Polymer blend and film therefrom

[Detailed Description of the Invention]

Field of the Invention a report Lima blend [ from / as a polyether Amide block copolymer Tetylene - vinyl alcohol copolymer / the present invention ], and such blend 8 -- a To be made film -- it is especially related with the manufacturing method of a molecular orientation film and such a film. PRIOR ART Giving the oxygen barrier property which was excellent when, as for 3i union (EVOH), ethylene vinyl alcohol was used for manufacture of the film for packing is known. And although KVOH Including OH Irm is developed and it is used now, the Individual physical property has given difficulty of a certain kind to EVOH to processing and use of an E'VOH content film. boiling EVOH firmly -- a frame -- as for Oku EvOH, a hole is not fabricated easily -- those of .EVOH for Arrangement are very difficult, and are only attained within Ah Si and 1 Operation parameter of the narrow range. these problems -- United States patent 4th and 3 4 7 and 3 3 No. 7 -- and -- said -- the specification of No. 29Q172 (September 20, 1982 application; applicant buoy bit L. Newsom) is recognized and indicated. The U.S. patent application of another relation is continuation application No. (August 5, 1981 application) 464730 of No. 290171. In each above-mentioned United States patent and application specification, improvement of the art about EVOH Including OH Irm is written, respectively. Although those improvement gives progress of technical knowledge, the problem of a certain kind relevant to use of IOH polymer is still unsolved. When EVOH by which it is also known that it will be easy to receive degradation of the oxygen barrier property under high humidity or a high vapor content is used, in order to make it EVOH be under the environment of low humidity, EVOH is usually used in combination with the polymers layer of others which are arranged so that a damp course may be given between the environment and the EVOH layer which have potentially a flood part content which must have been permitted. Therefore, generally in the multilayer structure containing a vapor barrier like polyethylene, EvOH is used. When molecular orientation of the EVOH is carried out, or when it is fabricated, without re-fusing after manufacture of EVOH Including OH Irm, it is also known that EVOH has a function of the moisture-sensitive nature which there is no Loss about or a little, therefore has been improved as a barrier ingredient of a film. However, it has been carried out for whether being Ming that the process for Arrangement of E'VOH is difficult on account of the physical property of EVOH. Generally, whether it is independent or EVOH is a form of a multilayer film, it has the tendency to split in the process for Arrangement. Although that mechanism is not clarified to be sure, this Junko connects with the degree of high crystal of an EVOH film, and explains, and salted entrails and roe of the ayu, or sweetfish are not found, either. Even if what the mechanism is, it has been carried out for whether being Ming that processing of EVOH after film formation is very difficult. This difficulty is checking large-scale use of EVOH in the form by which for Arrangement was carried out. Some film for Arrangement which can be permitted functionally (the high EVOH Including OH all degree of cloudy weather which cannot permit these many commercially although it can manufacture is shown.) While improving the processability of an EVOH film, law is written in a U.S. Pat. No. 4,451,599 specification. It is said that it blends with a certain Doku's plasticizer-qEVOH, and improves the performance in a molecular orientation process. Such, although a plasticizer satisfies a plasticization operation, a plasticization PVOH film is easily made for Arrangement and the low moisture-sensitive nature predicted may be attained, the plasticizer shifts towards the surface of a film, and if a certain time passes, the surface quality of a film will be changed. About some use, an another means by which in many cases change of Yo Si influence woken up surface quality must have been permitted by shift exudation of a plasticizer, and id denatures the character of Ah Si, therefore an EVOH layer although it may not be is desired on requirements with serious surface quality of a film. One another method of improving character of an EVOH film is written in a U.S. Pat. No. 4,347,332 specification. Blending nylon with EVOH with a plasticizer for nylon, and manufacturing a transparent desirable film is proposed. Although a transparent desirable film can be manufactured if it does in this way, It is found out that it gets worse gradually until gel begins to appear in a film and the stop of extrusion operation comes to be comparatively needed after a short time, when pushing out some of those J IJ Married ゝ for film formation. The problem which an invention tends to solve The fundamental target of the present invention is making it suit for [ of EVOH ] the commercial extrusion which manufactures the transparent barrier film which denatures EVOH so that the physical characteristic which is not desirable may be avoided, and is commercially received by it, and Arrangement. Therefore, a difficult problem is To ru to the discovery of a compound which does not start the problem of the exudation which could take blend 9 for EVOH in order to form a compatibility blend, and has improved the character which is EVOH, and which is not, and was moreover seen with the conventional plasticizer, or an ON planar change. similar film Yo Si whom a glance target of the present invention EvOH'f[ UnDenatured ]: contains -- in order to make a strong new film, it is providing the new constituent of denaturation EVOH which can be pushed out continuously over a long time. A target is in offer of a new EVOH film which can make easily a lengthwise direction (- axis) and those of both directions (2 axes) in every direction for Arrangement another glance of the present invention. A target is that the film produced by making it such is transparent, i.e., the low degree of cloudy Si is shown, another glance of the present invention. as for the degree of IJk person being low, the functional compatibility of material, therefore a good thing are important also for whether it is accepted commercially with the state where for Arrangement was carried out. a film is good like EVOH[1 body -- oxygen barrier Indicator should be carried out and it is Ox -- the oxygen barrier property improved at high humidity (like [ the state for undivided / it Relative softness with a thing and / of EVOH for Arrangement ]) should be shown. Targets are are a physical property on the surface of a film, and that surface friction characteristic , is generally constant irrespective of time progress especially glance of the present invention another common. The means for solving a problem Most, shape is taken by the broad sense in compatibility Bren of 71? Li Engineering-Tell amit ゝ fluke copolymer (T) EBA and the ethylene vinyl alcohol copolymer of 99 % of the weight of amount charge of about 602 Ii(s)~abbreviation of about 40-fold [ amount Bun of abbreviation IM~] j■ Chi, and the present invention is broken into it. The present invention also provides the polymer film made from the compatibility blend with the above-mentioned polyether amide block copolymer and an ethylene vinyl alcohol copolymer. It is made for a film to turn into a film of at least three layers which becomes each of that surface from two layers of nylon, and one layer of the blend feather between them including [ as a result ] the layer of a nylon polymer in some example with this preferred film. It adjoins on either of those nylon layers, or both, and an additional layer may be attached. With a multilayer film, the ease, economical efficiency, and abuse-proof nature of processing may be given. In the most desirable mode, molecular orientation of the film of the present invention is carried out in multilayer structure. - As for the ratio for Arrangement about for Axis alignment, the ratio for Arrangement about Ah Si and for 2 axis Arrangement is to about 4X4 even in about 5/1. The thickness of the layer of a blend of Ah Si and the ethylene vinyl alcohol copolymer Toppol ether amide block copolymer of them of the overall thickness of the film in such a desirable film for Arrangement constitutes about 20~50% of the overall thickness of a film in about 1.0 mil generally. According to the present invention, the manufacturing method of a film is also provided. The film manufacturing method of the present invention is Work Si about a mixture with the Ho Rieti Ruamit ゞ block copolymer of about 1 % of the weight thru/or about 40-fold ff1l., about 60 % of the weight, or about 99% of the weight of an ethylene vinyl alcohol copolymer, One layer of the Plane r ingredient of the above-mentioned mixture exists in this film that pushes out this mixture via an extrusion machine and the Di device, and it spreads with Fecum, and it cools this film. It consists of things. In order to make the most desirable fill □ Beam of the present invention, the above-mentioned process carries out simultaneous extrusion of the nylon layer on each surface of the above-mentioned blend layer, and includes the process of making a three-layer film. The three-layer film contains the nylon layer on each surface with the core layer of the above-mentioned blend. This film is completed by receiving re-heating and molecular orientation in the most desirable mode. Even if it uses directly the film manufactured in this way as it is, it is good also as a film of a still more complicated structure in combination with other film layers. the layer of the blend by the present invention -- the inside of a multilayer film -- much more -- it carries out, and may be introduced and formation and the lamination process of each layer can constitute such a multilayer film. Such a film can be preferably manufactured by carrying out simultaneous extrusion processing to all the Ho IJ Maher rye-clues, and, subsequently may carry out for [ of all the layers ] Arrangement simultaneously by a case. the change about the formation method of a film -- for a person skilled in the art -- being obvious -- □ To. It is a chart showing the Shear hardness of Drawing 1 and PEBA polymer as compared with other polymer and rubbers. A useful EVOH copolymer usually includes the vinyl alcohol unit up to at least about 55 % of the weight and about 80 % of the weight in the present invention. A desirable EVOH copolymer usually includes about 60~75% of the weight of a vinyl alcohol unit. The remainder of a gvoH molecule mainly consists of an ethylene unit. Although the acetic acid vinyl unit of the amount of survival is included in 'lil!VOH molecule, this is usually because EVOH is manufactured by the hydrolysis reaction of an ethylene-vinyl acetate copolymer. It is hydrolyzed highly and commercial EvOH is usually hydrolyzed to 99 % of the weight or more. an especially desirable EVOH copolymer -- [by Japan composition incorporated company -- tour Nord (Soarno]) ET, the DJ, and (a A gap is also a trademark) Kula L / stock meeting aJ A r EV'AL EP-E And (it is i EP-F'J (all are trademarks).) The PEBA copolymer useful to the present invention contains the Ho IJ ether part with nine copies of polyamide in the main chain. The general formula of such a copolymer is downward glance "Through Si, and is Be necessarily. In the above-mentioned formula, the composition ratio of P E/P A in P E= and the l Rieta part above-mentioned copolymer may change at least nine copies of :pA== polyamide between 20/80 and 80/20. The 5 poly Engineering-Tell ingredient which may be any of conventional Nay d A [ like nylon 6, Nylon 66, nylon 6/66, Nylon 11, and Nylon 12 ] nine ingredients of whose polyamide are, It is usually (however, there is certainly nothing then) chosen from polyoxy ethylene and rl Rioqui Cipro pyrene And □yN Reoxytetramethane. The melting point of publicly known 0PEBA is about 120~205degreeC. The Shore hardness is by abbreviation 65D thru/or 60A, as shown in IVi of Drawing 1. 3 whose desirable PEBA is [PKBAXJ (trademark) of Ato Siemi (Atto Chemie) -- a typical thing -- [PEBAX5512J -- Lari and this thing -- the melting point of 195 degreeC, and Shoah hardness all To have of 55D. Since this PEBA A j Carries out low hardness which performs softening denaturation of hard weak EvOH when blended with EVOH, it is desirable. To out of which PEBA of others which showed the good result comes Atto-Shea Emmy r'EBAX 3533J Hint rPEBAX4033J. "FEBAX and 3533J conceive the melting point of 152 degreeC, and the Shoah hardness of 80A, and carry out the eaves of the melting point of [PEBAX 403311.168"C, and the Shoah hardness of 40D. Blend 9 of EVOH of the present invention and PEBA is weight, about 1% thru/or about 40 charges PEBA @ Include it corresponding to about 60 Chi thru/or about 99% of E'VOH, and it, and the PEBA functions as a denaturing agent. A general use. PEBA is [ 1~2o Chi and EVOH of the desirable range of a sake ] 80~99%. specific EAOH for which this desirable range is used, for example, and PEBAy+" -- boil the environment etc. which were meant when Limmer, a processing method, the overall last structure, and the last packaged goods encountered -- the Si right and left are carried out. The plasticization function to A dog and its effect of five constituents whose above desirable PEBA(s) of the minimum (about 1 Chi) about PEBA are the things showing the point of losing the effect in the desirable effect of a plasticization function gradually, It can detect by measuring change of the character of the film which a film transforms, without producing Ripping. In an example of such modification measurement, the result extended until it fractures the strip of a film as in the Instron tensile test machine is shown by a fracture pace of expansion and its tensile test as the maximum tensile strength. In another measuring method, extension molecular orientation of the film [ Continuous ] is substantially carried out by the 446,009th item (December 1, 1982 application) specification of a U.S. patent application, the device as especially shown in Drawing 3, and a method. The tensile test is especially useful as controlled various environmental conditions and a means to detect the difference in a plastic film since it can carry out by temperature conditions especially. in the following -- Akira -- it is -- like, even if the film comrade of different composition has the same character substantially on many 1 conditions of a certain - group, he may have the character which is different on a set of another terms and conditions. For example, in polymer Bren Ha of the present invention containing low-concentration PEBA, and room temperature, different tractive characteristics from un-plasticizing EVOH may not be shown. In such a case, there is a possibility that it may be surmised that PEBA is not functioning as a plasticizer. However, when carrying out this examination by the high temperature of the order of 80 degrees C~100 degreeC, the difference in remarkable plastic deformation may be accepted. The increase in the point-of-rupture pace of expansion at the time of comparing with un-plasticizing EVOH is accepted to be the proof of improvement in plastic deformation brought about from the plasticizing effect of PEBA. Therefore, occasionally for collection of the proof of the functional difference between the new film of the present invention, and the film of the former which EVOHI used which does not carry out FEBAI combination, it is required to use the test condition selected and controlled carefully. A stretch orientation examination is above-mentioned U.S. patent application 44th (it carries out on the operation conditions carefully selected and controlled so that it was indicated by LO No. 09 Ming M Miro 13'.). the plastic deformation which has arisen the more by definition the more the quantity of a stretch orientation possible about a given film is large is thick -- it is -- . The improvement in an increase of the extension ratio about the film of the plasticized composition is the proof which the plasticizing effect given with a plasticizer produced. The constituent which contains PEBA to 40 Chi depending on specific PEBA and specific EVOH which are used is meant. the degree of # of PEBA -- an arrow -- probably in six things dZ for which a part is reduced, the oxygen barrier property usually given by EVO'H gets by dilution of EVOH concentration with < Be strong. Each other is offset by the reduction which Benefits of a plasticizing effect and oxygen barrier property cannot permit above the maximum of 40 Chi of PEBA. eye the present invention -- one another mode is the film made from the above-mentioned PEBA-EVOH blend. Although a monolayer film can be manufactured with a conventional extrusion method, good -- better -- the typical simultaneous extrusion thing in which 7 To make such a film as some simultaneous extrusion things is made from nylon / blend 9 structure by a thickness of 04~2.0 mil, and the thickness of the blend layer constitutes about 20~50% of the thickness of a two-layer complex. Another typical simultaneous extrusion thing is made from nylon / Plane '/Nay' A structure Te, and a thickness of 0.4~20 mil, and the thickness fled [ nine layers of ] constitutes about 20~50% of the thickness of a three-layer complex. As compared with above-mentioned EVOH-nylon Fred, the advantageous character for A low of an EVOH-PEBA blend of the present invention is that can process it continuously via an extrusion Di device over a long time, and generation of gel and other Verima degradation do not arise. As a secondary examining method for comparing the processability of EVOH-PEBA blend 9 with the conventional EVOH-nylon friend, both blend ''' was separately examined in the Bubble Bender mixer. Heated and fused each blend, and it mixed continuously for 1 hour, and recorded on the Torquera continuation target in which mixture is used with Heartfelt. In both cases, in early stages, the torque for mixture was eight or less 1 feet pound. Although the torque increased at a uniform rate about EVOH-nylon blend 8, there was torque about EVOH-P]1EBA blend ゝ to -1 almost fixed. the connoisseur of the following [ torque / composition of those blends, and / after 1 hour mixture / last ] -- he was Si. 80%EVOH-20%PEBA O, and 62 foot bond 980%EVOH-20% Nay o76/66 Examination data of the 9.79 Phi-bond' above, Although A shrine in the extrusion machine and the Di device which carry out processing treatment of the conventional EVOH-nylon blend has the restriction about processing treatment time and scales are shown, about the processing treatment of the blend of Fi'VOH-PEBA, it is not shown at all that there is such a thing. As a first examining method, although this artificer gave the EVOH-PEBA blend to prolonged conventional extrusion processing, it became clear that there was no time restriction in extrusion processing of the Bren F''' constituent of the 1 present invention. since PEBA includes the polyamide block of Yoshinari Si's percentage like nylon -- extrusion characteristic 1[as the extrusion characteristic of nylon with same PEBA -- naturally it will come out to expect it as what is carried out. However, when a nylon independent is set to EVOH fled 9, PEBA in blend ゝ gives the important functionality which is not necessarily acquired, so that it may be seen by the above-mentioned examination. as mentioned above, the most effective use (and -- especially related with use in humidity environment) of EVOH as an oxygen barrier is attained in the state of the state by which for Arrangement was carried out, 2 axes, or uniaxial orientation. The present invention also provides the condition of use of this most effective EVOH. First, the problem in for [ about EVOH / usual ] Arrangement is a thing about the To be rigid fearfulness and hard nature, And Myriad, which remembers that these are what generally originates in the degree of crystal When it is going to carry out those for Arrangement, and the processing operation must be made to make the minimum the opportunity of crystal formation at the time of extrusion, therefore it is going to carry out for [ of the film ] Arrangement, the film should be quickly cooled, when coming out from extrusion Di. The examples of the method that it is permissible in order to attain this are the method of carrying out the cast of the film to a cooling roller (Tillousose) like a cast extrusion method, and the method of letting a film pass during cooling fluid object intermediation like a tube water-cooled extrusion method. once a film is manufactured, it will rank next and will be re-heated - axis -- or for 2 axis Arrangement is carried out. Even if it carries out with the operation which followed such for Arrangement and film formation, it can also carry out as separate operation. It seems that PEBA functions as a plasticizer for E/VOH in the process for Arrangement. However, in connection with the problem of the exudation to the film surface which was common about the conventional plasticizer when PEBA@ Using, and it, change of the film surface quality (especially surface friction coefficient) by time progress was not accepted. A good uniaxial orientation ratio is to about 5/1. The good ratio for Arrangement about for 2 axis Arrangement is to about 4x4. If the ratio for Arrangement is generally high (any for - axis and 2 axis Arrangement), character with good Yo Si will be attained. Therefore, the desirable ratio for Arrangement is by the ratio for Maximum allocation which can be effectively attained with equipment used. Therefore, the ratio changes according to the for machine for Arrangement used. Above, for 2 axis Arrangement, in both oriented axes, although shown like, it may be as the Yoshinari Si side from the same quantity, and the only requirements are those things [ that the amount of extensions in each axis is up to about 4 times of an early unextended size ] which are the same quantity (or equivalent). therefore -- those of 2x4 for Arrangement are what can be permitted -- 4x2 or 4x3 -- " -- or 3x4 can be permitted similarly. [ for example, ] Therefore, the same quantity biaxial drawing ratio of a certain range includes the arbitrary amount extension ratios of 2 axis different between the both ends of the range. the film which is obtained in the case of which extension ratio is uniform -- Ah Si -- it is transparent. fill nonuniformity create from BrenP of EvOH and PEBA -- it turns out that a Yo Si profit Was done result gives a fundamental understanding of an operation of the blend as polymer to things ,. The underlying concept acquired is producing a film with the ductility and toughness which functioned as it being weak originally and PEBA giving the pliability, flexibility, and toughness to EVOH which is easy to destroy, denatured the character of EVOH and have been improved by it. This concept suits about all the PEBAylflJ Maher. Those for Arrangement of the film of a certain kind by which for Arrangement must have been satisfactorily carried out if there is no such There for Blend become possible by including PEBA. FEBAf and by making it contain, those for Arrangement become easy, it forces 179 again and the film of a certain kind which can carry out for Arrangement even if there is no PEBA ft Including 1 turns into a film. Therefore, in some, those for Arrangement become possible by the gold layer of PEBA, and when it is others, those for Arrangement are easy-ized. About selection of specific PEBA which should be used, flexible PEBA is the quite small amount used, and can give required ductility in the middle to the ratio for Arrangement of a degree. For the big toughness required of the film attached for advanced Arrangement (especially for 2 axis Arrangement), since hard PEBA gives big toughness more substantially than flexible PEBA, it is usually desirable. About Hoshi of a wrapped object, when toughness is serious requirements, toughness all giving the first meaning purpose of using PIA has importance, therefore ppB* of high toughness (Shoah hardness is high) will be selected. Therefore, although the specific selection of PEBA which should be used is influenced to some extent by the environment where Arrangement-oriented Support, use Orientation force method, and a film should be placed, selections of specific PEBA are all the Sculpture receptacle sell things also by the factor of the music. The main factors which affect the EV OI/P E B A ratio under blend * are the selected specific end uses which were EVOH(ed) and meant. E V OI-1 as an oxygen barrier (since Talent is usually the 1st object, selection of specific EVOH polymer is usually the 1st phase in Establishment of EVOH-PEBA blend 9.) Within the limits of E V O set up about one of PEBA(s) subsequently selected so that it could approve if selection of specific EVOH was completed, and a 1-1/P E B A ratio, the quality of the Appear range is It can be burned. If there is no Invalid parameter drop help of the quality range, the history of the selection of at least 1 power of those specific polymers of strange is carried out. With within the limits for which is mainly used in order to denature EVOH, in order that EVOH may promote [ Ah Si and Up 'fcPEBA ] processing of EVOH by a first meaning functional polymer, and the polymer of a specific combination is obtained from Be necessarily by them, A polymer desirable as an object of change, substitution, or denaturation in Almost which does not satisfy necessary-xi Meter is PEBA. however, then another, if you don't do so that another selection of PEBA or the denaturation of PEBA gives a necessary parameter -- it is used, carrying out EVOHI selection. For example, F2VOH desirable to packing of use in humid environment, for example, meat, or cheese has an ethylene content [ that it is comparatively high (for example, 38~48%) ]. The thing of an ethylene content high among all the E'VOH$ Limmer is relatively flexible, and as for those improvements, since there are Ah Si and a tendency that is ductility much more, as far as those pliability and the ductile improvement in Deception are concerned, it is common that a More Si demand is not carried out. Some A child of the denaturation as which the blend ゝ [ depend ] which EVOHi used is required from EVOH will have a ratio of the direction near [ in that in the rate case ] the maximum of the range of a predetermined E V OH/PEBA ratio. Of course, specific PEBA selected also affects it. EVOH desirable for use in dry environment has a comparatively low ethylene content like 29~35 Chi like packing of a dry snack like potato chips. The thing of an ethylene content low among all the EVOH4 Limmer is relatively hard, and since there is a weak tendency, the quantity of an improvement of pliability and ductility is usually needed still more greatly. Since the quantity (grade) of such blend 9 EVOH@ Used and the denaturation demanded from E'VOH is somewhat large, the ratio of the direction near the minimum of the range of a predetermined E V OH/P E B A ratio will be carried out one. Of course, a much more big EVOH/PEBA ratio can be used, when [ flexible ] it can select PEnA1 and moreover in addition necessary pliability and necessary toughness can be given. it is related with a specific multilayer film structure -- it is most expedient to make the film which carries out Yo Si processing and contains one layer of the blend in E'VOH-PEBA Plane-Wo and a simultaneous extrusion method. In Okay., nine layers of the blend makes not the layer of the outside in a multilayer structure but an inside layer at the time of simultaneous extrusion. Nylon / blend / [nylon] Wo implication, and this thing can be used for a typical multilayer structure as one ingredient for subcollection parts or a still more complicated film structure. As a classic example of the film collection object of the completed form which contains [nylon / blend / nylon] as one ingredient, some are following. Nylon / Plane r / nylon / sealant nylon / friend '' / nylon / ETA / sealant nylon / Frien # / nylon / M/EVA / sealant nylon / Bren-# / nylon / Contact / EVA / Contact / sealant OPP / adhesives / nylon / blend 4 / nylon / Contact / ETA / Contact / sealant (polypropylene for EVA-ethylene-vinyl acetate copolymer 0PP= Arrangement) Sealand = heat-sealing polymer Contact = adhesive polymer Typical material used for the adhesive polymer layer of the above-mentioned structure, There are [cXA 3101J (trademark) of A by Carboxy denaturation polymer by Ah Si's, for example, Kemp REXX (Chemplex), "Prewarl" (trademark) and Du 11, a typical material used for the sealant layer of upper RB -- eye Onomer and HVA -- and -- low -- dense -- it is 11i and polyethylene (LDPE), and Use rfJ also of the blend 9 of some things of such materials may be carried out. Two functional requirements of that Ah Si and its one have Pleasant adhesive strength to an adjacent layer and its 2 are in a sealant layer by having heat-sealing nature. heat sealing -- between the film surfaces of sealant layer 8 opposite ll1l. of a film -- all -- carrying out No way -- a heat-sealing bar to heat - shift -- that of Yo Si To do is preferred for carrying out. Of course, it is possible to change the process of to make idiomatic denaturation of a certain kind on a film and a film, without having a bad influence on the functionality by which the sense figure was carried out to 7' Irumu of the present invention. - which it is [ - ] desirable to carry out uniaxial orientation as for the illustration film collection object of the above-mentioned listing, for example, makes a stretch orientation carry out in the direction of length (machinery), and makes the film for Arrangement -- things are made and this thing is [ packing of dry snack food etc. ] desirable to Drunkard. Similarly, for [ of the film ] 2 axis Arrangement can be carried out, and it can be turned to other packing uses. Of course, it is also very expedient to add another layer to the film after the operation for Arrangement. Such an addition layer, for example, OPP, gives another functional characteristic. In the design of a certain kind of film, that it is desirable improving the adhesive strength in a certain specific boundary side can reinforce the adhesive strength for two layers which uses adhesive polymer in the form of a thin layer, and touches, when adhesive strength is needed in a There simultaneous extrusion film (refer to the example of the above-mentioned listing). U.S. Pat. No. 4,233,367 (Tsuckner and line) -- said -- the extrusion possible adhesives of a large number which are written in the specification of No. 4.23Q826 (a knot and one) and 4,254,169 (Schroeder) can be used. The typical adhesives for using it with the film of the present invention are "PLEXAR" (trademark) of a Kemp REXX company, [N'ovatec AP J of Mitsubishi Kasei Corp., and [CXAJ (trademark) of E. I. du Pont de Nemours & Co. These adhesives (it is Carboxy (-C-) 1 so that adhesives (adhesive polymer) l'i and desired junction nature may be given) It is the polymer or copolymer of an olefin system which denatured. these adhesion i resin is marketed -- probably, Si and those directions for use will be clear to a person skilled in the art. Example 1 [5oarnol ET J Yelenl of an ethylene (trademark) O vinyl alcohol copolymer, and [PEBAX5512J Vered and E'VOH80 Chi of a copolymer (trademark) : It mixed by PEBA 20% of weight ratio. These solids carried out the dry type blend at room temperature, and used let as the homogeneous mixture. the Berez k cast simultaneous extrusion method mixed in this way -- each field of a blend layer -- 1-Wo attachment To of nylon 6 -- pushing out like -- Te, and nylon/blend "-- the three-layer film of /nylon was made. Thus, the thickness of the obtained film was 2 or 85 mil. Uniaxial orientation was carried out by the extension ratio of this fill nonuniformity 3.5:1. The thickness of the obtained whole oriented film was about 1 mil. The thickness of the blend layer was about 0.4 mil. This film for Arrangement is transparent and this shows good compatibility. The degree of cloudy weather was measured by the ASTM D 1003 method, and was 1 Chi. The sample of this film for Arrangement. It examined about oxygen permeability and the degree of cloudy weather. The degree of oxygen penetration was 49 cc/rr? 724 hours in 22, 8degreeC (under 73), and relative humidity 100 Chi, and the degree of cloudy weather was 1 Chi. The degree of oxygen penetration of this examination film in 200 cc!= Chi and 22 or 8 degreeC (under 73) is only 2 under the test condition with the same overall thickness and the same, same degree of oxygen penetration of the corresponding film for undivided that it ingredient thickness ratio t Has.. It was 5 cc / m"7 day. Example 2 Although simultaneous extrusion of the film was carried out and for Arrangement was carried out like Example 1, the friend ratios in this example were 90% of the weight of EvOH, and 10% of the weight of PEBA. The degree of oxygen penetration at 228degreeC (under 73) and 100% relative humidity is 32 cc/l? seven days, and the degree of cloudy weather is rash at 1 Chi. 0% phase relativity -- strange and there is the degree of oxygen penetration in 22.8 degreeC -- I CC/ m" -- it will be rash in seven days or less. carrying out like Examples 1 and 2 -- a contrast film -- Work Si -- although for Arrangement was carried out, PEBA was not used at all. Therefore, the core layer of a three-layer film was 100%EVOH. As for the degree of oxygen penetration at 22.8degreeC (under 73), and 100% relative humidity, Necessary of the degree of cloudy weather was 39% on 24.CC/rr? / day. The film was roll top Te milk white. Although this film may function as a barrier film, that appearance with the high degree of cloudy weather cannot be permitted for a commercial use, and is unsuitable to sale. Example 3 Vered of Vered I[FEBAX5512J of [8 oarnolE-T J, and 80% of "5oarnol ETJ:20% "dry blending was carried out like Example 1 by the weight ratio of P EB A XJ. A 4.25-mil film was made from simultaneous extrusion. For 2 axis Arrangement was carried out by the extension ratio of obtained film'k 2.5 X 2.5. The film for obtained Arrangement has a good speed, and showed the degree of oxygen penetration on 30 CC/rr? the 7th with 22, 8degreeC (73 degrees F), and ioo% relative humidity. Example 4 It carries out like Example 3, however is blend ratio i90%. The film of 4.25-mil thickness was made as [5oarnolET J and 10 % [PEBAX 5512J. For 2 axis Arrangement was carried out by this Distraction ratio of film'i 2.5 X 2.5. The degree [ in / the film for obtained Arrangement has good transparency, and / 228degreeC (under 73), and 100% relative humidity (100%R, H) ] of oxygen penetration, 27 the effect which were QC/lr? / day when low concentration carries out FEBAI addition to EVOH -- corresponding to PEBA of 1~5 Chi, and it, it experimented in the addition on 95~99% of effect Examining money sake about blend 8 of the concentration of EvOH especially. PEBA of the conventional film which does not contain the film of these composition PEBA2, and 10 Chi, and EVOHi of 90 Assault -- it comes out as contrasted with the film of the included present invention. Example 5~10 and comparative example 2 A three-layer base film with an overall thickness of 3.5 mil was made using the cast simultaneous extrusion device. Two outside layers were nylon 6. The inner side layer (core layer) of each film is the blend of EVOH ([5oarnol DEJ) and a polyether amide 9 fluke bowl polymer (1'-PEBAX 4033J), and is Buddy fc, The whole film structure was in the nylon layer / blend layer / nylon layer, and weight % of each class was 30/40/30. All the films were manufactured under the same processing conditions. The uniaxial stretch orientation of the sample of these three-layer base films was carried out, and it was ductility (stretchability) all evaluated. The stretch orientation of all the oriented films was carried out under the same conditions. The degree of clothes surface temperature of the contact roll under extension was about 110degreeC. It was Annealing temperature 11154degreeC. All the films were good at 3.5/1 of extension ratios. Subsequently, about each sample, the extension ratio was gradually increased until the film fractured. The extension ratio of the point which produced the fracture was recorded. By example, the thing of blend 9 Togi carries out the ground board of Ah Si and this to same three layers of prior art film that used 100 Chi EVOH as a core layer, and this result serves as an index of reversibility having been given by PEBA at them, when acting as an old man of the extension ratio which carried out the same as the above to clothes 2. It is pushed out like Example 5~10, a stretch orientation is carried out, and the three-layer film (Ratio solutioning Li 2) of a prior art is fc. Even if it exists while a little PEBA(s) like % 1 Chi blend from Table 2, it turns out that the maximum extension ratio of a three-layer film is increased by steadily about 10~20%. The optical property of all the fill □ Beam of Example 5~10 is Off. It was very good until it continued till the point of rupture of Irumu. Example 5~100 base film was examined also about film transparency and oxygen barrier property. carrying out the stretch orientation of the sample of each base film by 3.5/1 of extension ratios -- fc3 -- the transparency and oxygen barrier property of them are shown in Table 3. As comparative example 3, the control experiment using three layers of prior art film with the core layer of 100ChiEVOH1, i.e., Q %PEBA, was also conducted. This result is also collectively shown in Table 3. The result of Table 3 shows that low-concentration PEBA addition [ like 1~5 Chi ] whose transparency of the film for Arrangement is is also improved. The result of oxygen permeability makes an effective thing check similarly with it being about the blend of Ga concentration about the blend of PEBA of a ratio [ like Example 11~16 ] whose oxygen barrier property of EVOH is, and EVOH, so that it may be Example 1~4. Example 17~22 and comparison example 4 The monolayer film by the present invention was made by the monolayer film all extrusion-molding method of composition of each example and comparison example 4 shown in a table 4 examined about the maximum pace of expansion. For the pace-of-expansion examination, the filmstrip of 1-inch (2,546IIL) width was grasped to those jaws, where 2 inches (5, 08 A) of two jaws of the Instron tensile test machine are detached. A sample is put in an envelopment object after them, and the pace-of-expansion examination enabled it to carry out at the temperature selected and controlled. When the inner side of an envelopment object reached desired Test temperature, the jaw comrade was pulled apart gradually and examination filmstrip was expanded. The examination stopped, when a film fractured. a pace of expansion (te comes out and computes and shows fc7 test result in Table 4 by the average value of five samples each.) It turns out that an effect is for a little PEBA(s) like 1 Chi to raise the pace of expansion in 100 degreeC from Table 4. PKBA of about 4 Chi is effective for raising the pace of expansion in 80~90 degreeC. * The optical ' character of all the films of Example 17~20 was very good. Now, although a person skilled in the art will make a small amount of nylon the EVOH/PEBA blend of the present invention blend 9 and will understand scales, he requires blending a small amount of such nylon with EV OH/P E B A Bren r of the present invention within the limits of the present invention. In the examination of the film (a monolayer film is also included) of the present invention, it was not accepted at all that the surface quality of a film changes with time. Therefore, not giving the surface quality which changes to an EVOH-PEBA blend layer, and thing , for which the function of PEBAFiEVOH is not blocked conclude PEBA.

[Brief Description of the Drawings]

Drawing 1 is a chart showing the Shoah hardness of PEBA polymer as contrasted with other Ho IJ Maher and the Shoah hardness of rubber, and scales D and A of Shoah hardness are shown in the horizontal axis. Representative patent attorney Kyozo Yuasa ' (besides five persons) A page [ 1st ] continuation ■ Int, C1, and 'classification symbol agency winding-up number written amendment Showa -- seven persons/60-year, and nine days Showa -- the title of /Year patent application 2 person 86 No. 2 and an invention A 1000 Sommarf * Wren F A flame - ?" -- Ina(ing) -- mosquito - relation with the person incident which carries out 3 Yawaran 3 buoy +vk Filter correction Applicant-for-a-patent address Azusa 1 degree1 tin, 7+77, 7 A, 4th [ Knee ] generation J! ■ people 5, object of amendment