Production method for purified polysaccharide fibers, purified polysaccharide fibers, fiber-rubber complex, and tire

Patent metadata

Field	Value
Publication number	US-9670596-B2
Application number	US-201314402154-A
Country	US
Kind code	B2
Filing date	May 21, 2013
Priority date	May 21, 2012
Publication date	Jun 6, 2017
Grant date	Jun 6, 2017

Abstract

The present invention provides a production method for purified polysaccharide fibers in which carbon disulfide emission is suppressed while efficiently producing purified polysaccharide fibers having excellent strength, purified polysaccharide fibers produced by using the production method, a fiber-rubber complex using the purified polysaccharide fibers, and a tire having excellent tire characteristics using the fiber-rubber complex. The production method for purified polysaccharide fibers of the present invention is a production method for purified polysaccharide fibers of wet-spinning or dry-wet-spinning polysaccharide by bringing a polysaccharide solution obtained by dissolving a polysaccharide raw material in a liquid including an ionic liquid into contact with a solidification liquid including an ionic liquid, in which a concentration of the ionic liquid in the solidification liquid is 0.4% by weight to 50% by weight and the anionic moieties of the ionic liquid in the polysaccharide solution and the ionic liquid in the solidification liquid have one or more types selected from the group consisting of a phosphinate ion, a phosphate ion, and a phosphonate ion.

First claim

The invention claimed is:

1. A production method for purified polysaccharide fibers of wet-spinning or dry-wet-spinning polysaccharide, the method comprising:
dissolving polysaccharide raw material in a dissolving liquid including an ionic liquid to obtain a polysaccharide solution, and
bringing the polysaccharide solution into contact with a solidification liquid including an ionic liquid and a poor solvent for the polysaccharide raw material to obtain purified polysaccharide fibers,
wherein a concentration of the ionic liquid in the solidification liquid is 20% by weight to 70% by weight,
wherein each of the ionic liquid in the polysaccharide solution and the ionic liquid in the solidification liquid is formed of a cationic moiety and an anionic moiety, and
wherein the anionic moiety is at least one member selected from the group consisting of a phosphinate ion, a phosphate ion, and a phosphonate ion represented by the following formula (C2):

in the formula, each of X 1 and X 2 independently represents a hydrogen atom, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms.

2. The production method for purified polysaccharide fibers according to claim 1 ,
wherein the ionic liquid includes a recycled product recovered from a solidification liquid used when producing purified polysaccharide fibers, and the amount of the recycled product is 90% by weight or greater, based on the total weight of the ionic liquid.

3. The production method for purified polysaccharide fibers according to claim 2 ,
wherein the recycling rate of the ionic liquid is 93% by weight or greater.

4. The production method for purified polysaccharide fibers according to claim 1 ,
wherein a plurality of solidification baths is disposed, from upstream toward downstream of a process of spinning the polysaccharide using the plurality of solidification baths which holds the solidification liquid, such that the concentration of the ionic liquid in the solidification liquid which is held is sequentially lowered, and
wherein, on a front side of the solidification bath of the uppermost upstream, the polysaccharide solution is extruded, thereafter, a semi-solid product of purified polysaccharide fibers is obtained by passing through the solidification bath, and the semi-solid product is solidified by sequentially using the other solidification baths toward downstream, whereby purified polysaccharide fibers are obtained.

5. The production method for purified polysaccharide fibers according to claim 1 ,
wherein the polysaccharide is cellulose.

6. The production method for purified polysaccharide fibers according to claim 1 ,
wherein the solidification liquid is formed of the ionic liquid, water, and/or an organic solvent.

7. The production method for purified polysaccharide fibers according to claim 6 ,
wherein the organic solvent is a polar solvent.

8. The production method for purified polysaccharide fibers according to claim 1 ,
wherein each temperature of all the solidification liquids is 5° C. to 60° C.

9. The production method for purified polysaccharide fibers according to claim 1 ,
wherein each retention time of the polysaccharides or the intermediates in all the solidification baths is 300 seconds or less.

10. The production method for purified polysaccharide fibers according to claim 1 ,
wherein each retention time of the polysaccharides or the intermediates in all the solidification baths is 120 seconds or less.

11. The production method for purified polysaccharide fibers according to claim 1 , comprising:
a process of recycling the ionic liquid from the solidification liquid using a spray dry method.

12. The production method for purified polysaccharide fibers according to claim 1 ,
wherein the ionic liquid in the polysaccharide solution and the ionic liquid in the solidification liquid are the same compound.

13. The production method for purified polysaccharide fibers according to claim 1 ,
wherein the cationic moiety is one or more types selected from the group consisting of an imidazolium ion, a pyridinium ion, an ammonium ion, and a phosphonium ion.

14. The production method for purified polysaccharide fibers according to claim 13 ,
wherein the cationic moiety is the imidazolium ion.

15. The production method for purified polysaccharide fibers according to claim 14 ,
wherein the cationic moiety is the imidazolium ion represented by the following general formula (C1):

in the formula, R 1 represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, R 2 represents a hydrogen atom or a methyl group, and R 3 represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.

16. The production method for purified polysaccharide fibers according to claim 1 ,
wherein the ionic liquid in the polysaccharide solution and/or the ionic liquid in the solidification liquid is 1-ethyl-3-methylimidazolium diethylphosphate.

17. The production method for purified polysaccharide fibers according to claim 1 ,
wherein the distance D from a place where the polysaccharide solution is extruded to be a fiber shape to a place where the extruded polysaccharide solution is in contact with the solidification liquid is 50 mm to 120 mm.

18. A purified polysaccharide fiber produced by the production method for purified polysaccharide fibers according to claim 1 .

19. A purified polysaccharide fiber produced by bringing a polysaccharide solution obtained by dissolving a polysaccharide raw material in a polar solvent or a liquid including an ionic liquid into contact with a solidification liquid and wet-spinning or dry-wet-spinning a polysaccharide, containing:
a main component formed of two or more types of polysaccharides, the polysaccharide having the largest content within the main component being a first main component,
wherein a proportion of the first main component is 97% by weight or less, based on all components constituting the purified polysaccharide fibers.

20. The purified polysaccharide fiber according to claim 19 ,
wherein the proportion of the first main component in all components constituting the purified polysaccharide fiber is 90% by weight or less.

21. The purified polysaccharide fiber according to claim 19 ,
wherein a proportion of a polysaccharide fiber obtained from the polysaccharide raw material is 60% by weight or greater.

22. The purified polysaccharide fiber according to claim 19 ,
wherein the main component is cellulose and hemicellulose.

23. The purified polysaccharide fiber according to claim 19 ,
wherein a proportion of the main component in all components constituting the purified polysaccharide fiber is 90% by weight or greater.

24. The purified polysaccharide fiber according to claim 22 ,
wherein a proportion of the hemicellulose in all components constituting the purified polysaccharide fiber is 0.1% by weight to 40% by weight.

25. The purified polysaccharide fiber according to claim 19 ,
wherein the polar solvent is dipole molecules or zwitterionic molecules.

26. The purified polysaccharide fiber according to claim 19 ,
wherein the polar solvent is N-

Assignees

• Bridgestone Corp

Inventors

• Koide Mitsuharu
• Sugimoto Kenichi

Classifications

• D01D5/06

  Wet spinning methods {(D01D5/0046 takes precedence)} · CPC title

• B60C2001/0083

  Compositions of the cap ply layers · CPC title

• D02G3/48

  Tyre cords {(tyre reinforcements B60C9/00; metal cords for reinforcing rubber or plastic articles D07B1/0606)} · CPC title

• D01F13/02

  of cellulose, cellulose derivatives or proteins {(recovery of sodium sulfate from coagulation baths C01D5/006)} · CPC title

• C08L1/02

  Cellulose; Modified cellulose · CPC title