CA1053592A - Container - Google Patents

Abstract

Abstract of the Disclosure A molded container having a wall composed of a thermoplastic resin oriented in at least one direction on the wall face, wherein the container wall has a layer of a blend composed mainly of a plurality of melt-extrudable thermoplastic resins, each of which has a solubility parameter ( Sp ) of at least 9.5, at east one of said thermoplastic resins has an oxygen permeabi-lity lower than 5 X 10-11 cc.cm/cm2.sec.cmHg, said thermoplastic resins are chosen so that the difference ( .DELTA.Sp ) of the solubility parameter in said thermoplastic resins is not greater than 4.5. the elongation of said resin blend is higher than the arithmetic mean ( ? ) of elongations of the respective thermoplsatic resins, and wherein the container has a thermal shrinkability ( .delta. ) of at least 5 % in the orientation direction of said container wall.

- 1'-

Description

105;~591'~
'l~hls lIIv~ntlon relate~ to plastic containers formed by plastic proce~s~ , espe~1ally plastic bottles, pl~stic cups ~nd other plastlc containers formed by draw-blow molding and plastic containers formed by plastic processing of sheets or films. More particu-larly, the invention relate~ to plastic containers having a desirable combination of a high gds barrier property to o~ygen, carbon dioxide gas and the like with high mechanical streng~h, hardness, creep resistance and transparency.
In the instant specification, by the term " plastic proce~ing " i6 meant cold or warm resin proces~ing conducted by utilizing plastic deformation of a resin, which includes ~o-called " draw molding ".
The term " biaxial draw-blow molding " used herein has the same meaning as customarily adopted in the art.
Namely, the " biaxial draw-blow molding " means a molding method in which a pari~on formed by extrusion molding, injection molding or the like i8 drawn in a qplit mold in the axial direction and simultaneouæly or successively drawn by blowing a gas in a direction rectangular to the axial direction. Further, the term " draw molding of a sheet or film " used herein means not only an ordinPry elongating draw molding method but also a draw forming method, an ironing molding method, a v~cuum molding method and a compre~ed air molding method.
It is known to prepare a biaxially drawn blow-molded

- 2 - ~ -.

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drticle by mol~lrl~ ~ thermopl~stlc resln sueh as a polyolefin, especlally poly~ropylene, i~to a bottomed or bottomless p~ri~on ( hereinafter referred to as " pipe " or " tube " in some cases ) and performi~g in sequence or simultaneously the step of elongating the parison in the axial direction at a relatively low temperature~ for ex~mple, ~t a temperature lower than the melting point of the resin, and the step of infl~ting the pari~on in a direction rec~angular to the axial direction.
It also iB known to prepare biaxially drawn cup-like molded articles by molding a thermopla~tic resin such as a polyolefin, especially polypropylene, into a sheet or film, and subjecting the sheet or film to plastic molding such as draw forming at a relatively low temperature, for example, at a temperature lower than the melting point of the re~in, as taught in KDN~TSTOFFE. Bd., 1975, H. 10, 666/69.
In molded articles prepared according to these known plastic processing methods, various effect~ by the biaxial drawing orientation are manifested.
Namely, they are excellent over ordinary heat-molded articles with respect to mechanical strength, hardness, creep resistance and transparency. These molded articles, however, are ~till insufficient as containers to be used ~n fields where a high pressure resistance and a high gas barrier property are required, for example, as containers.for filling and preserving carbonated . . . .. .... .,. . : : , ~:
: : . : . . . . -.. . ~ . :, , ., . . . . : - . ;

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dr1nk~, beer, Gther liquid f`oods, liquid medicines, liquid chemic~l~, liquid cosmetic~ and aerosol contentq.
'rhe above-mentloned polyolefin resins are excellent in the adapt~bility to biaxial draw molding and in transp~rency and mechanic~l strength, but they àre defective in that the permeability of gases such as oxygen and carbon dioxide gas is relatively high. It is 3ubstantially impossible to apply a technique of such plastic molding~to thermoplastic re~in9 excellent in the gas barrier property ( ga~ impermeability ) to oxygen, carbon dioxide gas and the like because of their poor drawability.
AS the melt-extrudable thermoplastic resin excel-lent in the gas barrier property, there have heretofore been known ethylene-vinyl alcohol copolymers ( saponified ethylene-vinyl acetate copolymer~ ) and various copoly-amides. In general, these thermoplastic re~ins excellent in the gaY barrier property have a low elongation, and when they are subjected to plastic processing, partial elongation or formation of pores is caused and it is very difficult to obtain ~atisfactory molded articlesO Especially, when a thermoplastic re~in excellent in the gas barrier property is subjected to biaxial draw-blow molding, since the elongation in a direction rectangular to the extru~ion direction is ordinarily ;ow, troubles such a~ longitudinal tears are readily cau~ed when the parison is drawn in said direction rectangular to the extrusion direction~

.. . - . . . . - :
: . . . . . : .
- . . . . .
, 105;~5~' We found that when ~ plurality of thermoplastic resins excellent in the gas barrier property, which cannot or can h~rdly be subjected to plastic molding such as biaxial draw-blow molding because of the fore-going trouble~ if used singly and which have a ~olubi-lity parameter ( ~p value ), detailed hereinafter, of at least 9.5, are selected and combined so that the difference ( A Sp value ) of the solubility parameter in the~e thermoplastic resins i9 not greater than 4.5, plastic processing ~uch as biaxial draw-blowing of the resulting re~in blend becomes pos~ible, and that a molded article of the resin blend formed by pla~tic proce~sing has a gas permeability much lower than the arithmetric mean of the gas permeabilities of the respeotive reslns and is excellent in such properties as tran~parency, strength and creep resistance. Based on these findings, we have now completed the present invention.
It is therefore a primary object of the present invention to provide a molded container formed by plastic processing which has a de9irable combination of a high gas barrier property to oxygen, carbon dioxide ga~ and the like with high transparency, strength, creep resistance and hardness.
Another object of the present invention is to provide a technique of preparing a molded container according to plastic processing from a thermoplastic re~in having a high gas barrier property which cannot , ., i .. .... , ~ , , , :: . .. : . . .
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or c~n h~rdly b~ olded according to plastic processing such as biaxial draw molding.
~ till another object of the present invention i9 to provide pressure-resi~tant gas-barrier pla~tic bottle9 or cup-like se~mless containers ~uitable for filling and preserving carbonated drinks, beer, other liquid foods, liquid medicines, liquid chemicals, liquid cos-metics, aerosol contents and the like.
In accord~nce with one aspect of the present invention, there is provided a molded container having a wall compo~ed of a thermoplastic re~in oriented in at least one direction on the wall face, wherein the container wall has a layer of a blend composed mainly of a plurality of melt-extrudable thermoplastic resin~, each of which has a solubility parameter ( ~p ) o~ at least 9.5, at least one of said thermoplastic resins has an oxygen permeability lower than 5 x 10 11 cc-cm/cm2.
sec.cmHg, said thermoplastic re~ins are cho~en 90 that the difference ( ~Sp ) of the solubility para-meter in qaid thermoplastic re~in~ is not greater than4.5, the elongation of said resin blend is hggher than the arithmetic mean () of elongations of the respective thermoplastic resins, and wherein the container has a thermal shrinkability ( 6 ) of at least 5 ~ in the orientation direction of said container wall.
In accordance with another aspect of the present invention, there is provided a container molded according to plastic processing, having a wall composed of a : ~' ' - ,, -':
:: . . ,. :

: - ,, . : .-.:. , , ........ :

~ 0535g'~thermo~lastlc re~in ~rLented in at least one direction on the w~11 face, wherein the container wall has a multi-layer structure including at least one layer of a blend composed o~ a plurality of melt-extrudable thermoplastic resins, each of which has a solubility parameter ( ~p ) of at lea~t 9.5 and at least one layer composed of a thermoplastic re~in having a moi~ture permeability lower than 100 x 10 12 g-cm/cm2.qec.cmHg as measured at a temperature not e~ceeding 50C., at least one of said thermoplastic resins in the blend layer has an oxygen permeability lower than 5 x 10 11 cc-cm/
cm .sec.cmHg, said thermoplastic resins of the blend layer are chosen so that the difference ( A~p ) of the solubility parame~er in said thermoplastic resins is not greater than 4.5, the elongation of said resin blend is higher than the arithmetic mean ( ~ ) of elongations of the respective thermoplastic re~ins in the resin blend, said multi-layer structure has an interlaminar bonding strength of at least 20 glcm, and wherein the multi-layer structure has a thermal shrin-kability (6 ) of at least 5 ~/0 in the orientation direc- ~:~
tion of said container wall.
In accordance with still another aspect of the present invention, there is provided a container formed by biaxial draw-blow molding of a parison composed of a thermoplastic resin or by plastic processing of a film or sheet composed of a thermoplastic resin, wherein said parison or said film or sheet has a multi-layer "' " , ' "'' ' ' ~'. ' ' ' ' " ',"' '; ' " ' " ' ' " ;
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~tru~ture in(~luding at le~st one layer of ~ blend composed mainly of a plurality of melt-extrudable thermopla~tic resins, e~ch of which haa a ~olubility parameter ( Sp ) of at least 9.5, and at least one layer composed of a thermoplastic reain in which the sum of the instantaneoua modulua ( Bg ) and retardation modulu~ ( El ) at a temperature of 2~a. and a stress of 7 x 107 dyne/cm2 i~ at least 1 x 101 dyne/cm2 is and which has a steady atate flow viscoaity ( ~ ) of at least 1 x 1017 poise and a retardation time ( tR ) shorter than 6 x 106 sec, at least one of said thermo-plastic reains in said blend haa an oxygen permeability lower than 5 x 10 11 cc~cm/cm2.sec.cmHg, the thermoplas~
tic re9in~ of said blend are choaen 80 that the difference ( ~Sp ) of the solubility parameter in ~aid thermopla9tic reain~ is not greater than 4.5, the elongation of said reain blend ia higher than the arithmetic mean ( ~ ) of elongations of the reapective thermoplaatic resin~ in the resin blend, and wherein said molded container hae a thermal shrinkability (~ ) of at leaat 5 ~ in the orientation direction of said container wall.
The preaent invention will now be deacribed in detail.
In the accompanying drawings, Figo 1 is a curve illuatrating the relation between the copolyamide/
ethylene-vinyl alcohol copolymer weight ratio and the elongation (~), Fig. 2 is a aectional view illustrating one example of a bottomed parison that is used for the .

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105;~S~Z , productloll o~` Gne L~olded cont~iner of the pre~ent in-ventlon, ~ . S is ~ dia~ram illu3trating the biaxial dr~w-blow molding method, and Fig~. 4 to 7 are diagrams illu~trating the steps of the vacuum plug a38ist molding method.
Resin Blend In the pre3ent invention, in view of the mechanical properties ~uch a~ creep re3istance and the gas barrier property, it i9 impor.t~nt that the container of the present inventiun molded by pla~tic processing ~hould have a layer of a blend composed mainly of a plurality of melt-extrudable thermoplastic resins, each of which ha~ a 901ubility parameter of at least 9.5.
In the instant specification and claims, the solubility parameter ( Sp value ) i8 defined as the square root of the cohesion energy density ( cal/cc ) as taught in, for example, " Polymer Handbook, Chapter 4 "
compiled by J. Brandrup et al and published by John Wiley & Sons, Ino. in 1967. '~his ~olubility parameter is ~lso closely concerned with the intensity of the hydrogen bond of a thermopla~tic resin, and in general, thermoplastic polymers having on the main or side chain polar groups such as hydroxyl, amide, ester and nitrile groups and chlorine atoms have a relatively high solubility parameter exceeding 9.5, though the value differs to some extent depending on the content and distribution state of such polar groups.
Sp values of typical thermoplastic resins are a~

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shown in T~ble 1. E`rom l`able 1, it will readily be understood that polar group oontaining polymers such as polyvinyl alcohol and poly~crylonitrile have a high solubility parameter~ ~owever, these polymers are not melt-extrudable. ~ccordingly, the~e monomers must be used after they are modified so tha-t they can be melt-extruded.
Table 1 Sp Values L(cal/cc~l/2] of Thermoplastic Reqins Resin ~p Value polyethylene 8.0 polypropylene 7.9 polybutadiene 8.1 polystyrene 8.56 polyisobutylene 7~8 polyvinyl acetate 9.4 polyvinyl chloride 9.53 polymethyl methacrylate 9.6 polymethacrylonitrile 10.7 polyethylene terephthalate 1007 cellulose diacetate 10.9 .
polyvinylidene chloridé 12.2 polyhexamethylene adipamide 13.6 polyvinyl alcohol 12.6 polyacrylonitrile 15.4 Solubili'ty parameters ( Sp values ) of copolymers can be approximately obtained from arithmetic means of solubility para~eters of homopolymers of respective .. . . . . .. .
-..
.. - , , lOS3SC~2 monomer~ con~tituting the oopolymer~. E~or example, ~pproximate ~p values o~' ethylene-vinyl alcohol copoly-mer~ can be calculated according to the ~ollowing formula:
~p = ~Sp-El~ + V~p-VM (1) wherein E9p stands for the Sp value of polyethylene, stand~ f`or the mole percent of ethylene in the copolymer, V~p stands for the Sp value of poly-vinyl alcohol a~d VM ~t~nds for the mole percent of vinyl alcohol in the copolymer.
Sp values of ethylene-vinyl alcohol copolymers ~ :
differing in the vinyl alcohol (V~)/ethylene ( Et ) ratio, which are calculated from the above formula, are well in agreement with the mea~ured value~ as shown in ~able 2.
: Table 2 V~/Et Molar Ratio Measured Sp Value Calculated SP Value 46/54 9.85 - 10.25 10.05 50/50 10.0 - 10.5 10.25 75/25 11.25 - 11.65 11.45 Similarly, approximate Sp value~ of copolymers of ethylenically un~aturated nitrile monomers with comono-mers can be calculated from the following formula:
m Sp = hsp ~ + n~ SPn Mn (2) wherein ~sp stands for the Sp value of a homopolymer of an ethylenically unsaturated nitrile, ~ stand~
for the mole percent of the ethylenically un~aturated ~-.;
~ ~i : . . . .. . :

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monomer in the copolymer, ~p~ stand~ for the Sp value o~ a homopolymer of the comonomer, Mn stands for the mole percent of the monomer in the copolymer, ~.
and m is a number of at least 1 which corresponds to the number of kinds of comonomers contained in the copolymer.
~p Values of commercially available polyamide~ are in the range of from 9.5 to 13.6 as ~hown in Table 3, .Table 3 Polyamide ~P Value Polylauryllactam ( nylon 12 ) 9.5 Polyundecanamide ( nylon 11 ) 9.9 Polycaprolactam ( nylon 6 ) 12.7 Polyhexamethylene-sebacamide ( nylon 6-10 ) 12.5 Polyhexamethylene-adipamide ( nylon 6-6 ) 13.6 CaprolactamJhexamethylene diammonium 1) 12.8 adipate copolymer ~ :

1) Nylon 6/nylon 6-6 copolymer ( caprola¢tam ¢ontent is 91 mole /~0 ) : 20 In the present invention, in order to attain a good plastic processability, e.gO, a good adaptability to biaxial draw molding, and a high gas barrier pro-perty, it i~ important that a plurality of melt-e~trudable thermoplastic polymers, each of which has an ~p value of at least 9.5, are chosen and combined 90 that at least one of the thermoplastic polymers has an oxygen permeability lower than 5 x 10 11 cc~cm/cm2.sec.cmHg ( as measured at a temperature of ~7Co and a relative 1{~53591~
humidity of O ,~ ) ~nd the difference of ~he solubility p~rameter ( ~ip v~lue ) in the thsrmoplastic re~ins is not greater than ~050 It is pre~erred that the oxygexi permeability of e~ch of the thermoplastic resins ohosen 5and used be lower than 5 x 10 11 cc-cm/ om2-9ec.cmHg.
()xygen permes.bilities of typical thermoplastic resin~ are shown in Table 4.
Table 4 Oxygen Yerrneabilities ( P02 ) of Various Re~ins Resin P02 x 10 (cc.cm/cm .~ec.
cmH~) (at 37¢. ~d O ,~
low den~ity polyethylene (d=0.922 g/cc) 105 medium density polyethylene (d=0.935 g/cc) 56 high den8ity polyethylene (d=0.955 ~/co) 29 polystyrene (atactic) 125 ethylene/vinyl acetate copolymer ( vinyl 137 a~etate content=17 ,~ by weight) ~urly~)-A (ionomer manufactured by Du Pont; 96 acid content=3.5 mole y!O; Na+ type) polypropylene (i30tactic, undrawn) 51 polypropylene (i~ota¢tic, bia~cially drawn) 19 polyvinyl chloride (undraw~) 1.7 polyvinyl chloride (biaxially drawn) 0.75 vinylidene chloride/ vinyl chloride copolymer 103 (vinyl chloride content=12 ,~ by weight; undrawn) vinylidene chloride/ vinyl chloride copolymer 0052 (vinyl chloride content=12 ~p by weight; biaxially 8tretched) ~)polymer (polymet;hyl methacrylate re~in 4.3 manufactured by American ayanamid) .
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~ 4 ( continued ) Uxygerl ~erme~bilitie~ ( B0~ ) of Various Re9in~

~esln P~2 x 1011 (cc.cm/cm2.aec.
cmHg) (at 37C. and 0 ~ RH) high nitrile resin (1) LA~-Bu~-k + l~ *~ 0.50 (grafted); butyl rubber incorporated]
high nitrile resin (~ k-Bu*~ + vinyl 0.47 ether (grafted); butyl rubber incorporated]
Cycopa ~ 930 (acrylonitr~le resin manufactured 0.29 by Borg-Warner) ABS resin 4.9 polycarbonate 47 polyethylene terephthalate (undrawn) 4.0 polyethylene terephthal~te (biaxially drawn) 2.2 nylon 6/nylon 6-6 copolymer (undra~m) 0 33 nylon 6/~ylon 6-6 copolymer (biaxially drawn) 0.80 nylon 6 (undrawn~ 0.32 nylon 6 (biaxially dra~m) 0.40 polybutylene terephthalate (undrawn) ~.6 polybutylene terephthalate~polytetramethylene 9.2 oxide block copolymer acrylic acid-grafted ethylene/vinyl alcohol 10.1 copolymer poly-4-methyl-pentene-1 (undrawn) 9400 -polytetrafluoroethylene 15 D 7 saponi~ied ethylene~vinyl acetate copolymer (1) 0.033 (Eval~Y manufactured by Kuraray; ethylene content=25.4 mole o~ ~aponif cation degree=99.2 ~o) sapon ~ied ethylene/vinyl acetate copolymer (2) 0.26 (Eval manufactured by ~uraray; ethylene content=49.5 mole %; ~aponi~ication degree=9508 ~0) Note~:
~: acrylonitrile :. : "

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.
~; but~diene methyl methacrylate ~ s wlll be apparent from Table 4, ethylene-vinyl alcohol copolymers ( saponified ethylene-vinyl acetate copolymer~ ) have an especially high ga~ impermeability among various thermoplastic resins. ~ccordingly, in the present invention, it iB preferred that an ethylene-vinyl alcohol copolymer be used as one of thermoplastic resins con~tituting the resin blend.
In general, it is preferred that the vinyl alcohol content of the ethylene-vinyl alcohol copolymer be in the range of from 50 to 75 mole c~. In other word~, it is preferred that the ethylene content be 25 to 50 mole ~ When the vinyl alcohol content in the copolymer is lower than 50 mole ~, the permeabillty to ga~es ~uch as ~ygen i~ higher than in the copolymer having the vinyl alcohol content in the above range. If the vinyl alcohol content in the copolymer exceeds 75 mole ~, the hydrophilic characteri~tic of the oopolymer is enhanced 2~ and the water vapor permeability is increased. ~urther, the oxygen permeability of the copolymer is greatly influenced by the humidity and the melt-moldability i9 degraded. ~herefore, use of an ethylene-vinyl alcohol copolymer having such high vinyl alcohol content is not preferred for attaining the ob~ect~ of the pre-sent invention.
These ethylene-vlnyl alcohol copolymers can be obtained, for e~ample, by saponifying a copolymer of , .

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.
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etnylene Wit;ll ~ Lower Iatty acLd ester such as vinyl form~te, vinyL ~cetate or vinyl propionate, especially an ethylene-vinyl hcetate copolymer, as di~cloQed in the specific~-tions of U. ~ tent No. 3,183,203 and U. S. Patent No. 3,419,654. The degree of qaponifica-tion of the e~hylene-vinyl ester copolymer has important influences on the oxygen permeability of the final molded container. In the present invention, it is preferred that the ethylene-vinyl alcohol copolymer used be a copolymer obtained by saponifying at lea~t 96 ~, especially at least 99 ~0, of the vinyl ester in the ethylene-vinyl e~ter copolymer. In other words, it is preferred that the amount of the remaining vinyl ester be smaller than 4 mole ~, especially smaller th~n 1 mole ~, based on the vinyl groups in the copo-lymer. ~his ethylene-vinyl alcohol copolymer may -comprise as a comonomer component a copolymerizable olefin such as propylene, butene, isobutylene or hexene-l in an amount not having bad influences on ga~
permeation characteristics such as oxygen impermeability and carbon dioxide gas impermeability, for example, in an amount of up to 3 mole ~jO.
The molecular weight of the ethylene-vinyl alcohol ~ -copolymer is not particularly critical. In general, any of ethylene-vinyl alcohol copolymers having a film-forming molécular weight can be u~ed. The intrinsic viscosity l~] of the ethylene-vinyl alcohol copolymer is, for exampIe, measured with respect to a solution .

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1~53s/2;a in ~ rmL~ d ~ vent comprisi~g 8s2 by wei~lt of phenol ~nd 15 ~ by we~ ht o~ whte:r at a temperature of 30 C.
ln the presen-t invention, it i~ preferred that the intrinsic Vi~C09i ty lTI~ of the ethylene-vinyl alcohol copolymer used be in -the range of 0.07 to 0.17 ~/g a~ measured according to the above method.
A9 ~nother in~-tance of the thermoplastic polymers having a high g~s barrier property, which satisfies the above requirement of the ~olubility parameter, there can be mentioned variou~ homopolyamides and copolyamides, and blends thereof~
~s such polyamide, there can be mentioned, for example, homopolyamides ~d copolyamides having amide recurring units expressed by the following formula (3) or (4) and blends thereof:
-G0-~-NH- ~3) or -co-Rl-CO~H-R2-l~H- (4) wherein R, Rl and ~2 each stand for a linear alky-lene group~
In view of the gas barrier property to oxygen, carbon dioxide gas and the like, it i3 preferred to use homo- `
polyamides and copolyamides in which the number of amide groups i~ 3 to 30, especially 4 to 25, per 100 carbon atoms in the polyamide, and blends o~ these polyamides. Examples of preferred homopolyamides include polycaprolacta~ ( nylon 6 ), poly-~-aminoheptanoic acid ~ nylon 7 ), poly-~-aminononanoic acid ( nylon 9 ), ~ . .

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poly~ c~n~-mide ( nylon 11 j, polyl~uryllactam ( nylon ~ )oly~hyL~ne diaLuirle adipamide ( nylon 2-6 ), polyte~ra~e~hylene adipamide ( nylon 4-6 J, polyhexa-methylene adlpamide ( nylon 6-6 ), polyhexamethylene sebacamide ( nylon 6-10 ), polyhexamethylene dodecamide ( nylon 6-12 ), polyoctamethylene adipamide ( nylon 8-6 ), polydecamethylene adipamide ( nylon 10-6 ) and poly-dodecamethylene sebacamide ( nylon 10-8 ).
Example~ of pre,ferred copolyamide~ include caprolactam/lauryl lactam copolymers, caprolactam/
hexamethylene diammonium adipate copolymers, lauryl lactam/hexamethylene diammonium adipate copolymers, hexamethylene diammonium adipate/hexamethylene diammo-nium sebacate copolymers, ethylene diammonium adipate/
hexamethylene diammonium adipate copolymer~ and capro-lactam/hexamethylene diaamonlum adipate/hexamethylene diammonium sebacate copolymers.
'~he~e homopolyamides and copolyamide~ may be used in the form of ~o-called blends. For example, a blend of polycaprolactam and polyhexamethylene adipamide and a blend of polyc~prolactam and a caprolactam/hexamethylene diammonium adipate can be u~ed in the present invention.
In addition, an aromatic polyamide containing in the molecule chain at least 70 mole ~0 of structural unit~ derived from metaxylylene diamine or a mixed xylylene diamine containing paraxylylene diamine in an amount o~ up to 30 % based on the mixed xylylene diamine and an a,~-aliphatic dicarboxylic acid having 1()53S'~;~
6 to 1~ c~rbon ~toms c~n be used ln the form o~ a blend l~ith ~n ethylerle-virlyl ~lcohol copolymer ~uch mentioned above, though this aromatic polyamide i~
slightly inferior to the ~bove-mentioned aliphatic polyamides with reqpect to the moldability.
'~he molecular weight o~ the polyamide u~ed is not particul~rly critical in the present inven~ion, and any of polyamides having a film-forming molecular weight can be used. In gener~l, however, it is pre-ferred that the relative viscosity ( ~ rel ) of thepolyamide be ln the range of from 1.8 to 3.5 as measured with respect to a ~olution of 1 g of the polymer in 100 cc of 98 p sulfuric acid at 20C. h polyamide having ~ relative viscosity lower than 1.~ is defective in that when a blend of this polyamide with other thermoplastic re~in is biaxi~lly drawn and blow-molded, a molded article excellent in the mechanical strength can hardly 'be obtained. ~ polyamide having a relative visco~ity higher than 3.5 i~ ordinarily insufficient in the melt-moldability.
As another instance of the thermopla~tic re~in valuable for formation of the re~in blend that i~ used in the present invention, there can be mentioned aromatic polyester~, though they are inferior to the above-mentioned ethylene-vinyl alcohol copolymers and polyamides with respect to the ga~ impermeability as seen from Table 4. l~ore specifically, there can be used aromatic polye'sters having recurring units represented .: .. ~ .
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by the 1`oilc)w~ f~rl~ul~ (Ci) or (6):
u o--~t S--o--C--1~4--~-- ( 5 ) or _~S-o-~-R4-o- (6) ,~
wherein RJ st~nds for a linear alkylene group and R4 s~ands for an aromatic hydrocarbon group.
~s specific example~ of such aromatic polyester, there can be mentioned polyethylene terephthalate, polybutyl-ene terephbhalate, ethylene/butylene terephthalate copo-lymers, ethylene terephthalate/ethylene isophthalate ::
copolymers and polyoxyethylene benzoate.
hs another in~tance of the melt-extrudable thermoplastic polymer satisfying the foregoing require-ments of ~p and ~2 values, there can be mentioned so-called high nitrile thermoplastic polymers, there can be mentioned thermopla9tic copolymers comprising 40 to 97 mole ~, preferably 60 to 86 mole ~, based on the total polymer, of a nitrile group-containing ethylenically unsaturated monomer such as acrylonitrile, ;~:
methacrylonitrile or a mixture thereof with the remaining amount of at least one comonomer selected from the group consisting of conjugated diene type :
hydrocarbons such a~ butadiene and isoprene, esters of ethylenlcaliy un~aturated carboxylic acids such as methyl methacrylate and ethyl acrylate, vinyl ethers such as methyl vinyl ether, and monovinyl aromatic , . . . . . .- ......... ... , ., ............................ ,, ,., j,, . , ... .. ~ :
. . .: . .: - . . . . . . : . ........................ ............... . .. .

. :- ~ .

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SUcil ~S 9 tyrer~e ~nd vlnyl toluene.
~ hlorine-~ont~lning t~lerrnopl~tic polymers such a~ polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinylidene chloride copolymers and internally plasticized vinyl chloride resin~ involve problems in connection with the therm~l stability and melt-moldabi-lity. However, al40 these polymers can be u~ed in the present invention on condition that organic tin type stabili~ers, metal soap type stabilizers, known plasti-cizers and lubricants hre appropriately incorporatedin these polymers.
In accordance with one preferred embodiment of the present invention, a plurality of thermoplastic resin9, each having a P02 value lower than 5 x 10 11, especially lower than 4.3 x 10 11, are mixed to form a blend. In this preferred embodiment of the present invention, at least two members selected from ethylene-vinyl alcohol copolymers, polyamides, aromatic polyester~, high nitrile resins and chlorine-containing polymers are combined to form a blend in which the above-mentioned Sp value is not greater than 4.5.
~ combina~ion of (a) an ethylene-vinyl alcohol copolymer and (b) a polyamide is most preferred as the resin combination for form~tion of the resin blend that is u~ed in the present invention. ~his ethylene-vinyl alcohol copolymer/polyamide blend has an espe-cially good adaptability to biaxial draw molding and prcvides a dra~-molded cont iner especially excellent ~ - 21 -- , ~ - ,,,. . -,. , : , . : -: - ~:

- . . , . :

10535C~Z
lrl t,~ p~rlIle~billty t~ oxygen, carbon dioxide g~Y clnd tne llke, the transparency, the creep resistance, the hardness .lnd other mechanical propertle~. Among combinations of the above resins (a) and (b), one compricling (a) ~n ethylene-vinyl ~lcohol copolymer hav-ing an ethylene content of 25 to 50 mole ~ and a vinyl acetate content lower than 1 mole ~ and (b) a carprol-actam/hexamethylene diammonium adip~te copolymer having a caprolactam content of 85 to 90 mole ~/0 gives be~t results with respect to the above-mentioned properties~
Suitable combinations of thermoplastic polymers other than mentioned above include a combination of an ethylene-vinyl alcohol copolymer ~nd an aromatic poly-e~ter such as mentioned above, a combination of a polyamide and an aromatic polye~ter, and a combination of a polyamide and a high nitrile resin.
Further, blends o~ three or more of the ~oregoing thermoplastlc resins having a high ga~ barrier property, for example, a blend of an ethylene-vinyl alcohol copolymer, a polyamide and a high nitrile resin and a blend of an ethylene-vinyl alcohol copolymer, a polyamide and an aromatic polyestery can be used in the present invention.
. In accordance with another embodiment of the pre-sent invention, a blend of (~) a thermoplastic re~in having a P02 value lower than 5 x 10 11 and (~) a thermoplastic resin having a P02 value not lower than 5 x 10 11 and.a solubility parameter ( ~p ) of at least -' "-` 105~5g~Z
.5 1~ u~ed ~s the resin blend.
i~3 tne tnermo~lastic resin (~), variou~ thermopla~- -tic resirls mentioned ~bove can be u~ed, and as the thermoplastic re~in (B), ~here can be employed, for example, acrylic re~ins such ~9 polymethyl metha¢rylate ~nd polyethyl acrylate, and polycarbonate resins ( ~p value = 1~.1 ).
In the present invention, it is important that a plurality of thermoplastic resins are blended at such -a mixing ratio that the elongation of the resulting resin blend is higher than the arithmetic mean ( E ) of elongations of the re3pective thermoplastic resinsO
In the instant specification and claims, the elongation ( E ) iS defined as a value represented by the following formula:
= 10~ ( ~t ~ Lo ) (7) wherein Lt denotes the breakage length in a parison, sheet or film in the direction where breakage ~irst occurs, between the extru~ion direction and the direction rectangular thereto, and ~o designates the original length in the direc-tion where breakage first occur~.
The arithmetric mean ( ) of elongations is de~ined as a value expres~ed by the following formula:
m ~ = 1 ~1 + E2-X2 + m m n-l (8) wherein ~n stands for the elongation of a sheet " 105;~59;~
formed by extrusion-molding 8 olely the individual thermopl~tic resin contained in the bl~nd, Xn stands for the weight percent of said individual re~in in -the blend, and m i~ a ~umber o~ at lea~t 2 which represents the number o~ kinds of thermo-plastic resins contained in the blend.
In the present invention, a plurality o~ thermo-plastlc resins are blended at 9uch a mixing ratio that the elongation of the resulting blend i8 higher thsn the arithmetric mean ( ~ ) calculated according to the , above formula (8).
From results shown in Table 8 in Example 2 given hereinafter and Fig. 1 of the accompanying drawings, it will readily be understood that when a plurality of thermoplastic resins are combined according to the present invention 90 that the foregoing requirements are satiRfied, the draw moldability can be unexpectedly highly improved. More specifically, when an undrawn sheet formed from an ethylene-vinyl alcohol copolymer and an undrawn sheet formed ~rom a nylon 6/nylon 6-6 copolyamide are simultaneously biaxially drawn at a temperature of 120C. and a drawing speed of 30 cm/min~
they exhibit elongations of 25 ~ and 130 ~, respectively.
In contrast, when a sheet is prepared from a blend comprising the above ethylene-vinyl alcohol copolymer and the above copolyamide at a specific ratio and the sheet is biaxially drawn under the same conditions, the sheet has an elongation ( indicated by a solid line in ` ~0535g~
Fi~. 1 ) much higher than the arithmetric mean ( ~ ) of the elongations of the tWG resins ( indicated by a dot line in ~ig. 1 1, and in case of a blend in which th~ copolyamide/ethylene-vinyl alcohol copolymer weight ratio i~q 60/4~, an extr~ordinarily high elongatio~, 230 ~, can be obtained. ~here~ore, according to the present invention, even in case of a thermoplastic resin having a low adaptability to biaxial drawing, if it i~ blended with one or more of other thermopla~tic resinq so that the above requirement~ are sati~fied, the poor biaxial draw-moldability can be remarkably improved. -The reason why the biazial draw-moldability i8 remarlably improved in the present invention ha8 not been completely elucidatedO However, in view of the faot that each o~ thermopla~tic resins used in the present invention ha~ polar groups forming strong hydrogen bonds in the polymer chain as seen from its high solubility parameter and the fact that each of these thermopla5tic resins is soluble in solvents having a high polarity, it i9 construed that it may be one of cau~es of ~uch remarkable improvement of the biaxial draw-moldability that a plurality of thermoplastic resins in the blend have an action of plasticizing one another.
In the present invention, also the gas barrier property can be rem~rkably improved by drawing a blend comprising a plurality of thermoplastic resins. Thi~

- 25 - .

, . . ~ . . - , .

~QS~
will re~dily be understood fro~ results shown in Table n ~x~mple ~ givesl hereina~`-ter.
'~he mixing ratio of ~ plurality of ther~opla3tic resin~ in the blend that is used in the present inven-tion is considerably changed depending on the kinds ofthe resins and the dr~w ratio ~dopted at the molding step for obtaining the intended draw-molded container.
In the present invention, however, it generally i~ pre-ferred th~t (A) a re in having a lower oxygen permeabi-lity, for example, ~n ethylene-vinyl ~lcohol, and (~) a resin having a higher oxygen permeability, for example, a polyamide or polye~ter, be mixed at a mixing weight ratio of ( h) : (B) r~nging from 90 : 10 to 10 : :
90, e~pecially from 80 ; 2~ to 20 ; 80, so that the elongation of the blend is much higher than the arith-metric mean ( ~ ) of the elongation~ `of the resin~ (A) and (B).
One or more of polymers having a 801ubility parame~
ter lower than 9.5 may be incorporated in the blend that is u~ed f~r formation of draw-molded containers in the present invention in such an amount a~ will ~`
not degrade the biaxial draw-mol~ability or the ga~
barrier property, in general, in an amount of up to 40 ~0 by weight. ~s 3uch polymer, there can be mentioned, for example, polyo~efins such as low den~ity polyethyl-ene, medium density polyethylene, high density polyethy-lene and ethylene-propylene copolymers, elastomers such a~ ethylene-butadiene rubbers, ethylene-propylene-diene .-rubbers, polybutadiene, butadiene-styrene rubber~, .

~ 105;~59~
but~diene-~cryl.on.itrile rubber~, polyi~oprene ~nd poly-isobutylene~ e~hylene-vinyl acetate copolymer~, and ionomersO
In the present invention, the above-mentioned blend m~y be molded into a parison, sheet or film in the form of a ~ingle layer or may be used in the form of a multiple layer for formation of a parison, sheet or film.
Multi-~ayer ~tructu In accordance with another preferred embodiment of the pre~ent invention, a multi-layer draw-molded article ha~ing an interlaminar bonding strength of at least 20 g/cm and having a highly improved gas barrier property, is formed from a parison, sheet or film having 1~ a multi-layer structure including at least one layer o~ -the above-mentioned blend and at least one layer o~ a thermopla~tic resin having a moi9ture permeability lower than 100 x 10 12 g-cm/cm2-~ec-cmHg as measured at a temperature lower than 50a.
If the w~ter vapor permeability of the above-mentioned blend i~ high or the permeabillty o~ oxygen or other gas i9 increased in a high humidity atmosphere, it is necessary to protect a layer of the blend with a resin having a low water vapor permeability. For example, if a material to be packaged by a container i9 a dry prodiuct, it i~ necessary to protect the blend on the outside of the container~ namely from the outer atmosphere, and in the case where a content to be - 27 - .

-~0535gZ
p~ck~ged is ~ liquid or contaln~ water, it i3 nece~9ary to protect the blend on both the outside and in~ide of the cont~iner, n~mely fr~m the outer atmo~phere and from the content. In accordance with thi~ pre~erred embodiment of the present invention, the high ga~
barrier property of t~e blend can be further improved by laminating on the blend a layer of a thermoplastic resin having a water vapor permeability lower than 100 x 10 12 g.cm/cm2.~ec..cmHg.
For reference, values of the water vapor permeabi-lities of variou~ thermopla~tic resins are ~hown in Table 5.
'l'able 5 Water Vapor Permeabilitie~ (PH20) of Variou~ Resin~

Re~in PH20 x 1012 (g.cm/cmZ- , ~ec.cmHg) (a~ mea~ured at 25~. and 90 ~ RH) low density polyethylene (d=0,922 g~cc) 7.2 medium den~ity polyethylene (d=0.938 g/cc? 2.0 high den~ity polyethylene (d=0.954 g~cc) 104 acid-modified.polyethylene (Adme ~ manufaGt- 4.0 ured by Mitsui Petrochemical) acid-m~dified polypropylene (Adme ~ manufact- 6.5 ured by Mit~ui Petrochemical) polypropylene (isotactic, undrawn) 4.1 ~.
polypropylene (i~otactic, biaxially drawn) 1.9 polystyrene (atactic) 89 ethylene-vinyl acetate copolymer (vinyl 15 acetate content=17 ~0 by weight) :

:. . . - - . - . : . .
- : , . ; ,, . :
;, `': ' ' ~ ' ' ' . ' ,. ::.,', ~

. . .

10535~;~
Table 5 . .
Water Vapor Permeabllities (YH20) of Variou~ Resins Resin PH20 x 1~12 (g-cm~cm2.
sec.cmHg) (as mea~ured at 25C. ana 90 ~ RH) S~rl ~ -A (ionomer manufactured b -Du Pont; 10 - 14 acid content=~.5 mole ~lO; I~a~ type~
polybutene-l 7.1 polypentene-l 15 poly-4-methylpentene-1 61 - 98 polyvinyl chloride 30 vinylidene chloride-vinyl chloride 2.0 copolymer (Dow Chemical) Cycopac~-9~0 (acrylonitrile re~in manufaat- 90 ured by Borg-Warner) polymethyl methacrylate 110 polyethylene terephthalate (undrawn) 12 polyethylene terephthalate (biaxially drawn) 9.0 polybutylene terephthalate 9~2 polycarbonate 120 polytetra~luoroethylene 2.6 ~ .
polytrifluoroethylene a. 023 polyoxymethylene 76 SM re~in (poly-p-xylylene adipamide re~in 51 manufactured by Toyobo) nylon 6 356 nylon 6-6 54.4 nylon 6/nylon 6-6 copolyamide 320 ~apo~fied ethylene-vinyl acetate copolymer 150 (~va~Y manufactured by Euraray; ethylene content=25.4 mole ~; ~aponi~ication degree =99-2~h) ~,~

; .. . , , , ~.
:
.: , .

-" 1(35;35g'~
~ he bollding ~trengtn c~f a mult~ yer ~heet or ~`iLm tend~ ~o be oonslderably lowered by pla~tic pro-cesslng. 'l`he re~son i; con~idered to be that different stres~es are causea on interfaces of respective layers depending on viscoela~tlc properties of reQin~ of the respective layers during dr~w~molding and these ~tre~e~
often exert action~ of peeling off the inter~aces.
In cups formed by heat molding the above-me~tioned laminated sheet Gr film, from the practical viewpoint, it is nece~3ary that the '~ peel strength ( bonding strength ) must be higher than 70 glcm; otherwise, the cups cannot pass the pra~tical falling te~t and the like.
'~he bonding strengtn of cups prepared by dr~w-forming, de3cribed hereinafter, of the same laminated sheet or film is lower than the bonding ~trength of cups pre-pared by heat molding for the above-mentioned rea~on.
However, it wa~ found that in case of cup~ prepared by draw-forming, if the bonding ~trength i9 at lea~t 20 glom, they have a practically sufficient strength ana they can pass the practical falling test. The rea~on ha~ not yet ~een completely elucidated, but it i8 con-strued that since viscoelastic properties of the resin~
of the outer and inner l~yers are remarkably impraved and, for example, the modulus of elasticity i9 remarkably increased, the degree of deformation given by the same stress is m~ch reduced, and even when falling or shaking forces are impo~ed on cup~, the component of the force applied vertipally to the interfaces of the laminated ~ .

., ., .. ~ - .. .- - . ~ , . .. - .. . . ,, . " : ..

, . : j- ,., . .- --. :: - . -:.. : - ..

~ (15~5!~;~
l~yerY, na~ely tlle peeling force, i~ reduced. Dat~
are detaiLed in ~x~mple 11 given hereinafter.
~ the resin con~tituting the moisture-resista~t layer, there are preferably employed polyolefins auch a~ low density polyethylene, medium density polyethy-lene, high den~ity polyethylene, polypropylene, ethylene-propylene copolymers, polybutene-l, polypentene-l and poly-4-methylpentene-1, and copolymer~q of olefin~
wlth car~onyl group-c~ntaining ethylenically unsaturatea monomers, ~quch as ethylene-vinyl acetate copolymers, ion~mers, ethylene-acrylic acid eqter copolymer~, maleic acid-modified polypropylene and acrylic acid-grafted polyethylene. In these copolymer~, it is preferred that the carbonyl group concentration be in the range o~ from 120 to 800 meq/10~ g o~ the po-ymer. In additio~ to the foregoing ole~ins and olefin/carbonyl group-containing monomer copolymer~, there can be used poly~luoroethylene type re3in~ ~uch a~ polytrifluoroethylene and polytetra-fluoroethylene a~ the moi9ture re~istant layer-constituting resin, though they are in~u~icient to some extent with respect to the moldability.
In accordance with still another embodiment of the present invention, a multi-layer draw-molded container having a much improved creep resistance i~
prepared ~rom a parison ( pipe ), ~heet or film having a multi-layer structure including at least one layer of the above-mentioned blend and at least one layer composed of a thermoplastic resin in which the sum of : . : : ~
` ' ~.` :' ` : ':
- . '.

~0535g'~
.,~
the lnstant~ecus modulus ~ Eg ) ~nd retardation modulus ( El ) ~t a te~per~ture 0~' 23C. and a stress of 7 x 107 dyne/cm2 i~ at 1e~t 1 x 1~1 dyne/cm2 and which ha~ a steady state flow visco~ity ( ~ ) of at least 1 x 1017 poiBe and a retardation time ( tR ) shorter than 6 x 106 sec, wherein the in~erlaminar bonding strength i~
at least 20 glcm.
In general, when a stres~ impo~ed on a vis-coelastomer such as a thermopla~tic polymer ~or a time t, if the time t i9 short, the viscoelastomer behave~
as an elastomer and if the time t is increa~ed, influe-nce~ by viscosity are manifested as well as influences of elasticity and the sy~tem take~ a viscoelastic behavior. If the value of the time t is sufficiently large, viscous flow is generated. These vi9coela~tic characteristlcs can be illu~tratively expres~ea by the above factor~ as Eg, El, ~ and t When molded contai~ers are usea as pre~ure-re~istant contai.ners ~uch aJ containers for carbonated drink~ or aero~ol containers, materials con3tituting the container walls are re~uired to have not only an excellent gas barrier property but al90 hardne~3 and creep re~i~tance ~u~ficient to resist the pre~sure o~
the content and a high impact resistance in combination.
In accordance with the above-mentioned preferred embodiment of the present invention, a layer of a thermoplastic resin having the above-mentioned specific viscoelastic characteristic~ is laminated on a layer of - ~2 -- , -: . . ................... .:. .
., ~: .-- . . ; ,. . : . " - . .: . - , ., . .~ . . , ,. 10535g'~
~r~e clbeve-~elltiGrled blend, whereby the creep resistance and hardness r~quired of ~ pre3sure-r~si~tant container c~n be remarkably impr~ved over a con-tainer compo~ed of a sin~,rle layer of the blend. Moreover, the impact resistance can also be remarkably improved by adopt~
ion of this multi-layer struct~reO
~ mong the above-mentioned viscoelastic c~aracteri-stics, the sum ( Eg + El ) of the instant~neous modulu3 and retardatio~ modulus i~ concerned with the hardnes~
of the vessel. In view of the pressure resistance oY ;~
the container, in the pr-esent invention it is important that under conditions of a temperature of 23a. and a stress of 7 x 107 dyne/cm2, the value of ( Eg I El ) must be at least 1 x 101 dyne/cm2, e~pecially at lea~t 2 x 101 dyne/cm2. ~rther, the 3teady ~tate flow viscosity ( ~ ) and the retardation time are concerned with the creep resistance. In the present invention, in order to prevent creep, it is important that ~ must be at lea~t 1 x 1017 poise, especially at least 5 x 1017 poise, and tx must be 9horter than 6 x 106 ~ec, e~pecially lower than 3 x 106 ~ec.
Values of viscoelastic characterist~cs of Yariou~
thermoplastic resins ~re illustrated in ~able 6 for reference.

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.~b~rev.i1~o~;, u~ed in 'i`~ble 6 h~ve the following n~nin~
hi~r~ density polyethylene i~o-P~: isotactic polypropylene ~E~; tetr~fluoroethylerle-hexafluoroethylene copolymer ~S: polystyrene P~; polyvinyl chloriae HNR; acrylonitrile-styrene-butadiene resin having an acrylonitrile content of 62 mole PTFE: polytetr~fluoroethylene PC~E; polychlorotrifluoroethylene .
ABS: acrylonitrile-butadiene-styrene copolymer having a styrene content of 51 mole ~ ;
~MA: polymethyl methacrylate PE~: polyethylene terephthalate Among thermopla3tic resins exemplified in Table 6, those having viscoel~stic parameters within the ranges defined in the present invention are used as the creep-re~i~t~nt thermoplastic resin. l~ore speci-fically, there can ~e mentioned, in the order of imp~rtance, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, ~3~ resin, polyacetal, nylons, polymethyl ~ethacrylate, isotactic polypro-pylene and polystyrene.
When the container of this embodiment i~ used as a pre~qsure-resistant container, it is preferred th~t a thermoplastic resin having reduced dependencies of the above-mentioned viscoelastic parameters on the - : . -~ .
.. , , ~ . . .
, ~

1()53592 i~r~,sur~ ~n(l tc;~perci~ur~ be u~ed as the creep-resi~tant l~yer-consti~utin~ :re~in. ~'or ~x~mple, polyethylene terephthal~te, polycarbonate, i~otactic polypropylene and polystyrene are preferably emplored.
In the present invention, ~arious bo~ding and laminating methods can be adopted for formation of a multi-layer str~ctur~ includi~g a blend l~yer excelle~t m the gas lmpermeability and a layer of a thermo-plastic resin excellent in the moi3ture resistance or the creep resistance. ~or example, when the blend layer contain~ a thermopla~tic resin having carbonyl groups on the main or ~ide chain, ~uch a9 a polyamidc, since the bler~d has, in general, a high hot-adhesivene~
to a thermoplastic r~sin excellent in the moisture re~iætance or the creep resi~tance, a laminate 9truc-ture can be formed by co-melt-extru~ion without using particular bonding means. When a carbonyl group-containing thèrmoplastic polymer is not contained in the blend layer or the moi~ture-resi~tant ar creep-re3i~tant layer or when it is intended to ~urther impro~e the ~nterlaminar peel strength even i~ su¢h carbonyl group-containing layer i8 contained, it i9 preferred to incorporate in one or both of the adjacent blend layer and moisture-resistant or creep-resistant layer a polymer containing carbonyl groups derived from functional group~ of a free carboxylic acid, a carboxylic acid salt, a carboxylic acid es~er, a carboxylic acid amide, a carbo~ylic acid anhydride, a carbonic acid - . ~ - . . . .

. .

~os;~s9z ester, uretilane or urea at a concentration of 120 to 1400 meq, especially 130 to 1200 meq, per 100 g of the polymer, in an amount of 0. 5 to 15 parts by weight per 100 parts by weight of the resin blend or the moi~ture-resistant or creep-resistant thermoplastic resin.
Examples of ~uch carbonyl group~containing polymer are illustrated in detail in JapaneYe ~atent Application Laid-Open Specification No. 39678/74. hmong these car-bonyl group-containin~ polymer9, there are preferably employed an ionomer ( ~urlyn~-~ manufactured by Du Pont ), maleic anhydride-modified polypropylene, an ethylene-acrylic acid ester copolymer and a polyalkylene oxide-polyester block copolymer.
Optional multi-layer structures can be adopted in the container of the present invention, ~o far as the blend layer and the moisture-resistant or creep-resistant layer are located adjacently to each other. Example~
of such multi-layer structures are as follow9:
(1) Two-~ayer 3tructure:
~lend layer/moisture-resistant or creep-resi~tant resin layer (2) Symmetric '~hree-~ayer Structure:
i~ioisture-resistant or creep-resistant resin layer/
blend layer/moisture-resistant or creep-resistant layer, and blend layer/moisture-resistant or creep-resistant layer/blend iayer In~tead of incorporation of a carbonyl group-containing polymer into one or both of the adjacent .-... .. .
.~. . -~ 0s3sg~
blend ~nd l~iSture-reSi~tant or creep-resl~tant resin layer, there may be adopted a technique according to which an adhesive l&yer composed o~ suQh carbonyl group-containlng layer is intervened between the blend layer ~nd the moisture-resistant or creep-re~i~tant layer. In this ca~e, the following multi-layer ~truct-ure~ c~n be formed:

(3) A9ymmetric 'l'hree-Layer Structure:
l~ioiqture-resis~ant or creep-re~istant resin layer/
c~rbonyl group-containing polymer adhe~ive layer/blend layer

(4) ~ymmetric Five-Layer Structure:
Moisture-re3i~tant or creep-resistant resin layer/
carbonyl group-containing polymer adhesive layer/blend layer~carbonyl group-containing po~ymer adhesive layer/
moisture-resi~tant or creep-resi~tant resin layer In the foregoing multi-layer structures, it is preferred that the thicknes~ of the blend layer be 80 to 0.5 ~0, e~pecially, 50 to 2 yO, of the total thickness.
Molding l~lethods Plastic cont~iners of the present invention can - be prepared ~ocording to optional known molding methoas except that the above-mentioned blend or a multi-layer ~truc~ure of a layer of the blend and a layer of the creep-resistant or moisture-resistant thermoplastic resin is fdrmed into a parison ( tube ), sheet or fil m .
~or example, a parison that is used for the biaxial draw-blow molding can be prepared by any of known means ~ 40 -.~" ... . , .. . ~ . .. . . . . . . .

: . .

~ ~05355~Z
gUCh ~9 ex~ru~ion molding or iniection molding.
For exHmple, the resin blend is extrusion-molded into a pipe ~nd tne pipe is cut in a prescribed length.
This cut pipe is formed in a mouthed and bottomed parison 1 as shown in Fig. 2 by using a suitable mold such as a ~plit mold. Referring now to ~ig. 2, this parison 1 comprise~ a cylinder 4 having one end ~ opened and the other end 3 closed to form a bottom. ~ lid clamping mechanism such as a bead ~ or male screw 5 i~ formed integrally with the cylinder 4 on the open end 2 or in the vicinity thereof. 'l'he molding temperature for forming the pari~on is not particularly critical ~o ~ar as the temperature i~ higher than the so~tening point of the resin. In gener~l, it is preferred that the tem-perature be selected w~thin a range of from 1~0 to 350C.
80 that the end portio~ of the pipe ~s completely fusion-bonded.
A mounted and bottomed parison 1 may be prepared by injection molding usi~g an openable ~nd closable ~;
mold having a cavity as shown in ~ig. 2 without forming a parison in advance by extrusion molding.
Conditions for extrusion molding or injection molding are not particularly critical. ~or example, in case of a blow-molded ~tructure having a single layer of the above-mentioned blend, a dry blend of a plurality o,f thermopl~stic resins or a kneaded compound of a plurality of thermoplastic resins is heated in a cylinder ordinarily at 180 to 350C. and is extruded .. : - . . . . ~

~05;35~'~
through a die or injected through a nozzle in ~ moldu ~he extrusion pre~sure is changed depending on the ~i~ds and comblnations of the resins or on the size o~
an e~ruder. In general, it is preferred to adapt an e~tru~ion pre~ure of 2 to 700 Xg~cm2. In ca~e of injection molding, the extrusion pressure i8 changed depending on the ~inds and combinations of the resin3 or on the size of the injector or mold, but in general, a pressure of 5 to 1000 ~g~cm~ may be used. ~ Dulmage screw or a metering 3crew can be used a~ the extruder, and a cro~s--heaa type or spider type die cu~tom~rily used for e~trusion of pipes or pariSonQ of a single layer or multi-layer structure can be used as the die.
An injection molding machine having in a cylinder a ~i-plunger provided with a screw for preliminary pla~tici-zation or an injection molding ~achine including preliminary pla~ticization means by a cylinder or a screw can be usedO A straight-hydraulic mold or toggle mold can be u~ed.
The above-mentioned blend and moisture-resistant or creep-resistant thermoplastic re~in are co-e~truded in the form of a multi-layer structure by using extru-ders in a number corresponding to the number of resin layers to be extruded, for example, an extruder for the blend, an extruder for the moisture-resistant or creep-resistant resin and an extruder for the carbonyl group-containing polymer adhesive, and re~pecti~e resin flow~ are extruded through a multiple die to form a ., , :
: . , ~ - , - -~ ~OS359Z

parison h~ving ~ multi-layer structureO ~190 in ca~e of in~ection molding of a multi-layer structure, in-~jection moldin~ machines in a number corre3pondi~g to the number of resin layers are used, and a plurality of resin flows are injected in the cavity o~ a mold through a composite nozzle.
~ mouthed and bottomed parison formed by such e~trusion molding or injection molding i8 drawn in a split mold in ~he axidl direction of the pari~on and 9imultaneou91y or successively drawn i~ a directio~
rectangular to the axial direction by blowi~g a fluid into the parison.
~or example, as sho~n in Fig. 3 illustrating one embodiment of the proce~s for preparing blow-molded container9 of the present invention, a p3ri30n 1 is supported by a mandrel 9 and a holding member 10 and fed into a cavity 7 defined by openable and clo~able parts 6,6 of a split mold. ~he mold parts 6,6 are clo~ed to hold a mouth portion 3 of the pariJon 1. The paired mandrel 9 and holding member 10 and the mold parts 6,6 move relatively to each other in the vertical direction to draw the parison 1 in the axial direction thereof.
Simultaneously, a fluid is blown into the pari~o~ 1 from a fluid blow-in opening 8 formed on the mandrel 9 to draw the pari~on in a direction rectangular to the axial directio~ thereof. Thus, the parison is molded into a ~orm of a bottle. When a fluid is blown from the opening 8 while moving the mandrel 9 ana the split mold 6 ~ 43 -. .

... , . . , , . , - . , -, , , , . . ~ - . .. ~ .

lOS;3S~2 relatively to each other, aa qhown in Fig. 3, the parison ia drawn biaxially simul-taneouqly. When a fluid i~
blown into the pari~on 1 from the blow-in opening 8 formed on the mandrel 9 or other needle after comple-tion of the relative movement of the mandrel 9 and the split mold 6, so-called successive biaxial drawing i~
accomplished. ~ continuous pipe can be used for biaxial draw-blow molding instead of a preformed mouthed and bottomed parison. In this ca~e, prior to drawing, the pipe is engaged with a neck finish portion of the mold 6 to form a mouth portion, and formation of a pari~on bottom by fu3ion bonding and holding of the resulting pari~on are performed by the holding member 10.
For example, a molding process as disclosed in Japane~e Patent Publication ~o. 2~478/69 can be u~ed appropriately according to the kinas and combinations of re~ins. ~urther, there may be ~dopted a moldin~
proce~s ln which both the ends of a bottomle~s re~in pipe ( parison ) are clipped by elamps, the pipe i~ -drawn in the longitudinal direction, the pipe i8 then gripped by a blowing mold, a ~luid i~ introdu¢ed from one end o~ the pipe to inflate the pipe and the bottom portion is formed by fu~ion bonding simultaneously with blow molding.
Conditions for biaxial draw-blow molding are changed depending on the composition of the resin blend used and on other factors. In general, when parison-constituting resins are crystalline, draw-blow molding . ~ . . , , : : : , ;
:: . : : -- :~ , -,. ~ .. . . . . -: : .

~0535~
can be performed at a temperature between the cry~talli-~ation temperature and the melting point, and when pari~on-con~tituting resins are amorphous, draw-bl~w molding can be performed at a temperature between the

5 glas~ tran~ition point a~d the crystallization initiat-in~ temperature or flow initiating temperature, ~r example, in case of relatively highly crystalline resins ~uch as polypropylene and poly-4-methylpentene-1, draw-blow molding i3 carried out at a temperature lower than the melting point of the resia. In ca~e of relatively lowly cry~talline re~in~ ~uch as polyethylene terephtha-late, ethylene terephthalate-ethylene i~ophthalate copolymer~ and polybutylene terephthalate, draw-blow molding is carried out at a temperature higher than the gla~ transition temperature but lower than the cry~tal-lization initiating temperature of the resin. ~urther, in case of amorphous or extremely lowly cry~talline resin~ 9uch a~ polyvinyl chloride, polyvinylidene chlo-ride, acrylonitrile-styrene copolymers and acrylonitrile-styrene-butadiene copolymers, draw-blow molding is carried out at a temperature between the gla~s transition tem-perature and flow initiating temperature of the res~n.
In ca~e of resins having a relatively high crystalliza-tion rate, such as polypropylene, polybutylene tereph-thalate and polyethylene terephthalate, if draw-blow molding is'carried out under the above-mentioned temperature conditions after cooling a parison violently at a tempera~ure lowering rate of 1 to 5000C. per .. .. ...

:-'. . : , . . - -. .,::. .

:, -, , -. : . , . , .:

10535Y~'~
.
minute, prefer~bly 5 to l~u~C. per minute, the tran~pa-rency of the molded article can be remarkably improvedO
~eedleq~ tc ~ay, when the re~in blend or multi-layer pari40n shows therm~l behaviors inherent of respective re~ins, it i8 neces~ary.to determine the temperature conditions based on a resin having a higher crystalliza-tion temperature or gla~s transition ~oint.
The drawability of a parison of the blend o~ the present invention or a pari~on having a multi-layer structure including a layer of the blend and a layer of the moi~ture-resi~tant or creep-re~istant thermoplastic reein can be determined by measuring load-elongation curve~ of the pari~on at respective temperature~.
More specifica~ly, the lower limit of the temperature range ~or draw-blow molding can easily be determined as a lowest temperature at which necking i9 not causea in a ~ample cut from the parison.
The effect of biaxial drawing in the axial direc-tion of a pari~on and a direction rectangular i~ evalua-ted ba~ed on the thermal ~hrinkability ( ~ ) of thedrawn sample which is calculated according to the following formula after the drawn sample has been allowed to stana in an atmosphere maintained at 50 to 150C~ for 10 to 15 minute~:

~ = 100 x ( L9 - Le :Ls wherein Ls de~ignate~ the length of the draw-blow molded s~mple and Le stands for the equilibrium 10535'~'~
' length after the above ~hrinkage treatment.
Namely, if the value of the thermal Yhrin~ability ( ~ ) of the drawn ~ample i~ at lea~t 5 ~0, preferably at least 7 o/0, it can be said ~hat the creep resistance, hardness and tran~parency are improved by drawing and orientation, though thi~ value differs to some extent depending on the composition of the blend.
In general, in order to attain a sufficient draw-ing effect, it is preferred that the draw ratio in the axial direction of a parison be 1.1 to 5.0, especially 1.2 to ~.5, and that the draw ratio in the direction rectangular to the axial direction be 1.5 to 7.5, especially 2O0 to 6.0, The drawing speed iæ changed depending on the kindS of resins and the drawing is carried out at ~uch a speed that the above-mentioned impro~ements can be attained by the drawing. In general, it i~ preferred - that the drawing be performed at a speed of 10 ~0 per minute to 6000000 ~:0 per minute.
~æ the fluid to be blown into a parison through a mandrel or needle, there can be u3ed air, nitrogen, carbon dioxide gas, steam and mixtures thereof. It i9 preferred that the pressure of the fluia be in the range of from 3 to 30 ~g/cm2 ( gauge ).
~ sheet or film to be used for plastic procesæing can be prepared by optional means, for example, a molding method u~ing a T die and an inflation molding method.
Conditions for molding of such sheet or film are , :

.

, . ! . , ' ~ , . . , ~ . ~ .

~ ~5359~
not particul~rly ri~lc~l. FOI' exam~le, a molded 3truc-ture comprising a eingle l~yer o~ tne blend of the present invention is prepared by heating ~ dry blend or preliminarily ~neaded compound of a plurality of thermoplastic resins in a cylinder ordinarily main-tained at 180 to 350C. and extruding the melt through a ~ die or a tubular die for ir.flation molding of film~
in the form of a sheet or film. The extrusion pressure i8 changed depending.on the kinds and combinations of the resins or the size of an extruder, but in general, it is preferred that extrusion be carried out under a pressure of 2 to 1000 Kg~cm~. h Dulmage screw or meter-ing screw can be used as the extruder. Dies customarily used for molding of sheets, for example, a fish tail die, a manifold die ( T die ) and a screw die, can be used, and a T die or inflation die can be used for formation of films. Further, the above-mentioned resin blend can be formed into a sheet or film according to an injection molding method, a heat-compression molding method or a roll molding method.
When the above-mentioned resin blend i~ co-extruded with the above-mentioned moisture-resistant or creep-resistant thermoplastic resin to form a multi-layer sheet or film, means mentioned above with respect to extru-sion molding or injection molding of multi-layer parisons can be adopted. Xn case of the heat-compression molding method, if the biend is used for formation of an inter-mediate layer and the moisture-resistant resin is used .. . . .
.. . . . .

, . ,-~ ~ .

.

-`" 105;~92 for for~ ,n ,,f outer c~nd inner l~yers, prescribed c~ln~s ef ~he resins are filled in d m~ld in an ~rder of the mois~ure-re~is~ant resin, tne re~in blend ~nd the m~i~ture-re3istcmt resin, the resins are then heated a~ an appropriate temperc1ture for an appropriate time and they are compressed to obtain a multi-layer struc-ture having a form of a sheet or film.
~lastic processing of the so formed .sheet or film composed of a single layer of the blend or having a multi-layer struc t ure including a layer of the blend ~nd a layer of the moisture-re~istant or creep-re~istant resin can be performed under conditions described here-inbefore with respect to biaxial draw-blow molding of parisonsO In general, it i~ preferred that the sheet or film be drawn at a draw ratio of L1 to 20, e~pecially 1.5 to 5.
An embod~ent of pla~tic processing of a film or cheet composed of a aingle ~ayer of thebblend or having a multi~layer structure incluaing a layer of the blend and a layer of the m~isture-resistant or creep-resictant re~in will now be describea by reference to Fig~. 4 to 7.
Referring t~ Fig. 4, a sheet or film 11 is heated at a prescribed ternperature cmd clamped by a chamber 13 and clampB 14 and ~5. Then, as shown in Fig~. 5 and 6, the sheet ~r film 11 is pushed into a female mold 16 to a prescribed depth by mecms of a plug 7. Then, a9 shown in Fig. 7, vacuum valve 17 is opened to effect vacuum '~

.... .
: ' ., . .. , . ~ ., , . . . . - . . ~ . ~

~ lns3s~s~

suction and ~Lu~e ~ne sheet or film 11 to ~dhere closely to tile inner fr~ce of tne mold 16. 'i`~is molding method i5 freq~ently u~ed for forming container~ from thin sheets and is ordinarily called " plug assist molding method ''0 In addition to the above-mentioned vacuum molding method, there can be adopted an air-pressure forming method, a sheet blow mol~ing method, a draw molding method, a draw-ironing molding method, a compression molding method, and other special high energy molding methods such as a forward, backward or forward-backward extrusion method using a thick sheet and an explosive forming method.
Further, a pouch-like or bag-like container can be obt~ined by drawing the above-mentioned sheet or film biaxially according to known means to form a biaxially drawn film and bonding the facing side edge portions of the filmO For bonding such biaxially drawn film, an epoxy type or isocyanate type adhesive may be u~ed.
In the case where the moisture-resistant or creep-resistant reqin layer formed as the innermo~t layer i8 composed of a heat-sealable resin, for example, poly-ethylene or polypropylene, the facing side edge portion~
of the biaxially drawn film can be bonded by heat sealing.
Molded Structure ~`ormed by Pla~tic Processing ~ccording to the pre~ent invention, by using a ~:
combination of a plurality of thermoplastic resins satisfying th~ foregoing various requirements, preferably . ~ .

., . ~- .

.

-~` 105359Z `
an ethylene-vinyl alcohol copolymer and a polyamid~, for molding of a pari~on, sheet or ~ilm, it i~ pos~ibla to p~rform biaxial draw molding whi~h i~ impo~ibls or diIîic~lt when the resin~ are used 8i~1~y, and it al80 ic pos~ible to enhanee the draw ratio at the moldin~
step.
~ ccording to the present invention, since tho draw latio i8 thUY ~nhanced remarkably, it i~ ~oe~ible ~o highly improve propertie~ o~ resulting mol~ed article~
~uch aa ¢ontainers, ~or example, creep resi~tance, mechanical strength and hardne~. A~ a result, it becomes possible to reduce the thi¢knes~ and weight i~
containers and to reduce the Quantitieo o~ resin~ used. -:
Moreover, since the reai~ blend u~ed i8 excellent in the gas impermeability a~d thi~ excellent ga~ imper-meability $g enha~ced by bi~ial dra~'molding, even i~
the thickne~s of the contai~er wall i~ made muah ~maller tha~ in conventional gas barrier plaetic ao~tainers, an excellent ga~ barrier property can be atta~ned. ~hese are prominent advantage~ attained by the present inven-tion.
In the draw-molded container of the pre~ent inven- :
tion, the unit ~olume ( the volume o* the eontainer per græm of the resin ) i9 ordinarily 0.01 to 5 dB/g, e~pe- .
¢ially 0.05 to 2 dB/g, though the value~ dif~er to .
30me extent depend m g on the use of the container, ~nd the thickne~s of the container wall may be 0.02 to 5 mm, ~.
especially 0.05 to 3 mm. A desirable ¢ombination of a .~

, ~, .~ ,. .

- , . - . .. . .. . ,. . ~ ... ~ ~ . . . .
. . . , : -: - ~ . - :

.- :. - .: . . . . . . . .. ,, . .: .. . . . .

` -` 10535~'~
high ~dS b~rrler property with high mechanical strength, creep resist~nce, hardne3s arld tran~p~rency can be att~ined while the unit volume and wall thickness are ad~usted within the above range~.
In the draw-molded container of tha present inven-tion, since the container is composed of a blend of a plurality of specific thermoplastic resins and it is biaxially drawn, the oxygen permeability is less than 1/2, especially less.than 1/3, of the oxygen permeabili-ty of an undrawn container, the carbon dioxide gas permeability is le~s than 2/3, e~pecially le~s than 1/29 of the carbon dioxide ga~ permeability of an undrawn con-tainer, and the water vapor permeability i~ less than 2/3, especially less than 1/2, o~ the w~ter vapor per-meability of an undrawn container, when compared basedon the ~ame thicknes9 of the blend layer. When bubbling alcoholic drinks such a~ beer or carbonated refre~hing drinks are contained in plastic container~, the Ylavor is greatly influenced even by a minute amount of oxygen permeating through the container wall. According to the present invention, the oxygen barrier property can be maintained at such a high level as mentioned above and hence, the effect of preserving these drinks can be remarkably improved. Moreover, ~ince the container Z5 of the present invention i~ excellent in the carbQn dioxide gas barrier property, the reduction o~ gas pres~ures of co~tents can be maintained at a level much lower than in conventional pla~tic container~0 .

-. .
,. . ~ . .. . . ., , : ,., ~ . . . :
~ , . . ~ :

105359'~
~ ecause of these advantage~, the draw-molded con-tainer of the present invention i~ very u~eful for preser~ing, without substantial deterioration or qu~ntity 1098, various liquid and pasty food~ and drink~, for example, bubbling alcoholic drink~ such ae beer, other alcoholic drinks such as Japanese ~ake, whi~ky, distilled ~pirits, wines, gin fizz and other coc~ail~, carbonated drinks such as cola, cider and plain soda, fruit drinks such as ~traight fruit juices, e.g., lemon juice, orange juice, plum juice, grape Juice and strawberry ~uice and processed fruit juices, e.g., ~ector~, vegetable juices such aq tomato juice, synthe-tic drink~ and vitamin-incorporated drinks formed by blending a ~accharide 3uch as ~ugar or fructo~e, cltria acid, a colorant and a perfume optionally with vitamins, lactic acid beverage~, condiment~ such as soy, ~auce, vinegar, ~weet sake, dressi~gJ mayon~aise, ketchup, soybean paste J lard and edible oil J and foods auch as bean curdJ jam, butter and margarine; liquid medicinee, liquid agricultural chemical~J liquid co~metic~ and detergent~; ketones such as acetone and methylethyl ketone; aliphatic hydrocarbon~ such a~ n-hexa~e and .
n-heptane; alicyclic hydrocarbons such as cyclohexane;
aromatic hydrocarbons such as benzene, toluene and ~ylene; chlorine-containing carbon tetrachloride, tetrachloroethane and tetrachloroethylene; liquid fuel~ :
and oils such as gasoline, kerosine, petroleum bendine, fuel oil, thinner, grea~e, silicone oil, light oil and .. . , . - - . , . -.. . . . - . , - . - .
,. , ~. .. .

. : ~ - , .
. - ::: . . : . . ..
:. . : . , . . ,, -~- ::- . . - : . . . . . .
. . .

1053~
machine oil; arld propellants such as liquefied FreonR( Product of Du Pont ).
The present invention will now be de~cribed in detail by reference to the following Example~ that by no means limit the scope.of the invention.

,. ~ , ., - 10535Y~Z
Exam~le 1 Two or more resins i~dicated below were dry-blended at mixing weight ratios i~dicated in Table 7. The~e re~in blends were blow-molded into tube~ having a diameter of 40 mm and a thicknes~ of 0.2 ~m by using an extruder having a diameter of 50 mm and an effective length of 1100 mm. For comparison, respective re~in~
were independently blow-molded into similar tube~
( having a thicknesa of 0.2 mm ). ReJins used are a~
follows:
EV: an ethylene-vinyl alcohol copolymer having an ethylene content of 25 mole v/O, a Yinyl acetate content o~ 0.5 ~:' mole ~ and a vinyl alcohol content of 74.5 mole ~ and being characterized by an Sp value of 11.3 ( cal/cc )1/2, an intrinsic vi~co~ity of 0.12 ~/g anid melting point of 182C. as measured accordiing to the differential thermal analysis method ( DTA method ) at a temperature-elevating rate of 10C./min ~ :
Nl: polycaprol~ctam characteri~.ed by an Sp value of 12.7 ~:
( cal/cc )1/2, a relative viscosity of 1.9 and a melting point of 219C. a~ measured according to the above-mentioned D~ method N2; a caprolactam/hexamethylene diammonium adipate copo-lymer ( Nylon 6/6-6 copolymer ) characterized by an 3P value of 12.8 ( cal/cc )1/2, a relative ~isco~ity of 3O3~ a caprolactam concentration of 91 mole ~ and a melting point of 193~. a~ measured according to the above-mentioned D~A method ~ 55 -: . . . - , -. .
. . : - , ., ,, ~ , - - -, .
: : . . . . - . . : . , . : . : - : . :.
- . . . ~ . , :, ,. - . , ~ . .. : . ... . . .
: . . ,. .. ~ :. -.. .. .. .
:~ . . . , - , ,, , . , , -.

: - - . - - ,. :; ..

PE~: polyethylene terephthalate characterized by an ~p value of 10~7 ( cal/cc )1~2, ~n intrin~ic viscoeity o 0.10 ~/g as measured at 30C. in a 50/50 weight ratio mixed ~olvent of phenol and tetrachloroethane and a melting point of 256C. a~ measured according to the above-mentioned DTA method AS; Cycopac ~ 9~0 ~ product of Borg-Warner Co. ) having an Sp value of 1107 ( cal/cc )1/2 ana a gla~ tra~si-tion point of 107O. a~ mea~ured according to the above-mentioned DTA method ~T; XT ~ polymer ( product of ~merican Cyanamia Co, ) ~ -having an Sp value of 9.8 ( cal/cc )1/2 and a glas~
tran~ition point of 102C. as mea~ured according to the above-mentioned DTA method ~u: Surlyn~ A ( product of DU Pont ) ( ionomer ) having an ~p value of 7.9 ( cal/cc )l/~ and a melting point of 104C. a~ mea~ured according to the above-mentioned DTA method HD: high denQity polyethylene having a den~ity of 0.95 glcc, a melting point of 142C. a~ mea~ured according to the above-mentioned DTA method and an ~p value of 7 9 ( cal/Cc )1/2 ~D: low denQity polyethylene having a density of 0.92 ~:
g/cc, a melting point of 108a. as measured according to the above-mentioned DT~ method and an ~p value of 8~1 ( cal/cO )1/2 PP: i~otactic polypropylene having a den~ity of 0.90 g/cc, a melting point of 154C. as measured according to ;

~' ~

.. .. .. .. - , .... .

~os355~Z ~
the above-mentioned DTA method and an Sp value of 7.9 ( cal/Cc )1/2 PS: atactic poly~tyrene having a melt in~ex of 6.0 e/10 mm~ a glas4 transition point of 92C. a~ mea~ured according to the abore-mentioned DTA method and an Sp value of 8.6 ( caV cc )1/2 Each tube was cut open i~ a direction parallel to the extrusion direction and wa~ subjected to simultaneoua biaxial drawing by u~ing a biaxial drawing machine ( manufactured by Iwamoto Seisakusho Co. ). The drawing wa~ carried out at 120C. The initial length of the sample wa~ 80 mm in either the axial direction or the direction rectangular to the axial direction. ~he drawing ;
speed was 300 mm/min. The elongation ( e ) was determlned according to the formula (7) given hereinbefore. In this drawing te~t, breakage occurred preferen~ially in the direction rectangular to the axial direction. '~est results are ~hown in Table 7.

~ 57 -,. . ~-.
- ,- ........... .

. - -: , , . ~ :

10535gZ
o -u~ o r~ ~ o ~ ~ o ~ o o ~ u~ o ~ o o o ~ W ~ ~ O U~ O ~ ~ ~
h ~ ~ 13 :
~d ~
a) rl ~:~

a) . , .
o ~ ~ U~ O U~ o rl O O . . ~ . .
~1 O
rl~ O
h I w ,~

, .
Vl~IIIIIIIIIIIIIIIII
.,_ o~ O ~ O O O O o : :
,~ : ' 1~ OO~OOOOOOOOOOOOOOO
~; ~ o o o o o o o o o o o U~
~1 ~ ~ ~ ~ ~ ~1 X

~1 '''''',,,,,, :

v O
~ ~ ' FLl ¢ ~q 2; ~; ~ ~
.~ ..

`;, - 5~ -10535g2 o -Lr` o ~ o o O ~ ~ ~1 ~ ~ ~, ~ ~ ~1 ~
h _, ~ I ~ V
sO~ : ' Q) r/
:~ ~ , ' _ ~ ~' a~
rl~ g L~ O U~
~ ~ O t~ O ~O I I I I I
0 5~--C) ~ ~
~rl--O
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r- ~
~ ~ Q~
D
E~
o o o a~

O O O O ~ U~ U~
rl ml u~ u~ ~n u~

~J O o o 3 ~ Ir~`J C~l N C~
~ ~ 1 #

~ ql\III\~
m ~o ~o E~
F~ l Pl ~J 0,1 Q N N V~ 4'2 ~ ~1 '$ ~ ~ ~; ~!; ~ 2; ~Z; ~I p~

., 59 l(~S35~'~

will be ~pp~rent from the reaults ~nown in ~able 7, in e~ch of the resin blends in which the ~p value of e~cn resin is at least ~.5 I cal/cc )1/2 and the difference ( ~p ) of the ~p value in the re~in~ i8 not greatar than 4.5 ( cal/cc )1/2, the elongation (e) is higher than the arithmetic mean () of elongations of the respective resins. ~his tendency is mo~t conspi-cuous in a combination o~ an ethylene-vinyl alcohol copolymer (EV) with a polyamide re~in ( Nl or ~2 ).
~urther, this tendency i8 not ~ubstantially ohanged even if a small amount o~ a re~in having an Sp value lower than 9.~ ( cal/cc )1/2 i~ incorporated in a blend of EV and ~2.
ExamPle 2 An ethyle~e-vi~yl alcohol copolymer ( BV ) having the same propertiec a~ de~cribed in Example 1 and a caprolactam~hexamethylene diammoniu~ adipate copolymer ( nylon 6/6-6 copolymer, N2 ) having the same propertie~
as described in Example 1 were dry-blended at various mixing weight ratios indicated in Table 8, and the re~ulting blends were blow-molded into tube~ ha~ing a diameter of 40 mm and a thicknes~ of 0.2 mm under the ~ame conditions by usmg the ~ame extruder as described in Bxample 1. In the same manner as des~ribed in Example 1, each tube was cut open in the e~trusion direction ( axial direction ) and subjected to the ~imultaneou~ biaxial drawing test by using the same biaxial drawing machine a~ de~cribed in ~xample 1 to .

.

. . : : ., ~ . ; ' ,.:

105;~5~'~
obtain re~ults ~hown in Fig. 1.
From the reQ~lts ~hown in Fig. 1, it i9 seen that the elongation ( ~ ) of each blend o~ the ethylene-vinyl alcohol copolymer ( EV ) and the nylon 6/6-6 copolymer ( ~2 ) i~ higher than the arithmetic mean ( ~ ) o~ tha elongations of the re~pective resins. It alQo i~ ~een that the elongation i~ highe~t when the N2/EV mi~ing wei~ht xatio i~ about 60J40.
~ample~ formed from re~pective re~in blend~ were simNltaneou~ly biaxially drawn under the ~ame conditions as described above by u~ing the same biaxial drawi~g machine. The draw ratiu was 100 ~ in each direct~on.
With re~pect to these biaxially drawn ~amples and corresponding undrawn samples, the ozygen permeability ( P02 ) and the carbon dioxide ga9 permeability ( PC02 ) were measurea at a temperature of 37~. and a relative humidity of o ciO by u~ing a ga~ permeation te~ter.
~urther, the water vapor tran~mis~ion r~te ( QH20;
calculated as 50 ~ thickness ) was measured according to the method of JIS Z-0208 with re~pect to each sample.
Still ~urther, with re~pect to each of the 100 biaxially drawn sample~, the thermal ~hrinkability ( o,~
in either the axial direction ( MD ) or the direc~lo~
( ~D ) rectangular to the axial direction wa~ determined according to the formula (9) given hereinbefore after ~tanding in an oven maintai~ed at ~40C. for 15 minutes.
Te~t results are shown in Table 8.

. . ' ' ' '. . : .': ' ' . ' . . ' , , ~ ,. , ,'. ' ' ' ', , , `

ll~S;~S~'~
C--.~,. . . . .
0 ~~t) N
~J
GO a~
Q * . . . ~ .
0 O~ ~ ~ ~ o~
o ~ O
l ~ ~
O h Lf~ O cs~ t-- o u~ ~ ~ ~ ~ ~ L~ ~
r~ ~ ~ ~ o .,~
~ o ~
~a o ~ ' h ~ ~ Ir~
o~ ~i bD ~
o ~ ~ o o o oo o c~ ~.~ ~x X
a) ~ l ~ N
a2 O ~ 0 0c~C~l ~ ~
. O O O ~ ~U~ ~ o 01~ r-l V O O O O O
a) ~
~ o ~ 8 ~ o ~ o o o o o o o ~ o ~ ~ # ~ ,~
u~ ~ P
o o ~: O d~ N
P~ ~5 o O O ,1 ~~1 ~ a~ '' bD ~
O ~ O O O O O O ~ ;
O ~ * ~ # ~ ~
N Ci~ ) O
~Q o ~ ~ r~
C~J ~1 O O O O
OO O O O O
O r~
. ~ I I I I I I 1 6~
O ~ O OO OO O O O
o ~ ~ xx ~ rd ~ ~ ~ ~ ~ ,~ ,,,~ ,, .
o ~! ~
O O~1 ~I r~ N ~.
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+~
q~ O ~ .
~rl . ~D .
#~ O ~ :
O O O O O O o~ :
~I CO U~ 'J m N O ~d ~ ~J ~ ~ ~ O~ O~ O~
~rl C~ ~ ~ ~ OD O
~ ~ "
æ:~

,1 - ,. - .

.. . .~ . ;
.. . .. . . . . ... .

--- 105. ~9~

From the re~ults sho~n in Table ~ will readily be understood that in ca~e of EV alone, the mea~urement i8 impossible becau~e it cannot be drawn at a draw ratio of 100 ,~, and tha~ in case of N2 a~one, each of the oxy-gen permeability, the carb~n dioxide permeability and the water vapor transmission rate ( P02, PC02 and QH20 ) of the 100 ~ drawn sample was higher than in the undrawn sample; namely, the gas barrier property is degraded by drawing. In con~ra~t, in case of blendQ of EV and N2, each gas permeability of each drawn sample is lower than that of the corresponding undrawn sample, and the thermal ~hrinkability ( ~ 3 i~ higher than that of the sample of N2 alone. '~hus, from the results shown in Table 8, it is apparent that in blends of EV and N2, the gas barrier property is improved by the drawing effect~
Example 3 By using an inner layer and outer layer extruder installed with a ~ull-flighted screw having a diameter it~i of 65 mm a~d an e~fective length of 1430 mm and provided with a melt channel branched in two flow passages, an intermediate layer extruder provided with a full-flighted screw having a diameter of 50 mm and an effective length of 1100 mm and a three-ply aie for formation of a multi- `
~5 layer structure, a pipe having an inner diameter o~ 40 mm, a length of 110 mm ( the length o~ the screwed portion of 10 mm ) and a thickness of 2.4 mm as shown in ~ig. 2 was blow-molded. The same polyethylene terephthalate ( PE~ ) a~ used in Example 1 was used for .";, :

.
-. . , . ~ .
., ,. , .: ..... . .... . .

-- ~ 0 S 3 S9'~
the inner ~nd outer lsyer~, and (~) the ~ame ethylene-vinyl alcoho~ aopolymer as ueed in ~ample 1, (b) the same caprolaatam~he~amethylene diammonium ad~pst~
copolymar ( nylon 6/6-6 copolymer ) a~ ~a~d i~ ~ample 1 or ~c) a 40/60 wei~ht rat~o blend o~ th~ a~ove-~entioned ethylene-vinyl alcoh~l oopoly~r a~d the abo~e-mentioned nylon 6J6-6 copolymer ~as used ior the ~ntermet~ato layer. Tho out~r la~or ; ~ntormodiate layor : inuer layor thick~o~s ratio wa~ 1 ; ~ ; 1.
For compariso~, the aboYe-~ention~d PET alone was blow-molded into a pip~ o* the ~ame ~hapo by u~ing th~ outer and in~er layer o~trudcr alone, and the aboYo-montioned ~thylRn~-vinyl alcohol alone, th~
abovo-ma~tionad nylon 6/6-6 copolymer ~lon~ and th~
above-mo~tioned bl~nd (c) Plon~ wsre ~oparatcly blow-~old~d into pip~8 oi the ~amQ shape by using the inter-medl~te layer estruder alone.
Each o~ tha 30 prepared 7 pipe~ WaB heated at 110C. ~or 5 minuteæ and a cylindr~cal bottle ha~ing an ~nn~r diameter of 100 mm, a height of 150 ~ irom th0 bottom to the ~houlder portion, an i~er Gapaoity Or 1178 c~ and a unit volume of 0.22 - 0.29 d~/g wa~ prepared fro~ the heated pipe by using a mold maintained at 20¢. according to the suc¢essive bia-1al draw-aolding method illu~trated in Pig, 3. The dra~
3~1ti-lay~r b~tt~e co~posed of the above-montionea P~T
and (a) wa~ de3ignated a~ bottle ~, the drawn multi-layer bottle co~po~ed of the above-mentioned PET and - - ~,, . . , - .

, - :

. ~ .- . , - ,; , : , . . .. . -.

1~535'~Z
(b) ~8 de~ig~ated as bottle B, the drawn multi-layer bottle coupo~ed of th~ above-me~tioned P~T and ( a) ~as desig~ated a~ bottle C, the dra~ bottlo oompoeed of the abo~e-mentioned P~ alo~e ~a~ dosi~ated a~ bottle D, th~ ~rawn bottle o~mpo~ed o~ ~he abo~e-men~io~ed othy~eno-vinyl al¢ohol copolymer alone was de~ at~
as bottle ~, th~ bottlo oompo~ oi th~ abo~o-~o~tio~ed nylon 6/6-6 copolymer alon~ ~ao desig~ated a6 bottle F, and th- bottle co~po~od o~ th~ abave-mentioned bl~d 10 ( c) alone wa8 designated 88 bottle G.
~ or comp~rison, ~even corr~sponding cyli~drical multi-lsyer, 8~ngle resin snd resin blend bottleo ~rere ~olded by uolng the above-montionod extruders ~ old ~or ~ormi~g bottl-s aooording to a ~now~
dire¢t blow-~olding method ( hollow ~olding method u~ing a ~ol~n pari~o~ ). 3~n¢e eanh o~ those 7 bottlse wa~ ~ormed ~rom a molten pari~on according to the hollow moldi~g method, it ~as io~d ~8 a re~ult o~
tho polarizin~ ~luorophoto~etry that eaoh ~a~ an u~dr~wn bottle. ~he~e undra~n bottles corres~onting to the abo~e-~e~tio~ed bottl~ ~ to G wero de~ignated a~
bottles J, ~ , P and Q, respectively.
With reapect to eaoh oi the ~o prepared bottles, the moldability ~a~ evaluated by the vi~ual ob~ervation test by a panel o~ 5 men and th~ oxygen permeation rate, Q2 wa~ det~mined a¢cording to the method ai9-clo~d in Japanese P~tent Bpplication ~id-Open Specifi¢ation ~o. 49379/75. Further, 1000 g of service . - 65 -., ~, 1 0 5 3 5 9'~
~ . ~
water ~8 ~illed in eaoh o~ 3 bottle~ of on~ ~ind, snd th~ mouth portion of ea¢h bottl~ ~a8 heat-~ealed with an ~luminum ioil-laminated iilm. T~en, tho bottleo ~ere sllo~ed to ~tand in a~ at~o~phere mAintai~ed at a temp~ra~ure of 50a. and a relative humidity o~ 10 ~or 7 days, and the ~ater deare~se ratio Lw wa~ calcu-lated aooording to the iollowing ron~uls:
Lw - 100 x L ~o - Lt 3/~o ~herein Lo ~tsnd~ ~or the qu~ntity oi initiaaly char~ed water, i.e., 1000 g a~d Lt ~ta~ds ror ~n :
av~rago qusntity o~ ~ater a~ter ~ta~ding ~or 7 daya.
Separat~ly, 1200 g o~ ~aline wat~r ~a8 ~illed in eaoh o~ 10 bottles of one ~ind and the bottlo~ were allow~d to ~tand ~till in an atmo~phere maintained at - 1C.
i~ 3 aay~ ana nights. Th~n, th~ bottle~ lrere i~mediatoly l~t to fall on ~ concreto ~loor ~rom a hei~ht Or 1.2 m at a temperature oi 20C. ~o that the bottome o~ the bottles 2~it on the Iloor Iaco. Tho ralling ~tre~gth :
Fb ~a~ doto~inad according to tho rollo~ring ioruula:

~b = 100 x ~ 10 l-~Fl ]

wher~n Fl dsnote~ th~ ~umber oi bottles which ar~ ~ot broken at the abo~e ialling test.
Coca Cola ~ ( registered trademark ) ~ 1000 g ) illed in a bottle and the bottle ~la8 then allo~ed to ctand at 25C. ~or 48 hours. Tho carbon dio~ide ga~ pr~ssure chahge ~C02 wa~ determi~od according to .

lOS;~'~9~
.~
th~ rollo~ing romluls:
IC02 - 100 ~ ~ Po - Pt ~Po ~horeln Po ~tands ~or the inltisl c~rbon dlosid~
~a8 preeaure ( about 3 1~8t ¢~2 ) and Pt stanao ior tho aarbon dio~$de ~ pressure aiter star~ding ior 48 hour8.
~loreover, the deioml~tio~ ratio Df 7ras deters~l~od ac¢ordi~g to tha iollo~ng ~orsul~:
D~ = 100 ~c [ Vt - Vo ]/Vo lQ ~here~n Vo ~ta;nde ~or the i~itial volu~e oi th-bottlo al~d Vt ~ta~ds ~or the ~olwllo of tho bottlo a~tor ~taI~di~g for 48 hour~ irom I~llin~ OI ~ooa aola~.
~ squ~re ~peci~n iomled by cuttiz~g tho bottle 15 ~1 alo~6 50 mm ln the a~al direction ( ND ) ~nd alo~ 50 ~ in th~ aire¢tion ( TD ) recta~gular to th-l direGtio~ wa~ a~lo~d to stand i~ an ov~ ~
taincd at 130~. for 15 minute~ a~a the then~al shri~-kability wa8 deten~ncd in sither the ~ID direction or 20 the TD directioll according to the ~oala (9) ~ive~
hereinbefore .
Obtslned result~ are shown in Table 9.

,,, -- - , ; ,,;,, ~ --.. , , ............... - . , ... . .- . . -.

. .... . , ~,, . . ~ .

lOS~S~2 ~ ~ ~ ~ ~ N ~
_ ~1 h ~ :

R rt ~n ~ ~ ~ u~
;~; a~ ~ ~ ~ ~ ~ N ~ ~ ~ o V V V V V V ~/
,1 ~
~_ ~ ~ ~ ~ ~~ ~ o ~4 o o o ~ 0 _ '\ ~ '`
8~1 o o~ * o~, o ~
~0 ~a--l o ~ o o * o o o o o o o o o ~ ~ ~
oD ~ ~ O ~ o _ ~ ~ .
O~ t_ ~ ~ ~ ~ ~ u~ ~ ~1 a~ o ,1 N N t`J N ~ N t~ ~ ~ ~ ~ ~ a~
o o o o ~ o o o o o ~
q~
a~ a~ ~
o ~ ~

N ~ ~ ~ r~ ~ ~ ~1 ~ ~ ~ N U~ ~ ~ 0 o 3 ' ~ ~t O ~t N
à
C) ~o :~

O O O td ~ O o o o o o o o h P4 p ~t rl o ,~ o ~o ,q m r~ o o Q~
0 ~ *
o ~ ~ c~ ~ ~1 h C~ 3 ;E: Sz; P~
a~

. . , : . , -1 0 5 3 5~
, ~
Fro~ ~he re~ult~ ~ho~ i~ Table 9, it ~ill r~dily be understood that the ethylene-v~nyl alcohol copolysor (B) can~ot b~ bis~ially dra~-blo~ moldod accordi~g to bhe dra~ moldi~g me~hod ~nd that undr~wn bottl~8 ( J
to Q ) ara in~erior to bia~islly drawn blow-~oldod bottl~e ( ~ to G ) becau~e the 1083 0~ the carbo~ diosido pres~ure i9 great and the bottle deformstion i~ large.
Prom the results show~ in ~able 9, it will al80 be apparent that a bott~e (C) having a multi-layer ~tructure includ~ng inner ~nd outer layors o~ the pol~-ethylene terQphthalate resin and an ~ntor~diato layer o~ the bl~nd o~ the aboYe-mention~d eopol~a~ide a~d ethylo~-vinyl alcohol copoly~er haYe ga~ barrier charactoristic~ 2' ~2 a;~d Iw, ~ighl~ improlred by the drawing ei~eot, as i~ seen ~rom th~ ~ valuos, and it i8 al80 e~¢ell~nt in mechanioal propertie~ ~uch a~
the deformation resi~ta~co ~d ialli~g ~tr~ngth. It will al~o bo u~der~tood that the gaJ bsrrlor proporty of the bottle ei tho abo~ bl~nd c~n be i~proved by the dra~ing efiect~ -xa~ple 4 By u~i~g the eam~ inner ~nd outer layer estrud~r, i~tonmediate lay~r o~truder and thrs~-ply dio a~ uood in Bsumple 3, ~nd-op~ned botto d e3s pipes ~ tube~ ) oî
a three-la~er ~tructure having a total ~all thick~os~
oi about 10 mm, an innor di~otcr oi ~0 mm and a ho~ht oi 30 mm from the bottom to t~e ohoulder were formed according to 8 known co-e~tru~ion method. ~8 the - : , .- - ~ :: : . -.. . . ..

.. , ~

10 5 3 S ~ ~
inter~ediate layer-constituting reoin, there wa8 used a 40/60 weight ratio mixturo o~ the ~a~e othylo~e-~inyl aloohol copoly~er and caprolaotam~h~xamethyl~ dia~mo-nlu~ adipato copolymer ( ~ylon 6/6-6 eopoly~r ) ~a 5 ueod in ~ple 3. ~ tb,e outer and i~n~r l~yer-co~t~t~ti~g re~i~, thore was employea (a) an ~thylon~-propyleno copolymer having an ethyleno co~te~t of sbout 10 mole ~ and a melting point oi 157C., (b) a product obtaiued by che~ically ~oditying the abore ethyle~e-propylene copolymer (a) with 1 mole ~ o~ m81el¢ anhydride( the ~elt~ng polnt was 156C. ), tc) 8 prod~ct obtained by che~ically ~odifyin~ tho above ethylone-propyle~e copoly~or (a) ~ith 3 mole ~ of ~aleic anhydrid0 ( the ~olting point ~88 15~~. ~ or (d) a produot obtainet by chemically ~odifying th~ above ethyl~ne-propylene copoly~flr (a) with 5 ~ole ,~ oi maleic anhydrido ( tho melting polnt ~a~ 154¢. ). Tho outer lay~r;i~tor-msaiate lay~r~ r lsyor t~iclmo~a ratio ~/aa 1 ~
in oach pipa. The oarbonyl group concentratio~ and 20 ~i~coelaotic propertie~3 oi the et~ylone-prop~len~
copolymers (a) to (d) ar~ shown in Tablc 10.

- .; . ~ ~, . - . . . :.

10535g2 r- * ~ '.
~oo F

N N

o g~, o , 0_1 h h 0 ~ m~i ~g~o H 0 ~ 1;

~ -- ~ lns3~s;~
~ ach of the 90 prep~red 4 bottomlo~ pipes ( tub~s ) waa hest0d at 148 + la. ior 20 ~lnute8, snd both th~ ends o~ the pi pe wer~ clipped by ClBmp8 and the pipe wae first draw~ in the longitudinal directio~.
Tben, the pipe was supported by a ~old ~or blo~ moldi~g ana air W88 introdu~ed under prec8ure fro~ o~e and t~
in~late the pipe in the lateral dir~ctio~, ~hHreby tho blow molding oi the pipe wa~ e~f~cted a~d ~ :
biarially dra~-blow molded bottle h~ving a sym~tric three-layer ~tructure ~a~ obtained. The ~o ror~ed bottl~ had a cylindrical 8hap~ having an inner diaoflter o~ 100 ~m, a height of 150 ~ irom the bottom to th~
shoulder, an average wall thic~ne3a oi 0.6 mm, ~n in~er c~paclty oi about 1180 cc and a unit volu30 oi about 0.31 d~/g. The bottle haviDg a ~ulti-layer ~tructure including an intermediat~ layer of tho ~0~60 ~iBht ratio misture o~ ths above-~entio~ed ethylene-vinyl aacohol copoly~r and nylon 6J6-6 copoly~er aad outer and inner layer~ o~ the eth~len0-propyl~ne eopD~ymer (a) ~a8 de~ignated ae bottl~ OPR, the bottle -;~
having a multi-layer structure includi~g a~ ~ter-~ed~ate layer o~ the above copolymer mi3ture a~d inner and outer layers o~ the above-~entlo~ed ~odiii~d ethylene-propylene copolymer (b) ~a~ aesignated a~
bottle OP~, the ~ottle ha~ing a multi-layer etructuro in~lud~ng an intermediate layer oi ths abo~e copoly~er ~i2ture i~nd inner ~nd outer lisyer~ o~ the abovs-~ntioned modiiiod ethylé~-propyl~n~ copoly~er tc) ~Q8 d~ignatoa . - 72 -~053S'~
.. ~ , as bottle OPT, aad the bottle h~vin~ a ~Nlti-layor etructure lncluding an inter~odi~te layor of the aboYe copolym~r ~sture ~d in~er and outer layere o~ t~e abovo-~e~tio~ed ~odi~iod othyleno-propylone copoly~er (d) ~a~ desigDated aa bottle O~U.
For comparison, bo~tlea ha~i~g the 8ame ~hape, ~ze and re~in layer structure a~ doscribed abo~o wero prepared by u8ing tho 8am~ o~truder~ and mold ~Dr blo~ ~olding as d~corlb~d above according to a kno~
d~rect blow molding mothod ( hollow ~olding oi a ~olton p~ri~on ). ~ince eaQh of the ~o prepared 4 multi-layer bottles ~a~ for~ed from a molten pari~on according to the hollow blow molding, it wao ~ound as a result Or X-ray diffr~ctiometry and polarizing fluorophoto~etry thst each layer of the bottle wa~ undrawn. ~hese undrawn bottle corres~o~ding to the above bottleo OP~, OP3, OP~ and OPU were designated a~ bottle~ DBR, DB3, DB~ and DBU, re~pecti~ely.
With re~pect to each of thc iorego~ 8 bottlo~, the oxygen per~eatio~ rato ~2 and iallIng ~tren~h Eb were te~ted in the ~a~e mannor a~ de~cribed i~
l~ample 3. From the body portion o~ sach bottle, three ~pecimeno having a ~lidth o~ 10 ~ ( cut in t~o lateral direction of the bottle ) and a length o~ 100 mm ( cut in the longitudinal direction ) wero ¢ut, aad the T peel 3tr~ngth Tp was mea~ured ln an atmo~h~r~
m~intainod at room temperature ( 20a. ) ~nd a r~lative humidit~ oi 64 ~ a~ a p~lln~ spesd o~ 100 ~m~in. ~ .-Obta~ned result~ are sho~ in ~able 11.

, ~ 73 -- .
. . . . . .
, ~ , . . .

.~
'- 10535g2 ~:
h ~ O Q~
ti~ 0 ~ h ~ ~ U~ o ~ U~ ~ O

D
~ ~a ~

I_ d E~
~, 0 .
~ ~ ~ O ~ o ~ a~ ~ o ~. .
~~

_ 8 ~ ~
_ ,, ~`.. ~, .

J u~ N
..
~' _ q3 &
. ~

.~, .. . . . . . ~ . . . . . ..

. - - . . .

~)5;~5~
From the re~ult~ ~holm .~ Tsble 11, it Yill readil~ be understood that Q2 and Fb arc improv~d b~r bia~i~l draw-blo~ molding even 1~ the inner ~and out~r lager arc co~poscd o~ a polypropylene typo r-olD, a~ld 5 that i~ the polypropylano. type reeln con~tituti~g ~t~n~r snd out~r layors io che~ically D~od~ d ~lith a oar~o~yl grou~-cont~ining org~lc compov;~, f~c?r~ a~
~rld~, the interla~inar poel strength Tp ~etwoe~
the t~o adj~cent layers i~ improved a~d thi~ impro~ed interla~inar pe~1 ~tr~gth i8 not sub~ta~tially dogradod by dra~ing.
Coca Cola ~ ( registered tr~dename ) ( 1000 g ) wa~ iillsd in eaGh of the for~going 8 thre~-layer bottles, and th~ filled bottle wa0 sllowed to stana ~t 25C. f~r 48 hour~. Then, ths carbon dio~ide ga8 pro~sure change ~C02, th~ bottle deior~tio~ D~ a~d the thermal shrinkabilitg ~ i~ either th~ MD or ~D
dire¢tion on the bottle wall wcre ~ea~urad according to the methoas describ~d in Bsa~ple 3 to obta~n result~
aho m in Table 12.

~ .

~, ' , ~, .

S;3~'3~
Table 12 Bottle LCO D~
2 ( ~,) 2qD TD

OP~ 9 14.3 7.1 7.3 5 OP~ 8 14.6 7.0 7.3 OPT 8 15.0 7.0 7.1 OPU 7 15.2 7.2 7.3 DBR 44 >60 <2 <2 -DB~ 41 > 60 ~ 2 < 2 10 DBT 40 ~ 60 < 2 ~ 2 DBU ~0 > 60 ~ 2 < 2 ' ~ , ' ~le 5 ~ bottomls~ pipe havi~g a 8~1110triC five-layer ~:
stracturo .ra~ prepared aocording to a lcno~m co--~tru- .
~ion method by u~i~g a~ an inte~eaiate-laycr eon~tituting reoi~ a 48: 52 ~l~ing ~eight r~tlo ~ture of the ~amo ethyl~e-vinyl alcohol ~opoly~r (J3Y) a~d caprola~tua/hesa~eth~lone di~cn~ t-oopol~er ~N2) as d0~cribed 1~ li~ple l, 81a 11~1 adhel~iv~
layer-co~titutillg resin (a) pol~rpropyleno ¢ho~i~ y modiried with ~tyrane and 0aleic ~nhydrids ( ~lting point = 165C.; oarbo~yl group con¢~ntration = 125 meq~100 g; hereina~ter referred to as " ~PP " ), (b) a re~in compoaition fon~ed by adding 0.2 part by ~ei~ht o~ cobalt ~cetate to 100 parts by ~eight o~ an ethylen~-vinrl acetate copol~mer ~he~ically ~odi~ied ~t~
acrylic acid ~nd maleic anhydrid0 ( melting point = 110a.;

~ - 76 -~ . . ~.... .

-: ~. - - :' - ' .. . - :
. . , . .~ - . . .

~-~ 10531Sg2 carbonyl group aonc~tratio~ = 198 ~oq~100 ~; h~rsi~-af t~r r~ferrod to ~8 1~13V~. ) or ( c) a 50 ~
~roigtlt rstio mixturo of tho above-~e~tlo~ed )5;P~ ~a nd as ~ ~nner layer- ~a ou1;or lay-r~oo~tituti~g 5 re~ otaotic polypropylono ( ioo-PP; molt~g poillt _ 167C. ) sho~n ~ Table 5 g~re~ hero~boforo.
~ n tnr~er a~d out~r l~or o~t~uaor u~ed ~a~
t~Lled ~ith a full~ htd ~ore~r ~av~g ~ ai~et0r o~ 65 ~ and a~ oifooti~- length of 1430 m~ ~nd provlded ~ith a ~elt ohannel bra~hod into 2 ~low plL~18ag~8. ~1 ~dheai~e layer o~trador wod lra~ ~tall~a ~rith a ~ull-~li~ted 80relr h~lg a ai~-t~r o~ 50 ~ ~d e:t~ooti~ro lo~gth o~ llO0 ~ ~nd provid~d with a ~elt ~el b~ohod into 2 nOl~ pa8-~8. ~~ te~dlato 15 layer estruaer u9ed wal~ pro~id~d Yith a ~lon t~rpe ~ore~ ha~ g a di~m~ter oi ~ f~eoti~e l~gth o~ 880 m~ ply co-o~trwio~ d~- w-d ~8 ~i~tai~ed at a tompor~turo oi 210a. Tho ~o pr~
p~poe-had the Ql~l~ dir~eio~s a~ t~o~e o~ pipee 0 cbtai~ed i~ Bxa~ple 4. Th~ ~nr~or s~d outer la~or s lay~r: ~tona~diate lay~r thiok~ee~ ~tlo ~a~ 1; 0.05; 0.1.
Th0 eo obtained 3 Ici~d~ o~ pipe~ wer- h~toa at 159 f ~C. ~or 30 D~nutes a~d ~hey ~ler- fo~od ~to 25 bia~ially draw-blow ~old~d cylindri~ bottls~ or ~
~tric 5-lager structuro }~vi~g thc ~a~o ~ap~ ~d dl~io~s ~ tho~- o~ the bottlo~ for~-d in ~plo ~, under the ~ co~dit~on~ aocordi~g to th~ sa~e `-` 105;~55~
prooodur~ a~ de~crib~ iD ~mple ~. Tho bottl-eo~pri~K an adh-~i~ la~r Or th- abov0 ~ r (~) ~ de~ atod a~ bottl~ OPY, th~ bottlo oo~risi~6 an ~Ih~vo l~yor o~ the ~bolro pol~er (b) 1~8 d~Aig-~tod a~ bottle OPW a~d the bottlo aol~pri~ing ~
adhe~i~re layer o~ the abo~ polymer bland (a) ~ dooig-~ut0d a~ bottlo OPX.
For compari90n, bottleJ o~ ~ ~atria 5~ r ~tnloture having the ~ hapo ~nd di~len~lo~
~0 d~eribod abo~e and ao~pri8~Lg ~ to~edi~to l~rer oo~pos~d o~ th~ ~bore-m~ntioned ethyleDo~ l alcohol copol~er ( BV) alon~ or ¢aprolact~/he~cthylen- d~
~onium ad1pats copolymor (1~2) elono, ~ ~e~ la3r-r oomposed of the above~antio~od ~sho~ioall~r ~od~ d polyols~in (a), ~b) or (G) l~d l~er a~d ~utor layors ~o~posed oi tho above-~o~tion~ i~etactio pol~propy-lone ~r~ prepar~d undor the ~o bottol-l0~0 pip0-o~trudlng and bottle bia~ ra~g oondition~ aB
do~cribed abo~e.
The bottle ool~pri~g a~ adho~ivo lay-r Or IIPP
snd ~n inte~od~ato layer o~ B~ a}ono w a~sie~tod a~ bottle BBV-a9 the bottlo oompr~#i~g an adh-~iv l~yer oi IKEVl~ ~nd an iDto~0diato layer o~ Blr ~lo~o ~ do~i~atod a~ b, t~o bottlo compriJ~g an al~hO8iVO ls,yor oi NP~ a,la ~ ~ten ediat~ layer o~
BV ~lon~ do~ nated ~ bottlfl l~BV-c, tho bottle co~pri~g ~ adho~ive l~yer oi ~IPP ~nd an intermdl~te ~
la~ar oi ~2 ~lono ~8 do~ atoa a~ bottle 1~N2-a, the .
~, , ,. ~ . -. . .
.
~ . . ~ , -., . . . . ~ .. . .

1053sg;~
bottlo co~pri~ng ar~ adho8i~e l~yer Or ~s7~ ula i~ltormodiabo layer of ~2 s;lon~ d~eig~tod ~a ~ott~o R~2-b, alld th~ ~ottlo co~prldng ~m adheeive l~-r of nd an ~t~n~odi~ta layer oi 112 alon~ ~8 d~
5 ~t~ bottle R~12-c.
~ ith roap~ct to ea~ih o~ ths eo ~ro~arl~d 9 biazi~ y dra~r-blo~r ~olded ~ottlee hav~g a s~_otric 5-layer ctructur~, the ~old~bility, o~ygen pon~atio~
~te Q2~ water tocr~L-o ratio L~ s stro~gth 10 Ib and i~terla~in0.r p~ol strongth Tp bot~ee~ the ~
8i~ and intemlodiato lay~r~ ~ero deto~in-d aeoor~li~g to the ~ethod~ doscribed ~n ~4~plo~ d 4 to obtaiD
ro~ults sho~m in T~ls 13.

.. .. . .

- . : - ~ .
. - , -1053S~2 ~o *
._ U~ o U~ o o E1 ~ t~ t~ h _ o o o Q O O O o o 8 g _ ~ ~

~ ~ o o o o o o o o o ~ ..
,~ _ . . . . . . . . . ~.... , o o o o o o o o o A e ~ ~ P~

E~0~ ~ r~ ~I t~- co C~

';3 ~ ,~ a7 ~ oo h d ~
o ~$ h o D. o D. D. o D.
a~ , 8 ~ , 8 ~ ~1 3 ,~ , 1 1,0 s~ e) *

-- 80 -- .

'., :

,., . : ., : -: . .. , `: ' ~' '' ' ' . ' ' ~'.'. ~, ' " '`:

~''`- 105;3~
From th~ results sho~n in Table 1~, it ~ill road$1y be under~tood that the bi~x~ally dra~-blo~
~olded bottle OP~ haring a ey~etric 5-layer ~tructure ~noludi~g an int~rmcdiato lay~r of th~ blend o~ EV a~d ~2, an adhe~i~e layer oi thc blend ( MP~ ) of ~PP and HBV~ a~d inner and outer l~yers o~ the i~otacti~ polr-propylene i~ most a~cellent collectively in the moldabi lity, o~ygen permeability~ ~alling otre~gth a~d ~tor-lami~ar pe~l ~treng~h.
~a~ 6 ~ bia~ially draw-blow ~olded bottle o~ a ~mnotric 5-layer ~tructure wa~ for~ed under the sa~o pipe-~old~n~
~nd bia~i~l draw-blow ~olding conditio~s a~ ~e~criboa ~n E~a~ple 5 by using aa the int~rmediate layer-oon~titut~g polg~r a three-componont poly~er ble~d ~or~d bg inoor-porating 10 part~ by wei~ht oi ~urlyn ~ A ~ iono~or manufacturod by Du Pont; ion typo _ Na + ; uelt~ng point = 104~C.; ~p value = 7.9 ( oal/cc )1/2 ] into 100 part~ by w~ight o~ a 48 ; 52 ~i~ing ~eight ratlo ~i~tura of the ~ame ethylono-~lnyl aloohol copolymor S~V) ~nd oaprol~cta~Jhe~ame~hyl-ne diam~oniu~ aalpste copol ~ er ( N2 ~ aa used in EDa~ple 5, a~ tho adh~iv layer-con~titutlng reein the ~a~o 50 : S weight r~tio ~i~ture ( MPE~ ) oi ~P~ a~d ME~ aa w ed in Ezampl~ 5 and the inner a~d outer lay~r-constituting re~n tho sa~o i80taotlc polyprop~leno ae ue~d in EDs~ple 5. ~he ahap~, din~aio~ a~d layer thickn~ss ratio of the 80 prepar~d bottlo were the ~aDa a~ those of the bottle~

~ - 81 -, . . - , .
-, . ~ . , -- -.
.- ! . .. ` ::
:,- :'" '' ' .`, .
"'. ' .. . .. . - . . , ~...... .
. : ' . '' : '~ ' .
-:` ' ~' . : -~` 105,;~5~
prep~d in ~ple 5. ~rhia bottlo ~ d-oiB~a~sd a~
bottl~ OPY.
Propertiee oi tho bottlo OPY ~oro deto~-a ac~or-d~g ~o the ~o ~thoda ae adopt~ll ~ ~a~pl- 5. Tho 5 ~oldability ~a8 good, tho o~gen p-~eat~on r~t~
10.~ ocJcm2-day-at~, t~o ~ator t0~roa~- ratio ~ 0.05 ,9~ alling ~tro~ 0 ~ d the BY-~ poel str~gth ~ 710 g/cm. Ii tho~e ro~t~ ar~ co~par~l ~ith the results obta~od ~ith ro~poot to tho bottlo O~Y in ~amplo 5 ( s~e Tabl~ 13 ), it ~ill readilg bo undor~tood that evon ir about 10 parb~ by ~ight oi polyDer haYin~ an Sp valu~ lower than 9.5 ( oal/cc )1/2, such a0 th~ above-~ention~d 9url~n~ ~ io i~corpor~ted into 100 part~ by ~ight oi tho resin ble~d oon~titut~g an interme~iate layer, propertie~ o~ the reeulting dra~n bottlo are not subst~ntially degrad~d.
With ro~pect to each oi th~ bottl~ OPY obtain-a in B~ple 5 and tho bottle OPY o~tairled ln thi~ l~pl-, the oarbon dio~ide g~o pro~suro ~ I.002, th~ d-io~
20 tio~ ratio Df and tho thon~l ohrinlcsb~ 1 itg ~ in either th~ IID or TD dir-~tion ~er- d-tonli~ed aoaording to t~e ~thods de~criked ~ B~pl- 3 to obta~ results sho~m ~abl~
_blo 14 25 B~ple : Bottle LC02 D~
No. , (~ D TD

OP~ 63 10.7 5.2 5.7

6 OPY 70 10.8 5,3 5. 5 _ 82 --.,:, - ~ , : , .
- ~
... . , . . . . . -... . . ... .. - . . .

` 1()5;~59 ~pl,~ 7 ~ bi~Yl~ly d~r-blo~l ~old~t bottle~ Or a ~ trio 5-layer structure ~ propar~d b~ u~g tho ~- co-est~dor and ~ply o~tru~io~ dio ( ~ainta~d at 245a~ ) 5 ~u uood in B~a~ple 5 undor th~ ~o botto~ pip~molain~
~nd draY-blo~ soldi~g eo~itioJl~ ~9 il~ B~al~lple~ 4 ( ~coopt that the d$o te~peraturo 1~18 ~god to 2~,5C. at tho pipo-~old~ng step ). Tho ~h~p~ ~d d~sion~ o~ th-bottl- wero tho ~o a~ tho~o or th~ bottlo~ obta 10 i~ B~ple 5, but the outer a~a lnner lager r; iate~odi~t~ l~rer thicl~noss ratio ~ cha~
to 1: 0.05; 0.025. ~ho r~sino u0~d ~or 3~8p~o1;i~ `-la~ers llerc a~ sho~ bolo~ !his bia~i~lly drall-blo~
~oldod bottle having 9. 5-la~er tnlct~r- ~1a8 doBi~tod 15 a~ bottle OPZ.
I~lter~od~ate ~syer:
~ ~ixtur~ oi the ~o ~ol~oaprolacta~ (ITl) ~ u~ed i~ ~a~plo 1, ~n othylone-vi~yl aloohol ~opol;y~or ha~ng ~L ~thyl~ne contont oi 49.5 ~olo ~, a ~riDyl ac-t~to con-20 tent Or 3.2 ~ol~ d a ~ l sloohol co~t of ~7.3 ~ol~ d bciDg o~aractor~zod ~ a~ ~p valu~ Or 10.1 ( c~l/cc )1/2, a D~elt~g po:L~t o~ 155C~ a~ n~e~ n~d ~ocoraing to tho l~othod doscr~od i~ ~ample 1 ~md ~ o~
~n per~o~bility ( P02 ) oi 0.21 ~ 10 L~ oc-~Jco2-soc-25 ~ag ( 37C., 0 ,q~ hcro~at`tor ref~rrod to ~ BV2 ) ~nd poly-p~ c~ ido ( ~ro~atio poly~ido; h-r in-ait~r re~orred to a~ ~13 ) oharaot0rizod hy an Bp wllue . :~
o~ 11.9 ( oal~cc )1/2, a ~elti~g polnt o~ 2~0C. a~

: : -: . ; -:
;:: : - . . ,. . ~

3--O5;~Dg~ ' ~a~ured according to the ~ethod de~cribed i~ B~ ple 1 snd an o~ygen par~oability of O.O~l ~ 10 11 c~.~/ca2.
~c. cm~g ( 37~C., O ,qi~ EIEI ) ~ ln ~hich the mi~i~g r~tio oi ~11/ EV2 ) : 113 was ~ 35f 65 ) : 40 .
5 ~dheo~ve Layer:
}SPB~ uE~ed ~ B~a~ple 4.
I~er and Outer Layers:
~ b,e oa~e othyle~e-propyle~e copolyDIer ( a) Or an othylo~e co~te~t o~ 10 mole ,~ a~ u~ Exa~ple 4.
~or co~pari~on, a bottle oi a ~ etr~c 5-laycr ~tructure having tho eame shap0, diDlenoion~ la~or-uan~titut~ resin~ and la~er thi¢~so~ r~tio a~ thos~
oi the abovo-mention~d bottlo OPZ wa~ preparea a¢cord~g to a ~o~n direct blow ~olding met~od ( hollo~ ~old~ng o~
a molt~ parison ) by u~ing tho ua~s ~t~uder and blo~g mold as me~tioned abov0. 2hi~ diroct blow-mo~aod ~ottle wa~ dosignatsd as bottle DBZ~
~ ccordi~g to the methoda deacribed in ~Ya~plo 3, with re~pect to oaGh o~ the ~orogo~ng bottleo OPZ and DBZ, tho o~ygen permeatio~ rate Q2~ wster d~oro~eo ratio ~w, falling ~trenBth ~b, o~rbon d~o~ido gae proo-~ure cha~ge ~CO~, deformation ratio Df and therDal shrinkability ~ in either the MD or ~D direction o~ th~
bottle w~ll wer~ deternin0~ to obtain re~ult~ ehown ~n ~abl~ 15.

-, ~ ., . ~ - -- . , . . - . . -~` ~0~3S~'~
T ~1~ 15 Bottlo~2 ~w Fb LC02 D~
[oc/m2-da;~-atm] (~) ~.L (~ (~j ~D TI) OPZ 26.4 0.09 0 85 13.9 7.~ 7.2 Dl~Z103 0 . Z0 30 172 > 60 ~ 2 ~ 2 From th~ re~ult~ ~ho~ i~ ~ablo 15, it ~
r~adily b~ derotood that aloo in ~e oi~ ~ bottl- Or ~ 8~1111110tric 5-laycr ~tr~ctur- ¢osllpoeod o~ ~ho abo~
10 ~entioned r~ o, tho resi~t~o~ to po~tio~ o~ o~rg~n, ~rbon dio~lde gae ~a ~at-r ~por o~ bo hl{~ly i~rov~d b~ bia~ial dra~-blow mold~ coDductd ~t ~ t~pe~tur~
low~r than the melt~ng poiDt oi ~ rooin ha~sg a lo~eot ~el~ing point a1no~g th~l bottlll-co~titut~ r~s~ d 15 al~o m~chanieal proporties euoh a~ th~ do~o~a~io~
r~ists~ce ~na ~alling str~th ca~ be hi~ly i~proved.
l~a~ple 8 T~ro or Dlor~ resin~ ated b-lollr Yoro d~r-blen~d at mi~ing ~reight ratio~ ina~oatea i~ Tab~c 16.
20 ~h~e re~in blon~ o~truded ~to ~he~t~ hz~;viD,g a width oi 150 ~ a~d a thial~es~ o~ 0.5 br u~ng ~
o~truder ~ring a di~-t~r of 50 ~s ~d a~ o~rocti~-l~gth o~ 1100 ~. For ¢o~parison, reapoative r-s~a woro i~dep~l~tly e~truded into similar ~eots ( ~ving 25 a thick~os~ oY 0~,5 D~ ~. Ib~in8 u~ed sro a~ ro~lo~r~:
~: an ot~yl~o~ yl alcohol copol~er h~ g a~ oth~l ~o oonte~t o~ 25 mole 9Z, a vinyl acetate ao~ nt o~
0.5 ~ol~ ,g aDd a ~yl aleohol co~t~t o~ 74.5 ~ol~

, ~05~5~'~
a~d boin~ oharaot-ri~o~ by ar~ alu- o~
( ~l/oo )1~2, e~ iI-tri~-ic V180011ity 0~ 0.12 ~g a~d molt~ po~t o~ 1829C. ~ ~s~r-d a3aorain~
to th~ diIiere~tial thon~l a~ly81~ ~ethod ~ethod ) at a ts~pqrature-ol o~ti~g rat~ o~ 10a./~i~
lll~ polycaprolact~ o~araoterized by an 8p ~ralu~ oi 12.7 ( caltco )1/2, a rolative ~I~OOOity o~ 1.9 a~d neltirl~ point of 219C. a~ ~-a-ured aoaor~li~g to the ~bovo-~entloned DTJ~ mothod N2: a caprolacta~ho~othyleno dia~o~iu~ adip~to copo~r (. Iilylon 6/~6 oopDl~-r ) ~raoteri~-d bg a~L 3p ~a~u~ oi 12.8 ( oa3./cc )1~2 ~ ti~
visco~ty of 3,.3, a caprolact~ conoentr~tio~ Or 9 ~ol~ ,~ ~d a ~eltlng poi~t o~ 19~O. ~ u-aellrod a¢co~ding to the abo~e-~-ntion~ thod Pli~!: polyethyle~e tQr0phthalate ohar~ct~r~z~d b ~uo o~ 10.7 ( ~/c~ )1/2, a~ int~.-~.c rl~co~it~
oi 0-09 ~/B a~ meaoured ~t 30C. i~ ro~t ratio ~xed l~olvent o~ ph~nol A~ld tetraehloroothan~
a~d a ~eltir~ point o~ 256C. ~ m-asured ac~orain~
to ~he ~ovo-~-~tionod ~ ~ethod ~: Cycopac(~)930 ( product o~ Bor~War~sr aO. ) ha~ing a~ ~3p ~ralue o~ 11.7 ( oal~co )1/2 a~d a ~ t~8i-tio~ poi~t o~ 107C. ao ~oa~urea accordi~g to the above-m~ntionod D~ ot~od ~CI!: ~!(~) pol~or ( produot o~ ~rioa~ ay~id Co. ) ~ar~g a~ ~p ~alu~ oi 9.8 ~ 2 and ~ gl~
t~itio~ p~t o~ 102a. a~ ~18~ aooora~g to ,.,.. . ~ ~

53~g~
th~ ~bovo~ ntlonod DT~ ~-thod url~ ( product o~ Du Pont ) ( lo~ol~-r ) h~rl~g p valua oi 7 9 ~ aa )1/2 ~ .d ~ lt:Lng po~.t o~ 104C. e~ ur~ aoeo~d~g to tho ~bo~
~t~onod D~ ~othod ~D: hi~h de~ity ~olyethylen- hav~g ~ donolty o~ 0.9~, 6~CQ, ~ lt:L~g po~t of 140~C. a~ ~oa~uroa s,aoorl-~g to the 9,bo~e-~ntio~ mothoa u~ 3p l~alue of 7.9 ( oal~ 0¢ )1/2 10 I~ lo~ denaity p~l~ot~ ne h~ g a don~it~ oi 0.92 g/co, a ~elt~g po~t oi 108a. a~ m~surd aocordi~g to the abo~e-~e~tio~d DTd method a~d a~ 9p ~ oi 8.1 ~ l/c~ )V2 ~: ieotactic polypropyl~e ha~i~g a dOEnoity or 0.~0 g~cc, a ~tin~ poi~t o~ 15~Oo a~ ~e~ur~ ~ooording to tho abo~e-mentiond DT~ ~othod ~d ~ 9p valuo o~

7.9 ( c~/cc )1/2 ~: at~ctio pol7~tyro~e having a ~elt indez oi 6.5 g/10 ~, ~ ~aea trancltion point Or g2cO 8~ u~urea acocrdin~ to th~ abo~ nttoned D~ ~othoa and a~
~alu~ o~ 8.6 ( caVcc )1~2 ~C31 ~hoot wa~ llub je~t~d to ~ tan-ouB biasl~l dn~ g b~r u~g a bia~ial dr~lng ~ohinc ~ ~uiaatured by I~a~oto ~ ahl~ho aO. ). Tho dra~ring ~a~ carrl0d out at 120Ç. ~he lnitial l~n~th of tho u~ple ~ 80 in elth~r the ~trusion dir~ation or tho dir~ctio~
r~ct~ig~lar to th6 e~trusion dlrection. 'rhe dra~
~p~od ~ 00 ~J~. ~hs olong~tion ( ~ ) ~ detor-- s - - .

:.' : ' !: :' ' . ~ ' .
': :. ' ' , ' :

t)53sgz ~ined ~ooording to th~ ~ormula (7) giv~n horoi~be~or~.
ID this draw~g test, br~akaBe oc~urrol proi!er~lly iII tho diroction rectaD~lar to th~ o~truslo~ dir~atlo~.
~!e~t reault~ ars sho~ able 16~

., ~05;~S9'~
~_ u~oo~,oU~o~ ?~u~u~o~~U'8u~ou~o ~g ~ -9 ~ u~o~ ooou~ ~ ~
~ ~ o o ~ V ~ ~ U~
,~ gto ~oPs , ~1 ~
E~
~ vl ~ " ~ " ~ ooa~
~ ~ :
~ O~OOOOOOO~O~N~

OOOOOOOO~OOOQOOOOOOOQ~
~3 ~ 0~ 0 ~ O O ,0~ 0 ~ O ,~ O I~U~U~U~U~U~U~IA~
S: j ~ ~ ~ m æ ~ ~ ~ N ~ ~ N ~ ~

., 1~5;~5'.3'~
~ ~ri~ 1 bc ~p~r~nt f`ro~- the ro~ult~ ~o-m 1 Tabl~ 16, in ~ach o~ th~ ro~in blondo iD hi~ ~o qaluo o~ e~ch r~ i8 at l~t 9 . 5 ( ~l/cc )1/2 the d~f~erence ( ~,~ ) oi tho gp lralu- i~ th- r~
18 not gro~ter tha~ 4.5 ( oal~co )1/2, tho ~llon~ption (e) i~ hlgher tha~ th~ ar~th~etio ~oa~ (e) o~ ~on~
tlon~ o~ the ro~pooti~o ro~ . Thi~ t-ndo~
11108t c0~8pic~ou~ ~ ~ oo~bin~t$on oi a~ ethyl~--~ayl slcohol copoly~er ( :~V) lrith a po~ ya~id~ ro~ ( 111 or 1l2 J. Furthor, thi~ t~ndRllGy i8 not sub~ta~tially c~god o~on if a ~ ount of a r~
~p ~alu~ lo~or than 9.5 ( cal/ca )V2 io lDcorpor~tod i~ a blo~d of 2Y ~nd ~2.
~ample 9 ~n othyl~no~in~l ~laohol aopoly~er ( BV ) havi~g properties as do~crlb~ npl- 8 s~d a capro~aotam/ho~ thyl0ne dia~moniu~ ~dip-to oo~ r ( n~n 6~6-6 ~opol~or, N2 ) ha~ g ~ho Ba~ prop-rti~
~ d~oribJId in ~r~pl- 8 ~ rQ dry-~lond~d ~t ~arioue 2C~ g wai~ht r~tio~, ~ the r-sultl~lg ble~ls ~r-r~
ertrudod i~to ~h~ct~ h~ving a ~ridth o~ 100 ~ a~l~ a thio~o~8 of` 0.5 ml~ und~r tho ~uae co~ditio~ ~y u~ing the sa~e ost~d-r ~8 do~ribed in l~ple 8. In the ~o aann~r 8ll de~cribed 1~ B~ple 8, oa~ oho-t ~B
~ub.ie~ted to the a~ulta~ous bia~l drawing t-st b~ u~lng th~ ~o blssi~l drawing ~ e a# da~cr~bod ill E~pl~ 8.
Th~ o~t~incd r-~ult~ ar~ lar to the~e obta~ed -- 90 -- ~

' . . ~ ' -,, . . .~ , :
- .
! , 1~535g'~
i~ ~pl o 2 ( Aho~n in Fig. 1 ) . ~oly, t~ lo~g--tlon (E) oi the blond oi DV and ~12 ia hi~Qor th~
arlth~-tic m~ ) aa~ lt~ rrOIII th~ ~lon~tioll-OI l~V and ~2, and the olong~tion o~ th- bloDd i~
5 h~ t ~on the ~V/112 ~ g ~ciB~t ratio lo a~out ~0/ 60.
~o~ult~ obtai~od by d-tor~ni~g P02, PC02, ~E120 ( ~18 ~laulatad a~ thicl~oss ) and then~al l~hrillkability ~ in oithor tho e~truoion dir~ation, ISD
10 or th~ dir~otion recta~gular to the o~tru~ion d1roctio~l, ~D ~lth rasp~at to th~ ioregoillR dra~m sheots a~
mdra~ shoQts are quito s~ilar to re~t~' obt~iaol in ~amp10 2 ( ohow~ a~10 8 ).
B~plo 10 B~ u~ing an ~n~or 1ayor ~d outer layor ~truder i~tallod with a Iu11-n1gh~od ~aro7 h~ng a d1a~let-r o~ 65 ~m and a~ effooti~ro 10;6th oi 1~30 ~ aad provi~
a ~elt cl~ d braa~ tlro ilo~
i~to~li~t~ lay~r ~trud-r pro~idsa ~th ~ iull-20 ni{~tod ~crow }~r$~g a dia~-tor o~ 50 ~ ~d ~
~octi~e 1~gth of 1100 ~ ana ~ thro--p1~g T aiO
for ~onu~tioII oi a multi-la;sror ~tr~ ho~t g a width o~ 200 ~ and a ~hic~m-s~ oi 1.0 ~
~ e~ Th~ ~me po1yeth~10n~ terephthalate 25 ( ~Bq! ) a~ u~ed in B~ple 8 lta~ u8d ~or the i~n~r a~ outer la~er~, ~nd (a) the ~e ethr1eno-~ri~1 alcoho1 oopol~er a~ u~d in l~ple- 8, (b) tho u~-oapro1aQta~/ho~ thy10ne d~s~Qniu~ ad1pato eopo1~or :

-- 91 -- `
~-~
:~, , - - . - . ,.. . -, . -.. , . : . . . . . . . . .

1~5;35'3~
( nylon 6/6-6 eopol~aor ? ~ ~ed in B~pl~ 8 or ~c) a 40/60 l~ight r~tio bl~ld o~ ths abo~R-~tionod et~yler-~-vinyl aloohol eopol~or a~d the abo~ ~tio~
Ilglo~l 6/6-6 ~opol~or ~ao u~ or th- i~t~d~t-5 l~yer. The outor l~yer s ~ten~ ato layor; ~-r layer th~oJ~o~o r~tlo ~iaB ~ . For Go~pari-oD~
t~o abovo-~eIltlo~ed ~ alo~o ~ o~tru~io~-io~0a i~to ~ ~oot of tho ~ hapo b;y u~ing the outer ~d i~er lay~r e~ctrudor ~one, a~d the sbo~ nt~on-d 10 oth~ 0-~inyl alcohol alone, tho abov-D~ntiond D;~lo~ 6/6-6 copol~-r alono ~nd tho s~ov0-~ea~tio~-d bl~t (c) alvne were ~-p~ratdy o~tru~ion-~or~d lnto shoet~ of the oa~e ~hape by u-i~g tho into~ to layor e~ctrudor alono.
Ba~h o~ t~e oo propar~ 7 sil~et~ ~a~ h-atea ~t lloa. ~or 5 l~utoJ ond a cyl~drical cup ha~g Ul i~er diulletor o~ 100 ~, a hoight of 150 ~, 4n inn~r city oi L150 cc ~d a u~it ~olul~o o~ 0.22 - 9.29 d~g llas preparoa ~ro~ the hoa~od ~o~t ~y uoi~g -20 ~old ~ t~i~od at 20C. according ~o tho bi~
drur~ vaouum moldiDg m~thod ~7luotrat~d 1~ Fig . ~, 5, 6 ~nd 7. Tha dra~m ~ulti-lay-r cup co~poood o~
~bo~r~ontiohod P~ nd (a) Yao desi~t4t a~
th~ dra~n ~ulti-la~r-r cup ao~ooad o~ the ~bo~e~tion-d 25 P~r ~nd (~ de~lig~ted ~8 au~ ~, the dra~ ~ultl-l~rer ~up ~o~po~ed o~ th~ e,bov~ti~od P~T ~d (o) ~as do~ig~ted as a~p 8a, tho dra~ a~p compo~od oi t~
~bov~ntio~od PB~ alo~e ~ de~ig~tod as ~up ' ~0S~592 dra~m cu~ oo~po~ed oi tho a~ovo~o~t~ ol~od ethyl~
vi~yl alcohol copoly~or ~lo~o ~a~ to~ td ~ oup ~1, t~e cup col-poooa oi th~ abovo-~ontlonod ~lon 6~ 6-6 oopol~or alon~ desig~atod a~ cup ~, a~ aup 5 OOl~pONed o~ aboY~-~ontionod b~ Qd (O) a10~10 1~
d~oi~atodaa~ oup ~G.
For eo~parison, ~ovon oorr0eponding c~lindri~al ti-~ayor~ singlo roo~ ~nd ro~n blolld aup~ ~r~
~ld-a by u~ing the abovo-no~tio~ed ~trudors ana ~ ~old 10 ror ion-ing oupo aoco~l1ng to a lmo~n th~ oror~ing thod ( ~thod ior vscuum-molalng ~olt~n oh-eto ).
~inc- ~ch of theso 7 aup~ ~ fono~d ~ ~olt-n et acco2~1ing to the vacuu~ l~oldlng ~-thod, it ~SL8 round ~ a reoult- oi the polari&i~g iluorophoto~etry 15 th~t oaah ~as an undraw~ cup. ~heco urldr~n; aupa corre~ponding to tho ~bo~e-m~tioned ~upo ~ to ~ro d~ natod as bottlos ~J, 8E, X~L, ~, ~, ~? a~d ~Q, r~pectiv~ly.
Wlth respect to o~ oi t~o BO prepa~d aup~, t~o 20 ldab1lity~w~s e~al~ted by tho ~i~l ob~rvation t-ct by a p~el o~ 5 me~ and th- o~r~o~ po~t~on rat~, Q2 ~las deteml~ned aoaordi~g to th- ~-thod dl~
~108~ l Japsn~l~e Pate~t ~p~lioatios ~id-Op~
~pea~Iia~tio~ ~lo. 4~37~/75. hlrth~r, 1000 g oi ~or~ico 25 wat~r ~ illed i~ oa~h o~ 3 c~p~ of o~o ki~a, ~d outh po~tio~ o~ eao~ cup ~a8 hoat-aealoA lffth a~
oi~ natoa ~i~. Th~, tho ~upa lr~ro .
~llo~ d to stan~ at~o~phore ~intai~ a t~-.. . .

. . . . . , . : : - . .- . : , . . .:

i~)s~5g~
per~ture of 50C. and a relativo hu~idity of 10 ,~ ior 7 days, and t2~Q water docr~Ls~ ratio Lw ~ l~atod acoo~ding to the rollowing ror~
L~ = 100 Y L Lo - Lt ~/ Lo wheroln ~o ~tand~ ~or tho qu~tity o~ i~iti~
charg~d ~atar, i.o., 1000 6 ~d Lt ~t~d~ ior 8~L
a~erage quantity o~ water a~t~r st~di~g ~or 7 da~rs .
~parately, 1200 g p~ 8ali~ ator ~ ~llloa ~ e~o~
of 10 cups of o~e ki~d ~d th- ~up~ ~r0ro allowod to ct~d ~till in a;~ atm~pher~ mainta~nod at - 1O. i~
3 dayc as~d ~hts. Then, tho oup~ uer- i~modiatel~ lot to ~all on a çoncrete ~loor rro~ a hoight Or 1.2 ~ at a te~perature Or 20C. ~o ths,t the bottomo Or the aup hit o~ the iloor f`ace. The rall~g ~tron~th Fb dete~ined accordl~g to ths îollow~ng ron~ula:

F~ = 100 ~ 10 loYl ]

~herein Fl de~otee the nu~b~r Or ¢ups ~hiah are not broken at the ~bove ralling te~t.
Cocs Cola(~ ( registered tr~de~rlc ) ( 1000 g ) .
1~8 ri~led i~l Q CUp a~ld the cup ~ae thon ~lo~red to st~lad at 25C. ~or ~8 hours. ~he co,rbon dioside pre~suro ¢hange ~¢2 ~ determined a¢cordiDg to tho Iollo~g ro~ula: .
L~ao2 = loo x L Po - Pt ]/Po herein Po ata~ds ~or tho i~itial carbo~ dio~ito ~3ae preseure ( about 3 ~ m2 ) a~d Pt ~ta~do ~or ~, - . ,. .
. ~ ' , . " ' ~ ' ' ':
:, ' . '~ ' . .: ' .
'.'~ ' ~' ' ' . -~~` ~05;~

the carbor dio~ide ga~ pro~ur~ a~tor stand~
~or ~8 hour~0 }loroovor, tho te~o~atiol~ ratio D~ l~a8 dote~i~d accorai~l~ to tho iollo~ing ror~ula;
D~ = 100 ~c [ ~t - Vo 3/~o horoln Vo ~t~nda ~or th- ~itlal volu~o o~ th-~up and ~t otands ~or tho rol~o oi th0 ~up a~t~r ~ta~ding ~or 48 hour~ iro3s iilling Or aoQ~ aola(~
~ aquare ~pocim~ io~d by cuttl~g ~o ¢up ~
along 50 mm in the a~ial dir00tion ( ~ID ) and ~lo~g 50 ~ in tho dire¢tion ( ~I) ) ro¢tan~ular to tho directlon ~ allowed to stand in an oven ~i~t~ t 130C. ror 15 D~ ute~ a~d th~ ther~ hr~kabllltg detar~inod in either the ~lD d~r~tion or the 'rD ~$ro~-tion aacord~g to the iomtula (9) gL~en h~r~$n~e~ol~e~
Obtainod r~8ult8 are ~ho~ i~ Tablo 17.
',~ :

... . .. - ~ -, . .- .. . ..
- - . . - . ~ .... . . . .
. . . : -, . ~ : , 10~

E~ . . o cr ~ ~ cJ ~ o N t~J N Ql 1 b~
_ ~

-; ~ V V V '\/ V \/ V ,~ ' o t * t~
AA A

8 _l o cr ~ N O ~ U:~ t~ O O
N N ~ ~ ~ ~3 ,q ~11 ~ ~ O C~ O O * O O O O O O C) ~ ~
,~ ~ o ~ 8 $
~1 ~ _ a~ O ,~
E~ ~ ~* c~ J N C~J ~ ~ ~ ~ ~ ~ a~ ~
~ _ . *
o o o oc~. o o o o o ~1 'I '~ 8 ~ ;
~1 t D
O d . * o . . . . o a ~ U~ O ~ C~
~ i~

o ~ d h ~ d ,~
~rl r-l o O O bD O O O O O O O O
~1 :,, ... , . . ~ . . . ~ . ~ .
; ~- .. .

-, :: - :

35g~
FroDI tho r~ult~ ~ho~ in Tablo 17, it ~ l ro~t~ly ~e u~Lder~tood t~st ths eth71el~o-r~yl ~loohol copol~r t~) oannot bo bia~ially dra~ ol~ed acoordl~g to t~e a~..ing ~aouw~ ~oldizlg ~ethod s~ld t~at w~dralm aup~
( 9J to 9~ ) are ~iorior to biazially dral~-solaod aupa ~ 911 to 9~ ) beoauf~e the 1088 of tho oarbo~ dio~
proooure io great ~a the cup d~ro~stion i~ l~rgo.
the re~ults ~ho~ Tablo 17, it l~ill aloo bo appar~nt that a cup ( ~a) having a ~ulti-layor tru~tur inoluding inner and outer lay0ro oi tho polyethylo~o tersphthslate resin and an inter~diata la~r o~ tho bls~d oi the above-~s~tion0d copolya~ide and ethyl~na-~inyl aloohol copoly~r h~ve ga~ barri~r ohar~ct-rlatio~, QP2, LC02 a~d Lw, highly i~proved by th~ drawing ~ t, as i8 s~en ~ro~ the ~ valuoe, and it i~ al~o e~oelle~t - -~
in ~eohanioal properties ~uch a~ tho d~orsatio~ r~si~-tanco and falli~g Jtr~gth. It ~ loo b- undoratood .
that thc gs~ barrier proporl;y oi tho cup oi tho abov l~e~d ca~ bo i~pro~e~ bg tho dra~i~g o~ioct.
B~ lo 11 By U~ g tho oa~o i~nor ~d out-r ~ r o;stru~l-r, ~te~ediate layor e~ctr~tor ~d thr~-ply ~ dio a~ u~o~
i~ E~a~plo 10, ~ho~tY oî ~ throo-~,ayor ~tr~eturo ~a~g a total ~all thi~cno~ o~ a~out 1.0 ~ d a vidth o~
200 ~ ~ero ~oroed aocord~g to a knolm o~Jion ~ethod, ~ the intorm~diato lager-con~tituting rosi~, thers ~
u~d a 40/60 woight ratio ~i~t~- Or t~o samo oth~leno-~inyl alcohol copolymar and caprolactam/h~a~ethylo~

~ ~ , ', . .,: , - - - ~ , . . .

- .
, . . ~ ,. ..

1~53SgZ
dia~onlum adipato oopoly~er ( nylo~ 6/6-6 ~opo~yoor ) a~ u~d in EY&~pl~ 8. AB th~ outer ana inn0r ~aror-oonstituting re~ln, there w~0 ~ployffd (a) an ot~ylo~--propylono copoly~er ha~in~ a~ thyl-ne ~nto~t oi ~bout 10 ~ by weight, (b) a produet obtalned by cho~lcally ~odliy~ng the abo~e ethylone-propyl~o eopolyaer ~ith maleic snhydrid~, ~c) a produ~t obtai~ct ~y ohamically ~odi~ying the abo~e ethyl-n~-propyl-~ oo~o-ly~er (a) ~ith ~aloic anhydr~to at a ~i~hor d~ro~ of ~ iioatlo~ tha~ b) ( a hi~or ~lei~ a~hydr~do oo~tont ) or (d) a p~o~u¢t obtaiu~d ~ oho~i~ r ~o~
fy~g t~o abo~o eth~lens-prop~l~e oopol~r (a) l~ith ~loio anhydride at a hig~er dogroe Or sodi~ioatio~ th~
i~ (c) ( a higher ~aloio a~hydrido oont~t ). Tho o~t-r layer:i~ton~ediato la~er~ Ler layer thlclcD~ t)o 1;1 in ~ach eho4t.
~a~h o~ the ~o proparea ~ ot~ h-atod ~t 1~0C. ~or 20 minuteo s,nd ron-od into cup~ by uoin~ a nold he~tod at 20a. aC20rdlng to t~0 bia~i~l dra~ing ~uu~ ~oldi~ method sho~n ~n Figo. 4, 5, 6 ~d 7.
~h~ ~o ior~ed aup h~d a ¢~lindric~1 ~hape hQ~ing an in~er diamoter o~ 100 ~, a ~ight of 150 u~, an avor~g ~all thickn-s~ o~ 0.6 m~ and an inner ~apaoity o~ ~bout 1150 c~.
Th~ cup ha~lng a ~ulti-layer ~truoturo i~oludl~g 4n int~rm~diate layor o~ ~h- 40/60 ~eight rat$o mi3ture o~
tho abo~ e~tioned ~hylene-vi~yl aloohol ~opoly~-r ~nd ~ylon 6/6-6 copolgmer a~d outer and in~or lay~ra oi the ~ . .

.
... . . . : . .. ,~
. , ... -.... . "

lOS;~Sg~
ot~ylono-propylono oopolymer ( a) lraa de~i~at0~ up 0~, t~ oup having a multi-layer Dtruotur~
u~ int~diate lRyRr o~ tho abovo oopol~or ~
~d inn~r ~d outor lay-re o~ tho abo~ entio~-d 5 modiri-a ethyl~no-propy;l o~ ~opoly~-r (b) ~ d-~ie~t-~l cup 0~1, th~ cup ha~ng a ~ulti-la~-r ~tru~tur~
ing an inton~ediato la~rer Or th- abore ~opol~ar l~tura inn0r Imd outor layors o~ th~ abo~e-maltionod ~odiii-d cthyl~n~-p~opyl0ne ao~oly~r (e) ~ to~ t~d o aJ cup o¢, ana tho cu~ hsving ~ nulti-layer ~tru~ture including an ~nter~ediate layer o~ the abo~o copoly~or ~i~ture ~nd inner a~d outor la~ers of the abo~
ntioned modi~ed ethyl-no-propy~ çopoly~er (d) de~ienated a8 ~up OD.
For co~par~son, ~up~ ha~ing tho ~s~o ~hapo, i~o ~d ree~ layer ~trllcturo ao do~cribod abo~o ~Tore proparo~
by usin~ tho suDe o~trudor~ ~Dd ~old ~or ~old~g cup-a~ do-orilD-d abo~o aooording to a ~mo~n thor~o~orJi~g ~ethod ( ~aouua ~oldlng oi ~o~t0n shoot ). 3inco oach o~ ;~h- ~o propar~d ~ ~ ti-layor cup~ ~a~ ~or~0d rrO~ a ~lton ~h~ot accord~ng to the vaouu~ ~oldi~, it ~a~ ~ound aa a re~ult or ~-r~y d~rrr~ctio~otry s~d polarl~ iluorophoto~etry that each layer of th- oup ~a~ u~dra~. ~h~se undrann cup~ corre~po~ding to th-abo~- oup~ O~, OB, oa ~a OD ~ re deoi~ated as oupo D~, ~, D¢ and ~D, re~pectl~oly.
W~th respoet to e~ch o~ the ~o prepared 8 cupo, th~ interla~inar T pesl otre~8th and ~all~g ~tre~gth Fb :, _ 99 _ ..... .. . . ...................... .

-- : , , , . :: . -10535g2 ~ore d-t~ d aacordi~g to ~he method~ dl~s~rl~-d ~
~a~ple~ 4 a~d 10 to obtain r~ulta eho~ ablo lfl.
T~ble 18 alp a~=~ '~
b~tlr-en out~r lsy~rbotv0~ r a~d i~t~modiatolayor a;~d iDt0r~
lay~r ~ed~at~ lay0r ~ 7 5 100 oa 23 21 10 D~ 10 9 100 D3 50 ~6 90 ga 75 71 10 From tho re~ult~ ~ho,m ~ 2ablo 18, it ~ ro~
~o u~dsr~tood t}~t in cas- oi drad-~olded oup~ t~o pool ~tro~gth io hi~her than 20 g~o~, the Fb v~lu~
r~arkabl~ reduo~d " a~d th~t in o~e OI cupo ~o~od 20 ~ocording to th~ cu~to~r~ tho~oromli~g mothod, ii tho p-d str ngth ia hi~r th~ 70 g~ h~ al~e ia ra~rka~ly reduc-d. Tn ehort, i~ o o~ dra~ olae~
a~p9, an ~dhe~lio~l ~treneth c~pable oi r-~isting to practi¢~l application to~te, ~uah ae the rall~g tr~th 2~ t~t, t~ muah lowor thsll in oase of oup~ ~or~od acoordi~g to th~ to~ary the~o~orsling D18thOt.
~a~ple 12 T~o or ~oro o~ t~ ~a~e et~lene-vi~yl aloohol ~... . . . . .
, . - ... ~ ~
. . . . : - . , :, ., . , . .. ~ . ~ . . . -~ OS~35~;~
copol~mer (EV), polyoaprolaota~ aprolacta~
h~e~h~lone dia~oniu~ ~ te copol~r (N2), at~otlo poly~tyrene (P3), i~otactic polrprop~en0 (PP)t ~ pol~er ( ~ ) a~ad gurly~ U ) a~ doJorlb~
5 l~ple 8 ~r~ dr~-blo~dod at mi~cing weight r~tios 0holm in ~able 19, and th~ dry bl~d~ wore e~:trudea into #hoet~ in~S a thick~e~ o~ about 0.5 m~ b~ wl~g th- ~
~e o~tr~lder ~- uoed ~ l~ple 8. Then, eaoh ahe-t ~-~la8 ~omled i~to ~ oup ha~ing th~ 8~e ~hape a~ th~t or ~ -th- cup Io~sd in ~pl0 10 ~md a ~rall thiclc~sos o~ 0.3 by ~g the s~e mold a~ used in B~l- 10 ao~ord- ;
~g to a ~olid pha9Q alr-pre8~Ure ~0~ g laothod ( plug al~8i8t air-pres~ure fo~i~g m~thod ) .
For comparison, ~o~o o~ ~heets pre~ar~d ~ro~ th~
foregoing re8in ble~d~ ~ers ~on~-d i~to cup8 ~laYing tho . .
~e 8hape a~ de~cribed abo~o acocrd~g to a lmo~
ofox~ing method ( melt ~olding method ).
The ~old~bility, the ~ppearanoo ~d tho o~rg n pcr~-~tion rate detorai~od acoord~g to the ~cthoa 20 do~er~bed in l~tample 10, ~ rore o~ td Irith r J-pcct to cach of the Be prepared cup~, ~r~ eho~m in ~sble 19 o . - - - ~ . . . ~- -- - , .

:. .. ~ . : -- .-o_ ~LOS;~S~ , ~ ~ r - ~ ~
e~
0O ~ ~ a~
P r- ~ u~ 0 ~ t- ~ ~ I u~ ~ ~o ~ ~0 _ ~3 r~ O ~ ~U ~1 C~l ~1 N t-~
~\ ~D
o ~ d 0~ ~_ 0 ~ ~ ~ h C~ ~ O
h O O O ~e o 0o o ~ o P~ 0 ~ ~ ~ ~ P~ ~ ~ d P. +~ ~ I ~ ~ ~ ~ ~ ~1 0 v 1~
P.~
O rl h ~ ~1 0 ~ ~ O
h .~
O ~ ~ * ~1 o o o o ,~ o o o o ~ ~ o o ~a ~ ~ ~ ~ ~ c~
~ gD ~ qo ~ g ~: X a~ P' ., ~rl . o ~ :
~I ~oo~
~1 I ~ ~
~_ 0 ~ o o o o C~ ~ o ~ U~
rl'd h~rl U~ u~ a) ~ lJ~ ~ O C) O O 1 ~~ ~ O ~
E~~ ~rlOOOOOOO'I OOOOO
X ~D cl-- ~ ~ ~ ~ ~ ' ~ H ~ ~ ' ~3 ~ ~ ~ ~ ., ~ " ~ ~ , ~ ,, ~ ~ ~
o~ ~1 ~ d ~ d ~
~o ~ m ~ ,~ ~ ~ 4 ~_ ~ ~ q O ~ O I I I I I I O ,~ O d o U~ U~ o o o o ~ U~

o o ~

m ~ d ; 2; z ~ ~ Z z; z~ ; x * * *

-- . ,. ~ . -.
.. . . ~ . -- : .- ;

.;. . : ~ .. . . - . : .. . : ~
- - -.

lOS;35~2 A~ ~ill be apparont fro~ the rosults sho~n in T~ble

9, i. CUp9 I ormcd by the solid phase air~ oml-~3 meth~d, the oxygen perm~at~on rQ~i~tR~off all~ tra~a-psroncy aro rem~rkablg i~provcd by the drawi~g e~ieat 5 and are much high~r than in aup8 ~or~ed by the heati~g ~oldi~g m~thod. Further, in aonnectioll o~ the Dlolda~i-lity, ocaurrence of an u~desired phonome~on of thiok~o~
non-unifo~ity can bc e~ectively prevented ~y adopt~on of the ~olid phase air-pressurs ion~in~ IDothOd. ~rom the re~ults ~hown in ~abl~ 19, it ~ill al~o bo ~oon that in caso o~ a resi~ combina$io~ in ~hioh the dit~er-Q~ae ( ~p ) of th~ solubility param~ter i~ gr~ater than 4.5, ior e~ample, i~ case o~ a combination of ~1 and P~ or ~2 and PP, the drawability i8 muoh in~erior and ~oldi~g ac~ording to th~ solid phase air-pre~ure ~ormi~g method i8 impoosible.
E2CamP1e 1~
By uoing a 3ymmetric 5-ply T die ~or multi-layer e~tru~io~ ~noluding the same inn~r and outer lay~r e~t-ruder s~d intenmedi~te lay r e~truder a~ deecrl~a $nB~a~plo lO and an adh~ la~er e~truder in~talled ~th a ~ull-flighted screw h~ving a diamoter o~ 40 ~m a~d aDi offeotiv~ length o~ 890 ~m, sheets o~ a ~ysm~-trio multi-layer structure having a width oi 200 mm and a th~cknes~,of about 1 mm were propared ~o that th~
~nner and outer layer: adheBiVe layer ; lnt~r~0di~te layer thi~knese ratio wa~ 1 : 0.05 ; 0~1. Re~ns used rOr respoct`ive layer~ are a~ ~ollow~:

~ 03 .."

105;~5~32 Inten~diate layor:
ture oontaining the ~ame polyoaprolaetal~ (1l1) and oaprolactam/he~ thylen~ diam~o~ium adipat~
copolym~r (~2) ~ desaribed ln Es~ple 8 and ~>oly-p-~ylylene-sdipamide ( e,ro~atic poly~mide, 113 ) ha~l;l~g 9p v~ue o~ 11.9 ( oa:L/¢c 31/2, a m~lting po~nt or 240C. a3 Dl~a~ured accord~g to the ~thod d~oribed in 13~:ample 1 aI~d a~ o~ygen pe~meability o~ 0.041 x

10 11 cQ.Q~/cm2.sec.'EIg as measurod at ~7C~ and 0 ,9~ I, at a mi~g l,reight ratio indicated ~n ~abl~ 20.
~lheslvo Lay~r ( dispo~od on e~ch ~idc of` intemlediat-l~yer );
~he ~ame ma~eic aDhydri~e-modi~ied ~thylene-propyle~e ¢opolymer a~ described in Example 11.
Inner and Outer Layers ( disposca on both sidee oi adheeive layor~ ):
~he ~ame i90tactic polypropylene ae deecribed in ~smple 8.
~a¢h of the ~o obtained 4 ~heets wa~ uniformly h~sted in an atmosphere maintainod at 150C. for 30 ~inuto~ and molded into a cup having the sa~o ~hape a~
that o~ the.¢up obtained in Example 10 according to the ~olid pha~e air-pre~ure iorming mothod.
For compari~on, each of the iorsgoing 4 ~hoets w~
iormRd i~to a cup ha~lng the aa~e ahape aa de~crlbod above ~ccordlng to the thermoiorring ~ethod.
With re~pect to eaoh ef the ~o prepared cup~, tho moldability was eYamined, the haze ( Hz ) Wa8 determinod ~:

: - 104 -,,. ~ . . , . -: . . , :

.
.. ~. . . -.

~053sg2 -accord~n~ to the mcthod o~ JI~ K-6714, and tha o~Cyg~ll po~msation rate (Q23 wa~ d~termiIlod a¢cording to the method describ~d in Example 10. Obtained rosult~ are ~ho~n in Tabla 20.

.
.

~ ~-105;35~2 ~ C~
~o~ ..... a~`
,, ~ ~ ,, -' ~
~D"
o_ -m u~ ~ ~ ~ N ~I N ~ '~
~1~ o Oi oo o~
æ

~ d D~ ~ ~o ~5~

h h O O O O C~ O O O
0~ ~ ~ ~ S ~
0 ~ 1~
~ ~ 11 11 1~ 11 11 11 11 11 e~ e ~ .

# 0 ~ O O O ~ ~0 0 ~ ~0~ e~ ~
P O ~

: . .. - - : . :
,,. , .. .. .. .. . . ~ .
:: - - .: . . . . .:
- ., : ., ... ; - , : : : .
. ~ .. .... . . .

~053S~
From the re~ult~ ~ho~m in Table 20, it rill roadily be u~der~tood that ill aup~ prepared according to th-solid phaHe ai~pro~ure îo~ng m~lthod, tho transpa-r~ncy and ox~gen permeation roai~ta2l¢e aan be r~ar~bly 5 ~mproved a~d are much hiBber th~n in aup8 ioml~d by th~ the~ofo~ing mqthod.
~ mple ~
t~ of a symmetri¢ 5-layer structuro having a width v~ 200 mm and a total thicklless of 1 m~ in whioh 1~) tho outer and innor layer: adheoive layer: i~ton~- s di~to layer thi~kness ratio oi 1 : 0.05 : 0.1 ~ero prepared by using the ~ die typo ~hBot iorm~ng Daohi~
described ln E~a~plo 13. Resins used ~or ro~peotive layer~ are as iollows:
Intermediate Layer:
~ mi~ture co~taini~g the aame sthyleno-vinyl alcohol copolymer (BV) a~d caprolactam~h~amethylono d~ammonl~m adipate ~pgly~er (N2) a~ do~orib~d in ~amplo 8 at ~n Er/~2 ~i2ing weight ratio oi 7~/~0 or 50/50.
~dhe~ive Lay~r: -: ~ mixture of modi~iea polypropglene ( QB 010 ~:
manuiact~red by Mit~ui Potroch~mtc~l Oo.; hereinaiter :
ro~orred to as " oMPl " ) formed bg chemiaally modi~ying i80taotio polyprop~lene ~ith an unsatursted oarbo~yli~
a~id and a~ u~eaturatea carboxylia acld-modiiied ethyla~e-vinyl acstate ~opolymer ( modi~ied ~Y~; hereina~t~r rs~erred to a~ " CWP2 ~l ) di~closed as an adhesive re~in ~or bonding polyol~n to an ethylene-~inyl alcohol :;

,. . . ..
.- . . .
- - .;
- '~ , ,.

1(15~9~
copolymer in J~pane~ Pabent ~ppliation L~ld-O~en Specl~ioation No. 76~66/76, at a C~Pl/C~P2 ~i~ing weight ratio oi 30/70 or 50/50.
Inner and Outer ~ayer~:
~he ~a~ i90ta~tic polypropylen~ ( PP ) a~
deccribed in ~*3mpl~ ~0 Ba~h of the so preparsd 4 ~heot~ ~a~ uniforaly h~ated in an atmoaphe~e ~ai~tained at 150a~ for 30 m~nutes. ~hen, a c~p~ ~ero prepared ~rom the ~o ~,~at-treated ~he~t~ according to the ~ame ~olid phase a~r-prossure ~orming method and thermoforming mcthod a~
deccrlbsd i~ EXamP1Q 130 With ro8peot to ea~h of tho ~o prepar~d oupc, the haze ( Hz ), o~yge~ permeation rate and the ~ peol str~gth ( adb~sion ~trength oi sam~lo 2 c~ i~ width :~
at a peeli~g 9p~d O:e 100 n~in ) wore detersli~ed aooording to tho ~ame methodo ~8 deoarib~d in ~a~plo 13 to obt~in r98ult8 shown in ~!able 21.
Four oup~ indic~ted in ~ablo 21 were ~ lod with ~ 50 mi~ture oi wator and ~alad oll, a3~d each cup had the mouth portio~h~at-soaled wlth an alwainum-la~ina~ed i~ ~d ~as allowed to ~ta;~d 8t~l1 ln an sutoclsve maintain~d at 120a, a;~d 1.5 at~pher0s ~or 60 Dlinutes, iollowing whiob the water/a~lad o~l mi~ture ~ di~oharged ~rom the oup. The appeara~oe ~onditions ~ peeli~g betwoen the adJacent layors, ~:
da~age and dei~or~ation ) of ths 80 heat-troated aup~
w~re e~in~d to obtai~ result~ ~hown in Table 21.

.. . .........

. .

~0~3S~Z
From tho r~ult~ ~ho~~ Table 21, it w~ll ro~dily be under~tood that ill OUpA mold~d accordlng to tho ~olid pha~e air-pro~sur~ io~m~ng ~ethod, th~ tN~-parency and o~ygen perm6ation resist~n~e ca~ b~ highly 5 ~proved and ar~ much hi~h~r tha~ in cup~ i~or~ed s,ocord-~ng to thc cuatoma~y the~ofon~ing method.

. , , . , . :
, ~:, :-... . .

.
. -.. . - : . . ~
. ~. . .

0 ~ qD
O ~ ~ ~ ~ ~
~ ,c g~ ~\
q~ ~ h ~ h ~ * * c 1:1 * *
0~ a, 0 ~ a o q~ h h ~:~ o o ~C~0~ ~ ~
r~

h ~D
~ ~ ,~
o _b o O~Pi _~
:rt _ ~ ~D ~ ~ ~ ~P~ ~ :
N li~ 0 ~t ~ ,.
.
h O O O ~ O O O O
~ ~ O O O~ o O ~C~
.~ ~a o t~ ~ ~ ~~ ~ ~ ~u~
~ ~ ~ ~t ~ t 11 11 1111 ~ ~ CU ~ ~~ ~ ~ ~ ~
X~ g ~g~gg~

~ O , .
O
~ ~ O S O ~t O ~ O
~ 0 c~ ~ ~ ~S~ ~ ~ ~ ' a ~ h 0 ~1) P~ t p~
0~1~ ~ Yt l~t ~ lYt ,~S;~ a ~t 0 ~ ~t ~o 0~ ~ S

~0 '~ bD ~ ~ O
C~ ~~ ~ o ~t ~ ~ d ~ h~ d d o 0 o~o ~
al ~ ~ ~ *

- llo - 10535~2 ,~ . .

`~ lOS~S~
~3~ample 15 ~3heot~ of a ~ etric 5-l~yer structure h~l~ing a width of 200 ~ and a total thiclmeo~ o~ hich the innor and outer lsyer:adheslvo lsy~r:inton~lodl~t~
layer thickness rat10 o~ 1: 0.05: 0.1 were pr~plLr~
by u~ the ~ame T die type ehoot iorming alachin~
described in li~:ample 1~. ~e~ine u~ot ior respoct$Yo ls,y~rs s,re as follo~s:
Intermediate Layer~
A mi~ct~re fon~ed by d~-blondi~g at a ~oi~t r~t~o Or 50J 50 the aame othylene-~yl alcohol copol~or ( BV) and caprolactam/he~ ethyl~no dia ~ o~ium adipato copolymer ~ N2 ) a~ doscri~d ~ B~a~ple 8.
~dhesive Layor;
A mi~ture formed by dry-bl~nding the aa~o c~prol-actam4he~methyle~e diammonium adipate oopolymer ( ~2 ) a~ doscribed in B~ample 8 and th~ same maleic ~nhydride-modiiied ethy~ene-propyleno copolymer ( a) a~ de~oribed in B~amplp 11 at an N2J(d) mi~ing weight ratio o~ 40~60.
Tnner a~d Outer ~ayer: :
The same ethylen~-propylone copolymer ( PP~ ) 80 desoribed~ ~n Ezamp~e 11.
~a¢h of the 80 preapr~a sheets ~as unifor~ly ~eatod in an atmo~here ma~ntainad at 150C. ior 30 minu~ee, ana tho heatea sheet~ were molded into ~up~
ao¢ording to the sam~ solid ph~oo air-pressuro iorming methOa ana thermo~orming method as deacribed in B~a~ple 13.

--- ~ ~ . .... .

. . :: - - . : . .-.
.: ~ - - - .. . ..
. .. . . - - . .. - . -..... : .. - . -~
,, ,...... .. ~ .-. - - -, :~ . :

lC~S;~S~Z

For oompari~on, cup~ having the ~Qme ~ha~G, dl~n-ei~n~, thickness and thickne~ ~atio as des~ri~d ~bovG
~ere ~old~d in the ~ame ~anner R~ d~scrlbed ~bo~s ~coor- -ding to the solid pha~e air-prossure ior~in~ ~o~hot aDd ~h~ ther~oformlng ~ethod by U8i~g as the i~tor~ediat~
lR~er-constituting re~in a ml~turo formod ~y dry~ nai~
tho abor~ ethylone-vinyl alcohol copolymer (~Y) a~d tho ~am8 isotaatio polypropyleno ~ PP ) and #urlyn ~ A ( $U ) as dsscribed in ~ample 8 at a~ BV/PP/~U ~ g w~i~ht }o ratio oi 50/40/10, as ths adheaiYe lay~r-con~tituting resln a misture fo~ed by dry-ble~ding th~ ~a~e U~8~U-rated carbo~ylic aoid-modi~i d ethylen~-vi~yl aa~tat~
¢opolym~r (C~P2) and unsaturQtea carbo~yli~ ~cid-~odi~ied polypropyl~ns (CMPl) ~ aes¢ribed ln B~a~pl-l~ at a CMPl/CMP2 mi~ing ~ight ratio oi 40~60 and ~
th~ innor and outer layQr-constituting re~in the abo~ -~ontioned ethylene-propy~0n~ copol~m0r (PPB).
With re~pe~t to ea4h of ~he oo preparod ~ cu~o, th~ haze (Hz) of thB eup sid~ wall, th~ o~yge~ per~eation rate Q2 and tho l~t~rlsminar ~trongth wero doton~ined accor~ing to th~ m~thods doocirib~d in B2a~le 14 to obtain ro~ult~ ~ho~ in Tabl~ 22.

.. . ~ , : . . , ~ . .

: , - :
. . : , - . :

~4 A losj~5~ ?

h N Il) N ~ ~ N

P~
a~
~0 r~
O E~
~D ~' h C~ ~ 110 0~. ~I N
~ aD
~_ ~
~0 ~ C>
~,~

~:
_. ~ O ~ ~
N N r~ O
:~
~1 N

r1 t~J rl ~1 ~ Z; ~ ~ ~

~ ~ ~ .
.
O ~Z; ~ :Z; p~
~! h O ID

~ tlD
~ ~ h ~1 a:
b ~ O o h~ ~ o ~
,~
O O-r~ O
~:

lC~S3S5~'~
Thls ~xample lllustrate~ retorable container~ ior ~hich an e~pecially h~8h adh~eion ~trength i9 required.
~rom the result~ shown in Tablo 22, it will r~adily be under~tood that i~ 8 ~olded structur~ ao~pri~ing an inter~diate layer composed of a mi~ture Or an ethylone-~inyl alcohol aopolymer and a capro~actamJhfl~amethyle~e diam~onium adipat~ copolymer, the o~ygen porme~tion re~istance can be hiehly improved by the dra~l~g ~if~at ~ccording to the ~olid phase alr-pressure forming. T~e haze ( Hz ) of this cup ia a little in~rior to ~hat Or a thermoformed cup havi~g the sa~e intermediate lay~rO
The rea~on i8 that the adhe~i~e layer ie composed of a so-aalled non-~ompatible mi~ture. ~owe~er, the adhesion ~trength of this cup i8 muGh higher than that o~ t~e thermoformed cup. On the other hsnd, in a comparatiY~
cup comprising an interm~diate layer compo~ed of a ~i~c-ture of sn ethylene-vinyl aloohol copolymer, polyprop~l-ene and ~urlyn(~ , any of the haze, o~rgen permeation resistsnce and peel ~tren~th i~ not improv~d by the 20 draw~ng effect a¢cording to the 801ia pha~e air-pre~urod form~g

Claims (19)

What We Claim Is:

1. A molded container having a wall composed of a thermoplastic resin oriented in at least one direction on the wall face, wherein the container wall has a layer of a blend composed mainly of a plurality of melt-extrudable thermoplastic resins, each of which has a solubility parameter ( Sp ) of at least 9.5, at least one of said thermoplastic resins has an oxygen permeabi-lity lower than 5 x 10-11 cc.cm/cm2.sec.cmHg, said thermoplastic resins are chosen so that the difference ( .DELTA.Sp ) of the solubility parameter in said thermoplastic resins is not greater than 4.5, the elongation of said resin blend is higher than the arithmetic mean ( ? ) of elongations of the respective thermoplastic resins, and wherein the container has a thermal shrinkability ( .delta. ) of at least 5 % in the orientation direction of said container wall.

2. A molded container as set forth in claim 1 wherein the thermoplastic resin having an oxygen perme-ability lower than 5 x 10-11 cc.cm/cm2.sec.cmHg is an ethylene-vinyl alcohol copolymer having an ethylene content of 25 to 50 mole %.

3. A molded container as set forth in claim 1 wherein the thermoplastic resin having an oxygen perme-ability lower than 5 x 10-11 cc.cm/cm2.sec-cmHg is at least one member selected from homopolyamides and copolyamides having 3 to 30 amide groups per 100 carbon atoms in the molecule.

4. A molded container as set forth in claim 1 wherein the thermoplastic resin having an oxygen per-meability lower than 5 x 10-11 cc.cm/cm2.sec.cmHg is an aromatic polyester.

5. A molded container as set forth in claim 1 wherein the thermoplastic resin having an oxygen permea-bility lower than 5 x 10-11 cc.cm/cm2.sec.cmHg is a ther-moplastic polymer containing 60 to 86 mole % of a nitrile group-containing ethylenically unsaturated monomer.

6. A molded container as set forth in claim 1 wherein the blend is composed of a plurality of thermo-plastic resins having an oxygen permeability lower than 4.3 x 10-11 cc.cm/cm2.sec.cmHg.

7. A molded container as set forth in claim 1 wherein the blend is one formed by combining at least two members selected from ethylene-vinyl alcohol copolymers, polyamides, aromatic polyesters, high-nitrile resins and chlorine-containing polymers so that the .DELTA.Sp value is not greater than 4.5.

8. A molded container as set forth in claim 1 wherein the blend is one formed by mixing weight ratio (A) : (B) of from 90 ; 10 to 10 : 90 so that the elonga-tion of the blend is higher than the arithmetric mean ( ? ) of elongations of respective resins.

9. A molded container as set forth in claim 1 wherein the blend contains up to 40 % by weight based on the blend of a polyolefin, a styrene polymer, an elasto-mer, an ethylene-vinyl acetate copolymer or an ionomer.

10. molded container as set forth in claim 1 which is formed from a parison of said thermoplastic resin blend by biaxial draw-blow molding and has a unit volume of 0.01 to 5 d? per gram of the resin blend.

11. A molded container as set forth in claim 1 which is a seamless cup-like container formed from a sheet or film of said thermoplastic resin blend by plastic processing and having a unit volume of 0.01 to 5 d? per gram of the resin blend.

12. A molded container having a wall composed of a thermoplastic resin oriented in at least one direction on the wall face, wherein the container wall has a multi-layer structure including at least one layer of a blend composed of a plurality of melt-extrudable ther-moplastic resins, each of which has a solubility parameter ( Sp ) of at least 9.5 and at least one layer composed of a moisture-resistant thermoplastic resin having a moisture permeability lower than 100 x 10-12 g.cm/cm2.sec.

cmHg as measured at a temperature not exceeding 50°C., at least one of said thermoplastic resins in the blend layer has an oxygen permeability lower than 5 x 10-11 5 x 10-11 cc.cm/cm2.sec.cmHg, said thermoplastic resins of the blend layer are chosen so that the difference ( .DELTA.Sp ) of the solubility parameter in said thermoplastic resins is not greater than 4.5, the elongation of said resin blend is higher than the arithmetic mean ( ? ) of elongations of the respective thermoplastic resins in the resin blend, said multi-layer structure has an interlaminar bonding strength of at least 20 g/cm, and wherein the multi-layer structure has a thermal shrin-kability(.delta.)of at least 5 % in the orientation direction of said container wall.

13. A molded container as set forth in claim 12 wherein the moisture-resistant thermoplastic resin is a polyolefin or a copolymer of an olefin with a carbonyl group-containing ethylenically unsaturated monomer.

14. A molded container as set forth in claim 12 wherein the multi-layer structure includes an inner layer of said moisture-resistant thermoplastic resin, an intermediate layer of the blend and an outer layer of said moisture-resistant thermoplastic resin.

15. A molded container as set forth in claim 12 wherein the moisture-resistant thermoplastic resin is a polyolefin, the layer of the blend is formed adjacently to the layer of the polyolefin, and a thermoplastic polymer having a carbonyl group content of 120 to 1400 meg/100 g of the polymer is incorporated in the blend or polyolefin in an amount of 0.5 to 15 parts by weight per 100 parts by weight of the blend or polyolefin.

16. A container formed by biaxial draw-blow molding of a parison composed of a thermoplastic resin, wherein said parison has a multi-layer structure including at least one layer of a blend composed mainly of a plurality of melt-extrudable thermoplastic resins, each of which has a solubility parameter ( Sp ) of at least 9.5, and at least one layer composed of a creep-resistant thermoplastic resin in which the sum of the instantaneous modulus ( Eg ) and retardation modulus ( E1 ) at a temperature of 23°C.
and a stress of 7 x 107 dyne/cm2 is at least 1 x 1010 dyne/cm2 and which has a steady state flow viscosity ( ?? ) of at least 1 x 1017 poise and a retardation time ( tR ) shorter than 6 x 106 sec, at least one of said thermoplastic resins in said blend has an oxygen permeability lower than 5 x 10-11 cc.cm/cm2.sec.cmHg, the thermoplastic resins of said blend are chosen so that the difference ( .DELTA.Sp ) of the solubility parameter in said thermoplastic resins is not greater than 4.5, the elongation of said resin blend is higher than the arithmetic mean ( ? ) of elongations of the respective thermoplastic resins in the resin blend, and wherein said molded container has a thermal shrinkability ( .delta. ) of at least 5 % in the orientation direction of said container wall.

17. A container formed by plastic processing of a film or sheet composed of a thermoplastic resin, wherein said film or sheet has a multi-layer structure including at least one layer of a blend composed mainly of a plura-lity of melt-extrudable thermoplastic resins, each of which has a solubility parameter ( Sp ) of at least 9.5, and at least one layer composed of a creep-resistant thermo-plastic resin in which the sum of the instantaneous modulus ( Eg ) and retardation modulus ( E1 ) at a temperature of 23°C. and a stress of 7 x 107 dyne/cm2 is at least 1 x 1010 dyne/cm2and which has a steady state flow viscosity ( ?? ) of at least 1 x 1017 poise and a retardation time ( tR ) shorter than 6 x 106 sec. at least one of said thermoplastic resins in said blend has an oxygen permeability lower than 5 x 10-11 cc.cm/cm2.
sec.cmHg, the thermoplastic resins of said blend are chosen so that the difference ( .DELTA.Sp ) of the solubility para-meter in said thermoplastic resins is not greater than 4.5, the elongation of said resin blend is higher than the arithmetic mean ( ? ) of elongations of the respec-tive thermoplastic resins in the resin blend, said multi-layer structure has an interlaminar bonding strength of at least 20 g/cm, and wherein said molded container has a thermal shrinkability ( .delta. ) of at least 5 % in the orientation direction of said container wall.

18. A molded container as set forth in claim 16 or 17 wherein the creep-resistant thermoplastic resin is a member selected from the group consisting of polyethy-lene terephthalate, polybutylene terephthalate, poly-carbonates, acrylonitrile-butadiene-styrene resins, acrylonitrile-styrene resins, polyacetals, polyamides, polymethyl methacrylate, isotactic polypropylene, poly-styrene, polyacrylates, polyphenylene oxide and poly-sulfones.

19. A molded container as set forth in claim 16 or 17 wherein said parison or said sheet or film has a multi-layer structure including an inner layer of said creep-resistant thermoplastic resin, an intermediate layer of said blend and an outer layer of said creep-resistant thermoplastic resin.