There is disclosed a multi-layer laminate molding having a layer structure that a main material layer made mainly of a polyethylenic resin at the outer side and an ethylene-vinyl acetate copolymer saponified product layer or polyamide resin layer at the inner side are laminated through at least an adhesive material layer, the adhesive material layer comprising a resin composition containing (A) 60 to 95% by weight of at least one resin selected from the-group consisting of (1) a high density polyethylenic resin having specified physical properties, (2) a linear low density polyethylenic resin having specified physical properties, (3) a modified high density polyethylenic resin obtained by grafting unsaturated carboxylic acid and the like onto the above (1), and (4) a modified linear low density polyethylenic resin obtained by grafting unsaturated carboxylic acid and the-like onto the above (2), and containing at least 0.1% by weight of (3) and/or (4) and (B) 40 to 5% by weight of a linear ultra low density polyethylenic resin having specified, physical properties said resin composition having a proportion of the unsaturated carboxylic acid and the like grafted of 0.001 to 50% by weight, the difference in acoustic impedance between the main material layer and adhesive material layer being at least 8.5.times.10.sup.-3 g/cm.sup.2 .multidot..mu.sec. This multi-layer laminate molding is excellent in barrier properties, and non-destructive detection of the adhesive material layer can be carried out easily by the supersonic wave reflection method.

TECHNICAL FIELD 
The present invention relates to a multi-layer laminate molding having a 
laminate structure of at least 3-kind 3-layers between which a specified 
adhesive material layer is sandwiched, and more particularly, to a useful 
multi-layer laminate-molding of a containers a wrapping bag, various 
members, and the like, in which the presence or absence of the adhesive 
material layer can be detected in a non-destructive state by using a 
supersonic wave reflection method, and which is excellent in barrier 
properties and has greatly suitable characteristics for quality control or 
process control. 
BACKGROUND ART 
As has heretofore been well known, multi-layer laminate moldings obtained 
by laminating a-non-polyolefinic resin, such as a polyamide resin (PA), a 
polyester resin, a saponified-product of an ethylene-vinyl acetate 
copolymer (ethylene-vinyl alcohol copolymer), a halogen-containing resin, 
e.g., a polyvinyl chloride resin (PVC) and a polyvinylidene chloride resin 
(PVDC), a polycarbonate resin (PC), and a polymer alloy of a polyphenylene 
oxide resin and PA, a foil of metal, such as aluminum, iron, copper, tin, 
nickel and the like, an alloy containing the metal as a major component 
(for example, stainless steel), and the like, a synthetic resin film 
having aluminum, silica and the like vacuum-deposited thereon, and so 
forth, have functions of barrier properties against gas and steam, an 
improvement in the appearance, such as surface gloss, coating properties, 
and so forth, and are widely used as various moldings, such as wrapping 
containers, wrapping bags, and industrial members. 
Many of these multi-layer laminate moldings employ, as a main material 
layer, from viewpoints of an economical point, moldability and 
workability, sealability, moisture resistance and water resistance, and to 
forth, a structure that a high-pressure-process polyethylenic resin (low 
density polyethylenic resin), a moderate or low-pressure-process 
polyethylenic-resin (linear low density to high density polyethylenic 
resin), a polypropylenic resin an olefinic copolymer resin and a 
composition containing these as the major component and various fillers, 
such as calcium carbonate, talc, mica, glass fibers, carbon fibers, 
organic fibers and the like; compounded thereto; if necessary. 
Since these polyolefinic resins have a non-polar molecular structure, they 
are poor in adhesive properties to, affinity to, and compatibility with 
the aforementioned-non-polyolefinic resins, metallic materials and the 
like, and imparting the aforementioned characteristics by polar monomer 
modification (graft polymerization) of the polyolefinic resin, using a 
copolymer of olefin (particularly ethylene) and a polar monomer, 
compounding (blending) a polar resin, or treating with chemical, or 
physical means, is widely employed. Particularly in the case that molding 
is conducted by a coextrusion method, it is well known that with a 
so-called modified polyolefinic resin modified with a polar monomer, as an 
adhesive material, a multi-layer laminate with the aforementioned various 
materials is produced (for example, Japanese Patent Publication Nos. 
12782/1986 and 39448/1980, and "'87-2 (Wrapping Material Report), Trend of 
Market and Course of Development of Coextrusion Multi-Layer Films and 
Sheets (Sogo Hoso Shuppan Co, Ltd., published on Feb. 27, 1987, pages 285 
to 293). 
When such multi-layer laminates are produced, it is considered that with 
one-way Containers and the like which are relatively short in the period 
of use, and are not subject to high impact at the step of production of 
products or commodities, and at the step of transportation, there is no 
high need for performance such as interlayer adhesive strength. However, 
with moldings such as containers, bags, members and the like which are 
required to have long term durability and high resistance against 
vibration and-various types of impact, not only adhesive performance and 
durability of the adhesive material layer are of great importance, but 
also it is more important and necessary to confirm the presence or absence 
of the adhesive material layer constituting the molding, at a desired 
position. 
If in the multi-layer laminate molding, particularly a container, a bag and 
the like, there is a site where the adhesive layer is, entirely or 
partially, removed owing to an unidentified cause, it is a risk that 
mechanical characteristics could be reduced. In the evaluation of 
durability over a long period, when the contents are liquid or gaseous, 
there is a possibility that the contents remain in the disconnected point, 
exerting influences on the whole of the multi-layer laminate molding, 
reducing the performance, and moreover reducing the appearance, and 
finally reducing the product value. Moreover, there is a possibility that 
water, moisture and the like from the atmosphere remain in the 
disconnected point, exerting the same influences as above. 
Accordingly, when there are such possibilities, it is necessary to confirm 
that the adhesive material layer in the multi-layer laminate molding is 
present over the whole of the desired place. There has not been known a 
method which enables to detect the presence of the adhesive material 
layer, easily and economically, without destructing the multi-layer 
laminate molding. 
Although as a method of confirming in advance the presence of the adhesive 
material layers of the multi-layer laminate molding, a method in which 
part of the laminate molding is cut and the cross section of the cut 
portion is examined by various techniques (for example, examination using 
a magnifying loupes, an optical microscope, and the like), is in general 
use, a sample used for this confirmation cannot be used as a molding. In 
accordance with this method, it is only assumed that the adhesive material 
layer in the multi-layer laminate molding could be present; this method is 
not a sufficiently sure method . 
On the other hand, in multi-layer laminate moldings which are of relatively 
high transparency, the presence of the adhesive material layer can be 
confirmed by employing an optically analytical technique and so forth. 
However, this method is limited to relatively thin ones, and influenced by 
the molecular structure of the non-polyolefinic resin material Therefore, 
the method lacks reliability. 
Moreover, a method may be considered, in which the adhesive material layer 
is colored by using an adhesive material in which a colorant, such as 
pigment, is compounded, and the presence of the adhesive material layer is 
confirmed with the sight or by the use of a color difference meter and so 
forth. However, the method imposes serious limitations to the product 
appearance, and when-the outer-layer is opaque and the thickness of the 
layer is large, the method is not applicable. 
Accordingly, in general, the aforementioned methods confirming in advance, 
and a technique in which the presence of the adhesive material layer 
is-controlled by checking the amounts of the adhesive material used before 
and after molding of the product, and by comparing the amount of the 
adhesive material used with the amount calculated or estimated from the 
thickness, surface area and density of the adhesive material layer in the 
laminate molding, are employed. In addition, there is proposed a method in 
which a detecting medium, such as iron powder or glass fiber, is 
introduced into a specified layer in multi-layer extrusion molding, and 
detected by the use of a magnetic sensor or a supersonic wave head, 
respectively (Japanese Patent Application Laid-Open No. 260417/1988). This 
introduction, however, is not practical in respect of reduction in 
adhesive properties, durability, flexibility, impact resistance and so 
forth. 
In recent years, it has been proposed to use a laminate molding as a fuel 
oil container, such as an automobile tank, which is required to have long 
term durability and high resistance against vibration and various types of 
impact. 
Heretofore, metallic tanks have been used, but the trend is moving to tanks 
made of synthetic resins from view-points of reduction in the-weight of 
the tank, freedom of the shape, an increase in the volume, anti-rusting 
properties, and so forth (for example, Tsuzuki et al. "Plastics" Vol. 23, 
No. 8, page 52 (1972), ibid,, Vol. 23, No. 5, page 113 (1972), ibid., Vol. 
23, No. 11, page 131 (1972), "Nikkei New Materials" published on Feb. 29, 
1988, pages 34 to 35, and Hara et al., "Plastics" Vol. 39, No. 6, page 109 
(1988)). In addition, for improving gas-liquid barrier property of fuel 
oil there is proposed a fuel oil container comprising a plurality of 
layers, in which the number of layers in the tank is increased, and as the 
material of each layer, a high density polyethylenic resin, a modified 
polyethylenic resin, a polyamide resin and the like are used (for example, 
Kurihara et ale, SAE Technical Paper Series, No. 870304 (23 to Feb. 27, 
1987), Fukuhara, "Plastics Age" Vol. 35, No. 3, page 129 (1989)). In 
connection with the structure, there are a 3-type 3-layer structure in 
which a high density polyethylenic resin is used as the outer layer, a 
modified polyethylenic layer is used as the intermediate layer, and a 
polyamide resin is used as the inner layer, and a 3-type 5-layer structure 
in which a high density polyethylenic resin is used as the inner and outer 
layers, a polyamide resin is used as the intermediate layer, and an 
adhesive layer is provided between each of the inner and outer layers, and 
the intermediate layer; they are considered greatly promising as fuel 
tanks having permeation resistance against fuel oil. 
As similar ones, there are, for example, multi-layer. moldings comprising 
at least a modified polyolefinic resin layer having adhesive properties to 
a polyamide resin/a polyamide resin layer, or a modified polyolefinic 
resin layer/polyamide resin layer/a modified polyolefinic-resin layers A 
polyamide resin such as polyamide 6 (Nylon 6) and the like has excellent 
permeation resistance against fuel oil, particularly gasoline. 
On the other hand, in view of recent circumstances, so-called alcohol mixed 
gasoline-as obtained by mixing alcohol, such as methyl alcohol, ethyl 
alcohol or the like, with gasoline has already been used in areas mainly 
with South America, and this tendency is gradually spreading over areas 
with North America as the center. Investigation of material exhibiting 
good barrier performance when used for such so-called alcohol mixed 
gasoline confirmed that a saponified product of an ethylene-vinyl acetate 
copolymer (hereinafter referred to as "EVOH") is excellent. 
Moreover, in addition to the fact that polyethylenic adhesive materials 
heretofore known are seriously insufficient in respect of adhesive 
properties to EVOH or PA and long term adhesive durability, it is greatly 
important, as described hereinafter, in containers having such a 
multi-layer structure that the positive presence of the adhesive material 
layer between the main material layer and the barrier material such as 
EVOH or PA is confirmed. 
The reason is that a fuel oil tank mounted on a car is estimated to be one 
of the important safety parts and is required to-have greatly severe and 
high level performance Accordingly the case is the same with a multi-layer 
fuel tank provided with permeation resistance against fuel oil. For a 
modified polyethylenic resin as the adhesive material and the barrier 
layer to be used in such tanks, more stringent performance as a tank are 
required. With regard to the adhesive resin as used herein, it is 
necessary that adhesive properties to the polyethylenic resin and EVOH or 
PA and the long term durability under various circumstances are excellent, 
excellent mechanical-characteristics, thermal characteristics and chemical 
characteristics are possessed, and moldability and workability are good. 
Moreover, since these characteristics are exhibited greatly on condition 
that the adhesive material layer surely exists in the molding, it is more 
important to establish a method of confirming the presence or absence of 
the adhesive material layer. 
In summary, if in the multi-layer liquid fuel oil tank, there is a site 
where the adhesive layer is, entirely or partially, removed owing to an 
unidentified cause, not only mechanical characteristics such as impact 
resistance are reduced, but also in connection with the long term 
durability, the fuel oil and the like remain in the removed site, 
seriously reducing various performances of the tank and causing serious 
problems. For this reason, with commodities such as the aforementioned 
multi-layer laminate fuel oil tanks, confirmation of the presence of the 
adhesive material layer has become an indispensable, important item of 
control. However, an established technique to confirm the presence of the 
adhesive material layer without destructing the product having such a 
multi-layer structure, has not been known at all as described 
hereinbefore. Although detecting the . presence of the EVOH layer in the 
above multi-layer structure without destructing the container can be 
attained by using a super sonic wave reflection method, it is difficult to 
detect the presence of the adhesive material layer in the multi-layer 
laminate molding having the structure of EVOH or PA layer/adhesive 
material layer/main material layer, without destructing the molding, and 
no attempts has been made. 
Although the invention described in the aforementioned Japanese Patent 
Application Laid-Open No. 260417/1988 is fairly effective more concrete 
examples and data of various materials are not available, and moreover it 
is considered that the invention has a problem in respect of follow-up 
properties in detection when the rate of injection of the multi-layer 
parison is high. Furthermore, since it is important, as described above, 
that the presence of the layer in the container is finally confirmed, the 
invention is considered to be inadequate in those points. 
In addition, multi-layer laminate moldings such as containers and bags for 
use in industrial chemicals, or edible oil and water-containing 
foodstuffs, more particularly juice, fruits, vegetables, meat, fish and so 
forth, are required to have particularly high barrier properties, water 
resistance and durability in order to prevent deterioration of quality of 
the contents, and it is important that the adhesive material layer is 
detected without breaking the molding. 
As described above, as multi-layer laminate moldings, such as containers 
and bags, for which are required long term durability, barrier properties, 
and high resistance against vibration and various types of impact, for 
example, fuel oil containers and edible oil containers, no sufficiently 
satisfactory ones have been proposed yet. 
Thus the present inventors have made various investigations about a method 
of detection using supersonic wave and a combination of a main-material 
layer composed mainly of a polyolefinic resin and an adhesive material 
layer in order to overcome the above problems of, the prior art techniques 
and, as a result, it has been discovered that non-destructive detection of 
the adhesive material layer using the supersonic wave reflection method, 
which has not heretofore been known, can be attained by using a specified 
adhesive material and controlling a difference in acoustic impedance 
between the main material layer and the adhesive material layer to a 
specified value or more. 
Based on the findings, the present invention has been accomplished, and the 
object of the present invention is to provide a multi-layer laminate 
molding which Is excellent in characteristics such as barrier properties, 
permits non-destructive detection of an adhesive material layer, and is 
free of a site where the adhesive material layer is removed even if 
partially. 
DISCLOSURE OF INVENTION 
That is to say, the present invention provides a multi-layer-laminate 
molding having a layer structure that a main material layer containing a 
polyethylenic resin as a major component at the outside and a layer of a 
saponified product of an ethylene-vinyl acetate copolymer (EVOH) or a 
layer of a polyamide resin,(PA) at the inside-are laminated with at least 
an adhesive material layer sandwiched therebetween, wherein: 
the adhesive material layer comprises a resin composition containing: 
(A) 60to 95% by weight of a polyethylenic resin selected from the group 
consisting of: 
(1) high density polyethylenic resin having a density of at least 00930 
g/cm.sup.3, a number of short chain branches per 1,000 carbon atoms of the 
main chain of not more than 20, and a melt flow rate of at least 0.01 g/10 
min; 
(2) a linear low density polyethylenic resin having a density of from 0.910 
g/cm.sup.3 to less than 0.935 g/cm.sup.3, a melt flow rate of 0.1 to 50 
g/10 min, a melting point as determined by a differential scanning 
calorimeter (hereinafter abbreviated to "DSC") of 115.degree. to 
130.degree. C., and a number of short chain branches per 1,000 carbon 
atoms of the main chain of 5 to 30; 
(3) a modified high density polyethylenic resin obtained by grafting 
unsaturated carboxylic acid and/or its derivative onto the above high 
density polyethylenic resin (1); and 
(4) a modified linear low density pollyethylenic resin obtained by grafting 
unsaturated carboxylic acid and/or its derivative onto the above linear 
low density polyethylenic resin (2), 
said polyethylenic resin containing at least 0.1% by weight of the modified 
high density polyethylenic resin (3) and/or the modified linear low 
density polyethylenic resin, (4), and; 
(B) 40 to 5% by weight of a linear ultra low density polyethylenic resin 
having a density of from 0.890 g/cm.sup.3 to less than 0.910 g/cm.sup.3, a 
number of short chain branches per 1,000 carbon atoms of the main chain of 
18 to 60, a melt flow rate 0.1 to 30 g/10 min, and a melting point as 
determined by DSC of 110.degree. to 125.degree. C., 
said resin composition having a density of at least 0.925 g/cm.sup.3 and a 
proportion of unsaturated carboxylic acid and/or its derivative grafted of 
0.001 to 5.0% by weight, and 
a difference in acoustic impedance between the main material layer and the 
adhesive material layer as determined using a supersonic wave of 20 to 25 
MHz is at least 8.5.times.10.sup.-3 g/cm.sup.2 .multidot..mu.sec.

BEST MODE FOR CARRYING OUT THE INVENTION 
Hereinafter the multi-layer laminate molding of the present invention is 
described in detail. The multi-layer laminate molding of the present 
invention, as described above, has the layer structure that through at 
least a specified adhesive material layer, a main material layer 
containing a polyethylenic resin as a major component at the outside and 
an EVOH layer or PA layer at the inside are laminated. 
(1) Main Material Layer 
As the polyethylenic resin to be used as the main component of the main 
material layer in the present invention, an ethylene homopolymer and a 
copolymer of ethylene and another .alpha.-olefin can be listed. The 
.alpha.-olefin is generally an olefin having 3 to 12 carbon atoms 
(preferably 3 to 8 carbon atoms). Typical examples of the .alpha.-olefin 
are propylene, butene-1, hexene-1, octene-1, 4-methylpentene-1, and the 
like. 
In the main material layer, only the aforementioned polyethylenic. resin 
may be used, or a small amount (20% by weight at most) of elastomer or 
other synthetic resin uniformly compatible with the polyethylenic resin 
used may be compounded. As the elastomers which can-be used, 
polyisobutylene, ethylene-propylene, copolymer rubber (EPR), 
ethylene-propylene-diene terpolymer rubber (EPDM), acrylonitrile-butadiene 
copolymer rubber (NBR), block or random styrene-butadiene copolymer rubber 
(SBR), and the like can be listed. As the other synthetic resins, 
copolymers of ethylene and vinyl acetate, methyl ester, ethyl ester, butyl 
ester of acrylic acid or methacrylic acid, etc., can be listed. In 
addition,.different-polymers such as PA, a polyester resin, EVOH and PVC 
may be compounded within the range that-does not seriously reduce the 
basic characteristics of the polyethylenic resin as the major component. 
In the major material layer, fillers generally added to the aforementioned 
polyolefinic resin may be added. The amount of addition is preferably 
adjusted to not more than 30% by weight. As the fillers, calcium 
carbonate, talc, mica, glass fibers, carbon fibers, metal fibers, other 
inorganic fibers, and organic polymer fibers (for example, polyester 
fibers, polyamide fibers) can be listed. 
In the present invention, when the elastomer, the other synthetic resin, 
and the filler are compounded to the aforementioned polyethylenic resin, 
the amount of these components compounded is such that the total amount is 
not more than 40% by weight. If the total amount is more than 40% by 
weight, there occurs unconvenience that moldability and workability, 
impact resistance, fuel oil resistance, and so forth are reduced. 
In the multi-layer laminate molding of the present invention, although the 
melt flow rate (measured according to JIS-K7210 under condition 4 of Table 
1; hereinafter referred to as "MFR") of the polyethylenic resin as the 
major component of the main material layer is not critical, it is, from a 
viewpoint of moldabiity and workability, generally at least 0.005 g/10 
min, preferably at least 0.01 g/10 mi, and particularly preferably at 
least 0002 g/10 min. 
Preferred among the polyethylenic resin are an ethylenic polymer selected 
from an ethylene homopolymer and a copolymer of ethylene and 
.alpha.-olefin having a density of at least 0.930 g/cm.sup.3, particularly 
preferably at least 0.935 g/cm.sup.3. In addition, there can be used an 
ethylenic polymer composition having a density of at least 0.930 
g/cm.sup.3, particularly preferably at least 0.935 g/cm.sup.3, as obtained 
by compounding, to these ethylene homopolymer and copolymer of ethylene 
and .alpha.-olefin, low density polyethylene having a density of less than 
0.930 g/cm.sup.3 and a copolymer of ethylene and a monomer other than the 
.alpha.-olefin, and a propylene homopolymer and a copolymer of propylene 
and ethylene or other .alpha.-olefin, etc. Of these ethylenic polymers, 
moderate to high density polyethylene having a density of at least 0.935 
g/cm.sup.3 is particularly suitable. 
(2) Barrier Material Layer 
In the present invention, as the barrier material, EVOH or PA is used. EVOH 
and PA have excellent barrier properties against fuel such as gasoline. 
EVOH in particular has high barrier properties against alcohol, water and 
the like. 
(a) Layer of Saponified Product of Ethylene-Vinyl Acetate 
Copolymer (EVOH) 
EVOH which can be used, can be produced, for example, by saponifying an 
ethylene-vinyl acetate-copolymer (EVA) with an alkali and the like. The 
copolymerization proportion of ethylene in EVA is usually 20 to 80 mol% 
and particularly preferably 25 to 75 mol%. If the copolymerization 
proportion of ethylene is less then 20 mol%, moldability and workability 
are poor. On the other hand, if it is more than 80mol%, the multi-layer 
laminate molding obtained is not satisfactory in the point of barrier 
properties against-permeation of gas or liquid. Although the degree of 
saponification is not critical, it is usually at least 90% and 
particularly preferably at least 95% from a viewpoint of barrier 
properties. If the degree of saponification is less than 90%, similarly, 
the multi-layer laminate molding obtained is not sufficiently high in 
barrier properties. 
Although the molecular weight of EVOH is not critical, the melt flow index 
(MFI) as measured according to JIS-K7210, condition 4 (190.degree. C., 
2.160 g load), is 0.5 to 20 g/10 min and preferably 1 to 10 g/10 min. One 
type of EVOH may be used, or two or more types of EVOHs may be used in 
combination. In addition, a polyamide resin or thermoplastic polyvinyl 
alcohol having compatibility with EVOH can be used in blend with EVOH as 
long as it does not seriously reduce barrier properties or melt 
moldability is possible. In particular, blending thermoplastic polyvinyl 
alcohol with EVOH enables to obtain higher gas and liquid barrier 
properties. 
(b) Polyamide Resin Layer (PA Layer) 
As the polyamide resin that can be used, nylon 6, copolymer of nylon 6, 
modified nylon 6, nylon 11, nylon 12, and nylon 6--6 can be listed. Of 
these, the one having a melting point at the time of dry of not more than 
265.degree. C. is preferred, with the one having a melting point of not 
more than 235.degree. C. being particularly suitable. These polyamide 
resins may be used singly or,.as mixtures of two or more thereof. In 
addition, those obtained by bonding a foil of metal (for example, 
aluminum, iron, copper) or alloy (for example, stainless steel) to at 
least on surface of the polyamide resins, and various synthetic films on 
which the above metal or alloy, or silica is vacuum deposited, so-called 
metal vacuum deposited films, may be used. 
(3) Adhesive Material Layer 
In the multi-layer laminate molding of the present invention, the adhesive 
material layer comprises a resin composition comprising: (A) 60 to 95% by 
weight of a polyethylenic resin selected from the group consisting of (1) 
a high density polyethylenic resin having a density of at least 0.930 
g/cm.sup.3, a number of short chain branches per 1,000 carbon atoms of the 
main chain of not more than 20, and MFR of at least 0.01 g/10 min, (2) a 
linear low density polyethylenic resin having a density of from 00910 
g/cm.sup.3 to less than 0.935 g/cm.sup.3, MFR of 0.1 to 50 g/10 min, a 
melting point as determined by DSC of 115.degree. to 130.degree. C., and a 
number of short chain branches per 1,000 carbon atoms of the main chain of 
5 to 30, (3) a modified high density polyethylenic resin obtained grafting 
unsaturated carboxylic acid and/or its derivative onto the above high 
density polyethylenic resin (1), and a modified linear low density 
polyethylenic resin obtained by grafting unsaturated carboxylic acid 
and/or its derivative onto the above linear low density polyethylenic 
resin (2), said polyethylenic resin containing at least 0.1% by weight of 
the modified high density polyethylenic resin (3) and/or the modified 
linear low density polyethylenic resin (4), and (B) 40 to 5% by weight of 
a linear ultra low density polyethylenic resin having a density of from 
0.890 g/cm.sup.3 to less than 0.910 g/cm.sup.3, a number of short chain 
branches per 1,000 carbon atoms of the main chain of 18 to 60; MFR of 0.1 
to 30 g/10 min, and a melting point as determined by DSC of 110.degree. to 
125.degree. C., said resin composition having a density of at least 0.925 
g/cm.sup.3 and a proportion of unsaturated carboxylic acid and/or its 
derivative grafted of 0.001 to 5.0% by weight. 
Hereinafter, "modified" refers to those on which unsaturated carboxylic 
acid and/or its derivative is grafted, and "unmodified" refers to those 
not grafted. 
The high density polyethylenic resin for the high density polyethylenic 
resin (1) and the modified high density polyethylenic resin (3) as the 
component (A) constituting the adhesive material layer is a polyethylenic 
resin having a density of at least 0.930 g/cm.sup.3, a number of short 
chain branches per 1,000 carbon atoms of the main chain of 20 at most, and 
MFR of at least 0.01 g/10 mm. 
The high density polyethylenic resin is obtained by homopolymerizing or 
copolymerizing ethylene alone or ethylene and .alpha.-olefin having 3 to 
12 carbon atoms (preferably 3 to8 carbon atoms) in the presence of a 
so-called Phillips catalyst or Ziegler catalyst, and generally produced 
under a pressure of atmospheric pressure to 100 kg/cm.sup.2 (moderate or 
low pressure polymerization). Preferred examples of the .alpha.-olefin 
propylene, butene-1, hexene-1, 4-methylpentene-1, and octene-1. Its 
copolymerization ratio is not more than 6.5% by-weight and particularly 
preferably not more than 6.0% by weight. High density polyethylenic resins 
may be used singly or two or more-thereof may be used in combination. 
The density of the high density polyethylenic resin is at least 0.930 
g/cm.sup.3, preferably at least 0.933 g/cm.sup.3, and particularly 
preferably at least 0.935 g/cm.sup.3. Use of the high density 
polyethylenic resin is excellent in that stiffness, heat resistance, fuel 
oil resistance, surface hardness, and so forth of the product obtained are 
increased. 
Moreover, MFR is at least 0.01 g/10 min, preferably at least 0.015 g/10 
min, and particularly preferably at least 0.02 g/10 min. If HFR is less 
than 0.01 g/10 min, moldability and workability are inferior. Although the 
upper limit is not critical, it is usually 50 g/10 min and particularly 
preferably not more than 35 g/10 min. 
In particular, if MFR is less than 0.01 g/10 min, MFR of the grafted high 
density polyethylenic resin obtained is generally lowered well below the 
MFR of the high density polyethylenic resin used for graft modification, 
although depending or graft modification conditions, leading to not only 
the reduction of moldability and workability, but also serious reduction 
in compatibility in producing a mixture with an unmodified high density 
polyethylenic resin, so that no an uniform composition can be obtained. 
Accordingly, MFR of the modified polyethylenic resin is generally 
preferred to be at least 0.05 g/10 min. Particularly preferred is at least 
0.1 g/10 min. 
The linear low density polyethylenic resin (2) used like the above high 
density polyethylenic resin is the one produced industrially and utilized 
in a wide variety of fields because it is excellent particularly in 
environmental stress cracking resistance, transparency, heat-sealability, 
resistance to brittleness, property at low temperatures and so forth (for 
example, wrapping materials such as films and industrial materials such as 
pipes). This linear low density polyethylenic resin is produced by 
copolymerizing ethylene and the aforementioned .alpha.-olefin by the use 
of a so-called Ziegler catalyst according to any of the gas phase method, 
the solution method, and the slurry method. 
The density of the linear low density polyethylenic resin (2) is from 0.910 
g/cm.sup.3 to less than 0.935 g/cm.sup.3, preferably from 0.0912 
g/cm.sup.3 to less than 0.935 g/cm.sup.3 and particularly preferably from 
0.913 g/cm.sup.3 to less than 0.935 g/cm.sup.3. MFR is from 0.1 to 50 g/10 
min, preferably from 0.2 to 40 g/10 min, and particularly preferably from 
0.2 to 30 g/10 min. If MFR of the linear low density polyethylenic resin 
is less than 0.1 g/10 min, moldability and workability are poor. On the 
other hands if it is more than 50 g/10 min, the composition obtained is 
poor in mechanical strength. 
The melting point as determined by DSC of the linear low density 
polyethylenic resin is from 115.degree. to 130.degree. C., preferably from 
118.degree. to 130.degree. C. and particularly preferably from 118.degree. 
to 125.degree. C. If the melting point as determined by the DSC method is 
less than 115.degree. C., long term solvent resistance at high 
temperatures is low. On the other hand, if it is more than 130.degree. C. 
the density exceeds the upper limit of the range as described above. 
The number of short chain branches per 1,000 carbon atoms of the main chain 
of the linear low-density polyethylenic resin is from 5 to 30 and 
particularly preferably from 5 to 25. If the number of short chain 
branches per 1,000 carbon atoms of the main chain is less than the lower 
limit, or more than the upper limit, uniformity of the composition of the 
present invention becomes low in any case, which is not desirable. That 
is, when there is used a composition using a linear low density 
polyethylenic resin the number of the branches per 1,000 carbon atoms of 
the main chain of which is outside the aforementioned range, in the 
evaluation of long term solvent resistance (for example, fuel oil 
resistance) in particular, the decrease of tensile elongation is large, 
and moreover, under conditions that heat resistance is added (more 
specifically, durability test in an atmosphere of at least 100.degree. 
C.), the decrease of physical properties additionally occurs, both are 
considered due to the ununiformity of the composition. 
The modified polyethylenic resins used as the component (A) in the present 
invention (i.e., the modified high density polyethylenic resin (3) and the 
modified linear low density polyethylenic resin (4)) are obtained by 
grafting the unsaturated carboxylic acid and/or its derivative as 
described hereinafter onto the high density polyethylenic resin and/or 
linear low density polyethylenic resin as described above. This graft 
reaction is performed in the presence of a radical initiator. In this 
case, synthetic resins and elastomers (rubber) as described hereinafter, 
having affinity respectively to the high density polyethylenic resin and 
linear low density polyethylenic resin to be grafted, may be allowed to be 
present. This reaction can be performed by known methods, for example, the 
methods described in Japanese Patent Application Laid-Open Nos. 10107/1987 
and 132345/1986. 
As unsaturated carboxylic acid and its derivatives for use in the graft 
treatment in the present invention, monobasic unsaturated carboxylic acid 
and dibesic unsaturated carboxylic acid, and their metal salts, amides, 
imides, esters and anhydrides are listed. Of these, as the monobasic 
unsaturated carboxylic acid and its derivatives, those having 20 or less 
carbon atoms are generally preferred, with those having 15 or less carbon 
atoms being more preferred. In addition, as the dibasic unsaturated 
carboxylic acid and its derivatives, those having 30 or less carbon atoms 
are usually preferred, with those having 25 or less carbon atoms being 
more preferred. Typical examples of these unsaturated carboxylic acids and 
derivatives thereof are described in Japanese Patent Application Laid-Open 
No 10107/1987. Of these unsaturated carboxylic acids and derivatives 
thereof, acrylic acid, methacrylic acid, maleic acid and its anhydride, 
5-norbornen-2, 3-dicarboxylic acid and its anhydride, and glycidyl 
methacrylate are preferred, with maleic anhydride and 5-norbornic 
anhydride being particularly preferred. 
The amount of the unsaturated-carboxylic-acid and its derivative used in 
the graft modification is generally 0.01 to 5.0 parts by weight, 
preferably 0.01 to 3.0 parts by weight, and particularly preferably 0.02 
to 2.0 parts by weight, per 100 parts by weight of the polyethylenic resin 
to be grafted. If the proportion of the unsaturated carboxylic acid and 
its derivative is less than 0.01 part by weight as the total amount 
thereof, graft modification is conducted only insufficiently, and a 
problem arises in affinity or adhesive properties aimed at by the present 
invention. On the other hand, if it is more than 5.0 parts by weight, 
there is a risk that the graft modified high density polyethylenic resin 
and graft modified linear low density polyethylenic resin as obtained 
undergo gelation, coloration, deterioration and so forth; the increase of 
performance aimed at by the present invention is not observed. 
As the radical initiator, those having a decomposition temperature for the 
one-minute half life period of 100.degree. C. or more are usually used, 
with those of 103.degree. C. or more being preferred and those of 
105.degree. C. or more being particularly preferred. Suitable radical 
initiators include organic peroxides such as dicumyl peroxide; benzoyl 
peroxide, di-tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert-butylperoxy) 
hexane; 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane-3; lauroyl peroxide; 
and tert-butylperoxy benzoate. The proportion of the radical initiator is 
usually 0.001 part by weight, preferably 0.005 to 1.0 part by weight, and 
particularly preferably 0.005 to 0.5 part by weight, per 100 parts by 
weight of the polyethylenic resin to be grafted. If the proportion of the 
radical initiator is less than 0.001 part by weight, the effect of graft 
modification is exhibited only insufficiently, resulting in that not only 
a long time is needed for complete graft modification but also unreacted 
materials are present in admixture. On the other hand, if it is more than 
1.0 part by weight, excessive decomposition or crosslinking reaction 
undesirably occurs. 
Olefinic resins which can be allowed to coexist at the time of the above 
graft reaction, include a high-pressure-process low density polyethylenic 
resin and copolymers of ethylene and other vinyl monomers, such as an 
ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, an 
ethylene-methacrylic acid copolymer, an ethylene-methyl acrylate 
copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-butyl 
acrylate copolymer, and an ethylene-methyl methacrylate copolymer. As the 
elastomer, synthetic and natural rubbers, such as ethylene-.alpha.-olefin 
copolymer rubber, e.g., ethylene-propylene copolymer rubber, 
ethylene-propylene-diene terpolymer rubber, and ethylene-butene-1 
copolymer rubber, polyisobutylene rubber, polyurethane rubber, 
styrene-butadiene copolymer rubber, and polybutadiene rubber can be 
listed. These are generally used in an amount of not more than 10% by 
weight in the polyethylenic resin to be grafted, with the amount of not 
more than 5.0% by weight being particularly preferred. If the proportion, 
as total amount, of the olefinic resin and/or the elastomer in the total 
amount of the high density polyethylenic resin and/or the linear low 
density polyethylanic resin is more than 10% by weight, the basic 
characteristics of the high-density polyethylenic resin and/or the linear 
low density polyethylenic resin are sometimes deteriorated. 
The modified polyethylenic resins to be used as the component (A) in the 
present invention (i.e., the modified high density polyethylanic resin (3) 
and the modified linear low density polyethylanic resin (4)) are obtained 
by grafting the unsaturated carboxylic acid and/or its derivative as 
described hereinafter onto the high density polyethylenic resin and/or the 
linear low density polyethylanic resin as described above. This graft 
reaction is performed in the presence of a radical initiator. At this 
time, the synthetic resin and elastomer (rubber) as described hereinafter 
having affinity respectively to the high density polyethylenic resin and 
the linear low density polyethylenic resin to be grafted, may be present. 
This method can be performed by known methods, for example, the methods 
described in Japanese Patent Application Laid-Open Nos. 10107/1987 and 
132345/1986. 
As the reaction, a method in which the high density polyethylenic resin, 
etc. a to be processed by the use of an extruder, a Bumbury mixer, a 
kneader and the like, is kneaded in a molten state, a solution method in 
which polymers such as the high density polyethylenic resin and the linear 
low density polyethylenic resin are dissolved in a suitable solvent, a 
slurry method in which particles of polymers such as the high density 
polyethylenic resin are conducted in a suspension state, or a gas phase 
graft method is listed. 
The reaction temperature is selected appropriately taking into 
consideration the deterioration of polymers such as the high density 
polyethylenic resin and the linear low density polyethylenic resin, the 
decomposition of the unsaturated carboxylic acid and its derivative, the 
decomposition temperature of the radical initiator to be used, and so 
forth. To take the above method of kneading in a molten state as an 
example, the reaction temperature is usually 100.degree. to 350.degree. C. 
and preferably 150.degree. to 300.degree. C. Particularly preferred is 
180.degree. to 300.degree. C. 
In this manner, of course, the modified high density polyethylenic resin 
and the modified linear low density polyethylenic resin of the present 
invention are produced. For the purpose of increasing the performance, 
already known processing methods such as the method described in Japanese 
Patent Application Laid-Open No. 10107/1987, for example, a method in 
which treatment with an epoxy compound or a polyfunctional compound 
containing an amino group or a hydroxyl group, for example, is applied at 
the time of graft modification or after the graft modification, and 
further a method in which unreacted monomers (unsaturated carboxylic acid 
and its derivative) and various components by-produced are removed by 
heating washing and so forth, can be employed. 
In the multi-layer laminate molding of the present invention, it is 
necessary that the adhesive material layer contain the linear ultra low 
density polyethylenic resin as the component (B). A method of production 
of this linear super low density polyethylenic resin-is widely known, and 
in recent years, it is industrially produced by an improved slurry 
polymerization method or the gas phase polymerization method, for example, 
and widely utilized. 
Accordingly, unlike conventionally known ethylene-.alpha.-olefin random 
coplymers (density 0.86 to 0.91 g/cm.sup.3) of low crystallinity, having a 
degree of crystllization of several percents to about 30%, as obtained by 
polymerizing by the use of a vanadium catalyst system, it is a linear 
ultra low density polyethylenic resin produced according to the slurry 
method or the gas phase method by the use of a stereo-regular catalyst 
(so-called Ziegler catalyst) as described in, for example, Japanese Patent 
Application Laid-Open Nos. 68306/1982, 23011/1984 and 109805/1986. 
The linear ultra low density polyethylenic resin of the component (B) is a 
linear ultra low density polyethylenic resin-having a density of from 
0.890 g/cm.sup.3 to less than 0.910 g/cm.sup.3, MFR of 0.1 to 30 g/10 min, 
a melting point as determined by DSC of 110.degree. to 125.degree. C., and 
a number of short chain branches per 1,000 carbon atoms of the main chain 
of 18 to 60. 
In the present invention, if the density of the above resin is less than 
00890 g/cm.sup.3, a problem arises in the fuel oil resistance of the 
composition obtained. On the other hand, if it is more than 0.910 
g/cm.sup.3, the composition obtained is insufficient in impact resistance. 
For these reasons, the density is preferably 0.890 to 0.0910 g/cm.sup.3. 
If the MFR of the above resin is less than 0.1 g/10 min, moldability and 
workability are not desirable, and if it is more than 30 g/10 min, a 
problem arises, in respect of impact resistance. For these reasons, it is 
desirable that MFR be 0.1 to 10 g/10 min, with 0.2 to 8.0 g /10 min being 
particularly preferred. 
Furthermore, the melting point shown by DSC (about 5 mg of a sample is 
weighed, set on a DSC measuring apparatus, raised in temperature up to 
200.degree. C. from room temperature at a temperature-raising rate of 
10.degree. C./min, maintained at that temperature for 5 minutes, lowered 
in temperature to room temperature at a temperature-lowering rate of 
10.degree. C./min, and further raised in temperature at the above 
temperature-raising rate; the temperature of a peak of the maximum heat 
absorption region is referred to as a "melting point") is 110.degree. to 
125.degree. C. Particularly preferred are those of 112.degree. to 
125.degree. C. If the melting point is less than 110.degree. C,. the 
composition obtained is not sufficiently high in heat resistance, and if 
it is more than 125.degree. C., the effect of improving impact resistance 
is poor. 
The number of short chain branches per 1,000 carbon atoms of the main chain 
of the above resin is 18 to 60, preferably 18 to 50 and particularly 
preferably 20 to 50. If the number of short chain branches per 1,000 
carbon atoms of the main chain is less than 18, the multi-layer laminate 
molding has a problem in respect of impact resistance, and if it is more 
than 60, fuel oil resistance is considerably inferior. The short chain as 
used herein refers to the one substantially, comprising an alkyl group 
having 1 to 10, preferably 1 to 6 carbon atoms. 
In addition, from a viewpoint of the effect of improving impact resistance, 
the initial modulus in tension of the above polyethylenic resin is not 
more than 2.times.10.sup.3 kg/cm.sup.2, and preferably not more than 
1.5.times.10.sup.3 kg/cm.sup.2. Such polyethylenic resins are obtained by 
copolymerizing ethylene and the aforementioned .alpha.-olefin by the use 
of a Ziegler catalyst. 
For the resin composition constituting the adhesive material layer in the 
present invention is required that the above component (A) contains at 
least 0.1% by weight of the modified high density polyethylenic resin 
and/or the modified linear low density polyethylenic resin. If the content 
of the total modified polyethylenic resin is less than 0.1% by weight, 
there cannot be obtained an adhesive material aimed at by the present 
invention, satisfying affinity or adhesive properties to the 
aforementioned resin materials and metal materials, and so forth. The 
content of the modified polyethylenic resin is preferably at least 1.0% by 
weight, and particularly preferably at least2.5%. by weight. 
The resin composition constituting the adhesive material layer in the 
present invention comprises the aforementioned components (A) and (B) and 
in connection with their compounding proportions, the component (A) is 60 
to 95% by weight and the component (B) is 40 to 5% by weight, preferably 
the component (A) is 62 to 95% by weight and the component (B) is 38 to 5% 
by weight, and particularly preferably the component (A) is 62 to 93% by 
weight and the component (B) is 38 to 7% by weight. If the proportion of 
the linear ultra low density polyethylenic resin in the composition is 
less than 5.0% by weight, the laminate structure material obtained is 
inferior in impact resistance, and if it is more than 40% by weight, fuel 
oil resistance (particularly fuel oil resistance at 40.degree. C.) is 
significantly decreased, which is not desirable. 
The resin composition constituting the adhesive material layer in the 
present invention may contain, as well as the aforementioned components 
(A) and (B), an unmodified high density polyethylenic resin and/or an 
unmodified linear low density polyethylenic resin. That is, in general, in 
graft modification of a polymer (in the present invention, the high 
density polyethylenic resin or linear low density polyethylenic resin) 
with a monomer (in the present invention, the unsaturated carboxylic acid 
and its derivative), it is difficult that all polymers are grafted; part 
of the polymers remain ungrafted. In the present invention, high density 
polyethylenic resins or linear low density polyethylenic resins which are 
not grafted, may be used as such without isolation. In addition, 
unmodified high density polyethylenic resins and/or linear low density 
polyethylenic resins which are not subjected-to graft treatment may be 
compounded. 
In the present invention, when the unmodified high density polyethylenic 
resin (1) is added, the amount of use thereof is preferably not more than 
99.9% by weight of the component (A), with not more than 99.0% by weight 
being particularly preferred. If the proportion of the unmodified high 
density polyethylenic resin (1) is more than 99.9% by weight, adhesive 
properties are not sufficiently high. 
When the unmodified linear low density polyethylenic resin (2) is added, 
the amount of use thereof is preferably 2.5 to 75% by weight of the 
component (A), with 5.0 to 60% by weight being particularly preferred. If 
the proportion of the unmodified linear low density polyethylenic resin 
(2) is less than 2.5% by weight, uniformity of the composition in the 
total composition is inferior On the other hand, if it is more than 75% by 
weight, heat resistance and long term fuel oil resistance at high 
temperatures are inferior. 
With the resin composition constituting the adhesive material layer in the 
present invention, some of all components of the composition may be mixed 
in advance and the remaining components be mixed, or all components of the 
composition may be mixed at the same time. In any case, the proportion of 
the grafted monomer (unsaturated carboxylic acid and/or its derivative) in 
the adhesive material in the present invention is, as the total amount 
thereof, 0.01 to 5.0% by weight, preferably 0.01 to 2.0%. by weight, and 
particularly preferably 0.02 to 1.0% by weight. If the proportion of the 
grafted monomer occupying in the adhesive material is, as the total amount 
thereof, less than 0.001% by weight, various effects of the present 
invention cannot be exhibited sufficiently. On the other hand, even if it 
is mores than 5.0% by weight, no further improvement in the effects of the 
present invention can be obtained. 
The composition of the resin composition constituting the adhesive material 
layer in the present invention is required to satisfy the aforementioned 
various conditions and at the same time, to be chosen so that the density 
of the adhesive material is at least 0.925 g/cm.sup.3, and the difference 
in acoustic impedance between the main material layer and adhesive 
material layer as determined using a supersonic wave of 20 to 25 MHz is at 
least 8.5.times.10.sup.-3 g/cm.sup.2 .multidot..mu.sec. The density of the 
adhesive material is necessary to be at least 0.925 g/cm.sup.3, with at 
least 0.926 g/cm.sup.3 being particularly preferred. If the density of the 
adhesive material is less than 0.925 g/cm.sup.3, long term solvent 
resistance is not good. 
The acoustic impedance (hereinafter referred to as "Z.sub.1 ") of the 
adhesive material layer is at least 1.980'10.sup.-1 /cm.sup.2 
.multidot..mu.sec, preferably at least 1.982.times.10.sup.-1 g/cm.sup.2 
.multidot..mu.sec, and particularly preferably at least 
1.984.times.10.sup.-1 g/cm.sup.2 .mu.sec. If Z.sub.1 is less than 
1.980.times.10.sup.-1 g/cm.sup.2 .multidot..mu.sec, fuel oil resistance, 
heat resistance and so forth are not sufficiently high. 
On the other hand, although the acoustic impedance (Z.sub.O) of the main 
material layer is not critical, it is, as determined using a supersonic 
wave of 20 to 25 MHz, preferably at least about 2.00.times.10.sup.-1 
g/cm.sup.2 .multidot..mu.sec, desirably at least 2.10.times.10.sup.-1 
g/cm.sup.2 .multidot..mu.sec, and particularly preferably at least 
2.20.times.10.sup.-1 g/cm.sup.2 .multidot..mu.sec. 
However, in order that the presence or absence of the adhesive material 
layer can be detected by the non-destructive method, the acoustic 
impedance difference .vertline.Z.sub.0 -Z.sub.1 .vertline. between the 
main material layer and adhesive material layer is at least 
8.5.times.10.sup.-3 g/cm.sup.2 .multidot..mu.sec, preferably at least 
9.0.times.10.sup.-3 g/cm.sup.2 .multidot..mu.sec, and particularly 
preferably at least 9.5.times.10.sup.-3 g/cm.sup.2 .multidot..mu.sec. That 
is, when Z.sub.0 is 2.20.times.10.sup.-1 g/cm.sup.2 .multidot..mu.sec, 
Z.sub.1 is not more than 2.115.times.10 g/cm.sup.2 .multidot..mu.sec, and 
when Z.sub.0 is 2.00.times.10.sup.-1 g/cm.sup.2 .multidot..mu.sec, Z.sub.1 
is not more than 1.915.times.10.sup.-3 g/cm.sup.2 .multidot..mu.sec. If 
the acoustic impedance difference between the main material layer and 
adhesive material layer is less than 8.5.times.10.sup.-3 g/cm.sup.2 
.multidot..mu.sec, it becomes quite difficult to achieve supersonic wave 
detection of the presence or absence of the adhesive material layer in a 
non-destructive state. 
In preparation of each composition of the present invention, additives such 
as an antioxidant, a thermal stabilizer, an ultraviolet absorber, a 
lubricant, an antistatic agent, and a pigment (colorant) which are 
commonly used in the field of polyolefinic resins, can be compounded 
within the range that does not substantially damage the effects of the 
composition. 
As the mixing method for preparation of the composition, any of various 
mixing methods commonly employed in the field of synthetic resins, i.e., a 
method in which dry blending is carried out by the use of a mixer such as 
a tumbler or a Henschel mixer, and a method in which melt kneading is 
carried out by the use of a kneader such as an extruder, a kneader, a 
Bumbury mixer and a roll, can be employed. At this time, by carrying out 
two or more of these mixing methods, a more uniform composition can be 
obtained (for example, a method in which dry blending is conducted in 
advance, and the mixture thus obtained is further melt kneaded). 
In accordance with the-present invention, the multi-layer laminate molding 
of the present invention can be produced by laminating the main material 
and EVOH or PA through the aforementioned adhesive material layer (3) by a 
method commonly employed in the field of synthetic resin, and further 
molding into a desired shape. Lamination can be carried out by a method in 
which the main material, adhesive material and EVOH or PA are coextruded 
by the use of three or more extruders (for example, multi-layer blow, 
coextrusion inflation, and T-die film molding), a method in which EVOH or 
PA is used as a substrate, and the main material and adhesive material are 
coextruded thereon and coated (coating or lamination), and a method of 
heat contact-bonding. In addition, a method in which the materials are 
separately molded into films or sheets, and they are subjected to heat 
contact-bonding, is available. 
In connection with the layer structure of the laminate for the multi-layer 
laminate molding of the present invention, assuming that the main material 
layer is A, the adhesive material layer is B, and the EVOH or PA layer is 
C, there are A/B/C, A/B/C/B, A/B/C/B/A, or structures that these 
structures are repeated; and furthermore, assuming that other barrier 
material layer is D, the layer D may be provided between the layer B and 
the layer C, and further, if necessary, the layer B may be sandwiched 
between the layer C and the layer D. 
In the present invention, it suffices to be determined depending on desired 
physical properties of the objective molding and taking into consideration 
the characteristics of the resins which of the EVOH layer and the PA layer 
is used as the barrier material layer C. If necessary, EVOH and PA layers 
may be used in combination. 
In order to effectively utilize flashes produced at the time of product 
molding, they are commonly finely pulverized and, if necessary to make the 
composition uniform, melt kneaded by the use of an extruder and so forth, 
and recycled mainly for use in the main material layer, or there may be 
employed a layer structure that a fresh recycle layer E is provided at the 
outside of the layer A and between the layer A and layer B, such as 
A/E/B/C or E/A/B/C. 
In the present invention, when a container particularly for fuel oil or 
edible oil and so forth is produced, a method is typical in which blow 
molding is carried out by the use of a multi-layer blow molding machine 
provided with extruders adapted to coextrude the main material, EVOH or PA 
and the adhesive material in such a manner that the adhesive material is 
sandwiched between the main material and EVOH or PA, and further with a 
multi-layer die (in a cocentric circular form). The above blow molding 
method is described in detail in Japanese Patent Application Laid-Open No. 
104707/1987, "Polymer Digest" March, 1988 (Vol. 40, No. 3, pages 33 to 
42), and "Plastics Age" March, 1989, pages 129 to 136. 
In connection with the structure when the molding is a fuel oil container, 
assuming that the main material layer is A the adhesive-material layer is 
B, the EVOH or PA layer is, C, there are A/B/C, A/B/C/B, and A/B/C/B/A, or 
structures that these structures are repeated, and assuming that the other 
barrier material layer is D, the layer D may be provided between the layer 
B and layer C, and further, if necessary, another layer B may be provided 
between the layer C and the layer D, or the layer D may be provided at the 
outside of A and B, as in D/B/A/B/C and A/B/C/B/D. Of course, combinations 
of these (for example, D/B/A/D/B/C) may be used. 
In the molding of the present invention, the thicknesses of the main 
material layer, adhesive material layer and EVOH or PA layer are 
determined appropriately depending on performance required for the desired 
molding, performance of the molding machine, and application of use, 
shape, the type of the composition used and so forth. Particularly in 
containers for fuel oil or edible oil and so forth, in general, the 
thicknesses of the adhesive material layer and the EVOH or PA layer are 
each several micrometers to 3 mm, preferably 10 .mu.m to 2 mm and 
particularly preferably 10 .mu.m to 1 mm. The thickness of the main 
material layer is 0.3 to 10 mm, with 0.5 to 7 mm being particularly 
preferred. 
It is possible that flashes resulting from the production of the container 
thus obtained are ground by the use of a grinder and so forth and then 
finely divided by the use of an extruder, for example, so that the size of 
EVOH or PA is not more than about 100 .mu.m and, thereafter, they are used 
in admixture with the main material in about 5 to 50%. In this case, 
however, it must be-confirmed in advance that as compared with the case 
that no flash is used, the fuel oil container obtained is not inferior in 
respect of performance and long term durability, that is, there is no 
problem in the practical use thereof. 
In any of the case that melt kneading is carried out for production of the 
aforementioned adhesive material in the present invention and the case 
that lamination is carried out for the production of the multi-layer 
laminate molding, they are necessary to be carried out at temperatures at 
which various polyethylenic resins, synthetic resins, elastomers, EVOH and 
PA melt. If, however, they are carried out at high temperatures, they 
sometimes undergo heat decomposition. For the above reasons, in general, 
they are carried out at 170.degree. to 280.degree. C. and preferably 
190.degree. to 250.degree. C. 
The present invention is explained in greater detail with reference to 
Examples and Comparative Examples. 
Examples 1 to 12 and Comparative Examples 1 to 9 
(1) Production of Modified Polyethylene 
Various modified polyethylenic resins used as an adhesive material 
component in the examples and comparative examples were produced as 
follow. The polyethylenic resin is abbreviated to "PE". 
Modified PE (a) 
To powdered high density PE (hereinafter referred to as "HDPE") having a 
density of 0.952 g/cm.sup.3 and MFR=0.93 g/10 min was added 0.012 part by 
weight of 2,5-dimethyl-2,5-tert-butyl-peroxyhexane as a radical initiator, 
which were then dry blended for 2 minutes by the use of a Henschel mixer 
and, thereafter, 0.375 part by weight of maleic anhydride (hereinafter 
referred to as "MAH") was added thereto, and the mixture was dry blended 
for 2-minutes, by the use of a Henschel mixer, melt kneaded at a resin 
temperature of 257.degree. C. and pelletized. The amount of MAH grafted in 
the modified PE (a) thus obtained was 0.33% by weight as determined by the 
infrared ray spectral method. 
Modified PE (b) 
To powdered HDPE (2) having a density of 0.945 g/cm.sup.3 and MFR=0.44 g/10 
min was added 0.012 part by weight of 2,5-dimethyl-2,5-tert 
-butylperoxyhexane as a radical initiator, which were then dry blended for 
2 minutes by the use of a Henschel mixer and, thereafter, 0.375 par t by 
weight of MAH was added thereto, and the mixture was dry blended for 
additional 2 minutes by the use of a Henschel mixer, malt kneaded at a 
resin temperature of 260.degree. C. and pelletized. The amount of MAH 
grafted in the modified PE (b) thus obtained was 0.32% by weight as 
determined by the infrared ray spectral method. 
Modified PE (c). 
To linear low density PE (hereinafter referred to as "LLDPE") (LLDPE(3)) 
having a density of 0.925 g/cm.sup.3, MFR=0.78 g/10 min, melting 
point=120.5.degree. C. and a number of branching of 9.5/1000 C was added 
0.012 part by weight of 2,5-dimethyl-2,5-tert-butylperoxyhexane as a 
radical initiator, which were then dry blended for 2 minutes by the use of 
a Henschel mixer and, thereafter, 0.375 part by weight of MAH was added 
and the mixture was dry blended for additional 2 minutes by the use of a 
Henschel mixer, melt kneaded at a resin temperature of 255.degree. C. and 
pelletized. The amount of MAH grafted in the modified PE (c) thus obtained 
was 0.30% by weight as determined by the infrared ray spectral method. 
Modified PE (d) 
To LLDPE (4) having a density of 0.900 g/cm.sup.3, MFR=4.0 g/10 m, melting 
point=98.degree. C. and a number of branching of 72/1000 C was added 0.012 
part by weight of 2,5-dimethyl-2,5-tert-butylperoxyhexane as a radical 
initiator, which were then dry blended for 2 minutes by the use of a 
Henschel mixer and, thereafter, 0.375 part by weight of MAH was added 
thereto, and the mixture was dry blended for additional 2 minutes by the 
use of a Henschel mixer, melt kneaded at a resin temperature of 
232.degree. C. and pelletized. The amount of MAH grafted in the modified 
PE (d) thus obtained was 0.26% by weight as determined by the infrared ray 
spectral method. 
Characteristics of the unmodified linear ultra low density PE (hereinafter 
referred to as "L-ULDPE") used likewise are as follow: 
L-ULDPE (5) 
Having a density of 0.904 g/cm.sup.3, MFR=1.0 g/10 min, melting 
point=-120.degree. C. and a number of branching of 28/1000 C as produced 
by the slurry polymerization method. 
L-ULDPE (6) 
Having a density of 0.897 g/cm.sup.3, MFR==0.7 g/10 min, melting 
point=115.degree. C. and a number of branching of 47/1000 C as produced by 
the slurry polymerization method. 
L-ULDPE (7) 
Having a density of 0.907 g/cm.sup.3, MFR=6.5 g/10 min, melting 
point=121.degree. C. and a number of branching of 21/1000 C as produced by 
the slurry polymerization method. 
L-ULDPE (8) 
Having a density of 0.900 g/cm.sup.3, MFR=4.0 g/10 min, melting 
point=98.degree. C. and a number of branching of 72/1000 C as produced by 
the solution polymerization method. 
(2) Production of Adhesive Material 
The aforementioned modified polyethylenic resin (modified PE), unmodified 
polyethylenic resin (unmodified PE) and unmodified linear ultra low 
density polyethylenic resin (L-ULDPE) were mixed in the ratios shown in 
Tables 1 and 2, and melt kneaded at a temperature of 200.degree. to 
220.degree. C. by the use of a single screw extruder having a diameter of 
50 mm to produce adhesive materials (1) to (16) shown in Tables 1 and 2. 
The density (.rho.) of the adhesive obtained was measured according to 
JIS-K7112 method and with regard to the acoustic impedance (Z), a 
supersonic thickness meter produced by Nippon Panametrics Co., Ltd, which 
was provided with a vertical depth sensor having a piezo element as an 
oscillating plate, was used, the speed of sound (c) when a supersonic wave 
having a frequency of 20 MHz was hit on a press plate (30 mm.times.30 mm) 
of 2 mm thickness in the direction of thickness, was measured, and the 
acoustic impedance was calculated from the following equation: 
EQU Z.rho..times.c(g/cm.sup.2 .multidot..mu.sec) 
TABLE 1 
__________________________________________________________________________ 
Characteristics of 
Modified PE Unmodified PE 
L-ULDPE Adhesive Material 
Adhesive 
Amount Amount Amount 
Density 
Z.sub.1 
Material 
Type 
(wt %) 
Type (wt %) 
Type (wt %) 
(g/cm.sup.3) 
(g/cm.sup.2 .multidot. .mu.sec) 
__________________________________________________________________________ 
(1) (a) 
80 -- L-ULDPE (6) 
20 0.940 
2.115 .times. 10.sup.-1 
(2) (a) 
65 -- L-ULDPE (6) 
35 0.934 
2.050 .times. 10.sup.-1 
(3) (a) 
35 LLDPE (3) 
55 L-ULDPE (5) 
10 0.930 
2.021 .times. 10.sup.-1 
(4) (a) 
35 LLDPE (3) 
45 L-ULDPE (5) 
20 0.929 
2.015 .times. 10.sup.-1 
(5) (a) 
35 LLDPE (3) 
35 L-ULDPE (5) 
30 0.927 
2.003 .times. 10.sup.-1 
(6) (b) 
30 HDPE (1) 
45 L-ULDPE (7) 
25 0.937 
2.084 .times. 10.sup.-1 
(7) (a) 
50 LLDPE (3) 
15 L-ULDPE (5) 
25 0.932 
2.032 .times. 10.sup.-1 
(c) 
10 
(8) (a) 
20 HDPE (1) 
40 L-ULDPE (5) 
30 0.934 
2.049 .times. 10.sup.-1 
(c) 
10 
(9) (a) 
25 HDPE (1) 
25 L-ULDPE (5) 
20 0.933 
2.037 .times. 10.sup.-1 
(c) 
15 LLDPE (3) 
15 
__________________________________________________________________________ 
TABLE 2 
__________________________________________________________________________ 
Characteristics of 
Modified PE Unmodified PE 
L-ULDPE Adhesive Material 
Adhesive 
Amount Amount Amount 
Density 
Z.sub.1 
Material 
Type 
(wt %) 
Type (wt %) 
Type (wt %) 
(g/cm.sup.3) 
(g/cm.sup.2 .multidot. .mu.sec) 
__________________________________________________________________________ 
(10) (a) 
97.5 
-- L-ULDPE (6) 
2.5 0.948 
2.258 .times. 10.sup.-1 
(11) (a) 
50 -- L-ULDPE (6) 
50 0.923 
1.939 .times. 10.sup.-1 
(12) (b) 
10 HDPE (1) 
80 L-ULDPE (5) 
10 0.945 
2.217 .times. 10.sup.-1 
(13) (a) 
75 LLDPE (3) 
10 L-ULDPE (7) 
15 0.941 
2.165 .times. 10.sup.-1 
(14) (a) 
30 LLDPE (3) 
10 L-ULDPE (6) 
60 0.915 
1.870 .times. 10.sup.-1 
(15) (d) 
25 HDPE (1) 
60 L-ULDPE (5) 
15 0.930 
2.019 .times. 10.sup.-1 
(16) (a) 
50 LLDPE (3) 
20 L-ULDPE (8) 
30 0.925 
2.013 .times. 10.sup.-1 
__________________________________________________________________________ 
(3) Production of Multi-Layer Laminate 
As shown in Tables 3 and 4, using the aforementioned adhesive materials (1) 
to (16) as the adhesive material, and as the main material, HDPE (A) 
having high load melt index (measured according to JIS-K7210 under 
condition 7 of Table 1; hereinafter abbreviated to "HLMFR")=4.8 g/10 min, 
density=0.945 g/cm.sup.3 and acoustic impedance 
(Z.sub.0)=2.23.times.10.sup.-1 g/cm.sup.2 .multidot..mu.sec, or HDPE (B) 
having MFR=0.3 g/10 min, density=0.948 g/cm.sup.3 and Z.sub.0 
=2.26.times.10.sup.-1 g/cm.sup.2 .multidot..mu.sec, and additionally, as 
the EVOH, EVOH having an ethylene content of 29 mol%, a melting point as 
determined by the DSC method of 189.degree. C., MFR=4 g/10 min at 
230.degree. C. and a density of 1.20 g/cm.sup.3, molding of 3-type 5-layer 
multi-layer laminates (molding temperature 210.degree. C., thickness 
construction, each main material layer 1.5 mm, each adhesive material 
layer 0.10 mm, EVOH layer 0.08 mm) was conducted. 
From the flat portion of the-above laminate was obtained a 
multi-layer-piece having a width of 10 mm and a length of 150 mm, which 
was then measured for the initial adhesive strength P.sub.0 between the 
adhesive material layer and, the EVOH layer according to the T type 
peeling method by the use of a tension type tensile tester under condition 
of peeling speed of 50 mm/min, with the results shown in Tables 3 and 4. 
The same multi-layer piece was allowed to stand for 96 hours in an oven at 
115.degree. C. and then dipped for 1,000 hours in a mixed solution 
consisting of 90% by volume of commercially available regular gasoline and 
10% by volume of methanol at 40.degree. C. and, thereafter, after 
adjustment of condition for more than 50 hours in an atmosphere of 
23.degree. C. and 50%RH, was measured for adhesive strength P.sub.1, under 
the same conditions. By comparison with P.sub.0 for evaluation of long 
term heat resistance and fuel oil resistance, the degree of retention of 
adhesive strength (value of P.sub.1 with P.sub.0 as 100) was determined, 
and the evaluation is shown in Tables 3 and 4. 
Moreover, determination of detectability of the adhesive material was 
conducted by the following method. That is, the aforementioned apparatus 
used in measurement of acoustic impedance was used, a supersonic wave 
(freguency 20 MHz) was hit on each multi-layer laminate sheet, and pulse 
waves reflected from the respective interfaces were put-out on an 
osciloscope for observation of wave form, as provided with a polaroid 
camera for recording, and the pulse waves were recorded by the use of the 
camera. A model of record is shown in FIG. 1. FIG. 1 shows a pulse wave 
form of pulses reflected from the respective interfaces, as output on the 
osciloscope for observation, when a supersonic wave was hit on the 3-type 
5-layer multi-layer laminate-sheet from one main material layer side. 
Explaining, in more detail, the ordinate axis indicates the intensity of 
reflected wave, and the abscissa axis indicates a distance in the 
direction of thickness from one surface of the multi-layer laminate sheet. 
The pulse input from the left side of FIG. 1 shows a reflected wave 
intensity peak indicated by (A) on the surface of the main material layer, 
and then part of the pulse enters the laminate constituting material wall, 
passing through the thickness of the main material layer corresponding to 
the distance between peak A and Peak B, and reflected at the surface of 
the adhesive material layer (interface between the adhesive material layer 
and main material layer) as indicated by peak B. 
In FIG. 1, peaks A and B are in the opposite direction, which indicates 
that the acoustic impedance (Z.sub.1) of the adhesive material layer is 
lower than that (Z.sub.0) of the main material layer (Z.sub.0 &gt;Z.sub.1); 
naturally, if Z.sub.1 &gt;Z.sub.0, the peaks are in the same direction. 
Then, further part of the pulse, after passing through the thickness of the 
adhesive material layer (distance between peak B and peak C), is reflected 
at the interface between the adhesive material layer and EVOH layer as 
indicated by peak C. After passage through the EVOH layer (distance 
between peak C and peak D), it is reflected as indicated by peak D. 
When this measuring method is employed, assuming that the difference 
between the intensity peak of the reflected wave of the main material 
layer and the intensity peak of the reflected wave of the adhesive 
material layer is h.sub.1, and the difference between the peak of the main 
material layer and the peak of the EVOH layer is h.sub.2, if h.sub.1 
/h.sub.2 is less than 0.08, it is judged as "not detectable", and if 
h.sub.1 /h.sub.2 is 0.095 or more, it is judged as "detectable". The 
reason for this is that if h.sub.1 /h.sub.2 is less than 0.095, it becomes 
quite difficult to distinguish the peak from the interface between the 
main material layer and adhesive material layer, over the disturbance of 
wave form due to noise. 
The symbols shown behind the figures of h.sub.1 /h.sub.2 in Tables 3 and 4 
indicates detectability as evaluated on the following criteria: 
.circleincircle.: Greatly well detectable 
o: Well detectable 
.DELTA.: Detectable 
.times.: Detectable only with difficulty 
TABLE 3 
__________________________________________________________________________ 
Initial 
Degree of 
Difference 
Adhesive 
Retention 
in Acoustic 
Main Adhesive 
Strength 
of Adhesive 
Impedance 
h.sub.1 /h.sub.2 
Material Material 
(kg/cm) 
Strength (%) 
(g/cm.sup.2 .multidot. .mu.sec) 
(Detectability) 
__________________________________________________________________________ 
Example 1 
HDPE (A) 
(1) .gtoreq.13.5* 
89 13.5 .times. 10.sup.-3 
0.10 (.smallcircle.) 
Example 2 
HDPE (A) 
(2) .gtoreq.15* 
93 18.0 .times. 10.sup.-3 
0.12 (.circleincircle.) 
Example 3 
HDPE (A) 
(3) .gtoreq.16* 
92 20.9 .times. 10.sup.-3 
0.12 (.circleincircle.) 
Example 4 
HDPE (A) 
(4) .gtoreq.19.5* 
100 21.5 .times. 10.sup.-3 
0.12 (.circleincircle.) 
Example 5 
HDPE (A) 
(5) no peeling 
100 22.7 .times. 10.sup.-3 
0.13 (.circleincircle.) 
Example 6 
HDPE (A) 
(6) no peeling 
100 14.6 .times. 10.sup.-3 
0.11 (.smallcircle.) 
Example 7 
HDPE (A) 
(7) no peeling 
100 19.8 .times. 10.sup.-3 
0.12 (.circleincircle.) 
Example 8 
HDPE (A) 
(8) no peeling 
100 18.1 .times. 10.sup.-3 
0.11 (.smallcircle.) 
Example 9 
HDPE (A) 
(9) no peeiing 
100 19.3 .times. 10.sup.-3 
0.12 (.circleincircle.) 
Example 10 
HDPE (B) 
(8) .gtoreq.18* 
98 9.5 .times. 10.sup.-3 
0.09 (.DELTA.) 
Example 11 
HDPE (B) 
(6) no peeling 
100 17.6 .times. 10.sup.-3 
0.11 (.smallcircle.) 
Example 12 
HDPE (B) 
(5) no peeling 
100 25.7 .times. 10.sup.-3 
0.14 (.circleincircle.) 
__________________________________________________________________________ 
*indicates cutting of the layer comprising the main material layer and 
adhesive material layer 
TABLE 4 
__________________________________________________________________________ 
Initial 
Degree of 
Difference 
Adhesive 
Retention 
in Acoustic 
Main Adhesive 
Strength 
of Adhesive 
Impedance 
h.sub.1 /h.sub.2 
Material Material 
(kg/cm) 
Strength (%) 
(g/cm.sup.2 .multidot. .mu.sec) 
(Detectability) 
__________________________________________________________________________ 
Comparative 
HDPE (A) 
(10) 6.5 74 2.8 .times. 10.sup.-3 
0.03 (x) 
Example 1 
Comparative 
HDPE (A) 
(11) 9 27 29.1 .times. 10.sup.-3 
0.14 (.circleincircle.) 
Example 2 
Comparative 
HDPE (A) 
(12) 10 90 1.3 .times. 10.sup.-3 
0.01 (x) 
Example 3 
Comparative 
HDPE (A) 
(13) 11.5 96 6.5 .times. 10.sup.-3 
0.05 (x) 
Example 4 
Comparative 
HDPE (A) 
(14) 10.5 20 36.0 .times. 10.sup.-3 
0.15 (.circleincircle.) 
Example 5 
Comparative 
HDPE (A) 
(15) 5 5 to 25** 
21.1 .times. 10.sup.-3 
0.13 (.circleincircle.) 
Example 6 
Comparative 
HDPE (A) 
(16) 8 15 to 40** 
21.7 .times. 10.sup.-3 
0.13 (.circleincircle.) 
Example 7 
Comparative 
HDPE (B) 
(12) 7 83 4.3 .times. 10.sup.-3 
0.04 (x) 
Example 8 
Comparative 
HDPE (B) 
(16) 6.5 21 to 47** 
26.3 .times. 10.sup.-3 
0.14 (.circleincircle.) 
Example 9 
__________________________________________________________________________ 
**means that scattering is large. 
Examples 13 to 21 and Comparative Examples 10 to 16 
(1) Production of Modified polyethylene 
Various modified polyethylenic resins used as the adhesive material 
component in the examples and comparative examples were produced as 
follows. 
Modified PE (e) 
To 100 parts by weight of a powder of HDPE (8) having a density of 0.951 
g/cm and MFR of 0.85 g/10 min was added 0.01 part by weight of 
2,5-dimethyl-2,5-tert-butylperoxyhexane, which were then dry blended for 2 
minutes by the use of a Henschel mixer. Then, 0.35 part by weight of MAH 
was added, and the mixture was dry blended for additional 2 minutes. 
Pellets were produced while melt kneading the mixture obtained above, at a 
resin temperature of 255.degree. C. by the use of an extruder. The amount 
of MAH grafted in the modified PE (e) thus obtained was 0.32% by weight. 
Modified PE (f) 
Modified PE (f) was produced by carrying out dry blending and melt kneading 
in the same manner as in modified PE (e) except that in place of HDPE (8) 
used in the production of modified PE (e), HDPE (9) having a density of 
0.944 g/cm.sup.3 and MFR of 0.40 g/10 min was used. The amount of MAH 
grafted in the modified PE (f) was 0.31% by weight. 
Modified PE (g) 
Dry blending and melt kneading was conducted in the same manner as in the 
modified PE (e) except that in place of HDPE (8) used in the production of 
modified PE (e), LLDPE (10) having a density of 0.924 g/cm.sup.3 and MFR 
of 0.8 g/10 min (melting point 120.degree. C., number of ethyl group 
branches per 1,000 carbon atoms of the main chain 10) was used. The amount 
of MAH grafted in the modified PE (g) obtained was 0.29% by weight. 
Modified PE (h) 
Dry blending and melt kneading were conducted in the same manner as in the 
modified PE (s) except that in place of HDPE (8) used in the production of 
modified PE (e), L-ULDPE (11) having MFR of 1.8 g/10 min (melting point 
98.degree. C., number of branching 75) was used, and melt kneading was 
changed to 230.degree. C. The amount of MAH grafted in the modified PE (h) 
obtained was 0.26 g/cm.sup.3. 
Characteristics of unmodified L-ULDPE used likewise are as follows. 
L-ULDPE (12) 
Unmodified linear ultra low density polyethylenic resin having a density of 
0.905 g/cm.sup.3, MFR 1.02 g/10 min, a melting point of 120.degree. C. and 
a number of branching of 30 as produced by the slurry polymerization 
method. 
L-ULDPE (13) 
Unmodified linear ultra low density polyethylenic resin having a density of 
0.899 g/cm.sup.3, MFR of 0.93 g/10 min, a melting point of 114.degree. C. 
and a number of branching of 44 as produced by the slurry polymerization 
method. 
L-ULDPE (14) 
Unmodified linear ultra low density polyethylenic resin having a density of 
0.907 g/cm.sup.3, MFR of 9.0 g/10 min, a melting point of 121.degree. C. 
and a number of branching of 23 as produced by the slurry polymerization 
method. 
(2) Production of Adhesive Material 
Modified polyethylenic resin (modified PE), unmodified polyethylenic resin 
(unmodified PE) and unmodified linear ultra low density polyethylenic 
resin (L-ULDPE), their types and compounding amounts being shown in Table 
5, were dry blended in advance for 5 minutes by the use of a Henschel 
mixer. Each mixture obtained was kneaded while melting at a in temperature 
of 215.degree. C. by the use of an extruder (diameter:,50 mm) to produce 
pellets (composition). The compositions (adhesive materials) (17) to (32) 
thus obtained were measured for density and acoustic impedance in the same 
manner as in Example 1. The results are shown in Table s 5 and 6. 
TABLE 5 
__________________________________________________________________________ 
Characteristics of 
Modified PE Unmodified PE 
L-ULDPE Adhesive Material 
Adhesive 
Amount Amount Amount 
Density 
Z.sub.1 
Material 
Type 
(wt %) 
Type (wt %) 
Type (wt %) 
(g/cm.sup.3) 
(g/cm.sup.2 .multidot. .mu.sec) 
__________________________________________________________________________ 
(17) (e) 
80 -- -- L-ULDPE (13) 
20 0.939 
2.090 .times. 10.sup.-1 
(18) (e) 
65 -- -- L-ULDPE (13) 
35 0.932 
2.032 .times. 10.sup.-1 
(19) (e) 
35 LLDPE (10) 
55 L-ULDPE (12) 
10 0.930 
2.020 .times. 10.sup.-1 
(20) (e) 
35 LLDPE (10) 
45 L-ULDPE (12) 
20 0.928 
2.011 .times. 10.sup.-1 
(21) (e) 
35 LLDPE (10) 
35 L-ULDPE (12) 
30 0.927 
2.003 .times. 10.sup.-1 
(22) (f) 
30 HDPE (8) 
45 L-ULDPE (14) 
25 0.937 
2.082 .times. 10.sup.-1 
(23) (e) 
50 LLDPE (10) 
15 L-ULDPE (12) 
25 0.932 
2.030 .times. 10.sup.-1 
(g) 
10 
(24) (e) 
20 HDPE (8) 
40 L-ULDPE (12) 
30 0.934 
2.050 .times. 10.sup.-1 
(g) 
10 
(25) (e) 
25 HDPE (8) 
25 L-ULDPE (12) 
20 0.933 
2.037 .times. 10.sup.-1 
(g) 
15 LLDPE (10) 
15 
__________________________________________________________________________ 
TABLE 6 
__________________________________________________________________________ 
Characteristics of 
Modified PE Unmodified PE 
L-ULDPE Adhesive Material 
Adhesive 
Amount Amount Amount 
Density 
Z.sub.1 
Material 
Type 
(wt %) 
Type (wt %) 
Type (wt %) 
(g/cm.sup.3) 
(g/cm.sup.2 .multidot. .mu.sec) 
__________________________________________________________________________ 
(26) (e) 
97.5 
-- -- L-ULDPE (13) 
2.5 0.949 
2.267 .times. 10.sup.-1 
(27) (e) 
50 -- -- L-ULDPE (13) 
50 0.924 
1.948 .times. 10.sup.-1 
(28) (f) 
10 HDPE (8) 
80 L-ULDPE (12) 
10 0.945 
2.216 .times. 10.sup.-1 
(29) (e) 
75 LLDPE (10) 
10 L-ULDPE (14) 
15 0.940 
2.150 .times. 10.sup.-1 
(30) (e) 
30 LLDPE (10) 
10 L-ULDPE (13) 
60 0.916 
1.880 .times. 10.sup.-1 
(31) (h) 
25 HDPE (8) 
60 L-ULDPE (12) 
15 0.929 
2.011 .times. 10.sup.-1 
(32) (e) 
50 LLDPE (10) 
20 L-ULDPE (11) 
30 0.928 
2.003 .times. 10.sup.-1 
__________________________________________________________________________ 
(3) Production of Multi-Layer Fuel Oil Container 
As shown in Tables 5 and 6, the aforementioned adhesive materials (17) to 
(32) were used as the adhesive material, a high density polyethylenic 
resin (hereinafter referred to as HDPE (C)) having HLMFR of 50 g/10 min, a 
density of 0.945 g/cm.sup.3, and an acoustic impedance of 
2.23.times.10.sup.-1 g/cm.sup.2 .multidot..mu.sec was used as the main 
material, and as the barrier material, EVOH having an ethylene content of 
29 mol%, MFR (210.degree. C., 2.16 kg) of 3.1 g/10 min, and a melting 
point of 191.degree. C. was used. A 3-type 5-layer- multi-layer fuel oil 
container having an inner volume of 45 L (L=liter) and a total weight of 
5.8 kg was produced at 220.degree. C. by the use of a multi-layer blow 
molding machine having a 3-type 5-layer die in concentric circular form as 
provided with a molding machine to coextrude by the use of extruders 
having the respective diameters of 90 mm, 40 mm and 30 mm, in such a 
manner that the average thicknesses of the multiple layers were such that 
the inner and outer layers of the main material were 3.0 mm thick, the 
inner and outer layers of the adhesive material were 0.15 mm thick, and 
the EVOH layer was 0.10 mm thick. With regard to the adhesive strength 
prior to treatment of the container obtained, a piece having a width of 10 
mm and a length of 150 mm was cut away from the flat portion of the 
rectangular container and measured for the adhesive strength between the 
adhesive material and EVOH layer according to the T-type peeling method by 
the use of a Tension-type tensile tester at a peeling speed of 50 mm/min. 
In addition, likewise, test pieces were cut away, and each test piece was 
allowed to stand for 72 hours in an oven at 110.degree. C. and then dipped 
for 1,500 hours at 40.degree. C. in a mixed solution consisting of 85% by 
volume of commercially available regular gasoline and 15% by volume of 
methyl alcohol. Then, each test piece was taken out and held for 150 hours 
under conditions of temperature of 23.degree. C. and relative humidity of 
50%, and then measured for the adhesive strength after the treatment. 
In this way, the initial adhesive strength and degree of retention of the 
adhesive strength were measured, and the difference in acoustic impedance 
and detectability were measured in the same manner as in Example 1, with 
the results shown in Tables 7 and 8. 
Example 22 
The multi-layer fuel oil container obtained in Example 19 was finely 
divided by the use of a crusher, and pelletized while kneading at a 
temperature of 250.degree. C. by the use of a coaxial twin-screw extruder. 
Particle diameter of EVOH dispersed in the pellet obtained was observed by 
the use of an optical microscope, and the average particle diameter was 
found to be 30 .mu.m (maximum 55 .mu.m). A dry blend mixture of 30% by 
weight of the pellets and 70% by weight of HDPE (C) was obtained. Using 
the above mixture in place of the main material of Example 19, and the 
same adhesive material and EVOH as in Example 19, a 3-type 5-layer fuel 
oil container was produced in the same manner. 
The physical properties of the fuel oil container obtained were measured in 
the same manner as in Example 13. As a result, the initial adhesive 
strength was impossible to peel, the degree of retention of the adhesive 
strength was 100%, the difference in acoustic impedance was 
19.8.times.10.sup.2 g/cm.sup.2 .multidot..mu.sec, and h.sub.1 /h.sub.2 
=0.12; both of performance and detectability were excellent. 
TABLE 7 
__________________________________________________________________________ 
Initial 
Degree of 
Difference 
Adhesive 
Retention 
in Acoustic 
Main Adhesive 
Strength 
of Adhesive 
Impedance 
h.sub.1 /h.sub.2 
No. Material 
Material 
(kg/cm) 
Strength (%) 
(g/cm.sup.2 .multidot. .mu.sec) 
(Detectability) 
__________________________________________________________________________ 
Example 13 
HDPE (C) 
(17) .gtoreq.14.0* 
91 14.0 .times. 10.sup.-3 
0.10 (.smallcircle.) 
Example 14 
HDPE (C) 
(18) .gtoreq.15.5* 
91 19.8 .times. 10.sup.-3 
0.12 (.circleincircle.) 
Example 15 
HDPE (C) 
(19) .gtoreq.17.0* 
93 21.0 .times. 10.sup.-3 
0.12 (.circleincircle.) 
Example 16 
HDPE (C) 
(20) .gtoreq.19.5* 
100 21.9 .times. 10.sup.-3 
0.12 (.circleincircle.) 
Example 17 
HDPE (C) 
(21) No peeling 
100 22.7 .times. 10.sup.-3 
0.13 (.circleincircle.) 
Example 18 
HDPE (C) 
(22) No peeling 
100 14.8 .times. 10.sup.-3 
0.11 (.smallcircle.) 
Example 19 
HDPE (C) 
(23) No peeling 
100 20.0 .times. 10.sup.-3 
0.12 (.circleincircle.) 
Example 20 
HDPE (C) 
(24) No peeling 
100 18.0 .times. 10.sup.-3 
0.11 (.smallcircle.) 
Example 21 
HDPE (C) 
(25) No peeling 
100 19.3 .times. 10.sup.-3 
0.12 (.circleincircle.) 
__________________________________________________________________________ 
*means cutting of the layer comprising the main material layer and 
adhesive material layer. 
TABLE 8 
__________________________________________________________________________ 
Initial 
Degree of 
Difference 
Adhesive 
Retention 
in Acoustic 
Main Adhesive 
Strength 
of Adhesive 
Impedance 
h.sub.1 /h.sub.2 
No. Material 
Material 
(kg/cm) 
Strength (%) 
(g/cm.sup.2 .multidot. .mu.sec) 
(Detectability) 
__________________________________________________________________________ 
Comparative 
HDPE (C) 
(26) 6.5 74 3.7 .times. 10.sup.-3 
0.03 (x) 
Example 10 
Comparative 
HDPE (C) 
(27) 9 27 28.2 .times. 10.sup.-3 
0.14 (.circleincircle.) 
Example 11 
Comparative 
HDPE (C) 
(28) 10 90 1.4 .times. 10.sup.-3 
0.01 (x) 
Example 12 
Comparative 
HDPE (C) 
(29) 11.5 96 8.0 .times. 10.sup.-3 
0.05 (x) 
Example 13 
Comparative 
HDPE (C) 
(30) 10.5 20 35.0 .times. 10.sup.-3 
0.15 (.circleincircle.) 
Example 14 
Comparative 
HDPE (C) 
(31) 5 5-25** 
21.9 .times. 10.sup.-3 
0.13 (.circleincircle.) 
Example 15 
Comparative 
HDPE (C) 
(32) 8 15-40** 
22.7 .times. 10.sup.-3 
0.13 (.circleincircle.) 
Example 16 
__________________________________________________________________________ 
**means that scattering is large. 
Examples 23 to 34 and Comparative Examples 17 to 24 
(1) Production of Modified Polyethylene 
Various modified polyethylenic resins used as the adhesive material 
component in the examples and comparative examples were produced as 
follows. 
Modified PE (i) 
To 100 parts by weight of a powder of HDPE (15) having a density of 0.950 
g/cm.sup.3 and MFR of 0.85 g/10 min was added 0.01 part by weight of 
2,5-dimethyl-2,5-tert-butylperoxyhexane, which were then dry blended for 2 
minutes by the use of a Henschel mixer. Then, 0.35 part by weight of MAH 
was added, and the mixture was dry blended for additional 2 minutes. :The 
mixture thus obtained was pelletized while melt kneading at a resin 
temperature of 260.degree. C. by the use of an extruder. The amount of MAH 
grafted in the modified PE (i) obtained was 0.32% by weight. 
Modified PE (j) 
Modified PE (j) was-produced by carrying out dry blending and melt-kneading 
in the same manner as in modified PE (i) except that in place of DPE (15) 
used in the production of modified PE (i), HDPE (16) having a density of 
0.943 g/cm.sup.3 and MRF of 0.40 g/10 min was used. The amount of MAH 
grafted in modified PE (j) was 0.30% by weight. 
Modified PE (k) 
Dry blending and melt kneading were carried out in the same manner as in 
modified PE (i) except that in place of HDPE (15) used in the production 
of modified PE (i), LLDPE (17) having a density of 0.924 g/cm.sup.3 and 
MFR of 0.8 g/10 min (melting point 120.degree. C., number of ethyl group 
branches per 1000 carbon atoms of the main chain 10) was used. The amount 
of MAH grafted in the modified PE (k) obtained was 0.28% by weight. 
Modified PE (l) 
Dry blending and melt kneading were carried out in the same manner as in 
modified PE (i) except that in place of HDPE (15) used in the production 
of modified PE (i), L-ULDPE (18) having a density of 0.0891 g/cm.sup.3 and 
MFR of 1.8 g/10 min (melting point 97.degree. C., number of branching 70), 
and melt kneading was conducted at 230.degree. C. The amount of MAH 
grafted in the modified PE (l) obtained was 0.25% by weight. 
In addition, as unmodified linear ultra low density polyethylenes for use 
in the production of the adhesive material, L-ULDPE (12), L-ULDPE (13) and 
L-ULDPE (14) of Example 13 (1) were used. 
(2) Production of Adhesive Material 
Modified polyethylenic resin (modified PE), unmodified polyethylenic resin 
(unmodified PE) and unmodified linear ultra low density polyethylenic 
resin (L-ULDPE), the type and compounding amount of which are shown in 
Tables 9 and 10, were dry blended in advance for 5 minutes by the use of a 
Henschel mixer. Each mixture obtained was kneaded while melting at a resin 
temperature of 210.degree. C. by the use of an extruder (diameter 50 mm) 
to produce pellets (composition). The density and acoustic impedance of 
the compositions (adhesive material) (33) to (49) were measured in the 
same manner as In Example 1. The results are shown in Tables 9 and 10. 
TABLE 9 
__________________________________________________________________________ 
Characteristics of 
Modified PE Unmodified PE 
L-ULDPE Amount of 
Adhesive Material 
Adhesive 
Amount Amount Amount 
Grafted MAH 
Density 
Z.sub.1 
Material 
Type 
(wt %) 
Type (wt %) 
Type (wt %) 
(wt %) (g/cm.sup.3) 
(g/cm.sup.2 .multidot. 
.mu.sec) 
__________________________________________________________________________ 
(33) (i) 
75 -- 0 L-ULDPE (13) 
25 0.240 0.937 
2.085 .times. 10.sup.-1 
(34) (i) 
65 -- 0 L-ULDPE (12) 
35 0.207 0.933 
2.038 .times. 10.sup.-1 
(35) (i) 
20 LLDPE (17) 
70 L-ULDPE (12) 
10 0.064 0.927 
1.992 .times. 10.sup.-1 
(36) (i) 
25 LLDPE (17) 
50 L-ULDPE (12) 
25 0.080 0.934 
2.051 .times. 10.sup.-1 
(37) (i) 
40 LLDPE (17) 
25 L-ULDPE (12) 
35 0.128 0.927 
2.000 .times. 10.sup.-1 
(38) (j) 
70 LLDPE (17) 
15 L-ULDPE (14) 
15 0.210 0.935 
2.070 .times. 10.sup.-1 
(39) (i) 
35 LLDPE (17) 
30 L-ULDPE (12) 
25 0.140 0.928 
2.011 .times. 10.sup.-1 
(k) 
10 
(40) (i) 
35 HDPE (15) 
10 L-ULDPE (12) 
25 0.126 0.930 
2.020 .times. 10.sup.-1 
(k) 
5 LLDPE (17) 
25 
(41) (i) 
40 HDPE (16) 
40 L-ULDPE (13) 
20 0.128 0.936 
2.072 .times. 10.sup.-1 
__________________________________________________________________________ 
TABLE 10 
__________________________________________________________________________ 
Characteristics of 
Modified PE Unmodified PE 
L-ULDPE Amount of 
Adhesi Material 
Adhesive 
Amount Amount Amount 
Grafted MAH 
Density 
Z.sub.1 
Material 
Type 
(wt %) 
Type (wt %) 
Type (wt %) 
(wt %) (g/cm.sup.3) 
(g/cm.sup.2 .multidot. 
.mu.sec) 
__________________________________________________________________________ 
(42) (i) 
25 HDPE (15) 
25 L-ULDPE (14) 
30 0.150 0.928 
2.015 .times. 10.sup.-1 
(k) 
25 2.258 .times. 10.sup.-1 
(43) (i) 
97.5 
-- 0 L-ULDPE (13) 
2.5 0.312 0.948 
2.193 .times. 10.sup.-1 
(44) (i) 
70 HDPE (16) 
20 L-ULDPE (12) 
10 0.224 0.943 
2.160 .times. 10.sup.-1 
(45) (i) 
75 LLDPE (17) 
15 L-ULDPE (14) 
15 0.240 0.941 
1.940 .times. 10.sup.-1 
(46) (j) 
50 -- 0 L-ULDPE (12) 
50 0.150 0.923 
1.886 .times. 10.sup.-1 
(47) (i) 
20 LLDPE (17) 
35 L-ULDPE (13) 
10 0.064 0.917 
1.971 .times. 10.sup.-1 
(48) (l) 
30 HDPE (15) 
60 L-ULDPE (12) 
25 0.075 0.926 
(49) (i) 
60 LLDPE (17) 
15 -- 0 0.192 0.930 
1.978 .times. 10.sup.-1 
L-ULDPE (18) 
25 
__________________________________________________________________________ 
(3) Production of Multi-Layer Fuel Oil Container 
As shown in Tables 11 and 12, the aforementioned adhesive materials (33) to 
(49) were used as the adhesive materials, and as the main materials, high 
density polyethylenic resins (HDPE (D)) having HLMFR of 5.0 g/10 min, a 
density of 0.945 g/cm.sup.3 and an acoustic impedance (Z.sub.0) of 
2.23.times.10.sup.-1 g/cm.sup.2 .multidot..mu.sec, and high density 
polyethylanic resins (HDPE (E)) having MFR of 0.5 g/10 min, a density of 
0.948 g/10 cm.sup.3 and Z.sub.0 o f 2.255.times.10.sup.-1 g/cm.sup.2 
.multidot..mu.sec were used. 
In addition, as the polyamide resin, a Nylon 6 (hereinafter referred to as 
"") having a relative viscosity of 4.2 was used. 
A car fuel tank having an inner volume of 45 L and a total weight of 6.5 kg 
was produced by blow molding at 232.degree. C. by the use of a multi-layer 
blow molding machine with a multi-layer die (concentric circular form) 
provided with molding machines to coextrude the main material and adhesive 
material, the type of each material being shown in Tables 11 and 12,and PA 
6 in such a manner that the thicknesses of main material layer/adhesive 
material layer/polyamide resin (PA 6) layer/adhesive material layer/main 
material layer were 3.0 mm/0.15 mm/0.10 mm/0.15 mm/3.0 mm. A multi-layer 
piece having a width of 10 mm and a length of 150 mm was cut away from the 
flat portion of the tank obtained, and measured for the initial adhesive 
strength P.sub.0 between the adhesive material layer and PA 6 according to 
the T-type pealing method by the use of a Tension-type tensile tester 
under the condition of peeling speed of 50 mm/min, with the results shown 
in Tables 11 and 12. 
Moreover, after the same multi-layer piece was allowed to stand for 72 
hours in an oven at 110.degree. C., it was dipped at 40.degree. C. for 
1,500 hours in a mixed solution comprising 90% by volume of commercially 
available regular gasoline and 10% by volume of methyl alcohol. Then, each 
piece was taken out and held for 168 hours under conditions of temperature 
of 23.degree. C. and relative humidity of 50%. After these treatments, the 
adhesive strength P.sub.1 was measured under the same conditions, and by 
comparison with P.sub.0 previously measured, the degree of retention of 
the adhesive strength (value of P.sub.1 when P.sub.0 was 100) 
was-determined for evaluation of the long term heat resistance and fuel 
oil resistance; evaluation is shown in Tables 11 and 12. 
Moreover, the difference (.DELTA.Z) in acoustic impedance between the main 
material layer and adhesive material layer, aforementioned h.sub.1 
/h.sub.2 and the judgement of the presence or absence of detection based 
thereon were conducted in the same manner as in Example 1, with the 
results shown in Tables 11 and 12. 
Example 35 
The multi-layer tank obtained in Example 30 was finely divided by the use 
of a crusher, and pelletized while kneading at a temperature of 
265.degree. C. by the use of a coaxial twin-screw extruder. Observation of 
dispersion particle diameter of PA 6 in the pellet obtained by the use of 
an optical microscope showed that the average particle diameter was 45 
.mu.m (maximum 70 .mu.m). A mixture comprising 30% by weight of the 
pellets, and 70% by weight of a high molecular high density polyethylenic 
resin having a density of 0.945 g/cm.sup.3 and HLMFR of 4.8 g/min was 
produced by dry blending. In the same manner as in Example 30 except that 
the one to which 1 part by weight of the high molecular weight high 
density polyethylenic resin had been dry blended, was used as the main 
material layer, a car fuel oil tank was produced. The detectability of the 
tank obtained was determined in the same manner as in Example 23, and 
h.sub.1 /h.sub.2 was 0.12; it was detectable. 
TABLE 11 
__________________________________________________________________________ 
Initial 
Degree of 
Difference 
Adhesive 
Retention 
in Acoustic 
Main Adhesive 
Strength 
of Adhesive 
Impedance 
h.sub.1 /h.sub.2 
No. Material 
Material 
(kg/cm) 
Material (%) 
(g/cm.sup.2 .multidot. .mu.sec) 
(Detectability) 
__________________________________________________________________________ 
Example 23 
HDPE (D) 
(33) .gtoreq.14* 
95 14.5 .times. 10.sup.-3 
0.11 (.smallcircle.) 
Example 24 
HDPE (D) 
(34) .gtoreq.17* 
100 19.2 .times. 10.sup.-3 
0.12 (.circleincircle.) 
Example 25 
HDPE (D) 
(35) .gtoreq.18 
91 23.8 .times. 10.sup.-3 
0.13 (.circleincircle.) 
Example 26 
HDPE (D) 
(36) .gtoreq.25* 
88 17.9 .times. 10.sup.-3 
0.11 (.smallcircle.) 
Example 27 
HDPE (D) 
(37) No peeling 
100 23.0 .times. 10.sup.-3 
0.13 (.circleincircle.) 
Example 28 
HDPE (D) 
(38) No peeling 
98 16.0 .times. 10.sup.-3 
0.11 (.smallcircle.) 
Example 29 
HDPE (D) 
(39) No peeling 
100 21.9 .times. 10.sup.-3 
0.12 (.circleincircle.) 
Example 30 
HDPE (D) 
(40) No peeling 
100 21.0 .times. 10.sup.-3 
0.12 (.circleincircle.) 
Example 31 
HDPE (D) 
(41) No peeling 
100 15.8 .times. 10.sup.-3 
0.11 (.smallcircle.) 
Example 32 
HDPE (D) 
(42) No peeling 
100 21.5 .times. 10.sup.-3 
0.12 (.circleincircle.) 
Example 33 
HDPE (E) 
(40) No peeling 
94 9.5 .times. 10.sup.-3 
0.09 (.DELTA.) 
Example 34 
HDPE (E) 
(40) No peeling 
96 26.3 .times. 10.sup.-3 
0.14 (.circleincircle.) 
__________________________________________________________________________ 
*means cutting of the layer comprising the main material layer and 
adhesive material layer. 
TABLE 12 
__________________________________________________________________________ 
Initial 
Degree of 
Difference 
Adhesive 
Retention 
in Acoustic 
Main Adhesive 
Strength 
of Adhesive 
Impedance 
h.sub.1 /h.sub.2 
No. Material 
Material 
(kg/cm) 
Material (%) 
(g/cm.sup.2 .multidot. .mu.sec) 
(Detectability) 
__________________________________________________________________________ 
Comparative 
HDPE (D) 
(43) 8 76 2.8 .times. 10.sup.-3 
0.03 (x) 
Example 17 
Comparative 
HDPE (D) 
(44) 11 92 3.7 .times. 10.sup.-3 
0.03 (x) 
Example 18 
Comparative 
HDPE (D) 
(45) 12 100 7.0 .times. 10.sup.-3 
0.06 (x) 
Example 19 
Comparative 
HDPE (E) 
(44) 11 97 6.2 .times. 10.sup.-3 
0.05 (x) 
Example 20 
Comparative 
HDPE (D) 
(46) 9 21 29.0 .times. 10.sup.-3 
0.14 (.circleincircle.) 
Example 21 
Comparative 
HDPE (D) 
(47) 10 28 34.4 .times. 10.sup.-3 
0.15 (.circleincircle.) 
Example 22 
Comparative 
HDPE (D) 
(48) 7 3-15* 
25.9 .times. 10.sup.-3 
0.14 (.circleincircle.) 
Example 23 
Comparative 
HDPE (D) 
(49) 8 20-35* 
23.2 .times. 10.sup.-3 
0.13 (.circleincircle.) 
Example 24 
__________________________________________________________________________ 
*means that scattering is large. 
Example 36 
Using the adhesive material (9) used in Example 9, high density 
polyethylene (HDPE (F)) having a density of 0.946 g/cm.sup.3 and MFR of 
0.3 g/10 min. as the main material, and as the barrier material, EVOH 
having an ethylene content of 30 mol*, a melting point by the DSC method 
of 188.degree. C., MFR at 230.degree. C. of 4.8 g/10 min, and a density of 
1.19 g/cm, a 3-type 5-layer multi-layer blow container with 20 liter 
volume having such average thicknesses that each of the inner and outer 
layers of the main material was 1.5 mm, each of the inner and outer layers 
of the adhesive material was 0.10 mm, and the EVOH layer was 0.05 mm was 
produced by the use of a multi-layer blow molding machine provided with 
extruders having the respective diameters of 90 mm, 40 mm and 30 mm, and 
having a 3-type 5-layer die in a concentral circular form. 
An attempt to measure the adhesive strength between the EVOH and adhesive 
material layers was made for a multi-layer piece cut away from the flat 
portion of the container obtained, but with no peeling. 
In addition, the piece was dipped at 40.degree. C. for 2,500 hours in 
edible oil containing linolic acid as the major component and then it was 
attempted to measure the adhesive strength between the EVOH layer and 
adhesive material layer in the same manner. However, no peeling occurred, 
and excellent adhesive durability was exhibited. 
Moreover, the above 20 liter multi-layer container was measured for a value 
of h.sub.1 /h.sub.2 as a measure of detectability in the same manner as 
above, using a supersonic wave of 20 MHz h.sub.1 /h.sub.2 =0.12; excellent 
detectability was exhibited. 
Industrial Applicability 
The multi-layer laminate molding of the present invention is excellent in 
barrier properties and at the same time, has greatly suitable 
characteristics from a viewpoint of quality control or process control 
that non-destructive detection of the adhesive material layer can be 
carried out easily by the supersonic reflection method. Accordingly, 
moldlings having the multi-layer laminate structure as in the present 
invention can be widely utilized, in a desired form, as wrapping 
containers of fuel oil edible oil and so forth, wrapping sheets, wrapping 
bags, industrial materials, and so forth.