JPH09255702A - Solvent composition for dissolving cellulose - Google Patents
Solvent composition for dissolving celluloseInfo
- Publication number
- JPH09255702A JPH09255702A JP6982796A JP6982796A JPH09255702A JP H09255702 A JPH09255702 A JP H09255702A JP 6982796 A JP6982796 A JP 6982796A JP 6982796 A JP6982796 A JP 6982796A JP H09255702 A JPH09255702 A JP H09255702A
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- solution
- dissolved
- polymerization
- naoh
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 239000002904 solvent Substances 0.000 title claims abstract description 17
- 229920000875 Dissolving pulp Polymers 0.000 title claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 62
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 32
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001868 water Inorganic materials 0.000 claims abstract description 22
- 239000011787 zinc oxide Substances 0.000 claims abstract description 16
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 abstract description 50
- 235000010980 cellulose Nutrition 0.000 abstract description 50
- 239000001913 cellulose Substances 0.000 abstract description 45
- 238000006116 polymerization reaction Methods 0.000 abstract description 24
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- 235000011121 sodium hydroxide Nutrition 0.000 description 17
- 238000004090 dissolution Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 238000001879 gelation Methods 0.000 description 8
- 239000000499 gel Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 229920001131 Pulp (paper) Polymers 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000004627 regenerated cellulose Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- ZURAKLKIKYCUJU-UHFFFAOYSA-N copper;azane Chemical compound N.[Cu+2] ZURAKLKIKYCUJU-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- KXXATCIIUIYGSY-UHFFFAOYSA-L tetraazanium copper hexahydroxide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[OH-].[Cu+2].[OH-].[OH-].[OH-].[OH-].[OH-] KXXATCIIUIYGSY-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、繊維やフィルムの
成形、コーティングに適したセルロース溶液を調製する
ためのセルロース溶解用溶媒組成物に関する。TECHNICAL FIELD The present invention relates to a solvent composition for dissolving cellulose for preparing a cellulose solution suitable for molding and coating fibers and films.
【０００２】[0002]
【従来技術】現在、工業的、かつ、実用的に利用されて
いるセルロースの溶媒あるいは溶解技術は、セルロース
にＮａＯＨを作用させた後二硫化炭素を反応せしめ、そ
の後ＮａＯＨ水溶液に溶解させるビスコース法、水酸化
銅テトラアンモニウムのアンモニア水溶液を溶媒とする
銅安法、ＮーメチルモルホリンＮーオキサイドを溶媒と
する有機溶媒法の３つである。しかしながら、セルロー
スの溶媒としては、ポリマーハンドブック（ｐｏｌｙｍ
ｅｒ ｈａｎｄｂｏｏｋ、３ｒｄ．ｅｄｉｔ．，ｗｉｌ
ｅｙ ｉｎｔｅｒｓｃｉｅｎｃｅ社）の第５章１３０頁
〜１３９頁に記載されているように、鉱酸系、無機塩
系、強塩基系、４級アンモニウム塩系、金属錯体系、非
水系/有機溶媒系など数多くの溶媒が知られている。本
発明に関係する強塩基系に関して、古くはＪｏｕｒｎａ
ｌ ｏｆ Ｐｒａｋｔ．Ｃｈｅｍ．，Ｎ．Ｆ．，１５
８，２３３（１９４１）に、天然セルロース、マーセル
化セルロース、再沈澱させたセルロースの１０重量％苛
性ソーダ水溶液に対する溶解性が示されている。これに
よると天然、マーセル化セルロースは重合度（ＤＰ）４
００迄、再沈殿させたセルロースは重合度１２００まで
可溶とされている。しかしながら、これらの事実にはか
なりの任意性が含まれるし、また可溶性とは言っても高
度に膨潤したゲルをも含めていたと予想される。また、
溶解したとしても極めて低濃度（１重量％以下）でしか
溶解していないものであり、工業的に利用できるもので
はない。これらの点は、アルカリがセルロースのラテラ
ルオーダー毎の分別溶解に用いられてきた事実、たとえ
ば、”高分子物質の精製と化学反応”ｐ１２８〜１３２
（高分子学会編、昭和３３年、共立出版）からも知るこ
とができる。更に、溶解してもすぐゲル化する溶液であ
ったことも示されている。2. Description of the Related Art At present, a solvent or dissolution technology for cellulose which is industrially and practically used is a viscose method in which after reacting cellulose with NaOH, carbon disulfide is reacted and then dissolved in an aqueous NaOH solution. A copper ammonium method using an aqueous solution of copper tetraammonium hydroxide as a solvent, and an organic solvent method using N-methylmorpholine N-oxide as a solvent. However, as a solvent for cellulose, a polymer handbook (polym
er handbook, 3rd. edit. , Will
ey interscience), Chapter 5, pp. 130-139, mineral acid-based, inorganic salt-based, strong base-based, quaternary ammonium salt-based, metal complex-based, non-aqueous / organic solvent-based, etc. Many solvents are known. Regarding the strong base system related to the present invention, Journa has long been used.
l of Prakt. Chem. , N .; F. , 15
8, 233 (1941) shows the solubility of natural cellulose, mercerized cellulose and reprecipitated cellulose in a 10 wt% aqueous sodium hydroxide solution. According to this, the degree of polymerization (DP) of natural and mercerized cellulose is 4
Up to 00, the reprecipitated cellulose is said to be soluble up to a polymerization degree of 1200. However, these facts contain considerable arbitrariness and are expected to have included highly swollen gels, albeit soluble. Also,
Even if it is dissolved, it is dissolved only at an extremely low concentration (1% by weight or less) and is not industrially applicable. These points are due to the fact that alkali has been used for the fractional dissolution of cellulose in each lateral order, for example, "Purification and Chemical Reaction of Polymer" p128-132.
You can also learn from (Kyoritsu Shuppan, 1933, edited by the Society of Polymer Science). Further, it is also shown that the solution was a gel that immediately dissolves.
【０００３】これらは、セルロースをアルカリに溶解し
て、これを工業的に利用することが、経済的にも、か
つ、技術的にも不可能であったことを示唆する。事実、
長いセルロース工業の歴史上、かかるセルロース/アル
カリ溶液が成型用ドープとして利用されたケースは殆ど
無い。最近になって、環境に優しいプロセスが期待され
るようになり、セルロースを安価でシンプルなアルカリ
に溶解させて利用しようとする試みが成されるようにな
った。たとえば、特開昭６０−４２４３８号公報や特開
昭６１−１３０３５３号公報には、アルカリ水溶液にセ
ルロースを３重量％以上溶解させたところの成形に適し
たドープが開示されている。また、特開昭６０−１３９
８７３号公報には、高分子材料を改質する目的で上記セ
ルロースのアルカリドープをコーティング材料に応用し
た例が開示されている。さらに、本発明者らは、特開平
５−１４０３３２号公報と特開平５−１４０３３３号公
報において、セルロースのアルカリドープから具体的に
セルロース成型品を作る方法を開示している。それによ
ると重合度にもよるが、重合度３４０で実用的なセルロ
ース濃度は５重量％であり、銅安法(１０重量％)やビス
コース法(８重量％)に較べると、経済的には必ずしも高
い方法とは言えない。また、本発明者らの知る限り、重
合度の高いセルロースを溶解しようとするとセルロース
濃度をさらに低くしなければならないし、高濃度に溶解
しようとすると重合度を下げても均一溶液が得られなか
ったり、均一溶解が出来たとしても溶液の安定性が悪く
なりゲル化し易くなる。これは溶解と溶解後生起するゲ
ル化反応とが競争反応して起こることに起因するものと
思われる。These suggest that it was economically and technically impossible to dissolve cellulose in an alkali and industrially utilize it. fact,
In the long history of the cellulose industry, such cellulose / alkaline solution has rarely been used as a dope for molding. Recently, an environment-friendly process has been expected, and an attempt has been made to dissolve cellulose in an inexpensive and simple alkali to use it. For example, JP-A-60-42438 and JP-A-61-130353 disclose dopes suitable for molding when 3% by weight or more of cellulose is dissolved in an alkaline aqueous solution. In addition, JP-A-60-139
Japanese Patent No. 873 discloses an example in which the above alkali dope of cellulose is applied to a coating material for the purpose of modifying a polymer material. Furthermore, the inventors of the present invention have disclosed in Japanese Patent Laid-Open No. 5-140332 and Japanese Patent Laid-Open No. 5-140333 a method for specifically producing a cellulose molded article from alkali dope of cellulose. Although it depends on the degree of polymerization, the practical cellulose concentration at a degree of polymerization of 340 is 5% by weight, which is more economical than the copper ammonium method (10% by weight) or the viscose method (8% by weight). Is not necessarily an expensive way. Further, as far as the inventors of the present invention know, when trying to dissolve cellulose having a high degree of polymerization, the concentration of cellulose must be further lowered, and when trying to dissolve at a high concentration, even if the degree of polymerization is lowered, a uniform solution cannot be obtained. Or, even if uniform dissolution is possible, the stability of the solution becomes poor and gelation easily occurs. This is considered to be caused by the competitive reaction between the dissolution and the gelation reaction that occurs after the dissolution.
【０００４】一方、米国特許第２，３２２，４２７，１
９４３号明細書によれば、水１００重量部にＮａＯＨ１
０重量部を溶解した溶液にＺｎＯの３重量部を溶解した
亜鉛酸塩苛性ソーダ溶液がセルロースの溶媒として働
き、かなり安定した溶液を与えることが開示されてい
る。溶解温度は５〜−５℃でセルロース濃度は約６％と
される。また、Ｍａｎｔｅｌｌ，Ｃ．Ｌ．，Ｔｅｘｔｉ
ｌｅ Ｒｅｓｅａｃｈ Ｊ．，１６，４８１（１９４
６）によれば、尿素を添加した亜鉛酸苛性ソーダやスズ
酸苛性ソーダ溶液を溶媒に用いると溶解温度が室温まで
高められることが記載されている。組成的には、酸化亜
鉛２％〜飽和、苛性ソーダ７〜１５％、尿素５〜１０％
である。この方法によれば、溶解温度が室温まで上がっ
たことから、溶液の安定性が増し、ゲル化が起こりにく
くなったことが示唆される。しかしながら、上述した技
術では高重合度のセルロースを溶解したり、ゲル化しな
い溶液を調製するにはまだ充分満足のいくものでは無か
った。On the other hand, US Pat. No. 2,322,427,1
According to the specification No. 943, 1 part of NaOH is added to 100 parts by weight of water.
It is disclosed that a zincate caustic soda solution in which 3 parts by weight of ZnO is dissolved in a solution in which 0 parts by weight is dissolved serves as a solvent for cellulose and gives a fairly stable solution. The melting temperature is 5 to -5 ° C and the cellulose concentration is about 6%. Also, Mantell, C.I. L. , Texti
le Research J.L. , 16, 481 (194
According to 6), it is described that the dissolution temperature can be increased to room temperature when a solution of caustic soda zincate or caustic soda stannate to which urea is added is used as a solvent. Compositionally, zinc oxide 2% to saturated, caustic soda 7 to 15%, urea 5 to 10%
It is. According to this method, the dissolution temperature increased to room temperature, which suggests that the stability of the solution was increased and gelation was less likely to occur. However, the above-mentioned technique has not been sufficiently satisfactory to dissolve a high degree of polymerization of cellulose or to prepare a solution that does not gel.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、従
来、困難であった重合度の高いセルロースを溶かした
り、高濃度、かつ、安定に溶解させるための溶媒を提供
することにある。本発明は、従来より高濃度にセルロー
スを溶かし、しかも、重合度の高いセルロースを溶解さ
せても、ゲル化することなく安定に溶解状態を保たせる
方法を種々の角度から検討した結果、驚くべきことにＬ
ｉＯＨ／ＮａＯＨ／ＺｎＯ／水系に於いて、特定範囲の
組成物のみが、セルロースの種類を問わず従来技術より
も高い溶解力を示すことを見いだし、本発明に到達した
ものである。SUMMARY OF THE INVENTION An object of the present invention is to provide a solvent for dissolving cellulose having a high degree of polymerization, which has been difficult in the past, or for dissolving it at a high concentration and stably. The present invention dissolves cellulose in a higher concentration than in the past, and even when cellulose having a high degree of polymerization is dissolved, the method of maintaining a stable dissolved state without gelation was examined from various angles, which is surprising. Especially L
In the iOH / NaOH / ZnO / water system, it was found that only the composition in a specific range has a higher dissolving power than that of the prior art regardless of the type of cellulose, and the present invention has been achieved.
【０００６】[0006]
【課題を解決するための手段】本発明は、ＮａＯＨが４
〜６重量％、ＬｉＯＨが４〜２重量％、水が９２重量％
から成る溶液に対して、酸化亜鉛を１重量％以上、飽和
濃度以内溶解してなることを特徴とするセルロースの溶
解に適したＬｉＯＨ／ＮａＯＨ／ＺｎＯ／水系溶媒組成
物である。According to the present invention, NaOH is 4
~ 6 wt%, LiOH 4 ~ 2 wt%, water 92 wt%
A solution of LiOH / NaOH / ZnO / water, which is suitable for dissolving cellulose, characterized in that zinc oxide is dissolved in a solution consisting of 1% by weight or more within a saturated concentration.
【０００７】本発明の構成上の最大の特徴は、特定組成
のＮａＯＨ／ＬｉＯＨ／水系組成物に酸化亜鉛を１重量
％以上、飽和濃度以内溶解して成る点にある。ここで、
特定組成のＮａＯＨ／ＬｉＯＨ／水系組成物がまず重要
で、ＮａＯＨが４〜６重量％、ＬｉＯＨが４〜２重量
％、水が９２重量％から構成される溶液は、再生セルロ
ースに対して高度に溶解力が向上したものとなってい
る。図１には、重合度が７５０の再生セルロースをセル
ロース濃度が５重量％で溶解させた時の相図を示してい
る。◎で示した組成領域は、均一溶解が可能でしかも室
温で１ヶ月以上ゲル化しない組成であり、それに隣接す
る○の領域は、均一溶解が可能であるが１ヶ月以内にゲ
ル化する組成である。△で示した領域は、高度に膨潤す
るが完全溶解に至らない組成であり、●と□はそれぞれ
ＮａＯＨ，ＬｉＯＨ単独系で溶解可能であるが数日以内
の間にゲル化する領域である。しかしながら、重合度７
５０の天然セルロースを溶解させた場合、◎の領域でも
均一に溶解させることは出来ない。本発明は、この再生
セルロースに対しては、特異な溶解力を持つ組成物に、
僅かにＺｎＯを添加することによって、天然セルロース
に対しても飛躍的に溶解性が向上し、重合度が１０００
以上のものでもゲル化させることなく溶解させることが
できる。本発明組成物において、ＮａＯＨやＬｉＯＨの
組成は前述した◎の組成以外の領域では、ＺｎＯを添加
しても高溶解力の発現は認められなかった。また、Ｚｎ
Ｏの添加量は、１重量％以上、飽和濃度以内が必要であ
る。ここでＺｎＯの飽和濃度は、添加時の温度やＮａＯ
Ｈ／ＬｉＯＨ／水の組成にも依存するが通常は、高々２
重量％以内であるものと考えられる。ＺｎＯの添加量が
１重量％未満の場合、天然セルロース系の溶解には必ず
しも優れているとは言えず、ゲル化したり、均一溶解が
出来ないことがあるので本発明の範囲から除外した。好
適には、飽和濃度以上添加・溶解させた後、デカンテー
ションを行い上澄み溶液を使用することが望ましい。The most significant feature of the present invention is that zinc oxide is dissolved in a specific composition of NaOH / LiOH / water composition in an amount of 1% by weight or more and within a saturated concentration. here,
A NaOH / LiOH / water system composition having a specific composition is of primary importance. It has improved dissolving power. FIG. 1 shows a phase diagram when regenerated cellulose having a degree of polymerization of 750 was dissolved at a cellulose concentration of 5% by weight. The composition region indicated by ⊚ is a composition that can be uniformly dissolved and does not gel at room temperature for one month or more, and the region adjacent to it is a composition that can be uniformly dissolved but gels within one month. is there. The area indicated by Δ is a composition that swells to a high degree but does not completely dissolve, and ● and □ are areas that can be dissolved in a single system of NaOH and LiOH but gel within a few days. However, the degree of polymerization is 7
When 50 natural celluloses are dissolved, they cannot be uniformly dissolved even in the area of ⊚. The present invention, for this regenerated cellulose, to a composition having a unique dissolving power,
By adding a small amount of ZnO, the solubility in natural cellulose is dramatically improved, and the degree of polymerization is 1000.
The above substances can be dissolved without gelation. In the composition of the present invention, when the composition of NaOH or LiOH was in a region other than the above-mentioned composition of ⊚, high solubility was not observed even when ZnO was added. In addition, Zn
The addition amount of O needs to be 1% by weight or more and within the saturated concentration. Here, the saturation concentration of ZnO depends on the temperature at the time of addition and NaO.
Usually at most 2 depending on the composition of H / LiOH / water
It is considered to be within the weight%. When the amount of ZnO added is less than 1% by weight, it cannot be said that the dissolution of the natural cellulosic material is necessarily excellent, and gelation or uniform dissolution may not be achieved, so it was excluded from the scope of the present invention. It is preferable to use the supernatant solution by decanting after adding and dissolving at a saturated concentration or more.
【０００８】本発明の溶媒組成物に供するセルロースと
しては、特別にアルカリ可溶化処理する必要がなく、更
に、結晶型を問わず、種々の天然セルロースや再生セル
ロースが使用できる。また、重合度も溶解させるセルロ
ース濃度によるが、通常１００以上３０００以下のもの
が使用できる。セルロース溶解時の温度は、低温ほど溶
解速度が速くなるので好ましいが、室温でも充分溶解さ
せることができる。溶解させるセルロース濃度は、用途
に応じて決めることができる。As the cellulose to be used in the solvent composition of the present invention, it is not necessary to carry out a special alkali solubilization treatment, and various natural celluloses and regenerated celluloses can be used regardless of the crystal type. Further, the degree of polymerization also depends on the concentration of cellulose to be dissolved, but usually 100 or more and 3000 or less can be used. The temperature at which cellulose is dissolved is preferably lower as the dissolution rate is faster, but it can be sufficiently dissolved even at room temperature. The concentration of cellulose to be dissolved can be determined depending on the application.
【０００９】重合度が１０６０の木材パルプの場合、５
重量％、重合度が３４０の木材パルプの場合、８重量％
でも容易に溶解させることができ、しかも室温で１ヶ月
経ってもゲル化しなかった。繊維やフィルムの成形には
５重量％以上のセルロース濃度が望ましい。一方、コー
ティング等に利用する場合には、溶液粘度との兼ね合い
でその濃度を決めればよい。For wood pulp having a degree of polymerization of 1060, 5
% By weight, 8% by weight for wood pulp with a degree of polymerization of 340
However, it could be easily dissolved and did not gel even after 1 month at room temperature. A cellulose concentration of 5% by weight or more is desirable for forming fibers and films. On the other hand, when it is used for coating or the like, its concentration may be determined in consideration of the solution viscosity.
【００１０】[0010]
【発明の実施の形態】以下、本発明を実施例により説明
するが、本発明はこれらに何ら限定されるものではな
い。実施例に先駆け、評価法の一部を述べる。制電性
（半減期）は、相対湿度４０％、２０℃の人工気候室中
で、ＪＩＳＬ−１０９４のＡ法に準拠して測定した。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below with reference to Examples, but the present invention is not limited thereto. Prior to the examples, a part of the evaluation method will be described. The antistatic property (half-life) was measured in an artificial climate room at a relative humidity of 40% and 20 ° C. according to JIS A-1094, Method A.
【００１１】吸水特性はバイレックス（Ｂｙｒｅｘ）法
を採用した。布帛のサイズは長さ２５ｃｍ、巾２．５ｃ
ｍで、巾側の一端を水に浸漬し、１０分経過後の水が浸
透した高さを計測した。For the water absorption property, the Byrex method was adopted. The size of the fabric is 25 cm long and 2.5 c wide
At m, one end of the width side was immersed in water, and the height at which water penetrated after 10 minutes was measured.
【００１２】[0012]
【実施例１】ＮａＯＨとＬｉＯＨとＺｎＯと水とからな
る４成分系の混合組成物において、表１に示すような種
々の組成の混合組成物を調製した。調製は２５℃で行っ
た。得られた混合組成物を一旦１０℃で放置させた後、
重合度が１０６０の木材パルプ(針葉樹パルプ)と銅安溶
液から再生させた重合度が７５０の再生セルロースの二
種のセルロースについて、その溶解性を調べた。本発明
では天然セルロースと再生セルロースの両者がゲル化す
ることなく均一に溶ける混合組成物をセルロース用溶解
組成物として規定した。表１には、溶解後の溶解状態や
安定性についても併せて載せている。実験例に於いて、
実施例はＮｏ５、６、８、１１、２２、２６であり、比
較例はＮｏ１、２、３、４、７、９、１０、１２〜２
１、２３〜２５、２７である。Example 1 A four-component mixed composition of NaOH, LiOH, ZnO and water was prepared to have various compositions as shown in Table 1. The preparation was performed at 25 ° C. After leaving the obtained mixed composition once at 10 ° C.,
Solubility of two types of cellulose, a wood pulp having a degree of polymerization of 1060 (softwood pulp) and a regenerated cellulose having a degree of polymerization of 750 regenerated from a copper ammonium solution, was examined. In the present invention, a mixed composition in which both natural cellulose and regenerated cellulose are uniformly dissolved without gelation is defined as a dissolution composition for cellulose. Table 1 also shows the dissolution state and stability after dissolution. In the experimental example,
The examples are Nos. 5, 6, 8, 11, 22, and 26, and the comparative examples are Nos. 1, 2, 3, 4, 7, 9, 10, 12 to 2.
1, 23 to 25, 27.
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
【実施例２】実施例１で調製したＮｏ６とＮｏ４の溶媒
組成物に重合度が４５０の酸加水分解木材パルプをセル
ロース濃度１.５ｗｔ％に成るよう４℃下で溶解させ
た。共に均一溶液であった。この溶液を平織りのポリエ
ステル布帛に付着率１％に成るようコーティングし、酸
洗、水洗、乾燥後の制電性（半減期ｓｅｃ）ならびに水
吸収特性(ｃｍ)を調べた。Ｎｏ６から得られた布帛の制
電性ならびに水吸収特性は６．１ｓｅｃ、２．３ｃｍで
あった。Ｎｏ４から得られた布帛の制電性ならびに水吸
収特性は８．４ｓｅｃ、４．７ｃｍであった。また、両
者を手でしごいたところ、Ｎｏ４から得られたものから
は白粉が発現した。このようにコーティング媒体として
は本発明組成物の方が遥かに優れていることが判る。Example 2 Acid-hydrolyzed wood pulp having a degree of polymerization of 450 was dissolved in the solvent compositions No6 and No4 prepared in Example 1 at 4 ° C. so that the concentration of cellulose was 1.5 wt%. Both were homogeneous solutions. This solution was coated on a plain weave polyester cloth so as to have an adhesion rate of 1%, and the antistatic property (half-life sec) and water absorption characteristics (cm) after pickling, washing with water and drying were examined. The antistatic property and the water absorption property of the cloth obtained from No. 6 were 6.1 sec and 2.3 cm. The antistatic property and water absorption property of the cloth obtained from No. 4 were 8.4 sec and 4.7 cm. Further, when both were squeezed by hand, white powder was developed from the one obtained from No4. Thus, it can be seen that the composition of the present invention is far superior as a coating medium.
【００１５】[0015]
【実施例３】実施例１で調製したＮｏ１１とＮｏ３の溶
媒組成物に重合度３４０の酸加水分解木材パルプを５ｗ
ｔ％で溶解し、均一溶液を得た。この溶液を１ヶ月２０
℃下で放置したところ、Ｎｏ１１から得られた溶液は、
流動性が初期と変わらず溶液状態を保持していたが、Ｎ
ｏ３から得られた溶液はゲル化していた。溶解１日後の
両者の溶液を０．０１ｍｍ直径の穴が５０個空いた紡口
から２０％の硫酸亜鉛を含む５％硫酸溶液に吐出させて
凝固させた後、ネルソンロール上で酸洗、水洗を行ない
５０ｍ／ｍｉｎで巻き取った。両者の引っ張り強伸度
は、２．６ｇ／ｄｘ１７％（Ｎｏ１１）、１．８ｇ／ｄ
ｘ１２％（Ｎｏ３）であり、明らかに本発明溶媒組成物
を用いた溶液の方が高い物性を示すことが判った。Example 3 No. 11 and No. 3 solvent compositions prepared in Example 1 were mixed with 5 w of acid-hydrolyzed wood pulp having a polymerization degree of 340.
It was dissolved at t% to obtain a uniform solution. This solution for 1 month 20
When left at ℃, the solution obtained from No11
Although the fluidity remained the same as the initial state and the solution state was maintained, N
The solution obtained from o3 was gelled. After 1 day of dissolution, both solutions were discharged from a spinneret having 50 holes with a diameter of 0.01 mm into a 5% sulfuric acid solution containing 20% zinc sulfate to coagulate, and then pickled on a Nelson roll and washed with water. And was wound up at 50 m / min. The tensile strength and elongation of both are 2.6 g / dx17% (No 11), 1.8 g / d
x12% (No3), and it was clear that the solution using the solvent composition of the present invention exhibits higher physical properties.
【００１６】[0016]
【発明の効果】本発明の溶媒組成物は、従来技術に比し
て高重合度のセルロースの溶解が可能で、室温でもゲル
化せず安定な溶液を得ることができる。かくして得られ
たセルロース溶液は、安定であるので繊維やフィルムの
成形に適することは言うまでもないが、特に、高重合度
のセルロース溶液が可能になるので機械的物性が高くな
る。特に、凝固剤に硫酸亜鉛を併用すると凝固時の体積
収縮率が高くなり、表層にスキン層を持つ緻密な凝集構
造体になる。また、本発明溶液は他素材に塗布すると極
めて剥がれ難くなるので耐久性の高いコーティング材料
に展開が可能となる。また、セルロースと反応する媒体
を添加することにより、原液の改質や化学反応媒体とし
ての利用が可能となる。INDUSTRIAL APPLICABILITY The solvent composition of the present invention is capable of dissolving cellulose having a higher degree of polymerization as compared with the prior art, and it is possible to obtain a stable solution without gelation even at room temperature. Needless to say, the cellulose solution thus obtained is stable and suitable for molding of fibers and films, but in particular, since a cellulose solution having a high degree of polymerization becomes possible, mechanical properties are improved. In particular, when zinc sulfate is used in combination with the coagulant, the volumetric shrinkage rate at the time of coagulation becomes high, and a dense aggregate structure having a skin layer on the surface layer is obtained. Further, when the solution of the present invention is applied to another material, it is extremely difficult to peel it off, so that it can be applied to a highly durable coating material. Also, by adding a medium that reacts with cellulose, it becomes possible to modify the stock solution and use it as a chemical reaction medium.
【図１】本発明のＮａＯＨ／ＬｉＯＨ／水系混合溶液に
重合度が７５０の再生セルロースをセルロース濃度が５
重量％で溶解させた時の相図。FIG. 1 shows a regenerated cellulose having a degree of polymerization of 750 and a cellulose concentration of 5 in the NaOH / LiOH / water mixed solution of the present invention.
Phase diagram when dissolved in wt%.
Claims (1)
〜２重量％、水が９２重量％から成る溶液に対して、酸
化亜鉛を１重量％以上、飽和濃度以内溶解してなること
を特徴とするセルロースの溶解に適したＬｉＯＨ／Ｎａ
ＯＨ／ＺｎＯ／水系溶媒組成物1. NaOH 4 to 6% by weight, LiOH 4
LiOH / Na suitable for dissolving cellulose, characterized in that zinc oxide is dissolved in 1% by weight or more and within a saturated concentration in a solution containing 2% by weight and 92% by weight of water.
OH / ZnO / water-based solvent composition
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06982796A JP3953545B2 (en) | 1996-03-26 | 1996-03-26 | Solvent composition for dissolving cellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06982796A JP3953545B2 (en) | 1996-03-26 | 1996-03-26 | Solvent composition for dissolving cellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09255702A true JPH09255702A (en) | 1997-09-30 |
| JP3953545B2 JP3953545B2 (en) | 2007-08-08 |
Family
ID=13413995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06982796A Expired - Fee Related JP3953545B2 (en) | 1996-03-26 | 1996-03-26 | Solvent composition for dissolving cellulose |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3953545B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009018709A1 (en) * | 2007-08-03 | 2009-02-12 | Zhen Fang | A method and an equipment of dissolving ligneous cellulosic biologic materials completely |
| WO2010025858A3 (en) * | 2008-09-02 | 2010-06-17 | Thüringisches Institut für Textil - und Kunststoff-Forschung e.V. | Functional cellulosic moldings |
| JP2015508109A (en) * | 2012-10-10 | 2015-03-16 | 湖北天思科技股▲ふん▼有限公司 | Dissolution method of cellulose |
| CN111333735A (en) * | 2020-04-16 | 2020-06-26 | 江南大学 | A kind of method for preparing low-substituted hydroxyethyl cellulose solution for spinning |
| CN114259892A (en) * | 2021-12-30 | 2022-04-01 | 宜宾丝丽雅股份有限公司 | A kind of ZnO solution preparation process |
| CN115028858A (en) * | 2022-05-11 | 2022-09-09 | 天津智鼎生物科技有限公司 | Method for promoting partial dissolution of bacterial cellulose and application thereof |
-
1996
- 1996-03-26 JP JP06982796A patent/JP3953545B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009018709A1 (en) * | 2007-08-03 | 2009-02-12 | Zhen Fang | A method and an equipment of dissolving ligneous cellulosic biologic materials completely |
| WO2010025858A3 (en) * | 2008-09-02 | 2010-06-17 | Thüringisches Institut für Textil - und Kunststoff-Forschung e.V. | Functional cellulosic moldings |
| US9243349B2 (en) | 2008-09-02 | 2016-01-26 | Smartpolymer Gmbh | Functional cellulosic moldings |
| JP2015508109A (en) * | 2012-10-10 | 2015-03-16 | 湖北天思科技股▲ふん▼有限公司 | Dissolution method of cellulose |
| CN111333735A (en) * | 2020-04-16 | 2020-06-26 | 江南大学 | A kind of method for preparing low-substituted hydroxyethyl cellulose solution for spinning |
| CN114259892A (en) * | 2021-12-30 | 2022-04-01 | 宜宾丝丽雅股份有限公司 | A kind of ZnO solution preparation process |
| CN115028858A (en) * | 2022-05-11 | 2022-09-09 | 天津智鼎生物科技有限公司 | Method for promoting partial dissolution of bacterial cellulose and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3953545B2 (en) | 2007-08-08 |
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