JPS6040101A - Continuous preparation of sheet alkali cellulose - Google Patents
Continuous preparation of sheet alkali celluloseInfo
- Publication number
- JPS6040101A JPS6040101A JP14824983A JP14824983A JPS6040101A JP S6040101 A JPS6040101 A JP S6040101A JP 14824983 A JP14824983 A JP 14824983A JP 14824983 A JP14824983 A JP 14824983A JP S6040101 A JPS6040101 A JP S6040101A
- Authority
- JP
- Japan
- Prior art keywords
- alkali
- cellulose
- sheet
- solution
- water
- 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
- 239000003513 alkali Substances 0.000 title claims abstract description 26
- 229920002678 cellulose Polymers 0.000 title abstract description 31
- 239000001913 cellulose Substances 0.000 title abstract description 31
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims abstract description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012046 mixed solvent Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract 3
- 239000011358 absorbing material Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 11
- 229920000742 Cotton Polymers 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- 239000004744 fabric Substances 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 101100313164 Caenorhabditis elegans sea-1 gene Proteins 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- JMBPWMGVERNEJY-UHFFFAOYSA-N helium;hydrate Chemical compound [He].O JMBPWMGVERNEJY-UHFFFAOYSA-N 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- -1 methyl ethyl Chemical group 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- UMFCIIBZHQXRCJ-NSCUHMNNSA-N trans-anol Chemical compound C\C=C\C1=CC=C(O)C=C1 UMFCIIBZHQXRCJ-NSCUHMNNSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 241000545744 Hirudinea Species 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000021962 pH elevation Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KBXWAKYDYYEGBF-UHFFFAOYSA-N propan-2-ol;dihydrate Chemical compound O.O.CC(C)O KBXWAKYDYYEGBF-UHFFFAOYSA-N 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は天然セルロースまたは再生セル［］−ス繊維に
りなろ布、不織布、紙等のシート状しルロースを連続的
に均質にアルレル化づる方法にｇ！Ｉづる。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for continuously and homogeneously allerminating natural cellulose or regenerated cellulose fibers into sheets of lullose, such as cloth, nonwoven fabric, and paper. Izuru.
最近、膨潤・吸水性レルロース工ーテル，特にカルボキ
シアルキルレルロースが注目されている。Recently, swelling and water-absorbing lerulose ethers, especially carboxyalkyl lerulose, have attracted attention.
これは白液・尿等の牛１１液体の吸収（Δどじ一Ｃ、あ
るいは各種油中の微０１水分の吸水月として、ｄつるい
ＣＬ他の分野において・し用途が拡大され、累月として
の重要度が高まってきている。This is used as absorption of cow 11 liquids such as white liquor and urine (ΔDojiichiC), or absorption of minute moisture in various oils. is becoming increasingly important.
実際的用途においては、（Φ々の形状へ加工しやりいと
いったことでシート状の形態のものが要望されている。For practical use, sheet-like products are desired because they can be easily processed into shapes of Φ.
現状は、通’７ｊｌの木材パルプ又は二１ツ１ーンリン
ターを解砕して；贋法に従ってアルＬル化及びカルボキ
シアルキル化した後、得られる単楳庁（１状物をアルコ
ール類の溶剤系中で抄造（特開昭５（ｉ−２６０９９号
公報）する技術が開始されているだり（゛ある。しかし
、この方法は膨大な聞の溶剤を使うため、イの揮散防止
および安全性の面等から完１ゝ畜開系の抄；前設ｈｊ品
が要る事など余り実用的ではｈい。At present, the wood pulp of 7JL or 21L of linter is crushed; after being subjected to arylization and carboxyalkylation according to the counterfeiting method, the resulting Paper making technology (Japanese Unexamined Patent Application Publication No. I-26099) has been started in Japan. However, this method uses a huge amount of solvent, so it is difficult to prevent volatilization and to be safe. etc., it is not very practical as it requires a complete 1゜cultivation system; it requires a pre-installed hj item.
シー１〜状ヒルロースを原料に、その形態を保持したま
ま連続的にカルボ４−ジアルキル化することが考えられ
るが、従来の技術範囲の延長線で考えたのではセル［１
−スエーテル！ｌＩ造技術において最Ｌ）ｉｐ要な役割
を果しＣいるアルノＪリレルロースを連続的に、均質に
、シート状形態を崩さず、さらに後工程のエーテル化剤
の利用率を低下さけない状態で１５することには多くの
問題がある。It is conceivable to continuously carbo-4-dialkylate C1-shaped hillulose as a raw material while maintaining its morphology, but if we consider this as an extension of the conventional technology,
-Suether! ArnoJ Lilylulose, which plays the most important role in II manufacturing technology, is produced continuously, homogeneously, without destroying its sheet-like form, and without reducing the utilization rate of the etherification agent in the subsequent process. There are many problems with doing this.
一方、セルロースのアルはル化の常法の一つとして、ヒ
ルロースシーｈ片を約１８％の水酸化ナトリウム水ンＰ
ｉ液に浸ｉｒｊ Ｌ、浸漬液を除去し、シー１−１７を
圧搾し、解砕して綿状にする方法が′ある。まｌこ溶媒
アルヒル化法ど称甘られ、有機溶媒（例えばイソプロピ
ルアルコール）、水、水酸化す１−リウムからなる２層
に分）１夕したアルはル化剤に線状にＷ１砕したしルロ
ースを混合接触さυてアルセル化を行う方法がある。こ
の場合、水酸化す１ヘリウムの有機溶媒−水系における
使用割合は２層程度である。On the other hand, as one of the conventional methods for alkalinization of cellulose, a piece of hirulose seaweed is dissolved in about 18% sodium hydroxide solution (P).
There is a method of immersing the irj L in the liquid, removing the immersion liquid, squeezing the sea 1-17, and crushing it into a cotton-like form. Solvent alhylation method (also known as ``solvent alhylation method''), which is divided into two layers consisting of an organic solvent (e.g. isopropyl alcohol), water, and 1-lithium hydroxide), is crushed linearly into a hydration agent. There is a method of arcelization using mixed contact with sululose. In this case, the proportion of helium hydroxide used in the organic solvent-water system is about two layers.
この発明の発明者は、溶媒アルセル化法のアル６セル化
機（１４について種々検討しているうちに、水酸化す１
ヘリウムが極めて肪い濃度にａ）いてｂ十分にアルセル
化が進行するということを意外にも見出した。さらに、
希アルカリのアルセル化剤を用いうれば、セルロースが
帯状シー１〜の状態でもアルセル化が行え、かつ連続的
に行いうろこと、さらにアルセル化が均一に進行づる知
見を（ｑ、この発明を完成するに到った。The inventor of this invention discovered that hydroxide
It has been surprisingly discovered that a) when helium is present at an extremely high concentration, b) arcelization proceeds sufficiently. moreover,
If a dilute alkali arcelizing agent is used, it is possible to carry out arcelization even when the cellulose is in the form of a band-like sheet, and the knowledge that the arcelization can be carried out continuously and evenly progresses (q, this invention has been completed) I came to the conclusion.
か＜ｌ、’Ｃ１この発明によれば、イソプロピルアルコ
ール、ｔ−ブヂルアルコール、］］１−ブヂルアルコー
ルアセ１−ンおよびメチルエヂルク゛１−ンから選ばれ
る有機？８媒約８０〜９６重量部と水約２０〜４重最部
の混合溶媒中に、水酸化アルノノリを約ｏ、ｏｏｉ−０
，５重用％溶解してなるアルはル化溶液を、シー１へ状
ヒルＩＪ−スに連続接触さゼ゛Ｃ，シー１〜状アルカリ
レルロースを１１することを特１攻とするシーＩ・状ア
ルカリセルロースの連続製造方法が提供される。<l,'C1 According to the invention, an organic compound selected from isopropyl alcohol, t-butyl alcohol, ]]1-butylalcohol ace1-one and methyl ethyl alcohol ace1-one is used. In a mixed solvent of about 80 to 96 parts by weight of 8 parts by weight and about 20 to 4 parts by weight of water, about 0.
, a special attack is made by continuously contacting an alkaline solution prepared by dissolving 5% alkaline relulose with a heliulase in the form of sheath I. A continuous method for producing .-like alkali cellulose is provided.
この発明に使用りるシー１へ状セルロースとは、７１ｊ
、不織布、爪などの何れであってもよい。しかし、連続
化＃Ｊ！さ口るに通した形態である必要がある。そのた
めには、連続シート形態のヒルロースが好ましい。その
際の１１」は、特に限定されないが、例えは５０ ｃｍ
〜２００ ｃｍが挙げられる。長手方向１，１．１−ン
トレス（あつＣしよい。The cellulose cellulose used in this invention is 71j
, nonwoven fabric, nails, etc. However, serialization #J! It needs to be in a clear form. For this purpose, hillose in the form of a continuous sheet is preferred. 11" in this case is not particularly limited, but for example, it is 50 cm.
~200 cm. Longitudinal direction 1,1.1-entres (hot C).
この発明にｄハＪる混合溶媒にＪ３いて使用する右１犬
！？？ ＩＩ！Ｉ！は、親水１１か昌く、かつ水をよく
混合しうる炭素数３又は４の脂肪族アルコールまたはケ
１ヘンが用いられる。具体的にはイソプロピルアルコー
ル、【−ブヂルアル］−ルあるいは１１−ブチルノ′ル
ー１−ル、又はノ’ｔｌ〜ンあるいはメチル１ブルグ１
ヘンか含まれる。This invention uses the right 1 dog to use J3 in the mixed solvent! ? ? II! I! For example, an aliphatic alcohol or alcohol having 3 or 4 carbon atoms which is hydrophilic and can be mixed well with water is used. Specifically, isopropyl alcohol, [-butyral]-ol, 11-butylol, or methyl
Contains weird.
イＪＩＡｕ溶媒と水との使用割合は、約８０〜９６重用
部：約２０〜４重ωａｌｌである。この使用Ａ’）合で
は、水ｎ塁化アルカリを上記ｍ溶解した際にＪ５いても
有機溶媒と水とが、実質的に均一な層を形成しつる。し
かし、有機溶媒の種類によって、上記の使用割合中でＵ
？ましい割合が若干ことなるので、適宜選択Ｊるのが望
まれる。例えばイソプロピルアルコール−水系では、８
５〜９５：１５〜５Ｃある。しかしながら、水−の使用
割合が２０部をこえてより人になるとアルセル化が十分
に進行せず、一部がヒル［１−スのままで残ることが判
明した。−力水の使用割合が４部より少いと、アルヒル
化に必要なアルカリの絶ｊｉＪ ｎ’１が（＋、（下し
、にり大量のアルセル化溶媒を接触さＪ必要があり、連
続工業住産土好ましくない。The ratio of the JIAu solvent and water used is about 80 to 96 parts by weight: about 20 to 4 parts by weight. In this use case A'), when the water n-base alkali is dissolved in the above m amount, the organic solvent and water form a substantially uniform layer even if J5 is used. However, depending on the type of organic solvent, U
? Since the desired ratios differ slightly, it is desirable to select them appropriately. For example, in an isopropyl alcohol-water system, 8
5-95: 15-5C. However, it has been found that when the proportion of water used exceeds 20 parts and becomes more concentrated, arcelization does not proceed sufficiently and a portion remains as leech. - If the proportion of water used is less than 4 parts, the amount of alkali necessary for alhylation will be reduced (+, (), and it will be necessary to contact a large amount of alkylization solvent, resulting in a continuous process. Domestic soil is not desirable.
水酸化アルカリとしては、水酸化プトリウムと水酸化カ
リウムがある。好ましいのは水酸化す１〜リウムである
。水酸化アルカリの混合ｉＢＤ中にか【］る１１’１度
は、ｏ、ｏｏｉ〜０．５重量％で、好ましく（は０．０
５〜０．２重量％である。Alkali hydroxides include puttrium hydroxide and potassium hydroxide. Preferred are mono-lithium hydroxides. The 11'1 degree dissolved in the mixed iBD of alkali hydroxide is o, ooi ~ 0.5% by weight, preferably (0.0
It is 5 to 0.2% by weight.
この発明のアルセル化は、シー１−状レルロ〜スとアル
セル化溶液とを接続接触させて行われる。The arcelization of the present invention is carried out by bringing the sheath-like relulose into contact with the arcelization solution.
連続接触の方法は、両者の十分な接触が連続的にされる
ように行われるべきである。接触は、シート状ヒルロー
スとアルセル化溶液とが向流、亜流又は交叉流でされて
もＪ、い。通常、自流で行うのか々ｆよしい。The continuous contact method should be such that sufficient contact between the two is continuous. The contact may be made in countercurrent, subcurrent, or crosscurrent flow between the sheet-like hillulose and the alcelization solution. It is usually best to do it yourself.
シー１〜状ヒルロースに対りるアルセル化溶液の接触Ｑ
ｌ化はシー１へ状セルロース１に対し５００〜、’＋
０００部の間か螢けられる。両者の接触時間は３０分〜
２１１．￥間、好ましくは１１１￥間である。接触湿度
は、約１０〜３０℃好ましくは約１５〜２０℃−（ある
。Contact Q of arcelization solution to C1-like hillulose
l conversion is 500~, '+
000 copies or so. The contact time between the two is 30 minutes ~
211. It is between ¥111, preferably between ¥111. The contact humidity is about 10-30°C, preferably about 15-20°C.
）１ルレル化溶液（Ｊ、予め所定濃度に調整して用いら
れるが、ヒルロースとの接触に用いられたアルセル化溶
ｄ夕はｄ１費された水酸化アルカリを？１１１うｌ＼く
所定ｈ１を添加りることによって繰り返し利用（さる。) 1 Lulerization solution (J, used after adjusting to a predetermined concentration in advance, but the alkali hydroxide used in contact with hirulose is 111 ml of alkali hydroxide and the predetermined h1) It can be used repeatedly by adding
↓ス土説明しｌここときこの発明の方法におりる一つの
大きな特徴は水酸化アルカリの使用濃Ｔ島が極めＣ希ｉ
ｔ’Ｑ ’Ｃ（ｌ／＋ることである。しかし、この１易
合この発明の発明者の実験によれば、反応が進行する理
由は、アルカリと水とがセルロース分子の近傍に選択的
に分配されて、その近傍にお（プるアル７Ｊり温度がア
ルヒル化に適した濃度に達づることによるとみられる。↓Explanation: One major feature of the method of this invention is that the use of alkali hydroxide is extremely rare.
t'Q'C(l/+) However, according to the experiments of the inventor of this invention, the reason why the reaction progresses is that alkali and water are selectively brought into the vicinity of cellulose molecules. This seems to be due to the fact that the temperature reaches a concentration suitable for alkylation.
一方アルカリの濃度の希薄なため、アルセル化溶液は均
一相液となりセルロース分子との接触ｈ＜より均一とな
り、従来例に比較して均一なう７ル）ｙリセルロースが
得られる。この均一なフ’／レノＪ１ノロルロースをＩ
Ｊｍ Ｍ’ｉｌとづれば、さらに均一４１セルロースニ
ーテールを１創ることができ、水や生１１液体に夕１づ
る］彰潤吸収性態が均質な製品が１１ノられるとし）う
利点がある。On the other hand, since the alkali concentration is dilute, the alcelization solution becomes a homogeneous phase liquid and the contact with cellulose molecules becomes more uniform, resulting in more uniform recellulose than in the conventional example. This homogeneous Fu'/Reno J1 Nororulose I
If JmM'il is used, it is possible to create a more uniform cellulose niter, which has the advantage of producing a product with homogeneous moisture-absorbing properties when added to water or raw liquids.
ざらにこの５’ｌ ｔ！１１の方法によれば次のごとき
利点がもたらされる。Zaraniko 5'l t! According to the method No. 11, the following advantages are brought about.
！Ｊな４つち連続２人であるため大１ｒｊのヒル［ｊ−
スを］二業生産するのに通ずる。! Because there are two consecutive J fours, the hill of the large 1rj [j-
This leads to secondary production.
従来法のセルロースニーデルのシーｈ化Ｉま抄紙時に、
人ｈ１の有機溶媒を用いて行う必要がある／〕〜、この
発明の原ｔｌであるシー１〜状セルロース【よ、例えば
水系抄紙、乾式の不織布化なとで作ること７Ｊ＼（さ４
！１ｊめＵイｉ利にシーミル状最終製品（シート状セル
［１−ス」ニーデル）にンｎくことができる。When making paper using the conventional method of cellulose needle sheathing,
It is necessary to carry out the process using an organic solvent of 7J\(Sa4
! It can be advantageously applied to a seamill-like final product (sheet-like cell needle).
この発明のシー１〜状アルカリセルロースは水媒アルヒ
ル化法によるごとき過剰のアルヒル化液の１１１２液処
１！ｌ！智の後処理が不要で直らにそのままニーｊル土
稈に供４ることができる。また、での土エーテル化］二
稈もこの発明において使用する溶媒系ど１１１１−のし
ので（Ｉうことかできる。The C1-like alkali cellulose of the present invention is obtained by processing 1112 solution of an excess alhylation solution such as that obtained by aqueous alhylation method. l! There is no need for post-processing, and it can be directly used as a needle. In addition, the solvent system used in this invention can also be referred to as 1111-Noshino (I).
以下、図面ににりこの発明を詳説する。第２図はこの発
明の方法を実施する装置の一例を示”ｌ’ ４ｒｌｆ成
説明図である。図にＪ３いて、アルセル化容器（１）の
Ｅ１目３１隔壁（２）どガイドロール（３）で構成され
ている。Hereinafter, this invention will be explained in detail with reference to the drawings. FIG. 2 is an explanatory diagram showing an example of an apparatus for carrying out the method of the present invention. ).
ヒルロースシ−１〜（１４）を入口のロール（４）を経
てアルヒル化容器内へ導入し、容器内°をＣ１通させ、
シールロール（５）を経（器外へ出り。Introduce the hirulose sea 1 to (14) into the alhyllization container through the inlet roll (4), and allow the inside of the container to pass through C1.
Pass through the seal roll (5) (out of the container).
イソプ１１パノール１、水そしてカレイソータ′より成
る均一アルセル化溶液はタンク曲で、：１．’ｌ♂）さ
れ、ポンプ（１２）と熱交換器（１３）を経て（６）の
流入１」よりアルヒル化容器内へ送入される。セルロー
スシー１− （１４）ど向ｔ７ｊ接ＦＦＩ！シた液は渦
流口（７）より１１１出されタンク（１１）に戻る消費
された液成分はｆ１６） Ｊ：り供給されタンク（１１
）内で漢１隻調整される。タンク（９）はアルｊＪりと
セルロースシー１〜への随伴液の貯溜タンクであり、中
に溜った液はポンプ（１０）でタンク（１旧こ戻される
。A homogeneous arcelization solution consisting of 1 part Isopol, 1 part Panol, water and Cali Sorta' was prepared in a tank: 1. 'l♂) and is sent into the alhylation vessel from the inlet 1' of (6) via the pump (12) and heat exchanger (13). Cellulose sea 1- (14) Which direction t7j contact FFI! The drained liquid is taken out from the vortex port (7) and returned to the tank (11).The consumed liquid component is fed to the tank (11).
), one Han ship is adjusted. The tank (9) is a storage tank for the accompanying liquid to the cellulose sea 1~, and the liquid accumulated therein is returned to the tank (1) by the pump (10).
アルセル化温度はアルヒル化容器のジｔ７クツ１〜（８
）と熱交換器６３）ににつて前記しＩこ所定の篇）度に
調整される。セルロースシー１−のアルヒル化器内）ｌ
ｉｊ留時開時間０分〜２時間好ましくは１時間程麿かよ
い。セルロースに対する溶液の接触ｍ比は５００−５０
００の間で選択される。）↑続的に調整されたアルカリ
ヒルロース［１５］は次の連続エーテル化（戊へ送られ
る。The alhylation temperature is the temperature of the alhyllization container.
) and the heat exchanger 63) are adjusted to a predetermined degree as described above. Cellulose sea 1- in the alhyllizer)
The opening time during the distillation is 0 minutes to 2 hours, preferably about 1 hour. The contact m ratio of solution to cellulose is 500-50
Selected between 00 and 00. )↑Continuously prepared alkaline hirulose [15] is sent to the next continuous etherification (Hori).
以上、向流接触装置６を用いて実施ｒぷ仔の説明を行な
ったが、状況によっては並流又は交叉接触法を選択覆る
小は可能であり、前述の装ｐ？ｌにＪ、り木光明の思想
が拘束されるものでは４７い。Above, we have explained the implementation process using the countercurrent contacting device 6, but depending on the situation, it is possible to select the cocurrent or cross-contacting method. J, Riki Mitsuaki's thoughts are not restricted to 47.
以下、実施例ににす、本発明をさらに具体的に詳説ｔこ
説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
第２図に示した装置に幅２０ｃｍ、１ ＋ｎ’当りの重
さが１００ｇの綿布を１２．６ｃｍ ／ ＩＩ！ｍの速
さぐ通した。一方アルヒル化溶液としてはイソプロパツ
ール９４．７ｊｆｉ １７１’％、水５．２重閤％水酸
化ナトリウム０．１重量％からなる均一溶液を１３Ｑ／
ｍｉｍの流ｒｉ１で送流し、綿（ｌｊと向流接触さＵた
。この間アルヒル化綿度は１５℃に保った。取り出され
たアルヒル化綿布についてアルカリ昂を分析した。リン
ブリング場所は第３図に示した如く、Ａ、、Ｂ、Ｃの各
部分を所定１１．１間毎に切り取り中和滴定法で分析し
た測定値を８１に示す。Example 1 A 12.6 cm/II! cotton cloth with a width of 20 cm and a weight of 100 g per 1+n' was placed in the apparatus shown in FIG. I passed the speed of m. On the other hand, as an alhylation solution, a homogeneous solution consisting of 94.7jfi 171'% of isopropanol, 5.2% of water and 0.1% of sodium hydroxide was used as 13Q/
The alkylated cotton cloth was flown through with the stream ri1 of mim and brought into countercurrent contact with the cotton (lj).During this time, the alhylated cotton fabric was kept at 15°C.The alkylated cotton cloth taken out was analyzed for alkali concentration. As shown in the figure, portions A, B, and C were cut out at predetermined intervals of 11.1 seconds and analyzed by neutralization titration, and the measured values are shown at 81.
表１
定常状態トす達後 ザンブリング揚所
すンブリングｕ：ｒ間 Ａ Ｉ３ ０
３分 ３．１８ ３．１２ ３．１５
５分 ３．１０ ３．１９ ３．１２
１０分 ３．０９ ３．ＩＧ ３．１１甲（１ン： Ｎ
ａ Ｏｆｆ ｎｕｌｌ ／１１０１クル二１−７． ｙ
５ ｔ＜実施例２
へ１２図に示した装置に幅２０ Ｃ１ｌ＋、′１川２当
りのルさが１５０ｇの再生ヒルロース不織布を１２．６
ｃｍ ／ ｍ１ＩＩｌの速さで通した、一方アルセル化
溶液としては、イソプロパ／ ）Ｌｉ ８９．４３ ｔ
Ｊ （ｉｌ ％ 、 水１０．４５小ｆｉ ９／、。Table 1 After reaching steady state Zumbling lift station Summbling u:r A I3 0 3 minutes 3.18 3.12 3.15 5 minutes 3.10 3.19 3.12 10 minutes 3.09 3. IG 3.11A (1n: N
a Off null /1101 Kuruni 1-7. y
5 t<Example 2 To the apparatus shown in Fig. 12, 12.6 pieces of recycled hillulose nonwoven fabric having a width of 20 C1l+ and a looseness of 150 g per 1 river 2 was placed.
cm/ml at a rate of 1 IIl, while as the alcelification solution, isopropa/ )Li 89.43 t
J (il %, water 10.45 small fi 9/,.
水酸化す１〜リウム０，１２Φ…％からなる均一溶液を
１０Ω／ｍｉｍの流量で送液し、不織布と向流接触さＩ
！／（。この間アルヒル化綿度は１５℃にイ＾つだ。A homogeneous solution consisting of 1% to 0.12Φ...% of sodium hydroxide was fed at a flow rate of 10Ω/min, and brought into countercurrent contact with the nonwoven fabric.
! /(During this period, the alkylated cotton temperature rose to 15℃.
取り出されたアルセル化不織布についてアルカリｍを分
析した。サンプリング場所は実施例１と同様である。測
定（ｉＱを表２に示Ｊ。The alkali m of the taken out arcelized nonwoven fabric was analyzed. The sampling location is the same as in Example 1. Measurements (iQ are shown in Table 2).
表２
定常状態到達後 サンプリング場所
サンプリング時間
Ａ １３ Ｄ
３分 ２，６２ ２．５５ ２，５９
５分 ２．ＧＯ２，６２２，（ｉ４
１０分 ２．５ｉ’ ２．６？ ２．６０１１１位：
Ｎａ ｏｒ−＋ ｍｏｌ ／１１１０１ りｔｖコース
ｐ５ｔＨ比較例
第２図に示した装置に幅２０ ｃｍ、Ｉ Ｉ１１’当り
の小さが１ ｏｏｇの綿布を１２．６ＣＩＩｌ ／ ｍ
ｉｍの速さで通した。一方アルセル化溶液としてはイソ
ブ【：ｊパノール８８．３ＥＤ Ｉｎ％、水９．６ルｈ
］％、水酸化プトリウム２．１小ｍ％からなる２層分Ｎ
１液をよく撹拌混合し１１ｆ３ｉｆ７ ｍ ｒ ｍの流
（トｂ送油し、綿イ１ｊと向流接触ざけた。Table 2 After reaching steady state Sampling location Sampling time A 13 D 3 minutes 2,62 2.55 2,59 5 minutes 2. GO2,622, (i4 10 minutes 2.5i' 2.6? 2.60111th place:
Na or-+ mol /11101 TV course p5tH Comparative example A cotton cloth with a width of 20 cm and a diameter of 1 oog per I11' was placed in the apparatus shown in Fig. 2 at a concentration of 12.6 CIIl/m.
I passed at the speed of im. On the other hand, as an arcelization solution, isobu[:j Panol 88.3ED In%, water 9.6lh
]%, two layers consisting of 2.1 small m% of puttrium hydroxide N
The first solution was thoroughly stirred and mixed, and a flow of 11f3if7 m r m (tob) was fed to bring it into countercurrent contact with the cotton parti1j.
この間、アルセル化温ｌｑは１５℃に保っ７１＋ 、、
取り出されたアルヒル化綿ｆｌｊについてアルカリ１１
を分析した。１ノンブリング場所は実施例１と同様であ
る。During this time, the arcelization temperature lq was kept at 15°C.
Alkali 11 about the taken out alhylated cotton flj
was analyzed. 1 non-bringing location is the same as in Example 1.
測定１１Ｃ１を表３に示づ。Measurement 11C1 is shown in Table 3.
表３
定常状態到達後 リンブリング場所
リンブリング１１．Ｙ間
八 〇〇
３分 ４．５０ ３．７６ ２，９８
５分 ３．１５ ２．８７ ４．０！ｉ１０分 ３，９
５ ３．２１ ２．３５甲位： Ｎａ ０１−ｌ ｍｏ
ｌ ／ｍｏｌグルコース残塁なお、第１図にイソプロパ
ノ−ルー水−水酸化す１−リウムーヒル［１−ス系にお
【）る分配曲線及び生成するアルカリセルロースの秤類
との関係を示しＩＪ。Table 3 After reaching steady state Ringing location Ringling 11. Between Y 8003 minutes 4.50 3.76 2,98 5 minutes 3.15 2.87 4.0! i10 minutes 3,9
5 3.21 2.35 instep: Na 01-l mo
Figure 1 shows the relationship between the distribution curve in the isopropanol-water-hydroxide 1-lium-hill [1-su] system and the balance of the alkali cellulose produced.
ＩＪ軸・・・ヒルロース近傍の水酸化プ１ヘリウムｆｉ
（ＮａＯＨｍａｔ’／ｍｏｌグル」−ス残阜）横軸・・
・溶媒相の水酸化す（−リウム早（■間％、対数目盛）
図中のＯ１△、■、Ａ、×印：アルカリｊ１１の実測点
おＪ：びアルカリセルロースの構造を示している。IJ axis...P1 helium hydroxide near hillulose
(NaOHmat'/mol group) horizontal axis...
・Solvent phase hydroxide (-Rium index (% between ■, logarithmic scale) O1△, ■, A, × marks in the figure: actual measurement points of alkali j11 and J: indicate the structure of alkali cellulose.
細破線：アルカリの分配曲線 数字は液相のＩＰΔ淵瓜（重量％） 太実線：アルカリセルロース相Ｊｊ３界線Thin dashed line: alkali partition curve Numbers are liquid phase IPΔ Fuchigo (wt%) Thick solid line: alkali cellulose phase Jj3 boundary line
第１図はイソプロパツール−水〜水酸化す１〜リウム〜
セルロース系にお【プろ水酸化す１〜リウムのヒルロー
ス近傍おにび溶媒イ０への分配＋ｌｂ線ならひに生成す
るアルカリセルロースの４１１ ’Ｐ 両図である。
第２図は本発明の７５法に用いられる製造装置の−例を
示す断面図である。
負１３図は本発明の方法によって得られたアルカリセル
ロースシー１〜のアルカリ吊分析のためのり一ンブリン
グ場所（Ａ、Ｂ、Ｃ）を示Ｊ部分平面図である。 （１
）・・・・・・アルセル化容器、（２）・・・・・・隔
壁。
（３３）・・・・・・カイトロール、 ［４Ｈ５］・・
・・・・シールロール（０）・・・・・・アルセル化液
送入口。
（７）・・・・・・アル［ル化液溢流口，（ε３）・・
・・・・ジ１７ケツト。
（９）曲・・・・・・タンク、 ００１（１２１・・・
・・・送液ポンプ。
０１３）・・・・・・熱交換器，０４）・・・・・・シ
ー１〜状レルロース。
（１５）・・・・・・アルカリセルロース、 ＋＋６）
・・・・・・薬剤補給口。
代理人 弁理士 野 河 信入部Figure 1 shows isopropanol - water - hydrogen oxide - lithium -
In the cellulose system, the distribution of mono-lithium hydroxide to the solvent I0 in the vicinity of hirulose + lb line is the resulting alkali cellulose 411'P. FIG. 2 is a sectional view showing an example of a manufacturing apparatus used in the 75 method of the present invention. Figure 13 is a partial plan view showing the glue sintering locations (A, B, C) for alkali suspension analysis of the alkali cellulose sheets 1 to 1 obtained by the method of the present invention. (1
)... Arcelization container, (2)... Partition wall. (33)...Kytrol, [4H5]...
... Seal roll (0) ... Arcelization liquid inlet. (7)... Aluminum liquid overflow port, (ε3)...
...The 17th. (9) Song...Tank, 001 (121...
···Feed pump. 013)...Heat exchanger, 04)...Ci 1~-like lerulose. (15)・・・Alkaline cellulose, ++6)
・・・・・・Medicine supply port. Agent Patent Attorney Nogawa Nobuiri Department
Claims (1)
ルコール チル」ＬヂルケＩ・ンから運ばれる有ＪＡＭ ６媒約８
０〜９６小１Ｊ１部と水約２０〜７１Ｉ重聞部の混合溶
媒中に、水酸化アルカリを約０．００１〜０．５重ｆＩ
１％溶解してなる１ルレル化溶液を、シー１〜状レルロ
ースに連続接剛ｉさｌ！（、シート状アルカリレルＵ−
スを寄ることを１′１徴とりるシート状アルカリＬルＩ
ー１−スの連し°，′警１３Δ）°ｊ法。 （２） シー１〜状レルロースが帯状の連続シー１〜の
形態くある特にＩ’ ｎｔ’をの範囲第１項記載の方法
。 （３（） 連続接触が、アルレル化溶液とシー１・状レ
ル【」−スどの向流、並流叉は交叉流ｔこよって行４？
れる特訂ｉ＋！’Ｉ求の範囲第１又は２Ｊｎに記載の方
法。 ０） 有機溶媒がイソプロピルアルコールである１・ｒ
許請求の範囲第１〜３項の何れかに記載の方法。 （５） 連続接触が約１０〜３０℃で行われる特轟′１
品求の範囲第１〜４項の何れかに記載の方法。[Scope of Claims] (1) Isobu [21-biruf7 alcohol, t-butyl alcohol tyl]
About 0.001 to 0.5 parts of alkali hydroxide is added to a mixed solvent of 1 part of 1J of 0 to 96 parts and about 20 to 71 parts of water.
Continuously apply a 1% Lerulose solution to the Lerulose. (, sheet-like alkaline U-
Sheet-like alkali llu I
-1-s series °,' 13Δ) °j method. (2) The method according to item 1, in which the sheath-like lerulose is in the form of a band-like continuous sheath. (3()) Continuous contact with the allergenation solution causes countercurrent, cocurrent, or crosscurrent flow.
Special edition i+! 'The method described in Section 1 or 2 Jn. 0) 1・r where the organic solvent is isopropyl alcohol
A method according to any one of claims 1 to 3. (5) Tokudoro'1 where continuous contact is carried out at approximately 10 to 30°C
The method according to any one of item ranges 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14824983A JPS6040101A (en) | 1983-08-13 | 1983-08-13 | Continuous preparation of sheet alkali cellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14824983A JPS6040101A (en) | 1983-08-13 | 1983-08-13 | Continuous preparation of sheet alkali cellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6040101A true JPS6040101A (en) | 1985-03-02 |
| JPH0357226B2 JPH0357226B2 (en) | 1991-08-30 |
Family
ID=15448563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14824983A Granted JPS6040101A (en) | 1983-08-13 | 1983-08-13 | Continuous preparation of sheet alkali cellulose |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6040101A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009173907A (en) * | 2007-12-27 | 2009-08-06 | Shin Etsu Chem Co Ltd | Method for producing alkali cellulose and water-soluble cellulose ether |
| EP2489677A1 (en) | 2011-02-21 | 2012-08-22 | Shin-Etsu Chemical Co., Ltd. | Methods for Preparing Alkali Cellulose and Cellulose Ether |
| US8853388B2 (en) | 2005-12-27 | 2014-10-07 | Shin-Etsu Chemical Co., Ltd. | Methods for preparing alkali cellulose and cellulose ether |
| US8865889B2 (en) | 2005-12-27 | 2014-10-21 | Shin-Etsu Chemical Co., Ltd. | Methods for preparing alkali cellulose and cellulose ether |
| US9115216B2 (en) | 2011-02-21 | 2015-08-25 | Shin-Etsu Chemical Co., Ltd. | Method for producing alkali cellulose comprising removal of cellulose particles |
| US9371399B2 (en) | 2011-02-21 | 2016-06-21 | Shin-Etsu Chemical Co., Ltd. | Methods for producing alkali cellulose and cellulose ether |
| US9481738B2 (en) | 2011-02-21 | 2016-11-01 | Shin-Etsu Chemical Co., Ltd. | Method for producing cellulose ether |
| CN106147259A (en) * | 2015-04-08 | 2016-11-23 | 中国科学院理化技术研究所 | Preparation method of surface hydrophobic flaky cellulose and flaky cellulose |
| US9534061B2 (en) | 2005-12-27 | 2017-01-03 | Shin-Etsu Chemical Co., Ltd. | Methods for preparing alkali cellulose and cellulose ether |
| US9580516B2 (en) | 2011-02-21 | 2017-02-28 | Shin-Etsu Chemical Co., Ltd. | Methods for producing alkali cellulose and cellulose ether |
| US9611333B2 (en) | 2005-12-27 | 2017-04-04 | Shin-Etsu Chemical Co., Ltd. | Methods for preparing alkali cellulose and cellulose ether |
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| CN104974357B (en) * | 2014-04-10 | 2018-04-20 | 中国科学院理化技术研究所 | Ultraviolet-resistant flaky cellulose material and preparation method and application thereof |
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Cited By (15)
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|---|---|---|---|---|
| US9617350B2 (en) | 2005-12-27 | 2017-04-11 | Shin-Etsu Chemical Co., Ltd. | Methods for preparing alkali cellulose and cellulose ether |
| US9611333B2 (en) | 2005-12-27 | 2017-04-04 | Shin-Etsu Chemical Co., Ltd. | Methods for preparing alkali cellulose and cellulose ether |
| US9534061B2 (en) | 2005-12-27 | 2017-01-03 | Shin-Etsu Chemical Co., Ltd. | Methods for preparing alkali cellulose and cellulose ether |
| US8853388B2 (en) | 2005-12-27 | 2014-10-07 | Shin-Etsu Chemical Co., Ltd. | Methods for preparing alkali cellulose and cellulose ether |
| US8865889B2 (en) | 2005-12-27 | 2014-10-21 | Shin-Etsu Chemical Co., Ltd. | Methods for preparing alkali cellulose and cellulose ether |
| JP2009173907A (en) * | 2007-12-27 | 2009-08-06 | Shin Etsu Chem Co Ltd | Method for producing alkali cellulose and water-soluble cellulose ether |
| US9115216B2 (en) | 2011-02-21 | 2015-08-25 | Shin-Etsu Chemical Co., Ltd. | Method for producing alkali cellulose comprising removal of cellulose particles |
| US9371399B2 (en) | 2011-02-21 | 2016-06-21 | Shin-Etsu Chemical Co., Ltd. | Methods for producing alkali cellulose and cellulose ether |
| US9371398B2 (en) | 2011-02-21 | 2016-06-21 | Shin-Etsu Chemical Co., Ltd. | Methods for preparing alkali cellulose and cellulose ether |
| US9481738B2 (en) | 2011-02-21 | 2016-11-01 | Shin-Etsu Chemical Co., Ltd. | Method for producing cellulose ether |
| JP2012172035A (en) * | 2011-02-21 | 2012-09-10 | Shin-Etsu Chemical Co Ltd | Method for preparing alkali cellulose and cellulose ether |
| US9580516B2 (en) | 2011-02-21 | 2017-02-28 | Shin-Etsu Chemical Co., Ltd. | Methods for producing alkali cellulose and cellulose ether |
| KR20120095795A (en) | 2011-02-21 | 2012-08-29 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Methods for preparing alkali cellulose and cellulose ether |
| EP2489677A1 (en) | 2011-02-21 | 2012-08-22 | Shin-Etsu Chemical Co., Ltd. | Methods for Preparing Alkali Cellulose and Cellulose Ether |
| CN106147259A (en) * | 2015-04-08 | 2016-11-23 | 中国科学院理化技术研究所 | Preparation method of surface hydrophobic flaky cellulose and flaky cellulose |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0357226B2 (en) | 1991-08-30 |
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