BIODEGRADABLE RESIN AND FILM PREPARED THEREBY

Abstract

The present invention provides a biodegradable resin having an intrinsic viscosity of 1.0 dL/g or more, and having a loss rate of intrinsic viscosity of 10% or more after treatment at 70° C. and 85% RH for 6 hr. The present invention also provides a biodegradable resin containing 70 wt% or more of polylactic acid and having a relative biodegradation rate up to 90% or more within 12 months when the degradability in home composting at 28° C. is evaluated according to the conditions specified in ASTM D5338-15. The biodegradable resin has the characteristics of fast biodegradation speed and stable storage, has good mechanical properties, optical properties and barrier properties, can be applicable to various aspects including packaging and express transportation, and will quickly biodegrade into carbon dioxide, water and other small molecules without contamination to the environment at the end of service life. The present invention also provides a biodegradable resin film using the biodegradable resin and a product thereof, and a multilayer film containing the biodegradable resin film and a product thereof.

Claims

1. A biodegradable resin, having an intrinsic viscosity of 1.0 dL/g or more, and having a loss rate of intrinsic viscosity of 10% or more after treatment at 70° C. and 85% RH for 6 hr.

2. A biodegradable resin, containing 70 wt% or more of polylactic acid and representing a relative biodegradation rate of 90% or more within 12 months when the degradability in home composting at 28° C. is evaluated according to the conditions specified in ASTM D5338-15.

3. The biodegradable resin according to claim 2, wherein the intrinsic viscosity is 1.0 dL/g or more.

4. The biodegradable resin according to claim 1, wherein the loss rate of intrinsic viscosity is 18% or more after treatment at 70° C. and 85% RH for 6 hr.

5. The biodegradable resin according to claim 1, wherein the loss rate of intrinsic viscosity is 10% or less after treatment at 50° C. and 85% RH for 6 hr.

6. The biodegradable resin according to claim 5, wherein the loss rate of intrinsic viscosity is 6% or less after treatment at 50° C. and 85% RH for 6 hr.

7. The biodegradable resin according to claim 1, containing carboxyl groups having a content of 0.1 × 10.sup.-4 mol/g or more.

8. The biodegradable resin according to claim 7, containing carboxyl groups having a content of 0.1 × 10.sup.-4 mol/g to 10 × 10.sup.-4 mol/g.

9. The biodegradable resin according to claim 1, containing 70 wt% or more of polylactic acid.

10. The biodegradable resin according to claim 2, containing 80 wt% or more of polylactic acid.

11. The biodegradable resin according to claim 2, wherein the polylactic acid has a number-average molecular weight of 50,000 or more.

12. The biodegradable resin according to claim 2, wherein the polylactic acid has an optical purity of 83 to 96%.

13. The biodegradable resin according to claim 2, wherein the polylactic acid has a melting enthalpy of 10 to 58 J/g.

14. The biodegradable resin according to claim 13, wherein the polylactic acid has a melting enthalpy of 20 to 35 J/g.

15. The biodegradable resin according to claim 2, having a secondary heating cold crystallization temperature between 120° C. and 135° C.

16. The biodegradable resin according to claim 1, further comprising a compound containing at least one of carboxyl groups, anhydride groups, sulfonic acid groups, hydroxyl groups and amine groups, and having a content of 0.1 to 10 wt%.

17. The biodegradable resin according to claim 16, wherein said resin contains carboxylic acid and/or carboxylic anhydride having a content of 0.1 to 10 wt%.

18. The biodegradable resin according to claim 17, wherein the carboxylic acid and/or carboxylic anhydride has 4 or more carbon atoms.

19. The biodegradable resin according to claim 18, wherein the carboxylic acid is one or more of succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, cyclohexanecarboxylic acid, benzoic acid and naphthoic acid; and the carboxylic anhydride is one or more of succinic anhydride, glutaric anhydride, benzoic anhydride, maleic anhydride, phenoxyacetic anhydride, phthalic anhydride, polysebacic anhydride, and copolymers containing maleic anhydride.

20. The biodegradable resin according to claim 1, containing 5 wt% to 50 wt% of one or more of polycaprolactone, poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate-co-terephthalate), polyhydroxyalkanoate, polypropylene carbonate, polyglycolic acid, or copolymers or derivatives of these polymers.

21. The biodegradable resin according to claim 1, containing 50 to 500 ppm of metallic element.

22. The biodegradable resin according to claim 21, wherein the metallic element is one or more of sodium, magnesium, aluminum, potassium, calcium, barium, zinc, iron, copper and tin.

23. The biodegradable resin according to claim 1, containing a dispersed phase having an average diameter of 0.5 .Math.m to 6.0 .Math.m.

24. The biodegradable resin film according to claim 1, having a relative biodegradation rate up to 90% or more within 12 months when the degradability in home composting at 28° C. is evaluated according to the conditions specified in ASTM D5338-15.

25. The biodegradable resin film according to claim 1, representing a relative biodegradation rate of 90% or more within 24 months when the degradability in soil is evaluated according to the conditions specified in ASTM D5988-18.

26. A biodegradable resin film prepared from the biodegradable resin of claim 1.

27. The biodegradable resin film according to claim 26, wherein at least one of the MD or TD direction is oriented.

28. The biodegradable resin film according to claim 27, wherein the degree of orientation of MD/ZD and/or TD/ZD is 170% or more.

29. The biodegradable resin film according to claim 26, wherein the total light transmittance is 90% or more, the haze is 40% or less, and the internal haze is 8% or less.

30. The biodegradable resin film according to claim 29, wherein the haze is 10% or less, and the internal haze is 5% or less.

31. The biodegradable resin film according to claim 26, containing a dispersed phase, wherein the aspect ratio of the dispersed phase on the MD/ZD side and/or TD/ZD side is 1.5 or more.

32. The biodegradable resin film according to claim 26, wherein at least one surface thereof has a roughness of 0.05 to 0.5 .Math.m.

33. The biodegradable resin film according to claim 26, wherein the thickness coefficient of variation is 10% or less.

34. The biodegradable resin film according to claim 26, wherein the tensile strength is 60 MPa or more, the elongation at break is 20% or more, and the tensile modulus of elasticity is 4500 MPa or less.

35. The biodegradable resin film according to claim 34, wherein the elongation at break is 100% or more, and the tensile modulus of elasticity is 3000 MPa or less.

36. A multilayer film comprising the biodegradable resin film of claim 26.

37. A packaging material film using the biodegradable resin film of claim 26.

38. An adhesive tape using the biodegradable resin film of claim 26.

39. A packaging material film using the multilayer film of claim 36.

40. An adhesive tape using the multilayer film of claim 36.

Description

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

[0089] The present invention can be further understood clearly by the specific examples of the present invention and comparative examples given below, but the scope of the present invention is not thus limited to the following examples.

[0090] Materials used in Examples and Comparative Examples are as follows:

[0091] A1: polylactic acid, made by Natureworks Inc., US; specification: 4032D; number-average molecular weight: 110,000; biomass material; optical purity: 98%.

[0092] A2: polylactic acid, made by Natureworks Inc., US; specification: 4060D; number-average molecular weight: 110,000; biomass material; optical purity: 78%.

[0093] B1: sebacic acid, made by Sinopharm Chemical Reagent Co., Ltd.; specification: AR; biomass material.

[0094] B2: adipic acid, made by Sinopharm Chemical Reagent Co., Ltd.; specification: AR; non-biomass material.

[0095] B3: glutaric anhydride, made by Sinopharm Chemical Reagent Co., Ltd.; specification: AR; non-biomass material.

[0096] B4: ammonium sebacate, made by Sinopharm Chemical Reagent Co., Ltd.; specification: AR; biomass material.

[0097] C1: Polycaprolactone (PCL), made by Ingevity Corporation, US; specification: Capa 6500D; number-average mocular weight: 70,000; non-biomass material.

[0098] C2: Poly(butylene succinate) (PBS), made by China Blue Ridge Tunhe Company; specification: TH803S; number-average mocular weight: 50,000; non-biomass material.

[0099] C3: poly(3-hydroxybutyrate) (P3HB), made by Ningbo Tianan Company; specification: Y3000; biomass material.

[0100] D1: zinc stearate, made by China Aladdin Reagent Company; specification: AR; non-biomass material.

[0101] D2: calcium citrate, made by Sinopharm Chemical Reagent Co., Ltd.; specification: AR; biomass material.

[0102] E1: epoxide, made by German BASF Corporation; specification: Joncryl ADR 4468; non-biomass material.

[0103] E2: Ternary random copolymer of styrene-acrylonitrile-glycidyl methacrylate (SAG-008), made by China Fine Blend Company; specification: Fine-blend SAG-008; non-biomass material.

[0104] The raw materials and samples used in the Examples and Comparative Examples were tested according to the experimental methods described below. Unless specifically stated otherwise, the test temperature was always 23° C.

[0105] Intrinsic viscosity (IV): A sample was dissolved in trichloromethane, then insoluble materials were removed by suction filtration using a sand core funnel with a pore diameter of 2-5 .Math.m to prepare a trichloromethane solution of which the solute content was 3±1 mg/mL, and the efflux time T of the sample solution was measured at 30° C. using an Ubbelohde type viscometer with a capillary tube diameter of 0.3-0.4 mm. In addition, the efflux time To of pure trichloromethane was tested under the same conditions. The intrinsic viscosity was calculated according to the equation below:

[00001]$\text{IV =}\left[\text{ln}\left(\text{T}/\text{To}\right)\right]/\text{c}$

[0106] Loss rate of intrinsic viscosity: A sample was placed in a PL-2J constant temperature and humidity chamber available from Espec Company for heat moisture treatment. The conditions of the heat moisture treatment were 70° C., 85%RH and 6 hr, or 50° C., 85%RH and 6 hr. The intrinsic viscosity (IV.sub.1) of the sample before heat moisture treatment and the intrinsic viscosity (IV.sub.2) of the sample after heat moisture treatment were tested as described above. The loss rate of intrinsic viscosity (ΔIV%) was calculated by the equation below:

[00002]$\text{Δ}\text{IV\% =}\left({\text{IV}}_1-{\text{IV}}_2\right)/{\text{IV}}_1\times 100\%$

[0107] Content of carboxyl groups: A sample with a mass of M was dissolved in trichloromethane, 2 drops of a 0.1 wt% cresol red’s ethanol solution were added, and calibrated with a KOH standard solution, the molar concentration of which is N, until reaching the end point that the solution changed from yellow to brownish red and did not fade within 15 seconds, and the volume of the KOH standard solution used was recorded as V. In addition, the same volume of trichloromethane was used, 2 drops of a 0.1 wt% cresol red’s ethanol solution were added, and calibrated with a KOH standard solution, the molar concentration of which is N, until reaching the end point that the solution changed from yellow to brownish red and did not fade within 15 seconds, and the volume of the KOH standard solution used was recorded as V0. The content of carboxyl groups was calculated according to the equation below:

[00003]$\text{Content of carboxyl groups =}\left(\text{V}-\text{V0}\right)\times \text{N}/\text{M}$

[0108] Number-average molecular weight: Measurements were performed for three times using a 1260 type gel permeation chromatograph (GPC) from Agilent Co., Ltd. by taking dichloromethane as a mobile phase, and then the average value was calculated.

[0109] Optical purity: Polylactic acid was extracted from the sample, measurements were performed for six times using an SAC-i type automatic polarimeter from ATAGO Company, Japan, by taking dichloromethane as a solvent, and the average value of the specific rotation of the polylactic acid in the extracted sample was calculated. The optical purity was calculated according to the equation below, wherein the specific rotation of a PLLA standard substance is -156°:

[0110] Optical purity = 100% × average of specific rotations of the sample/specific rotation of the PLLA standard substance

[0111] Biomass degree: According to the components of the sample, the parts by weight of organic matters in the components derived from a biological origin were denoted by M, and the parts by weight of organic matters in the components derived from an abiological origin were denoted by N. The biomass degree was calculated according to the equation below:

[00004]$\text{Biomass degree =}\text{M}/\left(\text{M + N}\right)\times 100\%$

[0112] Degradability in home composting: The biodegradability was evaluated at a compositing temperature of 28±2° C. under the remaining conditions that were according to the conditions specified in ASTM D5338-15. The resin having a relative biodegradation rate up to 90% or more within 12 months had degradability in home composting, denoted by O; otherwise, the resin did not have degradability in home composting, denoted by ×.

[0113] Degradability in soil: The biodegradability was evaluated according to the conditions specified in ASTM D5988-18. The resin having a relative biodegradation rate up to 90% or more within 24 months had degradability in soil, denoted by O; otherwise, the resin did not have degradability in soil, denoted by ×.

[0114] Degree of orientation: A 5 cm × 5 cm sample was taken, and polarization Raman spectrum acquisition was performed on the cross section of the sample film in a polarization mode by using a Raman spectrometer from Horiba, Japan. Peaks at 873 cm.sup.-1 (peak value denoted by P) and 1769 cm.sup.-1 (peak value denoted by Q) were measured as characteristic peaks. P and Q in the length direction (MD) of the film, in the width direction (TD) of the film, and in the thickness direction (ZD) were obtained. The values of P/Q in the three directions were calculated respectively, which were denoted as (P/Q) .sub.MD, (P/Q).sub.TD and (P/Q) .sub.ZD; then the values of (P/Q) .sub.MD/ (P/Q) .sub.ZD and (P/Q) .sub.TD/ (P/Q) .sub.ZD were calculated, and the measurement was repeated according to the above method for five times, with taking a measuring point interval of 200 .Math.m and an arbitrary measuring point direction each time; and the average value of (P/Q).sub.MD/(P/Q).sub.ZD and the average value of (P/Q).sub.TD/ (P/Q).sub.ZD were found. The average value of (P/Q) .sub.MD/ (P/Q) .sub.ZD and the average value of (P/Q) .sub.TD/ (P/Q) .sub.ZD were denoted as MD degree of orientation and TD degree of orientation, respectively.

[0115] Melting enthalpy of polylactic acid and secondary heating cold crystallization temperature: The temperature was raised from 0° C. to 215° C. at a rate of 10° C./min the first temperature raising process) using a DSC Q100 type differential scanning calorimeter from TA Co., Ltd., and held at 215° C. for 3 min. The temperature was cooled down to 0° C. at a rate of 10° C./min, and held at 0° C. for 3 minutes. The temperature was raised to 215° C. at a rate of 10° C./min the second temperature raising process), and the melting peak at a peak temperature of 130-180° C. in the second temperature raising process was measured as the melting enthalpy of polylactic acid, and the peak temperature of an exothermic peak in the second temperature raising process was used as a secondary heating cold crystallization temperature.

[0116] Average diameter d and aspect ratio of dispersed phase: The sample was dyed with RuO.sub.4, and was sliced in an ultrathin manner along the direction to be observed, and the cross section was observed using a transmission electron microscopy JEOL2010(TEM) from JEOL. The resin was observed in an arbitrary direction. The observation directions of the film were the MD/ZD side and the TD/ZD side. Five photographs of the sample were taken randomly at each different location at a magnification of 5000x, and after outlining the profile of the dispersed phases with a pen, the area S of each dispersed phase and the length L of the two farthest points on the profile were calculated using the image processing software ImageJ 1.46r. Then the diameter d of each dispersed phase was calculated according to the equation below (the diameter of a circle having an area equal to that of the dispersed phase was used as this diameter d):

[00005]$d=2\sqrt{\frac{s}{\pi }}$

[0117] wherein, the ratio of the length L of the dispersed phase to the diameter d of the dispersed phase is the aspect ratio of the dispersed phase.

[0118] Thickness and thickness coefficient of variation: Measurements were performed using a 7050 type thickness gauge from Sanyo Instruments, wherein 9 positions were selected uniformly on the sample, the thickness of each position was tested separately, and the average value was used as the thickness of the sample. The thickness coefficient of variation was calculated according to the equation below:

[0119] Thickness coefficient of variation= standard deviation of thickness/thickness × 100%

[0120] Transparency: A 5 cm × 5 cm sample was taken, and its haze and transmittance were measured using a haze meter HZ-V3 from SUGA, Japan, by taking D65 as a light source. A 3 cm × 5 cm sample was placed in a cuvette containing 95% analytically pure ethanol, and the haze measured by using D65 as the light source was used as the internal haze.

[0121] Surface roughness: A 5 cm × 5 cm sample was taken, and the arithmetic mean height Sa of the surface was measured as the surface roughness, using a non-contact surface tester VertScan-R5300 from Ryoka, Japan.

[0122] Tensile strength, elongation at break and tensile modulus of elasticity: A test piece in size of 150 mm × 10 mm was made by a DUMBBELL SD-100 test piece maker. The tensile strength and elongation at break of the test piece were measured by a tensile tester AG-IS 1KN made by Shimadzu Corporation, Japan, wherein the test length was 50 mm and the tensile speed was 100 mm/min. The test was repeated 5 times.

[0123] Contents of metallic elements: The total content of metallic elements sodium, magnesium, aluminum, potassium, calcium, barium, zinc, iron, copper and tin was measured using an inductively coupled plasma emission spectrometer Icap7600 from Thermo Fisher Scientific, US.

[0124] Water vapor permeability (WVP): A sample with a thickness of T was taken, and its water vapor transmission rate (WVTR) was tested in a test environment of 38° C. and 90% RH according to the standard ASTM F1249-13, using a 3/34G model water vapor transmission rate tester from AMETEK MOCON Comany, US. The water vapor permeability was calculated according to the equation below:

[00006]$\text{WVP = T}\times \text{WVTR}$

[0125] Oxygen permeability (OTP): A sample with a thickness of T was taken, and its oxygen transmission rate (OTR) was tested in a test environment of 20° C. and 0% RH according to the standard ASTM D3985-17, using a 2/22H model oxygen transmission rate tester from AMETEK MOCON Company, US. The water vapor permeability was calculated according to the equation below:

[00007]$\text{OTP = T}\times \text{OTR}$

EXAMPLES 1-21 AND COMPARATIVE EXAMPLES 1-4

[0126] The raw materials were subjected to mixing at 180° C. and 100 rpm for 6 min in a C4150-01 mixer produced by TOYOSEIKI, to prepare biodegradable resins containing the components as shown in Tables 1 and 2.

[0127] Subsequently, the biodegradable resin was molded at 180° C. and quenched in ice water using a MINI TEST PRESS type molding machine produced by TOYOSEIKI, so as to prepare a molded product with a thickness of 200 .Math.m, followed by being subjected to 3 × 3 simultaneous biaxial stretching at 80° C. and a tensile rate of 5%/s using a KARO-IV biaxial stretching machine from Bruckner Co., Ltd., and then was thermally treated at 140° C. for 10 seconds to prepare the biodegradable resin film.

[0128] The performances of the biodegradable resins in various examples and comparative examples were tested, with the results listed in Tables 1 and 2. For the biodegradable resin films in various examples and comparative examples, the results were listed in Tables 3 and 4. Wherein, in various examples, the film had substantially the same results as the corresponding performance test results of the resin in terms of intrinsic viscosity, loss rate of intrinsic viscosity after treatment at 70° C. and 85% RH for 6 hr, loss rate of intrinsic viscosity after treatment at 50° C. and 85% RH for 6 hr, content of carboxyl groups, number-average molecular weight, optical purity, biomass degree, degradability in home composting, degradability in soil composting, melting enthalpy of polylactic acid, secondary heating cold crystallization temperature, and content of metallic elements. In various examples, the test results of the average diameter and aspect ratio of the dispersed phase on the MD/ZD side of the film were substantially equivalent to the test results on the TD/ZD side.

[0129] One or more functional layers such as an evaporation layer, a heat seal layer, an adhesive layer, and a bonding layer can be added to the biodegradable resin film described in various examples according to needs. The evaporation layer can be designed to achieve a water vapor permeability of 10 g•.Math.m/m.sup.2 or less, preferably 5 g•.Math.m/m.sup.2 or less, and an oxygen permeability of 1000 cc•.Math.m/m.sup.2 or less, preferably 500 cc•.Math.m/m.sup.2 or less.

[0130] It can be seen that the biodegradable resin described in embodiments of the present invention has the characteristics of fast biodegradation speed and stable storage, and has high biomass degree. The biodegradable resin film described in embodiments of the present invention has uniform thickness, strong mechanical property, good transparency and smooth surface.

TABLE-US-00001 Item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Component A1 20 32 40 72 80 40 40 40 40.5 40.95 36 40 40 A2 60 48 40 8 0 40 40 40 40.5 40.95 36 40 40 B1 2 2 2 2 2 0 0 1 1 0.1 10 2 2 B2 0 0 0 0 0 2 0 0 0 0 0 0 0 B3 0 0 0 0 0 0 2 1 0 0 0 0 0 B4 0 0 0 0 0 0 0 0 0 0 0 0 0 C1 16.8 16.8 16.8 16.8 16.8 16.8 16.8 16.8 16.8 16.8 16.8 0 0 C2 0 0 0 0 0 0 0 0 0 0 0 16.8 0 C3 0 0 0 0 0 0 0 0 0 0 0 0 16.8 D1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 D2 0 0 0 0 0 0 0 0 0 0 0 0 0 E1 1 1 1 1 1 1 1 1 1 1 1 1 1 E2 0 0 0 0 0 0 0 0 0 0 0 0 0 Performance Intrinsic viscosity (dL/q) 1.27 1.3 1.31 1.31 1.32 1.13 1.51 1.41 1.36 1.68 1.01 1.31 1.29 Loss rate of intrinsic viscosity (%) After treatment at 70° C. 85%RH for 6 hr 44 42 39 37 33 42 45 45 34 10 30 31 29 After treatment at 50° C. and 85%RH for 6 hr 12 8 6 5 4 10 5 5 4 3 11 8 6 Content of carboxyl group (x10.sup.-4 mol/g) 2.1 2.1 2.1 2.1 2.1 2.9 3.3 2.9 1.1 0.2 10.1 2.1 2.1 Number-average molecular weight 71200 73200 73800 73800 74500 62100 87100 80400 77100 78400 54500 73800 72500 Optical purity (%) 83 86 88 96 98 88 88 88 88 88 88 88 88 Biomass degree (%) 82 82 82 82 82 80 80 81 82 82 82 82 99 Degradability in home composting O O O O O O O O O O O O O Melting enthalpy of plylactic acid (J/g) O O O O O O O O O O O O O Secondary heating cold crystallization temperature (°C) 115 120 128 130 135 127 129 129 126 133 115 128 120 Average diameter of dispersed phase (.Math.m) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.4 0.7 1.3 6 Content of metallic element (ppm) 261 190 190 190 190 190 190 190 190 190 190 190 190

TABLE-US-00002 Item Examp e 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Component A1 48.4 72.6 96.8 34.9 40 40.1 40 40.5 100 50 45 49.5 A2 48.4 24.2 0 34.9 40 40.1 40 40.5 0 50 45 49.5 B1 2 2 2 2 2 2 2 2 0 0 11 0 B2 0 0 0 0 0 0 0 0 0 0 0 0 B3 0 0 0 0 0 0 0 0 0 0 0 0 B4 0 0 0 0 0 0 0 0 0 0 0 1 C1 0 0 0 27 16.8 16.8 16.8 16.8 0 0 0 0 C2 0 0 0 0 0 0 0 0 0 0 0 0 C3 0 0 0 0 0 0 0 0 0 0 0 0 D1 0.2 0.2 0.2 0.2 0 0 0.2 0.2 0 0 0 0 D2 0 0 0 0 0.2 0 0 0 0 0 0 0 E1 1 1 1 1 1 1 0 0 0 0 0 0 E2 0 0 0 0 0 0 1 0 0 0 0 0 Performance Intrinsic viscosity (dL/g) 1.32 1.34 1.38 1.3 1.24 1.17 1.25 1.1 1.64 1.62 0.8 0.9 Loss rate of intrinsic viscosity (%) After treatment at 70° C. and 85%RH for 6 hr 37 33 29 28 34 30 34 27 4 9 15 18 After treatment at 50° C. and 85%RH for 6 hr 8 6 5 3 8 9 8 11 2 4 11 10 Content of carboxyl group (×10.sup.-4 mol/ g) 2.1 2.1 2.1 2.1 2.1 2.1 2.1 2.1 0.1 0.1 11.0 0.2 Number-average molecular weight 74500 75800 78400 73200 69200 64700 69900 60200 96000 94600 41500 47600 Optical purity (%) 88 93 98 88 88 88 88 88 98 88 88 88 Biomass degree (%) 99 99 99 72 82 82 82 83 100 100 100 100 Degradability in home composting O O O O O O O O x x x x Degradability in soil O O O O O O O O x x x x Melting enthalpy of polylactic acid (J/g) 22 34 45 25 29 29 25 20 38 19 33 33 Secondary heating cold crystallization temperature (°C) 137 137 137 125 125 126 120 110 114 104 100 102 Average diameter of dispersed phase (.Math.m) - - - 1 0.5 0.5 0.5 0.5 — — — — Content of metallic element (ppm) 190 190 190 190 230 30 190 190 30 30 30 30

TABLE-US-00003 Item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 8 Example 10 Example 11 Example 12 Example 13 MD orientation degree 2.4 2.3 2.3 2.4 2.4 2.5 2.4 2.4 2.4 2.4 2.4 2.4 2 TD orientation degree 2.7 2.4 2.4 2.3 2.5 2.5 2.4 2.4 2.4 2.4 2.4 2.3 2 Thickness (.Math.m) 20.3 20.5 20.1 19.6 19.3 20.1 19.3 20.9 20.1 19.3 20.1 19.3 24.1 Thickness coefficient of variation (%) 12 11 7 7 6 7 7 7 7 8 15 15 30 Average diameter of dispersed phase on MD/ZD side (.Math.m) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.2 0.4 1.4 5.9 Aspect ratio of dispersed phase on MD/ZD side 2.3 2.4 -2.5 2.3 2.4 2.2 2.1 2.4 2.5 2.3 2.4 1.3 1.2 Light transmittance (%) 95 95 95 95 95 95 95 95 95 95 94 95 90 Haze (%) 33 33 33 33 33 33 33 33 33 30 4 2 68 8 0 Internal haze (%) 11 11 11 11 11 11 10 10 10 9 15 24 29 Surface roughness (.Math.m) 0.240 0.260 0.300 0.350 0.400 0.310 0.320 0.290 0.310 0.250 0.450 0.410 0.800 Tensile strength (MPa) 73 75 76 74 77 64 87 83 80 79 43 70 5 2 Elongation at break (%) 140 142 146 148 145 125 151 151 151 156 90 107 10 Modulus of elasticity (MPa) 2300 2312 2387 2445 2368 2876 2678 2678 2456 2700 2400 2356 2800

TABLE-US-00004 Item Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 MD orientation degree 2.4 2.4 2.4 2.4 2.4 2.2 2.4 2.4 2.6 2.5 2.4 2.5 TD orientation degree 2.4 2.4 2.4 2.4 2.4 2.5 2.7 2.7 2.5 2.4 2.5 2.6 Thickness (.Math.m) 19.3 20. 1 19.3 20.1 19.6 21.9 19.6 20. 1 18.1 20.3 20.1 19.5 Thickness coefficient of variation (%) 18 20 22 4 7 7 8 8 32 40 45 40 Average diameter of dispersed phase on MD/ZD side (.Math.m) - - - 0.7 0.3 0.3 0.3 0.3 - - - - Aspect ratio of dispersed phase on MD/ZD side - - - 2. 7 2.3 2.4 2.4 2.2 - - - - Light transmittance (%) 93 93 93 93 94 94 94 94 93 93 93 93 Haze (%) 1 1 1 60 3 2 3 2 32 32 1 1 1 1 Internal haze (%) 1 1 1 23 3 3 3 3 1 1 1 1 Surface roughness (.Math.m) 0.100 0.110 0.130 0.500 0.310 0.300 0.320 0.300 0.011 0.009 0.011 0.014 Tensile strength (MPa) 86 87 85 69 78 73 79 60 88 72 38 44 Elongation at break (%) 19 1 2 10 162 140 135 135 120 10 3 7 8 Modulus of elasticity (MPa) 3824 3912 3994 2000 2400 2575 2311 2517 3824 3731 2500 2600