Note: Descriptions are shown in the official language in which they were submitted.
2 1 9 1 90 1
ADHESIVE RESIN COMPOSITION, LAMINATE COMPRISING
~IS COMP08ITION AS ADHESIVE LAYER, AND PROCE8S
FOR PREPARATION THEREOF
~ackqround of the Inventlon
This i8 a dlvislonal appllcatlon dlvlded out
of parent appllcation Serlal No. 2,022,799 flied on August 7,
1990 .
(1) Fleld of the Inventlon
The present lnventlon relates to an adhesive resin
composltlon and a iamlnate comprlslng thls resln as an
adheslve layer. More speclflcally, the subject matter of
thls appllcatlon 18 dlrected to a lamlnate comprlslng the
second adheslve resln mentloned hereinunder, while the
sub~ect matter of the parent applicatlon 18 dlrected to the
flrst adheslve resln composltlon mentloned herelnunder and a
lamlnate formed by uslng the same.
It should be noted that the "present lnventlon" ln
thls speclflcatlon lncludes the sub~ect matter of both parent
and this dlvlslonal appllcations. The present lnventlon
relates to an adhesive resin composltlon glving an excellent
adheslveness between a metal and a thermoplastic resin, and a
metal/resin sheath laminate to be used for a lamlnate sheath
cable, which is formed by uslng thls resin composltlon.
Furthermore, the present lnventlon relates to an adheslve
resln composltlon, of whlch the adheslve force is not reduced
even under contact with hlgh-temperature water, and a
lamlnate having an excellent gas-barrier property and being
capable of resisting a retort treatment, which ls formed by
67616-181D
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uslng thls adhesive resln compositlon.
(2) Descriptlon of the Related Art
An adheslve resln composltlon comprlslng three
~~ts, that 18, Q styrene resln, an ethylene/vlnyl
acetate copolymer resin and a polyethylene resln graft-
modifled with an unsaturated car~oxyllc acld or a derlvative
thereof has been publicly known. Thls adheslve resin
composltlon has an excellent adheslveness between a metal and
a thermoplastlc resln and also between a polyester resln and
an ethylene/vlnyl acetate copolymer, whlch are used for a
packaglng material or the llke to be sub~ected a retort
treatment.
Thls adheslve resln composltlon ls used for
laminate sheath cable havlng a resln sheath arranged on the
outer slde of a barrler materlal for a cable and
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a cable core, and since this lamlnate sheath cable i9
excellent ln such characteristics as mechanical
properties, corrosion resistance and moisture
resistance, this cable is widely used at the present.
In this laminate sheath cable, the above-mentioned
adhesive resin composition is used ror bonding a metal
tape composed of aluminum, copper or the like, to be
used as the barrier layer, to a sheath resin composed
mainly of low-density polyethylene.
The lamlnate metal tape 19 generally prepared by
extrusion lamination cr a metal and a Yheath resin or
bonding a metal layer to a rusion-bonding resin layer
rllm and a sheath resin layer rilm. In case Or
conventlonal rusion-bondlng resins, streaks are orten
formed on the laminated rusion-bonding resin layer.
These streaks are rormed because of local changes
Or the thickness cr the fusion-bonding resin layer and
the presence Or these streaks degrades the adhesion
between the metal and sheath resLn and reduces the
appearance characterigticg Or the product. Moreover,
cracks are rormed in a thin portion of the rusion-
bonding resin=layer and even the perrormances Or the
product are reduced.
In Japanese UnPx~m~n~d Patent Publication No. 61-
296044, we previougly proposed a thermoplastic resin
compositlon capable Or preventlng formation Or streaks
in the rusion-bonding resin layer, which comprises 97 to
45 parts by weight of an ethylene/vinyl acetate
copolymer, 30 to 1 parts by weight of a styrene polymer
resin, 15 to 1 parts by weight of polyethylene grart-
modified with an unsaturated carboxylic acid or a
derivative thereor and 30 to 1 parts by weight of a
monovinyl aromatic hydrocarbon/olefin block copolymer.
~hen a laminate metal tape is prepared by using this
thermoplastic resin composltion as the rusion-bonding
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resin, streaks are not formed in the rusion bonding
resin layer, but the adhesiveness between the metal and
a resin sheath layer is not completely satisractory.
Accordingly, development of an adhesive resin
composition which can prevent rormation of streaks in
the fusion-bonding (adhesive) resin layer and can give
an excellent adhesiveness between a metal and a resin
sheath layer iB eagerly desired.
Although the above-mentLoned adhesive resin
composition is uced ror the production Or a laminate Or
a polyester resin and a gas-barrier resin to be used ror
a packaging vessel or the like and shows a good
adhesiveness, lr a heat treatment such a high-
temperature filling treatment or a retort treatment is
carried out at the production of this laminate or at the
time Or eating or drinking a content in the packaging
vessel, the adhesive force iB sometimes reduced by
heating, resulting in peeling of the layer and reduction
Or the gas permeation resistance.
As the adhesive resin composition capable Or
retaining a high adhesive rorce bet~een layers Or a
laminate even after a high-temperature treatment such as
a high-temperature filling treatment or a retort
treatment, we previously proposed in Japanese Unexamined
Patent Publication No. 64-45445 an adhesive resin
composition comprising (a) 95 to 50 % by weight Or an
ethylene/c~-olefin copolymer having a melt flow rate Or
0.1 to 50 g/10 min, a density of o.850 to 0.900 g/cm3,
an ethylene content of 75 to 95 mole% and an X-ray
crystallinity lower than 30%, tb) 5 to 50 % by weight cr
an ethylene/vinyl acetate copolymer having a melt flow
rate Or O . 1 to 50 g/10 min and a vinyl acetate content
of 5 to 40~ by weight, and (c) 1.0 to 30 ~ by weight,
based on the sum of components (a) and (b), Or partially
or wholly grart-modified polyethylene having a grafting
~ 21ql~1
amount Or an unsaturated carboxylic acid or a derivative
thereof of 0.05 to 15 % by weight, a melt rlow rate cr
0.1 to 50 g/10 mln, a density Or 0.900 to 0.980 g/cm3
and an X-ray crystallinity of at least 30%, wherein the
grafting ratio cr the composition as a whole is 0.01 to
3 % by weight, the melt rlow rate o~ the composition as
a whole is 0.1 to 50 g/10 min and the crystallinity Or
the composition as a whole is lower than 35 %. In this
patent publication, we also proposed a laminate
comprisin~ a polyester or polycarbonate layer, an
intermediate layer composed Or this adhesive resin
composition and a saponiried olerin/vinyl acetate
copolymer layer.
The above-mentioned adhesive resln composition has
an excellent adhesiveness at normal temperature after a
high-temperature treatment, but interlaminar peeling is
sometimes caused in the above-mentioned laminate during
a high-temperature rilling treatment or a retort
treatment.
Accordingly, development Or an adhesive resin
composition capable Or completely preventing occurrence
Or interlaminar peeling in a laminate even under a high-
temperature rilling treatment or a retort treatment is
desired.
5ummary Or the Invention
The present invention is to solve the above-
mentioned problems of the conventional techniques, and
it is a primary ob~ect Or the present invention to
provide an adhesive resin composition capable cr
preventing formation of streaks in a rusion-bonding
resin layer and giving an excellent adhesiveness between
a metal and a thermoplastic resin sheath layer, and a
lamLnate rormed by using thLs adhesLve resLn
composLtion.
Another ob~ect Or the present invention is to
.....
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provide an adhesive resin composLtion having such an
excellent heat-Fesistant adhesiveness at a high
temperature that occurrence of interlaminar peeling in a
laminate can be completely prevented even during a
~evere treatment such as a high-temperature rilling
treatment or a retort treatment, while maintaining a
practical adhesion strength at normal temperature arter
a h~gh-temperature treatment.
Stlll another ob~ect of the present inventlon is to
provide a laminate having an excellent gas permeation
resistance and not causing interlamlnar peeling at a
high-temperature rilling treatment or a retort
treatment, which is formed by bonding a polycarbonate
layer or polyalkylene terephthalate layer and a
saponiried ethylene/vinyl acetate copolymer layer by
using an adhesive resin composition as set forth above.
A rirst adhesive resin composition having an
excellent adhesiveness between a metal and a
thermoplastic resin sheath layer according to the
present invention comprlses (a) 96 to ~5 parts by weight
of an ethylene/vinyl acetate copolymer, (b) 30 to 1
parts by weight Or a styrene polymer resln, (c) 15 to 1
parts by welght cr polyethylene graft-modirled wlth an
unsaturated carboxylic acld or a derivatlve thereof, (d)
20 to 1 parts by welght of a monovlnyl aromatlc
hydrocarbon/olefin block copolymer elastomer and (e) an
ethylene/~ -olefin copolymer, the total amount of
components (a), (b), (c), (d) and (e) being 100 parts by
welght.
1 A flrst laminate formed by using the above-
mentioned first adhesive resin compositlon according to
the presen~ invention comprises a layer Or a metal such
as aluminum, copper or iron, a layer of a thermoplastic
resin such as a polyamide, a saponiried ethylene/vinyl
acetate copolymer, polyethylene or a polyester, and a
2 1 9 1 901
layer of the flrst adheslve resln lnterposed between the two
layars.
The second adheslve resln composltlon of the
present lnventlon, whlch has e~cellent adheslveness between a
polyester resln such as a polyalkylene terephthalate or a
polycarbonate and a gas-barrler resln such as a saponlfled
ethylene/vlnyl acetate copolymer, lncludes the followlng four
~-~ir-~ts-
A flrst embodlment of the second adheslve
composltlon comprlses 100 parts by welght of a soft polymerand 1 to 30 parts by welght of partlaliy or wholly graft-
modlfled polyethylene ln whlch a graftlng amount of an
unsaturated carboxyllc acld or a derlvatlve thereof 18 0.05
to 15 % by welghtl the soft polymer belng a styrene
elastomer,
A second : 1o~ of the second adheslve resln
composltlon comprlses lbO parts by welght of a soft polymer
and 1 to 30 parts by welght of partlally or wholly graft-
modlfled polyethylene ln whlch a graftlng amount of an
unsaturated carboxyllc acld or a derlvatlve thereof ls 0.05
to 15 ~ by welght, the soft polymer comprlslng (a) at least
20 ~ by welght, preferably 20 to 90 ~ by welght, of a styrene
elastomer and (b) not more than 80 % by welght, preferably 80
to 10 % by weight of an ethylene/a-olefln copolymer havlng an
ethylene content of 45 to 95 mole%.
A thlrd embodlment of the second adheslve resln
composltlon comprlses 100 parts by welght of a soft polymer
and 1 to 30 parts by welght of partlally or wholly graft-
67616-181D
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modlfied polyethylene ln whlch a graftlng amount of an
unsaturated carboxyllc acld or a derlvatlve thereof 18 0.05
to 15 % by welght, the soft polymer comprlslng ~a) at least
20 % by welght, preferably 20 to 90 ~ by welght, of a styrene
elastomer and ~c) not more than 80 % by welght, preferably 80
to lO % by welght, of an ethylene/vlnyl acetate copolymer
havlng a vlnyl acetate content of 5 tq 40 % by welght.
A fourth ~ ir-- L of the second adheslve resln
composition comprlses 100 parts by welght of a soft polymer
and 1 to 30 parts by welght of partlally or wholly graft-
modlfled polyethylene ln Which a graftlng amount of an
unsaturated carboxyllc acld or a derlvatlve thereof 18 0.05
to 15 ~ by welght, the soft polymer comprlslng ~a) at least
20 ~ by welght, preferably 20 to 80 % by welght, of a styrene
elastomer, ~b) up to about 80 ~ by welght, preferably 10 to
70 ~ by welght, of an ethylene/~-olefln copolymer havlng an
ethylene content of 45 to 95 mole~ and ~c) up to about 80 %
by welght, preferably 10 to 70 % by welght, of an
ethylene/vlnyl acetate copolymer havlng a vlnyl acetate
content of 5 to 40 ~ by welght.
The lamlnate of the present lnventlon f ormed by the
second adheslve resln composltlon lncludes the followlng two
embodlments.
A lamlnate of the flrst embodlment comprlses ~I) a
polyalkylene terephthalate resln layer, ~II) an adheslve
layer composed of a second adheslve resln composltlon as set
forth above and ~III) a saponifled olefln/vlnyl acetate
copolymer layer.
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A lamlnate of the second embodlment comprlses (I) a
polycarbonate resln layer, (II) an adheslve layer composed of
a aecond adheslve resln composltlon as set forth above and
(III) a saponlfled olefln/vlnyl acetate copolymer layer.
Lamlnates of the flrst and second . '1-- ~8 are
prepared by meltlng the respectlve reslns ~nd~r~ ,.lly ln
dlfferent extruders, feedlng the melts to a dle havlng a
three-layer atructure and co-extrudlng them BO that the
adheslve realn composltlon 18 lnterposed between the two
other resln layers, or by formlng layers of two reslns other
than the adheslve resln composltlon ln advance and melt-
extrudlng the adheslve resln composltlon between the two
layers .
Petalled Descrlptlon of the Inventlon
Adheslve resln composltlons of the present
lnventlon, lamlnates formed by uslng these adhealve
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resin compositions and processes for the preparation Or
these laminates will now be described.
(A) Adhesive Resin Compositions
Ethylene/vinyl acetate copolymer
The ethylene/vinyl acetate copolymer used in the
present inventlon is a known ethylene/vinyl acetate
copolymer (EVA). In general, there is used~an
ethylene/vinyl acetate copolymer having a melt rlow rate
~MFR(E), ASTM D-1238, E~ Or 0.1 to 50 g/10 min,
preferably 1 to 30 g~10 min, and a vinyl acetate
conptent Or 5 to 40 ~ by weight, prererably 8 to 11 % by
weight in case of the rirst adhesive resin composition
or 10 to 35 % by welght in case Or the second adhesive
resin composition. Ir an ethylene/vinyl acetate
copolymer having MFR within the above-mentioned range
is used, the melt viscosity is reduced, the moldability
is improved and the adhesiveness is increased, and
especially in the case of the second adhesive resin
composition, the adhesiveness arter a retort treatment
can be rurther improved.
Styrene resin
The styrene polymer resin used ror the second
adhesive resin composition of the present invention
includes not only a homopolymer Or styrene but also
polymers and copolymers Or styrene, nuclear substitution
products thereor and substitution products Or styrene
rormed by substitution at the ~-position Or the double
bond, such as chlorostyrene, dichlorostyrene,
methylstyrene, dimethylstyrene and ~-methylstyrene.
In general, in the present invention, a styrene polymer
resin having a melt rlow rate ~MFR(G), ASTM D-1238, G~
Or 0.1 to 50 g/10 min, prererably 1 to 40 g/10 min, is
used. Ir a styrene polymer resin having MFR (G) within
the above-mentLoned range is used, an adhesive resin
composition having an excellent extrusion moldability is
,
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obtained.
Grart-modified polyethylene
The grart-modified polyethylene used in the present
invention i8 characterized in that the grarting amount
of an unsaturated carboxylic acid or a derivative
thereor is 0.01 to 15 ~ by weight, preferably 0.1 to 5
by weight in case of the rirst adhesive resln
composltion or 0.1 to 10 % by weight ln case Or the
second adhesive resin composition, the melt flow rate
(ASTM D-1238, conditlon E)ls 0.1 to 50 g/10 min,
preferably 0.3 to 30 g/10 mln, the denslty is 0.900 to
o.980 g/cm3, prererably 0.905 to 0.970 g/cm3, and the X-
ray crystalinity 18 at least 30 %, preferably 35 to 75 %.
In thls graft polyethylene, the polyethylene i8
partially or wholly graft-modlfled. The graft-modified
polyethylene can be a product formed by grart-modlrylng
an ethylene/~ -olefin copolymer of ethylene wlth a mlnor
amount, for example, up to 5 mole%, of at least one
other ~-olefln selected from propylene, 1-butene, 4-
methyl-1-pentene, 1-hexene, l-octene and l-decene.
The graft-modifled polyethylene is obtaLned by
partially or wholly graft-modifying polyethylene or an
ethylene/~ -olerin copolymer with an unsaturated
carboxylic acid or a derivative thereof. As the
unsaturated carboxylic acid and its derivative, there
can be mentioned, for example, unsaturated carboxylic
acids such as acrylic acidt maleic acid, fumaric acid,
tetrahydrophthalic acid, itaconic acid, citraconic acid,
crotonic acid, isocrotonic acid and Nadic acid~
(endocis-bicyclo~2,2,1~hept-5-ene-2,3-dicarboxylic
acid), derivatives thereof such as acid halides, amides,
imides, anhydrides and esters. As specific examples of
the derivative, there can be mentioned malenyl chloride,
maleimide, maleic anhydride, citraconic anhydride,
monomethyl maleate, dimethyl maleate and glycidyl
~ 2 l 9 l 90 1
-- 10 --
maleate. Among these compounds, an unsaturated dlcarboxyllc
acld or lts anhydrlde ir preferably used, and malelc acld,
Nadlc acld ~ and acld anhydrldes thereof are especlally
preferably used.
For the production of a modlflcatlon product by
graft copolymerizatlon of polyethylene wlth a graftlng
monomer selected from the above-mentloned unsaturated
carboxyllc aclds and derlvatlves, varlous known processes can
be adopted. For example, there can be adopted a process ln
whlch polyethylene ls melted, the graftlng monomer ls added
to the melt and graft polymerlzatlon 1B carrled out, and a
process ln whlch a solutlon of the graftlng monomer ln a
solvent ls added and graft polymerlzatlon 18 carrled out. In
each case, ln order to lncrease the graftlng efflclency of
the graftlng monomer, the reactlon ls preferably carrled out
ln the presence of a radlcal lnltlator. The graftlng
reactlon 18 generally carrled out at a temperature of 60 to
350~C. The amount used of the radlcal lnltlator lr generally
0.001 to 1 part by welght per 100 parts by welght of
polyethylene. As the radlcal lnltlator, there can be
mentloned organlc peroxldes and organlc peresters such as
benzoyl peroxlde, dlchlorobenzoyl peroxlde, dlcumyl peroxlde,
dl-tert-butyl peroxlde, 2,5-dlmethyl-2,5-
dl(pero~ob~n70ato)hexyne-3, 1-4-bls(tert-butylperoxy-
lsopropyl)benzene, lauroyl peroxlde, tert-butyl peracetate,
2,5-dlmethyl-2,5-dl(tert-butylperoxy)hexyne-3, 2,5-dlmethyl-
2,5-dl(tert-butylperoxyjhexane, tert-butylperbenzoate, tert-
butylperphenyl acetate, tert-butyl perlsobutyrate, tert-butyl
67616-181D
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per-sec-octoate, tert-butyl perplvalate and cumyl
perpivalate, and other azo compounds such as
azoblsisobutyrlnltrlle and dlmethyl azolsobutyrate. Among
these compounds, there are preferably used dlalkyl peroxldes
such as dl-tert-butyl peroxide, 2,5-dlmethyl-
~ 67616-181D
21 91 901
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2,5-di(tert-butylperoxy)-hexyne-3 and 1,4-bis(tert-
butylperoxyisopropyl)benzene.
Monovinyl aromatic hydrocarbon/olerin black copolymer
elastomer (styrene elastomer)
The monovinyl aromatic hydrocarbon/olerln block
copolymer elastomer (styrene elastomer) is a polymer
having a linear or branched block structure having a
monovinyl aromatic hydrocarbon polymer block on at least
one termlnal thereof, which is represented by the
general rormula of (A-B)n,(A-B ~ A' or (A-B ~ X wherein
A and A' represent a monovinyl aromatic hydrocarbon
polymer block, B represents an olefin polymer block, n
is an integer of from 1 to 5, m is an integer Or from 2
to 7 and X represents a polyfunctional compound having a
valency of m. Styrene and ~-methylstyrene are pre~erably
used as the monovinyl aromatic hydrocarbon, and styrene
is especially prererably used. As the olerin, there can
be mentioned conjugated diolefins such as butadiene and
isoprene, and ~-olerins such as ethylene, propylene and
1-butene. The polymer block formed by polymerizatlon of
a con~ugated diolefln can be hydrogenated. The block B
may be composed Or a copolymer Or butadlene or lsoprene
wlth styrene or ~ -methylstyrene, 80 far as olerln unlts
are contalned ln a maJor amount. In the present
lnvention, in the monovlnyl aromatic hydrocarbon/olefln
block copolymer elastomer (d), the amount of the
monovlnyl aromatic hydrocarbon polymer blocks is
generally 8 to 55~ by welght and prererably 10 to 35% by
weight. A block copolymer havlng monovinyl aromatic
hydrocarbon polymer blocks on both of the termlnals la
prererably used. These block copolymers are marketed,
ror ex~mple, under tradenames of Carlflex~ TR and
Krato ~ G (each being a registered trade mark for a
product supplled by Shell Chemlcals~.
Ethylene/~ -olerln copolymer
2 ~ q l 9o l
The ethylene/~ -olefin copolymer u3ed in the
present invention is an ethylene/ ~-olerin random
copolymer which is characterized in that the melt rlow
rate ~MFR(E), ASTM D-1238, condition E~ i9 0.1 to
50 g/10 min, preferably 0.3 to 30 g/10 min, the density
is o.850 to 0.900 g,~cm3, preferably 0.850 to 0.890
g/cm3, the ethylene content is 75 to 95 mole%,
prererably 75 to 90 mole%, in case Or the second
adhesive resin composition,Jor 45 to 95 mole%,
preferably 45 to 90 mole%, in case Or the second
adhesive composltion, and the X-ray crystallinity is
lower than 30 %, preferably lower than 25~.
Ir an ethylene/~ -olerin copolymer having the
above-mentioned characteristics is used, an adhesive
resin composition having an excellent adhesiveness can
be obtalned. Especially, in the second adhesive resin
composition, the adhesiveness after a retort treatment
and the adhesiveness to a polyolerin are highly improved.
An ethylene ~-olerin having 3 to 20 carbon atoms is
used ag the ~-olerin constituting this ethylene/~ -
olefin copolymer. As speciric examples, there can be
mentioned propylene, l-butene, l-hexene, 4-methyl-1-
pentene, l-octene, l-decene, l-tetradecene and
l-octadecene. These ~-olerin can be used alone or in
the rorm Or a mixture Or two or more Or them.
The ethylene/~ -olerin copolymer generally has a
melting point (ASTM D-3418) lower than 100 C.
Mixing ratios
In the rirst adhesive resin composition of the
pregent invention, the ethylene/vinyl acetate copolymer
(a) is used in an amount Or 96 to 45 parts by weight,
prererably 85 to 50 parts by weight, the styrene polymer
resin (b) is used in an amount Or 30 to 1 parts by
weight, preferably 25 to 5 parts by weight, the grart-
modified polyethylene (c) is used in an amount Or 15 to
- ~ 2191901
1 partE by welght, preferably 10 to 2 parts by welght, the
monovlnyl aromatic hydrocarbon/olefin block copolymer
elastomer (d) 18 used in an amount of 20 to 1 parts by
welght, preferably 18 to 3 parts by welght, and the
ethylene/a-olefin copolymer (e) is used in an amount of 20 to
1 parts by weight, 18 to 3 parts by weight, per 100 parts by
weight of the total amount of components la) through (e).
In the second adheslve resln compositlon of the
present inventlon, the graft-modified polyethylene ls used ln
an amount of 1 to 30 parts by welght, preferably 2 to 28
parts by welght, per lO0 parts by weight of the soft polymer.
In the first embodiment of the seconq adhesive
resin composition, the soft polymer is a styrene elastomer
In the second ~ of the second adhesive
resin composition, a styrene elastomer and an ethylene/a-
olefln copolymer are used ln comblnatlon as the so~t polymer.
In thls case, the soit polymer comprlses at least 20 % by
weight, preferably 20 to gO % by welght, of the styrene
elastomer, and up to 80 % by welght, preferably 10 to 80 % by
welght, of the ethylene/a-olefln copolymer, with the provlso
that the total amount of the styrene elastomer and the
styrene/a-olefln copolymer is lO0 ~ by welght.
In the thlrd ~ of the second adheslve
resln composition, a styrene elastomer and an ethylene/vinyl
acetate copolymer are used in combination as the soft
polymer. In this case, the soft polymer comprises at least
20 % by weight, preferably 20 to 90 ~ by welght, of the
styrene elastomer and up to 80 % by welght, preferably lO to
67616-181D
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: ~ 2191901
- 14 -
80 % by welght, of the ethylene/vlnyl acetate copolymer, wlth
the provlso that the total amount of the styrene elastomer
and the ethylene/vlnyl acetate copolymer 18 100 ~ by welght.
In the fourth . '-~ir ~ of the second adheslve
resln compositlon, an ethylene/a-olefln copolymer and an
ethylene/vlnyl acetate copolymer can be used together wlth
the styrene elastomer as the soft polymer. In thls case, the
so~t polymer comprlses at least 20 % by welght, preferably 20
to 80 % by welght, of the styrene elastomer, up to about 80 %
by welght, preferably 10 to 70 % by welght of the ethylene/a-
olefln copolymer, and up to about 80 % by welght, preferably
10 to 70 % by weight, of the ethylene/vlnyl acetate
copolymer, wlth the provlso that the total amount of the
styrene elastomer, the ethylene/a-olefln copolymer and the
ethylene/vlnyl acetate copolymer 18 lO0 % by welght.
The second adheslve resln composltlon of the
present lnventlon comprlses the styrene elastomer and the
graft-modlfled polyethylene as lndlspensable components, and
the graftlng ratlo of the entlre composltlon 18 0.01 to 3 %
by welght, preferably 0.05 to 2.5 % ~y welght, MFR of the
total composltlon 18 0.1 to 50 g/10 mln, preferably 0.2 to 40
g/10 mln, and the crystalllnlty of the total compoBltlon 1B
lower than 35 ~.
The adheslve resln composltlon of the present
lnventlon 18 prepared by mlxlng the above-mentloned amounts
of the above-mentloned components by known mlxlng means such
as a Henschel mlxer, a V-type blender, a rlbbon blender or a
tumbllng blender, or by melt-kn~ ng the above mlxture by a
67616-181D
21 91 901
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- .14a -
single-screw extruder, a twln-screw extruder, a kneader or a
Banbury mlxer and granulatlng or pulverlzlng the melt-kneaded
mlxturè.
Addltlves customarlly used ~or thermoplastlc
reslns, ~or example, a heat-reslstant stablllzer, a
weatherlng stablllzer, an antlstatic agent, a lubrlcant, a
sllp agent, a nùcieatlng agent, a dye or plgment and a
67616-181D
' ~ 2191qOl
- 15 -
plasticizer such as a hydrocarbon oll, can be added to
the adhesive resin composition of the present lnvention,
ao rar as the attainment of the ob~ects Or the present
inventLon is not hindered.
(B) Laminates and Process ror Preparation Thereor
In the laminate rorming by using the rirst adheslve
resin composition, the adhesive resin composition is
interposed between a metal such as aluminum, copper or
iron and a thermoplastic resin such as a polyamide, a
saponiried ethylene/vinyl acetate copolymer,
polyethylene, a polycarbonate or a polyester.
This laminate can be prepared, for example,
according to a process in which a film having a
thickness Or 10 to 200 ~m is formed from the adhesive
resin composition, the film is set between adherends,
that is, the metal and thermoplastic resin, and rusion
bonding is carried out to erfect lamination, or a
process ln which the adhesive resin composition and the
thermoplastic resin as the adhered are independently
melted in dirferent extruders and the melts are extruded
through a multi-layer dye to errect lamination.
The laminate rormed by using the second adhesive
resin composition Or the present invention comprises (I)
a polyalkylene terephthalate resin or polycarbonate
2S resin layer, (II) an adhesive layer composed Or the
second adhesive resin composition and (III) a
saponiried olerin/vinyl acetate copolymer layer.
The la~er (I) constituting the laminate of the
present invention is composed of a member selected from
a polyalkylene terephthalate resin and a polycarbonate
resin.
The polyester resin used is a polyester comprising
units of at least one dihydroxyl compound selected rrom
aliphatic glycols such as ethylene glycol, propylene
glycol, 1,4-butanediol, neopentyl glycol and
. .
2 1 9 1 901
.
- 16 -
hexamethylene glycol, alicyclic glycols such as
cyclohexanedimethanol and aromatic duhydroxyl compounds
such as bisphenol, and unit3 of at least one
dicarboxylic acid compound selected from aromatic
dicarboxylic acids such as terephthalic acid,
isophthalic acid and 2,6-naphthalene-dicarboxylic acid,
aliphatic dicarboxylic acids such as oxalic acid,
succinic acid, adipic acid, sebacic acid and undecane-
dicarboxylic acid and alicyclic dicarboxylic acids such
as hexahydroterephthalic acid. The polyester can be
modified with a small amount Or a polyhydroxyl compound
or polycarboxylic acid having a valency cr at least 3,
such as a triol or a tricarboxylic acid, 80 rar as the
polyester shows thermoplastic properties. As the
thermoplastic polyester, there can be mentioned
polyethylene terephthalate, polybutylene terephthalate
and a polyethylene isophthalate/terephthalate
copolymer.
The polycarbonate resin used in the present
invention includes various polycarbonates and
copolycarbonates obtained by reacting dihydroxyl
compounds with phosgene or diphenyl carbonate according
to known processes, As speciric examples Or the
dihydroxyl compound, there can be mentioned
hydroquinone, resorcinol, 4,4'-dihydroxy-
diphenylmethane, 4,4'-dihydroxydiphenylethane,
4,4'-dihydroxydiphenyl-n-butane, 4,4'-dihydroxydiphenyl-
heptane, 4,4'-dihydroxydiphenylphenylmethane,
4,4'-dihydroxy-diphenyl-2,2-
propane (bisphenol A), 4,4'-dihydroxy-3,3'-
dimethyldiphenyl-2,2'-propane, 4,4'-dihydroxy-3,3'-
dlphenyldiphenyl-2,2-propane, 4,4'-
dihydroxydichlorophenyl-2,2-propane, 4,4'-
dihydroxydiphenyl-1,1-cyclopentane, 4,4'-
dihydroxydLphenyl-1,1-cyclohexane, 4,4'-dihydroxy-
., :
' 2 1 9 1 901
- 17 -
diphenylmethylphenylmethsne, 4,4'-
diphydroxydiphenylethyl-phenylmethane, 4,4'-
dihydroxydlphenyl-Z,2,Z-trichlorol,l-ethane, 2,2'-
dihydroxydiphenyl, 2,6-dihydroxynaphthalene, 4,4'-
dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-
dichlorodiphenyl ether and 4,4'-dihydroxy-2,5-
diethoxyphenyl ether. Among these compounds, 4,4'-
dihydroxy-diphenyl-2,2-propane (bisphenol) is preferably
used, because the formed polycarbonate has excellent
mechanical properties and transparency.
The above-mentioned adhesive resin composition is
used ror the adhesive layer (II) Or the laminate Or the
present invention.
The layer (III) constituting the laminate of the
present invention is composed of a saponiried
olefin/vinyl acetate copolymer. A saponiried
olerin/vinyl acetate copolymer prepared by saponirying an
olerin/vinyl acetate copolymer having an olefin content
Or 15 to 60 mole%, preferably 25 to 50 moleS, to a
saponiricatLon degree Or at ieast 50 %, prererably at
least 90 S. Ir the olefin content is wlthin the above-
mentioned range, thermal decompositlon is hardly caused
and melt rormlng can be easily performed, and the
drawability, water resistance and gas permeation
resiatance are highly improved. Ir the saponirication
degree is higher than 50 %, the gas permeation
resistance is highly improved.
As the olefin to be copolymerized with vinyl
acetate, there can be mentioned ethylene, propylene, 1-
butene, l-hexane, 4-methyl-1-pentene, l-octane, 1-
decene, 1 tetradecene and l-octadecene. Among them,
ethylene is especially prererably used in view Or the
mechanical stability and moldability.
For the preparation Or the laminate of the present
inventlon, there can be adopted, for example, a
~ 21 ql ~01
- 18 -
co-extrusion process in whlch the polyalkylene terephthalate
resin or polycarbonate resln, the adheslve resln composltlon
and the saponlfled olefln/vlnyl acetate copolymer are melted
ln dlfferent extruders, the melts are supplled to a dle
havlng a multl-layer structure and the melts are co-extruded
80 that the adheslve resln composltlon forms an lntermedlate
layer, or a sandwlch lamlnatlon process ln whlch the
polyalkylene terephthalate resln or polycarbonate resln and
the saponlfled oleflntvlnyl acetate copolymer are formed lnto
layers ln advance and the adheslve resln composltlon ls melt-
extruded between the two layers. In vlew of the lnterlamlner
bondlng force, the co-extruslon process ls preferably
adopted. The co-extruslon process includes a
T-die method uslng a flat dle and an lnflatlon method uslng a
clrcular dle. ~lther a slngle manlfold type uslng a black
box or a multlple-manlfold type can be used as the flat dle.
Rnown dles can also be used ln the lnflatlon method.
The th1ckn~QQ of each layer of the lamlnates can be
approprlately determlned accordlng to the lntended use. In
general, when the lamlnate 18 used as a sheet of fllm, lt ls
preferred that the thlckness of the polyalkyl terephthalate
resln or polycarbonate resln layer be 0.02 to 5 mm, the
thlckness of the adheslve layer be 0.01 to 1 mm and the
saponlfled olefln~vlnyl acetate copolymer layer be 0.01 to 1
mm.
The lamlnate of the present lnventlon can further
have a structure of (I)~II~/(III)/~II)/(I) ln whlch layers
(I) are arranged on both the sldes, or a structure further
67616-181D
: .
' - 2191901
~ .
comprislng a polyolefin layer, for example, a structure of
polypropylene/ (II)t(III)/(IIj/(I) or polyethylene/
(II)/(III)/(II)/(I).
The present invention will now be described in
detail with re~erence to the ~ollowlng examples that by no
means limit the scope of the invention.
Exam~le 1
~igh-density polyethylene (Hizex* supplied by
Mitsui Petrochemical Industrles, Ltd.; MFR (E) - 5.5 g/10
min) was reacted with maleic anhydride to obtaln graft-
modified polyethylene having a maleic anhydrlde content of
0.5 % by welght, MFR (E) of 3.0 g/10 min and a gel content
lower than 0.1%.
To 5 parts by weight of the graft-modified
polyethylene were added 60 parts by weight of an
ethylene/vinyl acetate copolymer (vinyl acetate content = 10%
by welght, MFR (E) - 9.0 g/10 mln~ hereinafter referred to as
"EVA"), 20 parts by weight of polystyrene (supplied under
trademark "Denka Styrol GP200) by Denki Kagàku Kogyo, MFR (G)
- 25 g/10 min~ hereinafter referred to as "PS"), 10 parts by
weight of a polybutadiene block-hyd-ou~na~ed
polystyrene/polybutadiene/polystyrene block copolymer
(supplied under trademark "Krayton G1652" by 8hell Chemicala,
styrene content ~ 29% by weight) and 5 parts by weight of an
ethylene/propylene copolymer [MFR (E) - 1.0 g/10 min,
ethylene content - 80 mole%, X-ray crystallinity = 5%,
denslty = 0.870 g/cm ], and the mixture was melt-kneaded and
~Trade-mark
- 1 67616-181D
-
' ~ 219l~01
- l9a -
granulated by using an extruder provlded wlth a Dulmage screw
havlng a diameter of 40 mm to obtaln a composltlon (1).
The nht~lnPd composltlon (1) was melted at 200~ and
formed lnto a press sheet havlng a thlckness of 3 mm by uslng
a composltlon moldlng machlne. The physlcal propertles (MFR
and the denslty) of the press sheet were determlned. The
nht~1n~ results are shown ln Table 1.
h fuslon-bondlng fllm havlng a thlckness of 50 ~m
was formed from the composltlon (1) by uslng a moldlng
machlne provlded wlth a T-dle havlng a dlameter of 30 mm,
' 67616-181D
.: . ~ ,.; ~.. .
21 q 1 901
. . .
- 20 -
and the presence or absence of streaks on the formed film
was checked. By using this fusion-bonding film, an
aluminum foil was bonded to a polyethylene sheet under
conditions described below to obtain a laminate.
(Structure)
A foil/film of composition (l)/polyethylene sheet
A foil: 200 ~m in thickness, 10 mm in width and 15
cm in length
Composition (1) film: 50 ,um in thickness, 25 mm in
width and 15 cm in length
Polyethylene sheet: 2 mm in thickness, 25 mm in
width and 15 cm in length
(Bonding Conditions)
Temperature: 200~C
Pressure: 6 kg/cm2
Time: 3 minutes
A test piece having a width of 10 mm and a length of
15 cm for measuring the bonding strength was cut out from
the laminate by using a knife, and the 180~ peel strength
was measured at a pulling speed of 200 mm/min.
The obtained results are shown in Table 2.
Example 2
To 5 parts by weight of the maleic anhydride-grafted
high-density polyethylene used in Example 1 were added 70
parts by weight of EVA, 10 parts by weight of PS, 10
parts by weight of ICrayton G and 5 parts by weight of the
ethylene/propylene copolymer, and the mixture was melt-
kneaded and granulated in the same manner as described in
Example 1 to obtain a composition (2),
The physical properties (MFR and the density~ of a
press sheet of the obtained composition (2) are shown in
Table 1.
In the same manner as described in Example 1, a
fusion-bonding film having a thickness of 50 ,um was
., ~ .,-.
2 1 ~ 1 ~0 1
- 21 -
formed from the composition (2) and the presence or
absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this
film and the 180 peel strength was measured.
The obtained results are shown in Table 2.
Example 3
To 10 parts by weight of the maleic anhydride-
grafted high-density polyethylene used in Example 1 were
added 60 parts by weight of EVA, 15 parts by weight of
PS, 5 parts by weight of Krayton G and 10 parts by weight
of an ethylene/propylene copolymer, and the mixture was
melt-kneaded and granulated in the same manner as
described in Example 1 to obtain a composition (3).
The physical properties (MFR and the density) of a
press sheet of the obtained composition (3) are shown in
Table 1.
In the same manner as described in Example 1, a
fusion-bonding film having a thickness of 50,um was
formed from the composition (3) and the presence or
absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this
film and the 180 peel strength was measured.
The obtained results are shown in Table 2.
Example 4
To 5 parts by weight of the maLeic anhydride-grafted
high-density polyethylene used in Example 1 were added 65
parts by weight of EVA, lS parts by weight of PS, 10
parts by weight of Krayton G and 5 parts by weight of an
ethylene/butene copolymer ~MFR (E) = 3.5 g/10 min,
ethylene content = 85 mole%, crystallinity = 15%, density
= 0.885 g/cm ~, and the mixture wa5 melt-kneaded and
granulated in the same manner as described in Example 1
to obtain a composition (4).
The physical properties (MFR and the density) of a
press sheet Qf the obtained composition (4) are shown in
..:
21 q 1 qOl
.
- 22 -
Table 1.
In the same manner as described ln Example 1, a
fusion-bonding film having a thickness of 50 ~m was
formed'from the composition (4) and the presence or
absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this
film and the 180~ peel strength was measured.
The obtained results are shown in Table 2.
Comparative Example 1 =
To 5 parts by weight of the maleic anhydride-grafted
high-density polyethylene used in Example 1 were added 80
parts by weight of EVA, 15 parts by weight of PS and the
mixture was melt-kneaded and granulated in the same
manner as described in Example 1 to obtain a composition
(5)-
The physical properties (MFR and the density) of apress sheet of the obtained composition (5) are shown in
Table 1.
In the same manner as described in Example 1, a
fusion-bonding film having a thickness of 50 ~m was
formed from the composition (5) and the presence or
absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this
film and the 180~ peel strength was measured.
The obtained resultg are shown in Table 2.
Comparative Example 2 ~ . . .
To 5 parts by weight of the maleic anhydride-grafted
high-density polyethylene used in Example 1 were added 70
parts by weight of EVA, 15 parts by weight of PS and 10
parts by weight of Krayton G, and the mixture was melt-
kneaded and granulated in the same manner as described in
Example 1 to obtain a composition (6).
The physical properties (MFR and the density) of a
press sheet of the obtained composition (6) are shown in
Table L.
21 9 l 901
- 23 -
In the same manner as described in Example 1, a
fusion-bonding film having a thickness of 50,um was
formed from the composition (6) and the presence or
absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this
film and the 180~ peel strength was measured.
The obtained results are shown in Table 2.
Comparative E~a~ple 3 _ .. .
To 5 parts by weight of the maleic anhydride-grafted
high-density polyethylene used in ExampLe 1 were added 70
parts by weight of EVA, 15 parts by weight of PS and 10
parts by weight of the ethylene/propylene copolymer, and
the mixture was melt-kneaded and granulated in the same
manner as described in Example 1 to obtain a composition
(7)-
The physical properties (MFR and the density) of a
press sheet oi' the obtained composition (7) are shown in
Table 1.
In the same manner as described in Example 1, a
fusion-bonding film having a thickness of 50,um was
formed from the composition (7) and the presence or
absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this
film and the 180~ peel strength was measured.
The obtained results are shown in Table 2.
Comparative Example 4 ~ .
To 5 parts by weight of the maleic anhydride-grafted
high-density polyethylene used in Example 1 were added 60
parts by weight of EVA, lS parts by weight of PS, 10
parts by weight of high-density polyethylene ~MFR (E) =
8.2 g/10 min, density = 0.965 g/cm3, crystallinity =
81~ J and the mixture was melt-kneaded and granulated in
the same manner as described in Example 1 to obtain a
composition (8).
The physical properties (MFR and the density) of a
21 9 1 901
~ - 24 -
press sheet of the obtained composition (8) are shown in
Table l.
In the same manner as described in Example l, a
fusion-bonding film having a thickness of SO~um was
formed from the composition (8) and the presence or
absence of streaks was checked, and an aluminum foil/
polyethylene sheet laminate was obtained by using this
film and the 180~ peel strength was measured.
The obtained results are shown in Table 2.
1 0 = = =~
Table 1
MOa~Ut Example Example Example Example Compara- Compara- Compara- Compara-
Method 1 2 3 4 tive tive tive tive
. Example Example Example ~xample
., 1 2 3 4
MFR(E)
(g/lOmin) ASTM D 1238 5.2 4.5 6.8 6.4 7.4 5.2 5.9 6.5
Density
(g/cm3) ASTM D 1505 0.94 0.94 0.94 0.94 0.95 0.94 0-94 ~-95 't
Strain at
Yield Point
(kg/cm2) ASTM D 638 ~ 74 - - 86
Tensile
Force at
Break Point
(kg/cm2) ASTM D 638 97 110 100 99 64 130 96 103
Elongation O
(between
bench marks)
(%) ASTM D 638490 500 490 530 190 500 510 430
Shore
Hardness(D) ASTM D 2240 48 45 46 49 48 44 43 48
Vicat
Softening
Point ( C) ASTM D 1525 64 62 63 65 72 69 64 72
2 1 9 ~ 90 1
.
- 26 -
Table 2
.
Formation 180 Peel Strength (kg/10 mm)
Or streaks (bondin~ temperature = 200 C)
Example 1 O 5.2
Example Z O 4 9
Example 3 O 5.2
Example 4 O 5.1
Comparative
Example 1 X 5.1
Comparative
Example 2 O 3.0
Comparative
Example 3 X 4.0
Comperative
Example 4 O 2.5
Note
O : not observed
X : observed
. .
21 91 9~1
- 27 -
~xamPle 5
A 5-layer sheet was formed unde} conditions
described below by uslng a compo~ition (1) comprising 100
parts by welght of a ~tyrene elastomer (Rrayton* G 1652
supplied by 6hell Chemical~; hereinafter referred to as
"6EBS") and 10 parts by welght of maleic anhydride-~rafted
modified polyethylene (MFR = 1.0 g/10 min, density ~ 0.925
g/cm , crystallinity - 52%, butene content 3.6 mole~,
maleic anhydride grafting amount ~ 1.0 g/100 g of polymer~
hereinafter referred to as "MAH-PE-l"), polycarbonate
(Panlite* L-1250 supplied by Tei~in Kasei~ hereinafter
referred to as "PC"), a saponified ethylene/vlnyl acetate
copolymer (Kuraray Eval* EP-F supplled by Kuraray, MFR - 1.3
g/10 min, density ~ 1.19 g/cm3, ethylene content 32 mole~,
herelnafter referred to as "EVOH"), and polypropylene (Hipol*
F 401 supplied by Mitsui Petrochemical Industries, Ltd.
herelnafter referred to as "PP").
6heet structure-
PC/ ( 1 ) /eVOH/ ( 1 ) /PP20 Layer thickness (~m):
80/50/50/50/80
Extruders.
40-mm screw dlameter extruder, 260OC ~for PC)
30-mm screw diameter extruder, 250~C [for (1)]
30-mm screw dlameter extruder, 210~C (for EVOH)
40-mm screw dlameter extruder, 230~C (for PP)
Wlth respect to the obtalned 5-layer sheet, the
*Trade-mark
67616-181D
~ 2 l q l 901
- 27a -
interfaclal bonding strength (FPC, g~l5 mm) between the layer
~f 11) and the EVOH layer and the lnterfacial bondlng
strength ~FEVOH, g/15 mm~ between the FVOH layer and the
layer o~ (1) were measured at a peeling atmosphere
temperature of 23 or 80~C and a peeling speed oi 300 mm/min
according to the T-peel test.
me sheet was su~iected to a retort treatment at
67616-181D
.
,
2 1 9 1 901
~ - 28 -
131~C for 30 minutes. Then, the T-peel test was carried
out under the same conditions as described above.
The obtained results are shown in Table 3.
Example 6 ==
A 5-layer sheet was obtained and the T-peel test was
carried out in the same manner as described in Example 5
except that a composition ~2) comprising 75 parts by
weight of SEBS, 25 parts by weight of an
ethylene/propylene random copolymer (MFR = 1.0 g/10 min,
ethylene content = 80 mole%, density = 0.865 g/cm3,
crystallinity = 4~; hereinafter referred to as "EPR-l")
and 10 parts by weight of MAH-PE-l was used instead of
the composition (l) used in Example 5.
The obtained results are shown in Table 3.
Then, a 5-layer sheet was formed by using the
composition (2), the above-mentioned EVOH, polyethylene
terephthalate (formed by adding a crystallization
promoter to Jl35 supplied by Mitsui Pet; hereinafter
referred to as "PET") and PP under conditions described
below.
Sheet structure:
PET/(2)/EVOH/(2)/PP
Layer thicknesses (,um):
80/50/50/50/80
Extruders:
40-mm screw diameter extruder, 280~C (for PET)
30-mm screw diameter extruder, 250~C (for (2))
30-mm screw diameter extruder, 210~C (for EVOH)
40-mm screw diameter extruder, 230~C (for PP)
With respect to the obtained sheet, the interfacial
bonding strength (FPET, g/15 mm) between the PET layer
and the layer of (2) and the interfacial bonding strength
(FEVOH, g/15 mm) between the EVOH layer and the layer of
(2) were measured under the same conditions as described
above with respect to PC.
:. , . ,~ .
2l q 1 ~0 1
.
- 29 -
The obtained results are shown in Table 4.
Example 7 _ _. ......................... .. . -
A 5-layer sheet was obtained and the T-peel test was
carried out in the same manner as described in Example 6
except that a composition (3) comprlsing 80 parts by
weight of SEBS, 20 parts by weight of an ethylene/vinyl
acetate copolymer (MFR = 2.5 g/10 min, vinyl acetate
content = 25% by weight; hereinafter referred to as "EVA-
1") and 10 parts by weight of MAH-PE-l was used instead
of the composition (2) used in Example 6.
The obtained results are shown in Tables 3 and 4.
Example 8 ~
A 5-layer sheet was obtained and the T-peel test was
carried out in the same manner as described in Example 6
except that a composition (4) comprising 40 parts by
weight of SEBS, 45 parts by weight of an ethylene/l-
butene random copolymer (MFR = 3.5 g/10 min, ethylene
content = 89 moLe~, density = 0.885 g/cm3, crystallinity
= 15~ hereinafter referred to as "EBR-l"), 15 parts by
weight of EVA-l and 20 parts by weight of MAH-PE-l was
used instead of the composition (2) used in Example 6.
The obtained results are shown in Tables 3 and 4.
Example 9 , . . .~-----=~-= - -
A 5-layer sheet was obtained and the T-peel test was
carried out in the same manner as described in Example 5
except that a composition (5) comprising 20 parts by
weight of SEBS, 60 parts by weight of EBR-l, 20 parts by
weight of EVA-l and 10 partg by weight of MAH-PE-l was
used instead of the composition (1) used in Example 5.
The obtained results are 3hown in Table 3.
Example 10 _r:- ' ' ' ' ' '' ~ '
A 5-layer sheet was obtained and the T-peel test was
carried out in the same manner as descrlbed in Example 5
except that a composition (6) comprising 60 parts by
weight of SEBS, 20 parts by weight of E8R-1, 20 parts by
,. ..
21 9 1 90 1
- 30 -
weight of EVA-l and 10 parts by weight of MAH-PE-l was
used instead of the composition (1) used in Example 5.
The obtained results are shown in Table 3.
Comparative Example 5
A 5-layer sheet was obtained and the T-peel test was
carried out in the same manner as described in Example 5
except that a composition ~7) comprising 100 parts by
weight of EBR-l and 10 parts by weight of MAH-PE-l was
used instead of the composition ~1) used in Example 5.
The obtained results are shown in Table 3.
Comparat~ve Example 6 . --
A 5-layer sheet was obtained and the T-peel test was
carried out in the same manner as described in Example 5
except that a composition ~8) comprising 85 parts by
weight of EBR-l, 15 parts by weight of EVA-l and 10 parts
by weight of MAH-PE-l was used instead of the composition
~1) used in Example 5.
The obtained results are shown in Table 3.
Comparative Example 7
A 5-layer sheet was obtained and the T-peel test was
carried out in the same manner as described in Example 5
except that a composition ~9) comprising 40 parts by
weight of SEBS, 45 parts by weight of EBR-l and 15 parts
by weight of EVA-l was used instead of the composition
~1) used in Example 5.
The obtained results are shown in Table 3.
Table 3
Recipe (parts hy PC/EVOH Multi-Layer Sheet
weight) of FPC (g/15 mmwidth) FEVOH (g/15 mmwidth)
Composition 23 C 80 C Z3 C atmos- 23 C 80 C 23 C atmos-
atmosphere atmosphere phere after atmosphere atmosphere phere after
retort retort
treatment treatment
Example 5 SEBS 100 940 920 390 690 630 350 MAH-PE-1 10
Example 6 SEBS 75 1250 930 860 830 720 790 EPR-1 25
MAH-PE-1 10
Example 7 EvAS1 20 1190 1010 750 45~ 410 440
MAH-PE-1 lC
Example 8 SEBS 40 860 440 590 450 400 440 EBR-1 45
EVA-1 15
MAH-PE-1 20 ~
Example 9 SEBS 20 690 350 810 520 370 500 ~
EBR-1 60
EVA-1 20
MAH-PE-1 10
Example 10 SEBS 60 830 670 570 39~ 320 410
EBR-1 20
EVA-1 20
MAH-PE-1 10
Comparative EBR-1 100 910 180 110 1300 210 1030
Example 5 MAH-PE-l 10
Comparctive EBR-1 ô5 1600 120 1390 460 170 450
Example 6 EVA-1 1~
MAH-PE-1 10
Comparative SEBS 40 750 610 430 90 50 10
Example 7 EBR-1 45
EVA-1 40
Table 4
Recipe (parts by PET/EVOH Multi-Layer Sheet
weight) of FPET (g/15mm w1dth) FEVOH (g/15mm width)
Composition 23 C 80 C 23 C atmos- 23 C 80 C 23 C atmos-
atmosphere atmosphere phere after atmosphere atmosphere phere after
retort retort
treatment trea~ment
Example SEBS 75 960 890 880 810 700 800
6 EPR-l 25
MAH-PE-l 10
Example SEBS 80 840 320 730 460 420 410
7 EVA-l 20
MAH-PE-l 10
o
Example SEBS 40 520 380 510 460 390 430
8 EBR-l 45
EVA-l 15
MAH-PE-l 20
21 91 90l
- 33 -
In Examples 5 through lO and Comparative Examples 5
through 7, the crystallinity and density were measured
according to the following procedures.
(l) Preparation of Sample
The sheet was heated at 180~C by a hot press for lO
minutes and was rapidly cooled by a cooling press ~water
cooling) to prepare a sample.
(2) Crystallinity
The crystallinity of the sample obtained in (l)
above was determined by the X-ray diffractometry.
~3) Density
The density of the sample was measured at 23~C
according to the density gradient tube method.
As is apparent from the results of the foregoing
examples, since the first adhesive resin composition
comprises ~a) an ethylene/vinyl acetate copolymer, (b) a
styrene polymer resin, (c) graft-modified polyethylene,
(d) a monovinyl aromatic hydrocarbon/olefin block
copolymer elastomer and (e) an ethylene/d-olefin
copolymer at a specific ratio, streaks are not formed at
the extrusion molding, and a fusion-bonding (adhesive)
film having a good appearance is obtained. Eurthermore,
the adhesive resin composition of the present invention
can give an excellent adhesiveness between a metal and a
thermoplastic resin sheath layer.
Accordingly, the adhesive resln composition of the
present invention can be suitably used as a melt adhesive
for laminates of laminate sheath cables and films of
various packaging materials.
When the second adhesive composition of the present
invention is USed for bonding (I) a layer of a
polyalkylene terephthalate resin or polycarbonate resin
and (III) a layer of a saponified olefin/vinyl acetate
copolymer, the layers (I) and (III) can be so tightly
bonded that peeling of the layers (I) and (III) is not
21 91 901
- 34 -
caused even under high-temperature conditions as adopted
for a high-temperature filling treatment or a retort
treatment, and a practicalLy sufficient bonding strength
can be maintained at normaL temperature after this high-
temperature treatment.
AccordingLy, a laminate comprising the layers (I)
and (III) bonded by using the adhesive~resin composition
of the present invention has a high resistance to
permeation of gases such as oxygen and therefore, the
Laminate has excelLent properties as a retortabLe food
packaying materiaL.
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