Resin composition and applications thereof

Abstract

A resin composition contains an ethylene-vinyl alcohol copolymer (A) in which an ethylene unit content is from 10 to 60 mol %, a hindered amine-based compound (B) having a 2,2,6,6-tetraalkylpiperidine ring structure and having an alkoxy group bonded to a nitrogen atom in the structure, and a hindered phenol-based compound (C) having an ester bond or an amide bond. The resin composition contains 0.1 to 5 parts by mass of the hindered amine-based compound (B) and 0.2 to 5 parts by mass of the hindered phenol-based compound (C) with respect to 100 parts by mass of the ethylene-vinyl alcohol copolymer (A), and a mass ratio (C)/(B) is from 0.2 to 3.6.

Claims

1. A resin composition comprising: an ethylene-vinyl alcohol copolymer (A) in which an ethylene unit content is from 10 to 60 mol %; a hindered amine-based compound (B) having a 2,2,6,6-tetraalkylpiperidine ring structure and having an alkoxy group bonded to a nitrogen atom in the structure; and a hindered phenol-based compound (C) having an ester bond or an amide bond, wherein the resin composition comprises from 0.1 to 5 parts by mass of the hindered amine-based compound (B) and from 0.2 to 5 parts by mass of the hindered phenol-based compound (C), based on 100 parts by mass of the ethylene-vinyl alcohol copolymer (A), and a mass ratio of the hindered phenol-based compound (C) to the hindered amine-based compound (B), (C)/(B), is from 0.2 to 3.6.

2. The resin composition according to claim 1, wherein the hindered amine-based compound (B) has a molecular weight of at least 1000.

3. The resin composition according to claim 1, wherein the hindered phenol-based compound (C) has an amide bond.

4. An agricultural film comprising a gas barrier layer composed of the resin composition of claim 1.

5. The agricultural film according to claim 4, wherein the film is a soil fumigation film, a silage film, or a greenhouse film.

6. A grain storage bag comprising a gas barrier layer composed of the resin composition of claim 1.

7. A geomembrane comprising a gas barrier layer composed of the resin composition of claim 1.

8. A pipe comprising a gas barrier layer composed of the resin composition of claim 1.

9. The pipe according to claim 8, wherein the pipe is a hot water circulation pipe or a fuel pipe.

10. A master batch comprising: an ethylene-vinyl alcohol copolymer (A) in which an ethylene unit content is from 10 to 60 mol %; a hindered amine-based compound (B) having a 2,2,6,6-tetraalkylpiperidine ring structure and having an alkoxy group bonded to a nitrogen atom in the structure; and a hindered phenol-based compound (C) having an ester bond or an amide bond, wherein the master batch comprises from 2 to 20 parts by mass of the hindered amine-based compound (B) and from 1 to 14 parts by mass of the hindered phenol-based compound (C), based on 100 parts by mass of the ethylene-vinyl alcohol copolymer (A), and a mass ratio of the hindered phenol-based compound (C) to the hindered amine-based compounds (B), (C)/(B), is from 0.2 to 3.6.

11. A method of manufacturing a resin composition, the method comprising: obtaining a master batch in advance by melting and kneading 100 parts by mass of an ethylene-vinyl alcohol copolymer (A) in which an ethylene unit content is from 10 to 60 mol %, from 2 to 20 parts by mass of a hindered amine-based compound (B) having a 2,2,6,6-tetraalkylpiperidine ring structure and having an alkoxy group bonded to a nitrogen atom in the structure, and from 1 to 14 parts by mass of a hindered phenol-based compound (C) having an ester bond or an amide bond; and melting and kneading the obtained master batch and additional ethylene-vinyl alcohol copolymer (A), wherein a mass ratio of the hindered phenol-based compound (C) to the hindered amine-based compound (B), (C)/(B), is from 0.2 to 3.6.

12. The resin composition according to claim 1, wherein the mass ratio of (C)/(B) is from 0.3 to 1.1.

13. The resin composition according to claim 1, wherein resins contained in the resin composition consist essentially of the ethylene vinyl alcohol copolymer (A).

Description

EXAMPLES

(1) Though the present invention will further be described below with reference to Examples, the present invention is not limited thereby.

Manufacturing Example 1: Preparation of Master Batch Pellet and Film

(2) Master batch pellets were obtained by dry-blending 100 parts by mass of EVAL H171 (which was an ethylene-vinyl alcohol copolymer manufactured by Kuraray Co., Ltd. and had an ethylene unit content of 38 mol %, a melting point of 172° C., MFR (210° C., 2160 g load) of 3.4 g/10 minutes, and a degree of saponification of 99.8 mol % or higher), 0.64 part by mass of TINUVIN NOR 371 (which was a hindered amine-based compound manufactured by BASF Japan Ltd. and had an N-alkoxy-2,2,6,6-tetraalkylpiperidine structure), and 8.94 parts by mass of Irganox 1098 (which was N,N′-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] manufactured by BASF Japan Ltd.), melting and kneading them under conditions below, and thereafter pelletizing them.

(3) Extruder: twin screw extruder (Labo Plastomill manufactured by Toyo Seiki Seisaku-sho, Ltd.), 25 mm ϕ

(4) The number of die holes: 2 holes (3 mm ϕ)

(5) Set temperature: C1/C2/C3/C4/C5=175° C./225° C./225° C./220° C./220° C.

(6) Screw rotation: 60 rpm

Manufacturing Examples 2 to 28

(7) Master batch pellets were obtained as in Manufacturing Example 1 except for formulations as shown in Table 1.

Ethylene-Vinyl Alcohol Copolymer (A)

(8) EVOH1: EVAL H171 (which was an ethylene-vinyl alcohol copolymer manufactured by Kuraray Co., Ltd. and had an ethylene unit content of 38 mol %, a melting point of 172° C., MFR (210° C., 2160 g load) of 3.4 g/10 minutes, and a degree of saponification of 99.8 mol % or higher)

(9) EVOH2: EVAL L171 (which was an ethylene-vinyl alcohol copolymer manufactured by Kuraray Co., Ltd. and had an ethylene unit content of 27 mol %, a melting point of 191° C., MFR (210° C., 2160 g load) of 4.0 g/10 minutes, and a degree of saponification of 99.8 mol % or higher)

(10) EVOH3: EVAL E171 (which was an ethylene-vinyl alcohol copolymer manufactured by Kuraray Co., Ltd. and had an ethylene unit content of 44 mol %, a melting point of 165° C., MFR (210° C., 2160 g load) of 3.3 g/10 minutes, and a degree of saponification of 99.8 mol % or higher)

Hindered Amine-Based Compound (B)

(11) A1: TINUVIN NOR 371 (manufactured by BASF Japan Ltd.)

(12) A2: Hostavin NOW (manufactured by Clariant)

(13) A3: FLAMESTAB NOR 116 (manufactured by BASF Japan Ltd.)

Light Stabilizer Other Than Hindered Amine-Based Compound (B) According to the Present Invention

(14) A4: Chimassorb 2020 (which was manufactured by BASF Japan Ltd. and had a chemical formula name of a polycondensation of dibutylamine-1,3,5-triazine.N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylene diamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine)

Hindered Phenol-Based Compound (C)

(15) B1: Irganox 1098 (manufactured by BASF Japan Ltd.)

(16) B2: Irganox 1010 (manufactured by BASF Japan Ltd.)

Antioxidant Other Than Hindered Phenol-Based Compound (C) According to the Present Invention

(17) B3: Irgafos 168 (which was manufactured by BASF Japan Ltd. and had a chemical formula name of tris(2,4-di-tert-butylphenyl)phosphite)

(18) B4: AO-412S (which was manufactured by ADEKA Corporation and had a chemical formula name of pentaerythritoltetrakis(3-laurylthiopropionate))

(19) B5: Chimassorb 81 (which was manufactured by BASF Japan Ltd. and had a chemical formula name of 2-hydroxy-4-(octyloxy)-benzophenone)

Evaluation Test

(20) Master batch pellets obtained in each of Manufacturing Examples 1 to 28 were evaluated as below. Table 1 shows results.

(1) Evaluation of the Degree of Generation of Die Drool During Pelletization

(21) Production of a resin which adhered to a die during pelletization (die drool) was evaluated based on criteria below.

(22) A: No die drool was produced.

(23) B: Slight die drool was produced.

(24) C: Die drool was produced.

(2) Evaluation of Stability of Strand During Pelletization

(25) Stability of a strand during pelletization was evaluated based on criteria below.

(26) A: A strand was stable.

(27) B: A strand was not stable, with its thickness being decreased or increased.

(28) C: A strand became soft, which caused a problem in cutting by a cutter during pelletization.

(29) D: A strand sagged and could not be pelletized.

(30) TABLE-US-00001 TABLE 1 Hindered Hindered Mass Ratio Production Master EVOH (A) Amine (B) Phenol (C) in Master Stability Test Batch EVOH HA HP Batch Die No. No. Grade No. Type No. Type (A)/(B)/(C) Strand Drool Manufacturing Example 1 MB-1 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/0.64/8.94 A A Manufacturing Example 2 MB-2 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/1.65/13.19 A A Manufacturing Example 3 MB-3 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/3.30/11.54 A A Manufacturing Example 4 MB-4 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/5.88/11.76 A A Manufacturing Example 5 MB-5 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/11.76/5.88 A A Manufacturing Example 6 MB-6 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/13.41/2.23 A A Manufacturing Example 7 MB-7 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/19.13/1.71 A A Manufacturing Example 8 MB-8 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/14.37/7.19 A A Manufacturing Example 9 MB-9 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/19.48/9.74 B B Manufacturing Example 10 MB-10 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/15.00/5.00 A A Manufacturing Example 11 MB-11 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/19.39/4.85 A A Manufacturing Example 12 MB-12 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/10.61/9.55 A A Manufacturing Example 13 MB-13 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/9.46/11.35 A A Manufacturing Example 14 MB-14 EVOH1 H171 A2 Hostavin NOW B1 Irganox 1098 100/11.76/5.88 A A Manufacturing Example 15 MB-15 EVOH1 H171 A3 FLAMESTAB B1 Irganox 1098 100/11.76/5.88 A A NOR 116 Manufacturing Example 16 MB-16 EVOH1 H171 A1 Tinuvin nor 371 B2 Irganox1010 100/11.76/5.88 A A Manufacturing Example 17 MB-17 EVOH2 L171 A1 Tinuvin nor 371 B1 Irganox 1098 100/11.76/5.88 A A Manufacturing Example 18 MB-18 EVOH3 E171 A1 Tinuvin nor 371 B1 Irganox 1098 100/11.76/5.88 A A Manufacturing Example 19 MB-19 EVOH1 H171 — — B1 Irganox 1098 100/—/7.98 A A Manufacturing Example 20 MB-20 EVOH1 H171 A1 Tinuvin nor 371 — — 100/7.98/— A A Manufacturing Example 21 MB-21 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/25.08/12.54 C C Manufacturing Example 22 MB-22 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/10.46/15.69 D — Manufacturing Example 23 MB-23 EVOH1 H171 A4 Chimassorb 2020 B1 Irganox 1098 100/11.76/5.88 A A Manufacturing Example 24 MB-24 EVOH1 H171 A1 Tinuvin nor 371 B3 Irgafos168 100/11.76/5.88 A A Manufacturing Example 25 MB-25 EVOH1 H171 A1 Tinuvin nor 371 B4 AO-4125 100/11.76/5.88 A A Manufacturing Example 26 MB-26 EVOH1 H171 A1 Tinuvin nor 371 B5 Chimassorb 81 100/11.76/5.88 A A Manufacturing Example 27 MB-27 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/15.48/1.03 A A Manufacturing Example 28 MB-28 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/0.65/9.78 A A

Example 1

(31) A single-layered film having a thickness of 20 μm was obtained by dry-blending 100 parts by mass of obtained master batch pellets MB-3 and 200 parts by mass of EVAL H171 and forming a film under conditions below. Table 2 shows a mass ratio ((A)/(B)/(C)) among EVOH (A), the hindered amine-based compound (B), and the hindered phenol-based compound (C) in the obtained film.

(32) Extruder: single screw extruder (Labo Plastomill manufactured by Toyo Seiki Seisaku-sho, Ltd.), 20 mm ϕ

(33) Set temperature: C1/C2/C3/D=180° C./210° C./210° C./210° C.

Examples 2 to 14 and Comparative Examples 1 to 13

(34) Films were obtained as in Example 1 except for formulations as shown in Table 2. Table 2 shows a mass ratio ((A)/(B)/(C)) among EVOH (A), the hindered amine-based compound (B), and the hindered phenol-based compound (C) in each obtained film.

Evaluation Test

(35) The film obtained in each of Examples 1 to 14 and Comparative Examples 1 to 13 was evaluated as below. Table 2 shows results.

(1) Evaluation of Weatherability

(36) Weatherability of the obtained film was evaluated by immersing the film in 0.05 M of diluted sulfuric acid at room temperature for 30 minutes, thereafter removing the liquid attached to a surface of the film with Kimtowel (a product name), thereafter conducting an accelerated weathering test for 50 hours under conditions of irradiance of 1000 W/m.sup.2, a black panel temperature of 63° C., and a relative humidity of 50% with the use of EYE Super UV Tester (SUV W-151 manufactured by Iwasaki Electric Co., Ltd.), and comparing fracture strength before the test, YI before and after the test, fracture elongation, and a rate of decrease in elongation before and after the accelerated weathering test. YI measurement and the tensile test were conducted by methods below.

YI Measurement

(37) A colorimeter (NF-902 manufactured by Nippon Denshoku Industries Co., Ltd.) was employed. With YI of the film before the accelerated weathering test being denoted as YI.sub.0 and YI of the film after the test being denoted as YI.sub.1, ΔYI was calculated in accordance with an expression below. When ΔYI was negative, ΔYI was regarded as 0.
ΔYI=YI.sub.1−YI.sub.0

Tensile Test

(38) The tensile test was conducted under conditions of a temperature of 23° C., a relative humidity of 50% RH, and a tension rate of 500 mm/min. with the use of an autograph (AGS-H manufactured by Shimadzu Corporation). A specimen cut into 50 mm long×15 mm wide was employed.

(2) Production of Aggregates

(39) Aggregates like gel (equal to or greater than approximately 150 μm which could be recognized with naked eyes) in the obtained film were counted, and the count was converted to a count per 1.0 m.sup.2. Determination as below was made based on the number of aggregates.

(40) A: less than 20

(41) B: not less than 20 and less than 40

(42) C: not less than 40 and less than 60

(43) D: not less than 60

(44) TABLE-US-00002 TABLE 2 Composition Condition Master Batch EVOH (A) Hindered Hindered Parts Parts Amine (B) Phenol (C) MB by EVOH by HA HP No. Mass No. Grade Mass No. Type No. Type Example 1 MB-3 100 EVOH1 H171 200 A1 TINUVIN B1 Irganox NOR 371 1098 Example 2 MB-4 100 EVOH1 H171 915 A1 TINUVIN B1 Irganox NOR 371 1098 Example 3 MB-5 100 EVOH1 H171 915 A1 TINUVIN B1 Irganox NOR 371 1098 Example 4 MB-8 100 EVOH1 H171 1100 A1 TINUVIN B1 Irganox NOR 371 1098 Example 5 MB-9 100 EVOH1 H171 1430 A1 TINUVIN B1 Irganox NOR 371 1098 Example 6 MB-10 100 EVOH1 H171 750 A1 TINUVIN B1 Irganox NOR 371 1098 Example 7 MB-11 100 EVOH1 H171 700 A1 TINUVIN B1 Irganox NOR 371 1098 Example 8 MB-12 100 EVOH1 H171 800 A1 TINUVIN B1 Irganox NOR 371 1098 Example 9 MB-13 100 EVOH1 H171 700 A1 TINUVIN B1 Irganox NOR 371 1098 Example 10 MB-14 100 EVOH1 H171 915 A2 Hostavin B1 Irganox NOW 1098 Example 11 MB-15 100 EVOH1 H171 915 A3 FLAMESTAB B1 Irganox NOR 116 1098 Example 12 MB-16 100 EVOH1 H171 915 A1 TINUVIN B2 Irganox- NOR 371 1010 Example 13 MB-17 100 EVOH2 H171 915 A1 TINUVIN B1 Irganox NOR 371 1098 Example 14 MB-18 100 EVOH3 H171 915 A1 TINUVIN B1 Irganox NOR 371 1098 Comparative — — EVOH1 H171 — — — — — Example 1 Comparative MB-19 100 EVOH1 H171 400 — — B1 Irganox Example 2 1098 Comparative MB-20 100 EVOH1 H171 400 A1 TINUVIN — — Example 3 NOR 371 Comparative MB-27 100 EVOH1 H171 800 A1 TINUVIN B1 Irganox Example 4 NOR 371 1098 Comparative MB-7 100 EVOH1 H171 200 A1 TINUVIN B1 Irganox Example 5 NOR 371 1098 Comparative MB-1 100 EVOH1 H171 200 A1 TINUVIN B1 Irganox Example 6 NOR 371 1098 Comparative MB-2 100 EVOH1 H171 200 A1 TINUVIN B1 Irganox Example 7 NOR 371 1098 Comparative MB-6 100 EVOH1 H171 300 A1 TINUVIN B1 Irganox Example 8 NOR 371 1098 Comparative MB-23 100 EVOH1 H171 915 A4 Chimassorb B1 Irganox Example 9 2020 1098 Comparative MB-24 100 EVOH1 H171 915 A1 TINUVIN B3 Irgafos- Example 10 NOR 371  168 Comparative MB-25 100 EVOH1 H171 915 A1 TINUVIN B4 AO- Example 11 NOR 371 412S Comparative MB-26 100 EVOH1 H171 915 A1 TINUVIN B5 Chimassorb Example 12 NOR 371   81 Comparative MB-28 100 EVOH1 H171 500 A1 TINUVIN B1 Irganox Example 13 NOR 371 1098 Evaluation of Film Before Evaluation of Film After Composition Condition Weatherability Test Weatherability Test Mass Ratio in Resin Tensile Test Tensile Test Composition Fracture Fracture Fracture Rate of (A)/ Strength Elongation Elongation Decrease (B)/(C) (C)/(B) Speck (Mpa) (%) ΔYI (%) (%) Example 1 100/1/3.5 3.50 B 58.0 349.66 0.00 139.89 60.0 Example 2 100/0.5/1 2.00 B 68.5 356.75 0.02 128.71 63.9 Example 3 100/1/0.5 0.50 A 70.2 341.65 0.00 137.71 59.7 Example 4 100/1/0.5 0.50 A 74.0 372.63 0.01 149.01 60.0 Example 5 100/1/0.5 0.50 A 81.2 394.20 0.00 158.58 59.8 Example 6 100/1.5/ 0.33 A 72.6 367.16 0.00 159.22 56.6 0.5 Example 7 100/2/0.5 0.25 A 75.9 381.91 0.77 179.53 53.0 Example 8 100/1/0.9 0.90 B 69.0 379.03 0.00 152.55 59.8 Example 9 100/1/1.2 1.20 B 73.8 357.46 0.01 142.99 60.0 Example 10 100/1/0.5 0.50 A 72.0 360.12 0.00 126.00 65.0 Example 11 100/1/0.5 0.50 A 71.5 355.32 0.00 113.60 68.0 Example 12 100/1/0.5 0.50 A 69.5 344.98 1.51 141.45 59.0 Example 13 100/1/0.5 0.50 A 129.0 286.42 0.00 115.60 59.6 Example 14 100/1/0.5 0.50 A 98.0 371.85 0.00 149.76 59.7 Comparative 100/0/0 — A 98.0 386.24 0.41 2.00 99.5 Example 1 Comparative 100/0/1.5 — C 69.5 342.31 0.00 2.20 99.4 Example 2 Comparative 100/1.5/0 — A 71.2 355.32 3.39 153.94 56.7 Example 3 Comparative 100/1.5/ 0.07 A 72.1 360.10 2.64 156.16 56.6 Example 4 0.1 Comparative 100/5.6/ 0.09 A 70.7 338.69 8.89 248.05 26.8 Example 5 0.5 Comparative 100/0.2/ 14.00 C 62.8 337.40 0.00 114.35 66.1 Example 6 2.8 Comparative 100/0.5/4 8.00 C 57.6 300.56 0.00 108.44 63.9 Example 7 Comparative 100/3/0.5 0.17 A 68.4 350.74 3.02 190.43 45.7 Example 8 Comparative 100/1/0.5 0.50 A 71.2 354.87 0.00 100.00 71.8 Example 9 Comparative 100/1/0.5 0.50 A 70.1 348.34 2.76 135.23 61.2 Example 10 Comparative 100/1/0.5 0.50 A 69.8 342.28 2.86 128.85 62.4 Example 11 Comparative 100/1/0.5 0.50 A 71.1 351.85 2.26 132.82 62.3 Example 12 Comparative 100/0.1/ 15.00 C 70.0 345.22 0.00 2.00 99.4 Example 13 1.5

(45) It can be seen from Comparative Examples 1 and 2 that, when the hindered amine-based compound (B) was not contained, fracture elongation after the weathering test was poorer than in Examples. It can be seen from Comparative Example 3 that, when the hindered phenol-based compound (C) was not contained, ΔYI after the weathering test was poorer than in Examples. It can be seen from Comparative Examples 4 to 8 and 13 that, when an amount of addition of (B) or (C)/(B) was out of the scope of the present invention, deterioration of ΔYI, production of aggregates, or deterioration of fracture elongation as compared with Examples was observed. It can be seen from Comparative Example 9 that, when a hindered amine-based compound other than the hindered amine-based compound (B) was employed, fracture elongation after the weathering test was poorer than in Examples. It can be seen from Comparative Examples 10 to 12 that, when a hindered phenol-based compound other than the hindered phenol-based compound (C) was employed, ΔYI was poorer than in Examples.

Example 15

(46) A single-layered film having a thickness of 20 μm was obtained by dry-blending 100 parts by mass of an ethylene-vinyl alcohol copolymer (EVAL H171 (which was an ethylene-vinyl alcohol copolymer manufactured by Kuraray Co., Ltd. and had an ethylene unit content of 38 mol %, a melting point of 172° C., MFR (210° C., 2160 g load) of 3.4 g/10 minutes, and a degree of saponification of 99.8 mol % or higher)), 1.0 part by mass of TINUVIN NOR 371 having an N-alkoxy-2,2,6,6-tetraalkylpiperidine structure (which was a hindered amine-based compound manufactured by BASF Japan Ltd), and 0.5 part by mass of N,N′-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] (which was Irganox 1098 manufactured by BASF Japan Ltd.) and thereafter forming a film under conditions below. In a tensile test before the weathering test of the obtained film, an evaluation test as in Examples 1 to 14 was conducted to measure an SD value (a standard deviation). Table 3 shows results in comparison to Examples 5 in which an SD value was similarly measured. An SD value closer to 0 is preferred because variation in manufacturing stability and weatherability among products is less.

(47) Extruder: single screw extruder (Labo Plastomill manufactured by Toyo Seiki Seisaku-sho, Ltd.), 20 mm ϕ

(48) Set temperature: C1/C2/C3/D=180° C./210° C./210° C./210° C.

(49) TABLE-US-00003 TABLE 3 Composition Condition Evaluation of Film Before Weight Weatherability Test Hindered Hindered Ratio EVOH (A) Amine (B) Phenol (C) (phr) Fracture EVOH HA HP EVOH/ Strength No. GRADE No. Type No. Type HA/HP Speck (Mpa) Example 5 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/1/0.5 A 81.20 Example 15 EVOH1 H171 A1 Tinuvin nor 371 B1 Irganox 1098 100/1/0.5 B 76.45 Evaluation of Film Before Evaluation of Film After Weatherability Test Weatherability Test Tensile Test Tensile Test Fracture Fracture Rate of Elongation YI Elongation Decrease SD (%) SD ΔYI Evaluation (%) (%) Evaluation Example 5 3.08 395.20 7.85 0.00 A 158.58 59.9 A Example 15 10.25 380.20 25.40 0.00 A 150.20 60.5 A

(50) It can be seen that Example 5 which had gone through a master batch was lower in SD value and less in variation among products than Example 15 which had not gone through a master batch.

(51) It should be understood that the embodiment and the examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims rather than the description above and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.