CA2035570A1

CA2035570A1 - Polyolefin composition and use thereof

Info

Publication number: CA2035570A1
Application number: CA002035570A
Authority: CA
Inventors: Kuniyoshi Asano; Tomoyoshi Uemura; Hiroshi Takida
Original assignee: Individual
Current assignee: Arkema France SA
Priority date: 1990-02-01
Filing date: 1991-02-01
Publication date: 1991-08-02
Also published as: JP2865353B2; EP0440559A2; JPH03227339A; FI910465L; FI910465A7; FI910465A0; EP0440559A3

Abstract

PATENT APPLICATION
Country : JAPON
No. : 23017 Filed on : 1st February 1990 File : AM 0471 A B S T R A C T
* * * * * * * *

A POLYOLEFIN COMPOSITION AND USE THEREOF

* * * * * * * *

Company called : ATOCHEM
4 & 8 Cours Michelet La Défense 10 Authorized agent : Pierre POISSON

Inventors : Kuniyoshi ASANO
Tomoyoshi UEMURA
Hiroshi TAKIDA
* * * * * * * *

The present invention relates to a composition with barrier property comprising :
(A) 50 to 99.5 weight % of a polyolefin resin, (B) 0.4 to 50 weight % of a saponified ethylene-vinyl acetate copolymer, and (C) 0.1 to 15 weight % of a graft polymer obtainable by graf-ting an ethylenically unsaturated carboxylic acid or a deriva-tive thereof to a polyolefin resin and reacting the adduct with a polyamide oligomer, which composition satisfies the re-lation : M2/M1 = not less than 1.5 wherein M2 and M1 are the melt flow rates of (B) and (A), respectively, under a load of 2160 g at 210°C.
This composition can be used for the manufacture of film usable for packaging.

Description

2 ~

The present invention provides a polyolefin resin composition insuring excellent oxygen barrier property.
Prior Art Polyolefin resins, such as polyethylene and polypropylene, have good moldability and give shaped articles (or moldings) excellent in appearance, moisture resistance, mechanical properties and so forth and, as such, have found application in many uses such as film, sheet, container material, textile fiber and so on.
Problems that are to be Solved However, polyolefin resins are rather poor in gas barrier property, in particular oxygen barrier pro-perty, and therefore it is substantially impossible to use them by themselves as packaging materials for foodstuffs readily susceptible to oxidation and oxida-tive denaturation.
Therefore, if said resins could be provided with Gxygen barrier property by some or other means, they would be of still more increased utility value.
A measure taken therefor comprises laminating a layer of some other resin having good oxygen barrier property to a polyolefin resin layer or blending such other resin with a polyolefin resin. However, either method has both merits and demerits, physical pro-2~3~7~

perties obtainable thereby being not always satis-factory.
The inventors of the present invention also attempted to improve the oxygen barrler property of polyolefln resins by admixing therewith a saponified ethylene-vinyl actate copolymer whlch has particularly good oxygen barrler property. In some instance, however, such excellent physical propertles of poly-olefin resins as stretchabllity and flexibillty were sacrificed. Fully satlsfactory results have never been obtalned as yet.
Means for Solvlnq the Proble~s The intensive research underraken by the inventors of the present invention revealed that the above-men-tioned objects are accomplished ~r, in other words, the desired oxygen parrier property can be obtained without any impairment of the stretchability or flexibility intrinsic of polyolefins, by providing a polyolefin resin composition which comprises (A) 50 to 99.5 weight % of a polyolefin resin, (B) 0.4 to 50 weight % of a saponified ethylene-vinyl acetate copolymer, and (C) 0.1 to 15 weight ~ of - graft polymer obtain-able by grafting an ethylenically unsaturated carb-oxylic acid or a derivative thereof to a polyolefin r,~

resin and reacting the adduct with a polyamide oli-gomer, which composition satisfies the relation: M2/M1 = not less than 1.5 wherein M2 and M1 are the melt flow rates of (B) and (A), respectively, under a load of 2160 g at 210C. The present invention is predicated on the abo~e finding.
The present invention will hereinafter be des-cribed in detail, with emphasis placed on the above composition and particularly on uses therefor.
With regard to the polyolefin resin (A), there may be mentioned linear low-density, low-density and high-density polyethylenes, ionomers, ethylene-pro-pylene copolymer, crystalline polypropylene, poly-butene, ethylene-vinyl acetate copolymer, ethylene-acrylate ester copolymers, and so on. Particularly, linear low-density, low-density or high-density poly-ethylene, and isotactic polypropylene are of practical importance.
With regard to the above component (A), its melt flow rate (hereinafter referred to briefly as M1) as determined at 210C and under a load of 2160 g accord-ing to JIS K-6760 is in the range of 0.05 to 100 g/10 minutes and preferably 0.5 to 20 gJ10 minutes.
The saponified ethylene-vinyl acetate copolymer (3~ to be employed in accordance with the present invention is a copolymer with an ethylene content of 20 7 d to 60 mole %, preferably 25 to 55 mole %, t~ith a degree of saponification of its vinyl acetate component ~eing not less than 95 mole %.
With an ethylene content less than 20 mole %, the oxygen barrier property under high-humidity conditions is not as high as desired, while an ethylene content in excess of 60 mole % leads to decreases in oxygen barrier property, printability and other physical properties. When the degree of saponification or hydrolysis is less than 95 mole %, the oxygen barrier property and moisture resistance are sacrificed.
It should be understood that this saponified copolymer may contain small proportions of other comonomer ingredients including ~-olefins such as propylene, isobutene, ~-octene, ~-dodecene, ~-octa-decene, etc., unsaturated carboxylic acids or salts thereof, partial alkyl esters, complete alkyl esters, nitriles, amides and anhydrides of such acids, and unsaturated sulfonic acids or salts thereof.
With regard to (B), its melt flow rate ~MFR;
hereinafter referred to as M2) as determined at 210C
and under a load of 2160 g according to JIS K-6760 is in the range of 0.1 to 150 g/10 minutes and prefera~ly 5 to 100 g/10 minutes.
It is essential in the preparation of the composi-tion of the invention that (A) and (B~ be used in an 2~3~

M2/M1 ratio or at least 1.5, preferaoly 2 to 100 and, for still better results, 3 to 50.
With an M2/M1 ratio less than l.S, (B) is not dispersed in (A), the matrix component, in a lamellar fashion but dispersed as globular or nozzle-shaped particles so that the desired effect cannot be fully attained.
For improving the compatibility between (A) and (B), incorporation of (C) is essential in the practice of the invention.
The component (C) is a graft polymer obtainable by grafting an ethylenically unsaturated carboxylic acid or a derivative thereof to a polyole;~in resin and reacting this carboxylic acid or derivative thereof with a polyamide oligomer.
This graft polymer can be produced by dissolving or suspending a polyolefin resin in an appropriate sol-vent or putting it in a molten state, activating the polyolefin resin chain with a peroxide or diazo ini-tiator, grafting an ethylenically unsaturated carb-oxylic acid or a derivative thereof .hereto to give a polymer and mixing this polymer with a palyamide oligomer in molten state.
For this reaction, Brabender machine, Buss ~lender, single-screw extruder, Werner and Pfleiderer twin-~3~

screw extruder or the like is employed.
The degree of polymerization of the polyoleflnresin to be employed is about 350 to 45,000 and prefer-ably about 500 to 10,000. The melt flow rate (230~C, load 2160 g; the same applies hereinafter) is about 0.1 to 50 g/10 minutes for all practical purposes.
The reaction ratio of the polyolefin resin to the ethylenically unsaturated carboxylic acid or a deriva-tive thereof is 100/0.05 through 100/10 and preferably 100/0.5 through 100/3 as expressed on the weight basis.
If the ratio is 100tless than 0.05, the improving effect on compatibility will not be sufficient. On the other hand, if the ratio is 100~more ~han 10, the viscosity will be too high for practical molding.
The degree of polymerizatlon of said polyamide oligomer is 5 to 80, preferably about 15 to 55, for all practical purposes and the reaction ratio is 0.01 to 1 mole and preferably 0.05 to 0.9 mole per mole of the carboxyl group.
As examples of the polyolefin resin, there may be mentioned linear low-density, low-density or high-density polyethylene, ionomers, ethylene-propylene copolymer, crystalline polypropylene, polybutene, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer and so on. Importan~ for practical 2 @~ 3 ~ 7 ~

purposes are linear low-density polyethylene, low-density polyethylene, medium-density polyethylene high-density polyethylene, ethylene-propylene co-polymer, ethylene-vinyl acetate copolymer and crystal-llne polypropylene.
The ethylenically unsaturated carboxylic acid or derivative thereof to be grafted to such a trunk polymer includes, among others, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid and the corresponding anhydrides or half esters.
The polyamide oligomer can be prepared by the ~nown methods such as addition polymerization of a lactam, polycondensation of an aminocarboxylic acid, polycondensation of a diamine with a dicarboxylic acid, and so on.
Examples of the starting materials for said polyamide oligomer are various lactams such as E-capro-lactam, enantholactam, caprylolactam, laurolactam, ~-pyrrolidone, ~-piperidone, etc., ~-amino acids such as 6-aminocaproic acid, 7-aminoheptanoic acid, 9-amino-nonanoic acid, ll-aminoundecanoic acid, etc., di~asic acids such as adipic acid, glutaric acid, pimellic acid, suberic acid, azelaic acid, sebacic acid, un-decadioic acid, dodecadioic acid, hexadecadioic acid, hexadecenedioic acid, eicosadioic acid, eicosadiene-dioic acid, diglycolic acid, 2,2,4-trimethyladipic acid, xylylenedicarboxylic acid, 1,4-cyclohexanedi-carboxylic acid, terephthalic acid, isophthalic acid, etc., and diamines such as hexamethylenediamine, tetramethylenediamine, nonamethylenediamine, undeca-methylenediamine, dodecamethylenediamine, 2,2,4- (or 2,4,4-)trimethylhexamethylenediamine, bis(4,4'-amino-cyclohexyl)methane, metaxylylenediamine and so on. For molecular weight control, a monoamine such as lauryl-amine or oleylamine can also be used in an appropriate amount.
In the composition of the present nvention, the proportion of (A) should be 50 to 39.5 weight % and preferably 60 to 9S weight %, that of (B) should be 0.4 to 50 weight % and preferably 4.5 to 35 weight %, and that of (C) should be 0.1 to 15 weight % and preferably 0.5 to 10 weight %.
When the proportion of (A) is less than 50 weight % or that of (B) is over 50 weight %, the moldability, in particular stretchability, is adversely affected.
Conversely when the proportion of (A) is over 99.5 weight % or that of (B) is less than 0.4 weight %, the oxygen barrier property-improving effect is insuf-ficient.

~ 3 When the proportion of (C) is less than 0.1 weight %, the compatibility between (A) and (B) is poor and the oxygen barrier property-improving effect is also poor. Conversely when the proportion of (C) exceeds 15 weight %, long-run moldability is adversely affected.
While the composition according to the present invention is useful for a va.iety of applications such as shaped articles, adhesives, coatings and so on, it is most use~ul -or molding purposes and can be molded into pellets, ~ilm, sheet, containers, fibers, bars, pipe and other shaped articles by the melt-kneading technique. Such products can be crushed (for reclaim-ing) or pelleted for re-melt-molding.
For melt-molding of the composition, extrusion molding (e.g. ~-die extrusion, inflation molding, blow molding, melt s?inning or contour extrusion) and injection molding are mostly employed. The melt-molding temperature is selected in many cases from the range of 160 to 290C. In addition to the above techniques, two-color molding and injection-blow molding techniG~es may also be employed and shaped articles with good dimensional tolerances can be manufactured.
In the mol ing process, it is of course possible to use two or more different saponified ethylene-vinyl ' acetate copolymers varying in ethylene content and/or in the degree of saponification in combination. In melt-molding, it is also possible to incorporate suitable amounts of additives such as a plasticizer (for example, a polyhydric alcohol), stabilizer, sur-factant, crosslinking agent (for example, an epoxy compound, polyvalent metal salt, inorganic or organic polybasic acid or salt thereof), filler, colorant, reinforcing fiber (for example, glass fiber, carbon fiber, etc.) and so on. It is also possible to in-corporate a further thermoplastic resin in a suitable proportion. Such thermoplastic resin includes, among others, various polyolefins other then (A), modified polyolefins obtainable by graft-modification of such polyolefins with unsaturated carboxylic acids or derivatives thereof, polyamides, polyvinyl chloride, polyvinylidene chloride, polyesters, polystyrene, polyacrylonitrile, polyurethanes, polyacetal, poly-carbonates, melt-moldable polyvinyl alcohol resin and so on.
As mentioned hereinbefore, the composition of the present invention is not only used for the manufacture of a single-layer article solely composed of the composition but also used often as a laminated article including at least one layer of the composition. The ~1~ 3 eJ "~ ~ ~

layer of the composition of the present invention shows a characteristically high bonding affinity for the layer material to be laminated therewith.
In the manufacture of a laminated product accord-~ing to the invention, in which a different material is laminated to one side or either side of a layer of the composition of the invention, the following laminating methods, for instance, can be employed. Thus, the method which comprises melt-extruding a thermoplastic resin onto a film or sheet of the composition of the invention, the method which comprises melt-extruding the composition of the invention onto a substrate made of a thermoplastic resin or some other material, the method which comprises co-extruding the composition of the invention and a different thermoplastic resln, and the method in which a film or sheet of the composition of the invention is laminated to a film or sheet of a different material with a known adhesive such as an organotitanium compound, an isocyanate compound or a polyester compound can be mentioned.
As mating resins for co-extrusion, there may be - mentioned linear low-density polyethylene, low-density polyethylene, medi~lm density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ion-omers, ethylene-propylene copolymers, ethylene-acrylic ester copolymers, polypropylene, propylene-~-olefin (C4 20 a-olefin) copolymers, homo- or copolymers of olefins such as polybutene, polypentene, etc., and polyolefin resins in a broad sense as obtainable by modifying such homopolymers or copolymers of olefins by grafting of an unsaturated carboxylic acid or an ester thereof, polyesters, polyamides, copolymerized poly-amides, polyvinyl chloride, polyvinylidene chloride, acrylic resins, styrenic resins, vinyl ester resin, polyester elastomers, polyurethane elastomers, chlo-rinated polyethylene, chlorinated polypropylene and so on. A saponified ethylene-vinyl acetate copolymer can also be co-extruded.
When a film or sheet or the like shaped article is prepared from the composition of the invention and, then, extrusion-coated with a ~ifferent material or laminated to a film or sheet of a different material with an adhesive, said different material is not limited to said thermoplastic resins but may be vir-tually any other material (such as paper, metal foil, uniaxially or biaxially oriented plastic film or sheet, woven fabric, nonwoven fabric, metal filament, wood and so onl.
The laminar structure of said laminated product is optional. Thus, a layer of the composition of the ~J~ ~13~ d invention being designated as A (Al, A2, ~ and a layer of a different material, e.g. a thermoplastic resin, being designated as B (Bl, B2, - ), not only a two-layer structure of A/B but a variety oî other combinations such as B/A/B, A/B/A, Al/A2/B, A/Bl/B2, B/A/B, B2/Bl/A/Bl/B2, etc. can ~e employed for a film, sheet or bottle, for instance. In the case of a filament, a bimetal-type, core (A) - sheath (B), core (B) - sheath (A), eccentric core-sheath ana other combinations of A and B can be adopted.
For co-extrusion, A may be blended witn B or vice versa, or for improved interlayer adhesion, a suitable resin may be incorporated in at least one _ A and B.
The laminated product may be optional ~ configured.
Thus, fllm, sheet, tape, bottle, pipe, fil_~ent, or modified cross-section extrudate may be men_ioned.
The laminated product may, if necessa~I, be further subjected to a variety of processi-~s, such as heat treatment, cooling, rolling, printing, dry lamina-tion, solution- or melt-coating, bag produ .ion, deep-drawing, box-making, tubing, splitting and so on.
The aforementioned shaped articles and laminated products, in particular in the form of fil-s or sheets, can be improved in physical properties by --tretching or drafting, if required.

~ ~ 3 ~ ~t~

In the present invention, the composition ls melt-molded into a film material. The thic~ness of such film is virtually optional and may range from a few microns to several hundred microns. The term 'film' as used in this specification means a film in the broad sense of the term, thus including a sheet, tape, tube, container and so on.
The film obtained in the above manner is condi-tioned for absorption of moisture or drying, if neces-sary, and then stretched.
This stretching may be uniaxial or biaxial. The effects of the invention are better materialized when the stretching ratio or draft is as high as possible.
In the case of uniaxial stretching, the stretching ratio is preferably at least 1.5 times and, for still better results, not less than 2 times. In the case of biaxial stretching, the stretching ratio is preferably not less than 1.5 times, more desirably not less than 2 times and, for still better results, not less than 4 times on the area basis.
As to the stretching technique that can be em-ployed, there may be mentioned roll stretching, tenter stretching, tubular stretching and stretching blow processes, as well as high-draft deep drawing or vacuum molding. In the case of biaxial stretching, whichever ~ $ ~ b, ~ ~ 7 ~

of concurrent biaxial stretching and serial biaxial stretching can be adop~ed.
The stretching temperature is selected from the range of about 40 to 150C.
After completion of stretching, the product is thermally set. This thermal setting can be effected by the well-known technique. Thus, with the stretched film being held in tau~ condition, it is heat-treated at a temperature of 50 to 160C, preferably at 80 to 160C for about 2 to 600 seconds.
The resulting oriented film can be subjected to a variety of processings such as cooling, rolling, printing, dry lamination, solution- or melt-coa~ing, bag-making, deep-drawing, box-making, tubing, splitting and so on.
The film, sheet or container obtainable from the composition of the present invention is useful fGr packaging foodstuffs, pharmaceutical products, in-dustrial chemicals, agrochemical products and so on.
Effects The composition according to the invention which comprises (A), (~) and (C) can have markedly improved oxygen barrier property while retaining those excellent molding characteristics and physical properties (stretch-ability, flexibility, etc.) which are inherent to 7 ;~

polyolefins.
Examples The following examples are further illustrative of the composition of the present invention. In the following description, all parts and % are ~y weight unless otherwise indicated.
Preparation of samples Pol~olefin resln MFR Meltlng point Sample (9/10 min.) (C) P-1 . Polypropylene 3 168 P-2 Ethylene-propylene copolvmer 3 1'0 (Ethylene content 4%) P-3 Ethylene-propylene copolymer 5 ~50 (Ethylene content 7%) P-4 Polypropylene 15 16B
P-5 High-density polyethylene 10 125 Saponified ethylene-vinyl acetate copolymer Sample E-1 E-2 E-3 E-4 E-5 Ethylene content 30 34 ~0 45 30 (mole %) -Degree of saponification of ~ vinyl acetate component 99.7 99.4 99.2 99.7 99.7 (mole %) (9/10 min.) 25 10 48 60 3 7 ~

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Examples 1 throuqh 10 and Control Examples l_throu~h 7 Pellets of the composition of (A), (B) and (C) were mixed in a Henschel mixer and fed to a T-die extrusion machine for melt-kneading and extrusion from the T-die to produce a 30 ~-thick film. (In the evaluation of stretchability, a 180 ~-thick film was used.) The extrusion molding conditions were as follows.
Extruder: 40 mm-dia. extruder Screw : Full-flight type, L/D = 28, CR = 3 Extrusion temperature (C):
C1/C2/C3/C4/H/D1/D2 = 170/200/220/220/220/210/210 RPM of screw: 30 rpm or 85 rpm The data on the film are presented in Table 1.

2 ~ 7 ~

Table 1 Material Blending Phvsical properties Type M2/Ml ratio Oxygen permeability Stretch- Impact P/E/G (cc-20u/m2-dav-atm) ability strength 25C x (kg-cm/mm) 75~ RH
P-l 1E-1 8.3 70/20/10 220 ~ 520 - G-2 60(30!10 28 oJ 440 3" " 90~8/2 980 'o~ 600 4E-2 3.3 80/15/5 700 ~ 585 _-2 _ _ 5E-3 16 70/25/5 340 ~ 555 :xample 6 E-1 5 95/4/1 980 ~ 680 7E-3 3.2 75/20/' 550 oJ 510 p_5 8E-4 6 75/15/10 500 ~ 475 P-S
9E-4 " 75/15/10 620 ~ 635 '' " 90/5/5 830 o) 510 1E 1 8-3 78/22/0 700 x 210 2E-5 1 70/20/'01900 o 340 C3mpara- G-1 ~ive P-1 :xample 3 E-1 8.399.7/0.3/0.1 2800 o 700 G-1 35/60/. 35 x 160 5 " " 55~15/30500 ~ 380 - (Foreign matter found) 6 " " 98/22!C.052200 x 320 7P-1 - -- 3200 ~ 720 ~3~J~7Q

(Determination of physical properties) Oxygen permeability: Determined with a MOCON Oxtran 10!50.
Stretchability: Evaluated in terms of uneven stretching in concurrent biaxial stretching (5 x 5 times) at gOC
Impact strength: Determined with a film impact tester, impact head diameter 1 inch, 20C x 65% RH
Examples 11 throuqh 15 Inner layer (I): Low-density polyethylene (MFR: 16 g/10 minutes, 190C/2160 g) Adhesive layers (II) and (IV): Maleic anhydride-modified ethylene-vinyl acetate copolymer (MFR: 2 g/10 minutes, 190C/2160 g) Intermediate layer (III): The composition comprising (A), (B) and (C) according to the invention Outer layer (V): Low-density polyethylene (MFR: 16 g/10 minutes, 190C/2160 g) Using the above resin materials, a five-layer laminate of the construction and film thicknesses (~) (I)/(II)/(III)/(IV)/(V) = 20/5/60/5/20 was fabricated under the following conditions.
~ Moldin~ conditions Extrusion machines 60 mm-dia. extruder (for inner layer) 2 ~3 40 mm-dia. extruder (for intermediate layer) 40 mm-dia. extruder (for adhesive layers) 60 mm-dia. extruder (for outer layer) Screw: All full-flight type, L/D = 30, compression ratio 2.8.
RPM of screw:
50 rpm for inner layer 40 rpm for intermediate layer 40 rpm for adhesive layers 50 rpm for outer layer Die:
A T-die with a 5-l.ayer combining adapter Die width: ~00 mm Extrusion temperature:
Extruders for inner, ou~er and adheslve layers Cl = 170C C2 = 220~C
C3 = 210C C4 = 210C
Extruder for intermediate layer Cl = 170C C2 = 20aoc C3 = 210C C4 = ~ 0C
Combining adapter 210C
T-die 210C
The results are set forth in Table 2.

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Effects _ The composition according to the invention which comprises a polyolefin resin (A), a saponified ethylene-vinyl acetate copolymer ~B~ and a specific graft copolymer (C) gives shaped articles which exhibit excellent oxygen barrier property, with the excellent physical properties of the polyolefin resin being retained.

Claims

2. Claims 1. A polyolefin resin composition comprising (A) 50 to 99.5 weight % of a polyolefin resin, (B) 0.4 to 50 weight % of a saponified ethylene-vinyl acetate copolymer, and.
(C) 0.1 to 15 weight % of a graft polymer obtain-able by grafting an ethylenically unsaturated carb-oxylic acid or a derivative thereof to a polyolefin resin and reacting the adduct with a polyamide oli-gomer, which composition satisfies the relation: M2/M1 = not less than 1.5 wherein M2 and M1 are the melt flow rates of (B) and (A), respectively, under a load of 2160 g at 210°C.
Z. A shaped article obtainable by melt-molding a composition claimed in claim 1.
3. A laminated structure at least one layer of which is comprised of a composition claimed in claim 1.
4. A shaped article according to claim 2 or a laminated structure according to claim 3 which is at least uniaxially oriented.