JPH07103278B2 - Adhesive resin composition and laminate using the same - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to an adhesive resin composition and a laminate using the adhesive resin composition, and more specifically, the adhesive force is reduced even when contacted with high temperature water. The present invention relates to such an adhesive resin composition and a laminate using the adhesive resin composition, which has excellent gas barrier properties and can also be subjected to retort treatment.

TECHNICAL BACKGROUND OF THE INVENTION AND PROBLEMS THEREOF Polyester resins represented by polyethylene terephthalate resin are excellent in mechanical strength, rigidity, heat resistance, chemical resistance, oil resistance, transparency, etc., and these characteristics are utilized. It is widely used as a packaging material for films, sheets and containers. However, such polyester resin has a high permeability to gases such as oxygen, so that food,
It could not be used for packaging materials that require high gas permeation resistance such as chemicals and cosmetics.

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

A method of laminating a polyethylene terephthalate resin or a polycarbonate resin with a gas gas permeation resistance superior to those of the polyethylene terephthalate resin or the polycarbonate resin in order to enhance the gas permeation resistance of the polyethylene terephthalate resin or the polycarbonate resin. Is proposed. However, the adhesiveness between the polyethylene terephthalate resin or the polycarbonate resin and the saponified product of the ethylene / vinyl acetate copolymer is not always sufficient, and a part of the resin is peeled off during lamination or during use, resulting in a decrease in gas permeation resistance. However, there is a problem that the appearance or mechanical strength of the product may decrease.

In order to solve these problems, for example, JP-A-61-27
JP-A No. 1155 and Japanese Patent Application No. 61-254 discloses that a graft-modified ethylene / α-olefin random copolymer graft-modified with an unsaturated carboxylic acid or a derivative thereof is used as an intermediate adhesive layer, a polycarbonate layer or a polyester layer, Disclosed is a laminate in which an ethylene / vinyl acetate copolymer saponified product layer is adhered. These laminates have excellent gas permeation resistance and excellent adhesion at room temperature, but for example, these laminates are subjected to high-temperature filling or heat treatment such as retort treatment during production or eating. In such a case, the adhesive strength may be lowered by heating, which causes a problem that the layer is peeled off and the gas permeation resistance is lowered.

Therefore, it has been desired to develop an adhesive resin composition in which the adhesive strength of each layer does not decrease even when hot filling or retort treatment is performed.

OBJECT OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and the adhesive strength may be reduced even when severe treatment such as hot filling or retort treatment is performed. It is an object of the present invention to provide an adhesive resin composition that does not exist.

Further, the present invention uses the above-described adhesive composition, and a polycarbonate layer or a polyester layer, ethylene.
An object of the present invention is to provide a laminate formed by adhering a vinyl acetate saponified product layer, which has excellent gas permeation resistance and which does not reduce the adhesive force between layers even when subjected to high temperature filling or retort treatment. I am trying.

SUMMARY OF THE INVENTION The adhesive resin composition according to the present invention comprises: (a) Melt flow rate: 0.1 to 50 g / 10 minutes Density: 0.850 to 0.900 g / cm ³ Ethylene content: 75 to 95 mol% Crystallization by X-ray Degree: less than 30%, ethylene / α-olefin copolymer: 95 to 50% by weight (b) Melt flow rate: 0.1 to 50 g / 10 minutes Vinyl acetate content: 5 to 40% by weight Ethylene / acetic acid Vinyl copolymer: 5 to 50% by weight, and (c) Graft amount of unsaturated carboxylic acid or its derivative: 0.05 to 15% by weight Melt flow rate: 0.1 to 50 g / 10 minutes Density: 0.900 to 0.980 g / cm ³ Crystallinity by X-ray: 30% or more, partially or wholly graft-modified graft-modified polyethylene: 1.0 to 30% by weight based on 100% by weight of the total weight of (a) and (b) above , The graft ratio of the composition as a whole is 0.01 to 3% by weight, the MFR is 0.1 to 50 g / 10 minutes, and It is characterized in that degree is less than 35%.

The laminate according to the present invention comprises (I) a layer (A) selected from a polyester resin or a polycarbonate resin, (III) an olefin / vinyl acetate copolymer saponified layer (C), and (II) the above. It is characterized by being laminated via an intermediate layer (B) made of such an adhesive resin composition.

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

First, the adhesive resin composition according to the present invention will be described. This composition comprises (a) an ethylene / α-olefin copolymer, (b) an ethylene / vinyl acetate copolymer and (c) a graft modified polyethylene. It is configured to include. Each component will be described in detail below.

(A) Ethylene / α-olefin copolymer This ethylene / α-olefin copolymer has ethylene and α-olefin randomly copolymerized and has the following characteristics.

Melt flow rate: 0.1 to 50 g / 10 minutes, preferably 0.3 to 30 g / 10 minutes Density: 0.850 to 0.900 g / cm ^3, preferably 0.850 to 0.890 g / cm ³ Ethylene content: 75 to 95 mol%, preferably 75 to 90 Mol% X-ray crystallinity: less than 30%, preferably less than 25%.

If the amount is out of the above range, the adhesive strength of the obtained adhesive resin composition is lowered, which is not preferable.

Α-constituting the ethylene / α-olefin copolymer
As the olefin, an α-olefin having 3 to 20 carbon atoms is used, and specifically, propylene, 1-butene, 1-
Hexene, 4-methyl-1-pentene, 1-octene,
1-decene, 1-tetradecene, 1-octadecene, etc. are used, and these α-olefins are used alone or as a mixture of two or more kinds.

The melting point (ASTM D3418) of such an ethylene / α-olefin copolymer is usually 100 ° C or lower.

The ethylene / α-olefin copolymer is used in an amount of 95 to 50% by weight, preferably 90 to 60% by weight, based on the total weight of the (b) ethylene / vinyl acetate copolymer described later.

(B) Ethylene / Vinyl Acetate Copolymer This ethylene / vinyl acetate copolymer has the following properties.

Melt flow rate: 0.1 to 50 g / 10 minutes, preferably 0.3 to 30 g / 10 minutes Vinyl acetate content: 5 to 40% by weight, preferably 10 to 35% by weight This ethylene / vinyl acetate copolymer has the above-mentioned (a).
It is used in an amount of 5 to 50% by weight, preferably 10 to 40% by weight, based on the total weight of the ethylene / α-olefin copolymer.

(C) Graft-modified polyethylene This graft-modified polyethylene has the following properties.

Grafting amount of unsaturated carboxylic acid or its derivative: 0.05
To 15% preferably 0.1 to 10 wt% melt flow rate: 0.1 to 50 g / 10 minutes is preferably 0.3 to 30 g / 10 min Density: according 0.900~0.980g / cm ³ preferably 0.905~0.970g / cm ³ X-ray Crystallinity: 30% or more, preferably 35 to 75% In this graft-modified polyethylene, a part or all of polyethylene is graft-modified.

Graft-modified polyethylene optionally comprises ethylene and a small amount, for example up to 5 mol%, of one or more other α-olefins such as propylene, 1-butene, 4-methyl-1.
It may be a graft-modified ethylene / α-olefin copolymer which is a copolymer with -pentene, 1-hexene, 1-octene, 1-decene and the like.

The graft-modified polyethylene as described above 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. As the acid or its derivative, specifically, acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid,
Unsaturated carboxylic acids such as isocrotonic acid, nadic acid ^R (endocis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), or derivatives thereof such as acid halides, amides, imides, anhydrides , Ester, etc., and specifically, maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, etc. are used. Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid and nadic acid are particularly preferable.
^R or these acid anhydrides are preferably used.

In order to graft-copolymerize a graft monomer selected from such unsaturated carboxylic acids or their derivatives with polyethylene, various conventionally known methods can be adopted. For example, there is a method of melting polyethylene and adding a graft monomer for graft copolymerization, or a method of dissolving polyethylene in a solvent and adding a graft monomer for graft copolymerization. In any case, it is preferable to carry out the reaction in the presence of a radical initiator in order to efficiently graft-copolymerize the graft monomer. The grafting reaction is usually performed at a temperature of 60 to 350 ° C. The use ratio of the radical initiator is usually in the range of 0.001 to 1 part by weight with respect to 100 parts by weight of polyethylene. Radical initiators include organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide,
Di-tert-butyl peroxide, 2,5-dimethyl-2,5-
Di (peroxide benzoate) hexyne-3,1,4-
Bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5- Di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutyrate, tert-butylper-sec-octoate, tert-butylperpivalate, cumylperpivalate And tert-butyl perdiethyl acetate, and other azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate.
Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-
Di (tert-butylperoxy) hexane, 1,4-bis (t
Dialkyl peroxides such as ert-butylperoxyisopropyl) benzene are preferred.

This graft-modified polyethylene comprises the above-mentioned (a) ethylene / α-olefin copolymer and (b) ethylene /
1 to 3 per 100 parts by weight of the total weight of vinyl acetate copolymer
It is used in an amount of 0 parts by weight, preferably 2-28 parts by weight.

As described above, the adhesive resin composition according to the present invention comprises (a) an ethylene / α-olefin copolymer, (b) an ethylene / vinyl acetate copolymer, and (c) a graft-modified polyethylene. The graft ratio of the entire composition is
0.01 to 3% by weight, preferably 0.05 to 2.5% by weight.

The adhesive resin composition according to the present invention contains the components (a), (b) and (c) as described above in various known methods within the above range, for example, Henschel mixer, v-
A method of mixing with a blender, a ribbon blender, a tumbler blender, or after mixing, after melt-kneading with a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, etc.,
A method of granulating or crushing may be adopted.

In the adhesive resin composition according to the present invention, in addition to the above-mentioned components, a heat resistance stabilizer, a weather resistance stabilizer, an antistatic agent, a pigment, a dye, a rust preventive agent, etc. within a range not impairing the object of the present invention. It can also be blended.

Next, the laminate according to the present invention will be described. The layer (A) constituting the laminate is selected from (I) polyester 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, aromatic dihydroxy compounds such as bisphenol, and the like. A dihydroxy compound unit selected from two or more kinds of aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalene dicarboxylic acid, oxalic acid,
It is formed from an aliphatic dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, and undecadicarboxylic acid, an alicyclic dicarboxylic acid such as hexahydroterephthalic acid, or a dicarboxylic acid unit selected from two or more of these. The polyester may be modified with a small amount of a trihydric or higher polyhydroxy compound such as triol or tricarboxylic acid, or a polycarboxylic acid, as long as it exhibits thermoplasticity. Specific examples of these thermoplastic polyesters include polyethylene terephthalate, polybutylene terephthalate, and polyethylene isophthalate / terephthalate copolymers.

Polycarbonate resins are various polycarbonates and copolycarbonates obtained by reacting a dihydroxy compound with water sgene or diphenyl carbonate by a known method. Examples of the dihydroxy compound include hydroquinone, resorcinol, 4,4'-dihydroxy-diphenyl-methane, 4,4'-dihydroxy-diphenyl-ethane and 4,4'-dihydroxy-diphenyl-n.
-Butane, 4,4'-dihydroxy, diphenyl-heptane, 4,4'-dihydroxy-diphenyl-phenyl-methane, 4,4'-dihydroxy-diphenyl-2,2-propane (bisphenol A), 4,4 ' -Dihydroxy-3,3 '
-Dimethyl-diphenyl-2,2-propane, 4,4'-dihydroxy-3,3'-diphenyl-diphenyl-2,2-propane, 4,4'-dihydroxy-dichloro-diphenyl-
2,2-propane, 4,4'-dihydroxy-diphenyl-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'-
Dihydroxy-diphenyl-2,2,2-trichloro-1,1-
Ethane, 2,2'-dihydroxydiphenyl, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether and 4,4'-dihydroxy-2,5 -Diethoxyphenyl ether and the like. Of these, polycarbonate using 4,4'-dihydroxy-diphenyl-2,2-propane (bisphenol A) is preferable because it has excellent mechanical performance and transparency.

Further, the layer (C) constituting the laminate according to the present invention is composed of a saponified olefin / vinyl acetate copolymer,
As the saponified olefin / vinyl acetate copolymer,
An olefin / vinyl acetate copolymer having an olefin content of 15 to 60 mol%, preferably 25 to 50 mol%, saponified to have a saponification degree of 50% or more, preferably 90% or more is used. . If the olefin content is less than 15 mol%, thermal decomposition is likely to occur, melt molding is difficult, stretchability is poor, and water absorption and swelling are likely to occur, resulting in poor water resistance. On the other hand, when the olefin content exceeds 60 mol%, the gas permeation resistance becomes poor, which is not preferable.
Further, if the saponification degree is less than 50%, the gas permeation resistance becomes poor, which is not preferable.

Specific examples of the olefin copolymerized with vinyl acetate include ethylene, propylene, 1-butene, 1-hexene,
4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene can be exemplified,
Among them, ethylene is preferably used in terms of mechanical strength and moldability.

To produce the laminate according to the present invention, the polyester resin or polycarbonate resin, the adhesive resin composition, and the saponified olefin / vinyl acetate copolymer are melted in separate extruders, respectively, and then a die having a three-layer structure is formed. The co-extrusion molding method in which the adhesive resin composition is co-molded so as to be an intermediate layer, or in advance, a polyester resin or polycarbonate resin layer, and an olefin / vinyl acetate copolymerization other saponified material layer are molded, A sandwich laminating method or the like in which an adhesive resin composition is melt-extruded between these two layers can be adopted. Of these, the coextrusion molding method is preferable in terms of interlayer adhesion. As the coextrusion molding method, there are a T-die method using a flat die and an inflation method using a circular die. The flat die may use either a single manifold type using a black box or a multi-manifold type. Any known die can be used for the inflation method.

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 polyester resin or polycarbonate resin layer is 0.02 to 5 mm, as an adhesive. It is preferable that the intermediate layer has a thickness of 0.01 to 1 mm and the saponified ethylene / vinyl acetate copolymer layer has a thickness of about 0.01 to 1 mm.

The laminated body according to the present invention has a structure of (A) / (B) / (C) / (B) / (A) in which the (A) layer is arranged on both sides, or a structure further having a polyolefin layer. Good, for example polypropylene / (B) / (C) / (B) /
(A), polyethylene / (B) / (C) / (B) /
It may be a laminated body such as (A).

EFFECTS OF THE INVENTION According to such an adhesive resin composition of the present invention,
Provided is an adhesive resin composition in which the adhesive strength does not decrease even when subjected to severe treatment such as high temperature filling or retort treatment.

More specifically, the adhesive resin composition according to the present invention is used for adhering a layer (A) selected from, for example, polyester resin or polycarbonate resin, and an olefin / vinyl acetate copolymer saponified layer (C). And the layer (A) and the layer (C) are firmly adhered to each other, and the layer (A) and the layer (C) are bonded to each other even when exposed to severe conditions such as hot filling or retort treatment. Does not peel off.

In addition, the layered product obtained by laminating the layer (A) and the layer (C) has the layer (A) and the layer (C) firmly adhered to each other, and is represented by high temperature filling or retort treatment. Even when exposed to harsh conditions, layer (A) and layer (C) do not separate, and the gas permeability of oxygen and the like is small, so it has excellent properties as a packaging material for retort foods. ing.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Ethylene / propylene random copolymer (hereinafter referred to as EPR-1
Say: MFR 1.0g / 10min ethylene content 80mol%, density 0.8
65 g / cm ³ , 75% by weight of crystallinity 4%) and 25 parts by weight of ethylene / vinyl acetate copolymer (hereinafter referred to as EVA-1: MFR 2.5 g / 10 minutes, vinyl acetate content 25% by weight), anhydrous Maleic acid graft modified polyethylene (hereinafter referred to as MAH-PE-1: MFR
Composition (I) (1.0 g / 10 min, density 0.925 g / cm ³ , crystallinity 52%, butene content 3.6 mol%, maleic anhydride graft amount 1.0 g / 100 g polymer) 20 parts by weight (I) ( Maleic anhydride grafted amount 0.2 / 100 g polymer of composition (I),
Crystallinity 15%, MFR 1.2g / 10min) Polycarbonate (below
PC; trade name Teijin Panlite L-1250, manufactured by Teijin Kasei Co., Ltd., saponified ethylene / vinyl acetate copolymer (hereinafter referred to as EVOH; MFR 1.3 g / 10 min, density 1.19 g / cm ³ ethylene content 32 mol%, trade name Kuraray Eva EP-F
Using Kuraray Co., Ltd., a 5-layer bottle was molded under the following conditions.

Bottle composition: PC / (I) / EVOH / (I) / PC Thickness of each layer (μm): 200/50/50/50/200 Bottle shape: 200cc cylindrical bottle Extruder: 65mmφ extruder 280 ℃ (for PC ) 40mmφ extruder 250 ° C ((I)) 40mmφ extruder 210 ° C (for EVOH) Interfacial adhesion strength (FPC, g / 15mm) between PC layer and (I) layer of the obtained 5-layer bottle and EVOH The interface adhesion limit (FEVOH, g / 15 mm) between the layer and the (I) layer was determined by T-type peeling at a peeling speed of 300 mm / min. Further, this bottle was filled with hot water at 90 ° C., the bottle was deformed by hand, the hot water was discharged, and the occurrence of interfacial peeling of the bottle was visually inspected. The results are shown in Table 1.

Next, a five-layer sheet was molded using the composition (I), the EVOH, and polyethylene terephthalate (PET; J135 manufactured by Mitsui Pet Co., Ltd., with a crystallization accelerator added) under the following conditions.

Sheet composition: PET / (I) / EVOH / (I) / PET Thickness of each layer (μm): 150/50/50/50/150 Extruder 65mmφ Extruder 280 ℃ (for PET) 40mmφ Extruder 250 ℃ ( (I)) 40 mmφ extruder 210 ° C. (for EVOH) The obtained sheet was vacuum-molded into a cup shape at a mold temperature of 160 ° C. to crystallize the PET layer. Sampling was performed from the side wall of the obtained cup, and the interfacial adhesion strength (F
PET, g / 15 mm) and the interfacial adhesion strength (FEVOH, g / 15 mm) between the EVOH layer and the (I) layer were determined. In addition, 90 in this cup
After filling the bottle with ℃ hot water and deforming the bottle by hand, the hot water was discharged and the occurrence of interfacial peeling of the bottle was visually inspected.

The results are shown in Table 1.

Example 2 Instead of the composition (I) used in Example 1, ethylene-
1-butene random copolymer (hereinafter referred to as EBR-1; MFR3.0
g / 10 minutes, ethylene content 90 mol%, density 0.885 g / cm ³ , crystallinity 14%) 75 parts by weight, EVA-1 25 parts by weight, MAH-
Other than using composition (II) mixed with 20 parts by weight of PE-1 (maleic anhydride graft ratio of composition (II) 0.17 g / 100 g polymer, crystallinity 21%, MFR 2.4 g / 10 min) Was performed in the same manner as in Example 1.

The results are shown in Table 1.

Example 3 Instead of the composition (I) used in Example 1, ethylene was used.
1-butene random copolymer (hereinafter referred to as EBR-2; MFR2.0
g / 10 minutes, ethylene content 93 mol%, density 0.892 g / cm ³ , crystallinity 22%) 75 parts by weight, EVA-1 25 parts by weight, MAH-
PE-1 (20 parts by weight) was mixed with the composition (III) (composition (III) maleic anhydride graft amount 0.17 g / 100 g polymer, crystallinity 27%, MFR 1.9 g / 10 minutes) The same procedure as in Example 1 was performed.

The results are shown in Table 1.

Example 4 Instead of the composition (I) used in Example 1, EPR-16
5 parts by weight and ethylene vinyl acetate copolymer (hereinafter referred to as EVA-2
MFR 2.0g / 10min, vinyl acetate content 10wt%,) 3
5 parts by weight and maleic anhydride graft-modified polyethylene (hereinafter referred to as MAH-PE-2; MFR 3.5 g / 10 minutes, density 0.910 g / c
m ^3, crystallinity of 40%, butene content of 5.5 mol%, maleic anhydride grafting of the graft amount of maleic anhydride 0.5 g / 100 g polymer) composition obtained by mixing 25 parts by weight (IV) (composition (IV) Rate 0.1g / 100g polymer, crystallinity 20%, MFR 1.6g / 1
The same procedure as in Example 1 was carried out except that 0 minutes) was used.

The results are shown in Table 1.

Example 5 Instead of the composition (I) used in Example 1, EPR-17
5 parts by weight, EVA-1 25 parts by weight, and maleic anhydride graft-modified polyethylene (hereinafter referred to as MAH-PE-3; MFR4.3
g / 10 minutes, density 0.962g / cm ³ , crystallinity 72%, butene content
Composition (V) mixed with 0.5 mol% and 5 parts by weight of maleic anhydride grafted amount 2.2 g / 100 g polymer (composition (V)
Example 1 except that a maleic anhydride graft amount of 0.11 g / 100 g polymer, crystallinity 11%, MFR 1.3 g / 10 min.
It carried out similarly to.

The results are shown in Table 1.

Example 6 Instead of the composition (I) used in Example 1, EPR-18
5 parts by weight, 15 parts by weight of EVA-1 and 5 parts by weight of MAH-PE-3 were mixed (VI) (Maleic anhydride graft ratio of composition (VI) 0.11 g / 100 g polymer, crystallization Degree 9
%, MFR 1.2 g / 10 min) was used, and the same procedure as in Example 1 was performed.

The results are shown in Table 1.

Example 7 Instead of the composition (I) used in Example 1, an ethylene propylene random copolymer (hereinafter referred to as EPR-2; MFR 12g).
/ 10 minutes, ethylene content 80 mol%, density 0.865 g / cm ³ , crystallinity 4%) 75 parts by weight, ethylene-vinyl acetate copolymer (hereinafter referred to as EVA-3; MFR 15 g / 10 minutes, vinyl acetate Content 28% by weight) 25 parts by weight and MAH-PE-3 15 parts by weight of composition (VII) (composition (VII) maleic anhydride grafted amount 0.29 g / 100 g polymer, crystallinity 15 %, MFR1
Example 1 was repeated except that 1 g / 10 min) was used.

The results are shown in Table 1.

Comparative Example 1 Instead of the composition (I) used in Example 1, EPR-11
Other than using a composition (VIII) in which 00 parts by weight and MAH-PE-125 parts by weight (maleic anhydride graft ratio 0.2 g / 100 g polymer, crystallinity 14%, MFR 1.0 g / 10 min) Was performed in the same manner as in Example 1.

The results are shown in Table 1.

Comparative Example 2 Instead of the composition (I) used in Example 1, EPR-18
A composition obtained by mixing 0 part by weight and 20 parts by weight of EVA-1 (I
X) (composition (IX) maleic anhydride graft amount 0 g / 100 g polymer, crystallinity 7%, MFR 1.2 g / 10 min) was used, and the same procedure as in Example 1 was carried out.

The results are shown in Table 1.

Comparative Example 3 Instead of the composition (I) used in Example 1, EVA-11
Composition (X) in which 00 parts by weight and MAH-PE-125 parts by weight are mixed (composition (X) maleic anhydride graft amount 0.2 g / 1
Example 1 was repeated except that 00 g polymer, crystallinity 25%, MFR 2.1 g / 10 minutes) was used.

The results are shown in Table 1.

Comparative Example 4 Instead of the composition (I) used in Example 1, MAH-EPR-
1 (MFR 0.5g / 10min, ethylene content 80mol%, density 0.86
5 / cm ³ , crystallinity 4%, maleic anhydride graft amount 0.5g /
Example 1 was repeated except that 100 g polymer) was used.

The results are shown in Table 1.

Comparative Example 5 Instead of the composition (I) used in Example 1, MAH-EVA-
Example 1 was repeated except that 1 (MFR 1.2 g / 10 min, vinyl acetate content 25% by weight, crystallinity 18%, maleic anhydride graft amount 0.5 g / 100 g polymer) was used.

The results are shown in Table 1.

Comparative Example 6 Instead of the composition (I) used in Example 1, MAH-EPR-
70 parts by weight of MAH-EVA-1 was mixed with 30 parts by weight of MAH-EVA-1 (the composition (XI) had a maleic anhydride graft ratio of 0.5 g / 100 g polymer, crystallinity of 8%, and MFR0. 7g / 10
Min) was used, and the same procedure as in Example 1 was performed.

The results are shown in Table 1.

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Claims (1)

[Claims] (A) Melt flow rate: 0.1 to 50 g / 10 min Density: 0.850 to 0.900 g / cm ³ Ethylene content: 75 to 95 mol% Crystallinity by X-ray: less than 30%, ethylene -Α-olefin copolymer: 95 to 50% by weight (b) Melt flow rate: 0.1 to 50 g / 10 minutes Vinyl acetate content: 5 to 40% by weight, ethylene-vinyl acetate copolymer: 5 to 50 %, And (c) Grafting amount of unsaturated carboxylic acid or its derivative: 0.05 to 15% by weight Melt flow rate: 0.1 to 50 g / 10 minutes Density: 0.900 to 0.980 g / cm ³ Crystallinity by X-ray: 30 % Or more, graft modified polyethylene partially or wholly graft-modified: 1.0 to 100 parts by weight based on the total weight of (a) + (b).
30 parts by weight, the composition as a whole has a graft ratio of 0.01 to 3% by weight, an MFR of 0.1 to 50 g / 10 minutes, and a crystallinity of less than 35%. Resin composition.