ADHESIVE, ADHESIVE RESIN COMPOSITION AND LAMINATE COMPRISING IT

Abstract

To provide an adhesive excellent in adhesion to a thermoplastic resin and an ethylene/vinyl alcohol copolymer.

An adhesive comprising a hydrolyzate of a resin composition containing a thermoplastic resin (A), a copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester having a vinyl ester and/or acrylic acid ester content higher by at least 5 mol % than (A); and a modified product having (A) grafted by (B), and an adhesive resin composition comprising it.

Claims

1. An adhesive comprising a hydrolysate of a resin composition containing a thermoplastic resin (A), a copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester having a vinyl ester and/or acrylic acid ester content higher by at least 5 mol % than (A), and a modified product having (A) grafted by (B).

2. The adhesive according to claim 1, wherein the dispersed particle size of the resin containing (A) or (B) is from 0.01 to 50 m.

3. The adhesive according to claim 1, wherein the thermoplastic resin (A) contains at least one member of a homopolymer and a copolymer of a C.sub.2-12 -olefin.

4. The adhesive according to claim 1, wherein the thermoplastic resin (A) contains at least one copolymer of ethylene and a vinyl ester and/or an acrylic acid ester having a vinyl ester and/or acrylic acid ester content lower by at least 5 mol % than the copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester.

5. The adhesive according to claim 1, wherein the copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester has a vinyl ester and/or acrylic acid ester content of from 5 to 35 mol %.

6. The adhesive according to claim 1, which contains a crosslinking agent (C).

7. The adhesive according to claim 1, which has a vinyl alcohol content of from 0.5 to 40 mol % and a vinyl ester and/or acrylic acid ester content of at most 30 mol %.

8. An adhesive resin composition comprising the adhesive as defined in claim 1 and a polyvinyl alcohol and/or ethylene/vinyl alcohol copolymer which satisfies the following requirement (1): (1) an ethylene content of at most 55 mol %.

9. An adhesive resin composition comprising the adhesive as defined in claim 1 and a polyolefin.

10. A laminate comprising a layer formed from the adhesive as defined in claim 1, and at least one layer formed from another material.

11. The laminate according to claim 10, wherein another material is an ethylene/vinyl alcohol copolymer.

12. The laminate according to claim 10, wherein another material is a thermoplastic resin (A).

13. A laminate comprising a layer containing an ethylene/vinyl alcohol copolymer, a layer formed from the adhesive as defined in claim 1, and a layer containing a thermoplastic resin (A), laminated in this order.

14. A laminate comprising a layer formed from the adhesive resin composition as defined in claim 8 and a layer containing a polyolefin laminated on both sides of the above layer.

15. A laminate comprising a layer containing a polyvinyl alcohol and/or ethylene/vinyl alcohol copolymer and a layer containing the adhesive resin composition as defined in claim 9 laminated on both sides of the above layer.

16. A blow molded product comprising the laminate as defined in claim 10.

17. A sheet formed product comprising the laminate as defined in claim 10.

18. A film formed product comprising the laminate as defined in claim 10.

Description

EXAMPLES

[0067] Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted to such specific Examples.

[Saponification Degree]

[0068] The adhesives obtained in Examples were subjected to measurement in accordance with JIS K7192 (1999).

[Dispersed Particle Size]

[0069] Each of the adhesives obtained in Examples was subjected to press forming using a 50 t automatic pressing machine manufactured by SHINTO Metal Industries Corporation. Then, a cross section of the press formed product was adjusted by a Cryomicrotome (manufactured by RMC-Boeckeler, Ultramicrotome MT-XL+CR-X), and the adjusted surface was subjected to Ar plasma etching (2 W, 10 min), The etched surface was subjected to Os coating, and then the dispersed particle size was evaluated by SEM observation (manufactured by Keyence Corporation, SEM VE-9800).

[Adhesive Strength]

[0070] Adhesion of each of the adhesives obtained in Examples to adherends (LDPE or PP and EVOH) was examined. The adhesive strength was evaluated as follows. About 4 g of pellets were subjected to press forming using a 50 t automatic pressing machine manufactured by SHINTO Metal Industries Corporation. The size of the formed product was 150 mm150 mm0.1 mm. Then, the adherends were heat-sealed with the adhesive using a hot tack tester manufactured by TESTER SANGYO CO., Ltd., at a sealing temperature of 200 C. under a sealing pressure of 0.1 MPa for a sealing time of 1 second by sandwich heating, and the adhesive strength (N/15 mm width) by 180 peeling was measured using a tensile tester (manufactured by ORIENTEC CORPORATION, TENSILON RTE-1210) with a sample width of 15 mm at a tensile rate of 300 mm/min. LOPE, PP, PS and EVOH used for evaluation were as follows.

[0071] (1) LOPE: low density polyethylene having a melt mass flow rate of 7 g/10 min and a density of 922 kg/m.sup.3 (manufactured by Tosoh Corporation, tradename: PETROTHENE 204)

[0072] (2) PP: polypropylene having a melt mass flow rate of 6.5 g/10 min and a density of 900 kg/m.sup.3 (manufactured by Japan Polypropylene Corporation, tradename: NOVATEC FW4BT)

[0073] (3) PS: polystyrene having a melt mass flow rate of 2.4 g/10 min (manufactured by DIC Corporation, tradename: GH-8300-1)

[0074] (4) EVOH: an ethylene/vinyl alcohol copolymer having a melt mass flow rate of 5.7 g/10 min, and an ethylene content of 44 mol % (manufactured by Kuraray Co., Ltd., tradename: EVAL E105B)

Example 1

[0075] 70 parts by weight of a low density polyethylene having a melt mass flow rate of 16 g/10 min and a density of 920 kg/m.sup.3 (manufactured by Tosoh Corporation, tradename: PETROTHENE 350) as the thermoplastic resin composition (A), 30 parts by weight of an ethylene/vinyl acetate copolymer having a melt mass flow rate of 70 g/10 min, a density of 968 kg/m.sup.3 and a vinyl acetate content of 42 wt % (manufactured by Tosoh Corporation, tradename: Ultrathene 760, hereinafter referred to simply as EVA) as the copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester, and 0.1 part by weight of an organic peroxide (manufactured by NOF Corporation, tradename: PERHEXA 25B) as the crosslinking agent (C) were dry-blended, and melt-kneaded by a twin screw extruder at a molten resin temperature of 190 C. to obtain a graft product in the form of pellets. Then, the graft product was subjected to hydrolysis treatment at 60 C. in 1 part by weight of a sodium hydroxide methanol solution to obtain the present adhesive (saponification degree: 75 mol %, dispersed particle size: 0.1 to 2 m), Using the obtained adhesive, the adhesion to LOPE and to EVOH was evaluated, whereupon the results were as identified in Table 1.

Example 2

[0076] The present adhesive (saponification degree: 75 mol %, dispersed particle size: unmeasurable) was obtained in the same manner as in Example 1 except that 50 parts by weight of a low density polyethylene having a melt mass flow rate of 16 g/10 min and a density of 920 kg/m.sup.3 (manufactured by Tosoh Corporation, tradename: PETROTHENE 350) as the thermoplastic resin composition (A) and 50 parts by weight of an ethylene/vinyl acetate copolymer having a melt mass flow rate of 70 g/10 min, a density of 968 kg/m.sup.3 and a vinyl acetate content of 42 wt % (manufactured by Tosoh Corporation, tradename: Ultrathene 760) as the copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester were used. Evaluation was made using the obtained adhesive, whereupon the results are as identified in Table 1.

Example 3

[0077] The present adhesive (saponification degree: 75 mol %, dispersed particle size: 0.1 to 2 m) was obtained in the same manner as in Example 1 except that 30 parts by weight of a low density polyethylene having a melt mass flow rate of 16 g/10 min and a density of 920 kg/m.sup.3 (manufactured by Tosoh Corporation, tradename: PETROTHENE 350) as the thermoplastic resin composition (A) and 70 parts by weight of an ethylene/vinyl acetate copolymer having a melt mass flow rate of 70 g/10 min, a density of 968 kg/m.sup.3, and a vinyl acetate content of 42 wt % (manufactured by Tosoh Corporation, tradename: Ultrathene 760) as the copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester were used. Evaluation was made using the obtained adhesive, whereupon the results are as identified in Table 1.

Example 4

[0078] The present adhesive (saponification degree: 75 mol %, dispersed particle size: 0.1 to 2 m) was obtained in the same manner as in Example 1 except that 70 parts by weight of a low density polyethylene having a melt mass flow rate of 20 g/10 min and a density of 920 kg/m.sup.3 (manufactured by Tosoh Corporation, tradename: Nipolon-L M65, hereinafter referred to simply as LLDPE) as the thermoplastic resin composition (A) and 30 parts by weight of an ethylene/vinyl acetate copolymer having a melt mass flow rate of 70 g/10 min, a density of 968 kg/m.sup.3 and a vinyl acetate content of 42 wt % (manufactured by Tosoh Corporation, tradename: Ultrathene 760) as the copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester were used. Evaluation was made using the obtained adhesive, whereupon the results are as identified in Table 1.

Example 5

[0079] The present adhesive (saponification degree: 75 mol %, dispersed particle size: 0.1 to 2 m) was obtained in the same manner as in Example 1 except that 70 parts by weight of a polypropylene having a melt mass flow rate of 6.5 g/10 min and a density of 900 kg/m.sup.3 (manufactured by Japan Polypropylene Corporation, tradename: NOVATEC FW4BT, hereinafter referred to simply as PP) as the thermoplastic resin composition (A) and 30 parts by weight of an ethylene/vinyl acetate copolymer having a melt mass flow rate of 70 g/10 min, a density of 968 kg/m.sup.3 and a vinyl acetate content of 42 wt % (manufactured by Tosoh Corporation, tradename: Ultrathene 760) as the copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester were used. Evaluation was made using the obtained adhesive, whereupon the results are as identified in Table 1.

Example 6

[0080] The present adhesive (saponification degree: 20 mol %, dispersed particle size: 0.1 to 2 m) was obtained in the same manner as in Example 1 except that 70 parts by weight of an ethylene/vinyl acetate copolymer having a melt mass flow rate of 14/10 min, a density of 935 kg/m.sup.3 and a vinyl acetate content of 15 wt % (manufactured by Tosoh Corporation, tradename: Ultrathene 625) as the thermoplastic resin composition (A), 30 parts by weight of an ethylene/vinyl acetate copolymer having a melt mass flow rate of 70 g/10 min, a density of 968 kg/m.sup.3 and a vinyl acetate content of 42 wt % (manufactured by Tosoh Corporation, tradename: Ultrathene 760) as the copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester and 0.001 part by weight of an organic peroxide (manufactured by NOF Corporation, tradename: PERHEXA C) as the crosslinking agent (C) were dry-blended. Evaluation was made using the obtained adhesive, whereupon the results are as identified in Table 1.

Example 7

[0081] The present adhesive (saponification degree: 20 mol %, dispersed particle size: 0.1 to 2 m) was obtained in the same manner as in Example 6 except that 0.1 part by weight of the crosslinking agent (0-2) was added. Evaluation was made using the obtained adhesive, whereupon the results are as identified in Table 1.

Example 8

[0082] The present adhesive (saponification degree: 25 mol %, dispersed particle size: 0.1 to 2 m) was obtained in the same manner as in Example 1 except that 70 parts by weight of an ethylene/vinyl acetate copolymer having a melt mass flow rate of 14 g/10 min, a density of 935 kg/m.sup.3 and a vinyl acetate content of 15 wt % (manufactured by Tosoh Corporation, tradename: Ultrathene 625) as the thermoplastic resin composition (A), 30 parts by weight of an ethylene/vinyl acetate copolymer having a vinyl acetate content of 70 wt % (manufactured by The Nippon Synthetic Chemical Industry Co., Ltd., tradename: Soarblen DH) as the copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester and 0.1 part by weight of the crosslinking agent (C-2) were dry-blended. Evaluation was made using the obtained adhesive, whereupon the results are as identified in Table 1.

Example 9

[0083] The present adhesive (saponification degree: 40 mol %, dispersed particle size: 0.1 to 2 m) was obtained in the same manner as in Example 1 except that 70 parts by weight of an ethylene/vinyl acetate copolymer having a melt mass flow rate of 5:7/10 min, a density of 952 kg/m.sup.3 and a vinyl acetate content of 28 wt % (manufactured by Tosoh Corporation, tradename: Ultrathene 751) as the thermoplastic resin composition (A) and 30 parts by weight of an ethylene/vinyl acetate copolymer having a melt mass flow rate of 70 g/10 min, a density of 968 kg/m.sup.3 and a vinyl acetate content of 42 wt % (manufactured by Tosoh Corporation, tradename: Ultrathene 760) were used. Evaluation was made using the obtained adhesive, whereupon the results are as identified in Table 1.

Example 10

[0084] The present adhesive (saponification degree: 40 mol %, dispersed particle size: 0.1 to 2 m) was obtained in the same manner as in Example 1 except that 30 parts by weight of a hydrogenated styrene thermoplastic elastomer having a melt mass flow rate of 65 g/10 min (200 C., 5.0 kg) (manufactured by Kraton Corporation, tradename: KRATON G: G1726) as the thermoplastic resin composition (A) and 70 parts by weight of an ethylene/vinyl acetate copolymer having a melt mass flow rate of 70 g/10 min, a density of 968 kg/m.sup.3 and a vinyl acetate content of 42 wt % (manufactured by Tosoh Corporation, tradename: Ultrathene 760) were used. Evaluation was made using the obtained adhesive, whereupon the results are as identified in Table 1.

TABLE-US-00001 TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Loss angle of adhesive under 500 Pa 78 76 75 79 77 80 70 68 65 76 Adhesive strength To EVOH 15 16 20 16 15 6 14 19 18 10 (N/15 mm width) To LDPE, 20 17 15 24 22 14 11 7 6 8 To PP, or To PS

Comparative Example 1

[0085] The present adhesive (saponification degree: 70 mol %) was obtained in the same manner as in Example 1 except that 0.1 part by weight of the crosslinking agent (C-1) was dry-blended with a low density polyethylene having a melt mass flow rate of 16 g/10 min and a density of 920 kg/m.sup.3 (manufactured by Tosoh Corporation, tradename: PETROTHENE 350) as the thermoplastic resin composition. Evaluation was made using the obtained adhesive, whereupon the adhesion to EVOH was low. The results are shown in Table 2.

Comparative Example 2

[0086] The present adhesive (saponification degree: 70 mol %) was obtained in the same manner as in Example 1 except that 0.1 part by weight of the crosslinking agent (C-2) was dry-blended with an ethylene/vinyl acetate copolymer having a melt mass flow rate of 70 g/10 min, a density of 968 kg/m.sup.3 and a vinyl acetate content of 42 wt % (manufactured by Tosoh Corporation, tradename: Ultrathene 760) as the copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester. Evaluation was made using the obtained adhesive, whereupon the adhesion to EVOH was low. The results are shown in Table 2.

Comparative Example 3

[0087] The present adhesive (saponification degree: 75 mol %) was obtained in the same manner as in Example 1 except that no crosslinking agent was used. Evaluation was made using the obtained adhesive, whereupon the adhesion to EVOH was low. The results are shown in Table 2.

Comparative Example 4

[0088] The present adhesive (saponification degree: 0 mol %) was obtained in the same manner as in Example 1 except that no hydrolysis treatment was conducted. Evaluation was made using the obtained adhesive, whereupon the adhesion to EVOH was low. The results are shown in Table 2.

TABLE-US-00002 TABLE 2 Comp. Comp. Comp. Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Loss angle of adhesive 79 70 84 79 under 500 Pa Adhesive strength To EVOH 0.5 10 0.5 1.2 (N/15 mm width) To LDPE, 13 0.4 12 14 To PP, or To PS

Example 11

[0089] 75 Parts by weight of adhesive 1 produced by the following production method, and 25 parts by weight of an ethylene/vinyl alcohol copolymer having a melt mass flow rate of 5.4 g/10 min and an ethylene content of 44 mol % (manufactured by Kuraray Co., Ltd., tradename: E-105B, hereinafter referred to as EVOH 1) were dry-blended and charged into a labo plastomill set at 200 C., and kneading was started. 3 Minutes after initiation of kneading, kneading was completed, and the kneaded product was cooled to room temperature to obtain an adhesive resin composition. Using the obtained adhesive resin composition, adhesion to LDPE was evaluated, whereupon the result was as identified in Table 3.

[Method for Producing Adhesive 1]

[0090] 70 Parts by weight of a high pressure low density polyethylene having a melt mass flow rate of 45 g/10 min and a density of 924 kg/m.sup.3 (manufactured by Tosoh Corporation, tradename: PETROTHENE 209, hereinafter referred to as (A-1)), 30 parts by weight of an ethylene/vinyl acetate copolymer having a melt mass flow rate of 70 g/10 min, a density of 968 kg/m.sup.3 and a vinyl acetate content of 42 wt % (19 mol %) (manufactured by Tosoh Corporation, tradename: Ultrathene 760, hereinafter referred to as (B)) as the copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester, and 0.1 part by weight of an organic peroxide (manufactured by NOF Corporation, tradename: PERHEXA 25B) were dry-blended, and melt-kneaded by a twin screw extruder at a molten resin temperature of 190 C. to obtain a sample in the form of pellets. Then, the sample was subjected to hydrolysis treatment at 60 C. in a 1 wt % sodium hydroxide methanol solution to obtain the present adhesive (saponification degree of copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester of 50 mol %).

Example 12

[0091] An adhesive resin composition was produced in the same manner as in Example 11 except that 50 parts by weight of the adhesive 1 and 50 parts by weight of EVOH 1 were used, and adhesion of the obtained adhesive resin composition to LOPE was evaluated, whereupon the result was as identified in Table 3.

Example 13

[0092] An adhesive resin composition was produced in the same manner as in Example 11 except that 30 parts by weight of the adhesive 1 and 70 parts by weight of EVOH 1 were used, and adhesion of the obtained adhesive resin composition to LOPE was evaluated, whereupon the result was as identified in Table 3.

Example 14

[0093] An adhesive resin composition was produced in the same manner as in Example 11 except that 50 parts by weight of the adhesive 1 and 50 parts by weight of an ethylene/vinyl alcohol copolymer having a melt mass flow rate of 1.7 g/10 min and an ethylene content of 32 mol % (manufactured by Kuraray Co., Ltd., tradename: F-171B, hereinafter referred to as EVOH 2) were used, and the adhesion of the obtained adhesive resin composition to LOPE was evaluated, whereupon the result was as identified in Table 3.

Example 15

[0094] An adhesive resin composition was produced in the same manner as in Example 11 except that 50 parts by weight of adhesive 2 produced by the following production method and 50 parts by weight of EVOH 1 were used, and the adhesion of the obtained adhesive resin composition to LOPE was evaluated, whereupon the result was as identified in Table 3.

[Method for Producing Adhesive 2]

[0095] The present adhesive (saponification degree of copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester of 50 mol %) was produced in the same manner as in the production of the adhesive 1 except that 30 parts by weight of (A-1) and 70 parts by weight of (B) were used.

Example 16

[0096] An adhesive resin composition was produced in the same manner as in Example 11 except that 50 parts by weight of adhesive 3 produced by the following production method and 50 parts by weight of EVOH 1 were used, and the adhesion of the obtained adhesive resin composition to LDPE was evaluated, whereupon the result was as identified in Table 3.

[Method for Producing Adhesive 3]

[0097] The present adhesive (saponification degree of copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester of 50 mol %) was produced in the same manner as in the production of the adhesive 1 except that 70 parts by weight of an ethylene/vinyl acetate copolymer having a melt mass flow rate of 14 g/10 min, a density of 935 kg/m.sup.3 and a vinyl acetate content of 15 wt % (5.4 mol %) (manufactured by Tosoh Corporation, tradename: Ultrathene 625) was used instead of (A-1) and 30 parts by weight of (B) was used.

TABLE-US-00003 TABLE 3 Ex. Ex. Ex. Ex. Ex. Ex. 11 12 13 14 15 16 Adhesive Adhesive 1 75 50 30 50 Adhesive 2 50 Adhesive 3 50 EVOH EVOH 1 25 50 70 50 50 EVOH 2 50 Adhesive strength (N/15 10 8 3 8 5 8 mm width) to LDPE

Comparative Example 5

[0098] An adhesive resin composition was produced in the same manner as in Example 1 except that EVOH 1 was used, and the adhesion of the obtained adhesive resin composition to LDPE was evaluated, whereupon the result was as identified in Table 4.

Comparative Example 6

[0099] An adhesive resin composition was produced in the same manner as in Example 11 except that 50 parts by weight of adhesive 4 produced by the following production method and 50 parts by weight of EVOH 1 were used, and the adhesion of the obtained adhesive resin composition to LOPE was evaluated, whereupon the result was as identified in Table 4.

[Method for Producing Adhesive 4]

[0100] Adhesive 4 (saponification degree of copolymer (B) of ethylene and a vinyl ester and/or an acrylic acid ester of 50 mol %) was produced in the same manner as in the production of the adhesive 1 except that 100 parts by weight of (B) was used.

Comparative Example 7

[0101] An adhesive resin composition was produced in the same manner as in Example 11 except that 50 parts by weight of adhesive 5 produced by the following production method and 50 parts by weight of EVOH 1 were used, and the adhesion of the obtained adhesive resin composition to LDPE was evaluated, whereupon the result was as identified in Table 4.

[Method for Producing Adhesive 5]

[0102] Adhesive 5 was produced in the same manner as in the production of the adhesive 1 except that 100 parts by weight of (A-1) was used.

Comparative Example 8

[0103] An adhesive resin composition was produced in the same manner as in Example 1 except that 50 parts by weight of adhesive 6 produced by the following production method and 50 parts by weight of EVOH 1 were used, and the adhesion of the obtained adhesive resin composition to LDPE was evaluated, whereupon the result was as identified in Table 4.

[Method for Producing Adhesive 6]

[0104] Adhesive 6 was produced in the same manner as in the production of the adhesive 1 except that the graft product was not subjected to a hydrolysis treatment.

TABLE-US-00004 TABLE 4 Comp. Comp. Comp. Comp. Ex. 5 Ex. 6 Ex. 7 Ex. 8 Adhesive Adhesive 1 0 Adhesive 4 50 Adhesive 5 50 Adhesive 6 50 EVOH EVOH 1 100 50 50 50 EVOH 2 Adhesive strength 0.5 0.5 0.6 0.3 (N/15 mm width) to LDPE

Example 17

[0105] 75 Parts by weight of adhesive 1 described in Example 11 and 25 parts by weight of a high pressure low density polyethylene having a melt mass flow rate of 3 g/10 min and a density of 924 kg/m.sup.3 (manufactured by Tosoh Corporation, tradename: PETROTHENE 205, hereinafter referred to as LOPE (MFR3)) were dry-blended and charged into a labo plastomill set at 200 C., and kneading was started, 3 Minutes after initiation of kneading, kneading was completed, and the kneaded product was cooled to room temperature to obtain an adhesive resin composition. The adhesion of the obtained adhesive resin composition to EVOH and LOPE was evaluated, whereupon the results were as identified in Table 5.

Example 18

[0106] An adhesive resin composition was produced in the same manner as in Example 17 except that 50 parts by weight of adhesive 1 described in Example 11 and 50 parts by weight of LOPE (MFR3) were used, and the adhesion of the obtained adhesive resin composition to EVOH and LOPE was evaluated, whereupon the results were as identified in Table 5.

Example 19

[0107] An adhesive resin composition was produced in the same manner as in Example 17 except that 40 parts by weight of adhesive 1 described in Example 11 and 60 parts by weight of LOPE (MFR3) were used, and the adhesion of the obtained adhesive resin composition to EVOH and LOPE was evaluated, whereupon the results were as identified in Table 5.

Example 20

[0108] An adhesive resin composition was produced in the same manner as in Example 17 except that 50 parts by weight of adhesive 1 described in Example 11 and 50 parts by weight of a high pressure low density polyethylene having a melt mass flow rate of 8 g/10 min and a density of 919 kg/m.sup.3 (manufactured by Tosoh Corporation, tradename: PETROTHENE 203, hereinafter referred to as LOPE (MFR8)) were used, and the adhesion of the obtained adhesive resin composition to EVOH and LOPE was evaluated, whereupon the results were as identified in Table 5.

Example 21

[0109] An adhesive resin composition was produced in the same manner as in Example 17 except that 50 parts by weight of adhesive 2 described in Example 15 and 50 parts by weight of LOPE (MFR3) were used, and the adhesion of the obtained adhesive resin composition to EVOH and LOPE was evaluated, whereupon the results were as identified in Table 5.

Example 22

[0110] An adhesive resin composition was produced in the same manner as in Example 17 except that 75 parts by weight of adhesive 3 described in Example 16 and 25 parts by weight of LOPE (MFR3) were used, and the adhesion of the obtained adhesive resin composition to EVOH and LOPE was evaluated, whereupon the results were as identified in Table 5.

TABLE-US-00005 TABLE 5 Ex. Ex. Ex. Ex. Ex. Ex. 17 18 19 20 21 22 Adhesive Adhesive 1 75 50 40 50 Adhesive 2 50 Adhesive 3 75 Polyolefin LDPE (MFRS) 25 50 60 50 25 LDPE (MFRS) 50 Adhesive strength (N/15 4 2.5 2 3 7 6 mm width) to EVOH Adhesive strength (N/15 12 12 12 12 3 10 mm width) to LDPE

Comparative Example 9

[0111] An adhesive resin composition was produced in the same manner as in Example 17 except that LDPE (MFR3) was used, and the adhesion of the obtained adhesive resin composition to EVOH and LDPE was evaluated, whereupon the results were as identified in Table 6.

Comparative Example 10

[0112] An adhesive resin composition was produced in the same manner as in Example 17 except that 50 parts by weight of adhesive 4 described in Comparative Example 6 and 50 parts by weight of LDPE (MFR3) were used, and the adhesion of the obtained adhesive resin composition to LOPE was evaluated, whereupon the result was as identified in Table 6.

Comparative Example 11

[0113] An adhesive resin composition was produced in the same manner as in Example 17 except that 50 parts by weight of adhesive 5 described in Comparative Example 7 and 50 parts by weight of LOPE (MFR3) were used, and the adhesion of the obtained adhesive resin composition to LOPE was evaluated, whereupon the result was as identified in Table 6.

Comparative Example 12

[0114] An adhesive resin composition was produced in the same manner as in Example 17 except that 50 parts by weight of adhesive 6 described in Comparative Example 8 and 50 parts by weight of LOPE (MFR3) were used, and the adhesion of the obtained adhesive resin composition to LOPE was evaluated, whereupon the result was as identified in Table 6.

TABLE-US-00006 TABLE 6 Comp. Comp. Comp. Comp. Ex. 9 Ex. 10 Ex. 11 Ex. 12 Adhesive Adhesive 1 0 Adhesive 4 50 Adhesive 5 50 Adhesive 6 50 Polyolefin LDPE (MFR3) 100 50 50 50 LDPE (MFR8) Adhesive strength 0.5 5 0.5 0.3 (N/15 mm width) to EVOH Adhesive strength 12 0.5 12 12 (N/15 mm width) to LDPE

[0115] The entire disclosures of Japanese Patent Application No. 2016-100425 filed on May 19, 2016, Japanese Patent Application No. 2017-040422 filed on Mar. 3, 2017 and Japanese Patent Application No. 2017-041726 filed on Mar. 6, 2017 including specifications, claims and summaries are incorporated herein by reference in their entireties.