Resin composition and multilayered structure using same

Abstract

A resin composition, containing: (A) polyolefin; (B) a saponified ethylene-vinyl acetate copolymer having an ethylene content of from 20 to 65 mol % and a degree of saponification of vinyl acetate units of 96% or more; (C) a saponified ethylene-vinyl acetate copolymer having an ethylene content of from 68 to 98 mol % and a degree of saponification of vinyl acetate units of 20% or more; (D) a random copolymer consisting of ethylene and vinyl acetate; (E) a pigment comprising titanium oxide particles comprising a surface coated with a compound of a metal other than titanium or a silicon compound; and (I) a lubricant; wherein a mass ratio (AB) is from 3 to 99.5, a mass ratio (B/C) is from 1 to 100, a mass ratio of (D/C) is from 0.1 to 15, a mass ratio (E/C) is from 0.04 to 50, and a content of (C) is from 0.01 to 2.4 parts, particularly 0.33 to 1.5 parts, by mass based on 100 parts by mass of (A) and (B). A molded product, in particular a multilayered structure, obtained by melt molding the resin composition has good dispersibility of the pigment, and improved uneven coloration.

Claims

1. A resin composition, comprising: (A) a polyolefin; (B) a saponified ethylene-vinyl acetate copolymer comprising an ethylene content of from 20 to 65 mol % and having a degree of saponification of vinyl acetate units of 96% or more; (C) a saponified ethylene-vinyl acetate copolymer comprising an ethylene content of from 68 to 98 mol % and having a degree of saponification of vinyl acetate units of 20% or more; (D) a random copolymer consisting of ethylene and vinyl acetate; (E) a pigment; and (I) a lubricant, wherein: a mass ratio of the polyolefin (A) and the saponified ethylene-vinyl acetate copolymer (B), (A/B), is from 3 to 99.5; a mass ratio of the saponified ethylene-vinyl acetate copolymer (B) and the saponified ethylene-vinyl acetate copolymer (C), (B/C), is from 2 to 18; a mass ratio of the random copolymer consisting of ethylene and vinyl acetate (D) and the saponified ethylene-vinyl acetate copolymer (C), (D/C), is from 0.1 to 15; a mass ratio of the pigment (E) and the saponified ethylene-vinyl acetate copolymer (C), (E/C), is from 0.1 to 1.2; a content of the saponified ethylene-vinyl acetate copolymer (C) is from 0.33 to 1.5 parts by mass, based on 100 parts by mass of a total amount of the polyolefin (A) and the saponified ethylene-vinyl acetate copolymer (B); a content of the lubricant (1) is from 0,00001 to 1 parts by mass, based on 100 parts by mass of the total amount of (A) and (B); the pigment (E) comprises titanium oxide particles comprising a surface coated with a compound of a metal other than titanium or a silicon compound; and the titanium oxide particles have an average particle diameter of from 0.01 to 0.4 m.

2. The resin composition of claim 1, further comprising: (H) a conjugated polyene compound, wherein a content of the conjugated polyene compound (H) is from 0.000001 to 1 parts by mass, based on 100 parts by mass of the total amount of (A) and (B).

3. The resin composition of claim 1, wherein the content of the lubricant (I) is from 0.00005 to 11.5 parts by mass, based on 100 parts by mass of the total amount of (A) and (B).

4. The resin composition of claim 1, further comprising: a metal salt (F) of fatty acid, wherein a mass ratio of the metal salt (F) of fatty acid and the pigment (E), (F/E), is from 0.1 to 3.

5. The resin composition of claim 1, wherein the pigment (E) comprises titanium oxide particles comprising a surface coated with at least one of an oxide, sulfide, nitride, carbide, boride, chloride, carbonate, hydroxide, sulfate, nitrate, phosphate, or carboxy late of aluminum, silicon, zirconium, zinc, magnesium, or calcium.

6. The resin composition of claim 5, wherein the titanium oxide particles are coated with alumina (Al.sub.2O.sub.3), silica (SiO.sub.2), or both.

7. The resin composition of claim 6, wherein the titanium oxide particles are coated with both alumina (Al.sub.2O.sub.3) and silica (SiO.sub.2).

8. The resin composition of claim 7, wherein the pigment (E) comprises titanium oxide particles coated with a mixture of alumina (Al.sub.2O.sub.3) and silica (SiO.sub.2).

9. The resin composition of claim 1, wherein the titanium oxide particles have an average particle diameter of from 0.1 to 0.3 m.

10. The resin composition of claim 1, wherein the titanium oxide particles have an average particle diameter of from 0.15 to 0.25 m.

Description

EXAMPLES

(1) In present Examples, the following raw materials were used. In Production Examples, Examples, and Comparative Examples below, parts are based on mass, unless otherwise specified.

(2) [Polyolefin (A)]

(3) A-1: polypropylene [density of 0.90 g/cm.sup.3, melt index of 1.4 g/10 minutes (ASTM-D 1238, 230 C., load of 2160 g)]

(4) A-2: low density polyethylene [density of 0.919 g/cm.sup.3, melt index of 1.0 g/10 minutes (ASTM-D 1238, 190 C., load of 2160 g)]

(5) [EVOH (B)]

(6) B-1: ethylene content of 32 mol %, degree of saponification of 99.7 mol %, limiting viscosity of 1.1 dL/g at 30 C. in aqueous phenol (water/phenol=15/85 (mass ratio)), density of 1.15 g/cm.sup.3, melt index of 1.6 g/10 minutes (ASTM-D 1238, 190 C., load of 2160 g)
B-2: ethylene content of 32 mol %, degree of saponification of 99.8 mol %, limiting viscosity of 0.092 dL/g at 30 C. in aqueous phenol (water/phenol=15/85 (mass ratio)), density of 1.15 g/cm.sup.3, melt index of 6.6 g/10 minutes (ASTM-D 1238, 190 C., load of 2160 g)
[S-EVOH (C)]
C-1: ethylene content of 89 mol %, degree of saponification of 97 mol %, melt index of 5.1 g/10 minutes (ASTM-D 1238, 190 C., load of 2160 g)
[EVAc (D)]
D-1: vinyl acetate content of 19 mass %, melt index of 2.5 g/10 minutes (ASTM-D 1238, 190 C., load of 2160 g)
[Pigment (E)]
E-1: titanium oxide (rutile type titanium dioxide obtained by a chlorine method, white inorganic pigment, TiO.sub.2, average particle diameter of 0.19 m, chlorine content of 42 ppm)
[Metal Salt (F) of Fatty Acid]
F-1: calcium stearate
F-2: zinc stearate
[Hydrotalcite (G)]
G-1: ZHT-4A produced by Kyowa Chemical Industry Co., Ltd.
[Conjugated Polyene Compound (H)]
H-1: sorbic acid
[Lubricant (I)]
I-1: ethylenebis stearic acid amide
[Others]
Adhesive Resin: MODIC AP P604V produced by Mitsubishi Chemical Corporation (brand for polypropylene), density of 0.90 g/cm.sup.3, melt index of 3.2 g/10 minutes (ASTM-D 1238, 230 C., load of 2160 g),
Antioxidant: pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]

(7) Measurements were carried out in the following methods respectively for a multilayered film obtained in Example regarding a dispersed particle diameter of the EVOH (B) particles contained in a recovery layer, whiteness of the multilayered film, and uneven coloration of a thermoformed container.

(8) [Dispersed Particle Diameter of EVOH Contained in Recovery Layer]

(9) A multilayered film was carefully cut with a microtome in a direction perpendicular to the film surface and a recovery layer was further taken out using a scalpel. Platinum was vapor deposited on the exposed cross section in a reduced pressure atmosphere. The cross section with platinum vapor deposited thereon was taken in a picture using a scanning electron microscope (SEM) with 10000 magnification, a region in this picture including approximately 20 particles of the EVOH (E) was selected, particle diameters of the respective particle images in the region were measured, and their average value was calculated to define it as a dispersed particle diameter. For the particle diameters of the respective particles, a longer diameter (longest part) of the particles observed in the picture was measured to define it as the particle diameter. The film was cut vertically in a direction of extrusion, and the picture was taken from a direction vertical to the cross section.

(10) [Whiteness of Multilayered Film]

(11) A multilayered film was measured using a spectroscopic color difference meter (Spectro Color Meter SE2000, manufactured by NDK, Incorporated) in accordance with a method of ASTM E313. Whiteness was applied only in a case of the pigment (E) being titanium oxide. High whiteness indicates good dispersion of the pigment in the resin composition.

(12) [Uneven Coloration of Thermoformed Container]

(13) Five thermoformed containers were prepared at random and a side of each container was seen through a fluorescent lamp to visually check the following conditions.

(14) A: No shadow is found at all in all containers.

(15) B: Shadows can be found in several areas when looked carefully.

(16) C: Shadows can be found.

(17) In accordance with the following methods, titanium oxides coated with alumina and/or silica (E-2 through E-5) were obtained.

(18) E-2:

(19) Based on 100 parts of E-1 (titanium oxide) as the pigment (E), 4.0 parts, in terms of alumina, of an aqueous sodium aluminate solution was added and it was stirred for 30 minutes. To this, 20% sulfuric acid was added gradually for adjustment at pH=7.0 to be further matured for 2 hours. After maturation, a slurry of titanium oxide having a surface coated with the water-containing alumina was filtered, and washed with running water, followed by drying. The titanium oxide thus obtained was ground in a steam mill to obtain titanium oxide (E-2) having a surface coated with alumina and having an average particle diameter of 0.2 m. The amount of chlorine contained in E-2 was 35 ppm.

(20) E-3:

(21) Octyltriethoxysilane was diluted with pure water in 2-fold and it was stirred and hydrolyzed for 10 minutes to prepare a hydrolysis product solution. The octyltriethoxysilane hydrolysis product solution was added when grinding E-2 above in a steam mill, and coating treatment was carried out on a surface of the titanium oxide in an amount of coating at 0.3% based on the titanium oxide pigment weight to obtain titanium oxide having a surface coated with alumina and an alkylsilane compound (E-3). The amount of chlorine contained in E-3 was 34 ppm.

(22) E-4:

(23) Based on 100 parts of E-1 (titanium oxide) as the pigment (E), 3.2 parts, in terms of alumina, of an aqueous sodium aluminate solution and 2.1 parts, in terms of silica, of an aqueous sodium silicate solution were added and it was stirred for 30 minutes. To this, 20% sulfuric acid was gradually added for adjustment at pH=7.0 to be further matured for 2 hours. After maturation, a slurry of titanium oxide having a surface coated with a mixture of alumina and silica in a water-containing state was filtered, and washed with running water, followed by drying to obtain titanium oxide having a surface coated with a mixture of alumina and silica. The titanium oxide thus obtained was ground in a steam mill to obtain titanium oxide having a surface coated with a mixture of alumina and silica and having an average particle diameter of 0.24 m (E-4). The amount of chlorine contained in E-4 was 20 ppm.

(24) E-5:

(25) Based on 100 parts of E-1 (titanium oxide) as the pigment (E), 3.2 parts, in terms of alumina, of an aqueous sodium aluminate solution and 2.1 parts, in terms of silica, of an aqueous sodium silicate solution were added and it was stirred for 30 minutes. To this, 20% sulfuric acid was gradually added for adjustment at pH=7.0 to be further matured for 2 hours. After maturation, a slurry of titanium oxide having a surface coated with a mixture of alumina and silica in a water-containing state was filtered, and washed with running water, followed by drying to obtain titanium oxide having a surface coated with a mixture of alumina and silica. Subsequently, while titanium oxide was stirred in a Henschel mixer, 0.2 parts of trimethylolethane (polyol) was added to be stirred for 10 minutes, and it was further ground in a steam mill to obtain titanium dioxide (E-5) having a surface coated with polyol and a mixture of alumina and silica and having an average particle diameter of 0.24 m. The amount of chlorine contained in E-5 was 20 ppm.

(26) In accordance with the following methods, masterbatches (MB1 through MB10) were obtained.

(27) MB1

(28) Using C-1 as the S-EVOH (C), D-1 as the EVAc (D), F-1 as the metal salt (F) of fatty acid, G-1 as the hydrotalcite (G), and an antioxidant, they were blended by dry blending to have a mass ratio of C-1/D-1/F-1/G-1/antioxidant=25/67.5/5/2.5/0.2. A mixture thus obtained was melt kneaded at an extrusion temperature of 200 C. using a corotating twin screw extruder (TEX-30N manufactured by Japan Steel Works, Ltd.) of 30 mm, followed by pelletizing to obtain a masterbatch (MB1).

(29) MB2

(30) In a same manner as MB1 other than using C-1 as the S-EVOH (C), D-1 as the EVAc (D), F-1 as the metal salt (F) of fatty acid, G-1 as the hydrotalcite (G), and an antioxidant and blending them by dry blending to have a mass ratio of C-1/D-1/F-1/G-1/antioxidant=10/82.5/5/2.5/0.2, a masterbatch (MB2) was obtained.

(31) MB3

(32) In a same manner as MB1 other than using C-1 as the S-EVOH (C), D-1 as the EVAc (D), F-1 as the metal salt (F) of fatty acid, G-1 as the hydrotalcite (G), and an antioxidant and blending them by dry blending to have a mass ratio of C-1/D-1/F-1/G-1/antioxidant=25/71.5/1/2.5/0.2, a masterbatch (MB3) was obtained.

(33) MB4

(34) In a same manner as MB1 other than using C-1 as the S-EVOH (C), D-1 as the EVAc (D), F-1 as the metal salt (F) of fatty acid, G-1 as the hydrotalcite (G), and an antioxidant and blending them by dry blending to have a mass ratio of C-1/D-1/F-1/G-1/antioxidant=25/52.5/20/2.5/0.2, a masterbatch (MB4) was obtained.

(35) MB5

(36) In a same manner as MB1 other than using C-1 as the S-EVOH (C), D-1 as the EVAc (D), F-1 as the metal salt (F) of fatty acid, G-1 as the hydrotalcite (G), and an antioxidant and blending them by dry blending to have a mass ratio of C-1/D-1/F-1/G-1/antioxidant=5/85/5/5/0.2, a masterbatch (MB5) was obtained.

(37) MB6

(38) In a same manner as MB1 other than using C-1 as the S-EVOH (C), D-1 as the EVAc (D), F-1 as the metal salt (F) of fatty acid, G-1 as the hydrotalcite (G), and an antioxidant and blending them by dry blending to have a mass ratio of C-1/D-1/F-1/G-1/antioxidant=85/5/5/5/0.2, a masterbatch (MB6) was obtained.

(39) MB7

(40) Using C-1 as the S-EVOH (C), D-1 as the EVAc (D), F-1 as the metal salt (F) of fatty acid, and an antioxidant, they were blended by dry blending to have a mass ratio of C-1/D-1/F-1/antioxidant=25/70/5/0.2. A mixture thus obtained was melt kneaded at an extrusion temperature of 200 C. using a corotating twin screw extruder (TEX-30N manufactured by Japan Steel Works, Ltd.) of 30 mm, followed by pelletizing to obtain a masterbatch (MB7).

(41) MB8

(42) In a same manner as MB1 other than using polyolefin (A-2) instead of the EVAc (D), a masterbatch (MB8) was obtained.

(43) MB9

(44) Using C-1 as the S-EVOH (C), D-1 as the EVAc (D), F-2 as the metal salt (F) of fatty acid, G-1 as the hydrotalcite (G), and an antioxidant, they were blended by dry blending to have a mass ratio of C-1/D-1/F-2/G-1/antioxidant=25/67.5/5/2.5/0.2. A mixture thus obtained was melt kneaded at an extrusion temperature of 200 C. using a corotating twin screw extruder (TEX-30N manufactured by Japan Steel Works, Ltd.) of 30 mm, followed by pelletizing to obtain a masterbatch (MB9).

(45) MB10

(46) Using C-1 as the S-EVOH (C), D-1 as the EVAc (D), F-1 and F-2 as the metal salt (F) of fatty acid, G-1 as the hydrotalcite (G), and an antioxidant, they were blended by dry blending to have a mass ratio of C-1/D-1/F-1/F-2/G-1/antioxidant=25/65/2.5/5/2.5/0.2. A mixture thus obtained was melt kneaded at an extrusion temperature of 200 C. using a corotating twin screw extruder (TEX-30N manufactured by Japan Steel Works, Ltd.) of 30 mm, followed by pelletizing to obtain a masterbatch (MB10).

Example 1

Production of Recovery

(47) Using A-1 as the polyolefin (A) for outermost layers, B-1 as the EVOH (B) for an innermost layer, MODIC AP P604V for the adhesive resin layers, three-type five-layer coextrusion of polyolefin layer/adhesive resin layer/EVOH layer/adhesive resin layer/polyolefin layer=200/20/20/20/200 was carried out with a feedblock die to prepare a multilayered film. The respective resins were supplied to the feedblock using a 32 mm extruder for the polyolefin layers, a 25 mm extruder for the adhesive resin layers, and a 20 mm extruder for the EVOH layer, respectively, and it was carried out at the temperature for extrusion at 220 C. for each resin, and also at 220 C. in a die section and a feedblock section.

(48) Subsequently, the multilayered film thus obtained was ground with a grinder of 8 mm diameter meshes to obtain a recovery. A recovery thus obtained had a mass ratio of polyolefin (A-1)/EVOH (B-1)/adhesive resin=85.9/5.5/8.6.

(49) [Preparation of Multilayered Structure Containing Pigment]

(50) Using a mixture of a recovery, a masterbatch (MB1), and a pigment (E-1) dry blended at a mass ratio of recovery/masterbatch (MB1)/pigment (E-1)=100/3/0.3 for outermost layers, the EVOH (B-1) for an innermost layer, and MODIC AP P604V for the adhesive resin layers, three-type five-layer coextrusion of mixture layer/adhesive resin layer/EVOH layer/adhesive resin layer/mixture layer=200/20/20/20/200 was carried out with a feedblock die to prepare a multilayered film. The respective resins were supplied to the feedblock using a 32 mm extruder for the mixture layers, a 25 mm extruder for the adhesive resin layers, a 20 mm extruder for the EVOH layer, respectively, and it was carried out at the temperature for extrusion at 220 C. for each resin, and also at 220 C. in a die section and a feedblock section.

(51) The whiteness of the multilayered film having mixture layers and the particle diameter of the EVOH (B) in the mixture layers were measured. Results are shown in Table 1 in collection.

(52) The multilayered film having the mixture thus obtained was thermoformed to obtain a thermoformed container. Forming conditions were as follows. Thermoforming Machine: vacuum pressure deep draw forming machine, model FX-0431-3 (manufactured by Asano Seisakusho)

(53) Compressed Air Pressure: 5 kgf/cm.sup.2

(54) Die Shape (Round Cup Shape): top of 75 mm, bottom of 60

(55) mm, depth of 75 mm, drawing ratio S=1.0

(56) Die Temperature: 70 C.

(57) Sheet Temperature: 130 C.

(58) Heater Temperature: 400 C.

(59) Plug Dimensions: 4565 mm

(60) Plug Temperature: 120 C.

(61) The uneven coloration of the thermoformed container thus obtained was evaluated. Results and conditions were shown in Table 1 in collection.

Example 2

(62) In a same manner as Example 1 other than using a masterbatch (MB2) instead of the masterbatch (MB1), a multilayered film having mixture layers was prepared to obtain a thermoformed container, and they were evaluated. Results are shown in Table 1 in collection.

Example 3

(63) In a same manner as Example 1 other than using a masterbatch (MB3) instead of the masterbatch (MB1), a multilayered film having mixture layers was prepared to obtain a thermoformed container, and they were evaluated. Results are shown in Table 1 in collection.

Example 4

(64) In a same manner as Example 1 other than using a masterbatch (MB4) instead of the masterbatch (MB1), a multilayered film having mixture layers was prepared to obtain a thermoformed container, and they were evaluated. Results are shown in Table 1 in collection.

Example 5

(65) In a same manner as Example 1 other than coextrusion molding using a mixture of a recovery, a masterbatch (MB1), and a pigment (E-1) dry blended at a mass ratio of recovery/masterbatch (MB1)/pigment (E-1)=100/3/0.05 for outermost layers, a multilayered film having mixture layers was prepared to obtain a thermoformed container, and they were evaluated. Results are shown in Table 1 in collection.

Example 6

(66) In a same manner as Example 1 other than preparing a recovery having layer thicknesses of polyolefin layer/adhesive resin layer/EVOH layer/adhesive resin layer/polyolefin layer=200/20/4/20/200 in the production of a recovery of Example 1, a multilayered film having mixture layers was prepared to obtain a thermoformed container, and they were evaluated. The mass ratio of each component of the recovery was polyolefin (A-1)/saponified ethylene-vinyl acetate copolymer (B-1)/adhesive resin=89.9/1.1/9. Results are shown in Table 1 in collection.

Example 7

(67) In a same manner as Example 1 other than using a masterbatch (MB7) instead of the masterbatch (MB1), a multilayered film having mixture layers was prepared to obtain a thermoformed container, and they were evaluated. Results are shown in Table 1 in collection.

Example 8

(68) In a same manner as Example 1 other than, using polyolefin containing a pigment having polyolefin (A-1) and a pigment (E-1) dry blended at a mass ratio of polyolefin (A-1)/pigment (E-1)=100/0.3 for outermost layers, B-1 as the EVOH (B) for an innermost layer, MODIC AP P604V for the adhesive resin layers, preparing a multilayered film by carrying out three-type five-layer coextrusion of polyolefin layer/adhesive resin layer/EVOH layer/adhesive resin layer/polyolefin layer=200/20/20/20/200 with a feedblock die in the production of a recovery of Example 1, a multilayered film having mixture layers was prepared to obtain a thermoformed container, and they were evaluated. Results are shown in Table 1 in collection.

Example 9

(69) In a same manner as Example 1 other than using a masterbatch (MB5) instead of the masterbatch (MB1), a multilayered film having mixture layers was prepared to obtain a thermoformed container, and they were evaluated. Results are shown in Table 1 in collection.

Example 10

(70) In a same manner as Example 1 other than using a masterbatch (MB8) instead of the masterbatch (MB1), a multilayered film having mixture layers was prepared to obtain a thermoformed container, and they were evaluated. Results are shown in Table 1 in collection. It should be noted that the content of the polyolefin (A) shown in Table 1 represents a total of the polyolefin (A-1) and the polyolefin (A-2).

Comparative Example 1

(71) In a same manner as Example 1 other than preparing a recovery using a multilayered film having layer thicknesses of polyolefin layer/adhesive resin layer/EVOH layer/adhesive resin layer/polyolefin layer=200/20/120/20/200 in the production of a recovery of Example 1, a multilayered film having mixture layers was prepared to obtain a thermoformed container, and they were evaluated. The mass ratio of each component of the recovery was polyolefin (A-1)/saponified ethylene-vinyl acetate copolymer (B-1)/adhesive resin=67.4/25.8/6.7. Results are shown in Table 1 in collection.

Comparative Example 2

(72) In a same manner as Example 1 other than using a masterbatch (MB6) instead of the masterbatch (MB1) in Example 1, a multilayered film having mixture layers was prepared to obtain a thermoformed container, and they were evaluated. Results are shown in Table 1 in collection.

Comparative Example 3

(73) In a same manner as Example 1 other than using a mixture of a recovery, a masterbatch (MB1), and a pigment (E-1) dry blended at a mass ratio of recovery/masterbatch (MB1)/pigment (E-1)=100/3/0.025 for outermost layers in Example 1, a multilayered film having mixture layers was prepared to obtain a thermoformed container, and they were evaluated. Results are shown in Table 1 in collection.

(74) TABLE-US-00001 TABLE 1 Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8 Resin Composition Conditions Composition (parts by mass) Polyolefin (A) 85.9 85.9 85.9 85.9 85.9 89.9 85.9 85.9 EVOH (B) 5.5 5.5 5.5 5.5 5.5 1.1 5.5 5.5 S-EVOH (C) 0.75 0.3 0.75 0.75 0.75 0.75 0.75 0.75 EVAc (D) 2 2.5 2.1 1.6 2 2 2.1 2 Pigment (E) 0.3 0.3 0.3 0.3 0.05 0.3 0.3 0.56 Metal salt (F) 0.15 0.15 0.03 0.60 0.15 0.15 0.15 0.15 of fatty acid Hydrotalcite (G) 0.075 0.075 0.075 0.075 0.075 0.075 0 0.075 Adhesive resin 8.6 8.6 8.6 8.6 8.6 9 8.6 8.6 Antioxidant 0.006 0.006 0.006 0.006 0.006 0.006 0.006 0.006 Mass Ratio (A/B) 15.6 15.6 15.6 15.6 15.6 81.7 15.6 15.6 (B/C) 7.3 18.3 7.3 7.3 7.3 1.5 7.3 7.3 (D/C) 2.7 8.3 2.9 2.1 2.7 2.7 2.8 2.7 (E/C) 0.4 1 0.4 0.4 0.07 0.4 0.4 0.75 (E/D) 0.15 0.12 0.14 0.19 0.02 0.15 0.14 0.28 (F/E) 0.5 0.5 0.1 2 3 0.5 0.5 0.3 Content of (C) *1 0.82 0.33 0.82 0.82 0.82 0.82 0.82 0.82 Evaluation Results EVOH particle 1.2 1.7 1.3 1.3 1.3 1.2 1.4 1.2 diameter () Uneven coloration A A A A A A A A Whiteness 92.3 91.3 91.6 92.0 90.1 92.1 90.5 92.3 Example Example Comparative Comparative Comparative 9 10 Example 1 Example 2 Example 3 Resin Composition Conditions Composition (parts by mass) Polyolefin (A) 85.9 87.9 67.4 85.9 85.9 EVOH (B) 5.5 5.5 25.8 5.5 5.5 S-EVOH (C) 0.15 0.75 0.75 2.5 0.75 EVAc (D) 2.5 2 0.15 2 Pigment (E) 0.3 0.3 0.3 0.3 0.025 Metal salt (F) 0.15 0.15 0.15 0.15 0.15 of fatty acid Hydrotalcite (G) 0.15 0.075 0.075 0.15 0.075 Adhesive resin 8.6 8.6 6.7 8.6 8.6 Antioxidant 0.006 0.006 0.006 0.006 0.006 Mass Ratio (A/B) 15.6 16.0 2.6 15.6 15.6 (B/C) 36.7 7.3 34.5 2.2 7.3 (D/C) 17 2.7 0.059 2.7 (E/C) 2 0.4 0.4 0.12 0.03 (E/D) 0.12 0.15 2 0.01 (F/E) 0.5 0.5 0.5 0.5 6 Content of (C) *1 0.16 0.80 0.80 2.78 0.82 Evaluation Results EVOH particle 2.1 2.0 2.3 2.5 1.3 diameter () Uneven coloration B B C C C Whiteness 90.2 90.4 87.1 88.9 86.1 *1 Content of (C) based on 100 parts by mass of (A) + (B) (parts by mass )

(75) According to the above results, in Example 1 having all of the mass ratio (A/B) of the polyolefin (A) and the EVOH (B), the mass ratio (B/C) of EVOH (B)/S-EVOH (C), the mass ratio (E/C) of pigment (E)/S-EVOH (C), and the content of the S-EVOH (C) in the range of claims, a molded object having a small particle diameter of the EVOH (B) and good dispersibility thereof, excellent in whiteness without uneven coloration was obtained

(76) In both Comparative Example 1 having a large thickness of the EVOH (B) in the recovery, and as a result, having a large amount of EVOH (B) and Comparative Example 2 having a large amount of S-EVOH (C) in the masterbatch, the particle diameter of the EVOH (B) in the resin composition became large, there was uneven coloration, and the whiteness was insufficient. In Comparative Example 3 having a small amount of pigment (E), the particle diameter of EVOH (B) was small. However, the dispersibility of the pigment was insufficient, there was uneven coloration, and the whiteness was insufficient.

Example 11

(77) The evaluation results of the multilayered film having mixture layers and the thermoformed container in Example 1 are shown again in Table 2 as Example 11. Further, a single layer film was prepared as follows for evaluation. Evaluation results are shown in Table 2.

(78) [Preparation of Single Layer Structure Containing Pigment]

(79) Using a mixture of the recovery obtained in Example 1, a masterbatch (MB1), and a pigment (E-1) dry blended at a mass ratio of recovery/masterbatch (MB1)/pigment (E-1)=100/3/0.3, extrusion molding of a 100 m single layer film was carried out for 48 hours. The extrusion molding of the mixture was carried out using a 32 mm extruder at a temperature for extrusion of 220 C. and at a temperature in a die section of 220 C.

(80) [Evaluation of White Streaks in Single Layer Film]

(81) The single layer film was cut out in 20 cm20 cm and presence of white streaks in the single layer film was visually checked to evaluate the presence of white streaks as follows. Results are shown in Table 2.

(82) A: No white streak was generated at all.

(83) B: Small white streaks were slightly generated.

(84) C: Large white streaks were generated.

(85) [Measurement of YI Value of Single Layer Film]

(86) As a surface color of the single layer film, a YI value was measured in conformity to JIS-K-7103. Results are shown in Table 2.

(87) [Measurement of Screw Adhesion Amount After Extrusion of Single Layer Film]

(88) After carrying out extrusion of a single layer film for 48 hours, 2 kg of LDPE (NOVATEC LD LA320 produced by Japan polyethylene Corporation) was continuously charged to carry out purging of the extruder, the adapter, and the die. After finished flowing the LDPE, the operation was stopped to take out a screw and the LDPE remained on the screw was eliminated, and the deteriorated screw build-up was collected to weight the mass of the screw build-up thus obtained. Results are shown in Table 2.

Example 12

(89) Based on 100 parts of EVOH chips of B-1 as the EVOH (B), 0.02 parts of 1-1 was added as the lubricant (I) for dry blending, and it was shaken until the lubricant (I) was dispersed uniformly on the surfaces of the EVOH chips to obtain a mixture of the EVOH (B-1) and the lubricant (I-1).

(90) In a same manner as Example 1 other than using the mixture obtained as above instead of B-1 in Example 1, a recovery was produced to prepare a multilayered film having mixture layers and a thermoformed container was obtained to evaluate them. Results are shown in Table 2 in collection. In addition, in a same manner as Example 11 other than using the recovery produced as above instead of the recovery obtained in Example 1 in Example 11, a single layer film was prepared to carry out evaluation of white streaks in the single layer film, measurement of a YI value, and measurement of a screw adhesion amount after extrusion of the single layer film. Results are shown in Table 2 in collection.

Example 13

(91) As the EVOH (B), 2000 parts of B-2 was put into 18000 parts of mixed solvent of water/methanol=40/60 (mass ratio) and it was stirred at 60 C. for six hours to be dissolved completely. To this solution, 2 parts of H-1 (sorbic acid) as the conjugated polyene compound (H) was added, and it was further stirred at 60 C. for one hour to completely dissolve H-1, and thus an EVOH solution containing the conjugated polyene compound (H-1) was obtained. This EVOH solution was continuously extruded from a nozzle having a diameter of 4 mm into a coagulation bath of water/methanol=95/5 (mass ratio) adjusted at 0 C. to coagulate the EVOH in strands. This strand was introduced into a pelletizer to obtain porous EVOH chips. After washing the porous EVOH chips thus obtained in order using 2000 parts of a 0.1 mass %, based on 100 parts of the chips, aqueous acetic acid solution and subsequently 2000 parts of ion exchanged water at 20 C., they were immersed in 2000 parts of an aqueous solution containing 0.092% boric acid at 20 C. for four hours. The EVOH chips were subjected to deliquoring and separation to carry out drying with a hot air dryer at 80 C. for four hours, and further drying at 100 C. for sixteen hours, and thus EVOH chips of the EVOH (B-2) containing the conjugated polyene compound (H-1) were obtained. The H-1 (sorbic acid) content in the EVOH chips thus obtained was 0.01 parts based on 100 parts of EVOH, and the boric acid content was 0.019 in terms of boron. The EVOH chips had a melt index (ASTM-D 1238, 190 C., load of 2160 g) of 1.6 g/10 minutes.

(92) In a same manner as Example 1 other than using the EVOH chips of the EVOH (B-2) containing the conjugated polyene compound (H-1) obtained as above instead of B-1 in Example 1, a recovery was produced to prepare a multilayered film having mixture layers and a thermoformed container was obtained to evaluate them. Results are shown in Table 2 in collection. In addition, in a same manner as Example 11 other than using the recovery produced as above instead of the recovery obtained in Example 1 in Example 11, a single layer film was prepared to carry out evaluation of white streaks in the single layer film, measurement of a YI value, and measurement of a screw adhesion amount after extrusion of the single layer film. Results are shown in Table 2 in collection.

Example 14

(93) Based on 100 parts of EVOH chips of the EVOH (B-2) containing the conjugated polyene compound (H-1) obtained in Example 13, 0.02 parts of 1-1 (ethylene stearic acid bisamide) was added as the lubricant (I) for dry blending, and it was shaken until the lubricant (I) was dispersed uniformly on the surfaces of the EVOH chips to obtain a mixture of the EVOH (B-2) containing the conjugated polyene compound (H-1) and the lubricant (I-1).

(94) In a same manner as Example 1 other than using the mixture obtained as above instead of B-1 in Example 1, a recovery was produced to prepare a multilayered film having mixture layers and a thermoformed container was obtained to evaluate them. Results are shown in Table 2 in collection. In addition, in a same manner as Example 11 other than using the recovery produced as above instead of the recovery obtained in Example 1 in Example 11, a single layer film was prepared to carry out evaluation of white streaks in the single layer film, measurement of a YI value, and measurement of a screw adhesion amount after extrusion of the single layer film. Results are shown in Table 2 in collection.

Example 15

(95) In a same manner as Example 14 other than using a masterbatch (MB8) instead of a masterbatch (MB1), a recovery was produced to prepare a multilayered film having mixture layers and a thermoformed container was obtained for evaluation. Results are shown in Table 2 in collection. In addition, in a same manner as Example 14 other than using the recovery produced as above instead of the recovery obtained in Example 14 in Example 14, a single layer film was prepared to carry out evaluation of white streaks in the single layer film, measurement of a YI value, and measurement of a screw adhesion amount after extrusion of the single layer film. Results are shown in Table 2 in collection. Here, the content of the polyolefin (A) shown in Table 2 represents a total of the polyolefin (A-1) and the polyolefin (A-2).

Example 16

(96) In a same manner as Example 12 other than using E-2 instead of E-1 as the pigment in Example 12, a multilayered film having mixture layers was prepared and a thermoformed container was obtained to evaluate them. In addition, in a same manner as Example 12 other than using E-2 instead of E-1 as the pigment in Example 12, a single layer film was prepared to carry out evaluation of white streaks in the single layer film, measurement of a YI value, and measurement of a screw adhesion amount after extrusion of the single layer film. Results are shown in Table 2 in collection.

Example 17

(97) In a same manner as Example 13 other than using E-2 instead of E-1 as the pigment in Example 13, a multilayered film having mixture layers was prepared and a thermoformed container was obtained to evaluate them. In addition, in a same manner as Example 13 other than using E-2 instead of E-1 as the pigment in Example 13, a single layer film was prepared to carry out evaluation of white streaks in the single layer film, measurement of a YI value, and measurement of a screw adhesion amount after extrusion of the single layer film. Results are shown in Table 2 in collection.

Example 18

(98) In a same manner as Example 14 other than using E-2 instead of E-1 as the pigment in Example 14, a multilayered film having mixture layers was prepared and a thermoformed container was obtained to evaluate them. In addition, in a same manner as Example 14 other than using E-2 instead of E-1 as the pigment in Example 14, a single layer film was prepared to carry out evaluation of white streaks in the single layer film, measurement of a YI value, and measurement of a screw adhesion amount after extrusion of the single layer film. Results are shown in Table 2 in collection.

Example 19

(99) In a same manner as Example 18 other than using a masterbatch (MB9) instead of a masterbatch (MB1) in Example 18, a multilayered film having mixture layers was prepared and a thermoformed container was obtained to evaluate them. In addition, in a same manner as Example 18 other than using a masterbatch (MB9) instead of a masterbatch (MB1) in Example 18, a single layer film was prepared to carry out evaluation of white streaks in the single layer film, measurement of a YI value, and measurement of a screw adhesion amount after extrusion of the single layer film. Results are shown in Table 2 in collection.

Example 20

(100) In a same manner as Example 18 other than using a masterbatch (MB10) instead of a masterbatch (MB1) in Example 18, a multilayered film having mixture layers was prepared and a thermoformed container was obtained to evaluate them. In addition, in a same manner as Example 18 other than using a masterbatch (MB10) instead of a masterbatch (MB1) in Example 18, a single layer film was prepared to carry out evaluation of white streaks in the single layer film, measurement of a YI value, and measurement of a screw adhesion amount after extrusion of the single layer film. Results are shown in Table 2 in collection.

Example 21

(101) In a same manner as Example 14 other than using E-3 instead of E-1 as the pigment in Example 14, a multilayered film having mixture layers was prepared and a thermoformed container was obtained to evaluate them. In addition, in a same manner as Example 14 other than using E-3 instead of E-1 as the pigment in Example 14, a single layer film was prepared to carry out evaluation of white streaks in the single layer film, measurement of a YI value, and measurement of a screw adhesion amount after extrusion of the single layer film. Results are shown in Table 2 in collection.

Example 22

(102) In a same manner as Example 14 other than using E-4 instead of E-1 as the pigment in Example 14, a multilayered film having mixture layers was prepared and a thermoformed container was obtained to evaluate them. In addition, in a same manner as Example 14 other than using E-4 instead of E-1 as the pigment in Example 14, a single layer film was prepared to carry out evaluation of white streaks in the single layer film, measurement of a YI value, and measurement of a screw adhesion amount after extrusion of the single layer film. Results are shown in Table 2 in collection.

Example 23

(103) In a same manner as Example 14 other than using E-5 instead of E-1 as the pigment in Example 14, a multilayered film having mixture layers was prepared and a thermoformed container was obtained to evaluate them. In addition, in a same manner as Example 14 other than using E-5 instead of E-1 as the pigment in Example 14, a single layer film was prepared to carry out evaluation of white streaks in the single layer film, measurement of a YI value, and measurement of a screw adhesion amount after extrusion of the single layer film. Results are shown in Table 2 in collection.

(104) TABLE-US-00002 TABLE 2 Example Example Example Example Example Example Example 11 12 13 14 15 16 17 Resin Composition Conditions Composition (parts by mass) Polyolefin (A) 85.9 85.9 85.9 85.9 87.9 85.9 85.9 EVOH (B) 5.5 5.5 5.5 5.5 5.5 5.5 5.5 Conjugated polyene 0.0006 0.0006 0.0006 0.0006 compound (H) Lubricant (I) 0.0011 0.0011 0.0011 0.0011 S-EVOH (C) 0.75 0.75 0.75 0.75 0.75 0.75 0.75 EVAc (D) 2 2 2 2 2 2 Pigment (E) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Metal salt (F) 0.15 0.15 0.15 0.15 0.15 0.15 0.15 of fatty acid Hydrotalcite (G) 0.075 0.075 0.075 0.075 0.075 0.075 0.075 Adhesive resin 8.6 8.6 8.6 8.6 8.6 8.6 8.6 Antioxidant 0.006 0.006 0.006 0.006 0.006 0.006 0.006 Mass Ratio (B/C) 7.3 7.3 7.3 7.3 7.3 7.3 7.3 (D/C) 2.7 2.7 2.7 2.7 2.7 2.7 (E/C) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 (E/D) 0.15 0.15 0.15 0.15 0.15 0.15 (F/E) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Type Pigment (E) E-1 E-1 E-1 E-1 E-1 E-2 E-2 Metal salt (F) E-1 F-1 F-1 F-1 F-1 F-1 F-1 of fatty acid Multilayered Film Evaluation EVOH particle 1.2 1.1 1.2 1.0 1.9 1.0 1.1 diameter () Uneven coloration A A A A B A A Whiteness 92.3 92.8 93.1 93.7 91.1 93.3 93.8 Single Layer Film Evaluation White streaks B B B A B A A YI value 8.5 7.4 6.3 5.5 6.5 4.9 4.6 Screw adhesion 2.8 1.5 1.7 1.3 1.9 1.2 1.3 degraded material amount (g) Example Example Example Example Example Example 18 19 20 21 22 23 Resin Composition Conditions Composition (parts by mass) Polyolefin (A) 85.9 85.9 85.9 85.9 85.9 85.9 EVOH (B) 5.5 5.5 5.5 5.5 5.5 5.5 Conjugated polyene 0.0006 0.0006 0.0006 0.0006 0.0006 0.0006 compound (H) Lubricant (I) 0.0011 0.0011 0.0011 0.0011 0.0011 0.0011 S-EVOH (C) 0.75 0.75 0.75 0.75 0.75 0.75 EVAc (D) 2 2 2 2 2 2 Pigment (E) 0.3 0.3 0.3 0.3 0.3 0.3 Metal salt (F) 0.15 0.15 0.22 0.15 0.15 0.15 of fatty acid Hydrotalcite (G) 0.075 0.075 0.075 0.075 0.075 0.075 Adhesive resin 8.6 8.6 8.6 8.6 8.6 8.6 Antioxidant 0.006 0.006 0.006 0.006 0.006 0.006 Mass Ratio (B/C) 7.3 7.3 7.3 7.3 7.3 7.3 (D/C) 2.7 2.7 2.6 2.7 2.7 2.7 (E/C) 0.4 0.4 0.4 0.4 0.4 0.4 (E/D) 0.15 0.15 0.15 0.15 0.15 0.15 (F/E) 0.5 0.5 0.7 0.5 0.5 0.5 Type Pigment (E) E-2 E-2 E-2 E-3 E-4 E-5 Metal salt (F) F-1 F-2 F-1/F-2 F-1 F-1 F-1 of fatty acid Multilayered Film Evaluation EVOH particle 0.9 0.7 0.7 0.8 0.8 0.7 diameter () Uneven coloration A A A A A A Whiteness 94.2 94.7 94.9 95.3 95.4 95.8 Single Layer Film Evaluation White streaks A A A A A A YI value 4.1 4.4 4.2 3.9 3.8 3.4 Screw adhesion 1.0 0.9 0.8 0.6 0.6 0.4 degraded material amount (g)