Resin compositions and multi-layered structures utilizing the same

The present invention provides resin compositions comprising a blend of two different saponified products of ethylene-vinyl acetate copolymers. The composition is much improved compared to a single EVOH in flexibility without adversely affecting the transparency and gas barrier property. Laminate films comprising at least one layer of said composition are excellent in resistance to dropping shock, ability to prevent air-back, skin-pack adaptability and shrink-packaging capability.

BACKGROUND OF THE INVENTION 
1. Field of the invention 
This invention relates to resin compositions being excellent in 
transparency and gas barrier property, as well as in flexibility as 
represented by resistance to dropping shock, flexural resistance, ability 
to prevent air-back, skin-pack adaptability, shrink-packaging capability, 
and the like; and further to multilayer structures comprising at least one 
layer of the composition. 
2. Description of the Prior art 
Saponified products of ethylene-vinyl acetate copolymers (hereinafter 
referred to as EVOH) are thermoplastic resins excellent in transparency, 
gas barrier property, resistance to oil and odor-keeping property as 
compared to other resins, and are thereby used for various gas-barrier 
films and for gas-barrier layers of various gas-barrier containers. 
However, multilayered films and multilayered containers comprising an EVOH 
as barrier layer often generate problems resulting from the high rigidity 
of EVOH. For example, a multilayered film or container filled with 
contents readily breaks when dropped onto the floor, a multilayered film 
filled with contents tends to generate thereon pinholes by action of 
bending and/or shock when transported, a multilayered tube often generates 
air-back, wrinkle generation upon skin-pack packaging, insufficient 
stretchability and/or shrinkage of films for shrink-packaging and so 
forth. 
Blending other thermoplastic resins with EVOH has been tried to overcome 
the above-mentioned drawbacks. Thus, for example, Japanese Patent 
Application Laid-Open No. 220839/1986 discloses that blending EVOH with an 
ethylene-carboxylic acid vinyl ester copolymer or ethylene-acrylic acid 
ester copolymer improves the flexural resistance; and Japanese Patent 
Application Laid-Open No. 81448/1986 (U.S. Pat. No. 4,645,695) discloses 
that blending EVOH with an ethylene-carboxylic acid vinyl ester copolymer 
or ethylene-acrylic acid ester copolymer modified with an 
.alpha.,.beta.-unsaturated carboxylic acid or its anhydride improves the 
shock resistance of EVOH. While these methods improve flexural resistance 
and impact strength of EVOH, they impair the transparency characteristic 
to EVOH, thereby being inapplicable to such uses as require transparency. 
Compositions comprising EVOH and polyamide are known to have high 
transparency. However, since blending of a polyamide results in a decrease 
in gas barrier property and worsens thermal stability at molding, thereby 
causing generation of gels in a short period of molding, such blended 
compositions have not been put to practical use. 
Japanese Patent Publication No. 48512/1976 and japanese Patent Application 
Laid-Open Nos. 73984/1977, 77160/1977, 101182/1977, 53089/1979, 
156082/1979 and 161447/1985 disclose about blending with EVOH a partially 
saponified product of ethylene-vinyl acetate copolymer (hereinafter 
referred to as "partially saponified EVA"), and that the use of such blend 
will give interfacial adhesiveness between EVOH and polyolefin or heat 
sealability at low temperatures. 
Actual preparation of molded articles such as film according to the process 
described in the above-mentioned prior arts has, however, encountered such 
problems as insufficient flexibility and poor thermal stability of 
obtained molded articles, poor surface appearance of obtained films such 
as streaks and pear skinned pattern and poor moldability due to frequent 
neck-in; and the process has thereby not been put into practical use yet. 
Nothing is thus known about the fact that a transparent gas-barrier resin 
composition can be obtained by blending EVOH with a partially saponified 
EVA both having specific melt indexes and vinyl alcohol component contents 
at a specific blending ratio, according to the present invention. 
There have yet been thus obtained no transparent resin compositions or 
multilayered structures thereof having improved the flexibility of EVOH as 
represented by resistance to dropping shock, flexural resistance, 
prevention of air-back, skin-pack adapatability, shrink-packaging 
capability. 
SUMMARY OF THE INVENTION 
As stated above, there has been desired development of resin compositions 
or multilayered structures comprising them having sufficient flexibility 
for achieving sufficient resistance to dropping shock, flexural 
resistance, prevention of air-back, skin-pack adaptability, 
shrink-packaging capability and the like, without adversely affecting the 
transparency and the gas barrier property of EVOH. 
The present inventors have made an intensive study to develop an excellent 
resin composition having high transparency, flexibility and gas barrier 
property. At first a film formed from a blend of an EVOH with a partially 
saponified EVA had many streaks and a pear skinned surface and was poor in 
transparency. Further the film formation itself was poorly achieved 
because of frequent neck-in. However, upon further investigation of a wide 
variety of both EVOH's and partially saponified EVA's for blends thereof, 
it was found that a film having excellent transparency and surface 
appearance can first be obtained with good formability when an EVOH having 
a specific melt index at 190.C-2160 g (hereinafter referred to as MI) and 
a specific vinyl alcohol component content is blended with a partially 
saponified EVA having a specific MI and a specific vinyl alcohol component 
content at a specific blending ratio and the invention was completed. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
Hereinbelow the present invention will further be illustrated in detail. 
EVOH (A) used in the invention has an ethylene content of 25 to 50 mol % 
and a saponification degree of vinyl acetate component of at least 90%, 
preferably at least 95%. If the ethylene content is less than 25 mol %, 
the molding temperature will be close to the decomposition temperature, 
thereby rendering the molding difficult to perform; and if the ethylene 
content exceeds 50 mol %, the gas barrier property will be insufficient. 
An EVOH having a saponification degree of vinyl acetate component of less 
than 90% also has an insufficient gas barrier property. The MI of EVOH 
used in the invention is not more than 15 g/10 min, preferably not more 
than 7 g/10 min. If the MI exceeds 15 g/10 min, the blend of such EVOH 
with a partially saponified EVA will suffer a large neck-in at molding, 
resulting in unsuccessful molding. The MI is of EVOH is preferably at 
least 0.1 g/10 min, more preferably at least 0.5 g/10 min. 
The EVOH in the present invention may be one modified with not more than 5 
mol % of a copolymerizable monomer. Examples of such modifying monomer 
include, among others, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 
acrylic acid esters, methacrylic acid esters, maleic acid, fumaric acid, 
itaconic acid, higher fatty acid vinyl esters, alkylvinyl esters, 
N-(dimethylamonoethyl)-methacrylamide or its quaternary compound, 
N-vinylpyrrolidone, N,N-butoxymethylacrylamide, vinyltrimethoxysilane, 
vinylmethyldimethoxysilane and vinyldimethylmethoxysilane. 
The partially saponified EVA (B) used in the invention must have an 
ethylene content of 80 to 94 mol %, preferably 84 to 92 mol % and a 
saponification degree of vinyl acetate component of at least 20%, 
preferably at least 30%, most preferably at least 40%. The saponification 
degree of the partially saponified EVA is preferably not more than 98%, 
more preferably not more than 97%. When the ethylene content is less than 
80 mol %, its thermal stability becomes poor upon blending with EVOH. On 
the other hand when the ethylene content exceeds 94 mol %, the blending 
does not produce improvement effects on resistance to dropping shock, 
flexural resistance, prevention of air-back, skin-pack adaptability, 
shrink-packaging capability, and the like. A saponification degree of less 
than 20% will worsen the transparency. The saponified EVA must have an MI 
which satisfies the formula (1), and preferred from the standpoint of ease 
of molding are those EVA's having an MI of not more than 100 g/10 min, 
more preferably not more than 30 g/10 min, most preferably not more than 
20 g/10 min. The MI of the partially saponified EVA is preferably at least 
0.1 g/10 min, more preferably at least 0.5 g/10 min. 
The blending ratio of the EVOH (A) with the partially saponified EVA (B) is 
60 to 95 wt % of the former with 5 to 40 wt % of the latter, and 
preferably 70 to 90 wt % of the former with 10 to 30 wt % of the latter. 
The present invention employs a specific EVOH and a specific partially 
saponified EVA, whose MI's, contents of vinyl alcohol component and 
blending ratio yield a P-value by the following formula (1) of not more 
than 40, preferably not more than 15. The P-value is preferably at least 
0.6, more preferably at least 0.8. 
##EQU1## 
where: 
M=M.sub.A /M.sub.B (when M.sub.A .gtoreq.M.sub.B) 
M=M.sub.B /M.sub.A (when M.sub.Z &lt;M.sub.B) 
M.sub.A :MI of resin A 
M.sub.B :MI of resin B 
VA.sub.A : content of vinyl alcohol component in resin A (mol %) 
VA.sub.B : content of vinyl alcohol component in resin B (mol %) 
B:wt % of resin B blended in the composition 
The P-value obtained by formula (1) is very important with regard to the 
transparency of the composition; and the smaller the value, the better the 
transparency. When the P-value exceeds 40, the transparency is almost 
lost. This can be seen on a single-layer film prepared from the 
composition, where the film from a composition having a P-value exceeding 
40 has many streaks or pear skinned pattern and its transparency is 
extremely decreased. The generation of streaks or pear skinned pattern is 
found to be influenced also by the relative amounts of M.sub.A and 
M.sub.B. When M.sub.A &gt;M.sub.B, pear skinned pattern will readily generate 
and when M.sub.A &lt;M.sub.B streaks tend to be formed. Further, the 
transparency of the composition depends on the contents of vinyl alcohol 
component in EVOH and in partially saponified EVA in such a manner that 
the smaller the difference between the vinyl alcohol component of EVOH and 
that of partially saponified EVA, the better the transparency. The 
transparency further depends on the blending ratio of EVOH and partially 
saponified EVA, the transparency of the obtained film being better as the 
blending ratio of partially saponified EVA becomes small. It had never 
been known and therefore was quite unexpectedly found that, as described 
hereinabove, the ratio of MI's of EVOH and partially saponified EVOH has 
such big influence on the appearance of the film surface, and further the 
P-value obtained by formula (1) from MI ratio, difference in vinyl alcohol 
contents and the blending ratio has such a big influence on the 
transparency. 
In the present invention, practice of blending the EVOH with the partially 
saponified EVA is conducted using a Banbary mixer, single- or twin-screw 
extruder, Brabender Plastograph, and the like, and may also be done by 
directly charging the components to a molding machine of various types 
where they are kneaded with each other. Addition of a plasticizer upon 
kneading the composition is preferred because a larger softening effect is 
thereby obtained by synergetic effect of the plasticizer and partially 
saponified EVA. Examples of preferred plasticizers are alcohol-related 
plasticizers such as glycerine, diglycerine, 1,2-propanediol, 
1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 
1,4-butanediol, 1,2,6-hexanetriol, diethanolamine and diethylene glycol; 
while also used are dimethyl phthalate, diethyl phthalate, dioctyl 
phthalate, wax, liquid paraffine, phosphoric acid esters, and amides such 
as lauryl amide and o,p-toluenesulfonamide, 
N-ethyl-o,p-toluenesulfonamide. 
Other additives such as various resins, heat stabilizers, antioxidants and 
colorants may optionally be added within limits not to impair the effect 
and function of the present invention. Particularly effective heat 
stabilizers are those used for polyvinyl chloride such as hydrotalcite 
compounds, metal soap, lead-salt compounds and organotitanates; 
hindered-phenol compounds, hindered-amine compound, sulfides and 
phosphite, among which hydrotalcites are most preferred. 
The resin composition of the present invention is preferably used in a form 
of laminate, in which it can constitute any of intermediate layers, 
outermost layer and innermost layer. There are no particular limits in 
resins to be laminated with the resin composition of the present invention 
but, generally, preferred are ones having a high transparency, e.g. 
polyolefins such as low-density polyethylene, linear low-density 
polyethylene, polypropylene, ethylene-propylene copolymers and polybutene; 
olefin copolymers such as ethylene-vinyl acetate copolymers, 
ethylene-ethyl acrylate copolymers and ionomers, each of which has 
principally olefin; polyethylene terephthalate; polycarbonates; 
polyamides; polystyrene; polyvinyl chloride; water-crosslinked polyolefins 
(siloxane-crosslinked polyolefins); radiation-cured polyolefins and the 
like. Among these, more preferred are linear low-density polyethylene, 
ethylene-vinyl acetate copolymers, and polyamides. 
In the case where the interfacial adhesion between such resin and EVOH is 
insufficient, an adhesive resin layer is preferably provided therebetween. 
Any adhesive resin may be used as long as it will not cause any 
delamination when the laminate is in practical use but, preferably used 
are modified olefin copolymers comprising a polyolefin-related polymer 
such as polyethylene, an ethylene-vinyl acetate copolymer having a vinyl 
acetate content of not more than 45 wt % or an ethylene-(meth)acrylic acid 
ester having a (meth)acrylic acid ester content of not more than 45 wt %, 
modified by chemically bonding (e.g. by addition or by grafting) thereto 
an ethylenically unsaturated carboxylic acid or its anhydride. These 
adhesive resins can not only be provided between the layers but also be 
incorporated into either one or both of the layers. 
The laminates comprising the resin composition of the present invention can 
be molded into films, sheets, tubes pipes, bottles and the like. There is 
no particular limitation on the thickness construction of the laminate 
but, it is preferred for better transparency that the layer of the resin 
composition of the invention be used in a thickness of not more than 300 
.mu., more preferably not more than 200 .mu.. 
As methods for laminating the resin composition of the invention, mentions 
are made of coextrusion process, extrusion lamination process, dry 
lamination process and the like, among which particularly preferred is 
coextrusion process because the characteristics of the resin composition 
of the invention thereby exerts most. 
The laminates thus obtained can be used as containers having excellent 
resistance to dropping shock, tubes being excellent in preventive ability 
of air-back, bag-in-boxes excellent in flexural resistance, and films 
excellent in skin-pack adapatability and shrink-packaging capability. 
Further, laminates (pipes) comprising the resin composition layer and a 
layer of a resin selected from water-crosslinked polyolefins, 
radiation-cured polyolefins and polybutene can be used for floor-heating 
piping. In this case the resin composition is preferably used as an 
intermediate or the outermost layer.

Other features of the invention will become apparent in the course of the 
following descriptions of exemplary embodiments which are given for 
illustration of the invention and are not intended to be limiting thereof. 
EXAMPLE 1 
70 parts by weight of an EVOH having an ethylene content of 44 mol %, a 
saponification degree of vinyl acetate component of 99% and a melt index 
(MI) measured at 190.degree. C. under 2160 g according to ASTM D1238-65T 
of 5.5 g/10 min and 30 parts by weight of a partially saponified EVA 
having an ethylene content of 88 mol %, a saponification degree of vinyl 
acetate component of 80% and an MI of 4.8 g/10 min were blended and 
extruded through a 30-.phi. different direction twin-screw extruder into 
pellets ? -value=10.4). The thus obtained pellets were formed through a 
40-.phi. single-screw extruder into a film having a thickness of 25 .mu.. 
The obtained film was evaluated for surface appearance, formability, haze, 
loop stiffness, flexural resistance, Young's modulus and oxygen gas 
transmission rate (OTR). 
The evaluation of the film appearance was done on streaks, pear skinned 
pattern and gels by visual inspection with the results expressed in terms 
of ranking A through E shown in Table 1. The evaluation for the 
formability was done in terms of the degree of neck-in occurred as 
expressed by ranking A through E shown. 
TABLE 1 
______________________________________ 
Pear skinned 
Rank Streaks pattern Gel Neck-in 
______________________________________ 
A None None None None 
B Minute streaks 
Minute pear-skin 
C Streaks Pear-skin pattern 
A small A little 
amt of gels 
neck-in 
D Big & many Big pear-skin 
streaks pattern 
Film formation unsuccesful - 
Very many Frequent 
gels neck-in 
______________________________________ 
Haze was measured with Poic Integrated Sphere light transmission tester 
made by Nihon precision Optics Co. 
Loop stiffness was measured at 20.degree. C. and 65% RH with a loop 
stiffness tester made by Toyo Seiki Co. on a film specimen of 15 mm wide 
folded into a loop of 60 mm long for its repulsive force when compressed 
to a loop diameter of 20 mm. The loop stiffness is important as a measure 
for the ability of preventing air-back. Compositions having smaller loop 
stiffness are thought to be of higher ability to prevent air-back. 
Flexural resistance was evaluated using Gelbo Flex Tester made by Rigaku 
Kogyo Co. as follows. A specimen of 12 in..times.8 in. was made round such 
that the both ends meet to form a cylinder having a diameter of 3.5 
inches. The both ends of the thus formed cylinder was held at an initial 
holding distance of 7 inches and a holding distance when flexed to the 
maximum of 1 inch. The thus held specimen was subjected to 300 
reciprocating motions, one motion consisting of twisting it to an angle of 
440. in the first 3.5 inches of the stroke and the succeeding linear 
horizontal move of 2.5 inches, at a rate of 40 times/min under conditions 
of 20.degree. C. and 65% RH. Then the number of pinholes formed on the 
specimen was determined. 
Young's modulus was measured at 20.degree. C., 65% RH according to ASTM 
D-882-67. It is important as to skin-pack adaptability and 
shrink-packaging capability. A composition having a low Young's modulus 
may be suited for skin-pack and shrink-film packaging where a stretching 
process is involved. 
Oxygen gas transmission rate (OTR) or, oxygen permeability, was determined 
using OX-TRAN 10-50A made by Modern Control Co. 
The results of the evaluations are shown in Table 2. The film obtained in 
this Example was excellent in film appearance, formability and 
transparency, as well as flexibility as represented by loop stiffness, 
flexural resistance and Young's modulus, and in gas barrier property. 
EXAMPLES 2 THROUGH 11 
Compositions comprising EVOH's and partially saponified EVA's shown in 
Table 2 were evaluated in the same manner as in Example 1, to give results 
shown in Table 2. These compositions were also excellent in surface 
appearance, formability and transparency, as well as flexibility as 
represented by loop stiffness, flexural resistance and Young's modulus, 
and in gas barrier property. 
COMATIVE EXAMPLE 1 
An EVOH having an ethylene content of 44 mol %, a saponification degree of 
vinyl acetate component of 99% and an MI of 5.5 g/10 min was molded 
through a 40-.phi. single-screw extruder and formed into a film having a 
thickness of 25 .mu.. The obtained film was evaluated in the same manner 
as in Example 1 to give results shown in Table 2. The film had large 
values of loop stiffness, flexural resistance (number of pinholes 
generated) and Young's modulus, proving its poor flexibility. 
COMATIVE EXAMPLES 2 THROUGH 11 
Compositions comprising EVOH's and partially saponified EVA's shown in 
Table 2 were evaluated in the same manner as in Example 1, to give results 
shown in Table 2. 
The film of the composition of Comparative Example 2 had large values of 
loop stiffness and Young's modulus, and had a large number of pinholes, 
all of which show that it was short of flexibility. 
The film of the composition of Comparative Example 3 had a large OTR value, 
showing its insufficient gas barrier property. 
In Comparative Example 4, neck-in occurred frequently and the formability 
was poor. 
In Comparative Examples 5 and 6, large OTR values show that the 
compositions were poor in gas barrier property. 
In Comparative Example 7, very many gels generated on the film, which was 
not usable. Large number of pinholes generated in the test due to the 
production trouble above or from some other causes. 
The film of the composition of Comparative Example 8 had large values of 
loop stiffness and Young's modulus, and had a large number of pinholes, 
all of which shows that it was short of flexibility. 
In Comparative Example 9, haze value was large due to the low 
saponification degree of the partially saponified EVA, and the film was 
thereby poor in transparency. 
In Comparative Examples 10 and 11, serious streaks and pear skinned pattern 
generated due to the high P-value of more than 40, thereby causing large 
haze and rendering the film poor in transparency. 
EXAMPLE 12 
70 parts by weight of an EVOH having an ethylene content of 44 mol % a 
saponification degree of vinyl acetate component of 99% and an MI of 5.5 
g/10 min, 30 parts by weight of a partially saponified EVA having an 
ethylene content of 88 mol %, a saponification degree of vinyl acetate 
component of 80% and an MI of 4.8 g/10 min and 3 parts by weight of 
glycerine were made into pellets and the pellets formed into a film having 
a thickness of 25 .mu. in the same manner as Example 1. The 
film-formability was good. The thus obtained film had a haze of 2%, a loop 
stiffness of 100 mg and a Young's modulus of 40 kg/mm.sup.2. The film 
yielded no pinholes by 300-times Gelbo Flex test, showing its high 
flexibility. The OTR was 2.2 cc/m.sup.2.day.atm proving the high gas 
barrier property of the film. 
TABLE 2 
__________________________________________________________________________ 
EVOH (Resin A) Partially saponified EVA (Resin B) 
Et* Saponi- 
VA.sub.A 
MI Blend- 
Et* Saponi- 
VA.sub.B 
MI Blend- 
con- 
fication 
con- 
g/ ing con- 
fication 
con- 
g/ ing 
tent 
degree 
tent 
10 ratio 
tent 
degree 
tent 
10 ratio 
P- 
mol % 
% mol % 
min 
wt % 
mol % 
% mol % 
min 
wt % 
Value 
__________________________________________________________________________ 
Ex. 1 
44 99 55.4 
5.5 
70 88 80 9.6 4.8 
30 10.4 
Ex. 2 
44 99 55.4 
5.5 
93 88 80 9.6 4.8 
7 5.6 
Ex. 3 
44 99 55.4 
5.5 
60 82 95 17.1 
5.2 
40 6.7 
Ex. 4 
29 99 70.3 
1.2 
70 88 80 9.6 1.0 
30 15.3 
Ex. 5 
32 92 62.6 
1.7 
80 88 80 9.6 1.0 
20 18.4 
Ex. 6 
44 99 55.4 
5.5 
70 92 80 6.4 5.3 
30 14.8 
Ex. 7 
48 99 51.5 
10 80 88 80 9.6 14 20 9.0 
Ex. 8 
48 99 51.5 
13 80 88 71 8.5 16 20 10.0 
Ex. 9 
44 99 55.4 
5.5 
70 88 30 3.6 6.0 
30 13.1 
Ex. 10 
44 99 55.4 
5.5 
70 88 80 9.6 20 30 32.9 
Ex. 11 
44 99 55.4 
5.5 
70 88 80 9.6 1.5 
30 33.2 
Comp. 
44 99 55.4 
5.5 
100 -- -- -- -- -- -- 
Ex. 1 
Comp. 
44 99 55.4 
5.5 
97 88 80 9.6 4.8 
3 4.8 
Ex. 2 
Comp. 
44 99 55.4 
5.5 
50 82 95 17.1 
5.2 
50 7.8 
Ex. 3 
Comp. 
38 99 61.4 
18 70 88 75 9.0 25 30 15.1 
Ex. 4 
Comp. 
55 99 44.6 
20 70 82 95 17.1 
5.2 
30 10.0 
Ex. 5 
Comp. 
32 85 57.8 
1.5 
85 88 80 9.6 1.0 
15 10.1 
Ex. 6 
Comp. 
38 99 61.4 
12 70 78 70 15.4 
15 30 9.6 
Ex. 7 
Comp. 
44 99 55.4 
5.5 
70 97 80 2.4 6.1 
30 14.0 
Ex. 8 
Comp. 
44 99 55.4 
5.5 
70 88 10 1.2 4.5 
30 16.2 
Ex. 9 
Comp. 
44 99 55.4 
5.5 
70 88 80 9.6 25 30 41.1 
Ex. 10 
Comp. 
44 99 55.4 
5.5 
70 88 80 9.6 1.0 
30 49.8 
Ex. 11 
__________________________________________________________________________ 
Film properties 
Loop 
Flexural 
Young's 
OTR 
Film surface stiff- 
resistance 
modu- 
cc/m.sup.2 .multidot. 
pear- Forma- 
Haze 
ness 
No. of 
lus day .multidot. 
streaks 
skin 
gels 
bility 
% mg pinholes 
kg/mm.sup.2 
atm 
__________________________________________________________________________ 
Ex. 1 A A A A 2 150 
0 80 1.7 
Ex. 2 A A A A 1 200 
0 120 0.8 
Ex. 3 A A A A 3 60 
0 60 2.7 
Ex. 4 A B A A 4 200 
0 110 0.5 
Ex. 5 A B A A 2 200 
0 120 2.8 
Ex. 6 A A A A 3 160 
0 100 1.6 
Ex. 7 A A A A.about.B 
2 160 
0 90 1.8 
Ex. 8 A A A B 2 160 
0 90 1.8 
Ex. 9 A A A A 4 140 
0 80 1.6 
Ex. 10 B A A A 2 150 
0 90 1.5 
Ex. 11 A B A A 2 140 
0 90 1.4 
Comp. A A A A 1 410 
&gt;100 200 1.7 
Ex. 1 
Comp. A A A A 2 350 
&gt;100 190 1.0 
Ex. 2 
Comp. B C B B 10 70 
0 80 12.6 
Ex. 3 
Comp. A A B E 2 170 
3 100 1.4 
Ex. 4 
Comp. A A A C 2 120 
0 80 10.1 
Ex. 5 
Comp. A A B A 2 150 
0 90 10.8 
Ex. 6 
Comp. A A E C 4 170 
10 100 1.2 
Ex. 7 
Comp. A B A A 8 260 
53 150 1.5 
Ex. 8 
Comp. A C A A 25 160 
0 100 1.8 
Ex. 9 
Comp. E C A B 56 150 
0 90 1.9 
Ex. 10 
Comp. A E A A 42 160 
0 90 2.0 
Ex. 11 
__________________________________________________________________________ 
*"ET" stands for "Ethylene". 
EXAMPLE 13 
A 3-kind/5-layer laminated film having a total thickness of 85 .mu. was 
prepared by coextrusion with 3 extruders and a 3-kind/5-layer diehead, 
with the following construction. The composition used for the intermediate 
layer having a thickness of 15 .mu. was: 70 parts by weight of an EVOH 
having an ethylene content of 44 mol % a saponification degree of vinyl 
acetate component of 99% and an MI of 5.5 g/10 min and 30 parts by weight 
of a partially saponified EVA having an ethylene content of 89 mol %, a 
saponification degree of vinyl acetate component of 95% and an MI of 4.8 
g/10 min; and the intermediate layer had a P-value of 10.4. The 
composition was blended through an extruder into pellets prior to film 
formation. The outer and inner layers each had a thickness of 30 .mu. and 
comprised a linear low-density polyethylene copolymer containing 3.2 mol % 
of 4-methyl-1-pentene and having an MI of 2.1 g/10 min. Between the layers 
an adhesive resin layer of 5 .mu. thick each was provided, which comprises 
an ethylene-vinyl acetate copolymer modified with maleic anhydride 
containing vinyl acetate component in an amount of 20 wt % and maleic 
anhydride component in an amount of 0.5 wt %. 
The obtained laminate film was subjected to Gelbo Flex test, which 
proceeded until generation of pinholes on the film, whereby the oxygen gas 
transmission rate was determined at 20.degree. C., 65% RH at several steps 
before the start of pinhole generation. At that time the specimen at each 
step of the flex test was flattened to the original rectangle of 12 
in..times.8 in. and the center part of the rectangle was tested for OTR. 
The results are shown in Table 3. No appreciable change in the oxygen 
transmission rate was observed in the course of the flex testing up to the 
point of pinhole generation. Generation of pinholes had not been observed 
before 7,000 strokes were complete. One pinhole was first observed when 
the film was checked for pinholes after 7,100 strokes of the test. No 
delaminations between layers were observed during the test. The film had a 
haze of 4%, was good in transparency, and had no appreciable streaks or 
pear skinned pattern. 
COMATIVE EXAMPLE 12 
Example 13 was repeated except for using as the resin to be blended with 
EVOH for the intermediate layer an ethylene-vinyl acetate copolymer having 
an ethylene content of 89 mol % and an MI of 6 g/10 min to give test 
results also shown in Table 3. Though the flexural fatigue test showed a 
good result similar to that in Example 13, the film had a haze of 25%, 
being short of transparency. 
TABLE 3 
______________________________________ 
No. of strokes 
No. of Oxygen trans- 
in flexural 
pin- mission rate 
fatigue test 
holes cc/m.sup.2 .multidot. day .multidot. atm 
Haze 
______________________________________ 
Example 0 0 1.1 4 
13 1000 0 1.2 
2000 0 1.2 
3000 0 1.2 
7000 0 1.2 
Comp. 0 0 1.2 25 
Ex. 12 1000 0 1.2 
2000 0 1.2 
3000 0 1.2 
7000 0 1.2 
______________________________________ 
EXAMPLE 14 
A multilayered container having a capacity of 10 liters and a construction 
described below was prepared by coextrusion direct-blow molding using 2 
extruders and a 2-kind/3layer diehead. The intermediate layer had an 
average thickness of 15 .mu. and a P-value of 10.4 and comprised a 
composition made of 70 parts by weight of an EVOH having an ethylene 
content of 44 mol %, a saponification degree of vinyl acetate component of 
99% and an MI of 5.5 g/10 min and 30 parts by weight of a partially 
saponified EVA having an ethylene content of 89 mol %, a saponification 
degree of vinyl acetate component of 95% and an MI of 4.8 g/10 min. The 
composition was blended through an extruder into pellets prior to the 
molding. The outer and inner layers provided on both sides of the 
intermediate layer each had an average thickness of 300 .mu. and comprised 
a composition of 70 parts by weight of an ethylene-vinyl acetate copolymer 
having a vinyl acetate content of 5 wt % and 30 parts by weight of an 
ethylene-vinyl acetate copolymer modified with maleic anhydride containing 
vinyl acetate component in an amount of 20 wt % and maleic anhydride 
component in an amount of 0.5 wt %. The container was filled with 10 
liters of water and the container with the contents was dropped 3 times 
from a height of 1 meter to show no breakage, proving its high resistance 
to dropping shock. 
COMATIVE EXAMPLE 13 
Example 14 was repeated except for using an intermediate layer of the EVOH 
alone. In the dropping test, the container broke at the first dropping. 
EXAMPLE 15 
A multilayered tube having a capacity of 250 ml, an average total wall 
thickness of 350 .mu. and a construction described below was prepared by 
direct-blow molding using 3 extruders and a 3-kind/5-layer diehead. The 
intermediate layer had an average thickness of 20 .mu. and a P-value of 
10.4 and comprised a composition made of 70 parts by weight of an EVOH 
having an ethylene content of 44 mol % a saponification degree of vinyl 
acetate component of 99% and an MI of 5.5 g/10 min and 30 parts by weight 
of a partially saponified EVA having an ethylene content of 89 mol %, a 
saponification degree of vinyl acetate component of 95% and an MI of 4.8 
g/10 min. The composition was blended through an extruder into pellets 
prior to the molding. The outer and inner layers provided on both sides of 
the intermediate layer each had an average thickness of 150 .mu. and 
comprised an ethylene-vinyl acetate copolymer having a vinyl acetate 
content of 8 wt %. Between the layers interposed were adhesive resin 
layers each having an average thickness of 15 .mu. and comprising an 
ethylene-vinyl acetate copolymer modified with maleic anhydride containing 
vinyl acetate component in an amount of 20 wt % and maleic anhydride 
component in an amount of 0.5 wt %. The obtained tube was cut at the 
center to a length of 15 mm. The cut piece showed, when compressed with a 
loop stiffness tester by 10 mm, a repulsive force of 650 mg. 
COMATIVE EXAMPLE 14 
Example 15 was repeated except for using for the intermediate layer an EVOH 
having an ethylene content of 44 mol % and a saponification degree of 
vinyl acetate component of 99% and an MI of 5.5 g/10 min singly. Loop 
stiffness testing was conducted in the same manner as in Example 14, to 
obtain a repulsive force of 1500 mg.