POLYCARBONATE COMPOSITE USING SOLID DISPERSION OR MOLTEN DISPERSION OF ANHYDROSUGAR ALCOHOL, PRODUCING METHOD THEREOF, AND MOLDED ARTICLE COMPRISING SAME

Abstract

The present invention relates to a polycarbonate composite, a producing method thereof, and a molded article comprising same. More specifically, the present invention relates to: a polycarbonate composite comprising a matrix resin, which is a polycarbonate resin in which an anhydrosugar alcohol is copolymerized, and a nanomaterial dispersed in the matrix resin, wherein the polycarbonate composite exhibits a more remarkably improved tensile modulus and tensile strength than a conventional biopolycarbonate resin composite, by using, as a diol component, a solid dispersion or molten dispersion obtained by introducing a nanomaterial (dispersible substance) into an anhydrosugar alcohol (dispersion medium) in the form of an aqueous dispersion at the time of manufacture, and has uniform physical properties as the nanomaterial is uniformly dispersed in the composite; a producing method thereof; and a molded article comprising same.

Claims

1. A polycarbonate composite comprising matrix resin and nanomaterial dispersed in the matrix resin, wherein the matrix resin is polycarbonate resin which is a polymerization reaction product of a diol component comprising a solid dispersion or melt dispersion of anhydrosugar alcohol in which the nanomaterial is dispersed, and a carbonic acid diester component, and wherein the solid dispersion or melt dispersion of anhydrosugar alcohol is that obtained by incorporating the nanomaterial as aqueous dispersion form into the anhydrosugar alcohol.

2. The polycarbonate composite of claim 1, wherein the nanomaterial is selected from the group consisting of nanocellulose, carbon nanofiber, carbon nanotube, iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver, gold, platinum, kaolin, clay, talc, mica, silica, bentonite, dolomite, calcium silicate, magnesium silicate, asbestos, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, iron hydroxide, aluminum silicate, zirconium oxide, magnesium oxide, aluminum oxide, titanium oxide, iron oxide, zinc oxide, antimony trioxide, indium oxide, indium tin oxide, silicon carbide, silicon nitride, boron nitride, barium titanate, diatomite, carbon black, rock wool, graphene, graphite, graphene oxide, azo-based compound, diazo-based compound, condensed azo-based compound, thioindigo-based compound, indanthrone-based compound, quinacridone-based compound, anthraquinone-based compound, benzimidazolone-based compounds, perylene-based compounds, phthalocyanine-based compounds, anthrapyridine-based compounds, dioxazine-based compounds, polyethylene resins, polypropylene resins, polyester resins, nylon resins, polyamide resins, aramid resins, urethane resins, polystyrene resins, polylactic acid, cellulose acetate fiber, hemicellulose, lignin, chitin, chitosan, starch, or mixture thereof.

3. The polycarbonate composite of claim 1, wherein the nanomaterial is selected from the group consisting of nanocellulose, carbon nanofiber, carbon nanotube or mixture thereof.

4. The polycarbonate composite of claim 3, wherein the nanocellulose is selected from the group consisting of nanocellulose fiber, nanocellulose crystal or mixture thereof, and the carbon nanotube is selected from the group consisting of single-walled carbon nanotube, multi-walled carbon nanotube or mixture thereof.

5. The polycarbonate composite of claim 1, wherein the amount of the nanomaterial is from 0.2% by weight to 10% by weight, based on total weight of the composite.

6. The polycarbonate composite of claim 1, wherein the anhydrosugar alcohol is monoanhydrosugar alcohol, dianhydrosugar alcohol or mixture thereof.

7. The polycarbonate composite of claim 1, wherein the solid dispersion of anhydrosugar alcohol is that obtained by adding the nanomaterial as aqueous dispersion form to anhydrosugar alcohol and mixing them, melting the mixture at a temperature equal to or higher than the melting point of the anhydrosugar alcohol while removing moisture therefrom, and then cooling the melted mixture to room temperature.

8. The polycarbonate composite of claim 1, wherein the melt dispersion of anhydrosugar alcohol is that obtained by adding the nanomaterial as aqueous dispersion form to anhydrosugar alcohol and mixing them, and melting the mixture at a temperature equal to or higher than the melting point of the anhydrosugar alcohol while removing moisture therefrom.

9. The polycarbonate composite of claim 1, wherein the carbonic acid diester component is a carbonic acid diester component represented by the following chemical formula 1: ##STR00004## wherein each R.sub.1 may independently be selected from unsubstituted or halogen-substituted, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms or aralkyl group having 7 to 25 carbon atoms.

10. The polycarbonate composite of claim 1, wherein the diol component further comprises additional diol component other than the solid dispersion or melt dispersion of anhydrosugar alcohol.

11. The polycarbonate composite of claim 10, wherein the additional diol component is a diol component represented by the following chemical formula 2:
HO—X—OH  [Chemical formula 2] wherein X represents mononuclear or polynuclear arylene group having 6 to 30 carbon atoms; linear alkylene group having 1 to 15 carbon atoms; branched alkylene group having 3 to 15 carbon atoms; or cyclic alkylene group having 3 to 15 carbon atoms, and each of the arylene group, linear alkylene group, branched alkylene group and cyclic alkylene group may be unsubstituted or substituted with halogen atom, alkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryl group, nitro group or carboxyl group.

12. The polycarbonate composite of claim 1, which exhibits a tensile strength greater than 80 MPa.

13. The polycarbonate composite of claim 1, which exhibits a tensile modulus greater than 2,500 MPa.

14. The polycarbonate composite of claim 1, which exhibits a tensile strength standard deviation of 3 MPa or less.

15. The polycarbonate composite of claim 1, which exhibits a tensile modulus standard deviation of 200 MPa or less.

16. A method for preparing a polycarbonate composite, comprising a step of polymerization reaction of a diol component comprising a solid dispersion or melt dispersion of anhydrosugar alcohol in which the nanomaterial is dispersed, and a carbonic acid diester component, wherein the solid dispersion or melt dispersion of anhydrosugar alcohol is that obtained by incorporating the nanomaterial as aqueous dispersion form into the anhydrosugar alcohol.

17. The method for preparing a polycarbonate composite of claim 16, wherein the solid dispersion of anhydrosugar alcohol is that obtained by adding the nanomaterial as aqueous dispersion form to anhydrosugar alcohol and mixing them, melting the mixture at a temperature equal to or higher than the melting point of the anhydrosugar alcohol while removing moisture therefrom, and then cooling the melted mixture to room temperature.

18. The method for preparing a polycarbonate composite of claim 16, the melt dispersion of anhydrosugar alcohol is that obtained by adding the nanomaterial as aqueous dispersion form to anhydrosugar alcohol and mixing them, and melting the mixture at a temperature equal to or higher than the melting point of the anhydrosugar alcohol while removing moisture therefrom.

19. A molded article comprising the polycarbonate composite of claim 1.

Description

EXAMPLES

Part I

Preparation of Solid Dispersion Comprising Nanocellulose

Dispersion Comprising Nanocellulose Fiber (NCF) and Anhydrosugar Alcohol

Preparation Example I-A1: Preparation of Dispersion Comprising 1% by Weight of Nanocellulose Fiber

[0065] Into a rotary evaporator, 99 g of isosorbide (NOVASORB®, Samyang Corporation) and 100 g of aqueous solution (KB101, Asia Nanocellulose Co. Ltd.) wherein 1% by weight of nanocellulose fiber was dispersed, were fed and mixed uniformly. Then, under a temperature condition of 80° C. which was higher than the melting point of isosorbide, the mixture was melted while removing moisture under vacuum. Then, the melted mixture was cooled to room temperature to prepare isosorbide comprising nanocellulose fiber dispersed therein (solid dispersion). The solid dispersion comprised 1% by weight of nanocellulose fiber, based on total weight of the solid dispersion.

Preparation Example I-A2: Preparation of Dispersion Comprising 3% by Weight of Nanocellulose Fiber

[0066] Excepting that the amount of isosorbide was changed from 99 g to 97 g and the amount of aqueous solution containing 1% by weight of dispersed nanocellulose fiber was changed from 100 g to 300 g, the same method as Preparation Example I-A1 was conducted to prepare isosorbide comprising nanocellulose fiber dispersed therein (solid dispersion). The solid dispersion comprised 3% by weight of nanocellulose fiber, based on total weight of the solid dispersion.

Preparation Example I-A3: Preparation of Dispersion Comprising 5% by Weight of Nanocellulose Fiber

[0067] Excepting that the amount of isosorbide was changed from 99 g to 95 g and the amount of aqueous solution containing 1% by weight of dispersed nanocellulose fiber was changed from 100 g to 500 g, the same method as Preparation Example I-A1 was conducted to prepare isosorbide comprising nanocellulose fiber dispersed therein (solid dispersion). The solid dispersion comprised 5% by weight of nanocellulose fiber, based on total weight of the solid dispersion.

Preparation Example I-A4: Preparation of Dispersion Comprising 10% by Weight of Nanocellulose Fiber

[0068] Excepting that the amount of isosorbide was changed from 99 g to 90 g and the amount of aqueous solution containing 1% by weight of dispersed nanocellulose fiber was changed from 100 g to 1,000 g, the same method as Preparation Example I-A1 was conducted to prepare isosorbide comprising nanocellulose fiber dispersed therein (solid dispersion). The solid dispersion comprised 10% by weight of nanocellulose fiber, based on total weight of the solid dispersion.

Dispersion Comprising Nanocellulose Crystal (NCC) and Anhydrosugar Alcohol

Preparation Example I-B1: Preparation of Dispersion Comprising 1% by Weight of Nanocellulose Crystal

[0069] Excepting that 100 g of aqueous solution (CelluForce) containing 1% by weight of dispersed nanocellulose crystal was used instead of 100 g of aqueous solution (KB101, Asia Nanocellulose Co. Ltd.) containing 1% by weight of dispersed nanocellulose fiber, the same method as Preparation Example I-A1 was conducted to prepare isosorbide comprising nanocellulose crystal dispersed therein (solid dispersion). The solid dispersion comprised 1% by weight of nanocellulose crystal, based on total weight of the solid dispersion.

Preparation Example I-B2: Preparation of Dispersion Comprising 3% by Weight of Nanocellulose Crystal

[0070] Excepting that the amount of isosorbide was changed from 99 g to 97 g and 300 g of aqueous solution containing 1% by weight of dispersed nanocellulose crystal was used instead of 100 g of aqueous solution containing 1% by weight of dispersed nanocellulose fiber, the same method as Preparation Example I-A1 was conducted to prepare isosorbide comprising nanocellulose crystal dispersed therein (solid dispersion). The solid dispersion comprised 3% by weight of nanocellulose crystal, based on total weight of the solid dispersion.

Preparation Example I-B3: Preparation of Dispersion Comprising 5% by Weight of Nanocellulose Crystal

[0071] Excepting that the amount of isosorbide was changed from 99 g to 95 g and 500 g of aqueous solution containing 1% by weight of dispersed nanocellulose crystal was used instead of 100 g of aqueous solution containing 1% by weight of dispersed nanocellulose fiber, the same method as Preparation Example I-A1 was conducted to prepare isosorbide comprising nanocellulose crystal dispersed therein (solid dispersion). The solid dispersion comprised 5% by weight of nanocellulose crystal, based on total weight of the solid dispersion.

Preparation Example I-B4: Preparation of Dispersion Comprising 10% by Weight of Nanocellulose Crystal

[0072] Excepting that the amount of isosorbide was changed from 99 g to 90 g and 1,000 g of aqueous solution containing 1% by weight of dispersed nanocellulose crystal was used instead of 100 g of aqueous solution containing 1% by weight of dispersed nanocellulose fiber, the same method as Preparation Example I-A1 was conducted to prepare isosorbide comprising nanocellulose crystal dispersed therein (solid dispersion). The solid dispersion comprised 10% by weight of nanocellulose crystal, based on total weight of the solid dispersion.

Dispersion Comprising a Mixture of Nanocellulose Fiber and Nanocellulose Crystal, and Anhydrosugar Alcohol

Preparation Example I-C1: Preparation of Dispersion Comprising 1% by Weight of a Mixture of Nanocellulose Fiber and Nanocellulose Crystal

[0073] Excepting that a mixture of 50 g of aqueous solution containing 1% by weight of dispersed nanocellulose fiber and 50 g of aqueous solution containing 1% by weight of dispersed nanocellulose crystal was used instead of 100 g of aqueous solution containing 1% by weight of dispersed nanocellulose fiber, the same method as Preparation Example I-A1 was conducted to prepare isosorbide comprising nanocellulose fiber and nanocellulose crystal dispersed therein (solid dispersion). The solid dispersion comprised 1% by weight of a mixture of nanocellulose fiber and nanocellulose crystal, based on total weight of the solid dispersion.

Preparation Example I-C2: Preparation of Dispersion Comprising 3% by Weight of a Mixture of Nanocellulose Fiber and Nanocellulose Crystal

[0074] Excepting that the amount of isosorbide was changed from 99 g to 97 g and a mixture of 150 g of aqueous solution containing 1% by weight of dispersed nanocellulose fiber and 150 g of aqueous solution containing 1% by weight of dispersed nanocellulose crystal was used instead of 100 g of aqueous solution containing 1% by weight of dispersed nanocellulose fiber, the same method as Preparation Example I-A1 was conducted to prepare isosorbide comprising nanocellulose fiber and nanocellulose crystal dispersed therein (solid dispersion). The solid dispersion comprised 3% by weight of a mixture of nanocellulose fiber and nanocellulose crystal, based on total weight of the solid dispersion.

Preparation Example I-C3: Preparation of Dispersion Comprising 5% by Weight of a Mixture of Nanocellulose Fiber and Nanocellulose Crystal

[0075] Excepting that the amount of isosorbide was changed from 99 g to 95 g and a mixture of 250 g of aqueous solution containing 1% by weight of dispersed nanocellulose fiber and 250 g of aqueous solution containing 1% by weight of dispersed nanocellulose crystal was used instead of 100 g of aqueous solution containing 1% by weight of dispersed nanocellulose fiber, the same method as Preparation Example I-A1 was conducted to prepare isosorbide comprising nanocellulose fiber and nanocellulose crystal dispersed therein (solid dispersion). The solid dispersion comprised 5% by weight of a mixture of nanocellulose fiber and nanocellulose crystal, based on total weight of the solid dispersion.

Preparation Example I-C4: Preparation of Dispersion Comprising 10% by Weight of a Mixture of Nanocellulose Fiber and Nanocellulose Crystal

[0076] Excepting that the amount of isosorbide was changed from 99 g to 90 g and a mixture of 500 g of aqueous solution containing 1% by weight of dispersed nanocellulose fiber and 500 g of aqueous solution containing 1% by weight of dispersed nanocellulose crystal was used instead of 100 g of aqueous solution containing 1% by weight of dispersed nanocellulose fiber, the same method as Preparation Example I-A1 was conducted to prepare isosorbide comprising nanocellulose fiber and nanocellulose crystal dispersed therein (solid dispersion). The solid dispersion comprised 10% by weight of a mixture of nanocellulose fiber and nanocellulose crystal, based on total weight of the solid dispersion.

Polycarbonate Resin Composite Using Solid Dispersion Comprising Nanocellulose

Preparation and Property Evaluation of Polycarbonate Resin Composite Using Solid Dispersion Comprising Nanocellulose Fiber and Anhydrosugar Alcohol

Example I-A1: Preparation of Polycarbonate Resin Composite Using Solid Dispersion of Preparation Example I-A1

[0077] Into a 5-necked flask connected to nitrogen gas line and vacuum pump for pressure reduction equipped with trap for byproduct removal and having agitator, thermometer and heater, 100 g of solid dispersion prepared in Preparation Example I-A1, 29.6 g of cyclohexane dimethanol and 190.6 g of diphenyl carbonate were fed, and heated up to 100° C. under nitrogen atmosphere, and then after confirming that the reactant materials were melted, 100 mg of magnesium acetate tetrahydrate was added and agitation was started. After arriving at 160° C., the reaction was conducted while maintaining the temperature for 1 hour, and then the pressure was reduced slowly to 100 to 120 torr by using the vacuum pump, and while removing phenol generated as byproduct, the reaction was further conducted for 1 to 2 hours. Thereafter, the temperature was elevated slowly up to 220° C. and the pressure was reduced to 5 to 10 torr, and the reaction was further conducted for 1 hour. As a result, about 130 g of polycarbonate resin composite was obtained. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,500 g/mol, and PDI was 1.7.

[0078] In order to measure the amount of nanocellulose fiber in the obtained polycarbonate resin composite, 50 g of the polycarbonate resin composite was dissolved in 1 L of chloroform and the crystalline residue was filtered and dried in a vacuum oven for about 24 hours, and then its weight as measured was 0.31 g. Through this, the amount of nanocellulose fiber in the above-obtained polycarbonate resin composite was calculated as 0.62% by weight.

[0079] By using the above-obtained polycarbonate resin composite, four (4) identical samples for tensile test were prepared according to ASTM D638. For the four test samples, tensile strength and tensile modulus were measured by using universal test machine (UTM), and as a result, the average tensile strength was 97 MPa, and the average tensile modulus was 2,900 MPa.

Example I-A2: Preparation of Polycarbonate Resin Composite Using Solid Dispersion of Preparation Example I-A2

[0080] Excepting that 100 g of solid dispersion prepared in Preparation Example I-A2 was used instead of 100 g of solid dispersion prepared in Preparation Example I-A1, the same method as Example I-A1 was conducted to obtain about 128 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,210 g/mol, and PDI was 1.7.

[0081] The amount of nanocellulose fiber in the obtained polycarbonate resin composite was measured by the same method as in Example I-A1, and the result was 1.9% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example I-A1, and as a result, the average tensile strength was 98.5 MPa, and the average tensile modulus was 2,923 MPa.

Example I-A3: Preparation of Polycarbonate Resin Composite Using Solid Dispersion of Preparation Example I-A3

[0082] Excepting that 100 g of solid dispersion prepared in Preparation Example I-A3 was used instead of 100 g of solid dispersion prepared in Preparation Example I-A1, the same method as Example I-A1 was conducted to obtain about 126 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,620 g/mol, and PDI was 1.8.

[0083] The amount of nanocellulose fiber in the obtained polycarbonate resin composite was measured by the same method as in Example I-A1, and the result was 3.1% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example I-A1, and as a result, the average tensile strength was 101.5 MPa, and the average tensile modulus was 2,950 MPa.

Example I-A4: Preparation of Polycarbonate Resin Composite Using Solid Dispersion of Preparation Example I-A4

[0084] Excepting that 100 g of solid dispersion prepared in Preparation Example I-A4 was used instead of 100 g of solid dispersion prepared in Preparation Example I-A1, the same method as Example I-A1 was conducted to obtain about 130 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,840 g/mol, and PDI was 1.7.

[0085] The amount of nanocellulose fiber in the obtained polycarbonate resin composite was measured by the same method as in Example I-A1, and the result was 6.4% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example I-A1, and as a result, the average tensile strength was 105.75 MPa, and the average tensile modulus was 2,990 MPa.

Preparation and Property Evaluation of Polycarbonate Resin Composite Using Solid Dispersion Comprising Nanocellulose Crystal and Anhydrosugar Alcohol

Example I-B1: Preparation of Polycarbonate Resin Composite Using Solid Dispersion of Preparation Example I-B1

[0086] Excepting that 100 g of solid dispersion prepared in Preparation Example I-B1 was used instead of 100 g of solid dispersion prepared in Preparation Example I-A1, the same method as Example I-A1 was conducted to obtain about 125 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,200 g/mol, and PDI was 1.8.

[0087] The amount of nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example I-A1, and the result was 0.59% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example I-A1, and as a result, the average tensile strength was 93.5 MPa, and the average tensile modulus was 2,700 MPa.

Example I-B2: Preparation of Polycarbonate Resin Composite Using Solid Dispersion of Preparation Example I-B2

[0088] Excepting that 100 g of solid dispersion prepared in Preparation Example I-B2 was used instead of 100 g of solid dispersion prepared in Preparation Example I-A1, the same method as Example I-A1 was conducted to obtain about 128 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,150 g/mol, and PDI was 1.6.

[0089] The amount of nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example I-A1, and the result was 1.8% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example I-A1, and as a result, the average tensile strength was 94.5 MPa, and the average tensile modulus was 2,783 MPa.

Example I-B3: Preparation of Polycarbonate Resin Composite Using Solid Dispersion of Preparation Example I-B3

[0090] Excepting that 100 g of solid dispersion prepared in Preparation Example I-B3 was used instead of 100 g of solid dispersion prepared in Preparation Example I-A1, the same method as Example I-A1 was conducted to obtain about 131 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,500 g/mol, and PDI was 1.6.

[0091] The amount of nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example I-A1, and the result was 3.5% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example I-A1, and as a result, the average tensile strength was 96.0 MPa, and the average tensile modulus was 2,818 MPa.

Example I-B4: Preparation of Polycarbonate Resin Composite Using Solid Dispersion of Preparation Example I-B4

[0092] Excepting that 100 g of solid dispersion prepared in Preparation Example I-B4 was used instead of 100 g of solid dispersion prepared in Preparation Example I-A1, the same method as Example I-A1 was conducted to obtain about 125 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,670 g/mol, and PDI was 1.9.

[0093] The amount of nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example I-A1, and the result was 6.2% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example I-A1, and as a result, the average tensile strength was 100.0 MPa, and the average tensile modulus was 2,930 MPa.

Preparation and Property Evaluation of Polycarbonate Resin Composite Using Solid Dispersion Comprising a Mixture of Nanocellulose Fiber and Nanocellulose Crystal, and Anhydrosugar Alcohol

Example I-C1: Preparation of Polycarbonate Resin Composite Using Solid Dispersion of Preparation Example I-C1

[0094] Excepting that 100 g of solid dispersion prepared in Preparation Example I-C1 was used instead of 100 g of solid dispersion prepared in Preparation Example I-A1, the same method as Example I-A1 was conducted to obtain about 128 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,650 g/mol, and PDI was 1.8.

[0095] The total amount of nanocellulose fiber and nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example I-A1, and the result was 0.62% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example I-A1, and as a result, the average tensile strength was 94.5 MPa, and the average tensile modulus was 2,850 MPa.

Example I-C2: Preparation of Polycarbonate Resin Composite Using Solid Dispersion of Preparation Example I-C2

[0096] Excepting that 100 g of solid dispersion prepared in Preparation Example I-C2 was used instead of 100 g of solid dispersion prepared in Preparation Example I-A1, the same method as Example I-A1 was conducted to obtain about 130 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,630 g/mol, and PDI was 1.9.

[0097] The total amount of nanocellulose fiber and nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example I-A1, and the result was 1.87% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example I-A1, and as a result, the average tensile strength was 96.25 MPa, and the average tensile modulus was 2,900 MPa.

Example I-C3: Preparation of Polycarbonate Resin Composite Using Solid Dispersion of Preparation Example I-C3

[0098] Excepting that 100 g of solid dispersion prepared in Preparation Example I-C3 was used instead of 100 g of solid dispersion prepared in Preparation Example I-A1, the same method as Example I-A1 was conducted to obtain about 130 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,800 g/mol, and PDI was 1.8.

[0099] The total amount of nanocellulose fiber and nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example I-A1, and the result was 3.18% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example I-A1, and as a result, the average tensile strength was 100.5 MPa, and the average tensile modulus was 2,958 MPa.

Example I-C4: Preparation of Polycarbonate Resin Composite Using Solid Dispersion of Preparation Example I-C4

[0100] Excepting that 100 g of solid dispersion prepared in Preparation Example I-C4 was used instead of 100 g of solid dispersion prepared in Preparation Example I-A1, the same method as Example I-A1 was conducted to obtain about 130 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,450 g/mol, and PDI was 1.8.

[0101] The total amount of nanocellulose fiber and nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example I-A1, and the result was 6.49% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example I-A1, and as a result, the average tensile strength was 101.25 MPa, and the average tensile modulus was 2,993 MPa.

[0102] <Evaluation of Dispersion Uniformity of Nanocellulose Particles in Polycarbonate Resin Composite>

[0103] For each of the polycarbonate resin composites obtained in Examples I-A1 to I-A4, I-B1 to I-B4, and I-C1 to I-C4, the tensile strength and tensile modulus, and average value and standard deviation thereof were measured for four (4) samples for tensile test, and the results are shown in the following Table 1.

TABLE-US-00001 TABLE 1 Tensile strength (MPa) Tensile modulus (MPa) Sample Standard Sample Sample Sample Sample Standard Example 1 2 3 4 Average deviation 1 2 3 4 Average deviation I-A1 96 97 97 98 97 0.71 2,910 2,900 2,890 2,900 2,900 7.10 I-A2 99 98 98 99 98.5 0.50 2,910 2,930 2,920 2,930 2,923 8.30 I-A3 102 101 100 103 101.5 1.12 2,950 2,940 2,950 2,960 2,950 7.10 I-A4 106 105 106 106 105.75 0.43 2,980 2,990 2,990 3,000 2,990 7.10 I-B1 93 93 94 94 93.5 0.50 2,700 2,690 2,700 2,710 2,700 7.10 I-B2 94 95 94 95 94.5 0.50 2,790 2,780 2,780 2,780 2,783 4.61 I-B3 95 97 96 96 96 0.71 2,810 2,820 2,820 2,820 2,818 4.36 I-B4 101 99 100 100 100 0.71 2,930 2,940 2,930 2,920 2,930 7.10 I-C1 95 94 94 95 94.5 0.50 2,850 2,860 2,840 2,850 2,850 7.10 I-C2 97 96 95 97 96.25 0.83 2,890 2,900 2,910 2,900 2,900 7.10 I-C3 101 101 100 100 100.5 0.50 2,950 2,950 2,960 2,970 2,958 8.30 I-C4 100 102 101 102 101.25 0.83 3,000 3,000 2,980 2,990 2,993 8.30

[0104] As shown in the above Table 1, as a result of measuring the average and standard deviation of tensile strength for four (4) samples for tensile test of each of the polycarbonate resin composites obtained in Examples I-A1 to I-A4, I-B1 to I-B4, and I-C1 to I-C4 according to the present invention, the tensile strengths of the four (4) tensile test samples were equivalent such that the tensile strength deviations of the four (4) tensile test samples were so small as 1.12 MPa or less—from which it can be known that nanocellulose particles were dispersed uniformly in the polycarbonate resin composites.

[0105] In addition, as a result of measuring the average and standard deviation of tensile modulus for four (4) samples for tensile test of each of the polycarbonate resin composites obtained in Examples I-A1 to I-A4, I-B1 to I-B4, and I-C1 to I-C4 according to the present invention, the tensile moduli of the four (4) tensile test samples were equivalent such that the tensile modulus deviations of the four (4) tensile test samples were so small as 8.30 MPa or less—from which it can be known that nanocellulose particles were dispersed uniformly in the polycarbonate resin composites.

[0106] Furthermore, the average tensile strength values of four (4) samples for tensile test of each of the polycarbonate resin composites obtained in Examples I-A1 to I-A4, I-B1 to I-B4, and I-C1 to I-C4 according to the present invention were 93.5 MPa or more, and the average tensile modulus values thereof were 2,700 MPa or more—from which it can be known that the mechanical properties of the polycarbonate resin composites were excellent.

Part II

Polycarbonate Resin Composite Using Melt Dispersion Comprising Nanocellulose

Preparation and Property Evaluation of Polycarbonate Resin Composite Using Melt Dispersion Comprising Nanocellulose Fiber (NCF) and Anhydrosugar Alcohol

Example II-A1: Preparation of Polycarbonate Resin Composite Comprising 0.63% by Weight of Nanocellulose Fiber Dispersed Therein

[0107] Into a rotary evaporator, 99 g of isosorbide (NOVASORB®, Samyang Corporation) and 100 g of aqueous solution (KB101, Asia Nanocellulose Co. Ltd.) wherein 1% by weight of nanocellulose fiber was dispersed, were fed and mixed uniformly. Then, under a temperature condition of 80° C. which was higher than the melting point of isosorbide, the mixture was melted while removing moisture under vacuum, to prepare the melt dispersion in liquid phase. The melt dispersion comprised 1% by weight of nanocellulose fiber, based on total weight of the melt dispersion.

[0108] Then, into a 5-necked flask connected to nitrogen gas line and vacuum pump for pressure reduction equipped with trap for byproduct removal and having agitator, thermometer and heater, 100 g of the above melt dispersion, 29.6 g of cyclohexane dimethanol and 190.6 g of diphenyl carbonate were fed, and heated up to 100° C. under nitrogen atmosphere, and then after confirming that the reactant materials were melted, 100 mg of magnesium acetate tetrahydrate was added and agitation was started. After arriving at 160° C., the reaction was conducted while maintaining the temperature for 1 hour, and then the pressure was reduced slowly to 100 to 120 torr by using the vacuum pump, and while removing phenol generated as byproduct, the reaction was further conducted for 1 to 2 hours. Thereafter, the temperature was elevated slowly up to 220° C. and the pressure was reduced to 5 to 10 torr, and the reaction was further conducted for 1 hour. As a result, about 140 g of polycarbonate resin composite was obtained. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 31,000 g/mol, and PDI was 1.6.

[0109] In order to measure the amount of nanocellulose fiber in the obtained polycarbonate resin composite, 50 g of the polycarbonate resin composite was dissolved in 1 L of chloroform and the crystalline residue was filtered and dried in a vacuum oven for about 24 hours, and then its weight as measured was 0.316 g. Through this, the amount of nanocellulose fiber in the above-obtained polycarbonate resin composite was calculated as 0.63% by weight.

[0110] By using the above-obtained polycarbonate resin composite, four (4) identical samples for tensile test were prepared according to ASTM D638. For the four test samples, tensile strength and tensile modulus were measured by using universal test machine (UTM), and as a result, the average tensile strength was 95.75 MPa, and the average tensile modulus was 2,855 MPa.

Example II-A2: Preparation of Polycarbonate Resin Composite Comprising 1.89% by Weight of Nanocellulose Fiber Dispersed Therein

[0111] Excepting that the amount of isosorbide was changed from 99 g to 98 g and the amount of aqueous solution containing 1% by weight of dispersed nanocellulose fiber was changed from 100 g to 200 g, the same method as Example II-A1 was conducted to prepare the melt dispersion. The melt dispersion comprised 2% by weight of nanocellulose fiber, based on total weight of the melt dispersion. Then, by using the melt dispersion, the same method as Example II-A1 was conducted to obtain 138 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,890 g/mol, and PDI was 1.4.

[0112] The amount of nanocellulose fiber in the obtained polycarbonate resin composite was measured by the same method as in Example II-A1, and the result was 1.89% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example II-A1, and as a result, the average tensile strength was 98.0 MPa, and the average tensile modulus was 2,885 MPa.

Example II-A3: Preparation of Polycarbonate Resin Composite Comprising 3.21% by Weight of Nanocellulose Fiber Dispersed Therein

[0113] Excepting that the amount of isosorbide was changed from 99 g to 95 g and the amount of aqueous solution containing 1% by weight of dispersed nanocellulose fiber was changed from 100 g to 500 g, the same method as Example II-A1 was conducted to prepare the melt dispersion. The melt dispersion comprised 5% by weight of nanocellulose fiber, based on total weight of the melt dispersion. Then, by using the melt dispersion, the same method as Example II-A1 was conducted to obtain 132 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,900 g/mol, and PDI was 1.5.

[0114] The amount of nanocellulose fiber in the obtained polycarbonate resin composite was measured by the same method as in Example II-A1, and the result was 3.21% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example II-A1, and as a result, the average tensile strength was 100.5 MPa, and the average tensile modulus was 2,935 MPa.

Example II-A4: Preparation of Polycarbonate Resin Composite Comprising 6.34% by Weight of Nanocellulose Fiber Dispersed Therein

[0115] Excepting that the amount of isosorbide was changed from 99 g to 90 g and the amount of aqueous solution containing 1% by weight of dispersed nanocellulose fiber was changed from 100 g to 1,000 g, the same method as Example II-A1 was conducted to prepare the melt dispersion. The melt dispersion comprised 10% by weight of nanocellulose fiber, based on total weight of the melt dispersion. Then, by using the melt dispersion, the same method as Example II-A1 was conducted to obtain 135 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 31,050 g/mol, and PDI was 1.8.

[0116] The amount of nanocellulose fiber in the obtained polycarbonate resin composite was measured by the same method as in Example II-A1, and the result was 6.34% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example II-A1, and as a result, the average tensile strength was 102.25 MPa, and the average tensile modulus was 2,993 MPa.

Preparation and Property Evaluation of Polycarbonate Resin Composite Using Melt Dispersion Comprising Nanocellulose Crystal (NCC) and Anhydrosugar Alcohol

Example II-B1: Preparation of Polycarbonate Resin Composite Comprising 0.61% by Weight of Nanocellulose Crystal Dispersed Therein

[0117] Excepting that 100 g of aqueous solution (CelluForce) containing 1% by weight of dispersed nanocellulose crystal was used instead of 100 g of aqueous solution (KB101, Asia Nanocellulose Co. Ltd.) containing 1% by weight of dispersed nanocellulose fiber, the same method as Example II-A1 was conducted to prepare the melt dispersion. The melt dispersion comprised 1% by weight of nanocellulose crystal, based on total weight of the melt dispersion. Then, by using the melt dispersion, the same method as Example II-A1 was conducted to obtain 135 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,920 g/mol, and PDI was 1.9.

[0118] The amount of nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example II-A1, and the result was 0.61% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example II-A1, and as a result, the average tensile strength was 92.25 MPa, and the average tensile modulus was 2,645 MPa.

Example II-B2: Preparation of Polycarbonate Resin Composite Comprising 1.87% by Weight of Nanocellulose Crystal Dispersed Therein

[0119] Excepting that the amount of isosorbide was changed from 99 g to 97 g and 300 g of the aqueous solution containing 1% by weight of dispersed nanocellulose crystal was used instead of 100 g of the aqueous solution containing 1% by weight of dispersed nanocellulose fiber, the same method as Example II-A1 was conducted to prepare the melt dispersion. The melt dispersion comprised 3% by weight of nanocellulose crystal, based on total weight of the melt dispersion. Then, by using the melt dispersion, the same method as Example II-A1 was conducted to obtain 130 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,990 g/mol, and PDI was 1.4.

[0120] The amount of nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example II-A1, and the result was 1.87% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example II-A1, and as a result, the average tensile strength was 95.5 MPa, and the average tensile modulus was 2,693 MPa.

Example II-B3: Preparation of Polycarbonate Resin Composite Comprising 3.2% by Weight of Nanocellulose Crystal Dispersed Therein

[0121] Excepting that the amount of isosorbide was changed from 99 g to 95 g and 500 g of the aqueous solution containing 1% by weight of dispersed nanocellulose crystal was used instead of 100 g of the aqueous solution containing 1% by weight of dispersed nanocellulose fiber, the same method as Example II-A1 was conducted to prepare the melt dispersion. The melt dispersion comprised 5% by weight of nanocellulose crystal, based on total weight of the melt dispersion. Then, by using the melt dispersion, the same method as Example II-A1 was conducted to obtain 135 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 31,110 g/mol, and PDI was 1.6.

[0122] The amount of nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example II-A1, and the result was 3.2% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example II-A1, and as a result, the average tensile strength was 96.25 MPa, and the average tensile modulus was 2,728 MPa.

Example II-B4: Preparation of Polycarbonate Resin Composite Comprising 6.48% by Weight of Nanocellulose Crystal Dispersed Therein

[0123] Excepting that the amount of isosorbide was changed from 99 g to 90 g and 1,000 g of the aqueous solution containing 1% by weight of dispersed nanocellulose crystal was used instead of 100 g of the aqueous solution containing 1% by weight of dispersed nanocellulose fiber, the same method as Example II-A1 was conducted to prepare the melt dispersion. The melt dispersion comprised 10% by weight of nanocellulose crystal, based on total weight of the melt dispersion. Then, by using the melt dispersion, the same method as Example II-A1 was conducted to obtain 132 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 31,050 g/mol, and PDI was 1.8.

[0124] The amount of nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example II-A1, and the result was 6.48% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example II-A1, and as a result, the average tensile strength was 100.0 MPa, and the average tensile modulus was 2,795 MPa.

Preparation and Property Evaluation of Polycarbonate Resin Composite Using Melt Dispersion Comprising a Mixture of Nanocellulose Fiber and Nanocellulose Crystal, and Anhydrosugar Alcohol

Example II-C1: Preparation of Polycarbonate Resin Composite Comprising 0.60% by Weight of a Mixture of Nanocellulose Fiber and Nanocellulose Crystal Dispersed Therein

[0125] Excepting that 50 g of the aqueous solution containing 1% by weight of dispersed nanocellulose fiber and 50 g of the aqueous solution containing 1% by weight of dispersed nanocellulose crystal were used instead of 100 g of the aqueous solution containing 1% by weight of dispersed nanocellulose fiber, the same method as Example II-A1 was conducted to prepare the melt dispersion. The melt dispersion comprised 1% by weight of a mixture of nanocellulose fiber and nanocellulose crystal, based on total weight of the melt dispersion. Then, by using the melt dispersion, the same method as Example II-A1 was conducted to obtain 133 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,980 g/mol, and PDI was 1.9.

[0126] The total amount of nanocellulose fiber and nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example II-A1, and the result was 0.60% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example II-A1, and as a result, the average tensile strength was 93.5 MPa, and the average tensile modulus was 2,800 MPa.

Example II-C2: Preparation of Polycarbonate Resin Composite Comprising 1.92% by Weight of a Mixture of Nanocellulose Fiber and Nanocellulose Crystal Dispersed Therein

[0127] Excepting that the amount of isosorbide was changed from 99 g to 97 g, and 150 g of the aqueous solution containing 1% by weight of dispersed nanocellulose fiber and 150 g of the aqueous solution containing 1% by weight of dispersed nanocellulose crystal were used instead of 100 g of the aqueous solution containing 1% by weight of dispersed nanocellulose fiber, the same method as Example II-A1 was conducted to prepare the melt dispersion. The melt dispersion comprised 3% by weight of a mixture of nanocellulose fiber and nanocellulose crystal, based on total weight of the melt dispersion. Then, by using the melt dispersion, the same method as Example II-A1 was conducted to obtain 136 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,850 g/mol, and PDI was 1.7.

[0128] The total amount of nanocellulose fiber and nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example II-A1, and the result was 1.92% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example II-A1, and as a result, the average tensile strength was 94.75 MPa, and the average tensile modulus was 2,853 MPa.

Example II-C3: Preparation of Polycarbonate Resin Composite Comprising 3.19% by Weight of a Mixture of Nanocellulose Fiber and Nanocellulose Crystal Dispersed Therein

[0129] Excepting that the amount of isosorbide was changed from 99 g to 95 g, and 250 g of the aqueous solution containing 1% by weight of dispersed nanocellulose fiber and 250 g of the aqueous solution containing 1% by weight of dispersed nanocellulose crystal were used instead of 100 g of the aqueous solution containing 1% by weight of dispersed nanocellulose fiber, the same method as Example II-A1 was conducted to prepare the melt dispersion. The melt dispersion comprised 5% by weight of a mixture of nanocellulose fiber and nanocellulose crystal, based on total weight of the melt dispersion. Then, by using the melt dispersion, the same method as Example II-A1 was conducted to obtain 135 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,870 g/mol, and PDI was 1.6.

[0130] The total amount of nanocellulose fiber and nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example II-A1, and the result was 3.19% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example II-A1, and as a result, the average tensile strength was 96.75 MPa, and the average tensile modulus was 2,898 MPa.

Example II-C4: Preparation of Polycarbonate Resin Composite Comprising 6.29% by Weight of a Mixture of Nanocellulose Fiber and Nanocellulose Crystal Dispersed Therein

[0131] Excepting that the amount of isosorbide was changed from 99 g to 90 g, and 500 g of the aqueous solution containing 1% by weight of dispersed nanocellulose fiber and 500 g of the aqueous solution containing 1% by weight of dispersed nanocellulose crystal were used instead of 100 g of the aqueous solution containing 1% by weight of dispersed nanocellulose fiber, the same method as Example II-A1 was conducted to prepare the melt dispersion. The melt dispersion comprised 10% by weight of a mixture of nanocellulose fiber and nanocellulose crystal, based on total weight of the melt dispersion. Then, by using the melt dispersion, the same method as Example II-A1 was conducted to obtain 138 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,660 g/mol, and PDI was 1.7.

[0132] The total amount of nanocellulose fiber and nanocellulose crystal in the obtained polycarbonate resin composite was measured by the same method as in Example II-A1, and the result was 6.29% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in Example II-A1, and as a result, the average tensile strength was 100.75 MPa, and the average tensile modulus was 2,935 MPa.

[0133] <Evaluation of Dispersion Uniformity of Nanocellulose Particles in Polycarbonate Resin Composite>

[0134] For each of the polycarbonate resin composites obtained in Examples II-A1 to II-A4, II-B1 to II-B4, and II-C1 to II-C4, the tensile strength and tensile modulus, and average value and standard deviation thereof were measured for four (4) samples for tensile test, and the results are shown in the following Table 2.

TABLE-US-00002 TABLE 2 Tensile strength (MPa) Tensile modulus (MPa) Sample Standard Sample Sample Sample Sample Standard Example 1 2 3 4 Average deviation 1 2 3 4 Average deviation II-A1 95 96 95 97 95.75 0.83 2,860 2,850 2,860 2,850 2,855 5 II-A2 98 99 97 98 98 0.71 2,880 2,890 2,880 2,890 2,885 5 II-A3 102 100 99 101 100.5 1.12 2,940 2,940 2,930 2,930 2,935 5 II-A4 102 103 102 102 102.25 0.43 2,990 3,000 2,990 2,990 2,993 4.36 II-B1 91 92 93 93 92.25 0.83 2,640 2,640 2,650 2,650 2,645 5 II-B2 96 96 95 95 95.5 0.50 2,690 2,680 2,700 2,700 2,693 8.31 II-B3 97 96 95 97 96.25 0.83 2,720 2,730 2,730 2,730 2,728 4.36 II-B4 99 100 100 101 100 0.71 2,800 2,800 2,790 2,790 2,795 5 II-C1 94 93 93 94 93.5 0.50 2,790 2,800 2,800 2,810 2,800 7.10 II-C2 94 95 94 96 94.75 0.83 2,850 2,850 2,860 2,850 2,853 4.36 II-C3 97 97 97 96 96.75 0.43 2,890 2,900 2,900 2,900 2,898 4.36 II-C4 100 101 100 102 100.75 0.83 2,940 2,930 2,940 2,930 2,935 5

[0135] As shown in the above Table 2, as a result of measuring the average and standard deviation of tensile strength for four (4) samples for tensile test of each of the polycarbonate resin composites obtained in Examples II-A1 to II-A4, II-B1 to II-B4, and II-C1 to II-C4 according to the present invention, the tensile strengths of the four (4) tensile test samples were equivalent such that the tensile strength deviations of the four (4) tensile test samples were so small as 1.12 MPa or less—from which it can be known that nanocellulose particles were dispersed uniformly in the polycarbonate resin composites.

[0136] In addition, as a result of measuring the average and standard deviation of tensile modulus for four (4) samples for tensile test of each of the polycarbonate resin composites obtained in Examples II-A1 to II-A4, II-B1 to II-B4, and II-C1 to II-C4 according to the present invention, the tensile moduli of the four (4) tensile test samples were equivalent such that the tensile modulus deviations of the four (4) tensile test samples were so small as 8.31 MPa or less—from which it can be known that nanocellulose particles were dispersed uniformly in the polycarbonate resin composites.

[0137] Furthermore, the average tensile strength values of four (4) samples for tensile test of each of the polycarbonate resin composites obtained in Examples II-A1 to II-A4, II-B1 to II-B4, and II-C1 to II-C4 according to the present invention were 92.25 MPa or more, and the average tensile modulus values thereof were 2,645 MPa or more—from which it can be known that the mechanical properties of the polycarbonate resin composites were excellent.

COMPARATIVE EXAMPLES

Comparative Example A1: Preparation and Property Evaluation of Polycarbonate Resin Using Anhydrosugar Alcohol Wherein Nanocellulose Particles were not Dispersed

[0138] Excepting that 100 g of pure isosorbide (NOVASORB®, Samyang Corporation) was used instead of 100 g of the solid dispersion or melt dispersion prepared in the above Examples, the same method as the above Examples was conducted to obtain about 128 g of polycarbonate resin. The obtained polycarbonate resin was a transparent solid, and its number average molecular weight was about 30,100 g/mol, and PDI was 1.6.

[0139] The obtained polycarbonate resin did not comprise nanocellulose particles, and its tensile strength and tensile modulus were measured by the same method as in the above Examples, and as a result, the average tensile strength was 65.0 MPa, and the average tensile modulus was 2,000 MPa.

[0140] It can be confirmed that as compared with the polycarbonate resin composites of the above Examples according to the present invention, the polycarbonate resin not comprising nanocellulose particles of Comparative Example A1 showed very low average values of both of tensile strength and tensile modulus—i.e., poorer mechanical properties.

Comparative Example B1: Preparation and Property Evaluation of Polycarbonate Resin Composite Using Liquid Dispersion Wherein 1% by Weight of Nanocellulose Fiber Powder was Fed Directly

[0141] In an oven at 70° C., 99 g of isosorbide (NOVASORB®, Samyang Corporation) was heated to obtain 99 g of melted isosorbide. To the obtained 99 g of melted isosorbide, 1 g of nanocellulose fiber in powder form was fed directly, and agitated to disperse the nanocellulose fiber in the melted isosorbide. Then, by using a sonicator, the dispersing was further conducted at the same temperature for about 1 hour, to prepare isosorbide comprising nanocellulose fiber dispersed therein (liquid dispersion). The liquid dispersion comprised 1% by weight of nanocellulose fiber, based on total weight of the liquid dispersion.

[0142] Then, excepting that 100 g of the obtained liquid dispersion was used instead of 100 g of the solid dispersion or melt dispersion prepared in the above Examples, the same method as the above Examples was conducted to obtain about 132 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,250 g/mol, and PDI was 1.7.

[0143] The amount of nanocellulose fiber in the obtained polycarbonate resin composite was measured by the same method as in the above Examples, and the result was 0.52% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in the above Examples, and as a result, the average tensile strength was 73.3 MPa, and the average tensile modulus was 2,450 MPa.

[0144] It can be confirmed that as compared with the polycarbonate resin composites of the above Examples according to the present invention, the polycarbonate resin composite of Comparative Example B1 showed low average values of both of tensile strength and tensile modulus—i.e., relatively poorer mechanical properties.

Comparative Example B2: Preparation and Property Evaluation of Polycarbonate Resin Composite Using Liquid Dispersion Wherein 10% by Weight of Nanocellulose Fiber Powder was Fed Directly

[0145] Excepting that the amount of isosorbide was changed from 99 g to 90 g, and the amount of nanocellulose fiber in powder form was changed from 1 g to 10 g, the same method as Comparative Example B1 was conducted to obtain isosorbide comprising nanocellulose fiber dispersed therein (liquid dispersion). The liquid dispersion comprised 10% by weight of nanocellulose fiber, based on total weight of the liquid dispersion.

[0146] Then, excepting that 100 g of the obtained liquid dispersion was used instead of 100 g of the solid dispersion or melt dispersion prepared in the above Examples, the same method as the above Examples was conducted to obtain about 129 g of polycarbonate resin composite. The obtained polycarbonate resin composite was a transparent solid, and its number average molecular weight was about 30,150 g/mol, and PDI was 1.8.

[0147] The amount of nanocellulose fiber in the obtained polycarbonate resin composite was measured by the same method as in the above Examples, and the result was 3.0% by weight. The tensile strength and tensile modulus of the obtained polycarbonate resin composite were measured by the same method as in the above Examples, and as a result, the average tensile strength was 80.0 MPa, and the average tensile modulus was 2,500 MPa.

[0148] It can be confirmed that as compared with the polycarbonate resin composites of the above Examples according to the present invention, the polycarbonate resin composite of Comparative Example B2 showed low average values of both of tensile strength and tensile modulus—i.e., relatively poorer mechanical properties.

[0149] <Evaluation of Dispersion Uniformity of Nanocellulose Particles in Polycarbonate Resin Composite>

[0150] For each of the polycarbonate resin composites obtained in Comparative Examples B1 and B2, the tensile strength and tensile modulus, and average value and standard deviation thereof were measured for four (4) samples for tensile test, and the results are shown in the following Table 3.

TABLE-US-00003 TABLE 3 Tensile strength (MPa) Tensile modulus (MPa) Comparative Sample Standard Sample Sample Sample Sample Standard Example 1 2 3 4 Average deviation 1 2 3 4 Average deviation B1 70 78 68 77 73.3 3.27 2,100 2,800 2,000 2,900 2,450 403 B2 75 86 70 89 80.0 7.78 2,200 2,600 2,800 2,400 2,500 224

[0151] As shown in the above Table 3, in case of Comparative Examples B1 and B2 not according to the present invention, nanocellulose particles were not dispersed uniformly in the polycarbonate resin composite, and thus the tensile strength and tensile modulus showed large deviation according to the measured tensile test samples.

[0152] Concretely, as a result of measuring the average and standard deviation of tensile strength for four (4) samples for tensile test of each of the polycarbonate resin composites obtained in Comparative Examples B1 and B2, the tensile strength deviations of the four (4) tensile test samples were so large as ranging from 3.27 MPa to 7.78 MPa—which means that nanocellulose particles were dispersed non-uniformly in the polycarbonate resin composites.

[0153] Also concretely, as a result of measuring the average and standard deviation of tensile modulus for four (4) samples for tensile test of each of the polycarbonate resin composites obtained in Comparative Examples B1 and B2, the tensile modulus deviations of the four (4) tensile test samples were so large as ranging from 224 MPa to 403 MPa—which means that nanocellulose particles were dispersed non-uniformly in the polycarbonate resin composites.

[0154] As can be seen from above, in case of the above Examples according to the present invention, nanocellulose particles were dispersed uniformly in the polycarbonate resin composite, and thus the tensile strength and tensile modulus were high and uniform. However, in case of Comparative Examples B1 and B2 not according to the present invention, nanocellulose particles were not dispersed uniformly in the polycarbonate resin composite, and thus, as compared with the polycarbonate resin composites of the above Examples according to the present invention, their tensile strength and tensile modulus were relatively poorer and the properties were not uniform.