Fine cellulose fiber and production method for same

Patent metadata

Field	Value
Publication number	US-11015291-B2
Application number	US-201716085172-A
Country	US
Kind code	B2
Filing date	Mar 16, 2017
Priority date	Mar 16, 2016
Publication date	May 25, 2021
Grant date	May 25, 2021

Abstract

Provided is a method of producing fine cellulose fibers that are nanosized, that have a high crystallinity degree, and that are less vulnerable to fiber shape damage, the method including impregnating cellulose with a fibrillation solution to fibrillate the cellulose without mechanical crushing, and modifying the cellulose. The method of producing cellulose microfibrils of the present invention includes impregnating cellulose with a fibrillation solution containing a carboxylic acid vinyl ester or an aldehyde and an aprotic solvent having a donor number of 26 or more to fibrillate the cellulose. The aldehyde is at least one kind of aldehyde selected from the group consisting of an aldehyde represented by the following formula (1), paraformaldehyde, cinnamaldehyde, perillaldehyde, vanillin, and glyoxal:

R 1 —CHO  (1)

where R 1 represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, an alkenyl group, a cycloalkyl group, or an aryl group.

First claim

The invention claimed is:

1. A method of producing fine cellulose fibers, comprising impregnating cellulose with a fibrillation solution and without use of strong fibrillation equipment, the fibrillation solution containing an aprotic solvent having a donor number of 26 or more and a carboxylic acid vinyl ester or an aldehyde to fibrillate the cellulose,
the aldehyde being at least one kind of aldehyde selected from the group consisting of an aldehyde represented by the following formula (1), paraformaldehyde, cinnamaldehyde, perillaldehyde, vanillin, and glyoxal:
R 1 —CHO  (1)

where R 1 represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, an alkenyl group, a cycloalkyl group, or an aryl group.

2. The production method according to claim 1 , wherein a content of the carboxylic acid vinyl ester or the aldehyde is from 0.05 wt % to 50 wt % with respect to an entirety of the fibrillation solution.

3. The production method according to claim 1 , wherein the aprotic solvent having a donor number of 26 or more is at least one kind selected from the group consisting of a sulfoxide, a pyridine, a pyrrolidone, and an amide.

4. The production method according to claim 1 , wherein the aldehyde is at least one kind selected from the group consisting of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butanal, isobutanal, 2-methylbutanal, pentanal, hexanal, heptanal, octanal, nonanal, decanal, acrolein, benzaldehyde, cinnamaldehyde, perillaldehyde, vanillin, and glyoxal.

5. The production method according to claim 1 , wherein the carboxylic acid vinyl ester is at least one kind selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl cyclohexanecarboxylate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, vinyl octylate, divinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl pivalate, vinyl octylate, vinyl benzoate, and vinyl cinnamate.

6. The production method according to claim 1 , wherein the carboxylic acid vinyl ester comprises a compound represented by the following formula (2):
R 2 —COO—CH═CH 2   (2)

where R 2 represents an alkyl group having 1 to 24 carbon atoms, an alkylene group, a cycloalkyl group, or an aryl group.

7. The production method according to claim 1 , wherein the fibrillation solution further contains a cellulose modification reaction agent.

8. The production method according to claim 7 , wherein the cellulose modification reaction agent is at least one kind selected from the group consisting of a carboxylic acid halide, a carboxylic acid anhydride, a carboxylic acid, an isocyanate, an epoxy, and an alkyl halide.

9. The production method according to claim 1 , wherein the fibrillation solution further contains an acid catalyst or a base catalyst.

10. The production method according to claim 9 , wherein the acid catalyst is at least one kind selected from the group consisting of paratoluenesulfonic acid, pyridinium paratoluenesulfonate, an inorganic acid, and an organic acid.

11. The production method according to claim 9 , wherein the base catalyst is at least one kind selected from the group consisting of: a carbonate of an alkali metal or an alkaline earth metal; a hydrogen carbonate of an alkali metal or an alkaline earth metal; a carboxylate of an alkali metal or an alkaline earth metal; a borate of an alkali metal or an alkaline earth metal; a phosphate of an alkali metal or an alkaline earth metal; a hydrogen phosphate of an alkali metal or an alkaline earth metal; a tetraalkylammonium acetate of an alkali metal or an alkaline earth metal; a pyridine; an imidazole; and an amine.

12. The production method according to claim 9 , wherein a content of the acid catalyst or the base catalyst is from 0.001 wt % to 30 wt % with respect to an entirety of the fibrillation solution.

13. The production method according to claim 1 , wherein a weight ratio between the cellulose and the fibrillation solution is from 0.5/99.5 to 25/75.

14. The production method according to claim 1 , wherein the impregnating cellulose with a fibrillation solution is performed with stirring.

Assignees

• Kri Inc
• Futamura Kagaku Kk
• Asahi Chemical Ind

Inventors

• Lin Lianzhen
• Maruta Ayako
• Hori Masanori

Classifications

• D21H19/52

  Cellulose; Derivatives thereof · CPC title

• D21H19/34 Primary

  comprising cellulose or derivatives thereof · CPC title

• D21H11/18

  Highly hydrated, swollen or fibrillatable fibres · CPC title

• D21H11/20

  Chemically or biochemically modified fibres · CPC title

• D21C3/003

  with organic compounds (D21C3/20 and D21C3/222 take precedence) · CPC title