CA1292219C - Composition, process for producing the same and multi-layer structure - Google Patents

Abstract

Abstract of the Disclosure A composition comprises a matrix of an ethylene-vinyl alcohol copolymer having dispersed therein a drying agent in a particulate state, among grains of which drying agent a volume-area average diameter of the grains having a long diameter of not less than 10 µ is not greater than 30 µ. A multi-layer structure comprises layers of such a composition. Gas barrier property of the multi-layer structure is substantially scarecely reduced after a retort treatment and thus, the multi-layer structure is extremely useful for packaging of food, especially packaging of retorted food.

Description

COMPOSITION, PROCESS FOR PRODUCING THE SAME
AND MULTI-LAYER STRUCTURE

EI~Lo D~ IH3 IN ~urlcn The present invention relates to a composition having a high gas permeability resistance because of drying agent grains having good dispersion in an extremely particulate state in a blend of ethylene-vinyl alcohol copolymers (hereafter simply referred to as EVOH) and the drying agent without orming any big mass aggregated with each other, a process for producing the same and a multi-layer structure comprising the same.
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BRIEF DESCRIPTION OF THE PRIOR ART
Compositions comprising EVOH and drying agents are disclosed in U.S. Patent Nos. 4,425,410 and 4,464,443, indicating that multi-layer structures comprising the compositions have a small increase in oxygen permeability even after a retort (steam sterilization) treatment, as compared to the case in which EVOH
is use~d and are pre~erable as packaging materials.
When a container is prepared in accordance with the method disclosed in the U.S. patents supra and applied to storage o~
food which requires a retort, however, gas permeability :
;~ ~ resistance is improved as compared to the case of using EVOH but the degree of the improvement is still poor and the container is :

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unsatisfactory yet for purposes o improving storability of food which requires a steam sterili~ation treatment to a high degree.
On the other hand, as a method for preventing increase in a rate of oxygen permeability upon retort treatment of multi layer structures comprising EVOH, there are ~nown methods which comprises blending a drying agent in an adhesive resin layer, etc. proximate to EVOH, as shown in U.S. Patent No. 4,407,897 or Published Unexamined Japanese Patent Application No. 170748/82.
In these cases, the adhesive resin layer containing the drying agent should be used in a thick thickness in order to exhibit effective effects. Such causes a problem from an economical viewpoint and in addition, the effects are not satisfactory yet from a practical standpoint (Comparative Example 4).
Under such circumstances, the present inventors have made extensive investigations on molding techniques over a wide range for purposes of controlling a blended state of a blend composition and studied relationship between the blended state of the obtained composition and a rate of oxygen permeability of multi-layer structures upon a retort treatment. As a result, it has been found that graininess and dispersed state of the drying agent grains dispersed in an EVOH matrix greatly affect the rate of oxygen permeability and succeeded in obtaining the composition free rom the deects as described above.

SUMMARY OF THE INVENTION

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~25S2219 (The present invention is directed to a composition comprising a matrix of an ethylene-vinyl alcohol copolymer having dispersed therein a drying agent in a particulate state, among grains of which drying agent a volume-area average diameter of the grains having a long diameter of not less than 10 ~ is not greater than 30 ~, a process for producing the same and a multi-layer structure comprising the composition as a layer(s).
The structure, especially mul~i-layer structure, obtained using the composition of the presentlinvention results in gas permeability resistance to such a high degree that is comparable to the state prior to a retort treatment even after the retort treatment, which has been even unexpected. Containers prepared using such a multi-layer structure are extremely useful for packaging of food over a wide range.
lSDETAILED DESCRIPTION OF THE INVENTION
_ _ The ethylene-vinyl alcohol copolymer (EVOH) as used in the present invention is any optional product o~ hydrolysis of a ; copolymer of ethylene and vinyl acetate at the vinyl acetate unit contained therein. Copolymers which are suited for the purposes of the present invention include those particularly having the ethylene unit content of 25 to 60 mol~ and a saponifica-t;ion degree in the vinyl acetate component of at least 96~, preferabIy at least 99%. For the value of melt index (190C, 2160 g), a range of 0.2 to 60 9/10 mins.

2~ is exemplified. Further EVOH referred to `:

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21g in the present invention may be those modified with a copolymerizable monomer in a range of not greater than 5 mol~.
Examples of such monomers for modification include propylene, l-butene t l-hexene, 4-methyl-1-pentene, acrylic acid esters, methacrylic acid esters, maleic acid, fumaric acid, itaconic acid, higher fatty acid vinyl esters, alkyl vinyl ethers, N (2-dimethylaminoethyl)methacryalmides or quaternized products thereof, N-vinylimidazole or quaternized products thereof, N-vinlpyrrolidone, N-n-butoxymethylacrylamide, vinyltrimethoxy-silane, vinylmethyldiméthoxysilane, vinyldimethylmethoxysilane, etc.
As the EVOH matrix, two or more EVOH resins having a different composition can also be mixed and used as a mixture.
Further additives, for example, coloring agents such as pigments, dyes, etc.; antistatic agents, UV absorbants, plasticizers, heat stabi].izers, lubricants, etc. can be incorporated in the matrix within such a range that does not impair the effects o~ the present invention.
Further as the drying agent referred to in the present invention, there are suitable salts capable of forming hydrates, namely, salts which absorb water as the crystalline water~ in particular, phosphates such as monosodium phosphate, disodium phosphate, trisodium phosphate, trilithium phosphate and sodium pyrophosphate, etc., particularly anhydrides thereof are most ~Z2i~

suited for the present invention in view of the effects. Other hydrate-forming salts, for example, salts such as sodium borate, sodium sulfate, etc. and particularly anhydrides thereof are also suited for the present invention. ~urther other hygroscopic compounds, for example, sodium chloride, sodium nitrate, sugar, silica gel, bentonite, molecular sieve, highly water-absorbable resins, etc. may also be used. These drying agents can be used in admixture of two or more simultaneously.
In the present invention, it is necessary that the drying ~ agent be dispersed in the matrix of EVOH as fine grains and the drying agent grains have a volume-area average diameter of not greater than 30 ~, preferably 25 ~ or less, most preferably 20 or less, in the grains having a long diameter of 10 ~ or more.
By forming such a fine dispersion state, the multi-layer struc-ture having a high gas permeability resistance that has notbeen hitherto achieved can be first obtained. The composition having such a fine dispersion state can be obtained only by careful combination of particular processings suited for the purpose.

Flrst, it is desired to pay special attention to the drying agent in such a manner that the drying agent having a grain diameter as fine as possible be given upon precipitation from an ~aqueous so1ution of the salts through spray drying, etc. The drying agent qrains can be classified into 30 ~ or less, : `

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ZZ~9 preferably 10 ~ or less and then provided for use but in general, the salts dried are subjected to pulverization using a jet grinder, an impact grinder, a ball mill, a vibration baLl mill, etc. The ground grains are classified into ultrafine gxains of 30 ~ or less, preferably 10 ~ or less, using a classification machine such as an air classification machine, etc. The 30 ~ or less as used herein means that the grains exceeding 30 ~ are less than 0.1~; in the volume fraction, namely, the fine grain~ of 30 ~ or less are present at least 99.9~. The graininess of the ultrafine grains is a value determined by the Coulter counter method. Upon the measurement of the graininess, the grains are preliminarily sieved through a sieve having a mesh of 10 to 75 if necessary, in order to condense a small amount of coarse grains and, the coarse grains on the sieve is analyzed by the Coulter counter method so that the coarse grains can be analyzed with high accuracy.
Next, the ultrafine grains of the drying agent described above are mixed with EVOH. ~or mixing, there are a method for mixing the fine grains of the drying agent with powders, grains or pellets of EVO~ using a conventional mixer, for example, a HenscheI mixer, a super mixer, a tumbling mixer, etc.; a method which comprises mixlng the fine grains of the dryinq agent with a melt of EVOE~ to make a master batch and mixing the master batch with powders, grains, pellets or melts of EVOH. Then, the : ' mixture is kneaded at temperatures higher than the melting point of EVOH to prepare the composition. EVOH and the drying agent grains may also be directly fed in a kneader to effect kneading, without preliminary mixing of EVOH and the drying agent grains as described above. Upon this kneading operation, the fine grains of the drying agent tend to be aggregated with each other; even if the fine grains of 10 ~ or less are used, the remarkable effects of the present invention cannot be obtained if the fine grains are agglomerated and the agglomerates exceeding the volume-area average diameter set in the present invention are formed. Accordingly, the kneading operation is extremely important in the present invention. As the kneader to give the composition having a high dispersion state, ~here are most suited continuous twin rotor kneaders such as a continous intensive mixer, a kneading type twin scxew extruder (same directions or different direction), etc. but, there may also be used batch type twin rotor extruders such as a Banbury mixer, an intensive mixer, a pressure kneader, etc. Further as another continuous mlxing devices, there may also be used rotary disks havlng an attrition mechanism such as a stone mill, e.g., KCK
Kneader Extruder manufactured by KCK Co., Ltd. Among kneaders ; conventionally used, there are a single screw kneader equipped with a kneading part (Dulmage, CTM, etc.) or handy type kneaders ~such as a Brabender mixer, etcO; in the case of using such kneaders, however, it is diffi~ult to obtain the excellent composition of the present invention.
Of these kneaders, the most preferred kneader for the purposes of the present invention is a continuous intensive mixer. Commercially available models are FCM manufactured by Farrel Co., Ltd., CIM manufactured by The Japan Steel Works, Ltd., KCM, NCM, LCM or ACM manufactured by Kobe Steel, Ltd. and the like. From a practical standpoint, it is pre~erred that a device equipped with a kneader having mounted a~single screw extruder beneath the kneader be adopted to perform kneading and extrusion pelletization simultaneously.
For the kneading purpose of the present invention, there may also be used a twin screw kneading extruder having kneading disks or kneading rotors, for example, TEX manufactured by The Japan Steel ~orks, Ltd., ZSK manufactured by Werner & Pflenderer Co., Ltd., TEM manufactured by Toshiba Machine Co., Ltd., PCM
manufactured by Ikegai Iron Works, Inc., etc.
In using these continuous kneaders, the shape of a rotor or di~k plays an important role. In particular, a gap (tip clearance) between a mixing chamber and a rotor tip or a disk top ls important; if the gap is too narrow or two wide, the composition having good dispersion of the present invention cannot~be obtained. It is most suited that the tip clearance be in the range of 1 to S mm.

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3~z~g In order to obtain the composition having good dispersion of the present invention, it has been found that kneading should be made in a unit work of the kneader of at least 0.1 kwh/kg, preferably 0.2 to 0.8 kwh/kg. The unit work is determined by dividing energy (quantity of electric power consumed, kw) used for the kneading by an amount (kg) of the kneading treatment per an hour and its unit is kwh/kg. In order to produce the composition of the present invention, it is required that the kneading be performed at a unit work ~alue higher than that adopted for conventional kneading. To render the unit work at least 0.1 kwh/~g, it is insufficient to merely increase the rotation number of a kneader but it is preferred to cool the composition during kneading with a jacket, etc. thereby to lower the temperature and increase the viscosity. If the kneading is conducted in such a state that the viscosity is low, it is difficult to obtain the composition contemplated in the present invention. Accordingly, it is effective to conduct ~he kneading at a kneading temperature ranging from the melting point of EVOH
to a temperature higher than the melting point by 60C, more preferably ranging from the melting point of EVOH to a temperature higher than the melting point by 40OC, at a discharged resin temperature in an outlet of a kneading part.
It is desired that the rotation number of a rotor of the kneader be in the range of 200 to 1200 rpm, more preferably 400 _ g _ 2~9 to 1200 rpm. The inner diameter of the chamger in the kneader is generally 30 mm or more, preferably in the range of 50 to 400 mm (D). It is preferred that L/D of the kneader be 4 to 10.
Further the kneader may be single or two or more kneaders combined together may also be used.
Longer the kneading time, the better the results; in view of thermal deterioration or change of EVOH or from an economic standpoint, however, the kneading time is generally in the range of 10 to 600 seconds, preferably 20 to 200 seconds, most preferably 20 to 100 seconds.
There is no particular restriction to the ratio of EVOH to the drying agent used but the ratio of 97 : 3 to 50 : 50, particularly 95 : 5 to 70 : 30, by weight, is preferred.
Measurement of the graininess of the drying agent grain in the composition is made by the microscopic me hod; in general, the graininess is determined by visual observation or an image analysis device with respect to a photography of the grains. In the present invention, it is required that among the dispersed grains, the volume-area average diameter of the grains having a long diameter of 10 ~ or more is not greater than 30 ~. The long diameter as used herein means a distance between two parallel lines which give the longest distance when a projected image of each grain is inserted between the parallel lines. Regarding the grains having a long diameter of 10 ~ or more, an average grain ~:

~I Z~2~19 diameter must be determined. Various methods are known to determine the average grain diameter; a convenient method suited for the purpose of the present invention is that an average value D of a long diameter L and a diameter B in the direction rectangular to L is rendered an average diameter. This method is one of the methods often adopted to one skilled in the art.
Thus, when its average diameter DN is determined with respect to N numbers of grains in an appropriate measurement range (200 ~ x 200 ~), its volume-area average diameter DAV is defined as follows:

AV ~ DN /~DN

As has been made clear in the present invention, the volume-area average diameter of the grains having a long diameter of at least 10 ~, among the drying agent grains in the composition of the present invention, greatly affects the gas permeability resistance of the multi-layer structure comprising this composition as a layer(s). The reason is not necessarily clear but it is assumed that grains having a large grain diamter would be particularly disadvantageous for a hygroscopic effect or gas permeability rèsistance of EVOH.
From a practical viewpoint, it is most effective to use the thus obtained composition generally in a multilayered state with Z~19 the other thermoplastic resins. Examples of the thermoplastic resins include a polyolefine resin, a polyamide resin, a polyester amide resin, a polyester resin, a polystyrene resin, a polyvinyl chloride resin, an acrylic resin, a polyvinylidene chloride resin, a polyurethane resin, a polyacetal resin, a polycarbonate resin, etc. Among them, particularly lmportant for the present invention in their effects and practical efficiencies are a polyolefine resin; a polyamide resin, a polyester resin and a polystyrene resinl are also important.
Examples of the polyolefin resin includes polyethylene of high density, medium density or low density; polyethylene copolymerized with vinyl acetate, an acrylic acid ester, or ~-olefins such as butene, hexene, 4-methyl-1-pentene, etc.;
ionomer resins, polypropylene homopolymer, polypropylene graft-copolymerized with ethylene, or polypropylene copolymerized with a-ole~ins such as ethylene, butene, hexene, 4-methyl-1-pentene, etc.; poly-l-butene, poly-4~methyl-1-pentene, or modified poly-olelfins obtained by reacting the aforesaid polyolefins with maleic anhydride, etc.
Examples of the polyamide resin include polycapramide (nylon-6), poly-~-aminoheptanoic acid (nylon-7), poly-~-amino-nonaic acid (nylon-9), polyundecanamide (nylon~ , polylaurine lactam ~nylon-12), polyethylenediamine adipamide (nylon-2,6), polytetramethylene adipamide (nylon-4,6), polyhexamethylene adipamide (nylon-6,6), polyhexamethylene sebacamide (nylon-6,10), polyhexamethylenedodecamide (nylon-6,12), polyoctamethylene adipamide (nylon-8,6), polydecamethylene adipamide (nylon-10,6), polydodecamethylene sebacamide (nylon-10,8), or a caprolactam/
laurin lactam copolymer, caprolactam/he~amethylene diammonium adipate copolymer, laurine lactam/hexamethylene diammonium adipate copolymer, hexamethylene diammonium adipate~hexamethylene diammonium sebacate copolymer, ethylenediammonium adipate/hexa-methylene diammonium sebacate copolymer, ethylene diammonium adipate/hexamethylene diammonium adipate copolymer, caprolactam/
hexamethylene diammonium adipate/hexamethylene diammonium sebacate copolymer, etc.
Representative examples of the polyester resin include poly(ethylene terephthalate)(PET), poly(butylene terephthalate), poly(ethylene terephthalate /isophthalate), poly(ethylene glycol~cyclohexane dimethanol/terephthalate3, etc. and further include these polymers which contain as a copolymer component a diol such as ethylene glycol, butylene glycol, cyclohexane dimethanol, neopentyl glycol, pentanediol, etc.; a dicarboxylic : acid such as isophthalic acid, benzophenonedicarboxylic acid, dlphenylsulfone dicarboxylic acid, diphenylmethane dicarboxylic acid, propylenebis(phenylcarboxylic acid), diphenyloxide dicarboxylic acid, oxalic acid, malonic acid, succinic acid, : ~ 13 -~9~

glutaric acid, adipic acid, pimelic acid, sberic acidt azelaic acid, sebacic acid, diethylsuccinic acid, etc.
Examples of the polyvinyl chloride resin include a homopolymer of vinyl chloride alone and in addition thereto, a copolymer with vinyl acetate, a maleic acid derivative, a higher alkyl vinyl ether, etc.
Examples of the polystyrene resin include a homopolymer of styrene alone and in addition thereto, polystyrene obtained by graft copolymerization with butadiene, a styrene-butadiene rubber mixture, a styrene-maleic anhydride copolymer, etc.
The thermoplastic resins used in the present invention may also be used as admixture of two or more.
It has been exprimentally confirmed that the dispersion state o the fine graines of the drying agent in the composition does not principally change during the step of forming the multi-layer structure of~the composition of the present invention ln combination with the other thermoplastic re~ins described above.
The multi-layer structure of the present invention is molded into films, sheets, cups, bottles, tubes, etc. by subjecting the composition of the present invention and the other thermoplastic :
resin to molding processing such as a co-extrusion molding ; method, a multilayered co-injection molding method, a heat molding method, etc. It is generally preferred that the ~az~2;~:~9 composition of the present invention be used as an intermediate layer and the inner and outer layers be composed of thermoplastic resins such as polyolefins,etc. In the case of preparing such a multi-layer structure, it is preferred to use an interlayer adhesive resin. There is no particular restriction to such an interlayer adhesive resin but representative ~xamples include resins obtained by modifying (addition, grafting, etc.) thermoplastic resins (polyethylene, polypropylene, an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid ester copolymer, etc.) with an ethylenically unsaturated carboxylic acid or an anhydride thereof (maleic anhydride, etc.). In addition, there may be used polyesters having bound thereto aluminum element and a monocarboxylic acid as described in U S. Patent No. 4,496,714 issued on January 29, 1985 to Murata et al.
When the thermoplastic resins,, the EVO~ composition and the adhesive resin are desiqnated A, B and C, respectively, the layer construction of the multi-layer structure can be A/B, A/C/B, A/B/A, A/C/B/C/A, A/B/A/B/A, A/C/B/C/A/C/B/C/A, etc. but is not limited thereto.
The multi-layer structure of the present invention is characterized by containing the drying agent grains in the layer of EVOH in a highly dispersed state; layers other than the EVOH
layer, for example, a layer of the adhesive resin, may also contain the drying agent.

The multi-layer structure of the present inven~ion is readily distinguishable ~rom conventionally known plastic materials because gas permeability resistance under high humidity, especially gas permea~ility resis-tance when a retort treatment is per~ormed, is asgreat as incomparable to that o~ the plastic materials. The retort treatment is performed generally at 120~C by putting a container having packed therein food in an au~oclave called a retort pot. A treatment time varies depending upon kind of food;
one is sufficient when treated for 20 minutes and when a long period of time is needed, another requires the treatment for 120 minutes. Further the multi-layer structure of the present invention is extremely useful even for food containers which require so called boiling sterilization in which sterilization is effected in boiled water under normal pressure.
It has also been confirmed that the multi-layer structure of the present invention exhibits gas permeability resistance to a high degree even for utility in case that neither retort treatment nor boiling treatment is performed. Particularly in the case that the inner and outer layers are composed of resins having high moisture permeability such as polystyrene, polyvinyl chloride, polyester, etc., there is a tendency that moisture in the container (or outside the container) permeates through the inner and outer layers to reduce gas permeability resistance of EVOH in the case that the multi-layer structure is of a film 21~

shape; however, in the multi-layer structure containing the composition of the present invention, the effect of retaining gas permeability resistance is great, a period for storage of food can be markedly prolonged and the industrial significance is great.
Next, there are various processes for producing the multi-layer structure of the present invention as described above In particular, the production of the multi-layer structure by multi-layer injection molding is described hereafter.
For the multi-layer injection molding of the present invention, various known modes are used and include (l) simple multi-layer injection molding, (2) multi-layer injection direct blow molding and (3) multi-layer injection drawing blow molding.
In the case of (l), the mode comprises injection-molding a plasticized resin directly into a container mold in a multi-layer form as a concentric multi-layer structure and dwelling, which is per se known in Published Examined Japanese Patent Application Nos. 39174/86 and 9007/87, etc. The modes (2) and ~3) comprise injection-molding into a parison (also called prefoam sometimes1 mold in a multi-layered form to mold a concentric multi-layered colosed-end parison, transferring the closed-end parison into a blow mold and subjecting to blow foaming by a pressure fluid such as compressed air, compressed nitrogen, etc. Differences between (2) and ~3~ lie in that in (2) the parison is transerred into - 17 ~

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) the blow mold together with a core having a pressure fluid blowing inlet while the parison is not completely cooled but substantially in a melt state, whereas in (3), the parison is generally once cooled to separate from the core, reheated at temperatures higher than the glass transition temperature (generally a softening point) but lower than the melting point ~or a plasticizing temperature) and then transferred ~o the blow mold, and a blowing core equipped with a drawing rod is newly inserted to draw the closed cell parison in the blow mold to the axis direction and at the same time or thereafter, the pressure fluid is blown to effect blow forming. From an aspect of physical properties, it is different in that orientation of the resin hardly occurs in (2) whereas in (3), orientation occurs.
The8e di~er~nces are known in, for example, Published Examined . .. ..
;Japanese Patent.~AFplication No. 8971/83 and Patent Disclo~e No. 501082/81 (W~ 81/00230), Published Un~mined ~a~L~se Patent Application No.
34819/aS,:etc. wi~h respect to (2). Also with respect to (3), : the dlfferences are known in Published Unexamined Japanese Patent Appllcation Nos. 128520~82, 240409/85, 152411/86, 173924/86, Z033~32/86, 219644/86, 235126/86 and 152412/86, etc~ The significance of the co-injection of the present invention is described below in more detailO The co-injection méans a method :
for molding by closing operation once using a plurality of iniection cylinders. To the contrary, according to a known ~:

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method, large mold cavities are sequentially used by the number of layers; first, injection moldlng is performed using a mold cavity for a first layer and then, the mold cavity for the first layer is opened and its primary molded article is put in a larger mold cavity for a second layer. A resin for the second layer is injected into a gap formed between the mold cavity for the second layer and the primary molded article followed by thermal fusion of the primary molded article and the resin for the second layer.
The thus obtained two-layer secondary molded article is subjected to injection molding using a mold cavity larger than the secondary molded article thereby to mold in 3 layers. Such a multi-stage injection molding involves increased numbers of molds and steps and a long cycling time.
For brevity of explanation, the co-injection will be described, taking as an example a container composed of 2 kinds of the recins and 3 layers using thermoplastic resin A in innermost and outermost layers and ~VOH having dispersed therein the drying agent (herea~ter referred to as EVOH composition) as the intermediate layer. As the multi-layer injection device, a device equipped with 2 injection cylinders lS used. First the resin A is primarily injected in part into a mold from a nozzle through a hot runner block via a mold gate to fill the resin A
~halfway the mold. The EVOH composition molding the intermediate layer is concentrically injected simultaneously or se~uentially ~: :
: ~ - 19 during of after the primary injection to form the intermediate layer. After completion of the injection of the EVOH composi-tion, the resin A is injected (secondary injection) singly to completely envelope the EVOH composition layer therein. With respect to structure of a hot runner, the order of injection such as simultaneous injection, sequential injection, etc., timing of injection, there are ~arious modifications and the present invention is not limited to the example described above. In summary, the key of the co-injection according to the present invention is that while forming a skin layer by primarily inject-ing the resin for forming the innermost and outermost layers, the EVOH composition as the core is injected (in this case, the resin A is generally injected in parallel to spread the EVOH composi~
tion) and ~inally the resin for forming the innermost and outermost layers thereby to fully seal the EVOH composition therein. When the edge surface of the EVOH composition is exposed, moisture is absorbed from the edge surface so that a poor appearance such as whitening is caused and such is not preferred.
Herea~ter the present invention will be described more specifically with reference to the examples below, wherein parts are by weight unless otherwise indicated.
Example 1 1~2219 Anhydrous disodium phosphate powders were micronized and classified using a jet grinder tMicron Jet Model MJ-3, manufactured by Hosokawa Micron Co., Ltd.) and an air classification machine (Micron Separator, manufactured by the same company). By observation of raw powdery grains with a test glass using methanol as a dispersant~ it was confirmed that a number of grains of 500 ~ or more were contained and an average qrain diameter (mediandiameter ) was 86 ~ according to the Coulter counter. After pulveriæation was performed in a similar manner, the maximum grain diameter (according to the Coulter counter) was 13 ~ and its median diameter was 6.4 ~( grains having a grain `
diameter exceeding 13 ~ were less than 0.1~ in volume fraction).
After premixing a mixture of 20 parts of the anhydrous disodium phosphate fine powders and 80 parts of EVOH tethylene unit content of 32 mol%, melt index of 1.3 g/10 mins. at 190C
under a load of 2160 g, melting point of 181C {main endothermic peaak temperature at DSC (scanning speed) lOoC/min} pellets in a Henschel mixer, high speed mixing was performed to give the mixture. Then, kneading, extrusion and pelletization were performed using a counter-rotating continuous kneader (LCM-50, manufactured by Kobe Steel, Ltd.) ~wlth two-stage mixing rotors having an inner diameter of a mixing chamber of 54 mm (D), L/D of 5.8 (first stage) and L/D of 4~2 (second stage) and having a vent at the second-stage screw section, , 2~

having connected therewith a single screw extruder~
The mixing rotor adopted in this case has tip clearance with the mixing chamber was 3 mm. The opera-tion was performed at a kneading temperature (outlet temperature) of 206 to 220OC for a kneading time of 30 to 40 seconds at a rotor rotation number of 530 to 650 rpm in a unit work of 0.3 to 0.6 kwh/kg The composition pellets obtained were designated Composition 1.
The thus obtained pellets were subjected to a hot press machine at 220C to give a thin layer having a thickness of approximately 100 y. By an optical microscope, the dispersion state of the powders in this thin layer was observed. A
photography having an enlargement magnification of 800 times was obtained. In order to improve depth of the focus, an enlargement magnification was made 50 times and a drawing magnification of the photography was increased to make 800 times. With respect to 1~0 samples prepared in the same way,`
grains having a long diameter o 10 y or more at a region of 200 ~ x 200 y were measured with their average diameter, respectively, and the volume-area average diameter was calcuated to be 17.6 y.
Next, using a co-extrusion sheet molding device equipped with 3 extruders and having a 3 kinds-5 layers type feed ~lock, a die for sheet molding and a puller, co-extrusion was performed to give a multi-layer structure of a polypropylene/adhesive ~Z~l~

resin/the above-described composition/adhesive resin/poly-propylene (thickness: 600/50/100/50/600 ~). Polypropylene and the adhesive resin used herein were UBE POLYPRO E-103D
manufactured by Ube Industries, Ltd. and ADMER QF-500 (polypropylene modified with maleic anhydride) manufactured by Mitsui Petrochemical Industries, Ltd., respectively. ~ext, using a vacuum air pressure forming machine (manufactured by Asano Seisakusho Co., Ltd.), heat forming of this sheet was performed to prepare a cup container (opening diameter of 72 mm, bottom diameter of 65 mm, height of 35 mm).
The cup was subjected to a steam heating treatment at 120C in a retort pot by 3 kinds for 30, 60 a~d 120 minutes, the cup was withdrawn. In such a state that water was charged in the inside of the cup, the opening of the cup was connected with a device for measuring oxygen gas permeability (manufactured by Modern Controls Co., Ltd.) and a rate of oxygen permeability was measured (200C, 100% RH in the inside, 65% RH in the outside). The results are shown in Table 1. The rate o~
oxygen permeability after the retort treatment was approximately twice or less than that of a container which was not retorted, and gas permeability resistance was as good as sufficient for storage of food.
~ ~ A part of the cup contalner prior to the retort treatment ; wa~ cut, taken out and heated in xylene at 120C, whereby polypropylene and the adhesive resin were melted out to give a .

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film of the composition in the container. The dispersion state of the powders in this film was observed by an optical microscope. A photography having an enlargement magnification of 800 times was obtained. In order to improve depth of the focus, an enlargement magnification was made 50 times and a drawing magnification of the photography was increased to make 800 times (Figure l-l shows a photography of the same objective enlarged to 200 times and Figure 1-2 shows its model wherein numeral l denotes a matrix and numeral 2 denotes drying agent grains).
With respect to 10 samples collected from the wall of the container at different locations, grains having a long diameter of lO ~ or more at a region of 200 ~ x 200 ~ were measured with their average diameter, respectively, and the volume-area average diameter was ~alculated to be 17.7 ~.
Comparative Examples l to 3 Co-extrusion molding,thermoforming and retort treatment were performed in a manner similar to Example l except for using E WH
(that shown in Example l) in place of the composition shown in Example l and, a rate of oxygen permeability was measured. The : ::
results (Comparative Example l) are also shown in Tabla l. Not-withstanding that the oxygen permeability rate was the same as :: ~
~that prior to the retort treatment, the oxygen permeability rateafter the retort treatment showed 10 to 100 times that of Example 1 . ' :: ~
:: ~
~ ~ - 2~ -On the other hand, 20 parts of anhydrous disodium phosphate fine powders shown in Example 1 and 80 parts of EVOH in Example 1 were premixed and then the mixture was subjected to kneading, extrusion and pelletization at a temperature of 220OC using an ordinary full-flighted type single screw extruder (inner diameter of a cylinder, 50 mm) to give pellets of the composition (this was designated Composition 2). Further kneading was performed in a manner similar to Example 1 except that the unit work of the continuous twin rotor kneader upon kneading was made 0.08 kwh/kg (this is designated Composition 3). Co-extrusion molding, heat forming and retort treatment were performed in a manner similar to Example 1 except for using Composition 2 or Composition 3 described above in place of the composition of Example 1. Thereafter, each oxygen permeability rate was measured and the results are also shown in Table 1 as Comparative Examples 2 and 3. The oxygen permeability rates in Comparative Examples 2 and 3 were 10 to 40 times that of Example 1 and gas barrier property was inferior to that of Example 1.
A part of the cup container prior to the retort treatment was cut! taken out and heated in xylene at 120C, whereby polypropylene and the adhesive resin were melted out to give a film of the composition in the container. The dispersion state of the powders in this film was observed by an optical microscope. A photography having an enlargement magnification of ( 800 times was obtained. In order to improve depth of the focus, an enlargement magnification was made 50 times and a drawing magnification of the photography was increased to make 800 times (Figure 2-1 shows a photography of the same obje~tive enlarged to 200 times and Figure 2-2 shows its model wherein numeral 1 denotes a matrix, numeral 2 denotes drying agent grains and numeral 3 denotes drying agent grains ha~ing large graininess).
With respect to 10 samples collected from the wall of the container at different locations, grains having a long diameter of 10 ~ or more were measured with their average diameter, respectively, and the volume-area average diameter was:calculated to be 56.9 ~. Further measurement was made also with respect to Comparative Example 3 in a similar manner and the volume-area average diameter was 36.8 ~.
Examples 2 to 10 Various drying agents were micronized and used in place o~
; anhydrous disodium phosphate fine powders of Example 1. Kneading and extrusion were performed together with EVOH tshown in Example 1) in a manner similar to Example 1 to give pellets of the respective compositions. Further co-injection extrusion molding, thermo forming and retort treatment were performed and each oxygen permeability rate of the container obtained was measured. The inter-mediate layer of each cup was taken out and the volume-area average diameter (DAV) of grains having a long diameter of 10 ~ or more ~,IY `' 21~

among the dispersed dxying agent grains was determined by microscopic observation. The results are shown in Table 2.
The gas barrier property of the compositions of the present invention, especially the gas barrier property of the cups using the drying agents of Examples 2 to 5 after the retort treatment is extremely high and sufficient or storage of most foodstuffs. Further in Examples 6, 7 or 8 to lO, remarkable gas permeability resistance is noted with the retorted time for 30 to 60 minutes and useful for many foo!dstuffs sufficient for a retort treatment at this level. However, with a retort treatment over a long period of time for 120 minutes, there is a tendency that gas barrier property decreases.

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Example 11 and Comparative Examples 4 and 5 Co-extrusion was carried out using a co-extrusi.on sheet molding device as used in Example 1 to give a multi-layer structure sheet having a construction of polypropylene/adhesive resin/Composition l/adhesive resin/polypropylene (thickness:
217/40/48/37/225 ~) (Sheet C). After this sheet was subjected to a steam heating treatment at 120C in a retort pot (60 and 120 minutes), one surface was made RH of 100~ and the other surface was made RH of 65-~. An oxygen permeability rate (OTR) was measured at 20OC with change of time. The change in OTR during storage for 12 weeks is shown in Figure 3-C. The sheet shows OTR
of 0.2 to 0.3 cc/m2.day.atm 3 hours after the retort treatment.
On the other hand, 90 parts of adhesive resin ~Admer QF-500) and 10 parts of anhydrous disodium phosphate fine powders used in Example 1 were premixed and then the mixture was subjected to kneading, extrusion and pelletization using a continuous ex~ruder as used in Example 1 to.give pellets of the adhesive resin composition containing the drying agent (this was designated Composltion 4). A sheet havlng a thickness and construction corresponding to Sheet C of Example 11 was obtained in a manner similar to Example 11 except that EVOH (ethylene unit content of 32 mol%, melt index at 190C of 1.3 g/10 mins.) was used in place of Composition 1 and Composition 4 described above was used in place of adhesive resin ( Comparative Example 4, Sheet B ).

:

2;~:19 After this sheet was subjected to a steam heating treatment at 120C in a retort pot for 120 minutes, OTR
was measured with change of time under the same conditions as in Example ll. The results are shown in Figure 3-B.
For control, a sheet having a ~hickness and construction corresponding to Sheet C of Example ll was obtained in a manner similar to Example ll except that EVOH described above was used in place of Composition l in Example ll (Comparative Example 5, Sheet A~. After this sheet was subjected to a steam heating treatment at 120CC in a retort pot by 3 kinds ~or 30, 60 and 120 minutes, the cup was withdrawn, OTR was measured with change of time under the same conditions as in Example ll. The results are shown in Figure 3-A.

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In Figure 3, Sheet A of Comparative Example 5 shows the OTR
values of 2.6 (retorted for 30 minutes), 9.5 (retorted for 60 minutes) or 30 (retorted for 120 minutes) cc/m2.day.atm which gradually decreases during storage;
on the other h~nd,the multi-layer structure or Shee~ C of Example 11 of the present invention shows OTR less than 0.3 cc/m2uday.atm for 3 hours to 12 weeks after the retort treatment. Further Sheet B of Comparative Example 4 containing the drying agent in the adhesive resin shows l~wer OTR than that in Comparative Example 5 retorted for 120 minutes but OTR after the retort treatment is 10 times or more than the sheet of the present invention. It is thus evident that the multi-layer strùcture of the present invention shows a markedly low OTR after the retort treatment.
Example 12 and Comparative Example 6 A composition similar to Compositlon 1 of Example 1 was obtained except that EVOH (ethylene unit content o~ 32 mol~, melt index at 190C under load of 2160 of 4.4 g/10 mins., melting polnt of 181C) was used in place of Composition 1 in Example 1 (Composltion 5).
A mu1tl-layer draw-blowing container having an inner volume of 700 ml, which had an intermediate layer of Composition 5 and ~ ~ inner~and outer layers of polyethylene terephthalate resin : :

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(hereafter simply referred to as PET (1)) having an intrinsic viscosity ~n] (dissolved in a solvet mixtbre of 50 wt% of phenol and S0 wt% of tetrachloroethane and measured at a te~perature of 30OC~ of 0.75 was prepared by co-injection molding. Namely, using a co-injection molding device equipped with two injection cylinders A and B, PET (1) was charged in cylinder A (inner diameter of 38 mm) at a barrel temperature of 285OC and Composition 5 was charged in cylinder B (inner diameter of 16 mm) at a barrel temperature of 240C. Then a part of PET (1) was injected first into a parison cavity set at a temperature of 20OC
from a nozzle through a hot runner set at 280C via a mold gate.
The injection of PET (1) was discontinued for 1 to 2 seconds after the initiation of the injection and at thè same time, Composition S was concentrically injected into the aforesaid parison cavity from the nozzle through the hot runner via the mold gate. After discontinuation of the injection for 0.1 second,~PET (1) was continued to inject again together with Composition 5. By setting the amount of PET (1) injected in this case larger than the resin amount of Composition S injected simultaneously, fillin~ was made in such a manner that the fluidizing tip of Composition 5 was flnally enveloped in the fluidizing tip of PET (1). Then, the in~ection of Composition 5 was discont}nued and somewhat thereafter, the injection of PET
~1) was discontinued. ~hus, Composition 5 could be completely ~ 33 -enveloped by PET (1) by fully filling with the resin in the parison cavity. The total injection time was 2.8 seconds. After dwelling, the mold was opened and the obtained multi-layer parison was transferred to a temperature-controlled pot. The temperature o the multi-layer parison was set at 110C and then the thus temperature-controlled multi layer parison was transferred to a blow mold and drawn twice with drawing rods to the axis direction; almost simultaneously, the multi-layer parison was drawn 3 times with compressed air of approximately 10 kg/cm2 to the peripheral direction to fit along the shape of the mold. After cooling, the product was withdrawn to prepare a container having a weight of 26 g and a volume of 700 ml.
The total thickness of the thus obtained multi-layer draw blowing container was 300 ~ at the peripheral side wall of the waist and the layer construction was inner layer of PET (1~ (160 ~)/intermediate layer of Composition 5 (40 ~)/outer layer of PET
(1) (100 y). At the same time, a multilayer container was prepared in almost a similar manner except that a resin of EVOH
alone (ethylene unit content of 32 mol%, melt flow index at 190C
under a load of 2160 g of 5.1 g/10 mins.) was used in place of Composition 5 and comparison was made.
The total thickness of the thus obtained multi-layer draw blowing container was 300 ~ at the peripheral side wall of the waist and the layer construction was inner layer of PET (1) (160 :~2~ZZ:l~

~)/intermediate layer of EVOH (40 y)/outer layer of PET (1) (100 Next, water containing carbon dioxide was filled up in these bottles and carbon dioxide gas permeability was measured with the passage of time. The results are shown in Table 3.
Method of Evaluation (1) Permeability of Cabon Dioxide Gas Saturated aqueous carbon dioxide solution having a vapor pressure of 4 atms. at 20C was filled in a container and sealed.
The container was put in a sealed hox and the content of the boxy was purged with nitrogen gas, moisture of which had been adjusted to R8 of 65%. Carbon dioxide gas permeated through the container wall was detected by Permatran C-IV carbon dioxide gas permeability measurement device manufactured by Modern Controls Co., Ltd. and the number of days until carbon dioxide gas in the container reached 15% loss was measured.

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Table 3 Comparative Example 12 Example 6 Day until carabon dioxide gas in the container reached 15% loss 33 weeks 24 weeks ' :

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From the above table, it is understood that the storability of the container according to the present invention is improved.
~xample 13 and Comparative Example 7 Using a co-injection molding device equipped with three injection cylinders A, B and C, polypropylene (melt flow index at 230OC under a load of 2160 g = 7.0, specific gravity at 23C =
0.91) was charged in cylinder A, maleic anhydride-graft modified polypropylene (amount of maleic anhydride for modification = 0.01 mol~, melt flow index at 230OC under a load of 2160 g - 7.0, specific gravity at 23OC = 0.91) was charged in cylinder B and Composition 5 prepared in Example 12 was charged in cylinder CO
A mold for 4 cups (cup opening diameter of 72 mmt bottom diameter of 65 mm~ height of 35 mm, wall thickness of 285 ~) was mounted and the temperatare was set at 20OC. The barrel temperature of cylinders A and B was set at 240C and that of C
at 220OC.
First, polypropylene was injected from cylinder A so as to fill 85% of the mold volume set at a temperature of 240OC through a hot runner block, a nozzle through and a gate~ Nex~, the modified polypropylene was injected ~rom cylinder B in a similar manner so as to fill 7.5% of the mold volume, then Composition 5 was injected from:cylinder C in a similar manner so as to fill 7.5~ of the mold volume, and finally polypropylene was injected in a small quantity to seal the ~ottom outer layer with polypropylene. After dwelling and cooling, the mold was opened and the obtained 4 multi-layer cup-like containers were withdrawn.
The construction was, starting from the outermost layer, polypropylene (2~5 y)/modified polypropylene (20 ~)/Composition 5 (40 ~)/modified polypropylene (20 ~)/polypropylene (225 ~) and the total thickness was 530 ~.
Next, a multilayer container was prepared in almost a similar manner except that EVO~I (ethylene unit content of 32 mol%, melt flow index at 190C under a load of 2160 g of 5.1 g/10 mins., melting point of 181C) was used in place of Composition 5 (Comparative Example 7). The layer construction was, starting from the outermost layer, polypropylene (225 ~)/modified polypropylene (20 ~)/EVOH (40 ~)/modified polypropylene (20 ~)/polypropylene (225 ~).
The container was sealed with an aluminum foil lid and steam-treated at 120C in a retort pot for 30, 60 and 120 minutes. Then, in such a state that water was charged in the nside of the cup, the opening of the cup was connected with a device for measuring oxygen gas permeability and a rate of oxygen permeability was measured.~ The results are shown in Table 4.
The rate of oxygen permeability after the retort treatment was ; approximately three times or less than that of a container which .

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~9Z;~19 Example 14 and Comparative Example 8 Polyethylene terephthalate resin (melt flow index at 270C under a load of 2160 g of 2.0 g/10 mins., 265OC), Composition 1 (melt flow index at 190C under a load of 2160 g, 0.7 g/10 mins.) of Example 1 described above and,as an adhesive resin,modified ethylene-vinyl acetate resin having a vinyl acetate content of 24 wt~ and a maleic anhydride modification degree of 1.1 wt% were supplied to 3 extruders to mold a multi-layer pipe having an outer diameter of 25 mm, composed of 3 kinds/3 layers of polyethylene terephthalate resin/adhesive resin/Composition l~adhesive resin/polyethylene terephthalate resin. This pipe was cut into a length of 130 mm and the bottom was formed at one end of the pipe. Thereafter the neck was processed so as to make a cap mountable to prepare a closed-end parison.
This closed-end parison was heated to 110C and stretched hy 2.2 times with stretching rods to the axis direction and almost simultaneously, nitrogen gas under a pressure of 12 kg/cm2 was 11 blown to stretch by 2.8 times to the peripheral direction. Thus, I
I a blaxially stretched blow bottle having a volume of 1.5 liters was formed. In thls case, the blow mol~ was kept at 15C by chilled water. Then after dwelling, the mold was opened to give a multi-layer bottle (Example 14).

For purpose oE comparison, a multi-layer bottle having the same size was given in a similar manner except for using EVOH
(ethylene unit content of 32 mol~, melt flow index at 190 C
under a load of 2160 g, 1.3 g/10 mins.) in place of Composition 1 (Comparative Example 8).
The layer construction of the wall and a time required until the carbon dioxide loss reached 15% are shown in Table 5.

Table S

Time required Total for 15~ loss Layer Const- Thick- of carbon ruction ness (~) dioxide Example 14 PET(100 ~)/adhesive resin (6 ~)/Composi-tion 1 (20 ~)/adhesive resin (6 ~)/PET (240 ~) 372 32 weeks Comparative Example 8 PET(100 ~)/adhesive resin (6 ~)/EVOH
(20 ~)/adhesive resin (6 ~)/PET (240 ~) 372 23 weeks .

It is evident that the bot~le according to the present invention has extremely excellent carbon dioxide gas barrier.
Example 15 and Comparative Example 9 Three extruders A, B and C were used; isotactic polypropylene resin (melt index a~ 190C under a load of 2160 g -.

~2g~Z~9 0.8 g/10 mins., specific gravity at 23OC = 0.91) was charged in extruder A, maleic anhydride-graft modified polypropylene (amount of maleic anhydride for modification = 0.001 mol~, melt index at 190~C under a load of 2160 g = 1.0, specific gravity at 23OC =
0.91) was charged in extruder B at a barrerl temperature of 220OC
and Composition 1 prepared in Example 1 was charged in extruder C
at a barrel temperature of 220C. The mixture was combined in a die for multi-layer circulax parison kept at a temperature of 240OC so as to form 3 kinds/5 layers of isotactic polypropylene/~
maleic anhydride-graft modified polypropylene/Composition 1/-maleic anhydride-graft modified polypropylene/isotactic polypropylene to form a multi-layer parison. The parison was subjected to known direct blow molding (blow molding of melt parison) to form a multi-layer bottle (Example lS).
Next, a multi-layer bottle was molded in almost a similar manner except for using EVOH Composition 1 ~ethylene unit content : of 32 mol~, melt index of 1.3 g/10 mins.) (Comparative Example 9).
The bottle had a weight of 22 g and an inner volume of 500 ml. The average thickness and construction was polypropylene (1- i 50 u)/maleic anhydride-graft modified polypropylene (20 ,)/Composition 1 (30 ~)/maleic anhydride-graft modified :polypropylene (20 ~)/polypropylene (150 y) (Example 15~ and polypropylene (150 ~)/maleic anhydride-graft modi~ied .

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polypropylene (20 ~)/EVOH (30 ~)/maleic anhydride-graft modified polypropylene (20 ~)/polypropylene (lS0 ~) (Comparative Example 19) ~
Next, water was charged in each bottle and sealed with a cap and an inside plug. After it was steam-treated at 120C in a retort pot for 30, 60 and 120 minutes, the bottle was withdrawn and the opening of the cup was connected with a device for measuring oxygen gas permeability and a rate of oxygen permeability was measured. The results are shown in Table 6.

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The rate of oxygen permeability after the retort treatment of Example 15 was approximately comparable to that of a container which was not retorted, and ~he gas barrier proper~y was as good as sufficient for storage of food.
Example 16 Using a multi-layer injection molding machine e~uipped with 3 injection cylinders, 3 kinds of resins were injected into an inversed conical mol~ having an opening of 65 mm and a height of 65 mm to give a parison having a 5 layer structure of polypropylene/adhesive resin/composition/adhesive resin/polypropylene. Polypropylene and the adhesive resin used herein were E-103D manufactured by Ube Industries, Ltd. and Admer QBS30 manufactured by Mitsui Petrochemical Industries, Ltd. The composition was EVOH containing the drying agent grains shown in Example l (Composition l). The parison was subjected to direct blow to prepare an almost cylindrical container having an opening of 65 mm and a height of 70 mm. The construction thlckness was 300/8/45/8/300 ~. Water was charged in the container and a metal-made lid was mounted by double-seaming.
After the container was treated in a retort pot at 120C
for 30, 60 and 120 minutes, respectively, water was charged in the inside of the cup. In such a state, 2 pipes were mounted to the lid of the container and connected with a device for ~ 45 -measurement of oxygen permeability. The results are shown in Table 7.
A part of the cup container prior to the retort treatment was cut, taken out and heated in xylene at 120C, whereby polypropylene and the adhesive resin were melted out to give a film of the composition in the container. The dispersion state of the powders in this film was observed by an optical microscope. With respect to 10 samples collected from the wall of the container at different locations, grains having a long diameter of 10 ~ or more at a region of 200 ~ x 200 ~ were measured with their average diameter, respectively, and the volume-area average diameter was calculated to be 17.5 ~.
Example 17 Molding was performed in a manner similar to Example 16 except that a parison having a 3 layer structure of polypropylene/Composition 1 of Example l/polypropylene was prepared using a multi-layer injection molding machine equipped with 2 injection cylinders. Thus a container having a thickness construction of 300/45/300 ~ was prepared. Also with respect to the container, a metal-made lid was mounted and the rate of oxygen permeability after the retort treatment was measured. The results are shown in Table 7.
Comparative Examples 10 and 11 .

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A container having a thickness construction of 300/45/45/45/300 ~ was obtained in a manner similar to Example 16 except that EVOH (ethylene unit content of 32 mol~, melt index of 1.3 g/10 mins~, melting point of 181C) was used in place of Composition 1 (Comparative Example 10~.
Further a container having a thickness construction of 300/45/45/45/300 ~ was obkained in a manner similar to Comparative Example 10 except that adhesive resin (Admer QB530) containing 10 wt~ of fine powders of drying agent (disodium phosphate) was used in place of.the adhesive resin of Comparative Example 10 (Comparative Example 11).
With respect to the containers of Comparative Examples 10 and 11, each metal-made lid was mounted thereto in a manner similar to Example 16 and the rate of oxygen permeability after the retort treatment was measured. The results are also shown in Table 7.
The rates o~ oxygen permeability of the containers of Examples 16 and 17 after the retort treatment were lower than those in Comparative Examples 10 and 11 and excellent in storability.

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Claims (16)

1. A composition comprising a matrix of an ethylene-vinyl alcohol copolymer having dispersed therein a drying agent in a particulate state, among grains of which drying agent a volume-area average diameter of said grains having a long diameter of not less than 10 µ is not greater than 30 µ.

2. A composition as claimed in claim 1 wherein a ratio of said drying agent used in said composition is 3 to 50 wt%.

3. A composition as claimed in claim 1 wherein said ethylene-vinyl alcohol copolymer is a saponified ethylene-vinyl acetate copolymer having an ethylene unit content of 25 to 60 mol% and a saponification degree in the vinyl acetate component of at least 96%.

4. A composition as claimed in claim 1 wherein said drying agent is a salt capable of forming a hydrate.

5. A composition as claimed in claim 1. wherein said drying agent comprises as a main ingredient(s) at least one selected from monosodium phosphate, disodium phosphate, trisodium phosphate, trilithium phosphate and sodium pyrophosphate or a mixture of at least two of them.

6. A process for producing a composition comprising a matrix of an ethylene-vinyl alcohol copolymer having dispersed therein a drying agent in a particulate state, among grains of which drying agent a volume-area average diameter of said grains having a long diameter of not less than 10 µ is not greater than 30 µ which comprises kneading an ethylene-vinyl alcohol copolymer and a drying agent comprising fine grains having at least 99.9 %
(volume fraction) being not less than 30 µ in a proportion ranging 97 : 3 to 50 : 50 by weight at a unit work of at least 0.1 kwh/kg using a continuous twin rotor kneader.

7. A process for producing a composition as claimed in claim 6 wherein said unit work is 0.2 to 0.8 kwh/kg.

8. A process for producing a composition as claimed in claim 6 wherein said ethylene-vinyl alcohol copolymer is a saponified ethylene-vinyl acetate copolymer having an ethylene unit content of 25 to 60 mol% and a saponification degree in the vinyl acetate component of at least 96%.

9. A process for producing a composition as claimed in claim 6 wherein said drying agent is a salt capable of forming a hydrate.

10. A process for producing a composition as claimed in claim 6 wherein said drying agent comprises as a main ingredient(s) at least one selected from monosodium phosphate, disodium phosphate, trisodium phosphate, trilithium phosphate and sodium pyrophosphate or a mixture of at least two of them.

11. A multi-layer structure comprising a layer of a composition comprising a matrix of an ethylene-vinyl alcohol copolymer having dispersed therein a drying agent in a particulate state, among grains of which drying agent a volume-area average diameter of said grains having a long diameter of not less than 10 µ is not greater than 30 µ.

12. A multi-layer structure as claimed in claim 11 wherein a ratio of said drying agent used in said composition is 3 to 50 wt%.

13. A multi-layer structure as claimed in claim 11 wherein said ethylene-vinyl alcohol copolymer is a saponified ethylene-vinyl acetate copolymer having an ethylene unit content of 25 to 60 mol% and a saponification degree in the vinyl acetate component of at least 96%.

14. A multi-layer structure as claimed in claim 11 wherein said drying agent is a salt capable of forming a hydrate.

15. A multi-layer structure as claimed in claim 11 wherein said drying agent comprises as a main ingredient(s) at least one selected from monosodium phosphate, disodium phosphate, trisodium phosphate, trilithium phosphate and sodium pyrophosphate or a mixture of at least two of them.

16. A composition comprising a matrix of an ethylene-vinyl alcohol (EVOH) copolymer having dispersed therein a granular drying agent in a particulate state, wherein among the dispersed grains of drying agent, the volume-area average diameter of the grains having a long diameter of at least 10µ is not greater than 30µ and the ratio of EVOH to said drying agent ranges from 97:3 to 50:50.