. Especially when the amount of adsorbed water was large, the degree became large. On the other hand, at a temperature lower than 100 ° C., regardless of the amount of adsorbed water, it remained white, bonds were not sufficiently formed in and between the fine particles, and the particles were apt to collapse into the original particles and did not become transparent.
【表−２】 [Table-2]
【００１６】実施例３ 成型原料として実施例１と同じセルロース微粒子を用い
て、吸着水分量を５重量％に調節し、温度は１５０℃と
して、圧力が１００〜３０００キログラム／平方センチ
メートルの範囲で、５分間ホットプレス成形を行った。
表−３に得られたセルロース成形物の性状について示
す。圧力が低くなるにつれて透明度は低下し、３００キ
ログラム／平方センチメートルでは成形物の一部分しか
透明に成らなかった。更に、圧力が１００キログラム／
平方センチメートルになると、全体的に白色のままで、
微粒子内及び間に結合が十分に形成されず、元の粒子に
崩れやすく、透明にもならなかった。Example 3 The same cellulose fine particles as in Example 1 were used as a molding raw material, the adsorbed water content was adjusted to 5% by weight, the temperature was 150 ° C., and the pressure was 100 to 3000 kg / cm 2. Hot press molding was performed for a minute.
Table 3 shows the properties of the obtained cellulose molded product. The transparency decreased as the pressure decreased, and at 300 kg / cm 2, only a part of the molded product was transparent. Furthermore, the pressure is 100 kg /
When it comes to square centimeters, it remains white overall,
Bonds were not sufficiently formed in and between the fine particles, and the original particles were easily broken, and the particles did not become transparent.
【表−３】 [Table-3]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ２９Ｌ 7:00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical display location B29L 7:00
Claims (2)
有する板状素材。1. A transparent plate-like material made of cellulose fine particles as a raw material.
て得られた、平均粒径２０ミクロン以下、結晶化度０〜
２０％のセルロース微粒子の吸着水分量を３〜６重量％
の範囲に調節し、５００〜３０００キログラム／平方セ
ンチメートルの圧力、１００〜１８０℃の温度で加熱加
圧することによって得られる透明性を有する板状素材の
製造法。2. An average particle size of 20 μm or less and a crystallinity of 0 to 0 obtained by finely pulverizing natural cellulose.
Adsorbed water content of 20% cellulose fine particles is 3 to 6% by weight
And a pressure of 500 to 3000 kilograms / square centimeter and heating and pressurization at a temperature of 100 to 180 ° C. to obtain a transparent plate material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5991096A JPH09216950A (en) | 1996-02-09 | 1996-02-09 | Transparent plate material made of cellulose and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5991096A JPH09216950A (en) | 1996-02-09 | 1996-02-09 | Transparent plate material made of cellulose and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09216950A true JPH09216950A (en) | 1997-08-19 |
Family
ID=13126760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5991096A Pending JPH09216950A (en) | 1996-02-09 | 1996-02-09 | Transparent plate material made of cellulose and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09216950A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011153296A (en) * | 2009-12-28 | 2011-08-11 | Kao Corp | Biodegradable resin composition |
| JP2019023279A (en) * | 2017-07-21 | 2019-02-14 | 花王株式会社 | Asphalt composition, method for producing same and additive for asphalt |
-
1996
- 1996-02-09 JP JP5991096A patent/JPH09216950A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011153296A (en) * | 2009-12-28 | 2011-08-11 | Kao Corp | Biodegradable resin composition |
| JP2019023279A (en) * | 2017-07-21 | 2019-02-14 | 花王株式会社 | Asphalt composition, method for producing same and additive for asphalt |
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