Process for producing cellulose-nanofiber-filled microporous stretched polyolefin film, microporous cellulose-nanofiber composite film, and separator for non-aqueous secondary battery

Abstract

A method for producing a cellulose nanofiber-containing polyolefin microporous stretched film according to the invention includes: a first step of obtaining a cellulose powder dispersion mixture by uniformly dispersing a cellulose which has a powder particle shape and whose hydroxyl groups have been subjected to a lipophilizing treatment using a dibasic acid anhydride, in a plasticizer; a second step of melt-kneading the cellulose powder dispersion mixture and a polyolefin to obtain a polyolefin resin composition; a third step of extrusion-molding the polyolefin resin composition to obtain an extrudate; a fourth step of stretching the extrudate with a film stretcher to obtain a film; a fifth step of extracting out the plasticizer from the film; and a sixth step of thermally fixing the film from which the plasticizer has been extracted out for inhibiting contraction, while stretching the film at a temperature not higher than a melting point of the polyolefin, in which a twin-screw kneading extruder is used only once throughout the second and third steps.

Claims

1. A method for producing a cellulose nanofiber-containing polyolefin microporous stretched film, the method comprising: a first step of obtaining a cellulose powder dispersion mixture by uniformly dispersing a cellulose which has a powder particle shape and whose hydroxyl groups have been subjected to a lipophilizing treatment using a dibasic acid anhydride, in a plasticizer; a second step of melt-kneading the cellulose powder dispersion mixture and a polyolefin to obtain a polyolefin resin composition; a third step of extrusion-molding the polyolefin resin composition to obtain an extrudate; a fourth step of stretching the extrudate with a film stretcher to obtain a film; a fifth step of extracting out the plasticizer from the film; and a sixth step of thermally fixing the film from which the plasticizer has been extracted out for inhibiting contraction, while stretching the film at a temperature not higher than a melting point of the polyolefin, wherein a twin-screw kneading extruder is used only once throughout the second and third steps, and wherein the lipophilizing treatment comprises performing a monoesterification treatment.

2. The method for producing a cellulose nanofiber-containing polyolefin microporous stretched film according to claim 1, wherein the monoesterification is followed by performing a secondary propylene oxide addition treatment.

3. The method for producing a cellulose nanofiber-containing polyolefin microporous stretched film according to claim 1, wherein one kind or a mixture of several kinds among: liquid paraffin, nonane, decane, decalin, paraxylene, undecane and dodecane which are linear or cyclic aliphatic hydrocarbons; mineral oil fractions whose boiling point corresponds to that of liquid paraffin, nonane, decane, decalin, paraxylene, undecane and dodecane; and dibutyl phthalate and dioctyl phthalate which are phthalates having a liquid form at room temperature, is used as the plasticizer.

4. The method for producing a cellulose nanofiber-containing polyolefin microporous stretched film according to claim 1, wherein the cellulose powder is contained in an amount of from 0.01 to 30% by weight in the cellulose powder dispersion mixture.

5. A cellulose nanofiber microporous composite film comprising the cellulose nanofiber-containing polyolefin microporous stretched film produced by the production method according to claim 1, wherein the cellulose nanofiber microporous composite film comprises cellulose nanofibers dispersed and compounded in polyolefin, and wherein the cellulose nanofiber microporous composite film includes less aggregated cellulose than a comparative cellulose nanofiber microporous composite film which is prepared in the method according to claim 1 except for that the lipophilizing treatment is not performed.

6. The cellulose nanofiber microporous composite film according to claim 5, wherein an amount of cellulose in the polyolefin microporous stretched film is from 0.01 to 30% by weight based on a total weight of the polyolefin microporous stretched film.

7. A separator for nonaqueous secondary batteries, comprising the cellulose nanofiber-containing polyolefin microporous stretched film produced by the production method according to claim 1, wherein the separator comprises cellulose nanofibers dispersed and compounded in polyolefin.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is an outline view of a small-size kneader for use in the present invention.

(2) FIG. 2 is an explanatory view showing a stretched condition of a raw sheet produced by pressing with a mold after kneading with a kneader and stretched with a film stretcher.

(3) FIG. 3 is an outward appearance of a continuous kneader TEX30 that is a twin-screw kneading extruder.

(4) FIG. 4 is a photograph showing dispersion of a chemically-modified cellulose powder in paraffin in the presence or absence of lipophilizing treatment.

(5) FIG. 5 is a photograph showing a SEM image of the microporous film produced in Example 1.

(6) FIG. 6 is a photograph showing a SEM image of the microporous film produced in Example 2.

(7) FIG. 7 is a photograph showing a SEM image of the microporous film produced in Example 3.

MODE FOR CARRYING OUT THE INVENTION

(8) The present invention provides a method for producing a cellulose nanofiber-containing polyolefin microporous stretched film containing cellulose uniformly dispersed in the form of nanofibers therein, in which a cellulose powder dispersion mixture is obtained by uniformly dispersing a cellulose which has a powder particle shape and whose hydroxyl groups have been subjected to a lipophilizing treatment using a dibasic acid anhydride, in a plasticizer, and this mixture is kneaded and compounded with a polymer such as a polyolefin, using a twin-screw extruder only once; and provides a cellulose nanofiber microporous composite film and a separator for nonaqueous secondary batteries.

EXAMPLES

(9) Preferred embodiments of the method for producing a cellulose nanofiber-containing polyolefin microporous stretched film, the cellulose nanofiber microporous composite film and the separator for nonaqueous secondary batteries of the present invention are described below with reference to the drawings.

(10) For producing a CeNF composite separator according to the present invention, CeNF is highly uniformly dispersed in a plasticizer such as paraffin used in an ordinary wet process, whereby the conventional apparatus configuration is not changed but a twin-screw kneading extruder is used only once. Consequently, the present invention has made it possible to provide a separator for nonaqueous secondary batteries, including a cellulose nanofiber microporous composite film having high strength and high heat resistance.

(11) The raw material cellulose for use herein is, as it is, hydrophilic and is difficult to disperse in paraffin. In the present invention, one prepared through esterification or etherification of the hydroxyl groups in a cellulose nanofiber molecular structure, or one prepared through secondary addition treatment with propylene oxide or the like after the esterification treatment is dispersed in a plasticizer such as paraffin to prepare a suspension. The use of this suspension has made it possible to produce a microporous sheet using a conventional apparatus configuration and according to a wet process that is the same as an conventional process.

(12) The polyolefin in the present invention is a polyolefin resin that is used in ordinary extrusion, injection, inflation, blow-molding or the like, for which usable is a homopolymer, a copolymer, a multistage polymer or the like of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc. A polyolefin selected from a group of these homopolymer, copolymer, multistage polymer and others may be used singly or as combined. Representative examples of the polymers include low-density polyethylene, linear low-density polyethylene, middle-density polyethylene, high-density polyethylene, ultra-high-molecular-weight polyethylene, isotactic polypropylene, atactic polypropylene, ethylene-propylene random copolymer, polybutene, and ethylene-propylene rubber. In the case where the microporous film of the present invention is used as a separator for batteries, especially preferred is a resin containing a high-density polyethylene as the main component, in view of a high melting point and the necessary performance of high strength; and in view of the shutdown performance or the like, preferred is one that contains a polyethylene resin in an amount of 50% by weight or more of the resin component therein. On the other hand, when the proportion of an ultra-high-molecular weight polyolefin having a molecular weight of more than 1,000,000 accounts for more than 10 parts by weight of the polyolefin, it would be difficult to uniformly knead the mixture, and therefore, the proportion thereof is preferably 10 parts by weight or less.

(13) CeNF for use in the present invention has, when dispersed in a polyolefin, a nano-order fiber diameter and a part of the hydroxyl groups existing on the fiber surface are mono-esterified with a polybasic acid. Accordingly, the fiber can prevent self-aggregation and keeps high uniform dispersibility with the polyolefin, in addition, kneading and sheet formation using the fiber is easy, and a separator having mechanical and thermal properties more excellent than those of conventional separators can be obtained. In addition, after monoesterified, CeNF can be subjected to a secondary treatment such as propylene oxide addition (PO addition) for further improving the dispersibility thereof.

(14) As the plasticizer for use in the present invention, in addition to liquid paraffin and the like, linear or cyclic aliphatic hydrocarbons such as nonan, decane, decalin, paraxylene, undecane and dodecane; mineral oil fractions whose boiling point corresponds to that of these compounds; and phthalates having a liquid form at room temperature such as dibutyl phthalate and dioctyl phthalate, etc., may be mentioned.

(15) Further, the CeNF composite porous film of the present invention may be a single layer or a multilayer film. In the case of a multilayer film, at least one layer constituting the film may contain CeNF. The final thickness of the film preferably falls within a range of from 5 m to 50 m. When the film thickness is 5 m or more, the mechanical strength could be sufficient, and when the film thickness is 50 m or less, the occupied volume of the separator may reduce and would be therefore advantageous in point of battery capacity increment. The Gurley value of the porous film of the present invention is preferably within a range of from 50 sec/100 cc to 1,000 sec/100 cc. When the Gurley value thereof is 50 sec/100 cc or more in use as a separator for batteries, self-discharge would be low, and when the Gurley value thereof is 1,000 sec/100 cc or less, excellent charge/discharge characteristics can be obtained.

(16) Examples of the present invention are described below. However, the present invention is not whatsoever restricted by these Examples, etc. The properties of the microporous film of the present invention were evaluated according to the test methods mentioned below.

(17) Film Thickness and Porosity:

(18) The sample was cut out into pieces of 5050 mm square, and the thickness thereof was measured with a microgauge at 25 points in every sheet. The found data were averaged to obtain the film thickness. The porosity was calculated from the theoretical weight of the sheet that had been calculated from the measured weight, the density and the volume thereof.

(19) Gurley Value:

(20) The Gurley value was measured using a Gurley automatic measuring instrument (manufactured by TESTING MACHINES, INC.).

(21) In this measurement, the time taken until 100 cc of air passed through the sheet was counted, as stipulated in JISP8177, and was referred to as the Gurley value.

(22) Puncture Strength:

(23) The puncture strength was measured using an automatic puncture strength measuring instrument (KES-FB3-AUTO, manufactured by Kato Tech Co., Ltd.). The formed sheet was cut into pieces of 5050 mm square, and the puncture strength in each position at intervals of 5 mm was measured. The found data were averaged in every sheet to obtain an average value.

(24) FE-SEM Observation:

(25) Using an ion-sputtering apparatus (ESC-101 manufactured by Elionix Inc.), the formed sheet was processed for platinum deposition thereon in a thickness of about 3 nm, and then the surface thereof was microscopically observed using FE-SEM (SUPRA55VP, manufactured by Carl Zeiss AG).

Example 1

(26) As a cellulose powder sample, used was Ceolus FE-101 (manufactured by Asahi Kasei Chemicals Corporation), and in a ratio by weight of cellulose/succinic anhydride (SA)=100/11.81, these were kneaded with a pressure kneader at 125 C. for 20 minutes for monoesterification, and then, the unreacted matters were removed through acetone extraction (known SA processing). Subsequently, the SA-processed cellulose micropowder was mixed in paraffin, and swollen and stirred therein for 24 hours. The composition of the raw material is shown in Example 1 in Table 1. Using a kneader of FIG. 1, 30 parts by weight of Mitsui Hizex (030S) was mixed and kneaded in 70 parts by weight of the above-mentioned paraffin, and then stretched in a mode of simultaneous biaxial stretching, using a tenter of FIG. 2. The kneading condition and the stretching condition are shown in Table 2 and Table 3. After the biaxial stretching with the tenter, the liquid paraffin was defatted with methylene chloride, and then the film was heat-set at 118 C. for 10 minutes.

(27) TABLE-US-00001 TABLE 1 Summary of Cellulose Composite Polyolefin Raw Material (1) Name of (3) Name of CeNF Raw Material Kneading UMwPE (2) Name of CeNF Paraffin PE/Paraffin weight Fibrillation Constitution Machine (manufacturer) (manufacturer) (manufacturer) blend ratio ratio Treatment Example 1 (1) UHMwPE powder kneader 030s Ceolus FD-101 350P 30/70 0.5 wt % Absent (2) Es-Ce (Mitsui (Asahi Kasei (Moresco) (SA processed) Chemical) Chemicals (3) Liquid paraffin Corporation) Example 2 (1) UHMwPE powder kneader 030s Ceolus FD-101 350P 30/70 0.5 wt % Absent (2) Es-PO-Ce (Mitsui (Asahi Kasei (Moresco) (SA processed + Chemical) Chemicals PO addition) Corporation) (3) Liquid paraffin Example 3 (1) UHMwPE powder kneader 030s Ceolus FD-101 350P 30/70 0.5 wt % Absent (2) Ce (unprocessed) (Mitsui (Asahi Kasei (Moresco) (3) Liquid paraffin Chemical) Chemicals Corporation) Comparative (1) UHMwPE powder kneader 030s 350P 30/70 0.5 wt % Absent Example 1 (3) Liquid paraffin (Mitsui (Moresco) Chemical) Comparative (1) (UHMwPE + CeNF kneader 030s Ceolus FD-101 350P 30/70 0.5 wt % Present Example 2 (SA processed)) (Mitsui (Asahi Kasei (Moresco) blend pellets Chemical) Chemicals (2) Liquid paraffin Corporation) Comparative (1) (UHMwPE + CeNF TEX30 030s Ceolus FD-101 350P 30/70 0.5 wt % Present Example 3 (SA processed)) (Mitsui (Asahi Kasei (Moresco) blend pellets Chemical) Chemicals (2) Liquid paraffin Corporation) UHMwPE: Ultra-high-molecular-weight polyethylene Es-Ce: Monoesterified cellulose Es-PO-Ce: Monoesterified, PO-added cellulose Ce: Cellulose powder CeNF: Cellulose nanofiber SA processing: succinic anhydride monoesterification PO addition: Propylene oxide addition treatment Fibrillation: Starburst treatment

(28) TABLE-US-00002 TABLE 2 Kneading Condition Rotation Kneading Extrusion Temperature Number Time Rate Parameter ( C.) (rpm) min Kg/h Kneader 180 40 30 TEX30 180 300 10

(29) TABLE-US-00003 TABLE 3 Stretching Condition MD Stretching Condition TD Stretching Condition Stretching Draw Stretching Stretching Draw Stretching Temperature Ratio Speed Temperature Ratio Speed ( C.) times (mm/min) ( C.) times (mm/min) 110 5 to 6 3,000 to 6,000 110 5 to 7 3,000 to 6,000

Example 2

(30) In the method of Example 1, used was a cellulose nanofiber to which propylene oxide was added as the secondary treatment after the SA-processing. The raw material composition is shown in Example 2 in Table 1. The other conditions were the same as in Example 1.

Example 3

(31) In the method of Example 1, as a raw material, known cellulose without being subjected to the SA processing was used. The raw material composition is shown in Example 3 in Table 1. The other conditions were the same as in Example 1.

Comparative Example 1

(32) In the method of Example 1, a raw material not using a cellulose nanofiber was used to form a sheet. The raw material composition is shown in Comparative Example 1 in Table 1 described below. The other conditions were the same as in Example 1.

Comparative Example 2

(33) In the method of Example 1, an aqueous slurry prepared by subjecting a raw material cellulose to the SA processing followed by processing for starburst treatment was kneaded with 030S and dewatered, and the resultant cellulose nanofiber composite polyethylene pellets were used to produce a sheet. The raw material composition is shown in Comparative Example 2 in Table 1. The other conditions were the same as in Example 1.

Comparative Example 3

(34) An aqueous slurry prepared by subjecting a raw material cellulose to the SA processing followed by processing for starburst treatment was kneaded with 030S and dewatered, and the resultant cellulose nanofiber composite polyethylene pellets were used and continuously kneaded in TEX30 of FIG. 3 to produce a raw sheet. The raw material composition is shown in Comparative Example 3 in Table 1. The subsequent simultaneous biaxial stretching, defatting and heat-setting were the same as in Example 1.

(35) Comparison of Results

(36) Before and after SA processing, the dispersion condition in paraffin in 40 minutes after 18-hours swelling and stirring treatment is shown in FIG. 4. As compared with the unprocessed cellulose, the known SA-processed cellulose exhibited dramatically-improved dispersibility in paraffin.

(37) FIG. 5, FIG. 6 and FIG. 7 show SEM images of the microporous films produced under the conditions of Examples 1 to 3. FIG. 7 show a sample in which the unprocessed cellulose powder was, directly as it was, mixed with liquid paraffin and ultra-high-molecular-weight polyethylene powder, and the resultant raw material was kneaded with a kneader and formed into a film. From this, many clumps to be knots are seen in the polyethylene crystal fibers. It is considered that cellulose would have aggregated in those parts, and it is presumed that the dispersion condition in polyethylene would not be good. FIG. 5 shows a sample using a cellulose powder that had been previously SA-processed, and in this, the clumps reduced as compared with those in FIG. 7, and it is presumed that the dispersion condition in this would have been improved. Further, FIG. 6 shows a result of the sample that had been previously SA-processed and then processed for secondary PO-addition treatment. As compared with FIG. 5, few clumps are seen, and it is considered that the cellulose nanofiber would have well and uniformly dispersed in the ultra-high-molecular-weight HDPE.

(38) Table 4 shows main separator characteristics in Examples 1 to 3 and Comparative Examples 1 to 3. Comparing the results in Examples 1 to 3, the Gurley value that affects on the battery characteristics of lithium ion batteries is in an order of Example 2 <Example 1 <Example 3. The low Gurley value means easy passing of lithium ions through the sample. This indicates that, as compared with the others, the sample of Example 2 realized good CeNF dispersion with no aggregation, and good micropores were formed. The porosity was large in Example 1, in which, however, the micropore distribution is uneven, and this would be because, as compared with those in Example 2, pores having a large diameter would have been formed unevenly.

(39) The puncture strength is important for preventing film breaking due to impurities in winding operation for production of batteries, and for preventing short-circuiting at the film broken by the lithium ion dendrites formed due to degradation with time. As compared with that in Example 3, the puncture strength in Examples 1 and 2 greatly increased, which would result from the CeNF addition effect.

(40) Thermal shrinkability contributes toward safety of batteries. In particular, small TD shrinkage is effective for preventing short-circuiting between positive and negative electrodes due to sheet shrinkage by abnormal heat generation during runaway of batteries. Examples 1 to 3 are compared in shrinkage in TD, and it is seen that Examples 1 and 2 exhibit an improved effect as compared with Example 3. In particular, Example 2 has a small value, which would result from the CeNF addition effect.

(41) TABLE-US-00004 TABLE 4 Typical Characteristic Values of Separator 120 C. Gurley Puncture Thermal Kneading Porosity Value Strength Shrinkage (%) Machine (%) (s/100 cc) (kgf) MD TD Example 1 47.2 469.4 955 11.6 11.2 kneader Example 2 45.4 430.1 858 11.8 10.4 kneader Example 3 26.6 727.1 684 14.4 14.3 kneader Compara- 37.3 504.6 590 16.6 16.8 kneader tive Ex- ample 1 Compara- 20.2 1518.6 899 15.4 12.3 kneader tive Ex- ample 2 Compara- 44.6 321.8 1061 4.5 4.5 TEX30 tive Ex- ample 3 MD: machine direction, TD: transverse direction

(42) Examples 1 to 3 are compared with conventional separators not compounded with CeNF. Except those of Example 3, all the characteristic values of Gurley value, puncture strength and 120 C. thermal shrinkage were improved ones. However, the characteristics of porosity and Gurley value of Example 3 were worse than those of the samples not compounded with CeNF. This would be because the dispersion condition of CeNF was bad and therefore micropores could not be formed uniformly, which would have some negative influences on the porosity and the Gurley value.

(43) Comparative Example 2 is a result of film formation from polyethylene pellets previously compounded with CeNF, according to the same method. However, when the film formation was carried out with a kneader under the same condition, all the characteristic values were bad. On the other hand, as shown by Comparative Example 3, the characteristics of the film produced through continuous kneading of paraffin with TEX30 were all good. This would be because, in a wet process of separator production, in general, the results greatly vary depending on the kneading condition, and in particular, swelling that has some influence on compatibility with paraffin would be insufficient in the form of pellets, and therefore micropores could not be well formed in the film. In other words like the results of Comparative Examples 2 and 3, the results of Examples 1 and 2 indicate that the continuous kneading could further optimize sheet formation, and suggest that, merely by using a dispersion prepared by dispersing SA-processed CeNF in paraffin, it becomes possible to provide a separator whose characteristics can be improved to the level to which any one produced according to conventional methods could not achieve.

(44) Next, the gist of above-mentioned Examples 1 to 3 of the present invention is summarized as follows.

(45) Specifically, a method for producing a cellulose nanofiber-containing polyolefin microporous stretched film according to the present invention is a method including: a first step of obtaining a cellulose powder dispersion mixture by uniformly dispersing a cellulose which has a powder particle shape and whose hydroxyl groups have been subjected to a lipophilizing treatment using a dibasic acid anhydride, in a plasticizer; a second step of melt-kneading the cellulose powder dispersion mixture and a polyolefin to obtain a polyolefin resin composition; a third step of extrusion-molding the polyolefin resin composition to obtain an extrudate; a fourth step of stretching the extrudate with a film stretcher as shown in FIG. 2 to obtain a film; a fifth step of extracting out the plasticizer from the film; and a sixth step of thermally fixing the film from which the plasticizer has been extracted out for inhibiting contraction, while stretching the film at a temperature not higher than a melting point of the polyolefin, in which a twin-screw kneading extruder as shown in FIG. 3 is used only once throughout the second and third steps; in which the lipophilizing treatment includes performing a monoesterification treatment followed by performing a secondary propylene oxide addition treatment; in which one kind or a mixture of several kinds among: liquid paraffin, nonane, decane, decalin, paraxylene, undecane and dodecane which are linear or cyclic aliphatic hydrocarbons; mineral oil fractions whose boiling point corresponds to that of these compounds; and dibutyl phthalate and dioctyl phthalate which are phthalates having a liquid form at room temperature, is used as the plasticizer; and/or in which the cellulose powder is contained in an amount of from 0.01 to 30% by weight in the cellulose powder dispersion mixture. Additionally, a cellulose nanofiber microporous composite film according to the present invention is a cellulose nanofiber microporous composite film including the cellulose nanofiber-containing polyolefin microporous stretched film produced by the production method according to any of the above-described methods. Also, a cellulose nanofiber microporous composite film according to the present invention is a cellulose nanofiber microporous composite film in which the cellulose powder in the polyolefin microporous stretched film produced by the production method according to any of the above-described methods is contained in an amount of from 0.01 to 30% by weight based on a total weight of the polyolefin microporous stretched film. Furthermore, a separator for nonaqueous secondary batteries according to the present invention is a separator for nonaqueous secondary batteries, including the cellulose nanofiber-containing polyolefin microporous stretched film produced by the production method according to any of the above-described methods.

(46) While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

(47) The present application is based on a Japanese patent application No. 2013-117630 filed on Jun. 4, 2013, and the contents thereof are herein incorporated by reference.

INDUSTRIAL APPLICABILITY

(48) The method for producing a cellulose nanofiber-containing polyolefin microporous stretched film, the cellulose nanofiber microporous composite film and the separator for nonaqueous secondary batteries according to the present invention can contribute toward realizing film products having improved puncture strength.