Modified cellulose fibers and cellulose composite thereof
View Patent ↗An object of the invention is to provide cellulose fibers which can give a cellulose composite that renders high transparency, a reduction in linear expansion coefficient, and a high modulus of elasticity possible. The invention relates to: a process for producing modified cellulose fibers which includes a modification reaction step of reacting cellulose with an aromatic compound in an organic acid to thereby modify the cellulose with an aromatic-ring-containing substituent; cellulose fibers modified with aromatic-ring-containing substituent; a dispersion of the cellulose fibers; and a cellulose fiber composite obtained from the same.
1. A sheet of modified cellulose fibers which comprises cellulose fibers having an average fiber diameter of 100 nm or less and having a cellulose I type crystal structure in which 10% to 60% by mole of all hydroxyl groups of the cellulose have been modified with an aromatic-ring-containing substituent,
wherein the sheet of modified cellulose fibers have a haze value measured with illuminant C of 3 or less
wherein said haze value is measured after making a composite material by: immersing the cellulose fiber sheet having a thickness regulated so that the sheet has a basis weight of 40 g/m 2 , in a solution prepared by mixing 96 parts by weight of bis(methacryloyloxymethyl)tricyclo[5.2.1.0 2,6 ]decane with 6 parts by weight of pentaerythritol tetrakis(β-thiopropionate), 0.05 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 0.05 parts by weight of benzophenone; holding the sheet under vacuum overnight; subsequently sandwiching the sheet between two glass plates; performing a curing using an electrodeless mercury lamp; thereafter separating the sheet from the glass plates; and then heating the sheet in a 190° C. vacuum oven for 4 hours,
wherein the aromatic ring of each aromatic-ring-containing substituent is bonded to the cellulose by a connecting group selected from the group consisting of an ester group, an ether group and a carbamate group;
the aromatic-ring-containing substituent is a substituent derived from an aromatic hydrocarbon compound, a heterocyclic aromatic compound, or a non-benzenoid aromatic compound;
the aromatic-ring-containing substituent each may be configured of two or more moieties of any of the aromatic hydrocarbon compound, the heterocyclic aromatic compound, and the non-benzenoid aromatic compound, the moieties having been connected to each other with a single bond or an alkyl group having 1-3 carbon atoms; and
the aromatic-ring-containing substituent may be one in which hydrogen atom thereof has been replaced with an alkyl group having 1-12 carbon atoms.
2. The sheet of modified cellulose fibers according to claim 1 , wherein the cellulose fibers give a wide-angle X-ray diffraction image in which the ratio of the “average diffraction intensity in the scanning angle range of 18-19 degrees” to the “intensity of a diffraction peak derived from cellulose I type crystals in the scanning angle range of 20-24 degrees”, is 0.8 or less,
wherein the aromatic ring of each aromatic-ring-containing substituent is bonded to the cellulose by one connecting group selected from the group consisting of an ester group, an ether group and a carbamate group such that the aromatic-ring-containing substituent has a structure selected from the group consisting of one of the following formulae (1) to (3):
wherein Ar is selected from the group consisting of an aromatic hydrocarbon compound, a heterocyclic aromatic compound, and a non-benzenoid aromatic compound; and
wherein Ar is unsubstituted or a hydrogen atom of said Ar is replaced with an alkyl group having 1-12 carbon atoms.
3. The sheet of modified cellulose fibers according to claim 1 , wherein the modified cellulose fibers have an average fiber diameter of 80 nm or less.
4. The sheet of modified cellulose fibers according to claim 1 , wherein the modified cellulose fibers have an average fiber diameter of 4 nm to 100 nm.
5. A cellulose fiber composite which comprises a matrix and the sheet of modified cellulose fibers according to claim 1 .
6. The sheet of modified cellulose fibers according to claim 1 , wherein 11% to 60% by mole of all hydroxyl groups of the cellulose have been modified with an aromatic-ring-containing substituent.
7. The sheet of modified cellulose fibers according to claim 1 , wherein 15% to 60% by mole of all hydroxyl groups of the cellulose have been modified with an aromatic-ring-containing substituent.
8. The sheet of modified cellulose fibers according to claim 1 , wherein 10% to 55% by mole of all hydroxyl groups of the cellulose have been modified with an aromatic-ring-containing substituent.
9. The sheet of modified cellulose fibers according to claim 1 , wherein 10% to 50% by mole of all hydroxyl groups of the cellulose have been modified with an aromatic-ring-containing substituent.
10. The sheet of modified cellulose fibers according to claim 1 , wherein 10% to 45% by mole of all hydroxyl groups of the cellulose have been modified with an aromatic-ring-containing substituent.
11. The sheet of modified cellulose fibers according to claim 1 , wherein 10% to 40% by mole of all hydroxyl groups of the cellulose have been modified with an aromatic-ring-containing substituent.
12. The sheet of modified cellulose fibers according to claim 1 , wherein the haze value measured with illuminant C is 2 or less.
13. The sheet of modified cellulose fibers according to claim 1 , wherein the haze value measured with illuminant C is 1 or less.
14. The sheet of modified cellulose fibers according to claim 1 , wherein the thickness of the sheet ranges from 1 μm to 1,000 μm.
15. The sheet of modified cellulose fibers according to claim 14 , wherein the thickness of the sheet is at least 5 μm.
16. The sheet of modified cellulose fibers according to claim 14 , wherein the thickness of the sheet is at most 250 μm.