JP2021109920A - Method for producing cellulose solution - Google Patents
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- JP2021109920A JP2021109920A JP2020002654A JP2020002654A JP2021109920A JP 2021109920 A JP2021109920 A JP 2021109920A JP 2020002654 A JP2020002654 A JP 2020002654A JP 2020002654 A JP2020002654 A JP 2020002654A JP 2021109920 A JP2021109920 A JP 2021109920A
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 51
- 239000001913 cellulose Substances 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000002608 ionic liquid Substances 0.000 claims abstract description 50
- 238000011282 treatment Methods 0.000 claims abstract description 28
- 238000011221 initial treatment Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 229920000875 Dissolving pulp Polymers 0.000 claims description 3
- 206010042674 Swelling Diseases 0.000 claims 1
- 230000008961 swelling Effects 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 2
- BMQZYMYBQZGEEY-UHFFFAOYSA-M 1-ethyl-3-methylimidazolium chloride Chemical compound [Cl-].CCN1C=C[N+](C)=C1 BMQZYMYBQZGEEY-UHFFFAOYSA-M 0.000 description 2
- QVRCRKLLQYOIKY-UHFFFAOYSA-M 1-methyl-3-prop-2-enylimidazol-1-ium;chloride Chemical compound [Cl-].C[N+]=1C=CN(CC=C)C=1 QVRCRKLLQYOIKY-UHFFFAOYSA-M 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- HQWOEDCLDNFWEV-UHFFFAOYSA-M diethyl phosphate;1-ethyl-3-methylimidazol-3-ium Chemical compound CC[N+]=1C=CN(C)C=1.CCOP([O-])(=O)OCC HQWOEDCLDNFWEV-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BSKSXTBYXTZWFI-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;acetate Chemical compound CC([O-])=O.CCCC[N+]=1C=CN(C)C=1 BSKSXTBYXTZWFI-UHFFFAOYSA-M 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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Abstract
Description
本発明は、繊維やフィルムなどのセルロース材料の成形に用いられるセルロース溶液の製造方法に関するものである。 The present invention relates to a method for producing a cellulose solution used for molding a cellulose material such as a fiber or a film.
セルロースは周知のとおり、地球上に最も多く存在するバイオマス資源であり、環境配慮型素材として、溶解、成型に関しての研究が広く行われている。
セルロースは分子鎖間又は分子鎖内の強固な水素結合をもつため、一般的な溶剤では溶解させることが難しい。
As is well known, cellulose is the most abundant biomass resource on the earth, and research on dissolution and molding has been widely conducted as an environmentally friendly material.
Since cellulose has strong hydrogen bonds between and within the molecular chains, it is difficult to dissolve it with a general solvent.
これに対処する、イオン液体を用いたセルロースの溶解、そして、セルロース繊維の製造方法は、溶剤の全量回収と再使用により、環境負荷の少ない製造方法として知られている（例えば、特許文献１〜２参照。）。 A method for dissolving cellulose using an ionic liquid and producing a cellulose fiber, which copes with this, is known as a production method having a low environmental load by recovering and reusing the entire amount of the solvent (for example, Patent Documents 1 to 1). See 2.).
ところで、イオン液体に対するセルロースの溶解性は、イオン液体に含まれる水分量に著しく左右される。
このため、再生セルロースの製造工程などで、比較的高濃度のセルロース溶液を調製する必要がある場合には、できる限り含水率を低下させたイオン液体を用いる必要があり、セルロースを溶解できる濃度までイオン液体を濃縮する時間とエネルギが必要であった。
By the way, the solubility of cellulose in an ionic liquid is significantly affected by the amount of water contained in the ionic liquid.
Therefore, when it is necessary to prepare a relatively high-concentration cellulose solution in the manufacturing process of regenerated cellulose, it is necessary to use an ionic liquid having a water content as low as possible, to a concentration at which cellulose can be dissolved. It took time and energy to concentrate the ionic liquid.
セルロース溶液に用いるセルロース原料としては、一般的にパルプが用いられる。
セルロースのイオン液体への溶解性を高めるために、パルプを乾燥し、機械的に粉砕し、表面積を大きくしているが、乾燥や粉砕時にパルプの繊維が劣化する場合があり、また、乾燥や粉砕にかかる時間やエネルギが別途必要となるという問題があった。
また、パルプの溶解には、溶剤をパルプに十分に浸透させる必要があり、シート形状のパルプではシート内部まで溶剤がいきわたらないという問題があった。
このため、パルプの粉砕や、パルプに水を吸わせて溶剤を入りやすくする必要があった。
Pulp is generally used as the cellulose raw material used in the cellulose solution.
In order to increase the solubility of cellulose in ionic liquids, the pulp is dried and mechanically crushed to increase the surface area, but the fibers of the pulp may deteriorate during drying and crushing, and the pulp may be dried or crushed. There is a problem that the time and energy required for crushing are required separately.
Further, in order to dissolve the pulp, it is necessary to sufficiently permeate the solvent into the pulp, and there is a problem that the solvent does not reach the inside of the sheet in the sheet-shaped pulp.
For this reason, it is necessary to crush the pulp and to make the pulp absorb water to facilitate the entry of the solvent.
このようなセルロース溶液の課題に対して、特許文献１に記載された発明では、含水量が２０〜５０質量％であるイオン液体を使用してセルロース溶液を製造している。
しかしながら、イオン液体の濃縮は、含水量を２０〜５０質量％であるイオン液体を得る工程と、溶解時に残りの水を除去する工程に分けられており、濃縮によって得られたイオン液体に水を加えることで２０〜５０質量％に調整している。イオン液体の濃縮は比較的高効率な濃縮方法が公知であるが、溶解時に再度、多くの水を除去するのにかかるエネルギ消費が大きくなるといった問題がある。
In response to such a problem of the cellulose solution, in the invention described in Patent Document 1, a cellulose solution is produced using an ionic liquid having a water content of 20 to 50% by mass.
However, the concentration of the ionic liquid is divided into a step of obtaining an ionic liquid having a water content of 20 to 50% by mass and a step of removing the remaining water at the time of dissolution, and water is added to the ionic liquid obtained by the concentration. By adding it, it is adjusted to 20 to 50% by mass. A relatively highly efficient concentration method for concentrating an ionic liquid is known, but there is a problem that the energy consumption required for removing a large amount of water again at the time of dissolution becomes large.
また、特許文献２に記載された発明では、含水率５０質量％以上のパルプを使用してセルロース溶液を製造している。
しかしながら、シート状のパルプでは水の吸液が遅く、さらに、水を吸液したパルプにイオン液体を加えるため、水とイオン液体との液交換に時間を要するといった問題がある。
Further, in the invention described in Patent Document 2, a cellulose solution is produced using pulp having a water content of 50% by mass or more.
However, the sheet-shaped pulp absorbs water slowly, and further, since the ionic liquid is added to the pulp that has absorbed water, there is a problem that it takes time to exchange the liquid between the water and the ionic liquid.
本発明は、上記従来のイオン液体を用いるセルロース溶液の製造方法の有する問題点に鑑み、イオン液体の濃縮及びパルプの乾燥や粉砕にかかる時間とエネルギを削減し、パルプの溶解性に優れたセルロース溶液の製造方法を提供することを目的とする。 In view of the problems of the conventional method for producing a cellulose solution using an ionic liquid, the present invention reduces the time and energy required for concentrating the ionic liquid and drying or crushing the pulp, and has excellent solubility of the pulp. It is an object of the present invention to provide a method for producing a solution.
本発明は以下に示す手段により、シート状パルプをイオン液体に溶解させたセルロース溶液の製造が可能である。
すなわち、図１に示すように、一定範囲の含水量のイオン液体を使用して溶解条件を１次処理、２次処理に規定することで、シート状パルプを乾燥、粉砕処理をしない状態であっても、パルプの溶解性を向上することが可能となることを見出した。
ここで、パルプは、α−セルロースの含有量の高いものを使用することが好ましい。パルプのセルロース重量平均重合度が６００〜２０００の範囲で、α−セルロースの含有量が９０質量％以上であるパルプを使用することが好ましい。
本発明の１次処理は、含水率が５〜２０質量％のイオン液体とシートパルプを４０〜９０℃、１０分〜１２０分、パルプ質量と水分を含有したイオン液体質量の浴比（以下、単に「浴比」という。）が１：４〜１：１００の条件下で撹拌を行うことでパルプを膨潤させる。
さらに、２次処理として、減圧下、９０〜１２０℃で水を除去しながら撹拌することで、パルプを溶解し、セルロース溶液が得られる。
The present invention can produce a cellulose solution in which sheet pulp is dissolved in an ionic liquid by the means shown below.
That is, as shown in FIG. 1, by defining the dissolution conditions for the primary treatment and the secondary treatment using an ionic liquid having a water content in a certain range, the sheet pulp is not dried or crushed. However, it has been found that it is possible to improve the solubility of pulp.
Here, it is preferable to use pulp having a high content of α-cellulose. It is preferable to use pulp having a cellulose weight average degree of polymerization of pulp in the range of 600 to 2000 and an α-cellulose content of 90% by mass or more.
In the primary treatment of the present invention, the ionic liquid having a water content of 5 to 20% by mass and the sheet pulp are mixed at 40 to 90 ° C. for 10 to 120 minutes, and the bath ratio of the ionic liquid mass containing the pulp mass and the water content (hereinafter referred to as). The pulp is swollen by stirring under the condition of simply "bath ratio") of 1: 4 to 1: 100.
Further, as a secondary treatment, the pulp is dissolved and a cellulose solution is obtained by stirring under reduced pressure at 90 to 120 ° C. while removing water.
本発明のセルロース溶液の製造方法によれば、低エネルギでセルロースを溶解することができる。 According to the method for producing a cellulose solution of the present invention, cellulose can be dissolved with low energy.
以下、本発明のセルロース溶液の製造方法の実施の形態を説明する。
本発明のセルロース溶液の製造方法においては、セルロース原料としてシート状のパルプを用いるとともに、イオン液体として、含水率が５〜２０質量％であるものを用いる。
本発明の溶解溶剤であるイオン液体としては、１−ブチル−３−メチルイミダゾリウムクロリド（1-butyl-3-methylimidazolium chloride）（ＢｍｉｍＣｌ）、１−ブチル−３−メチルイミダゾリウムアセテート（1-butyl-3-methylimidazolium acetate）（ＢｍｉｍＡｃ）、１−エチル−３−メチルイミダゾリウムジエチルホスフェイト（1-ethyl-3-methylimidazolium diethyl phosphate）（ＥｍｉｍＤＥＰ）、１−エチル−３−メチルイミダゾリウムクロライド（1-ethyl-3-methylimidazolium chloride）（ＥｍｉｍＣｌ）、１−アリル−３−メチルイミダゾリウムクロライド（1-Allyl-3-methylimidazolium chloride）（ＡｍｉｍＣｌ）が挙げられるが、これらのイオン液体に限定されるものではない。イオン液体は、それぞれ１種を単独で使用してもよく、２種以上を併用してもよい。
Hereinafter, embodiments of the method for producing a cellulose solution of the present invention will be described.
In the method for producing a cellulose solution of the present invention, sheet-shaped pulp is used as a cellulose raw material, and an ionic liquid having a water content of 5 to 20% by mass is used.
Examples of the ionic liquid that is the dissolving solvent of the present invention include 1-butyl-3-methylimidazolium chloride (BimCl) and 1-butyl-3-methylimidazolium acetate (1-butyl). -3-methylimidazolium acetate) (BimAc), 1-ethyl-3-methylimidazolium diethyl phosphate (EmimDEP), 1-ethyl-3-methylimidazolium chloride (1-) Ethyl-3-methylimidazolium chloride) (EmmCl), 1-allyl-3-methylimidazolium chloride (1-Allyl-3-methylimidazolium chloride) (AmimCl), but are not limited to these ionic liquids. .. As the ionic liquid, one type may be used alone, or two or more types may be used in combination.
また、イオン液体は繰り返し使用したものでもよく、例えば、イオン液体中にヘミセルロースやリグニン、パルプ由来の無機成分を含んでいてもよい。
ここで、イオン液体の繰り返し使用とは、本発明で得られたセルロース溶液を、例えば、水やアルコール類のようなセルロースを凝固させることが可能な液体を用いて、セルロース溶液からセルロース成形体とイオン液体とを分離した後、イオン液体を含む凝固に使用した液体からイオン液体を濃縮して、再びセルロースの溶解溶剤に使用することを指す。
繰り返し使用するイオン液体は、必要に応じてヘミセルロースやリグニン、パルプ由来の無機成分を精製処理によって除去してもよい。
すなわち、１次処理での温度４０〜９０℃の範囲で、含水率５〜２０質量％で液体であるイオン液体であれば、この発明の効果は発揮される。
Further, the ionic liquid may be used repeatedly, and for example, hemicellulose, lignin, and an inorganic component derived from pulp may be contained in the ionic liquid.
Here, the repeated use of the ionic liquid means that the cellulose solution obtained in the present invention is mixed with a cellulose molded product from the cellulose solution by using a liquid capable of coagulating cellulose such as water and alcohols. After separating from the ionic liquid, it refers to concentrating the ionic liquid from the liquid used for coagulation containing the ionic liquid and using it again as a solvent for dissolving cellulose.
In the ionic liquid to be used repeatedly, hemicellulose, lignin, and inorganic components derived from pulp may be removed by a purification treatment, if necessary.
That is, the effect of the present invention is exhibited as long as it is an ionic liquid that is a liquid with a water content of 5 to 20% by mass in the temperature range of 40 to 90 ° C. in the primary treatment.
１次処理と２次処理の間の間隔は特に制限はないが、１次処理後すみやかに２次処理に移行することが望まれる。 The interval between the primary treatment and the secondary treatment is not particularly limited, but it is desirable to immediately shift to the secondary treatment after the primary treatment.
また、必要なセルロース濃度に調整するために、１次処理後に圧搾等により余剰な含水イオン液体を除去することもできる。 Further, in order to adjust the required cellulose concentration, excess hydrous ionic liquid can be removed by squeezing or the like after the primary treatment.
＜パルプの１次処理＞
水分率が２０質量％以下であり、かつシート形状のパルプを用いる。
パルプの水分率は好ましくは１７質量％以下、より好ましくは１５質量％以下である。
シートパルプのイオン液体への溶解を、１次処理として４０〜９０℃、パルプと含水状態のイオン液体の浴比が１：４〜１：１００の条件下で撹拌を行う。
シート形状のパルプの含水率が２０質量％以上であると、輸送コスト（水を運ぶことになる）やカビ等の微生物の繁殖が懸念されるため、防カビ剤等の薬剤の使用や、保存場所の温湿度管理等の手間がかかる。
イオン液体の含水率が５質量％以下であると、１次処理によるパルプシートへの吸液性が悪く、シート中心部まで吸液せず、未溶解物の原因となる。
イオン液体の含水率が２０質量％以上では、吸液性がほとんど変わらず、水を除去する時間が長くなる。
処理温度は４０〜９０℃で行い、好ましくは５０〜９０℃、より好ましくは６０〜９０℃の範囲である。４０℃以下では、吸液ムラが生じて均一な溶液が得られず、９０℃以上では、水分の蒸発が進み、１次処理の効果が十分に得られない。
処理時間は１０〜１２０分で行い、好ましくは２０〜１１０分、より好ましくは３０〜９０分の範囲である。１０分以下では、吸液が不均一であり、１２０分以上では、吸液性が変わらず、処理時間が長くなる。
処理時の浴比が１：４以下では、吸液ムラが生じて均一な溶液が得られず、浴比が１：１００以上では、１次処理に必要な容器が大型化する。浴比は１：４〜１：５０が好ましく、１：５〜１：２０がより好ましい。
１次処理の撹拌速度に特に規定はなく、数ｒｐｍ程度の低速撹拌でもよく、ミキサー等の数万ｒｐｍの高速回転でもよい。また、撹拌をせずに浸漬静置するだけでもよい。
１次処理中の圧力に特に制限はなく、常圧でもよく、加圧下、減圧下でもよい。
表１及び図２に、本発明の１次処理の一例で、シートパルプに含水イオン液体を浸漬して、６５℃加温下で静置したときのパルプシートの厚み変化の観察結果を示す。
厚みが１ｍｍのパルプシートを用いて、各含水量のイオン液体の吸液性を確認した。
表１及び図２に示すように、含水量によってパルプシートの吸液速度と吸液量が異なる。吸液速度と吸液量が高い条件では、パルプシート内部まで含水イオン液体が浸透していることを示し、本発明の１次処理において有利になる。含水率が５質量％以下のイオン液体を用いると、パルプ内部までイオン液体が浸透せず、２次処理において、未溶解セルロースの原因になり得る。
<Primary treatment of pulp>
Sheet-shaped pulp having a water content of 20% by mass or less is used.
The water content of the pulp is preferably 17% by mass or less, more preferably 15% by mass or less.
Dissolution of the sheet pulp into the ionic liquid is performed as a primary treatment under the conditions of 40 to 90 ° C. and a bath ratio of the pulp to the ionic liquid in a water-containing state of 1: 4 to 1: 100.
If the moisture content of the sheet-shaped pulp is 20% by mass or more, there are concerns about transportation costs (which will carry water) and the growth of microorganisms such as molds. It takes time and effort to control the temperature and humidity of the place.
When the water content of the ionic liquid is 5% by mass or less, the liquid absorption property to the pulp sheet by the primary treatment is poor, the liquid is not absorbed to the center of the sheet, and it causes an undissolved substance.
When the water content of the ionic liquid is 20% by mass or more, the liquid absorption property is almost unchanged, and the time for removing water becomes long.
The treatment temperature is 40 to 90 ° C, preferably 50 to 90 ° C, more preferably 60 to 90 ° C. At 40 ° C. or lower, uneven liquid absorption occurs and a uniform solution cannot be obtained, and at 90 ° C. or higher, water evaporation proceeds and the effect of the primary treatment cannot be sufficiently obtained.
The treatment time is 10 to 120 minutes, preferably 20 to 110 minutes, more preferably 30 to 90 minutes. At 10 minutes or less, the liquid absorption is non-uniform, and at 120 minutes or more, the liquid absorption property does not change and the treatment time becomes long.
When the bath ratio at the time of treatment is 1: 4 or less, uneven liquid absorption occurs and a uniform solution cannot be obtained, and when the bath ratio is 1: 100 or more, the container required for the primary treatment becomes large. The bath ratio is preferably 1: 4 to 1:50, more preferably 1: 5 to 1:20.
The stirring speed of the primary treatment is not particularly specified, and low-speed stirring of about several rpm may be used, or high-speed rotation of tens of thousands of rpm of a mixer or the like may be used. Further, it may be simply immersed and allowed to stand without stirring.
The pressure during the primary treatment is not particularly limited and may be normal pressure, pressurized or reduced pressure.
Table 1 and FIG. 2 show the observation results of the change in the thickness of the pulp sheet when the hydrous ionic liquid was immersed in the sheet pulp and allowed to stand at 65 ° C. in an example of the primary treatment of the present invention.
Using a pulp sheet having a thickness of 1 mm, the liquid absorbency of the ionic liquid having each water content was confirmed.
As shown in Table 1 and FIG. 2, the liquid absorption rate and the liquid absorption amount of the pulp sheet differ depending on the water content. Under the conditions of high liquid absorption rate and liquid absorption amount, it is shown that the hydrous ionic liquid has penetrated into the pulp sheet, which is advantageous in the primary treatment of the present invention. If an ionic liquid having a water content of 5% by mass or less is used, the ionic liquid does not penetrate into the pulp and may cause undissolved cellulose in the secondary treatment.
＜パルプの２次処理＞
パルプの２次処理を減圧下、９０〜１２０℃で行う。
ここで、減圧下とは、含水イオン液体中の水の蒸気圧未満の圧力下を指し、１ｋＰａ以下が好ましく、０．１ｋＰａ以下がより好ましい。
減圧装置としては、例えば、ダイヤフラム式減圧ポンプ、ドライポンプ、油回転減圧ポンプ等の一般的な減圧装置を使用することができる。
温度９０℃以下では、水分除去の効率が悪く、１２０℃以上では、熱によるセルロースの重合度低下を招く。
<Secondary treatment of pulp>
The secondary treatment of pulp is carried out under reduced pressure at 90 to 120 ° C.
Here, the reduced pressure refers to a pressure lower than the vapor pressure of water in the hydrous ionic liquid, preferably 1 kPa or less, and more preferably 0.1 kPa or less.
As the decompression device, for example, a general decompression device such as a diaphragm type decompression pump, a dry pump, or an oil rotary decompression pump can be used.
When the temperature is 90 ° C. or lower, the efficiency of removing water is poor, and when the temperature is 120 ° C. or higher, the degree of polymerization of cellulose is lowered due to heat.
上記１次処理、２次処理の条件で溶解を行うことで、シートパルプに十分に含水イオン液体が均一に浸透し、水を蒸発除去しながらシート状のパルプを溶解することができる。
本発明の製造方法においては、パルプとイオン液体との混合物中のセルロース含有量として、５〜２０質量％程度のセルロース溶液を得ることができる。
By dissolving under the conditions of the above primary treatment and secondary treatment, the hydrous ionic liquid sufficiently permeates the sheet pulp sufficiently, and the sheet-shaped pulp can be dissolved while evaporating and removing water.
In the production method of the present invention, a cellulose solution having a cellulose content of about 5 to 20% by mass in a mixture of pulp and an ionic liquid can be obtained.
以下、本発明を実施例によって詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
＜実施例１＞
シートパルプ＋含水ＢｍｉｍＣｌ→１次、２次処理
Georgia Pacific社製の未粉砕シートパルプ５０ｇを含水率測定のために、１１０℃オーブン内で４時間乾燥させたところ、含水率４質量％であった。
混錬機内にイオン交換水で９０質量％に希釈したＢｍｉｍＣｌを１００．０ｇ添加し、５０℃に加熱した。次いで、２０ｍｍ四方に裁断した含水率４質量％の未粉砕シートパルプ１０．４ｇを混錬機に添加した（浴比１：９．６）。混錬機内で５０℃、３０分間撹拌することで、パルプの１次処理とした。
次いで、この混錬機を１１０℃に加熱し、約０．１ｋＰａの減圧下で水分を蒸発除去しながら３時間撹拌することで、パルプの２次処理を行い、セルロース溶液を得た。
<Example 1>
Sheet pulp + hydrous BmimCl → primary and secondary treatment
When 50 g of unground sheet pulp manufactured by Georgia Pacific was dried in an oven at 110 ° C. for 4 hours for measuring the water content, the water content was 4% by mass.
100.0 g of BmimCl diluted to 90% by mass with ion-exchanged water was added into the kneader and heated to 50 ° C. Next, 10.4 g of uncrushed sheet pulp having a water content of 4% by mass cut into 20 mm squares was added to the kneader (bath ratio 1: 9.6). Stirring at 50 ° C. for 30 minutes in a kneader was used as the primary treatment of pulp.
Next, this kneader was heated to 110 ° C. and stirred for 3 hours while evaporating and removing water under a reduced pressure of about 0.1 kPa to perform a secondary treatment of pulp to obtain a cellulose solution.
＜実施例２＞
Georgia Pacific社製の未粉砕シートパルプ５０ｇを含水率測定のために、１１０℃オーブン内で４時間乾燥させたところ、含水率４質量％であった。
混錬機内にイオン交換水で８５質量％に希釈したＢｍｉｍＣｌを１０３．５ｇ添加し、９０℃に加熱した。次いで、２０ｍｍ四方に裁断した含水率４質量％の未粉砕シートパルプ１２．５ｇを混錬機に添加した（浴比１：８．３）。混錬機内で９０℃、３０分間撹拌することで、パルプの１次処理とした。
次いで、この混錬機を１１０℃に加熱し、約０．１ｋＰａの減圧下で水分を蒸発除去しながら３時間撹拌することで、パルプの２次処理を行い、セルロース溶液を得た。
<Example 2>
When 50 g of unground sheet pulp manufactured by Georgia Pacific was dried in an oven at 110 ° C. for 4 hours for measuring the water content, the water content was 4% by mass.
103.5 g of BmimCl diluted to 85% by mass with ion-exchanged water was added into the kneader and heated to 90 ° C. Next, 12.5 g of uncrushed sheet pulp having a water content of 4% by mass cut into 20 mm squares was added to the kneader (bath ratio 1: 8.3). Stirring at 90 ° C. for 30 minutes in a kneader was used as the primary treatment of pulp.
Next, this kneader was heated to 110 ° C. and stirred for 3 hours while evaporating and removing water under a reduced pressure of about 0.1 kPa to perform a secondary treatment of pulp to obtain a cellulose solution.
＜実施例３＞
Georgia Pacific社製の未粉砕シートパルプ５０ｇを含水率測定のために、１１０℃オーブン内で４時間乾燥させたところ、含水率４質量％であった。
混錬機内にイオン交換水で８５質量％に希釈したＢｍｉｍＣｌを２１１７．６ｇ添加し、７０℃に加熱した。次いで、７０ｍｍ×１４０ｍｍに裁断した含水率４質量％の未粉砕シートパルプ２０８．３ｇを混錬機に添加した（浴比１：１０．２）。混錬機内で７０℃、３０分間撹拌することで、パルプの１次処理とした。
次いで、この混錬機を１１０℃に加熱し、約０．１ｋＰａの減圧下で水分を蒸発除去しながら３時間撹拌することで、パルプの２次処理を行い、セルロース溶液を得た。
<Example 3>
When 50 g of unground sheet pulp manufactured by Georgia Pacific was dried in an oven at 110 ° C. for 4 hours for measuring the water content, the water content was 4% by mass.
2117.6 g of BmimCl diluted to 85% by mass with ion-exchanged water was added to the kneader and heated to 70 ° C. Next, 208.3 g of unground sheet pulp having a water content of 4% by mass cut into 70 mm × 140 mm was added to the kneader (bath ratio 1: 10.2). Stirring at 70 ° C. for 30 minutes in a kneader was used as the primary treatment of pulp.
Next, this kneader was heated to 110 ° C. and stirred for 3 hours while evaporating and removing water under a reduced pressure of about 0.1 kPa to perform a secondary treatment of pulp to obtain a cellulose solution.
＜比較例１＞
シートパルプ＋無水ＢｍｉｍＣｌ→１次、２次処理
Georgia Pacific社製の未粉砕シートパルプ５０ｇを含水率測定のために、１１０℃オーブン内で４時間乾燥させたところ、含水率４質量％であった。
混錬機内にあらかじめ水分を除去したＢｍｉｍＣｌを９０．０ｇ添加し、５０℃に加熱した。次いで、２０ｍｍ四方に裁断した含水率４質量％の未粉砕シートパルプ１０．４ｇを混錬機に添加した（浴比１：８．７）。混錬機内で５０℃、３０分間撹拌することで、パルプの１次処理とした。
次いで、この混錬機を１１０℃に加熱し、約０．１ｋＰａの減圧下で水分を蒸発除去しながら３時間撹拌することで、パルプの２次処理を行い、セルロース溶液を得た。
<Comparative example 1>
Sheet pulp + anhydrous BimmCl → primary and secondary treatment
When 50 g of unground sheet pulp manufactured by Georgia Pacific was dried in an oven at 110 ° C. for 4 hours for measuring the water content, the water content was 4% by mass.
90.0 g of BmimCl from which water had been removed in advance was added to the kneader and heated to 50 ° C. Next, 10.4 g of uncrushed sheet pulp having a water content of 4% by mass cut into 20 mm squares was added to the kneader (bath ratio 1: 8.7). Stirring at 50 ° C. for 30 minutes in a kneader was used as the primary treatment of pulp.
Next, this kneader was heated to 110 ° C. and stirred for 3 hours while evaporating and removing water under a reduced pressure of about 0.1 kPa to perform a secondary treatment of pulp to obtain a cellulose solution.
＜比較例２＞
シートパルプ＋含水ＢｍｉｍＣｌ→２次処理のみ
Georgia Pacific社製の未粉砕シートパルプ５０ｇを含水率測定のために、１１０℃オーブン内で４時間乾燥させたところ、含水率４質量％であった。
混錬機内にイオン交換水で９０質量％に希釈したＢｍｉｍＣｌを１００．０ｇ添加し、１１０℃に加熱した。次いで、２０ｍｍ四方に裁断した含水率４質量％の未粉砕シートパルプ１０．４ｇを混錬機に添加した（浴比１：９．６）。この混錬機を約０．１ｋＰａの減圧下で水分を蒸発除去しながら３時間撹拌することで、パルプの１次処理を省き２次処理のみを行い、セルロース溶液を得た。
<Comparative example 2>
Sheet pulp + hydrous BmimCl → secondary treatment only
When 50 g of unground sheet pulp manufactured by Georgia Pacific was dried in an oven at 110 ° C. for 4 hours for measuring the water content, the water content was 4% by mass.
100.0 g of BmimCl diluted to 90% by mass with ion-exchanged water was added into the kneader and heated to 110 ° C. Next, 10.4 g of uncrushed sheet pulp having a water content of 4% by mass cut into 20 mm squares was added to the kneader (bath ratio 1: 9.6). By stirring this kneader for 3 hours while evaporating and removing water under a reduced pressure of about 0.1 kPa, the primary treatment of pulp was omitted and only the secondary treatment was performed to obtain a cellulose solution.
＜セルロース溶液の溶解状態評価＞
セルロースの溶解状態は、ニコン社製の偏光顕微鏡を用いて評価した。２次処理後のセルロース溶液を偏光顕微鏡にて撮影した。撮影画像より、１視野あたりの複屈折を示す未溶解パルプの数をカウントすることで溶解状態の評価とした。
溶解状態評価の結果、本発明に係る実施例において、溶解状態がよい。
比較例１においてはパルプ未溶解の塊が多く見られている。
比較例２においては微細な未溶解が認められた。
上記結果から、パルプの粉砕、乾燥処理を必要とせず、１次処理、２次処理を行うことで２次処理のみと比較して、均質なセルロース溶液を得ることができることを確認した。
<Evaluation of dissolution state of cellulose solution>
The dissolved state of cellulose was evaluated using a polarizing microscope manufactured by Nikon Corporation. The cellulose solution after the secondary treatment was photographed with a polarizing microscope. The dissolved state was evaluated by counting the number of unsolved pulps showing birefringence per visual field from the photographed image.
As a result of the dissolution state evaluation, the dissolution state is good in the examples according to the present invention.
In Comparative Example 1, many undissolved pulp lumps are observed.
In Comparative Example 2, fine undissolved material was observed.
From the above results, it was confirmed that a homogeneous cellulose solution can be obtained by performing the primary treatment and the secondary treatment without requiring the crushing and drying treatment of the pulp, as compared with the secondary treatment alone.
以上、本発明のセルロース溶液の製造方法について、その実施の形態に基づいて説明したが、本発明は上記実施の形態に記載した構成に限定されるものではなく、その趣旨を逸脱しない範囲において適宜その構成を変更することができるものである。 The method for producing a cellulose solution of the present invention has been described above based on the embodiment thereof, but the present invention is not limited to the configuration described in the above embodiment and is appropriately used as long as the purpose is not deviated. The configuration can be changed.
本発明のセルロース溶液の製造方法は、イオン液体の濃縮及びパルプの乾燥や粉砕にかかる時間とエネルギを削減し、パルプの溶解性に優れているという特性を有していることから、繊維やフィルムなどのセルロース材料の成形、例えば、タイヤコード糸等のフィラメント糸の製造に用いられるセルロース溶液の製造に好適に用いることができる。 The method for producing a cellulose solution of the present invention has the characteristics of reducing the time and energy required for concentrating an ionic liquid and drying and crushing pulp, and having excellent solubility of pulp. Therefore, fibers and films It can be suitably used for molding a cellulose material such as, for example, for producing a cellulose solution used for producing a filament yarn such as a tire cord yarn.
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