JPH03106979A - Resin composition for bonding and laminate made by using it as adhesive layer - Google Patents

Abstract

PURPOSE:To provide a resin composition for bonding, excellent in high- temperature adhesiveness, etc., by mixing a styrenic elastomer with a polyethylene grafted with a specified amount of an unsaturated carboxylic acid (derivative). CONSTITUTION:100 pts.wt. flexible polymer comprising a styrenic elastomer is mixed with 1-30 pts.wt. graft polyethylene partly or wholly grafted with 0.05-15wt.% unsaturated carboxylic acid (derivative) (e.g. maleic anhydride) to produce a resin composition for bonding. The use of this composition for bonding, for example, between a polyethylene terephthalate layer and a saponified ethylene/vinyl acetate copolymer layer can produce a laminate free from delamination even under high temperature conditions, for instance, when it is treated in a retort, having low gas permeability, and suitable for food packaging material, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to an adhesive resin composition and a laminate using this adhesive resin composition. The present invention relates to an adhesive resin composition that does not cause any damage, and a laminate using this adhesive resin composition that has excellent gas barrier properties and is also compatible with retort processing.

Technical background of the invention Polyester resins, represented by polyethylene terephthalate resin, have excellent mechanical strength, rigidity, heat resistance, chemical resistance, oil resistance, transparency, etc., and use these properties to produce films and sheets. It is also widely used as a packaging material for containers, etc. However, such polyester resins have high permeability to gases such as oxygen, so they are not suitable for foods,
It could not be used for packaging materials that require high gas permeability, such as for drugs and cosmetics.

Polycarbonate resin also has transparency, heat resistance,
Although it has excellent aroma retention properties, it has high permeability to gases such as oxygen, and cannot be used in packaging materials that require high gas permeability, particularly for foods.

In order to increase the gas permeation resistance of polyethylene terephthalate resin or polycarbonate resin, a resin with better gas permeation resistance than these resins, such as a saponified ethylene/vinyl acetate copolymer, is laminated onto the polyethylene terephthalate resin or polycarbonate resin. A method is proposed. However, the adhesion between polyethylene terephthalate resin or polycarbonate resin and saponified ethylene/vinyl acetate copolymer is not always sufficient, and parts of the product may peel off during lamination or use, resulting in a decrease in gas permeability and the product. There has been a problem in that the appearance or mechanical strength of the material may deteriorate.

In order to solve these problems, for example,
270155 and Japanese Patent Application No. 61-254, a graft-modified ethylene/α-olefin random copolymer graft-modified with an unsaturated carboxylic acid or its derivative is used as an intermediate adhesive layer, and a polycarbonate layer or a polyester A laminate is disclosed in which a saponified ethylene-vinyl acetate copolymer layer is bonded to the saponified ethylene-vinyl acetate copolymer layer. These laminates have excellent gas permeation resistance and excellent adhesion at room temperature. In such a case, the adhesive force may be reduced by heating, which causes the layer to peel off, resulting in a reduction in gas permeability.

Japanese Patent Laid-Open No. 64-45445, filed by the applicant, discloses an adhesive resin composition that does not reduce the adhesive strength of each layer of a laminate even after high-temperature treatment such as high-temperature filling or retort treatment. (a) Melt flow rate: 0.1 to 50 g/10 min Density: 0.850 to 0.900 g/aj Ethylene content: 75 to 95 mol% Crystallinity by X-rays = less than 30%, Ethylene α
- Olefin copolymer = 95-50% by weight (b) Melt flow rate: 0.1-50g/10 min Vinyl acetate content: 5-40% by weight Ethylene-vinyl acetate copolymer = 5-50 Weight %, and (c) grafting amount of unsaturated carboxylic acid or its derivative: 0.05 to 15 weight % Melt flow rate h: 0.1 to 50 g/10
Partial density: 0.900-0.980g/a Partially or wholly graft-modified polyethylene with JX-ray crystallinity of 30% or more (2) above (a) +
It consists of 1.0 to 30% by weight based on 100% by weight of the total weight of (b), and the grafting rate as a whole of the composition is 0.0%.
1 to 3% by weight, an MFR of 0.1 to 50 g/10 minutes, and a crystallinity of less than 35%, a polyester layer or a polycarbonate layer, and the adhesive resin A laminate comprising an intermediate layer made of a composition and a saponified olefin/vinyl acetate copolymer layer is disclosed.

However, although the above-mentioned adhesive resin composition has excellent adhesion at room temperature after high-temperature processing, the above-mentioned laminate sometimes causes delamination during high-temperature filling or retort processing. .

Therefore, it has been desired to develop an adhesive resin composition that can completely prevent delamination of the laminate even during high-temperature filling or retort processing.

Purpose of the Invention The present invention completely prevents delamination of a laminate during harsh processing such as high-temperature filling or retort processing while maintaining practical adhesive strength at room temperature after high-temperature processing. The object of the present invention is to provide an adhesive resin composition that has excellent heat-resistant adhesive properties at high temperatures.

In addition, the present invention has excellent gas permeability and is formed by bonding a polycarbonate layer or a polyalkylene terephthalate layer and an ethylene/vinyl acetate saponified layer using the adhesive resin composition as described above. The object is to provide a laminate that does not cause delamination during hot filling or retort processing.

Summary of the Invention The first adhesive resin composition according to the present invention is a partial or This adhesive resin composition contains 1 to 30 parts by weight of graft-modified polyethylene, and is characterized in that the soft polymer is a styrene elastomer.

The second adhesive resin composition according to the present invention is partially or entirely grafted with an unsaturated carboxylic acid or a derivative thereof in an amount of 0.05 to 15% by weight based on 100 parts by weight of the soft polymer. This is an adhesive resin composition containing 1 to 30 parts by weight of modified graft-modified polyethylene, and the soft polymer is (a) styrenic elastomer 2.
(b) ethylene/α-olefin copolymer with an ethylene content of 45 to 95 mol%: 80 to 100% by weight;
0% by weight.

The third adhesive resin composite according to the present invention has a grafting amount of 0.05 to 15% by weight of unsaturated carboxylic acid or its derivative based on 100 parts by weight of the soft polymer. This is an adhesive resin composition containing 1 to 30 parts by weight of graft-modified polyethylene, and the soft polymer is (a) styrenic elastomer 2.
and (c) an ethylene/vinyl acetate copolymer having a vinyl acetate content of 5 to 40% by weight (80 to 0% by weight).

The fourth adhesive resin composition according to the present invention is partially or entirely grafted with an unsaturated carboxylic acid or a derivative thereof in an amount of 0.05 to 15% by weight based on 100 parts by weight of the soft polymer. This is an adhesive resin composition containing 1 to 30 parts by weight of modified graft-modified polyethylene, and the soft polymer is (a) styrenic elastomer 2.
(b) an ethylene/α-olefin copolymer having an ethylene content of 45 to 95 mol%, 0 to 80% by weight;
and (c) an ethylene/vinyl acetate copolymer having a vinyl acetate content of 5 to 40% by weight (0 to 80% by weight).

The first laminate according to the present invention includes (I) a polyalkylene terephthalate resin layer, and (n)
It is characterized by comprising an adhesive layer made of the adhesive resin composition as described above, and (III) a saponified olefin/vinyl acetate copolymer layer.

The second laminate according to the present invention includes: (1) a polycarbonate resin layer; (II) an adhesive layer made of the adhesive resin composition as described above; and (III) a saponified olefin-vinyl acetate copolymer. It is characterized by being composed of layers.

DETAILED DESCRIPTION OF THE INVENTION The adhesive resin assembly and the laminate using the same according to the present invention will be specifically described below.

First, to explain the adhesive resin composition according to the present invention, this composition contains a styrene-based elastomer and graft-modified polyethylene as essential components, and in addition to these essential components, ethylene.
α-olefin copolymers and ethylene/vinyl acetate copolymers can be included. Each component will be explained in detail below.

Styrenic elastomer This styrenic elastomer generally has a polystyrene block and a rubber intermediate block, the polystyrene portion forms physical crosslinks (domains) and serves as a crosslinking point, and the intermediate rubber block imparts rubber elasticity to the product. . The styrenic elastomer used in the present invention is a block copolymer (SEBS) in which the soft segment in the middle is ethylene/butylene (H) and the hard segment at the end is polystyrene (s). Such a styrene elastomer is manufactured and sold by Shell Kagaku ■ under the trade name "Krayton G".

Graft-modified polyethylene This graft-modified polyethylene has the following properties.

Grafting amount of unsaturated carboxylic acid or its derivative: 0.
05-15% by weight, preferably o. i ~ 10% by weight Mefiw 7 o-L/ 1to (ASTM D I2
38, Condition E): Preferably 0.1 to 50 g/10 min, more preferably 0.3 to 30 g/10 min, density usually 0.900 to 0.980 g/1, preferably 0.90
5-0.970g/cj Crystallinity by X-ray: Usually 30
% or more, preferably 35 to 75% In this graft-modified polyethylene, part or all of the polyethylene is graft-modified.

Optionally, the graft-modified polyethylene comprises ethylene and a small amount, e.g. up to 5 mol %, of one or more other α-olefins e.g. propylene, 1-butene, 4-methyl-
It may also be a graft-modified ethylene/α-olefin copolymer that is a copolymer with 1-pentene, tohexene, 1-octene, 1-decene, or the like.

The above-mentioned graft-modified polyethylene is obtained by graft-modifying a part or all of polyethylene or an ethylene/α-olefin copolymer with an unsaturated carboxylic acid or a derivative thereof. Examples of acids or derivatives thereof include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (endocysubicyclo[
2. Unsaturated carboxylic acids such as 2, II hept-5-ene-2,3-dicarboxylic acid) or derivatives thereof such as acid halides, amides, imides, anhydrides, esters, etc. are used, specifically, maleinol chloride, maleimide, etc. , maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, etc. are used. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, or their acid anhydrides are particularly preferred.

In order to produce a modified product by graft copolymerizing a graft monomer selected from such unsaturated carboxylic acids or derivatives thereof to polyethylene, various conventionally known methods can be employed. For example, there is a method of melting polyethylene and adding a graft monomer to perform graft copolymerization, or a method of dissolving polyethylene in a solvent and adding a graft monomer to perform graft copolymerization. In any case, in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a radical initiator. The graft reaction is usually carried out at a temperature of 60 to 350°C. The proportion of the radical initiator used is usually in the range of 0.001 to 1 part by weight per 100 parts by weight of polyethylene. Examples of radical initiators include organic peroxides, organic peresters such as penzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-ten+-butyl peroxide, 2.
5-dimethyl-2,5-di(peroxidebenzoate)hexyne-3,1,4-bis(let I-butylperoxyisopropyl)benzene, lauroyl peroxide, tcrt-butylberacetate, 2,5-
Dimethyl-2.5-di(fer t-butylberoxy)hexyne-3,2.5-dimethyl-2.5-di(
f<11 butylberoxy)hexane, ferl-butylperbenzoate, lerj-butylperphenylacetate, lert-butylberisobutylene h, fe
r+-butylper-1eC-octoate, Ietl-
Butylperpiparate, cumylperpiparate and!
eN-butylperdiethyl acetate and other azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate are used. Among these, dicumyl peroxide, di...1-butyl peroxide,
2,5-dimethyl-2,5-di(lerl-butylberoxy)hexane-3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, ■,
Dialkyl peroxides such as 4-bis(l e t l -butylperoxyisopropyl)benzene are preferred.

Ethylene/α-olefin copolymer In addition to the above-mentioned styrene elastomer and graft-modified polyethylene, ethylene/α-olefin copolymer is also used.
By including the olefin copolymer, the melt viscosity of the adhesive resin composition of the present invention can be lowered and the moldability can be improved, and the adhesiveness after retort treatment can be further improved. Furthermore, adhesion to polyolefins can be improved.

This ethylene•α-olefin copolymer is a random copolymerization of ethylene and α-olefin, and in the present invention, ethylene•α-olefin copolymer has an ethylene content of 45 to 95 mol%, preferably 45 to 90 mol%. α-olefin copolymers are used.

The ethylene●α-olefin copolymer used in the present invention generally has a melt flow rate (^STMD I23
8. Condition E) h<0.1 to 50 g/10 min, preferably 0.3 to 30 g/10 min, and the density is usually 0.85
0-0.900g/cd, preferably 0.850~0
．． 8908/alt', and the X-ray crystallinity is generally less than 30%, preferably less than 25%.

α- which constitutes this ethylene/α-olefin copolymer
As the olefin, α-olefin having 3 to 2 carbon atoms is used, and specifically, propylene, 1-butene, 1
-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, l-octadecene, etc., and these α-olefins may be used alone or in combination with
Used as a mixture of more than one species.

Such an ethylene●α-olefin copolymer is
7) Melting point (ASTM 0 341g) Normally 1 0
Below 0℃. Ru.

Ethylene/vinyl acetate copolymer In the present invention, in addition to the above-mentioned styrene-based elastomer and graft-modified polyethylene, ethylene/vinyl acetate copolymer is further included to kill the styrene-based elastomer and graft-modified polyethylene. By further including an ethylene/vinyl acetate copolymer in addition to the modified polyethylene and the ethylene α-olefin copolymer, it is possible to lower the melt viscosity of the adhesive resin composition of the present invention and improve the moldability. At the same time, the adhesion after retort treatment can be further improved.

In the present invention, an ethylene/vinyl acetate copolymer having a vinyl acetate content of 5 to 40% by weight, preferably 10 to 35% by weight is used.

The ethylene/vinyl acetate copolymer used in the present invention is
Generally, melt flow rate (ASTM DI238.
Condition E) is 0.1 to 50 g/10 min, preferably 0.3
~30g/10 minutes.

Blending ratio In the resin composition according to the present invention, the graft-modified polyethylene is used in an amount of 1 to 30 parts by weight, preferably 2 to 28 parts by weight, based on 100 parts by weight of the soft polymer.

In one embodiment of the invention, the flexible polymer is a styrenic elastomer.

In another embodiment of the present invention, an ethylene/α-olefin copolymer is mixed as the soft polymer in addition to the styrene elastomer.

In this case, the composition of the soft polymer is 20 to 100% by weight, preferably 20 to 90% by weight of the styrenic elastomer.
, ethylene/α-olefin copolymer is 0 to 80% by weight
, preferably 10 to 80% by weight. However, the total weight of the styrene elastomer and the ethylene/α-olefin copolymer is 100% by weight.

Furthermore, in a further aspect of the present invention, the above-mentioned styrenic elastomer is combined with ethylene as the soft polymer.
Vinyl acetate copolymer is added. In this case,
The amount of styrene elastomer is 20 to 100% by weight, preferably 20 to 90% by weight, and the amount of ethylene/vinyl acetate copolymer is 0 to 80% by weight, preferably 10 to 80% by weight.
is the amount of However, the total weight of the styrene elastomer and ethylene/vinyl acetate copolymer is 100% by weight.
It is.

Furthermore, in the present invention, as a soft polymer,
In addition to the above styrene elastomers, ethylene α-
Olefin copolymers and ethylene/vinyl acetate copolymers can be added. In this case, the styrenic elastomer is 20 to 100% by weight, preferably 20 to 90% by weight,
The amount of the ethylene/α-olefin copolymer is 0 to 80% by weight, preferably 10 to 70% by weight, and the amount of the ethylene/vinyl acetate copolymer is 0 to 80% by weight, preferably 10 to 70% by weight. However, the total weight of the styrene elastomer, ethylene•α-olefin copolymer, and ethylene/vinyl acetate copolymer is 100% by weight.

As described above, the adhesive resin composition according to the present invention contains a styrene elastomer and graft-modified polyethylene as essential components, and the grafting rate of the entire composition is generally 0.01 to 3% by weight, preferably 0. .05-2.5 wt% and MFR is 0.1-50 g/10
min, preferably from 0.2 to 40 g/10 min, and the crystallinity is less than 35%.

The resin composition according to the present invention consists of the above-mentioned styrenic elastomer and graft-modified polyethylene,
Furthermore, it contains an ethylene●α-olefin copolymer and/or an ethylene/vinyl acetate copolymer, and these components can be mixed using various known methods within the ranges mentioned above, such as a Henschel mixer, ▼ -Plender,
Manufactured by mixing in a ribbon blender, tumbler blender, etc., or by melting and mixing in a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, etc., followed by granulation or pulverization. I can do it.

In addition to the above components, the adhesive resin composition according to the present invention includes a heat stabilizer, a weather stabilizer, an antistatic agent, a pigment, a dye,
Rust inhibitors and the like can also be blended within a range that does not impair the purpose of the present invention.

Next, the laminate according to the present invention will be explained. The laminate according to the present invention includes (I) a polyalkylene terephthalate resin layer or a polycarbonate resin layer, and (n) an adhesive layer made of the above-mentioned adhesive resin composition. and (■) a saponified olefin/vinyl acetate copolymer layer.

Layer (I) constituting the laminate according to the present invention is selected from polyalkylene terephthalate resin or polycarbonate resin.

Polyester resins include aliphatic glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and hexamethylene glycol, alicyclic glycols such as cyclohexanedimethanol, and aromatic dihydroxy compounds such as bisphenol. dihydroxy compound units selected from two or more of the above, and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, undecadicarboxylic acid, etc. A polyester formed from aliphatic dicarboxylic acids such as hexahydroterephthalic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, or dicarboxylic acid units selected from two or more of these, and as long as it exhibits thermoplasticity, a small amount of triol may be added. Alternatively, it may be modified with a trivalent or higher valent polyhydroxy compound such as tricarboxylic acid, or polycarboxylic acid. As these thermoplastic polyesters, specifically, polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalate/terephthalate copolymer, etc. are used.

Polycarbonate resins are various polycarbonates and copolycarbonates obtained by reacting dihydroxy compounds with phosgene or diphenyl carbonate by known methods.

Specifically, the dihydroxy compound includes hydroquinone, resorcinol, 4.4'-dihydroxydiphenylmethane, 4.4'-dihydroxydiphenylethane, 4.4'-dihydroxydiphenyl-1-butane, 4.4'-dihydroxy-diphenyl-hebutane, 4.4'-dihydroxy-diphenyl-methane, 4.4'-dihydroxy-diphenyl-2.2-
Propane (bisphenol A), 4.4'-dihydroxy-3.3'-dimethyl-diphenyl-22-propane, 4.4'-dihydroxy-3.3'-diphenyl-diphenyl-2.2-propane, 4. 4'-dihydroxy-dichlorodiphenyl-2.2-propane, 4.4'
-dihydroxydiphenyl 1,1-cyclopentane,
4.4'-dihydroxy-diphenyl-1.1-cyclohexane, 4.4'-dihydroxy-diphenyl-methyl-phenyl-methane, 4.4'-dihydroxy-diphenyl-ethyl-phenyl-methane, 4.4 '-dihydroxydiphenyl-2.2.2-trichloro1.
1-ethane, 2.2'-dihydroxydiphenyl, 2.
6-dihydroxynaphthalene, 4.4'-dihydroxydiphenyl ether, 4.4'-dihydroxy-3.3
Examples include ゛-dichlorodiphenyl ether and 4,4'-dihydroxy-2,5-diethoxyphenyl ether. Among these, polycarbonate using 4,4' dihydroxy diphenyl-2,2-propane (bisphenol A) is preferred because it has excellent mechanical performance and transparency.

Moreover, the adhesive resin composition according to the invention described above is used for the adhesive layer (If) constituting the laminate according to the invention.

Furthermore, the layer (III) constituting the laminate according to the present invention is made of a saponified olefin/vinyl acetate copolymer, and this saponified olefin/vinyl acetate copolymer has an olefin content of 15 ~60 mol%, preferably 25 to 50 mol% of an olefin/vinyl acetate copolymer is saponified to a degree of saponification of 50% or more, preferably 90% or more. When the olefin content is within the above range, thermal decomposition is difficult and melt molding is difficult. It has excellent stretchability, water resistance, and
Excellent gas permeability. Moreover, when the degree of saponification is 50% or more, gas permeation resistance is excellent.

Specifically, olefins copolymerized with vinyl acetate include ethylene, propylene, and! -butene, l-hexene,
Examples include 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, and 1-octadecene, among which ethylene is preferably used from the viewpoint of mechanical strength and moldability.

To produce the laminate according to the present invention, a polyalkylene terephthalate resin or a polycarbonate resin, an adhesive resin composition, and a saponified olefin/vinyl acetate copolymer are melted in separate extruders, and then a three-layer structure is formed. A coextrusion molding method in which the adhesive composition is supplied to a die and co-extruded to form an intermediate layer, or a polyalkylene terephthalate resin or polycarbonate resin layer and a saponified olefin/vinyl acetate copolymer layer are prepared in advance. A sandwich lamination method or the like can be employed in which a material layer is formed and an adhesive resin composition is melt-extruded between these two layers. Among these, coextrusion molding is preferred in terms of interlayer adhesive strength. The coextrusion molding method uses a flat die.
- There are the Gouy method and the inflation method using a circular die.

The flat die can be either a single manifold format using a black box or a multi-manifold format. As for the die used in the inflation method, any known die can be used.

The thickness of each layer in such a laminate can be appropriately determined depending on the application, but usually when the laminate is obtained as a sheet or film, the thickness of the polyalkylene terephthalate resin or polycarbonate resin layer is 0.02 to 5. It is preferable that the adhesive layer as an adhesive has a thickness of about 0.01 to lmi+, and the saponified ethylene/vinyl acetate copolymer layer has a thickness of about 0.01 to lmi+.

Further, in the laminate according to the present invention, the (I) layer is arranged on both sides (I) / (II) / (III) / (n) / (1
) or a structure further having a polyolefin layer, for example, polypropylene/(■)/(I
II) / (II) / (I), polyethylene /
A laminate such as (■)/(III)/(If)/(I) may also be used.

Effects of the Invention The adhesive resin composition according to the present invention is effective when adhering a layer (I) selected from, for example, a polyalkylene terephthalate resin or a polycarbonate resin and saponified olefin/vinyl acetate copolymer waste (III). When used, the layer (
1) and the layer (IN) are strongly bonded, so that the layer (I) and the layer (III) will not separate even under high-temperature conditions such as high-temperature filling or retort processing. It has practically sufficient adhesive strength even at room temperature after treatment.

Therefore, the laminate formed by laminating layer (1) and layer (III) has low permeability to gases such as oxygen, and therefore has extremely excellent properties as a packaging material for retort food.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

In addition, in the following examples, the crystallinity and density are measured as follows.

(1) Preparation of sample After heating with a hot press at 180° C. for 10 minutes, the sample was rapidly cooled with a cooling press (water cooling) to prepare a sample.

(2) Crystallinity The sample prepared in (1) above was measured by X-ray diffraction.

(3) Samples with similar densities were measured at 23°C using the density gradient tube method.

Example 1 100 parts by weight of a styrene elastomer (hereinafter referred to as SEBS; trade name: Kraton G 1652 manufactured by Shell Chemical ■) and maleic anhydride graft modified polyethylene C (hereinafter referred to as MAI-PH-1) (!: IU. MFR l. [l)
g/10 min, density 0. 925g/an3, crystallinity 5
2%, phthene content 3.6 mol%, maleic anhydride graft amount 1. Polycarbonate (hereinafter referred to as PC; trade name: Teijin Panlite L-1250)
, manufactured by Teijin Kasei ■), saponified ethylene-vinyl acetate copolymer (hereinafter referred to as EVO II; MFR I. 3g/1
0 minutes, density 1. ] 9 g/aJ Ethylene content 32 mol%
, Product name: Kuraray Eval EP-F (manufactured by Kuraray), Polypropylene (hereinafter referred to as PP; Product name: Highball F40)
1 (manufactured by Mitsui Petrochemical Industries, Ltd.) under the following conditions.

Sheet configuration: PC/ (1)/EVOH/ (1
)/PP Thickness of each layer (μm): 8 0/5 0/5 0/
5 0/80 Extruder = 40IIIlφ extruder 280℃ (for PC)
30msφ extruder 250℃ (for (1)) 30mmφ extruder 210℃ (for EVOll) 40mmφ extruder 23
0°C (for P P) The obtained 5-layer sheet PC layer and (1
) layer interfacial adhesion strength (FPC, g/151
011) and the interfacial adhesion strength (FEVOH, g/15m) between the EVOH layer and layer (1) at a peeling atmosphere temperature of 23
It was determined by T-peeling at 80°C and 80°C at a peeling speed of 300 m/min.

Further, this sheet was subjected to retort treatment at 131° C. for 30 minutes, and then a T-peel test was conducted under the same conditions as above.

The results are shown in Table 1.

Example 2 Instead of composition (1) used in Example 1, SEB8
75 parts by weight, ethylene/propylene random copolymer (hereinafter referred to as EPR-1; AFRI.Og/10 minutes,
Ethylene content 80 mol%, density 0.865 g/a
j, crystallinity 4%), 25 parts by weight, and MAR-PE-1
A five-layer sheet was obtained in the same manner as in Example 1, except that Composition (2) mixed with 10 parts by weight of 10 parts by weight was used, and a T-peel test was conducted.

The results are shown in Table 1.

Next, a 5-layer sheet was formed using the composition (2), the EVOH, polyethylene terephthalate (PET; J135 manufactured by Mitsui Pet ■ with a crystallization accelerator added), and PP under the following conditions.

Sheet composition: PET/ (2)/EVOH/ (2)
/PP Film thickness of each layer (ttm): 8 0 / 5
0/5 0/5 0/80 Extruder 40mφ extruder 280℃ (for PET) 30m
φ extruder 250℃ (for (2)) 301IIIφ extruder 210℃ (for EVOH) 40 beats φ extruder 230℃
(For PP) Regarding the obtained sheet, the interfacial adhesive strength (FPEL g / 15 mm) between the PET layer and the (2) layer and the EVOH
Interfacial adhesive strength between layer and (2) layer (FEVOH, g/1
5 mm) was determined under the same conditions as the above PC.

The results are shown in Table 2.

Example 3 Instead of composition (2) used in Example 2, SEB3
80 parts by weight, 20 parts by weight of ethylene/vinyl acetate copolymer (hereinafter referred to as EVA-1; MFR 2.5 g/10 min, vinyl acetate content 25% by weight), and MAR-P.
A five-layer sheet was obtained in the same manner as in Example 2, except that the composite (3) mixed with 10 parts by weight of E-1 was used.
A mold peel test was conducted.

The results are shown in Tables 1 and 2.

Example 4 Instead of composition (2) used in Example 2, SEB3
40 parts by weight and ethylene-1-butene random copolymer (hereinafter referred to as ERR-1; MFR 3.5g71
0 minutes, ethylene content 89 mol%, density 0. 885g
/1, crystallinity 15%) 45 parts by weight, and EVA-115
A five-layer sheet was obtained in the same manner as in Example 2, except that a composite material (4) containing 20 parts by weight of MAR-PE-1 and 20 parts by weight of MAR-PE-1 was used, and a T-peel test was conducted.

The results are shown in Tables 1 and 2.

Example 5 Instead of composition (1) used in Example 1, SEB8
20 parts by weight and EBR-1 60 parts by weight and EVA-1
A 5-layer sheet was obtained in the same manner as in Example 1, except that composition (5) containing 20 parts by weight and 110 parts by weight of MAH-PE-1 was used, and a T-peel test was conducted.

The results are shown in Table 1.

Example 6 Instead of composition (1) used in Example 1, SEBS
60 parts by weight and EBR-1 20 parts by weight and EVA-1
A five-layer sheet was obtained in the same manner as in Example 1, except that composition (6) containing 20 parts by weight and 110 parts by weight of MAH-PE-1 was used, and a T-peel test was conducted.

The results are shown in Table 1.

Comparative Example 1 Instead of composition (1) used in Example 1, EBR-1
A five-layer sheet was obtained in the same manner as in Example 1, except that composition (7) in which 100 parts by weight and 110 parts by weight of MAR-PE-1 were mixed, and a T-peel test was conducted.

The results are shown in Table 1.

Comparative Example 2 Instead of composition (1) used in Example 1, EBR-1
85 parts by weight and EVA-1 15 parts by weight and MAH-
A 5-layer sheet was obtained in the same manner as in Example 1, except that composition (8) mixed with 10 parts by weight of PE-1 was used,
A T-peel test was conducted.

The results are shown in Table 1.

Comparative Example 3 Instead of composition (1) used in Example 1, SEBS
40 parts by weight and EBR-1 45 parts by weight and EVA-1
A 5-layer sheet was obtained in the same manner as in Example 1, except that Composition (9) mixed with 15 parts by weight was used, and a T-peel test was conducted.

The results are shown in Table 1.

Claims (1)

[Scope of Claims] 1) A partially or entirely graft-modified polyethylene in which the grafting amount of an unsaturated carboxylic acid or its derivative is 0.05 to 15% by weight based on 100 parts by weight of the soft polymer. 1. An adhesive resin composition comprising 1 to 30 parts by weight of the following: wherein the soft polymer is a styrene elastomer. 2) 1 to 30 parts by weight of partially or entirely graft-modified polyethylene, in which the graft amount of unsaturated carboxylic acid or its derivative is 0.05 to 15% by weight, based on 100 parts by weight of the soft polymer. A blended adhesive resin composition, wherein the soft polymer is (a) a styrene elastomer 20~
100% by weight and (b) ethylene content 45-95 mol%
An adhesive resin composition comprising 80 to 0% by weight of an ethylene/α-olefin copolymer. 3) 1 to 30 parts by weight of partially or wholly graft-modified polyethylene, in which the graft amount of unsaturated carboxylic acid or its derivative is 0.05 to 15% by weight, based on 100 parts by weight of the soft polymer. A blended adhesive resin composition, wherein the soft polymer is (a) a styrene elastomer 20~
100% by weight and (c) vinyl acetate content is 5-40% by weight
An adhesive composition comprising 80 to 0% by weight of an ethylene/vinyl acetate copolymer. 4) 1 to 30 parts by weight of partially or entirely graft-modified polyethylene, in which the amount of grafted unsaturated carboxylic acid or its derivative is 0.05 to 15% by weight, based on 100 parts by weight of the soft polymer. A blended adhesive resin composition, wherein the soft polymer is (a) a styrene elastomer 20~
100% by weight and (b) ethylene content 45-95 mol%
and (c) 0 to 80% by weight of an ethylene/vinyl acetate copolymer having a vinyl acetate content of 5 to 40% by weight. Adhesive resin composition. 5) (I) polyalkylene terephthalate resin layer, (II)
) A laminate comprising: an adhesive layer made of the resin composition according to any one of claims 1 to 4; and (III) a saponified olefin/vinyl acetate copolymer layer. body. 6) (I) a polycarbonate resin layer; (II) an adhesive layer made of the resin composition according to any one of claims 1 to 4; and (III) a saponified olefin/vinyl acetate copolymer layer. A laminate comprising: