READILY TEARABLE CO-EXTRUDED MULTILAYER BARRIER FILM AND PACKAGING MATERIAL

Abstract

A readily tearable co-extruded multilayer barrier film being a multilayer film formed from at least three layers, the readily tearable co-extruded multilayer barrier film comprising a layered body having a barrier layer (I) containing a polar resin (a) as a main component, and an adhesive layer (II) and an adhesive layer (III) laminated on both sides adjacent to the barrier layer (I), the adhesive layer (II) and the adhesive layer (III) each at least containing a modified polyolefin-based resin (b) modified with an unsaturated carboxylic acid or a derivative thereof, and a cyclic olefin-based resin (c).

Claims

1. A readily tearable co-extruded multilayer barrier film being a multilayer film formed from at least three layers, the readily tearable co-extruded multilayer barrier film comprising a layered body having a barrier layer (I) containing a polar resin (a) as a main component, and an adhesive layer (II) and an adhesive layer (III) laminated on both sides adjacent to the barrier layer (I), the adhesive layer (II) and the adhesive layer (III) each at least containing a modified polyolefin-based resin (b) modified with an unsaturated carboxylic acid or a derivative thereof, and a cyclic olefin-based resin (c).

2. The readily tearable co-extruded multilayer barrier film according to claim 1, wherein a content of the cyclic olefin-based resin (c) in each of the adhesive layer (II) and the adhesive layer (III) is from 10 wt. % to 80 wt. %.

3. The readily tearable co-extruded multilayer barrier film according to claim 1, wherein a glass transition temperature (Tg) of the cyclic olefin-based resin (c) is from 100° C. to 180° C.

4. The readily tearable co-extruded multilayer barrier film according to claim 1, wherein, for a viscosity η.sub.b of the modified polyolefin-based resin (b) and a viscosity η.sub.c of the cyclic olefin-based resin (c), a viscosity ratio R.sub.η=η.sub.c/η.sub.b is 0.2 or greater at a measurement temperature of 230° C. and a shear rate of 122/s.

5. The readily tearable co-extruded multilayer barrier film according to claim 1, wherein the adhesive layer (II) and the adhesive layer (III) each contain a mixed resin of the modified polyolefin-based resin (b) modified with an unsaturated carboxylic acid or a derivative thereof, the cyclic olefin-based resin (c), and the unmodified polyolefin-based resin (d) as a main component, and a melt flow rate (MFR) of the unmodified polyolefin-based resin (d) measured in accordance with JIS K 7210 is from 0.1 to 3.5 g/10 min.

6. The readily tearable co-extruded multilayer barrier film according to claim 5, wherein the unmodified polyolefin-based resin (d) is a linear polyethylene-based resin.

7. The readily tearable co-extruded multilayer barrier film according to claim 1, wherein a thickness ratio R of a total thickness t of the adhesive layer (II) and the adhesive layer (III) to a thickness T of entire film, R=(t/T), is 0.10 or greater.

8. The readily tearable co-extruded multilayer barrier film according to claim 1 formed from a five-layered structure obtained by laminating a resin layer (IV) and a resin layer (V) each containing a polyolefin-based resin (e) as a main component in an order of (IV)/(II)/(I)/(III)/(V).

9. A readily tearable co-extruded multilayer barrier film being a multilayer film formed from at least three layers, the readily tearable co-extruded multilayer barrier film being a layered body obtained by laminating at least a barrier layer (I) containing a polar resin (a) as a main component, and an adhesive layer (II) adjacent to the barrier layer (I), the adhesive layer (II) at least containing a modified polyolefin-based resin (b) modified with an unsaturated carboxylic acid or a derivative thereof, and a cyclic olefin-based resin (c), and a glass transition temperature (Tg) of the cyclic olefin-based resin (c) being from 100° C. to 180° C.

10. The readily tearable co-extruded multilayer barrier film according to claim 1, wherein an Elmendorf tear strength of the multilayer film measured in accordance with JIS K 7128-2 is 30 N/mm or less in a transverse direction (TD) relative to a machine direction (MD).

11. The readily tearable co-extruded multilayer barrier film according to claim 1, wherein the polar resin (a) is at least one type selected from the group consisting of olefin-based resins each having a polar group, polyamide-based resins, ethylene-vinyl alcohol copolymer-based resins, and polyester-based resins.

12. The readily tearable co-extruded multilayer barrier film according to claim 1, wherein the barrier layer (I) is formed from two or more types of the polar resins (a) and is formed from a layered body having two or more layers.

13. A packaging material using the readily tearable co-extruded multilayer barrier film according to claim 1.

14. A readily tearable adhesive resin composition comprising at least a modified polyolefin-based resin (b) modified with an unsaturated carboxylic acid or a derivative thereof and a cyclic olefin-based resin (c) having a glass transition temperature (Tg) of 100 to 180° C., and for a viscosity η.sub.b of the modified polyolefin-based resin (b) and a viscosity η.sub.c of the cyclic olefin-based resin (c), a viscosity ratio R.sub.η=η.sub.c/η.sub.b being 0.2 or greater at a measurement temperature of 230° C. and a shear rate of 122/s.

15. The readily tearable adhesive resin composition according to claim 14, wherein a mixed resin at least further containing an unmodified polyolefin-based resin (d) in addition to the modified polyolefin-based resin (b) and the cyclic olefin-based resin (c) as a main component, and a melt flow rate (MFR) of the unmodified polyolefin-based resin (d) measured in accordance with JIS K 7210 is from 0.1 to 3.5 g/10 min.

16. The readily tearable co-extruded multilayer barrier film according to claim 9, wherein an Elmendorf tear strength of the multilayer film measured in accordance with JIS K 7128-2 is 30 N/mm or less in a transverse direction (TD) relative to a machine direction (MD).

17. The readily tearable co-extruded multilayer barrier film according to claim 9, wherein the polar resin (a) is at least one type selected from the group consisting of olefin-based resins each having a polar group, polyamide-based resins, ethylene-vinyl alcohol copolymer-based resins, and polyester-based resins.

18. The readily tearable co-extruded multilayer barrier film according to claim 9, wherein the barrier layer (I) is formed from two or more types of the polar resins (a) and is formed from a layered body having two or more layers.

19. A packaging material using the readily tearable co-extruded multilayer barrier film according to claim 9.

Description

EXAMPLES

[0123] Examples and Comparative Examples of the present invention are described below.

Used Raw Material

(1-1) Polar Resin (a)

[0124] PA6/66 copolymer, density: 1130 kg/m.sup.3, viscosity value: 246 cm.sup.3/g (“Novamid 2030CA”, available from DSM Japan Engineering Plastics KK)

[0125] Ethylene-vinyl alcohol copolymer, ethylene content: 38 mol %, MFR (210° C., 2160 g): 4.0 g/10 min, density: 1.17 g/cm.sup.3 (“Soarnol ET3803RB” available from Nippon Synthetic Chemical Industry Co., Ltd.)

(1-2) Modified Polyolefin-Based Resin (b)

[0126] Modified PE 1: Maleic acid graft-modified polyethylene (available from Mitsubishi Chemical Corporation), density: 0.920 g/cm.sup.3, MFR: 3 g/10 min, viscosity: 526 Pa.Math.s (measurement temperature: 230° C., shear rate: 122/s)

[0127] Modified PE 2: Maleic acid graft-modified polyethylene (“MODIC M522” available from Mitsubishi Chemical Corporation), density: 0.920 g/cm.sup.3, MFR: 1.2 g/10 min, viscosity: 1260 Pa.Math.s (measurement temperature: 230° C., shear rate: 122/s)

(1-3) Cyclic Olefin-Based Resin (c)

[0128] COC 1: 8007 F: glass transition temperature: 78° C. (“TOPAS 8007F-600” available from Polyplastics Co., Ltd.)

[0129] COC 2: 7010 F: glass transition temperature: 110° C. (“TOPAS 7010E-600” available from Polyplastics Co., Ltd.)

[0130] COC 3: 6013 F: glass transition temperature: 138° C. (“TOPAS 6013F-04” available from Polyplastics Co., Ltd.)

[0131] COC 4: 5013 F: glass transition temperature: 134° C. (“TOPAS 5013F-04” available from Polyplastics Co., Ltd.)

(1-4) Unmodified Polyolefin-Based Resin (d)

[0132] LLDPE 1: UF320: density: 0.922 g/cm.sup.3, MFR: 0.9 g/10 min (“NOVATEC LL UF320” available from Japan Polyethylene Corporation)

[0133] LLDPE 2: NC566A: density: 0.918 g/cm.sup.3, MFR: 3.8 g/10 min (“HARMOREX NC566A” available from Japan Polyethylene Corporation)

(1-5) Polyolefin-Based Resin (e)

[0134] LLDPE 3: NF444A: density: 0.912 g/cm.sup.3, MFR: 2.0 g/10 min (“HARMOREX NF444A” available from Japan Polyethylene Corporation)

[0135] LLDPE 1: UF320: density: 0.922 g/cm.sup.3, MFR: 0.9 g/10 min (“NOVATEC LL UF320” available from Japan Polyethylene Corporation)

[0136] LDPE 1: LE306: density: 0.919 g/cm.sup.3, MFR: 1.0 g/10 min (“NOVATEC LD LE306” available from Japan Polyethylene Corporation)

[0137] LLDPE 4: UF425: density: 0.926 g/cm.sup.3, MFR: 0.8 g/10 min (“NOVATEC LL UF425” available from Japan Polyethylene Corporation)

Film Formation

(2-1) Co-Extrusion Five-Layered Air-Cooled Inflation Film Formation

[0138] Forming machine: Five-type five-layered air-cooled inflation forming machine (available from Placo Co., Ltd.)

[0139] Extruder: φ40 mm×5 extruders

[0140] Die: φ150 mm (stack die)

Physical Property Evaluation Methods

(3-1) Viscosity Ratio R.SUB.η

[0141] Using JIS K 7199 as a reference, the melt viscosities were measured by using the following instrument. For the obtained melt viscosities, the viscosity ratio R.sub.η was calculated by using values at the shear rate of 122/s.

[0142] Instrument: Capirograph 1B (available from Toyo Seiki Seisaku-sho, Ltd.)

[0143] Orifice length: 10 mm

[0144] Orifice diameter: 1 mm

[0145] Barrel diameter: 9.55 mm

[0146] Orifice inflow angle: Flat

[0147] Measurement temperature: 230° C.

(3-2) Amount of Shift L

[0148] As the index of the linearly tearable properties, the amount of shift L was measured by the method describe below.

(3-2-1) Test Piece

[0149] A strip-like test piece was formed by cutting 50 mm along the film machine direction (MD) and 250 mm along the transverse direction thereof (TD), and a reference line was drawn on the test piece along the TD in a manner that the short side, which was 50 mm, was equally divided into 25 mm In addition, 50 mm notch was formed along the reference line from one of the short sides.

(3-2-2) Jig for Measurement

[0150] A paperboard having a length of 250 mm, a width of 30 mm, and a thickness of approximately 4 mm was used. Note that, in the present test, four sheets of the paperboards each having a thickness of approximately 1 mm were laminated. (3-2-3) Tester

[0151] Instrument: Tensilon Universal Tester, available from Orientec Co., Ltd.

[0152] Distance between chucks: 65 mm

[0153] Tensile speed: 500 mm/min

[0154] Measurement environment: Temperature at 23° C., humidity at 50%

(3-2-4) Measurement of Amount of Shift L

[0155] The strip-like test piece was fixed on a jig for measurement by tape or the like in a manner that the reference line is along the long side of the jig. At the test piece end portion which had the notch and which was branched into two, the side fixed to the jig was fixed to a chuck at the upper portion of the tester, and the other side was fixed to a chuck at the bottom portion of the tester in a manner that the test piece was tilted at 45° relative to the tensile direction of the tester. The test piece was torn at the predetermined tensile speed, and the amount of shift L from the reference line at the end portion of the tearing was measured by a scale. A smaller amount of shift L indicates a linear tearing along the reference line.

(3-3) Elmendorf Tear Strength

[0156] Using JIS K 7128-2 as a reference, the Elmendorf tear strength was evaluated by using the following instrument. Note that the value is based on the measurement direction which was a transverse direction (TD) relative to the machine direction of the film.

[0157] Instrument: Digital Elmendorf Tearing Tester model SA (available from Toyo Seiki Seisaku-sho, Ltd.)

[0158] Measurement environment: Temperature at 23° C., humidity at 50%

(4) Readily Linearly Tearable Properties

[0159] From the results of the amount of shift L of (3-2) and Elmendorf tear strength of (3-3) described above, the readily linearly tearable properties were evaluated as described below.

[0160] Readily linearly tearable properties double circle: Amount of shift was less than 25 mm, and the tear strength was 30 N/mm or less.

[0161] Readily linearly tearable properties circle: Amount of shift was 25 mm or greater, and the tear strength was 30 N/mm or less.

[0162] Readily linearly tearable properties cross: Amount of shift was 25 mm or greater, and the tear strength was greater than 30 N/mm

(5) Low Curling Properties

[0163] The curling properties of the entire film were visually observed, and the case with small curling was evaluated as “circle”, and the case with large curling was evaluated as “cross”.

Example 1

[0164] Using the used raw materials described above, a five-layered inflation film which was obtained by laminating in the order of resin layer (IV)/adhesive layer (II)/barrier layer (I)/adhesive layer (III)/resin layer (V) by the co-extrusion air-cooled inflation method described in (2) above was obtained. The thicknesses of the layers were set to, from the side of the resin layer (IV), 30/10/20/10/30 μm, and the blow ratio was set to 1.4. The thickness ratio R of the adhesive layer relative to the entire film was set to 0.20, and the glass transition temperature of the cyclic olefin-based resin in the adhesive layer (II) and the adhesive layer (III) was set to 110° C. For the barrier layer (I), 2030CA, which was a PA6/66 copolymer, was used. The details of the resin types and the layer structure and the evaluation results are shown in Table 1.

Example 2

[0165] A five-layered inflation film, in which the glass transition temperature of the cyclic olefin-based resin in the adhesive layer (II) and the adhesive layer (III) of Example 1 described above was changed to 138° C., was obtained. The details of the resin types and the layer structure and the evaluation results are shown in Table 1.

Example 3

[0166] A five-layered inflation film, in which the thicknesses of the layers of Example 1 described above were changed to, from the adhesive layer (IV) side, 30/30/30/30/30 μm and the thickness ratio R was changed to 0.40, was obtained. The blow ratio was set to 1.2. The viscosity ratios η.sub.c/η.sub.d at 190° C. to 250° C. of the cyclic olefin-based resin (c) and the unmodified polyolefin-based resin (d) were set to 0.26 to 2.4. The details of the resin types and the layer structure and the evaluation results are shown in Table 1.

Example 4

[0167] A five-layered inflation film, in which the thicknesses of the layers of Example 1 described above were changed to, from the adhesive layer (IV) side, 40/10/30/10/40 μm and the thickness ratio R was changed to 0.15, was obtained. The viscosity ratios η.sub.c/η.sub.d at 190° C. to 250° C. of the cyclic olefin-based resin (c) and the unmodified polyolefin-based resin (d) were set to 0.26 to 2.4. The details of the resin types and the layer structure and the evaluation results are shown in Table 1.

Example 5

[0168] A five-layered inflation film, in which the thicknesses of the layers of Example 2 described above were changed to, from the adhesive layer (IV) side, 30/10/10/10/30 μm and the thickness ratio R was changed to 0.22, was obtained. The details of the resin types and the layer structure and the evaluation results are shown in Table 1.

Example 6

[0169] A five-layered inflation film, in which the thicknesses of the layers of Example 2 described above were changed to, from the adhesive layer (IV) side, 20/20/10/20/20 μm and the thickness ratio R was changed to 0.44, was obtained. The details of the resin types and the layer structure and the evaluation results are shown in Table 1.

Example 7

[0170] A five-layered inflation film, in which the thicknesses of the layers of Example 2 described above were changed to, from the adhesive layer (IV) side, 20/10/10/10/20 μm and the thickness ratio R was changed to 0.29, was obtained. The details of the resin types and the layer structure and the evaluation results are shown in Table 1.

Example 8

[0171] A five-layered inflation film, in which the thicknesses of the layers of Example 2 described above were changed to, from the adhesive layer (IV) side, 20/20/20/20/20 μm and the thickness ratio R was changed to 0.40, was obtained. The details of the resin types and the layer structure and the evaluation results are shown in Table 2.

Example 9

[0172] Using the used raw materials described above, a five-layered inflation film which was obtained by laminating in the order of resin layer (IV)/adhesive layer (II)/barrier layer (I)/adhesive layer (III)/resin layer (V) by the co-extrusion air-cooled inflation method described in (2) above was obtained. The thicknesses of the layers were set to, from the side of the resin layer (IV), 36/15/8/15/36 μm, and the blow ratio was set to 1.8. The thickness ratio R of the adhesive layer relative to the entire film was set to 0.27, and the glass transition temperature of the cyclic olefin-based resin in the adhesive layer (II) and the adhesive layer (III) was set to 138° C. For the barrier layer (I), ET3803RB, which was an ethylene-vinyl alcohol copolymer, was used. The details of the resin types and the layer structure and the evaluation results are shown in Table 2.

Example 10

[0173] A five-layered inflation film, in which the glass transition temperature of the cyclic olefin-based resin in the adhesive layer (II) and the adhesive layer (III) of Example 1 described above was changed to 78° C., was obtained. The details of the resin types and the layer structure and the evaluation results are shown in Table 2.

Example 11

[0174] A five-layered inflation film, in which the unmodified polyolefin-based resin (d) of Example 7 described above was changed to LLDPE2 (NC566A), was obtained. The details of the resin types and the layer structure and the evaluation results are shown in Table 2.

Example 12

[0175] A five-layered inflation film, in which the glass transition temperature of the cyclic olefin-based resin in the adhesive layer (II) and the adhesive layer (III) of Example 11 described above was changed to 134° C., was obtained. The details of the resin types and the layer structure and the evaluation results are shown in Table 2.

Example 13

[0176] A five-layered inflation film, in which the thicknesses of the layers of Example 9 described above were changed to, from the adhesive layer (IV) side, 47/4/8/4/47 μm and the thickness ratio R was changed to 0.07, was obtained. The details of the resin types and the layer structure and the evaluation results are shown in Table 2.

Example 14

[0177] Using the used raw materials described above, a three-layered inflation film which was obtained by laminating in the order of barrier layer (I)/adhesive layer (III)/resin layer (V) by the co-extrusion air-cooled inflation method described in (2) above was obtained. The thicknesses of the layers were set to, from the side of the barrier layer (I), 20/20/20 μm, and the blow ratio was set to 1.4. The thickness ratio R of the adhesive layer relative to the entire film was set to 0.29, and the glass transition temperature of the cyclic olefin-based resin in the adhesive layer (III) was set to 138° C. For the barrier layer (I), 2030CA, which was a PA6/66 copolymer, was used. The details of the resin types and the layer structure and the evaluation results are shown in Table 2.

Comparative Example 1

[0178] Using the used raw materials described above, a five-layered inflation film which was obtained by laminating in the order of resin layer (IV)/adhesive layer (II)/barrier layer (I)/adhesive layer (III)/resin layer (V) by the co-extrusion air-cooled inflation method described in (2) above was obtained. The thicknesses of the layers were set to, from the side of the resin layer (IV), 30/10/20/10/30 μm, and the blow ratio was set to 1.4. The thickness ratio R of the adhesive layer relative to the entire film was set to 0.2, and no cyclic olefin-based resin (c) was used in the adhesive layer (II) and the adhesive layer (III). For the barrier layer (I), 2030CA, which was a PA6/66 copolymer, was used. The details of the resin types and the layer structure and the evaluation results are shown in Table 3.

Comparative Example 2

[0179] A five-layered inflation film, in which the thicknesses of the layers of Comparative Example 1 described above were changed to, from the adhesive layer (IV) side, 30/30/30/30/30 μm and the thickness ratio R was changed to 0.4, was obtained. The details of the resin types and the layer structure and the evaluation results are shown in Table 3.

Comparative Example 3

[0180] Using the used raw materials described above, a five-layered inflation film which was obtained by laminating in the order of resin layer (IV)/adhesive layer (II)/barrier layer (I)/adhesive layer (III)/resin layer (V) by the co-extrusion air-cooled inflation method described in (2) above was obtained. The thicknesses of the layers were set to, from the side of the resin layer (IV), 47/4/8/4/47 μm, and the blow ratio was set to 1.8. The thickness ratio R of the adhesive layer relative to the entire film was set to 0.07, and no cyclic olefin-based resin (c) was used in the adhesive layer (II) and the adhesive layer (III). For the barrier layer (I), ET3803RB, which was an ethylene-vinyl alcohol copolymer, was used. The details of the resin types and the layer structure and the evaluation results are shown in Table 3.

Comparative Example 4

[0181] Using the used raw materials described above, a five-layered inflation film which was obtained by laminating in the order of resin layer (IV)/adhesive layer (II)/barrier layer (I)/adhesive layer (III)/resin layer (V) by the co-extrusion air-cooled inflation method described in (2) above was obtained. The thicknesses of the layers were set to, from the side of the resin layer (IV), 20/20/20/20/20 μm, and the blow ratio was set to 1.4. The thickness ratio R of the adhesive layer relative to the entire film was set to 0.4, and the cyclic olefin-based resin (c) was used in the resin layer (IV) and the resin layer (V), which were not adjacent to the barrier layer (I). The concentration of the cyclic olefin-based resin (c) in the resin layer (IV) and the resin layer (V) was 29.4 wt. %. The details of the resin types and the layer structure and the evaluation results are shown in Table 3.

Comparative Example 5

[0182] A five-layered inflation film, in which the thicknesses of the layers of Comparative Example 4 described above were changed to, from the adhesive layer (IV) side, 30/30/30/30/30 μm and the thickness ratio R was changed to 0.4, was obtained. The details of the resin types and the layer structure and the evaluation results are shown in Table 3.

Comparative Example 6

[0183] A five-layered inflation film, in which the thicknesses of the layers of Comparative Example 4 described above were changed to, from the adhesive layer (IV) side, 30/5/30/5/30 μm and the thickness ratio R was changed to 0.1, was obtained. The details of the resin types and the layer structure and the evaluation results are shown in Table 3.

TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4 Raw Blend- Thick- Blend- Thick- Blend- Thick- Blend- Thick- material ing ness ing ness ing ness ing ness Layer structure name (wt %) (μm) (wt %) (μm) (wt %) (μm) (wt %) (μm) Resin Polyolefin- NF444A 100 30 100 30 100 30 100 40 layer based resin LE306 (IV) (e) UF320 Cyclic 7010F polyolefin- based resin (c) Adhesive Modified Modified 20 10 20 10 20 30 20 10 layer polyolefin- PE1 (II) based resin Modified (b) PE2 Cyclic 8007F polyolefin- 7010F 39.2 39.2 39.2 based resin 6013F 39.2 (c) 5013F Unmodified UF320 40.8 40.8 40.8 40.8 polyolefin- NC566A based resin (d) Barrier Polar resin PA6/66 100 20 100 10 100 30 100 30 layer (I) (a) copolymer EVOH Adhesive Modified Modified 20 10 20 10 20 30 20 10 layer polyolefin- PE1 (III) based resin Modified (b) PE2 Cyclic 8007F polyolefin- 7010F 39.2 39.2 39.2 based resin 6013F 39.2 (c) 5013F Unmodified UF320 40.8 40.8 40.8 40.8 polyolefin- NC566A based resin (d) Resin Polyolefin- NF444A 100 30 100 30 100 30 100 40 layer based resin LE306 (V) (e) UF320 Cyclic 7010F polyolefin- based resin (c) Total thickness μm 100 100 150 130 Thickness ratio R — 0.20 0.20 0.40 0.15 Tg of cyclic polyolefin- ° C. 110 138 110 110 based resin (c) Viscosity ratio Rη — 1.1 3.1 1.1 1.1 Low curling properties ◯ ◯ ◯ ◯ Amount of shift L mm 14 13 22 11 Elmendorf tear N/mm 17 15 16 22 strength (TD) Readily linearly — ⊚ ⊚ ⊚ ⊚ tearable property evaluation Example 5 Example 6 Example 7 Raw Blend- Thick- Blend- Thick- Blend- Thick- material ing ness ing ness ing ness Layer structure name (wt %) (μm) (wt %) (μm) (wt %) (μm) Resin Polyolefin- NF444A 100 30 100 20 100 20 layer based resin LE306 (IV) (e) UF320 Cyclic 7010F polyolefin- based resin (c) Adhesive Modified Modified 20 10 20 20 20 10 layer polyolefin- PE1 (II) based resin Modified (b) PE2 Cyclic 8007F polyolefin- 7010F based resin 6013F 39.2 39.2 39.2 (c) 5013F Unmodified UF320 40.8 40.8 40.8 polyolefin- NC566A based resin (d) Barrier Polar resin PA6/66 100 10 100 10 100 10 layer (I) (a) copolymer EVOH Adhesive Modified Modified 20 10 20 20 20 10 layer polyolefin- PE1 (III) based resin Modified (b) PE2 Cyclic 8007F polyolefin- 7010F based resin 6013F 39.2 39.2 39.2 (c) 5013F Unmodified UF320 40.8 40.8 40.8 polyolefin- NC566A based resin (d) Resin Polyolefin- NF444A 100 30 100 20 100 20 layer based resin LE306 (V) (e) UF320 Cyclic 7010F polyolefin- based resin (c) Total thickness μm 90 90 70 Thickness ratio R — 0.22 0.44 0.29 Tg of cyclic polyolefin- ° C. 138 138 138 based resin (c) Viscosity ratio Rη — 3.1 3.1 3.1 Low curling properties ◯ ◯ ◯ Amount of shift L mm 10 17 13 Elmendorf tear N/mm 13 10 10 strength (TD) Readily linearly — ⊚ ⊚ ⊚ tearable property evaluation

TABLE-US-00002 TABLE 2 Example 8 Example 9 Example 10 Example 11 Raw Blend- Thick- Blend- Thick- Blend- Thick- Blend- Thick- material ing ness ing ness ing ness ing ness Layer structure name (wt %) (μm) (wt %) (μm) (wt %) (μm) (wt %) (μm) Resin Polyolefin- NF444A 100 20 80 36 100 30 100 20 layer based resin LE306 20 (IV) (e) UF320 Cyclic 7010F polyolefin- based resin (c) Adhesive Modified Modified 20 20 20 15 20 10 20 10 layer polyolefin- PE1 (II) based resin Modified (b) PE2 Cyclic 8007F 39.2 polyolefin- 7010F based resin 6013F 39.2 39.2 39.2 (c) 5013F Unmodified UF320 40.8 40.8 40.8 polyolefin- NC566A 40.8 based resin (d) Barrier Polar resin PA6/66 100 20 100 20 100 10 layer (I) (a) copolymer EVOH 100 8 Adhesive Modified Modified 20 20 20 15 20 10 20 10 layer polyolefin- PE1 (III) based resin Modified (b) PE2 Cyclic 8007F 39.2 polyolefin- 7010F based resin 6013F 39.2 39.2 39.2 (c) 5013F Unmodified UF320 40.8 40.8 40.8 polyolefin- NC566A 40.8 based resin (d) Resin Polyolefin- NF444A 100 20 80 36 100 30 100 20 layer based resin LE306 20 (V) (e) UF320 Cyclic 7010F polyolefin- based resin (c) Total thickness μm 100 110 100 70 Thickness ratio R — 0.40 0.27 0.20 0.29 Tg of cyclic polyolefin- ° C. 138 138 78 138 based resin (c) Viscosity ratio Rη — 3.1 3.1 1.2 3.1 Low curling properties ◯ ◯ ◯ ◯ Amount of shift L mm 16 5 ≥25 ≥25 Elmendorf tear N/mm 10 8 22 12 strength (TD) Readily linearly — ⊚ ⊚ ◯ ◯ tearable property evaluation Example 12 Example 13 Example 14 Raw Blend- Thick- Blend- Thick- Blend- Thick- material ing ness ing ness ing ness Layer structure name (wt %) (μm) (wt %) (μm) (wt %) (μm) Resin Polyolefin- NF444A 100 20 80 47 layer based resin LE306 20 (IV) (e) UF320 Cyclic 7010F polyolefin- based resin (c) Adhesive Modified Modified 20 10 20 4 layer polyolefin- PE1 (II) based resin Modified (b) PE2 Cyclic 8007F polyolefin- 7010F based resin 6013F 39.2 (c) 5013F 39.2 Unmodified UF320 40.8 polyolefin- NC566A 40.8 based resin (d) Barrier Polar resin PA6/66 100 10 100 20 layer (I) (a) copolymer EVOH 100 8 Adhesive Modified Modified 20 10 20 4 20 20 layer polyolefin- PE1 (III) based resin Modified (b) PE2 Cyclic 8007F polyolefin- 7010F based resin 6013F 39.2 39.2 (c) 5013F 39.2 Unmodified UF320 40.8 40.8 polyolefin- NC566A 40.8 based resin (d) Resin Polyolefin- NF444A 100 20 80 47 100 20 layer based resin LE306 20 (V) (e) UF320 Cyclic 7010F polyolefin- based resin (c) Total thickness μm 70 110 60 Thickness ratio R — 0.29 0.07 0.33 Tg of cyclic polyolefin- ° C. 134 138 138 based resin (c) Viscosity ratio Rη — 1.3 3.1 3.1 Low curling properties ◯ ◯ ◯ Amount of shift L mm ≥25 ≥25 13 Elmendorf tear N/mm 23 14 17 strength (TD) Readily linearly — ◯ ◯ ⊚ tearable property evaluation

TABLE-US-00003 TABLE 3 Comparative Comparative Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Raw Blend- Thick- Blend- Thick- Blend- Thick- Blend- Thick- Blend- Thick- Blend- Thick- material ing ness ing ness ing ness ing ness ing ness ing ness Layer structure name (wt %) (μm) (wt %) (μm) (wt %) (μm) (wt %) (μm) (wt %) (μm) (wt %) (μm) Resin Polyolefin- NF444A 100 30 100 30 80 47 40 20 40 30 40 30 layer based resin LE306 20 (IV) (e) UF320 30.6 30.6 30.6 Cyclic 7010F 29.4 29.4 29.4 polyolefin- based resin (c) Ad- Modified Modified 20 10 20 30 4 20 30 5 hesive polyolefin- PE1 layer based resin Modified 100 100 100 100 (II) (b) PE2 Cyclic 8007F polyolefin- 7010F based resin 6013F (c) 5013F Unmodified UF320 80 80 polyolefin- NC566A based resin (d) Barrier Polar resin PA6/66 100 20 100 30 100 20 100 30 100 30 layer (a) copolymer (I) EVOH 100 8 Ad- Modified Modified 20 10 20 30 4 20 30 5 hesive polyolefin- PE1 layer based resin Modified 100 100 100 100 (III) (b) PE2 Cyclic 8007F polyolefin- 7010F based resin 6013F (c) 5013F Unmodified UF320 80 80 polyolefin- NC566A based resin (d) Resin Polyolefin- NF444A 100 30 100 30 80 47 40 20 40 30 40 30 layer based resin LE306 20 (V) (e) UF320 30.6 30.6 30.6 Cyclic 7010F 29.4 29.4 29.4 polyolefin- based resin (c) Total thickness μm 100 150 110 100 150 100 Thickness ratio R — 0.20 0.40 0.07 0.40 0.40 0.10 Tg of cyclic ° C. — — — 110 110 110 polyolefin- based resin (c) Viscosity ratio Rη — — — — — — — Low curling ○ ○ ○ ○ ○ ○ properties Amount of shift L mm ≥25 ≥25 ≥25 ≥25 ≥25 ≥25 Elmendorf tear N/mm 41 38 41 82 94 59 strength (TD) Readily linearly — × × × × × × tearable property evaluation

Example 15 and Comparative Example 7

[0184] Using the PA6/66 copolymer in the barrier layer (I), Example 15 of the present invention (identical to Example 5 described above) and Comparative Example 7 having adhesive layers (II) and (III) formed only from a typical adhesive resin containing no cyclic olefin-based resin are shown as a comparison.

[0185] For each, using the used raw materials described above and resin types and layer structure shown in Table 3, a five-layered inflation film which was obtained by laminating in the order of resin layer (IV)/adhesive layer (II)/barrier layer (I)/adhesive layer (III)/resin layer (V) by the co-extrusion air-cooled inflation method described in (2-1) above was obtained. The evaluation results are shown in Table 4.

Example 16 and Comparative Example 8

[0186] Using the ethylene-vinyl alcohol resin in the barrier layer (I), Example 16 of the present invention and Comparative Example 8 (identical to Comparative Example 3 described above) having adhesive layers (II) and (III) formed only from a typical adhesive resin containing no cyclic olefin-based resin are shown as a comparison.

[0187] For each, using the used raw materials described above and resin types and layer structure shown in Table 3, a five-layered inflation film which was obtained by laminating in the order of resin layer (IV)/adhesive layer (II)/barrier layer (I)/adhesive layer (III)/resin layer (V) by the co-extrusion air-cooled inflation method described in (2-1) above was obtained. The evaluation results are shown in Table 4.

TABLE-US-00004 TABLE 4 Comparative Comparative Example 15 Example 7 Example 16 Example 8 Raw Blend- Thick- Blend- Thick- Blend- Thick- Blend- Thick- material ing ness ing ness ing ness ing ness Layer structure name (wt %) (μm) (wt %) (μm) (wt %) (μm) (wt %) (μm) Resin Polyolefin- NF444A 100 30 100 30 80 43 80 47 layer based resin LE306 20 20 (IV) (e) UF320 Cyclic 7010F polyolefin- based resin (c) Adhesive Modified Modified 20 10 20 10 20 8 4 layer polyolefin- PE1 (II) based resin Modified 100 (b) PE2 Cyclic 8007F polyolefin- 7010F based resin 6013F 39.2 39.2 (c) 5013F Unmodified UF320 40.8 80 40.8 polyolefin- NC566A based resin (d) Barrier Polar resin PA6/66 100 10 100 10 layer (I) (a) copolymer EVOH 100 8 100 8 Adhesive Modified Modified 20 10 20 10 20 8 4 layer polyolefin- PE1 (III) based resin Modified 100 (b) PE2 Cyclic 8007F polyolefin- 7010F based resin 6013F 39.2 39.2 (c) 5013F Unmodified UF320 40.8 80 40.8 polyolefin- NC566A based resin (d) Resin Polyolefin- NF444A 100 30 100 30 80 43 40 47 layer based resin LE306 20 (V) (e) UF320 30.6 Cyclic 7010F 29.4 polyolefin- based resin (c) Total thickness μm 90 90 110 110 Tensile elastic MPa 430 220 510 380 modulus (MD) Tensile elastic MPa 360 230 450 390 modulus (TD) Elemndorf tear N/mm 13 79 8 41 strength (TD) Degree of water g/(m.sup.2 .Math. day) 4.5 5.7 2.6 3.1 vapor permeation

Evaluation

[0188] As is clear from Tables 1 to 3, the five-layered films of Comparative Examples 1 to 3 had a large amount of shift at the time of TD tearing as well as a high tear strength because no cyclic olefin-based resin was used. Furthermore, the five-layered films of Comparative Examples 4 to 6 had a large amount of shift at the time of TD tearing as well as a high tear strength because, although the cyclic olefin-based resin was used, the cyclic olefin-based resin was contained in layers that are not adjacent to the barrier layer. It is conceived that this is because, due to the certain distance between the cyclic olefin-based resin-containing layer and the barrier layer, breakage of the cyclic olefin-based resin-containing layer exhibiting the readily linearly tearable properties did not spread sufficiently to the barrier layer.

[0189] On the other hand, Examples 1 to 13 based on the present invention each had a low tear strength and excellent readily tearable properties because the adhesive layers containing the cyclic olefin-based resin and the modified polyolefin-based resin, which are the characteristics of the present invention, are used in both of the layers adjacent to the barrier layer. Based on a comparison with Comparative Examples 4 to 6 described above, it is conceived that, from the perspective of readily tearable properties, it is important to contain the cyclic olefin-based resin in the layers adjacent to the barrier layer. Furthermore, as is clear from Example 1 and Example 10, when the glass transition temperature of the cyclic olefin-based resin was 100° C. or higher, and preferably 115° C. or higher, excellent linearly tearable properties as well as excellent readily tearable properties are achieved. Furthermore, as is clear from Example 7, Example 11, and Example 12, by selecting the unmodified polyolefin-based resin (d) having the particular MFR region, excellent linearly tearable properties as well as excellent readily tearable properties are achieved. For these glass transition temperature of the cyclic olefin-based resin and the MFR of the unmodified polyolefin-based resin, by using a resin component having the particular region, the morphology advantageous for the readily linearly tearable properties can be formed. In addition, as is clear from Example 9 and Example 13, by setting the thickness ratio of the adhesive layers relative to the entire film to the particular ratio or greater, excellent linearly tearable properties as well as excellent readily tearable properties are achieved. This is because the breakage behavior of the cyclic olefin-based resin-containing layer exhibiting the readily linearly tearable properties indicates the critical point that controls the tearing behavior as the entire film.

[0190] Example 14 used the adhesive layer (III) at least containing the modified polyolefin-based resin and the cyclic olefin-based resin having the glass transition temperature of 115° C. or higher in the layer adjacent to the barrier layer. Although the low curling properties was not sufficient because the barrier layer (I) was the surface layer, a layered body having excellent readily tearable properties and linearly tearable properties was obtained.

[0191] Based on a comparison of Example 15 and Comparative Example 7 and Example 16 and Comparative Example 8, when the layered bodies of the present invention and the layered bodies containing no cyclic olefin-based resins in the adhesive layers are compared, it is confirmed that the layered bodies of Examples of the present application each had a higher tensile elastic modulus in the MD and the TD, superior rigidity, readily tearable properties because each of Examples of the present application had a lower Elmendorf tear strength (TD), and superior water vapor barrier properties because the each of Examples of the present application had a lower water vapor permeation.

[0192] From these described above, Examples 1 to 16 based on the present invention exhibited excellent readily tearable properties as well as excellent barrier properties because the barrier layer was contained, and Examples 1 to 9 further exhibited excellent linearly tearable properties. Therefore, the present invention is suitable for readily tearable barrier film and readily tearable packaging material to which readily linearly tearable properties and easy opening are required.