DOUBLE-CROSSLINKED CELLULOSE NANOFIBER FILM WITH HIGH STRENGTH AND HIGH TRANSMITTANCE AND METHOD FOR MANUFACTURING THE SAME

Abstract

A method for manufacturing a cellulose nanofiber film is provided. The method includes preparing cellulose nanofiber dispersion, performing a chemical crosslinking by adding an epichlorohydrin-based material to the cellulose nanofiber dispersion to prepare a planar body and performing physical crosslinking in which a metal chloride is added to the planar body.

Claims

1. A method for manufacturing a cellulose nanofiber film, the method comprising: preparing a cellulose nanofiber dispersion having cellulose nanofibers; performing a chemical crosslinking by adding an epichlorohydrin-based material to the cellulose nanofiber dispersion to prepare a planar body; and performing a physical crosslinking in which a metal chloride is added to the planar body.

2. The method of claim 1, wherein the epichlorohydrin-based material comprises epichlorohydrin, glycine, glutaraldehyde, or a combination thereof.

3. The method of claim 1, wherein the epichlorohydrin-based material is added in an amount in a range of 0.1 parts by weight to 2 parts by weight based on 1 part by weight of the cellulose nanofibers.

4. The method of claim 1, wherein the chemical crosslinking is performed by adding the epichlorohydrin-based material to the cellulose nanofiber dispersion, and then mixing at a temperature in a range of 0° C. to 50° C. for 8 hours to 24 hours.

5. The method of claim 1, wherein the planar body is prepared by filtration under reduced pressure of the cellulose nanofiber dispersion.

6. The method of claim 1, wherein the metal chloride comprises CaCl.sub.2, MgCl.sub.2, AlCl.sub.3, FeCl.sub.3, or a combination thereof.

7. The method of claim 1, wherein the metal chloride is added in an amount in a range of 0.1 part by weight to 1 part by weight based on 1 part by weight of the cellulose nanofibers.

8. The method of claim 1, wherein the physical crosslinking is performed by contacting an aqueous solution comprising a metal chloride with the planar body at a temperature in a range of 0° C. to 50° C. for 4 hours to 24 hours.

9. The method of claim 1, wherein the preparing of the cellulose nanofiber dispersion comprises: chemically pretreating pulp derived from a plant; and fibrillating the pretreated pulp by friction grinding.

10. The method of claim 9, wherein the plant comprises lovegrass, bamboo, silver maple tree, tulip tree, trident maple, or a combination thereof.

11. The method of claim 1, wherein the cellulose nanofibers have diameters in a range of 5 nm to 100 nm.

12. The method of claim 1, further comprising: manufacturing the cellulose nanofiber film by post-treatment of the planar body.

13. The method of claim 12, wherein the manufacturing of the cellulose nanofiber film comprises: removing air bubbles in a solution in a vacuum chamber; drying the solution in a thereto-hygrostat; and hot-pressing or cold-pressing.

14. The method of claim 1, wherein the cellulose nanofiber film has a thickness in a range of 25 micrometers to 1000 micrometers.

15. A cellulose nanofiber film comprising: a cellulose nanofiber dispersion having cellulose nanofibers; an epichlorohydrin-based material; and a metal chloride, wherein a chemical crosslink is provided between cellulose nanofibers in the cellulose nanofiber dispersion and the epichlorohydrin-based material to provide a planar body, and wherein a physical crosslink is provided between the metal chloride and the planar body.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0026] FIG. 1 is a process flow chart showing a method of manufacturing a cellulose nanofiber film according to an embodiment.

[0027] FIG. 2 is a schematic view showing the chemical and physical crosslinking processes of the cellulose nanofiber film according to an embodiment.

[0028] FIG. 3 is a photograph of the cellulose nanofiber film manufactured in preparation example.

[0029] FIG. 4 is a graph showing the light transmittance measurement results of the cellulose nanofiber films manufactured in Comparative Example 1 and Examples 1-1 to 1-4.

[0030] FIG. 5 is a photograph showing the results of comparing the physical properties of the cellulose nanofiber film and the petroleum-based resin film in Experimental Example 3.

DETAILED DESCRIPTION

[0031] The advantages and features of the present disclosure and the methods for accomplishing the same should be apparent from the embodiments described hereinafter with reference to the accompanying drawings. However, the embodiments should not be construed as being limited to the embodiments set forth herein. Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art. The terms defined in a generally-used dictionary may not be interpreted ideally or exaggeratedly unless clearly defined. In addition, unless explicitly described to the contrary, the word “comprise,” and variations such as “comprises” or “comprising,” should be understood to imply the inclusion of stated elements but not the exclusion of any other elements.

[0032] Further, the singular includes the plural unless mentioned otherwise.

[0033] According to an embodiment, a method for manufacturing a cellulose nanofiber film includes preparing a cellulose nanofiber dispersion, chemical crosslinking, and physical crosslinking.

[0034] FIG. 1 is a process flow chart showing a method of manufacturing a cellulose nanofiber film. Hereinafter, a method of manufacturing a cellulose nanofiber film is described in detail with reference to FIG. 1.

[0035] In act S1, a cellulose nanofiber dispersion is prepared.

[0036] In certain examples, the preparing of the cellulose nanofiber dispersion may include pretreating the pulp derived from a plant and fibrillating the pretreated pulp.

[0037] The pulp derived from a plant may include, for example, wood pulp made from hardwoods and softwoods, non-wood pulp made from straw, bagasse, etc., deinked pulp (DIP) made from wastepaper, shredded paper, etc., and the like. These pulps derived from a plant may be used alone or in a combination of two or more.

[0038] The wood pulp may include, for example, chemical pulps such as hardwood kraft pulp (LKP), softwood kraft pulp (NKP), and the like, mechanical pulps (TMP), deinked pulps (DIP), and the like. These wood pulps may be used alone or in a combination of two or more.

[0039] Plants from which the pulps are sourced may include lovegrass, bamboo, silver maple tree, tulip tree, trident maple, or a combination thereof.

[0040] The pulp derived from a plant may be subjected to pretreatment such as beating and the like, if necessary, prior to fibrillation. This pretreatment may be performed by a physical method, a chemical method, or a physical and chemical method. The pretreatment by a physical or chemical method before the fibrillation may significantly reduce the number of fibrillation acts and amount of energy required for the fibrillation.

[0041] The pretreatment by a physical method may use the beating. When the pulp derived from a plant is treated through the beating, raw material fibers are evenly cut, solving a problem that the fibers are entangled with one another and agglomerated. From this point of view, the beating may be carried out until the pulp derived from a plant has freeness of less than or equal to about 120 ml or less than or equal to about 110 ml. The freeness may be measured with reference to Japanese Industrial Standard (JIS) P8121-2 (2012). The beating may be performed by using, for example, a refiner, a beater, or the like.

[0042] The pretreatment by a chemical method may include, for example, hydrolysis of polysaccharide by acid (acid treatment), hydrolysis of polysaccharide by enzyme (enzyme treatment), swelling of polysaccharide by alkali (alkali treatment), oxidation of polysaccharide by an oxidizing agent (oxidation treatment), reduction of polysaccharide by a reducing agent (reduction treatment), and the like, for example, performed through a carboxylation or methylation reaction.

[0043] For example, the pretreatment by a chemical method may be performed by adding the pulp derived from a plant to an oxidation treatment solution prepared by mixing sodium hypochlorite (NaOCl), sodium bromide (NaBr), and TEMPO. TEMPO ((2,2,6,6-tetramethylpiperidin-1-yl)oxyl) is a type of catalyst, which is commercially available and has water-soluble and safe characteristics.

[0044] TEMPO is oxidized into nitrosonium ions under certain conditions and reacts with a hydroxy group (—OH) of carbon No. 6 of the cellulose fibers. This hydroxy group is substituted with a carboxyl group (—COOH) or derivative thereof, or a carboxylate group (—COOM), wherein M is an alkaline metal or an alkaline-earth metal.

[0045] A solvent for preparing the oxidation treatment solution may include a polar solvent such as distilled water, methanol, ethanol, isopropanol, butanol, or a combination thereof.

[0046] The oxidation treatment may be performed at a pH in a range of 9.5 to 10.5, (e.g., at a pH in a range of 10 to 10.5), for 2 hours to 10 hours, (e.g., for 2 hours to 4 hours). When the oxidation treatment is performed at a pH of less than 9.5, a reaction rate may decrease, as a concentration of the hydroxide group (OH—) of the solution is lowered. Additionally, at the pH less than 9.5, a molecular weight of cellulose fibers may decrease, as an oxidative decomposition reaction is promoted by hypohalite. Further, when the pH is greater than 10.5, a polymer chain may be decomposed by the hydroxide group (OH—). When the oxidation treatment is performed for less than 2 hours, the substitution reaction may proceed to a lesser extent.

[0047] In addition, the pretreatment may be performed, in addition to the above methods, for example, by a chemical treatment such as a phosphate esterification treatment, an acetylation treatment, a cyanoethylation treatment, and the like.

[0048] The pulp derived from a plant is pretreated and then fibrillated (e.g., refined). Through the fibrillation, the pulp fibers are microfibrillated and become cellulose nanofibers (CNF).

[0049] The fibrillation of the pulp derived from a plant may be performed by using a homogenizer (e.g., a high-pressure homogenizer, a high-pressure homogenizing device, and the like), a grinder (e.g., a friction grinder and the like), a mill-type friction machine (e.g., a mill and the like), a refiner (e.g., a conical refiner, a disk refiner, and the like), or a combination thereof.

[0050] The cellulose nanofiber dispersion may include 1 wt. % to 3 wt. % of the cellulose nanofibers based on the total weight of the cellulose nanofiber dispersion. When the cellulose nanofibers are included in an amount of less than 1 wt. %, the drying time until a film with a desired thickness is formed gets excessively longer. As a result, efficiency in time, cost, energy, etc. may be deteriorated, Alternatively, when the cellulose nanofibers are included in an amount of greater than 3 wt. %, the cellulose nanofiber dispersion may be agglomerated like a gel due to high viscosity and thus hardly maintain a uniform solution state, causing difficulties in the process.

[0051] A solvent for preparing the cellulose nanofiber dispersion may include a polar solvent such as distilled water, methanol, ethanol, isopropanol, butanol, or a combination thereof.

[0052] The cellulose nanofibers included in the cellulose nanofiber dispersion may be nano-size fibers having a fiber diameter in a range of 5 nm to 100 nm and a fiber length of 1 μm or less.

[0053] Subsequently, in act S2 of a method of manufacturing, a chemical crosslinking is performed by adding an epichlorohydrin-based material to the cellulose nanofiber dispersion.

[0054] FIG. 2 is a schematic view showing the chemical and physical crosslinking process of the cellulose nanofiber film. Referring to FIG. 2, the epichlorohydrin-based material induces a chemical bond between hydroxy groups (—OH) of the cellulose nanofibers.

[0055] The epichlorohydrin-based material may use any crosslinking agent capable of inducing the chemical bond between the hydroxy groups (—OH). For example, the crosslinking agent may be epichlorohydrin, glycine, glutaraldehyde, or a combination thereof.

[0056] The epichlorohydrin-based material may be added in an amount in a range of 0.1 parts by weight to 2 parts by weight, (e.g., 0.4 parts by weight to 0.7 parts by weight), based on 1 part by weight of the cellulose nanofibers. When the epichlorohydrin-based material is included in an amount less than 0.1 parts by weight, a crosslinking effect may be insufficient. Furthermore, when the epichlorohydrin-based material is included in an amount greater than 2 parts by weight, excessive crosslinking may occur, deteriorating exterior flatness.

[0057] The chemical crosslinking in act S2 may be performed for 8 hours to 24 hours, (e.g., 12 hours to 16 hours). When the chemical crosslinking is performed for less than 8 hours, the crosslinking reaction may not sufficiently occur, but when the chemical crosslinking is performed for greater than 24 hours, self-crosslinking between epichlorohydrins may occur. The chemical crosslinking may be performed at a temperature in a range of 0° C. to 50° C. in the air, (e.g., at room temperature in a range of 20° C. to 30° C.).

[0058] When the chemical crosslinking is completed, the cellulose nanofiber dispersion is filtered under a reduced pressure, therein obtaining a planar body in a wet state.

[0059] Subsequently, in act S3, physical crosslinking may be performed by applying metal chloride to the planar body.

[0060] Referring to FIG. 2, when the metal chloride is added to the planar body in a wet state, an ionic bond between ester groups (—COO) of the cellulose nanofibers may be induced by metal inorganic ions, physically cross-linking the cellulose nanofibers.

[0061] The metal chloride capable of physically crosslinking the cellulose nanofibers may be CaCl.sub.2, MgCl.sub.2, AlCl.sub.3, FeCl.sub.3, or a combination thereof.

[0062] The metal chloride may be used in an amount in a range of 0.1 parts by weight to 1 part by weight, (e.g., 0.1 parts by weight to 0.5 parts by weight), based on 1 part by weight of the cellulose nanofibers. When the metal chloride is used in an amount less than 0.1 parts by weight, the crosslinking effect may be insufficient.

[0063] The physical crosslinking in act S3 may be performed by making the planar body contact with an aqueous solution including the metal chloride. The physical crosslinking may be performed for 4 hours to 24 hours, (e.g., 6 hours to 12 hours). When the physical crosslinking is performed for less than 2 hours, sodium (Na.sup.+) ions are not much substituted with metal ions (e.g., Ca.sup.2+). As a result, mechanical strength may not be as improved as expected. The physical crosslinking may be performed at a temperature in a range of 0° C. to 50° C. in the air, (e.g., at room temperature in a range of 20° C. to 30° C.).

[0064] When the physical crosslinking is completed, the planar body is filtered under a reduced pressure filter (e.g., vacuum-filtered), therein obtaining a film shape.

[0065] Optionally, a method of manufacturing may further include act S4 that includes a process of post-treating the planar body into a film.

[0066] Specifically, the process of forming a film through the post-treatment may include removing air bubbles in the solution in a vacuum chamber, drying the solution in a thermo-hygrostat, and optionally, hot- or cold-pressing.

[0067] The removing air bubbles may be performed by, for example, natural defoaming (e.g., stationary) after stirring by using a stirrer with wings or defoaming in a vacuum chamber.

[0068] The drying may be a process of semi-drying the cellulose nanofiber film in the thermo-hygrostat at temperature in a range of 20° C. to 60° C., (e.g., 40° C. to 50° C.), under relative humidity in a range of 50% to 90%, (e.g., 80% to 90% relative humidity). When the drying is performed at a temperature less than 20° C. a drying rate may be slower, and when the drying is performed at a temperature greater than 60° C., a shrinkage may occur due to a rapid moisture loss at the high temperature.

[0069] In act S4, the forming a film may optionally further include the hot- or cold-pressing the cellulose nanofiber film. For example, the semi-dried cellulose nanofiber film may be thermally compressed at a temperature in a range of 25° C. to 70° C., (e.g., 55° C. to 65° C.), maintaining a flat film shape. When the thermal compression is performed at a temperature less than 25° C., time for the final drying may be longer, but when the thermal compression is performed at a temperature greater than 70° C., discoloring may occur by the high temperature.

[0070] Another embodiment provides a cellulose nanofiber film formed by the manufacturing methods described herein.

[0071] The prepared cellulose nanofiber film is an environmentally-friendly nanofiber film having excellent mechanical properties and transparency and thus may replace transparent polymers. According to the method for manufacturing, the cellulose nanofiber film may have a thickness in a range of 25 μm to 1000 μm.

[0072] The cellulose nanofiber film may be variously used for automotive parts and industrial applications. Specifically, the cellulose nanofiber film may be mixed with polymers and prepared into a transparent composite material with a low coefficient of thermal expansion. The cellulose nanofiber film may replace glass or be applied as a protective film preventing scratching in new cars. Further, the cellulose nanofiber film may be mixed and cured with a specific polymer resin and thus applied as a protector for a display device such as a vehicle navigator and the like.

[0073] In addition, the cellulose nanofiber film may be applied to manufacture a large-area, high rigidity, and flat-panel composite products.

[0074] Furthermore, the cellulose nanofiber film may be applied to fields such as a separator for separating a specific component from a mixed gas, a separator for a secondary battery, and the like.

[0075] Hereinafter, specific embodiments of the disclosure are presented. However, the examples described below are only for specifically illustrating or explaining the disclosure, and the scope of the disclosure is not limited thereto.

PREPARATION EXAMPLE

Preparation of Cellulose Nanofiber Film

[0076] 10 g of cellulose pulp extracted from trees was mixed with 0.16 g of a TEMO catalyst, 1 g of NaBr, and 62 g of 6% NaClO in 1 L of distilled water, and then, pH of the mixed solution was continuously maintained at 10 by using an NaOH solution. When pH of the oxidation solution showed no more change, centrifugation was performed at 4000 rpm for 10 minutes, and then, a process of replacing a supernatant therein with distilled water was three times performed for washing. After performing a chemical pretreatment in a TEMPO oxidation method, cellulose nanofiber dispersion in which 1 wt. % of cellulose nanofiber was dispersed was prepared through 10 times friction grinding process under 1000 bars.

[0077] Subsequently, a predetermined amount of epichlorohydrin was mixed with 5 mL of the cellulose nanofiber dispersion and then, reacted for 12 hours and filtered under a reduced pressure (vacuum-filtered), preparing a planar body in a wet state.

[0078] Then, the planar body was made to contact with 15 mL of a 0.1 M CaCl.sub.2 aqueous solution for 8 hours and then, three times or more washed with distilled water to prepare a wet sheet.

[0079] The wet sheet was dried in a thermohygrostat at 40° C. under humidity of 90% for 8 days, forming a 31 μm-thick cellulose nanofiber film. A photograph of the cellulose nanofiber film is shown in FIG. 3.

Evaluation Methods

[0080] 1) Evaluation of Tensile Strength and Modulus

[0081] The cellulose nanofiber film was measured with respect to tensile properties at 1 mm/min in Instron 8872. A thickness of the cellulose nanofiber film was obtained by using a micrometer to measure each thickness at 10 positions and averaging the ten measurements.

[0082] 2) Evaluation of Light Transmittance

[0083] Light transmittance of the cellulose nanofiber film was obtained by measuring at 3 points by using Perkin Elmer Lambda 900 UV/VIS/NIR Spectrometer at room temperature and averaging the measurements.

EXPERIMENTAL EXAMPLE 1

Evaluation of Physical Properties According to Added Content of Chemical Crosslinking Agent

[0084] A cellulose nanofiber film was respectively formed by changing an amount of epichlorohydrin (ECH) into 0 microliters (μL), 12.5 μL, 25 μL, 50 μL, and 100 μL in the preparation example, and then, the cellulose nanofiber films were evaluated with respect to tensile strength and modulus, and the results are shown in Table 1.

TABLE-US-00001 TABLE 1 Tensile Elongation Young's Volume of ECH Strength at break Modulus (μL) (MPa) (%) (GPa) Comparative 0 (0 part by weight.sup.1)) 214.1 2.1 17.0 Example 1 Example 1-1 12.5 (0.25 parts by weight) 241.3 1.9 18.4 Example 1-2 25 (0.5 parts by weight) 298.2 2.3 20.3 Example 1-3 50 (1 part by weight) 256.5 2.0 19.9 Example 1-4 100 (2 parts by weight) 235.7 1.8 18.0 .sup.1)Part by weight of epichlorohydrin within Table 1 is defined based on 1 part by weight of cellulose nanofibers

[0085] Referring to Table 1, the cellulose nanofiber films according to Examples 1-1 to 1-4 exhibited improved tensile strength, compared with the cellulose nanofiber film according to Comparative Example 1, and particularly, the cellulose nanofiberfilm according to Example 1-2 exhibited the most excellent tensile strength and modulus.

[0086] In addition, the cellulose nanofiber films according to Comparative Example 1 and Examples 1-1 to 1-4 were evaluated with respect to light transmittance, and the results are shown in FIG. 4.

[0087] Referring to FIG. 4, the cellulose nanofiber films according to Examples 1-1 to 1-4 exhibited excellent light transmittance compared with the cellulose nanofiber film according to Comparative Example 1. In addition, the cellulose nanofiber films according to Examples 1-1 to 1-4 exhibited obtained light transmittance of about 86% at 600 nm.

EXPERIMENTAL EXAMPLE 2

Comparison of Physical Properties with Petroleum-Based Resin Film

[0088] As viewed from Table 1 above, Example 1-2 provided the test best results.

[0089] Properties of the cellulose nanofiber film (Example 2) formed by applying Example 1-2 and a cellulose nanofiber film (Comparative Example 2) (formed by applying neither chemical crosslinking nor mechanical crosslinking in the preparation example) were compared with those of a commercially available petroleum-based resin film such as a PET film, a plastic bag (black PE), and a zipper bag (PE), and the results are shown in FIG. 5 and Table 2.

TABLE-US-00002 TABLE 2 Transmit- tance Elongation Tensile Young's Thickness at 550 nm at break Strength Modulus (μm) (%) (%) (MPa) (GPa) Comparative 30 89 2.4 189.9 14.1 Example 2 Example 2 29 86-88 2.2 303.2 19.5 PET film 127 80 52.6 247.9 4.4 Plastic bag 22 2 68.4 36.4 3.3 (Black PE) Zipper bag 46 80 92.6 20.6 1.1 (PE)

[0090] Referring to FIG. 5 and Table 2, the cellulose nanofiber film according to Example 2 exhibited excellent rigidity and light transmission, compared with the commercially available petroleum-based resin films and Comparative Example 2.

[0091] While this disclosure has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the disclosure is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.