Modified cellulose nanofiber and rubber composition including the same

Patent metadata

Field	Value
Publication number	US-11261302-B2
Application number	US-201716315527-A
Country	US
Kind code	B2
Filing date	Jul 5, 2017
Priority date	Jul 7, 2016
Publication date	Mar 1, 2022
Grant date	Mar 1, 2022

Abstract

The present invention aims to provide a rubber composition having sufficient reinforcement and fatigue resistance even when a large strain is applied thereto, and the present invention is to provide a substituted carboxy group-containing modified cellulose nanofiber wherein at least part thereof has at least any one of a substituent represented by Formula (a): —CONH—R1 and a substituent represented by Formula (b): —COO—R1 (in Formulae (a) and (b), R1 is independently a C3-30 hydrocarbon having at least one unsaturated bond), and a rubber composition including the same.

First claim

The invention claimed is:

1. A substituted carboxy group-containing modified cellulose nanofiber, wherein at least part of a carboxy group-containing modified cellulose nanofiber comprises at least any one of a substituent represented by Formula (a) and a substituent represented by Formula (b) below:
—CONH—R 1 , and  Formula (a):

—COO—R 1 ,  Formula (b):

where R 1 is independently a C 3-30 hydrocarbon having at least one unsaturated bond.

2. The substituted carboxy group-containing modified cellulose nanofiber according to claim 1 , wherein the carboxy group-containing modified cellulose nanofiber is an oxidized cellulose nanofiber or a carboxymethylated cellulose nanofiber.

3. The substituted carboxy group-containing modified cellulose nanofiber according to claim 2 , wherein
the carboxy group-containing modified cellulose nanofiber is an oxidized cellulose nanofiber; and
a carboxy group content of the oxidized cellulose nanofiber is 0.6 mmol/g to 2.0 mmol/g with respect to a bone-dry mass of the oxidized cellulose nanofiber.

4. The substituted carboxy group-containing modified cellulose nanofiber according to claim 2 , wherein
the carboxy group-containing modified cellulose nanofiber is a carboxymethylated cellulose nanofiber; and
a degree of substitution with carboxymethyl group per glucose unit of the carboxymethylated cellulose nanofiber is 0.01 to 0.50.

5. The substituted carboxy group-containing modified cellulose nanofiber according to claim 1 , wherein the substituted carboxy group-containing modified cellulose nanofiber is at least any one of an amidation product of an aliphatic unsaturated amine and the carboxy group-containing modified cellulose nanofiber and an esterification product of an aliphatic unsaturated alcohol and the carboxy group-containing modified cellulose nanofiber.

6. The substituted carboxy group-containing modified cellulose nanofiber according to claim 5 , wherein
a reaction rate of the aliphatic unsaturated amine is 10% or more when the substituted carboxy group-containing modified cellulose nanofiber is the amidation product; and
a reaction rate of the aliphatic unsaturated alcohol is 10% or more when the substituted carboxy group-containing modified cellulose nanofiber is the esterification product.

7. A manufacturing method of a substituted carboxy group-containing modified cellulose nanofiber, the method comprising:
introducing at least any one of substituent selected from the group consisting of a substituent represented by Formula (a) and a substituent represented by Formula (b) below into at least part of a carboxy group-containing modified cellulose nanofiber; and
performing a dehydration condensation in water:
—CONH—R 1 , and  Formula (a):

—COO—R 1 ,  Formula (b):

where R 1 is independently a C 3-30 hydrocarbon having at least one unsaturated bond.

8. The manufacturing method according to claim 7 , wherein the dehydration condensation is performed by using at least one dehydration condensation agent selected from the group consisting of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide, a hydrochloride thereof, and 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride n-hydrate.

9. The manufacturing method according to claim 7 , wherein the introducing of at least one substituent selected from the group consisting of the substituent represented by Formula (a) and the substituent represented by Formula (b) is performed by introducing at least any one of an aliphatic unsaturated amine and an aliphatic unsaturated alcohol into the carboxy group-containing modified cellulose nanofiber.

10. The manufacturing method according to claim 9 , wherein
a reaction rate of the aliphatic unsaturated amine is 10% or more when the aliphatic unsaturated amine is introduced into the carboxy group-containing modified cellulose nanofiber; and
a reaction rate of the aliphatic unsaturated alcohol is 10% or more when the aliphatic unsaturated alcohol is introduced into the carboxy group-containing modified cellulose nanofiber.

11. A manufacturing method of producing a rubber composition, the method comprising:
manufacturing a substituted carboxy group-containing modified cellulose nanofiber by the manufacturing method according to claim 7 ; and
performing vulcanization after the dehydration condensation.

12. A rubber composition, comprising:
the substituted carboxy group-containing modified cellulose nanofiber according to claim 1 ; and
a rubber component.

13. The rubber composition according to claim 12 , further comprising sulfur.

Assignees

• Jujo Paper Co Ltd

Inventors

• Ito Kotaro
• Onogi Shinichi
• Yasukawa Yusuke
• Morita Masahiro

Classifications

• C08J2321/02

  Latex · CPC title

• C08L1/02

  Cellulose; Modified cellulose · CPC title

• C08L21/02

  Latex · CPC title

• B60C1/00

  Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition · CPC title

• C08L1/286 Primary

  substituted with acid radicals, e.g. carboxymethyl cellulose [CMC] (C08L1/282 takes precedence) · CPC title