TW200927788A - Polyamide-based laminated biaxially stretched film and evaporated polyamide-based laminated resin film - Google Patents

Abstract

The present invention provides a polyamide-based biaxially stretched film suitable for package uses, which has necessary properties of a film for package such as oxidant barrier ability, impact resistance and flexal fatigue resistance, furthermore, the film has the effect on preventing from product crush caused by vibration or impact during transport and protecting quality of content. The polyamide-based biaxially stretched film is composed of laminating a resin layer having main constituent of polyamide polymer containing metaxylene group onto a resin layer having main constituent of aliphatic polyamide resin (layer B), which has specific low number of pin hole and specific small oxidant transmittance; wherein main diamine component is metaxylene diamine or mixed xylene diamine consisted of metaxylene diamine and paraxylene diamine, and main dicarboxylic acid component is α -, ω -aliphatic dicarboxylic acid having 6 to 12 carbon atoms.

Description

。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 It is excellent in properties, impact resistance, and bending fatigue resistance. When it is used as a packaging material for food packaging, it has an effect of preventing deterioration of contents or protecting contents from vibration or impact during transportation. [Prior Art] ® Previously, a film composed of a polyamide polymer composed of benzodimethylamine as a constituent component has excellent oxygen barrier properties or heat resistance as compared with a film composed of other polymer components. And the film strength is also strong. On the other hand, an unstretched film or an extended film composed of an aliphatic polyamine represented by nylon 6 or nylon 66 is widely used as various packaging materials because of excellent impact resistance or bending fatigue resistance. . In the above-mentioned prior art film, a film composed of a polyamidamide polymer having a benzene dimethyl diamine as a constituent component is used in a processing step of vacuum packaging when it is used for a packaging material which is required to have bending fatigue resistance. When the product is transported, there is a problem that pinholes are generated due to bending fatigue. If pinholes are formed in the packaging material of the product, it may cause contamination of the contents, or the contents are spoiled or moldy, which may cause the price of the product to decrease. On the other hand, a film composed of the latter aliphatic polyamine has excellent film properties such as impact resistance or bending fatigue resistance, but has a problem that oxygen barrier property is poor. Further, in order to solve such problems, there is a proposal (for example, refer to Patent Documents 1 to 4) to disclose a polyamine polyamine 200927788 compound and an aliphatic polyamine having benzodimethylamine as a constituent component. The respective extruders are melt extruded to laminate and perform biaxial stretching. However, the techniques described in the above-mentioned patent documents can be said to be unsatisfactory in terms of good protection against impact or bending, such as good product storage stability and transportation. In the method of Patent Document 2, in order to obtain a good oxygen barrier property and bending fatigue resistance, it is necessary to use a large amount of a polyamide polymer having benzodimethylamine as a constituent component, and it is required to reduce packaging and distribution costs. Among them, it is not a good method. Patent Document 3 discloses a film which is capable of satisfying gas barrier properties and bending fatigue resistance, and is a gas barrier resin layer composed of polyamine which is mainly composed of benzodimethylamine. At least one side of the film is formed by laminating a resin layer composed of an aliphatic polyamine and a bending fatigue resistance improving agent. However, it is described that the ratio of the gas barrier resin layer is 40% or more to satisfy the gas. Barrier. The inventors of the present invention evaluated that the film using Patent Document 3 cannot satisfy the bending fatigue resistance under severe conditions. Patent Document 4 discloses a film which has both a bag-breaking property and a bending fatigue resistance, and is laminated on at least one side of a resin layer composed of a fatty steroid polyamine and a thermoplastic elastomer. A resin layer composed of a mixture of an amine and a semi-aromatic polyamide may be used. However, even if this method is used, a gas barrier film having bending fatigue resistance cannot be obtained. Further, in the current food circulation form, the method described in the above publication is still concerned, in particular, from the prevention of deterioration of contents such as vibration, shock, and friction when the packaging material is transported with high importance. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2001-307253 (Patent Document 3) JP-A-2001-341253 (Patent Document 4) JP-A-2006-205711 The polyamine-based resin film which is biaxially aligned is widely used as a packaging material because of excellent transparency, mechanical properties, gas barrier properties, impact resistance, and pinhole resistance. In particular, it is used for so-called heavy bag applications in which excellent impact resistance and pinhole resistance are required, and the like has been mainly used in bags such as rice bags which are larger than the prior bags. This large bag has a width of about 30 cm and a length of about 60 cm. © This type of bag is usually made by using a biaxially oriented polyamide resin as a base film and laminating various sealing materials (polyethylene, polypropylene, etc.) having heat sealability, usually by folding and heat-sealing three sides. Become a so-called three-way sealed bag. In general, the contents of foods and the like are often filled automatically after the bag is formed, and the biaxially oriented polyamide film is compared with the biaxially oriented polyester film, and the dimensional stability is poor, and the bag is curled. However, the automatic charging device cannot grasp the bag correctly and open the mouth of the bag, which may cause a problem that the contents of the food or the like are leaked out. This phenomenon occurs remarkably when the longitudinal biaxial stretching method is performed by C) lateral stretching, and the phenomenon becomes larger as it approaches the end of the film and is close to the end of the film. The reason why the center portion is half-cut and joined together causes a difference in shrinkage ratio and the size of the front side is different from the size of the back side. A technique for producing a film having a uniform physical property in the direction of the manufacturing width, that is, a film which suppresses bending, is related to the use of the unstretched sheet stage before the lateral stretching or the longitudinal stretching, and is used at right angles to the traveling direction of the sheet. A straight line drawn by an oil-based pen or the like, in which a bow-like curve is observed after lateral extension, a technique for improving the shape of the bow, 200927788, for example, it is known to separate the heat-fixing step into the first segment. And a method of providing a roller between the second stage and between them (Patent Document 5), or a method for adjusting the amount of movement of the temperature between the lateral stretching step and the heat treatment step at the time of simultaneous biaxial stretching (Patent Document 6), Or a method of slowly raising the temperature from the heat treatment step to the relaxation step and the highest temperature in the relaxation step when the lateral stretching of the biaxial stretching is simultaneous (Patent Document 7). However, in these methods, although the amount of bending of the bending line of the appearance is small, the strain of the film is substantially reduced and is not well evaluated. Although there is a certain degree of correlation between the bending line of the appearance and the actual strain, it is not sufficient to prevent the bag from being curled. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. The method of strain has described a method (Patent Document 8), which discloses that an unaligned polyimide film is stretched in the longitudinal direction (flow direction) and relaxed by several %, and then stretched at a stretching ratio of 125% or less with respect to the longitudinal direction. © extending in the lateral direction (perpendicular to the flow direction), and in the expander of the lateral extension step, a preheating temperature of 80 ° C or less and a two-stage heat setting step are provided. By doing so, it is possible to obtain a boil shrinkage ratio of 3% in all directions, a good flatness of the film, and a small dimensional change at the time of humidification. However, in this method, even if the respective shrinkage ratios are small, there is still a difference in shrinkage ratio in the width direction, and since the temperature is increased during high-speed machining, there is a problem that a failure occurs due to a difference in shrinkage ratio. Further, in the method of reducing the difference in physical properties in the width direction, it is disclosed that when the longitudinal direction is extended, a temperature distribution is applied to the film at the end portion to suppress the bending of the film which is subsequently extended in the lateral direction and thermally fixed. As a result, the oblique difference in the boiling shrinkage ratio can be reduced (Patent Document 9). However, this also does not solve the phenomenon that the difference in the shrinkage ratio in the longitudinal direction is different in the lateral direction. As in Patent Document 8, there is a problem in high-speed machining. Further, there is a method (Patent Document 10) which discloses that a non-oriented unstretched film is longitudinally stretched, followed by lateral stretching to produce a film, and both ends of the film are stretched after heat treatment and relaxation treatment after fixing and lateral stretching are completed. The method of reheating is performed by releasing from the clip of the expander type lateral stretching machine and using a floating heat treatment device for blowing hot air in an arc shape and adjusting the traveling direction tension, the reheating temperature, and the helium processing wind speed. However, even if this method cannot reduce the difference in the longitudinal heat shrinkage ratio in the width direction, when the half-cut bag is processed or formed at a high speed, there is a problem that the length of the front and back surfaces is different on one side of the bag. [Patent Document 8] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In order to make the film passability of the film in the post-processing step, a method for reducing the difference in the heat shrinkage ratio in the film width direction (the heat shrinkage ratio in the longitudinal direction of the film) is proposed by the applicant (Patent Document 11). A method for revealing a method of coating a continuous shielding plate by a gas supply passage (a hot air blowing outlet) which is disposed at a predetermined interval with respect to a direction in which the film is made in the heat-fixing step of the film, and the shielding plate is covered. The width is gradually increased toward the direction in which the film is proceeding, and the temperature from the central portion to the end portion in the width direction of the film is gradually increased, so that the amount of slack at the end portion is close to the amount of slack in the central portion. [Patent Document 11] JP-A-200 1 - 1 3 8462 -11-200927788 However, in the heat-fixing process, the method of covering the continuous shielding plate only in the air supply passage (the hot air blowing port) is because of the temperature in the heat fixing zone. When the fluctuation is large, when a long-length film (unprocessed roll) of 1,000 meters or more is produced, a portion having poor passability (that is, a portion having a large difference in heat shrinkage ratio in the width direction of the film) is formed. On the other hand, as a result of deliberation on a production technique for producing a highly uniform polyamine-based resin biaxially stretched film, there is a proposal (for example, refer to Patent Document 12) to disclose a film whose film thickness and hot water shrinkage The physical properties such as the rate or the refractive index are highly uniform and wrinkles are not generated between the films at the time of lamination, and the bag making process can be performed in a good yield. [Patent Document 12] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The sheet which is melt extruded by the head is cooled and solidified to form an unstretched sheet. In the case where the molten polyimide film is directly adhered to the moving heat sink without causing a thin layer of air interposed therebetween, the molten resin can be melted and solidified. It is quenched and an unstretched sheet having a low degree of crystallinity can be obtained. Therefore, in order to force the extruded molten sheet to adhere to the cooling body surface in a short time by the cooling of the cooling roller, a wire-shaped electrode is disposed between the extrusion die and the moving heat sink to make the uncured state. A method of depositing an electrostatic charge on the surface of the sheet to forcibly adhere the uncured sheet to the surface of the cooling body (hereinafter, the forming method of the uncured film which is forcibly adhered by electrostatic charge is referred to as an electrostatic forming method) ). However, when the pulling speed of the sheet is slow, although the adhesion of the static charge deposited on the surface of the sheet is possible, if the pulling speed is increased, the adhesion of the electrostatic force by -12-200927788 is impossible, and the thin layer of air is impossible. Between the sheet which is in a molten state and the surface of the moving cooling body, the thickness variation of the sheet becomes large, the cooling of the molten sheet becomes slow, uneven cooling occurs, and crystallization is performed, and crystallization is uneven and transparency is poor. Sheet. Moreover, oligomer precipitation of the polyamine polymer occurs on the surface of the moving cooling body. Therefore, in order to increase the amount of static charge deposited on the surface of the sheet, if the voltage applied to the electrode disposed between the extrusion die and the surface of the moving heat sink is increased, a difference is generated between the electrode and the surface of the heat sink. A discontinuous arc discharge destroys the flakes on the surface of the crucible heat sink and, in severe cases, destroys the surface coating of the heat sink. Therefore, the voltage applied to the electrode cannot be increased to some extent or more. When the electrostatic formation method was previously applied, as in Patent Document 3 described above, it is desired to sufficiently increase the film formation speed to produce a highly uniform polyamido resin film roll system. possible. Further, as described above, a poly-polyamine resin in which a polyamine polymer having benzodimethylamine as a constituent component and a molten resin such as an aliphatic polyamine having different fluidity is produced is in a molten state layer. When the laminated biaxially stretched film is formed, the adhesion stability of the molten resin sheet and the heat sink is particularly inferior, and there is a problem that a continuous thickness change (cross section) occurs in the sheet. Further, there is generally known a method in which a polyimide film which is biaxially stretched is provided with a sealing layer by a dry lamination method or an extrusion lamination method to form a heat-sealable polyimide film laminate. method. After the film laminate is subjected to printing as necessary, it is molded into, for example, a bag shape and is filled with contents such as seasonings such as miso or soy sauce, water-containing foods or medicines such as soups or sterilized bags, and the like. The opening is heat-sealed to become a package for general consumption. -13- 200927788 In the formation of each layer of the polyimide film laminate having such a sealing layer, there is a problem that the adhesion between the layers is lowered when moisture intrudes. This is the cause of breakage when used as a packaging bag. For example, a sterilized food bag made of a polyimide film laminated body having a sealing layer is subjected to boiling water treatment or distillation treatment, and this problem is apparent, and the bag is more likely to be broken. Moreover, as multi-color printing becomes more common with the advancement of packaging products, there is a problem that the adhesion between layers is lowered based on the presence of printing ink. Moreover, when the adhesive layer is interposed between the biaxially stretched polyimide film layer and the sealing layer, the adhesive force is easily affected by the type of the adhesive and the humidity, especially when a moisture-curing adhesive is used. The impact is clearly apparent, and there will be significant changes in adhesion due to the season. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] In order to solve the problems of the aforementioned polyamidide-based biaxially stretched film, the object of the present invention is to provide a polyamidide double layer suitable for packaging applications. A shaft-stretching film and a vapor-deposited polyamine-based laminated resin thin film, which are excellent in oxygen barrier properties, impact resistance, and bending fatigue resistance when used as a film for packaging, and are used as various packaging materials. It is possible to prevent the content from being deteriorated or discolored, and it is also effective in preventing breakage of the product due to vibration or impact during transportation or protecting the quality of the contents. Further, in order to provide a better aspect, a polyamine-based laminated biaxially stretched film suitable for packaging use is provided, and the film passability of the heat treatment step in the post-processing of the film is regardless of the post-processing. Conditions, the back of the bag on one side of the bag with a good overall length of the roll and the half-cut side of the bag--14-200927788 have little difference in shrinkage and no curling. At the same time, the film quality necessary for the film for packaging is the oxygen barrier property. It is excellent in impact resistance and bending fatigue resistance. When used as various packaging materials, it can prevent deterioration or discoloration of the contents. It also has an effect on preventing breakage of the product due to vibration or impact during transportation or protecting the quality of the contents. Further, in order to provide a better aspect, a polyamine-based biaxially stretched film suitable for packaging applications is provided, which is excellent in water-repellent resistance and heat-resistant water-repellent property after lamination. © [Means for Solving the Problem] In order to achieve the above object, the present invention adopts the following configuration. A polyamidominated biaxially stretched film characterized by a mixed benzylation consisting of m-xylylenediamine, or m-xylylenediamine and p-xylylenediamine. The diamine is used as the main diamine component, and the α,ω-aliphatic dicarboxylic acid component having 6 to 12 carbon atoms is used as the main dicarboxylic acid component, and the metaxylylene group-containing polyamine polymer is used as the main component. At least one side of the resin layer (tantalum layer), a polyamine-based laminated biaxially stretched film composed of a resin layer (anthracene layer) mainly composed of an aliphatic polyamine resin is laminated, and the following necessary conditions are satisfied (1) ~(3), (1) The ratio of the metaxylylene group-containing polyamine polymer in the resin layer (tantalum layer) mainly composed of the metaxylylene group-containing polyamine polymer is 99 weight % or more, and no thermoplastic elastomer is added or added in a ratio of less than 1% by weight, (2) a laminate film of the above-mentioned polyamide-based biaxially stretched film and a polyethylene film having a thickness of 40 μm at a temperature of 23 ° C In a 50% relative humidity environment, use a flex fatigue tester (Gelbo-Flex Tester) 1 minute -15- 200927788 The speed of the 40-cycle cycle is continuously performed for the bending test of the 2000 cycle, the number of pinholes is 1 以下 or less, and (3) the oxygen permeability of the temperature of 23 ° C and the relative humidity of 65%. 150ml/m2· MPa · day or less. 2. The polyamine-based laminate biaxially stretched film according to the above item 1, wherein the peeling strength is when the laminate film of the polyimide-based biaxially stretched film and the polyethylene film having a thickness of 40 μm is peeled off between the layers. 4 · ON/1 5 mm or more. 3. The polyamine-based laminated biaxially stretched film according to the above item 1, wherein the thermoplastic elastomer system is 0.5% by weight or more and 8.0 in the resin layer (B layer) mainly composed of C) aliphatic polyamide resin. It is added in the form of a mixing ratio of weight% or less. 4. The polyamidiminated biaxially stretched film of the above item 2, wherein the thermoplastic elastomer system is 0.5% by weight or more and 8.0% by weight in the resin layer (B layer) mainly composed of an aliphatic polyamide resin. Hereinafter, the metaxylylene group-containing polyamine polymer is added in a mixing ratio of 1.0% by weight or more and 12.0% by weight or less. The polyamine-based laminated biaxially stretched film according to the above item 1 or 2, wherein the polyamidamide-based laminated biaxially stretched film satisfies the following formula (I), Pa <l/[t(0.0 1 5x + 0.1 5)] (I) (wherein X represents the content (% by weight) of the metaxylylene group-containing polyamine polymer in the film, and Pa is expressed in Oxygen permeability (ml/m2·MPa·day) of a film having a temperature of 23 ° C and a relative humidity of 65%, and t is a film thickness (mm). 6. Polyamine-based laminate according to item 1 or 2 above. In the biaxially stretched film, the thickness of the layer A is 10% or more and 30% or less of the total thickness of the layer A and the layer B. 7. The polyamine-based laminate biaxially stretched film according to item 1 or 2 above, wherein -16·200927788 has a film thickness of 5 to 100 μm. 8. The polyamidiminated biaxially stretched film according to the above item 1 or 2, wherein the refractive index in a direction which forms an angle of 45 degrees with respect to the winding direction of the film, and a direction which forms an angle of 135 degrees with the winding direction of the film. The difference in refractive index Δ nab is 0·003 or more and 0.013 or less, and the following requirements (4) and (5) are satisfied, and (4) a film having a length in the width direction of the film of 80 cm or more is used in the film. Five samples were equally divided in the width direction, and five samples taken from the center portion of each of the film bundles divided into five in the width direction were taken to obtain a film winding direction after heating at 160 ° C for one minute. When the heat shrinkage rate is HS 160, the difference between the maximum 値 and the minimum HS of the HS 160 is determined as 'the difference is 0.15% or less. (5) All of the HS160 series of the above five samples are 0.5% or more and 2.0% or less. 9. A method for producing a polyamidamide-based laminated biaxially stretched film, which is characterized in that the method for producing the polyamidominated biaxially stretched film of the above item 8 is contained in a filming step. Forming an unstretched sheet by melt-extruding a raw material resin from an extruder; a biaxial stretching step of biaxially stretching the unstretched sheet obtained by the thinning step in the longitudinal direction and the transverse direction; and a heat fixing step The biaxially stretched film is thermally fixed; the heat setting step is performed by a heat fixing device that satisfies the following requirements (6) to (8): (6) is disposed in a direction opposite to the traveling direction of the film. a plurality of wide air supply passages 'for blowing hot air' (7) a plurality of air outlet passages are provided with a shielding plate for shielding hot air, -17- 200927788 (8) dimensions of the shielding plates in the traveling direction of the film The system is adjusted to have substantially the same size as the air outlet of each of the air supply passages in the traveling direction of the film, and the size of each of the shielding plates in the width direction of the film is relative to the traveling direction of the film. Adjust for a longer and longer way. 10. The method according to the above item 9, wherein the biaxial stretching step extends the film in the longitudinal direction after extending in the longitudinal direction, and is disposed between the lateral extension region and the heat fixing device. There is an intermediate zone where no air blow is applied. Ο 11. The method for producing a polyamine-based laminated biaxially stretched film according to item 9 above, wherein the heat fixing device is divided into a plurality of heat-fixing regions, and a temperature difference and a wind speed difference between mutually adjacent heat-fixing regions are obtained. Any one of the product systems is 25 ° C · m / s or less. The polyamidamide-based biaxially stretched film according to the above item 1 or 2, wherein the thickness is not in the range of 3 to 10%. 13. The method for producing a polyamine-based laminated biaxially stretched film according to the above item 12, wherein the step of melting the polyamide-based resin onto the surface of the moving cooling medium to obtain an unstretched sheet, in a molten state When the polyimide film is attracted while being in contact with the moving cooling medium surface, a corona discharge in a streamer corona state is performed between the multi-needle electrode to which the DC high voltage is applied and the molten resin sheet. 14. The polyamidiminated biaxially stretched film of the above item 1 or 2, which is formed by coating an adhesive modified resin composed of a copolymerized polyester on the outermost surface of at least one surface of the film. 15. The polystyrene-based laminated biaxially stretched film according to item 14 above, wherein the coating of the adhesive modified resin is coated with a coating of a copolymerized water-based dispersion of -18-200927788, the copolymerized polyester The aqueous dispersion system contains particles of a grafted polyester and an aqueous solvent having a polyester main chain and a radical polymerizable monomer containing a radical polymerizable monomer having a hydrophilic group. a grafted portion formed, and the average particle diameter of the grafted polyester particles is 500 nm or less, and the half-inch amplitude of the 13 C-NMR signal of the carbonyl carbon from the polyester backbone of the grafted polyester particles It is more than 300 Hz. 16. A vapor-deposited polyamine-based laminated resin film characterized by mixing benzene with m-xylylenediamine, or m-xylylenediamine and p-xylylenediamine Methyldiamine is used as a main diamine component; and a metaxylylene-containing polyamine polymer having a carbon number of 6 to 12 as an essential dicarboxylic acid component is used as a polydiamine polymer having a carbon dioxide number of 6 to 12; At least one side of the resin layer (tantalum layer) of the main body is formed by laminating at least one side of a polyamine-based biaxially stretched film composed of an aliphatic polyamine resin as a main resin layer (tantalum layer), and vapor-depositing inorganic substances And the following conditions (9) to (12) are satisfied, and (9) the meta-xylylene group in the resin layer (ruthenium layer) mainly composed of a metaxylylene group-containing polyamine polymer The ratio of the polyamine polymer of the base is 99% by weight or more, and the thermoplastic elastomer is not added or added in a ratio of less than 1% by weight, (10) the vapor-deposited polyamine-based resin film and the thickness of 40 The laminated film of micron polyethylene film is used in the environment of 23 t and 50% relative humidity. The flexural fatigue tester (Gelbo-FlexTester) has a pinhole number of 10 or less when the bending test is continuously performed for 20 oo cycles at an average speed of 40 minutes per cycle. (11) The above-mentioned vaporized polyamine-based laminated resin The laminate film of the film and the polyethylene film having a thickness of 40 μm was at a temperature of 23. (:, relative humidity 65% oxygen penetration -19- 200927788 rate is 50 ml/m2·MPa·day or less. (12) Lamination of the above vapor-deposited polyamine-based laminated resin film and a thickness of 40 μm ethylene film The film was subjected to a bending test using a flex fatigue tester (Gelbo-Flex Tester) at a temperature of 23 ° C and a relative humidity of 50% at an average clock of 40 cycles, at 23 ° C, relative humidity of 65. The oxygen permeability of % is 100 ml/m2 · MPa · or less. 17. The vapor-deposited polyamine-based laminated resin film of the above item 16 is a vapor-deposited polyamine-based laminated resin film having a thickness of 40 μm. When the laminated film of the polyethylene film is peeled off between the layers, the peeling strength is 4.0 N/15 5 mm. 18. The vapor-deposited polyamine-based laminated resin film of the above item 16, which is an aliphatic polyamide resin In the main resin layer (layer B), the thermoplastic system is added in a mixing ratio of 0.5% by weight or more and 8.0% by weight or less. 19. The vapor-deposited polyamine-based laminated resin film according to Item 17 above, In the resin layer (B layer) mainly composed of an aliphatic polyamine resin, thermoplastic The system is added in an amount of 5% by weight or more and 8.0% by weight or less, and the polyphthalamide polymer containing isophthalic acid is added in a ratio of 1.0% by weight or more and 12.0% by weight or less. The thickness of the layer A in the vapor-deposited polyamine-based laminated resin film of the seventeenth item is 10% or more and less than the total thickness of the layer A and the layer B. 21. The vapor-deposited polyamine layer according to the above item 16 or 17 The thickness of the film in the resin film is 8 to 50 μm. The temperature of the polymer is 1 minute in the temperature day, and the thin film of the olefin is mixed with the methyl group in the side of the sexual bomb, and its mixture is 30%, and its -20-200927788 22. The vapor-deposited polyamine-based laminated resin film according to Item 16 or 17, wherein the inorganic substance is one or more selected from the group consisting of aluminum, tantalum, titanium, surface, zirconium, hafnium, tin, copper, iron, and zinc. A metal or non-metal or an oxide, a nitride, a fluorine-containing material or a sulfide of the above-mentioned metal or non-metal. 23. The vapor-deposited polyamine-based laminated resin film according to the above item 16 or 17, wherein the inorganic substance is vapor-deposited The thickness of the film formed is 5.0 nm or more and 200 nm or less. [Effects of the Invention] 〇 The polyamine-based laminated biaxially stretched film of the present invention and the vapor-deposited polyamine-based laminated resin film have excellent oxygen barrier properties, and are excellent in impact resistance and bending fatigue resistance, and are prevented from being packaged in foods and the like. The content deterioration or discoloration has an effect, and the content can be protected from impact or vibration during transportation to cause bending fatigue, and can be effectively used as various packaging materials. The polyamine-based laminated biaxially stretched film of the present invention is more preferable. The aspect is used for the use of a content system called a hydrate, which is subjected to boiling sterilization or retort sterilization for sterilization of the contents. This sterilization is carried out on a container which is previously laminated and placed in a bag formed into a bag. Such a sterilized bag food bag is usually a biaxially oriented polyamido resin film as a base film, and laminated with various sealing materials (polyethylene, polypropylene, etc.) having heat sealability, and can be suitably used for folding. And a so-called three-way sealed bag formed by heat-sealing three sides or a form on which a label is applied" is a better aspect of the polyamine-based laminated biaxially stretched film of the present invention, which is resistant to water peeling and hot water resistance. It is excellent in peelability, and can be effectively used as various packaging materials including sterilized bag foods. -21 - 200927788 [Embodiment] Hereinafter, an embodiment of the polyamide-based layered biaxially stretched film of the present invention will be described in detail. a mixture of m-xylylenediamine or m-xylylenediamine and p-xylylenediamine used in the layer A constituting the polyamine-containing bilayer-stretched film of the present invention. a metaxylylene-containing polyamine polymer having benzenedimethyl diamine as a main diamine component and having a carbon dioxide number of 6 to 12 as a main dicarboxylic acid component , p-xylylenediamine® is preferably 30% or less in total benzenedimethyl diamine, and the constituent unit composed of benzenedimethyl diamine and an aliphatic dicarboxylic acid component is in the molecular chain. It is preferably at least 70 mol% or more. The metaxylylene group-containing polyamine polymer used in the present invention may, for example, be poly(m-xylylene hexamethylenediamine, poly-m-xylyleneheptylamine, poly-m-xylylene). Terpolymers and phthalic acid such as octylamine, poly-m-xylylene decylamine, poly-m-xylylene decylamine and poly-m-xylylenedodecandioxime a base/p-xylylene hexamethyleneamine copolymer, a meta-xylylene/p-xylyleneheptylamine copolymer, a meta-xylylene/p-benzoic acid diamine copolymer, Meta-xylylene/p-xylylene decylamine copolymer, m-xylylene/p-xylylene decylamine copolymer, m-xylylene/p-xylylene-12 a copolymer of a difunctional amine copolymer or the like and a component of the homopolymer or copolymer copolymerize a part of an aliphatic diamine such as hexamethylenediamine, such as a cycloaliphatic diamine of a pipe trap, such as p-double An aromatic diamine of _(2-aminoethyl)benzene, an aromatic dicarboxylic acid such as p-citric acid, an internal acid amine such as ε-caprolactam, an amine carboxylic acid such as aminoheptanoic acid An aromatic amine group such as p-aminomethylbenzoic acid The copolymer obtained by acid. -22-200927788 Further, the aliphatic polyamine resin used in the layer B constituting the polyamide-based biaxially stretched film of the present invention may, for example, be nylon 6 having ε-caprolactam as a main raw material. . Further, the other polyamide resin may be a polyamine resin obtained by polycondensation of an intrinsic amine of 3 or more rings, an ω-amino acid, a dibasic acid, and a diamine. Specific examples of the indoleamines include, in addition to the ε-caprolactam previously shown, heptane, octanosamine, laurylamine, and ω-amino acids, which may be exemplified by 6-amino groups. Acid, 7-amino heptanoic acid, 9-amino decanoic acid and 11-aminoundecanoic acid. Further, examples of the dicarboxylic acid include adipic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, sebacic acid 'undecanoic acid, dodecanoic acid, palmitic acid, and hexa Alkanoic acid, eicosadienedione acid and 2,2,4-trimethyl adipate. Further, examples of the diamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, pentamethylenediamine 'undecethylenediamine, 2, 2,4 (or 2,4,4)-trimethylhexamethylenediamine, cyclohexanediamine, bis-(4,4'-aminocyclohexyl)methane, and the like. Further, a small amount of an aromatic dicarboxylic acid such as p-citric acid, isodecanoic acid, 2,6-naphthalenedicarboxylic acid, benzenedicarboxylic acid or the like, or a small amount of an aromatic diamine may be contained, for example. Meta-xylylene quinone diamine and the like. Further, a polymer obtained by the above polycondensation or a copolymer such as these can be used, for example, 6, 7, 11, 12, 6.6, 6.9, 6.11, 6.12, 6Τ, 61, MXD6 (m-xylylene) can be used. Natamine 6 (metaxylenedipanamide 6), 6/6.6, 6/12, 6/6T, 6/61 and 6/MXD6. In the case of producing the polyamidiminated biaxially stretched film of the present invention, the polyamine resin may be used singly or in combination of two or more kinds. Further, among the above aliphatic polyamine-based resins, it is particularly preferable in the present invention that the relative viscosity is in the range of 2.0 to 3.5. The relative viscosity of the polyamide resin will affect the toughness and ductility of the obtained biaxially stretched film. 'Phase-23- 200927788 For those with a viscosity less than 2.0, the impact strength is insufficient, and the viscosity is greater than 3.5. The increase in stress causes a tendency to deteriorate. Further, in the case where the relative viscosity gram polymer of the present invention was dissolved in 50 ml of 97.5% sulfuric acid and measured at 1 °C. [△nab] The width direction of the unprocessed roll (roll mi 11) of the polyamidated laminated biaxially stretched film of the present invention Ο The winding direction of the take-up film constitutes an angle of 45 degrees and the volume Taking the winding direction of the film to form a difference of 135 degrees (absolute 値) of 0.003 or more, 0.013 to 8113 1) is less than 0. 〇 3 薄膜 film, does not produce the problem of: upper: physical difference in the width direction) . Further, it is difficult to adjust the heat shrinkage rate to a film which is strained by Δ. Further, in the present invention, the respective Aiiab at a position within 50 mm from the one end edge of the film to within 50 mm, and the larger one. [HS 1 60] Further, in the polyacetamide resin film of the present invention, when the cut portion is cut, the sample is taken from each of the cut portions from a position within a millimeter of the width of the film and from the other end edge by 50 mm. Two samples were obtained at 160 °C: the heat shrinkage rate of the film winding direction, that is, HS160, and the difference is the difference in heat shrinkage rate, in all tangential directions, and conversely, the phase is biaxially stretched, Means that a solution of 0.5 is used, and _nab is produced at a magnification of 2 5 (that is, it is better to reflect in the direction of the refractive index and degree of the direction. That is, the strain (ie, The nab is greater than 〇.〇1 3 to satisfy the determination of the Δ nab finger and the way from the other edge to the two 値 设定 设定 设定 设定 设定 之一 之一 之一 之一 之一 之一 之一 之一 之一 之一 之一 之一 之一1 〇 after the determination of the heat shrinkage rate of the HS160 take-up portion -24 - 200927788 difference is either 〇. 1 5 % or less. The polyamine-based laminated biaxially stretched film of the present invention has A/B (two kinds of two layers) or B/A/B (two kinds of three layers), or B/A/C (three kinds of three layers, with aliphatic aggregation The structure in which the quinone resin is a B-layer and a C-layer different resin layer of the main body is preferable. In terms of curl, it is particularly preferable to constitute a symmetrical layer, that is, B/A/B. Further, in the following description, Among the layers constituting the laminated film, a layer composed of a resin mainly composed of a metaxylylene-containing polyamine polymer and not located at the outermost center portion (that is, B/A/B or B/ The layer A of the A/C layer and the layer of the two layers (that is, the layer A of the thick B layer and the layer A of the thin A layer) are called core layers. The thickness of the outermost layer (that is, the B and C layers when the B/A/B or B/A/C layer is formed) and the thickness of the two kinds of two layers are mainly composed of the aliphatic polyamine resin. The layer (that is, the layer B when the layer of A/B of the thick B layer and the thin A layer is formed) is called a skin layer.

The thickness ratio of each layer of the polyamine-based laminated biaxially stretched film is preferably 10% or more, more preferably 15% or more, and particularly preferably 18% or more. The upper limit of the thickness ratio of the layer A is preferably 30% or less, more preferably 25% or less, and particularly preferably 23% or less. The lower limit of the thickness ratio of the B layer or the b layer and the C layer is preferably 70% or more, more preferably 75% or more, and particularly preferably 77% or more. The upper limit of the thickness ratio of the B layer, or the B layer and the C layer is preferably 90% or less, more preferably 85% or less, and particularly preferably 82% or less. When two kinds of three layers of B/A/B are formed, the thickness ratio of the surface layer b means the sum of the thickness ratios of the two surface layers, and the thickness of the surface layer B and the layer C when the three layers of B/A/C are composed. The ratio means the sum of the thickness ratios of the two skin layers. When the thickness ratio of the layer A is more than 30%, the pinhole is likely to increase because the bending fatigue resistance is deteriorated, which is not preferable. On the other hand, when the thickness ratio of the layer of A-25-200927788 is less than 10%, the gas barrier property tends to be deteriorated, but it is not awkward. Further, the resin forming the skin layer is mainly composed of an aliphatic polyamide resin and a thermoplastic elastomer can be added as necessary. The lower limit of the amount of the thermoplastic elastomer to be added to the aliphatic polyamide resin is preferably 0.5% by weight or more, more preferably 1.0% by weight or more, and particularly preferably 2.0% by weight or more. The upper limit is preferably 8.0% by weight or less, more preferably 7.0% by weight or less, and particularly preferably 6.0% by weight or less. When the amount of the thermoplastic elastomer added is less than 0.5% by weight, the effect of improving the bending fatigue resistance may not be obtained. On the other hand, when the amount of the thermoplastic elastomer added is more than 8.0% by weight, there is a case where it is not suitable for packaging applications such as foods requiring high transparency (haze). Moreover, in the resin forming the skin layer, thermoplastic elastomer, aliphatic polyamide resin and other resins may be added as necessary, and a lubricant, an anti-adhesive agent, a heat stabilizer, an antioxidant, and an anti-adhesion agent may be added. An electrostatic agent, a light stabilizer, an impact modifier, and the like. The thermoplastic elastomer which can be used in the present invention can be suitably used, for example, as a block of a polyamide resin such as nylon 6 or nylon 12 and a PTMG (polybutylene glycol) or PEG (polyethylene glycol). Or a polyamide-based elastomer such as a random copolymer, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, a copolymer of ethylene and butene, a copolymer with styrene or butadiene, or the like. An ionic polymer of an olefin resin such as an elastomer or a vinyl ionomer. Further, in the polyimine-based biaxially stretched film of the present invention, a metaxylylene group-containing polyamine polymer may be added as necessary in the resin layer constituting the skin layer. By adding a meta-6-200927788 guanamine polymer containing a metaxylylene group to the resin layer constituting the skin layer, it is possible to prevent the phase-to-peel separation of the interface of the aliphatic polyamide metal-plastic elastomer constituting the skin layer and to improve the use. The thin packaging material is resistant to bag breakage. When the metaxylylene group-containing polyfluorene is added, the upper limit of the addition ratio is preferably 12.0% by weight or less, more preferably 8% by weight or less, and particularly preferably 8.0% by weight or less. When the amount of the polyamide-containing polymer containing a substituent is more than 12.0% by weight, the impact resistance of the film may be used. Further, the lower limit of the amount of the metaxylylene group-containing polymer to be added is preferably 1.0% by weight or more, more preferably 2. 〇 ❹ or more, and particularly preferably 3.0% by weight or more. When the amount of the metaxylyleneamine-containing polymer added is less than 1.0% by weight, there is a case where the packaging material which is incapable of using a film is resistant to bag breakage. On the other hand, in the resin forming the core layer, it is necessary to contain a polyamide-containing polymer having a substituent. When a resin other than the polymethylamine polymer of dimethyl group is mixed with a resin which forms a core layer, if necessary, a resin containing a meta-xylyleneamine polymer may be mixed. It is 99% by weight or more, preferably 1 Torr, and in order to obtain good gas barrier properties, it is necessary to make the other resin ratio less than 1% by weight. In particular, when the thermoplastic elastomer is mixed, the content thereof is less than 1% by weight. In this way, the thermoplastic layer can be filled in the skin layer by a skin layer containing a relatively soft aliphatic polyamine resin as a main component on the outer side of the core layer of the hard dimethylpolyamine polymer as a main component. By exhibiting a good gas barrier property by containing a meta-xylyleneamine polymer, it is possible to exhibit a good bending and fatigue resistance by a thermal body and a polyamide resin. Fatty and hot film an amine polymerization with 10.0 benzoic acid having a weight loss of polydecylamine, a polydiphenylene ester or a heat containing phenyl group, containing: At the same time, the plasticity of the poly-plasticity is changed. -27- 200927788 In the resin forming the core layer, a lubricant, an anti-adhesive agent, a thermal stabilizer, an antioxidant, an antistatic agent, a light stabilizer, and the like may be added as necessary. Impact modifiers, etc. The polyamidiminated biaxially stretched film of the present invention is a laminate film laminated with polyethylene having a thickness of 40 μm at an environment temperature of 2 3 ° C and a relative humidity of 50% by the following The method and using a Golbo-Flex Tester to perform the bending test for a continuous 2000 cycle bending test at an average speed of 40 cycles per minute, preferably 10 or less, of course, the best is 〇 One. The method for measuring the number of pinholes described above is as follows. A film which is laminated with a polyolefin or the like and cut into a predetermined size (2 0.3 cm X 2 7.9 cm) and adjusted at a predetermined temperature for a predetermined period of time, and then the rectangular test film is wound into a predetermined length. Cylindrical. Subsequently, both ends of the cylindrical film are respectively fixed to the outer circumference of the disc-shaped fixed head of the bending fatigue tester and the outer circumference of the disc-shaped movable head, and the movable head is placed in the direction of the fixed head. Rotating a predetermined angle (440°) along the axis of the parallel and opposite heads while making it close to the fixed length (7.6 cm), and then linearly advancing by a predetermined length (6.4 without rotating) After the centimeters, the movement of the movable head to the first position is referred to as one-cycle bending measurement, and the predetermined cycle (2000 cycles) is continuously repeated at a predetermined speed (40 cycles per minute). . Subsequently, the number of pinholes generated in the predetermined range (497 cm 2 ) of the film after the test was fixed except for the portions fixed to the outer periphery of the fixed head and the movable head. By the number of pinholes in the above range, the polyamido-layered biaxially stretched film of the present invention can effectively exhibit the vibration or impact when the gas barrier -28-200927788 barrier packaging material is used for transportation. The resulting fracture or micro-cavity causes an effect of leakage or deterioration of quality of the contents. The number of pinholes is preferably 8 or less, and more preferably 6 or less. In order to make the polyamine-based biaxially stretched film of the present invention have a pinhole number of 10 or less, as described above, it is possible to use a metaxylylene-containing polyamine polymer as a main component. The resin layer (layer A) is as thin as possible, and is obtained by appropriately containing a thermoplastic elastomer in a resin layer (layer B) containing an aliphatic polyamine resin as a main component. The polyamine-based laminated biaxially stretched film of the present invention preferably has an oxygen permeability of 150 ml/m2·24H·MPa or less at a temperature of 23t and a relative humidity of 65%. When the oxygen permeability is in the above range, the polyamidated layered biaxially stretched film of the present invention can effectively exhibit deterioration of the quality of the contents after the gas barrier packaging material which is used for long-term storage is used. effect. The oxygen permeability is preferably 130 ml/m2. 24 H. MPa or less, and particularly preferably 110 ml/m2·2 4H·MPa or less. Further, in the present invention, since the gas barrier property of the metaxylylene fluorene-containing polyamine polymer itself has a limit, the lower limit of the oxygen permeability is substantially 60 ml/m2. In order to make the polyaniline-based biaxially stretched film of the present invention have an oxygen permeability of 150 ml/m 2.24 H or less, as described above, it is possible to appropriately adjust the polymethylene-containing polymer by appropriately adjusting The ratio of the metaxylylene-containing polyamine polymer in the resin layer (layer A) as the main component of the guanamine polymer is extremely large, and the thickness ratio of the layer A is 1 〇 to 30% of the total thickness of the film. The scope to reach. The polyamidamide-based biaxially stretched film of the present invention is χ (% by weight) representing the metaxylylene group-containing polyamine polymer in the film -29-200927788, and t (mm) indicating the thickness of the film, When Pa (ml/m2. MPa·day) indicating the oxygen permeability satisfies the relationship of the following formula (1), gas barrier properties, pinhole resistance, and lamination adhesion can be made high and sufficient, which is preferable. . By satisfying the relationship of the formula (I), it is possible to obtain a film having a small content of MXD 6 in the film and having high gas barrier properties, and having less reduction in bending fatigue resistance and excellent economy.

Pa<l/[t(0.〇i5x + 0.15)] (I) Further, X is preferably in the range of 5 to 50 (% by weight) 't in the range of 0.008 to 0.050 mm (8 to C) (50 μm). . For example, a resin having a high gas barrier property represented by a metaxylylene-containing polyamine polymer is mixed with, for example, a gas of an aliphatic polyamine resin and another resin having a low barrier property. The progress of the two types of resin dispersion and homogenization has an inhibitory effect on the formation of an effective gas barrier structure, and the more the mixing ratio is increased, the higher the degree of mixing and homogenization is, the lower the gas barrier property is. tendency. In addition, when the single layer of the gas barrier resin and the single layer of the other resin are laminated in an incompletely mixed state, the gas barrier property of the laminated film is optimal, but in the case of lamination of the molten resin, There is a slight sway at the interface between the two types of resins, and there is a case where the gas barrier property is somewhat lowered. The present inventors have found that a polyamidamide-based laminated film satisfying the relationship of the formula (I) can effectively exhibit gas barrier properties with a small gas barrier resin ratio. That is, since a thin layer of metaxylylene-containing polyamine which is a polyimine-based biaxially stretched film of the present invention which satisfies the relationship of the formula (I) exhibits an effective gas barrier property and can maintain flexibility, Less damage to impact resistance. When deviating from the relationship of (1), for example, to compensate for the decrease in gas barrier properties -30- 200927788, it is necessary to increase the content of metaxylylene-containing polyamine polymer, but increase the metaxylylene-containing polyfluorene. In the case of an amine polymer, the pinhole resistance is deteriorated, or the amount of addition of the thermoplastic elastomer must be increased in order to compensate for the decrease in pinhole resistance. In order to satisfy the relationship of the formula, it is possible to prevent the ratio of other resins by melting the layer A in the layer A containing the metaxylylene group containing the metaxylylene group as much as possible and melting. The method of blending as much as possible without mixing different resins during extrusion or by adjusting the kneading conditions, etc. 〇 The laminated film of the polyimide-based biaxially stretched film of the present invention and polyethylene is thin. In the case of peeling between layers, the peel strength is preferably 4.0 N/15 mm or more. The method for measuring the peel strength is as follows, and a laminated film laminated with a polyolefin film or the like is cut to have a width of 15 mm and a length. 200 mm, and the strength at the peeling angle of 180 degrees between the layers of the polyimide-coated biaxially stretched film layer and the polyolefin film layer was measured at a temperature of 23 ° C and a relative humidity of 65%. The peeling strength is in the above range, and the polyamide-based laminated biaxially stretched film of the present invention can effectively exhibit vibration or impact resistance when transporting a gas barrier packaging material using the same. The fracture or micro-cavity causes the effect of leakage or deterioration of the content. The peel strength is preferably 5.0 N/15 mm or more, and particularly preferably 5.5 N/15 mm or more. Further, the upper limit of the peel strength in the present invention Depending on the adhesive strength of the adhesive resin and the film, the upper limit is substantially 8.0 N / 15 mm. The peel strength of the polyamidated biaxially stretched film of the present invention is 4. ON / 1 5 mm or more. Means, to improve the formation of the aliphatic layer of the skin layer -31 - 200927788 The interaction of the amine resin with the interface of the added thermoplastic elastomer to prevent the phase separation is effective. The specific means is based on the aliphatic polyamine resin It is effective to appropriately add a metaxylylene group-containing polyamine polymer in a range of 1.0 to 12.0% by weight in the skin layer of the main component, thereby alleviating the strain caused by the alignment caused when the film is stretched. The effect of improving the peel strength between the aliphatic polyamide resin and the thermoplastic elastomer can be exhibited. Other means are to improve the thermoplastic elastomer and the aliphatic polyamide resin. Interaction, and by increasing the degree of melt-kneading, introducing a functional group for improving the compatibility with aliphatic polyamine in the thermoplastic elastomer, and appropriately adjusting the temperature or magnification of the film extension, heat-fixing The peeling strength can be further improved by a method such as temperature. The content preservation property of the packaging material using the polyamide film as the object of the present invention, or the protection against impact, bending, and vibration during transportation can be used by using The polyamidamide-based biaxially stretched film having the above-mentioned characteristics is well-balanced. The polyamidamide-based biaxially stretched film of the present invention exhibits excellent elastic resilience at normal temperature or low temperature, and is resistant to smashing. It is excellent in properties and bending fatigue resistance, and has good processing suitability for printing or lamination, and is a suitable laminated biaxially stretched film for various packaging materials. The thickness of the polyamidamide-based biaxially stretched film of the present invention is not particularly limited, and it is usually preferably 5 to 100 μm as the packaging material, and more preferably 8 to 50 μm in thickness. The thickness of 3 〇 micron is particularly good. The polyimine-based laminated biaxially stretched film of the present invention preferably has a thickness unevenness of 3% or more and 10% or less. The thickness unevenness is 8% or less, more preferably -32-200927788, and 6% or less is particularly good. Further, the thickness is not less than 3%, and the usual production technique is difficult. The polyamine-based laminated biaxially stretched film of the present invention can be produced by the following method. For example, a method in which a polymer constituting each layer is melted using a respective extruder and co-extruded from an extrusion die can be employed; the polymer constituting each layer is melt-extruded in a film form and then passed through a layer. The method of laminating the stacking method, and the method of combining the same, etc., are preferably carried out by melting the polymers constituting the respective layers by using respective extruders and co-extruding © from an extrusion die. The extension method can be manufactured by a platform-type sequential biaxial stretching method, a platform-type simultaneous biaxial stretching method, and a tubular method, and a platform-type sequential biaxial stretching method. Here, a film is produced by a melt coextrusion method and a plateau sequential biaxial stretching method as an example. The raw material resin is melt-extruded from two extruders according to a co-extrusion method, joined by a feed block, and extruded from a T-shaped die in a film form, and supplied to a cooling roll for cooling to obtain B. Two types of three-layered layers of layer/A layer/B layer constitute an unstretched film of tantalum. In this case, the resin meltability of each extruder is arbitrarily selected in the range of the melting point of the resin constituting each layer + l ° ° C to 50 ° C. From the uniformity of the film thickness or the prevention of deterioration of the resin, the layer A composed of the metaxylylene-containing polyamine polymer is 245 to 290 ° C, preferably in the range of 255 to 280 ° C. The B layer composed of the aliphatic polyamine resin is 230 to 280 ° C, preferably in the range of 25 ° C to 2 70 ° C. The obtained unstretched sheet is guided to a roll type longitudinal stretching machine, and the temperature in the range of 65 to 100 ° C is used, and the temperature in the range of 80 to 90 ° C is extended in the longitudinal direction by 2.0 to 5.0 times. Preferably, it is 3.0 to 4.0 times, and then introduced into the expander type horizontal-33-200927788 to the stretching machine, in the range of 80 to 140 ° C, preferably in the range of 100 to 130 ° C, the lateral extension is 3.0~ 6.0 times, preferably 3.5 to 4.0 times, heat-fixed in the range of 180 to 230 ° C, preferably 200 to 220 ° C, and in the range of 〇 to 8%, preferably 2 to 6 The range of % was subjected to relaxation treatment to obtain a polyamine-based laminate biaxially stretched film. In the present invention, a polyamine-containing layer biaxially stretched film which is capable of satisfying the scope of the claims, particularly Δ nab, and the necessary conditions (4) and (5), can be produced by the following method. The raw material, that is, the polyamine-based resin crystal granules, can be melt-extruded, and the obtained unstretched film (unstretched laminated film or unstretched laminated sheet) can be oriented in the machine direction (longitudinal direction) and transverse direction (width direction). After the biaxial stretching, the wound is wound up in a roll shape and heat-sealed by a method described later. The raw material resin is melt-extruded from two extruders according to a co-extrusion method, joined by a feed block, and extruded from a T-shaped die in a film form, and supplied to a cooling roll for cooling. An unstretched film composed of two types of three layers of a B layer/A layer/B layer is preferable. In this case, the resin meltability of each extruder is arbitrarily selected in the range of the melting point of the resin constituting each layer + 10 ° C to 50 ° C. From the basis of the uniformity of the film thickness or the deterioration of the resin, the layer A composed of the metaxylylene-containing polyamine polymer is 245 to 290 ° C to 25 5 to 2 80 °. The range of C is preferably from 230 to 280 ° C in the case of the B layer composed of the aliphatic polyamine resin, and preferably in the range of from 250 ° C to 270 ° C. Further, in order to adhere the sheet-like melt to the spin-cooling drum, it is quenched into an unstretched sheet, and a well-known method can be applied. For example, a method of using an air scraper for a sheet-like melt or applying an electrostatic charge can be suitably applied. Method and so on. These methods are preferred to use the latter. The method of cooling the air surface of the sheet can be carried out by a method known from -34 to 200927788, for example, a method of bringing the sheet surface into contact with the cooling liquid in the tank; and a method of applying the evaporated liquid to the air surface of the sheet using a spray nozzle; or And a method of cooling by blowing a high-speed air stream. The unstretched sheet thus obtained was further stretched in the biaxial direction to obtain a film. The method of extending the film in the biaxial direction may be carried out by extending the obtained unstretched sheet in the longitudinal direction by a roll or a spreader type stretching machine, and extending in the transverse direction orthogonal to the first extending direction. method. The extension temperature in the length direction is preferably 4 5 to 1 00 ° C, and the stretching ratio in the length direction is preferably 2.5 to 4.0 times, more preferably 3.0 to 3.6 times. When the temperature in the longitudinal direction is less than 45 °C, it is not preferable because the film is easily broken. Further, when it is more than 100 °C, the thickness of the obtained film is uniformly deteriorated, which is not preferable. When the stretching ratio in the longitudinal direction is less than 2.5 times, the thin planarity obtained is deteriorated, which is not preferable. Further, when the ratio is more than 4.0 times, the alignment in the longitudinal direction becomes strong, so that the frequency of the fracture in the lateral direction becomes large, which is not preferable. When extending in the width direction, the stretching temperature is preferably 80 to 2 1 0 ° C, more preferably 100 to 20 0 ° C. When the transverse stretching temperature is less than 80 ° C, the film is easily broken due to C), which is not preferable. Further, when the thickness is more than 210 ° C, the thickness of the film obtained is uniformly deteriorated, which is not preferable. The stretching ratio in the width direction is preferably 3.0 to 5.0 times, and is 3.5 to 4.5 times. When the stretching ratio in the width direction is less than 3.0 times, the thickness unevenness of the obtained film thickness is deteriorated, which is not preferable. When the stretching ratio in the width direction is more than 5.0 times, the frequency of fracture at the time of stretching becomes large, which is not preferable. Next, heat setting treatment is performed. The temperature of the heat setting treatment step is preferably 180 ° C or more and 230 ° C or less. The temperature of the heat setting treatment step is less than 18 〇. (: When the absolute shrinkage of the heat shrinkage rate is large, it is not good. Conversely, when the temperature of the heat-fixing treatment step is greater than 230 °C, the film becomes yellow or the machine strength is easily weakened by the -35-200927788' Further, the frequency of the fracture is increased, which is not preferable. The appropriate heat setting method is as follows. The heat-fixing treatment makes the leading end of the guide roller of the holding device narrow, and the heat shrinkage rate during the relaxation treatment, particularly the width direction of the control. The heat recovery is effective. The temperature of the relaxation treatment is preferably selected from the range of the heat setting treatment temperature to the glass transition temperature Tg of the polyresin film, to (heat treatment temperature) - l ° ° C to Tg + 10 ° c. The width relaxation rate is preferably 1 to 1. The effect is less when it is less than 1%, the planarity of the film is greater than 1%, or the film is turbulent in the expander, etc., which is described herein. After extending in the longitudinal direction, the method of extending the direction is performed, but the extension order may be reversed. Further, the extension and the lateral extension may be performed in one stage in each direction, or may be separated by two stages or more. not In addition to the method of stretching the film in order, the unstretched film may be simultaneously stretched in the longitudinal direction and the simultaneous biaxial stretching method. However, it is important to adopt the most suitable temperature condition or the stretching ratio to satisfy the characteristics of the present invention. It is sufficient if the film properties obtained in the most C) can satisfy the requirements of the present invention. Next, an example of a method for obtaining a polyimine-based biaxially stretched thin film which is capable of satisfying the special Δnab, the necessary conditions (4) and (5) of the patent application range will be described. Usually, the heat-fixing treatment of the stretched film is mostly carried out in a heat-fixing apparatus in which a plurality of air supply passages each having a strip-shaped hot air blowing port are vertically arranged in the longitudinal direction. Further, in the heat fixing device having such an air supply passage, in order to make the heating efficiency good, the air attached to the heat fixing device circulating fan suction heat fixing device is fixed to the shrinkage ratio of the amine to 10%, and the shaft is oriented in the wide longitudinal direction. After the horizontal and vertical cross-section, the film is fixed with a long setting, and the gas is heated, and the air is heated and then discharged from the hot air outlet of the air supply passage to perform the so-called "hot air blowing". The "hot air circulation" that attracts the air to be sucked by the circulating fan to blow out the hot air. Further, as described above, the difference in the heat shrinkage ratio in the width direction of the film (the difference between the HS160 at the one end edge and the HS160 at the other end edge) is caused by the fact that the heat treatment is not promoted in the longitudinal direction of the end edge of the film. Further, by the heat-fixing treatment, the central portion of the hot air blowing 2, 2·· is covered with the continuous large concealing shield S, s··· (refer to Japanese Laid-Open Patent Publication No. 2001-138462), the film of the short strip can be improved in the heat-fixing treatment at the low-temperature post-processing, but the passability of the long film or the high temperature is performed. There was no improvement in the passability of the heat treatment of the processing. In order to ascertain that the continuous large-sized shielding plate is attached to the hot air blowing port of the air supply passage, the inventors of the present invention cannot improve the "passivity of the long film _ or the "passivity during the heat setting treatment of the post-processing at a high temperature". The analysis of the phenomenon in the heat fixture is performed in detail. As a result, it was found that when the continuous large-sized shielding plate spanning the plurality of root air supply passages was covered by the hot air blowing port of the air supply passage, the shielding plate caused the flow of the hot air blown from the hot air blowing outlet of the air supply passage to be significantly restricted, resulting from The above-mentioned "hot air circulation" cannot be smoothly performed, and temperature fluctuation occurs in the heat fixing device. The inventors of the present invention presumed that the above-mentioned "temperature fluctuation phenomenon" may be caused by insufficient heat relaxation at the edge of the end of the film, and for the "passage of the long film" or the heat setting process of the post-processing at a high temperature. The passability has a negative impact. Further, the inventors of the present invention presumed that it is possible to improve the temperature of the heat-fixing device, the amount of wind, and the like, and to improve the coating method when the hot air blowing port of the air supply passage is covered by the shielding plate-37-200927788, the above-mentioned "hot air circulation". It is possible to smoothly perform the "temperature fluctuation phenomenon", and it is possible to improve the "passivity of the long film" and the "passivity during the heat setting process of the post-processing at a high temperature". Further, it was observed that the relationship between the temperature of the heat setting device, the air flow condition, the coating state of the shielding plate, and the passability of the film after the processing was grasped by the result of the trial and error, and the film was taken when the film was manufactured. The means of (A) has a tendency to improve the "passivity of the long film" or the "passivity during the heat setting process of the post-processing at a high temperature". Further, based on the above findings, the inventors of the present invention have found that the passability of the post-processing is good by adopting the following means (A) and using the following means (B) and (C). Film. (A) Adjustment of the temperature and air volume of the air supply passage of the heat fixture (B) Adjusting the blocking condition (C) of the hot air outlet of the air supply passage of the heat fixture between the extension zone and the heat fixture The above-described means will be described in order of the following steps of heating. Ο (A) Adjustment of temperature and air volume of the air supply passage of the heat fixing device In the manufacture of the film of the present invention, the temperature difference and the wind speed difference between the mutually adjacent heat fixing regions of the heat fixing device are both It is preferable that the temperature and the amount of the hot air blown from each of the air supply passages are adjusted in a manner of 2,500 ° C. m/s or less. For example, when the heat fixture is divided into the first to third heat-fixing zones, the temperature difference between the first zone and the second zone and the wind speed difference, and the temperature difference between the third zone and the third zone are The product of the wind speed difference is preferably adjusted to 250 ° C · m / s or less. By adjusting the temperature and the air volume of the hot air blown from the hot air outlet of the air supply passage in each of the heat fixing zones, the discontinuous shielding plate of -38 to 200927788, which will be described later, is attached to the hot air outlet of the air supply passage, and can smoothly In the "hot air circulation" of the heat-fixing device, it is possible to effectively suppress the "temperature fluctuation phenomenon", and it is possible to obtain a long film having good passability when the post-processing is performed by high-temperature heat-fixing treatment. Moreover, when the product of the temperature difference and the wind speed difference between the mutually adjacent heat fixing zones is greater than 250 ° C · m / s (for example, the temperature difference between the mutually adjacent heat fixing zones is set to 30 ° C, At the same time, the difference in wind speed between the heat-fixing zones adjacent to each other is set to l〇m/s)' because the "hot air circulation" in the heat fixing device is smoothly performed, and the "temperature fluctuation phenomenon" cannot be effectively suppressed. It is not good. Moreover, when the product of the temperature difference between the adjacent heat-fixing zones and the wind speed difference is greater than 25 0 ° C · m / s, it flows into the downstream from the upstream heat-fixing zone as the accompanying accompanying flow generated by the film. The temperature of the air in the heat-fixing zone becomes larger because it affects the temperature stability in the width direction of the downstream heat-fixing zone, which is not preferable. Further, the product of the temperature difference and the wind speed difference is preferably 200 ° C · m / s or less, more preferably 1 50 ° C · m / s or less. (B) Adjustment of the blocking condition of the air supply passage of the heat fixing device, in the film production of the present invention, as described above, after the hot air temperature and the air volume blown from the hot air blowing port of the air supply passage of each heat fixing zone, Instead of installing a continuous large shield plate that spans the plurality of air supply passages disposed in the heat fixture, the installation is as shown in Fig. 2 to blow the hot air of the respective air supply passages 3, 3 · · · The outlet (nozzle) 2, 2. · · Each of the shielding methods to install the rod-shaped shielding plate S, S. . . is better. Further, when the rod-shaped shielding plate is attached to each of the air supply passages, the shielding plates of the same length are not attached to the respective air supply passages, so that the length of the shielding plate is gradually increased from the inlet to the outlet of the heat fixing device. Refer to Figure 1). Further, in consideration of thermal expansion in the heat-fixing device of -39-200927788, it is preferable that the shielding is excellent, and if it is capable of withstanding heat-fixing or adhering the film, there is no particular limitation between the (C) extension region and the heat fixing device. After the biaxially extending polyamine-based resin film is laterally stretched, the film is manufactured by heat-fixing treatment, and between the longitudinal and laterally extending zone devices, the positively-integrated region is completely disposed between the extension zone and the heat fixture. More specifically, the extension zone and the heat fixing condition are set, and in the state of the extension zone and the hot square paper sheet, the middle zone of the hot air blown by the hot air of the paper sheet and the hot air of the heat fixing device When the film formed by the externally produced film is exposed to be insufficiently shielded, the heat-fixing device is insufficient, and it is not preferable in the post-processing. As described above, the "hot air circulation" in the above (A)' can be used to smoothly move the phenomenon. As a result, the width direction can be sufficiently relaxed, and the "heat-fixing treatment of the long film post-processing" can be improved. By suppressing the "temperature fluctuation phenomenon" of the material of the board by using a heat-fixing device provided with an air supply passage, the temperature of the same material is used and the film is not polluted (the setting of the intermediate portion) can usually be In the above-mentioned longitudinal direction, it is preferable to perform the blocking of the heating in the intermediate portion of the hot-air blowing of the heat-fixing heat-fixing treatment in the thin region of the present invention. The adjustment is made to be better than the way in which the film is manufactured, and the hanging device is suspended vertically in a vertical direction. Moreover, it can be connected without being surrounded by an active shell. In the case where the shielding effect of the shielding plate in the hot air in the intermediate zone is good, the film passing property is - (C), and in the heat fixing, the length of the end edge of the wave direction in the temperature can be suppressed. Passivity or "high temperature progress J. In addition, in the above description, the method of making the "hot air circulation" smooth is displayed. The above description reveals the technical idea that the film of the present invention can be obtained when the production level imparts thermal energy to the film, but if the manufacturer can easily implement the technical idea by a method different from the above method, The film of the present invention can also be obtained by different methods. In other words, even in other types of heat-fixing devices, the "hot air circulation" can be smoothly performed to suppress the "temperature fluctuation phenomenon", and the film is sufficiently sized to sufficiently lengthen the length of the end edge in the width direction. The heat energy can obtain a film which has improved "passage of a long film" or "passivity at the time of heat treatment after high temperature processing" of the film of the present invention. In the polyamidated biaxially stretched film of the present invention, in order to obtain a film having a particularly small thickness unevenness, in the melt extrusion step of the resin, the molten resin sheet extruded from the T-shaped die is flat on the cooling roll. When it is cooled to obtain an unstretched polyamine-based resin sheet, the melting is improved by generating a corona discharge in a streamer corona state between the electrode and the melt-extruded polyamic acid-based resin sheet. A method of adhering the resin sheet to the cooling roll is preferred. As a result, it is possible to obtain a current of several tens of times or more when compared with the above-described electrostatic molding method, and it is possible to obtain an unstretched sheet of a polyamide resin having stable properties and thickness. Here, the corona discharge in the state of the flow photocathode refers to a stable corona state in which the electrode and the ground plate (molten resin sheet) are bridged (refer to Japanese Patent Publication No. 62-41095). When the electrode is at a positive potential, the corona is concentrated in a rod shape from the tip end of the electrode, and when the electrode is at a negative potential, a corona that expands in a bell shape from the tip of the electrode in the form of a bell-shaped enlargement is formed in the flow of the present invention. The corona discharge in the state can be used in any state of corona discharge. In the present invention, when a polyacetamide-based resin sheet which is not extended to -41 to 200927788 is obtained by a corona discharge in a state of a light-emitting state, a discharge is arranged discontinuously in order to stably generate a corona discharge in a flow photo-state state. The point is better. Therefore, a multi-needle electrode (an electrode in which a long-shaped support body covered with an insulator such as tantalum is provided with a plurality of needle-like bodies in the same direction and having almost no gap) or a saw blade shape The electrode is preferred, but the invention is not particularly limited. The number of discharge points or the arrangement method can be arbitrarily selected. Further, the material of the discharge body may be any material if it is electrically conductive, and examples thereof include metal (particularly stainless steel), carbon, and the like. Further, it is preferable that the needle-shaped body of the multi-needle electrode has a sharp apex shape at the tip end. Further, when the tip end of the needle-like body has an acute angle, since the corona discharge state in the flow photo-current state is more stable, the thickness of the portion other than the tip end is preferably 0.5 to 5.0 mm φ (diameter), and 1.0 to 3·0. Mm φ is better. Further, it is not necessary to discharge the molten resin from all the needle-shaped bodies of the multi-needle electrodes, and it is possible to appropriately change the interval of the corona discharge in the flow photo-current state in accordance with the adjustment of the applied voltage or the like. Further, in the method of the present invention, in order to stably generate a corona discharge in a flow photo-state state, for example, it is preferable that the C) gap between the discharge point of the electrode and the molten resin sheet is 2 to 20 mm, that is, 2 to 10 mm is Very good. By arranging the discharge point in this manner, a flow photo-foam discharge with a stable brilliance is generated between the electrode and the polyamicamide-based resin sheet in a molten state, and a high current flows. Further, the thickness of the sheet formed by the present invention is not particularly limited, and is preferably 50 to 500 μm, more preferably 100 to 300 μm. On the other hand, the pulling speed of the sheet formed by the present invention is also not particularly limited. The maximum speed at which traction can be achieved by the prior electrostatic application molding method is about 50 ft/min, but in the method of the present invention, even if the traction speed is higher than about 80 ft/min, the adhesion can be adhered. Further, as described above, when the corona discharge in the corona state of the streamer-42-200927788 is used, the maximum speed at which the traction can be increased is drastically increased, but when the corona electricity in the state of the photo-halo state is used at the normal traction speed, The film is more stable and the frequency of breakage is significantly reduced. Further, as described above, when the corona discharge in the state of the flow photo-foam is performed, when the applied voltage is adjusted in the range of 7 to 14 kV, the thickness of the film roll is uneven, the physical properties are changed, or the unevenness is lowered. good. Further, in the method for producing a film roll of the present invention, the unevenness of the applied voltage is preferably within ±20% of the flat voltage (setting 値), and more preferably ±10% or less. 〇 Moreover, as described above, when the corona discharge in the state of the flow photo is performed,

The environment around the electrode is in a range of a humidity of 40 to 85% RH and a temperature of 35 to 〇, so as not to be in a dry state. However, when it is slightly humidified and not adjusted in a dew point, it is possible to prevent the oligomer (ε-caprolactam oligomer or the like) from adhering to the tip end of the electrode needle or the tip end of the saw blade, and it is a flow photo halo. The state of the corona discharge is better. Further, the humidity range is 60 to 80% RH, and the more preferable temperature range is 40 to 50 ° C. Next, the method of the present invention will be described using the drawings, and the fifth drawing is a sheet process of the method of the present invention. An explanatory diagram of an embodiment. In the drawing, the sheet-like melt 12 is extruded from the extrusion die 11, and is cooled and solidified by the cooling cylinder 13 to become the unstretched sheet 14. A voltage is applied to the electrode 16 by the DC high voltage power 15, and the flaky melt is caused to flow from the electrode 16 to the photo-electric discharge. In order to obtain a film having a small degree of unevenness in the polyamidated biaxially stretched film of the present invention, and winding the molten resin on a roll of a metal roll or the like, by using a void (that is, from a T-die) The distance from the outlet of the lip to the vertical direction of the chill roll surface is adjusted to 20~60 mm, and at the same time, the use of the ground release will be in the form of a 55-shaped 〇 〇 5 5 5 - - - - - - - - - - - - - A suction device such as a vacuum box (vacuum chamber) having a wide suction port is sucked in a direction opposite to the winding direction across a portion where the entire width of the molten resin contacts the molten resin and the cooled surface, thereby forcibly causing The method of adhering the molten resin to the metal roll is preferred. Further, at this time, the suction wind speed of the portion of the suction port is adjusted to 2. 0~7. 0 meters / second is better, to adjust to 2. 5~5. 5 meters / sec is better. Further, the suction port of the vacuum box may be a series. In order to easily adjust the suction wind speed at the suction port, the suction ports are divided into a plurality of sections in the lateral direction, and each section can adjust the respective suction wind speeds. Further, when the casting speed is increased, the accompanying flow causes the molten resin to adhere to the metal roll as the metal roll rotates, and the molten resin is promoted to the metal in order to make the suction by the suction device more effective. The degree of adhesion of the roller to the upstream side adjacent to the suction device is set to a shield plate which is widely formed using a soft material such as Teflon (registered trademark) (opposite to the direction of rotation of the metal roller with respect to the suction device) Side), to interrupt the accompanying flow is better. Further, it is preferable to suppress the unevenness of the suction wind speed of the vacuum box to an average suction wind speed (setting 値) ± 2 0 % or less, and it is more preferable to suppress it to within ± 1 〇 %. Further, it is preferable to provide a filter in the vacuum chamber so that the vacuum chamber and the draft speed are not changed by the dust of the oligomer or the like, and the suction force is adjusted by feeding back the differential pressure before and after the filtration. Further, the polyamidide-based biaxially stretched film of the present invention can contain a lubricant, an anti-adhesive agent, a heat stabilizer, an antioxidant, an antistatic agent, a light stabilizer, and the like in a range that does not impair the properties. Various additives such as impact modifiers. In particular, it is preferable to contain various inorganic particles for the purpose of improving the smoothness of the biaxially stretched film. Further, an organic slipper such as ethyl bis-stearic acid is added to reduce the surface energy, and it is preferable because the film constituting the film roll - 44 - 200927788 is excellent in slipperiness. Further, in the polyamidated biaxially stretched film of the present invention, heat treatment or humidity control treatment can be applied according to the use for improving dimensional stability, and corona treatment, coating treatment or flame treatment can be applied for improvement. Adhesion of the surface of the film, or processing by printing, vapor deposition, or the like. Hereinafter, a method of applying an adhesive modified resin to the surface of a polyamide-based biaxially stretched film in a preferred embodiment of the present invention will be described. Further, in the present invention, the "dispersant" means an emulsion, a dispersion or a suspension, and the "grafting" means that a graft portion composed of a polymer different from the main chain is introduced into the polymer main chain. The "branched polyester" means a polyester/aqueous solvent having a graft portion composed of a polymer different from the polyester main chain, and means a solvent mainly composed of water and containing an aqueous organic solvent as necessary. . (Copolymerized Polyester Aqueous Dispersion) The copolymerized polyester aqueous dispersion which can be used in the present invention contains particles of a grafted polyester, water, an aqueous solvent or an organic solvent, and exhibits a semi-transparent to milky appearance. The grafted polyester is preferably a graft portion having a polyester main chain and a ruthenium-based polymerizable monomer (containing a radical polymerizable monomer having a hydrophilic group). The average particle diameter of the grafted polyester particles in the copolymerized polyester aqueous dispersion measured by the laser light scattering method is preferably 500 nm or less, preferably 10 nm to 500 nm, and 10 nm. M ~ 300 nm is better. When the average particle diameter is more than 500 nm, the coating film strength after coating is low. The content of the grafted polyester particles in the copolymerized polyester aqueous dispersion is preferably from 1% by weight to 50% by weight, more preferably from 3% by weight to 30% by weight. When the -45-200927788 13C-NMR (measurement conditions: 125 MHz, 25 ° C, measurement solvent: heavy water, DSS signal: 5HZ or less) of the copolymerized polyester aqueous dispersion which can be used in the present invention is measured, The spectrum obtained by performing the Fourier transform of the weighting function, the half-inch amplitude of the signal from the carbonyl carbon of the polyester backbone is preferably 300 Hz or more, and the half-inch amplitude of the signal from the carbonyl carbon of the graft portion is 150 Hz or less. good. Generally, in 13 C-NMR, it is known that the chemical shift, the half-turn amplitude, and the relaxation time can reflect changes in the surrounding environment in which the observed carbon atoms are placed. For example, the signal of the polymer carbonyl carbon dissolved in heavy water can be observed to be 1 70 〜 to 200 ppm, and the half enthalpy amplitude is about 300 Hz or less. On the other hand, the signal of the polymer carbonyl carbon which is insoluble in heavy water can be observed to be 170 to 200 ppm, and the half enthalpy amplitude is about 300 Hz or more. By the polyester main chain and the graft portion in the grafted polyester particles, the particles in the copolymerized polyester aqueous dispersion which can be used in the present invention having the half-inch width as described above can be used in the aqueous dispersion medium. A core shell structure with a polyester main chain as a core is obtained. The core shell structure is referred to herein as is well known in the art, and the core portion is constructed by laminating a core portion of a core portion which is composed of a polymer which is insoluble in a dispersion medium and has an agglomerated state. And a shell portion composed of a polymer which is soluble in a dispersion medium and has a dissolved state. It is known that the structure is characterized in that a dispersion of a composite polymer which is formed by chemically bonding polymers having different solubility in a dispersion medium to each other is characteristically formed by merely mixing a polymer having different solubility to a dispersion medium. structure. Further, a mixture of polymers having different solubility in a dispersion medium cannot be present as a dispersion having a particle diameter of 500 nm or less. The particles in the copolymerized polyester aqueous dispersion which can be used in the present invention can be stabilized by the core-shell structure as described above, even if the emulsifier or organic co-solvent commonly used in the prior dispersion is not used. The dispersed state of the polymer particles to the dispersion medium. This is because the resin of the shell portion forms a sufficient hydration layer to protect the dispersed polymer particles. The coating film obtained by copolymerizing the polyester aqueous dispersion of this kind is excellent in adhesion to a polyamide film. Further, since the adhesion resistance is extremely excellent, even a film substrate having a relatively low glass transition point can be used without problems. Further, in the case of a laminate, the adhesion to the adhesive used for laminating the printing ink or the sealing layer is also very good. Therefore, by using the polyamide-based biaxially stretched film of the present invention, the obtained laminate (layered film) can remarkably improve the durability in the distillation treatment or the boiling water treatment. Further, the grafted polyester in the copolymerized polyester aqueous dispersion has a glass transition temperature of 30 ° C or less, preferably a soft grafted polyester of 10 ° C or less, which can further enhance the laminated body. Durability. (Polyester main chain) In the present invention, the polyester obtained by using the main chain of the grafted polyester is preferably a saturated or unsaturated polyester synthesized from at least a dicarboxylic acid component and a diol component. The obtained polyester may be one type of polymer or a mixture of two or more types of polymers. Moreover, polyesters which are inherently dispersed or insoluble in water are preferred. The polyester which can be used in the present invention has a weight average molecular weight of from 5,000 to 100,000, preferably from 5,000 to 50,000. When the weight average molecular weight is less than 5,000, the physical properties of the coating film such as the post-processability of the dried coating film are lowered. Further, when the weight average molecular weight is less than 5,000, since the polyester of the main chain itself is easily hydrolyzed, the formed grafted polyester cannot form a core-shell structure which will be described later. When the weight average molecular weight of the polyester is more than 100,000, the water dispersion becomes difficult to be -47 to 200927788. From the viewpoint of water dispersion, it is preferably 100,000 or less. The glass transition point is below 30 ° C, preferably below 10 ° C. The dicarboxylic acid component contains at least one aromatic dinonanoic acid, one aliphatic and/or alicyclic dicarboxylic acid, and at least one di-residual acid having a radically unsaturated unsaturated double bond. A citric acid mixture is preferred. The aromatic diacid in the diacid mixture is 30 to 99. 5 mole%, 40~99. 5% molar is preferred, aliphatic and/or alicyclic dicarboxylic acid is 〇~mol%% is preferably 〇~60 mol%, and the dicarboxylic acid having a radical polymerizable unsaturated hydrazone is 0. . 5 to 10 mol%, preferably 2 to 7 mol%, and more preferably ~6 mol%. The content of the dicarboxylic acid containing a radically polymerizable unsaturated double bond is less than 0. When the content is 5 mol%, the radical polymerizable monomer cannot be efficiently grafted with the ester, and the dispersed particle diameter in the aqueous medium tends to be large, and the dispersibility tends to be lowered. As the aromatic dicarboxylic acid, p-citric acid, isodecanoic acid, o-nonanoic acid, dicarboxylic acid, biphenyldicarboxylic acid or the like can be used. It is also possible to use sodium 5-sulfoisophthalate as necessary. 〇 As the aliphatic dicarboxylic acid, succinic acid, adipic acid, sebacic acid, diacid, dodecanedicarboxylic acid, dimer acid, an acid anhydride or the like can be used. As the alicyclic dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, these acid anhydrides and the like can be used. a dicarboxylic acid containing a radical unsaturated double bond, α, an unsaturated diacid capable of using fumaric acid, maleic acid, maleic anhydride, orconic acid, citraconic acid; containing an unsaturated double bond The alicyclic dicarboxylic acid can be preferably 2,5-northene dicarboxylic acid (endo-bicyclo-(2,2,1)-5-heptane-2,3-dicarboxylic acid) . A small carboxy group with 70 bis 3 acid poly phthalocyanine carboxylic acid carboxy group / olefin -48- 200927788 The above diol component is composed of an aliphatic diol having a carbon number of 2 to 10 and an alicyclic group having a carbon number of 6 to 12 At least one of an alcohol and a glycol containing an ether bond is used. As the aliphatic diol having 2 to 10 carbon atoms, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, i can be used. , 6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, and the like. As the alicyclic diol having 6 to 12 carbon atoms, 1,4-cyclohexanedimethanol oxime or the like can be used. The ether bond-containing diol can be obtained by adding diethylene glycol 'triethylene glycol, diethylene glycol, and adding 1 to several moles of ethylene oxide or propylene oxide to each of the two phenolic hydroxyl groups of the bisphenol. As the diol, for example, 2,2-bis(4-hydroxyethoxyphenyl)propane or the like can be used. It is also possible to use polyethylene glycol, polypropylene glycol and polybutanediol as necessary. In addition to the above dicarboxylic acid component and diol component, a trifunctional or higher polycarboxylic acid and/or a polyhydric alcohol can be copolymerized. 〇3-functional or higher polycarboxylic acid can use 1,2,4-benzenetricarboxylic acid (anhydride), pyroghuric acid (anhydride), diphenyl ketone tetracarboxylic acid (wild), 1,3,5-benzene Formic acid, ethylene glycol bis(dehydrated 1,2,4-benzenetricarboxylate), and glycerin (dehydrated hydrazine, 2,4-benzenetricarboxylate). As the trifunctional or higher polyhydric alcohol, glycerin, trimethylolethane, trimethylolpropane, and neopentylol can be used. The trifunctional or higher polycarboxylic acid and/or polyhydric alcohol is 0 to 5 mol% with respect to the total polycarboxylic acid component containing the dicarboxylic acid component or the total polyol component containing the above polyhydric alcohol. ~3 moles of the range used -49- 200927788 for better. (Grafted Portion of Grafted Polyester) The grafted portion of the grafted polyester which can be used in the present invention may be a polymer derived from a monomer mixture containing at least one hydrophilic group, or A radically polymerizable monomer which can be changed to a hydrophilic group in the future. The weight average molecular weight of the polymer constituting the graft portion is from 500 to 50,000, preferably from 4,000 to 50,000. When the weight average molecular weight is less than 50,000, hydrazine cannot sufficiently impart hydrophilicity to the polyester because the grafting ratio is lowered, and it is generally difficult to control the weight average molecular weight of the graft portion to less than 500. The grafted portion forms a hydrated layer of dispersed particles. In order to obtain a hydrated layer having a sufficient thickness of the particles and to obtain a stable dispersion, the weight average molecular weight of the graft portion derived from the radical polymerizable monomer is preferably 500 or more. In terms of polymerizability in solution polymerization, the upper limit of the weight average molecular weight of the graft portion of the radical polymerizable monomer is as described above, preferably 50,000. By controlling the molecular weight within this range, it is possible to appropriately obtain a polymerization initiator dose, a monomer dropwise addition time, a polymerization time, a reaction solvent, and a monomer composition, and if necessary, a chain transfer agent or a polymerization inhibitor is appropriately combined. . The glass transition point is below 30 °C, preferably below 10 °C. As the hydrophilic group having a radical polymerizable monomer, a carboxyl group, a hydroxyl group, a sulfonic acid group, a decylamino group, a fourth-order ammonium salt, a phosphoric acid group or the like can be used. An acid anhydride, a glycidyl group, a chlorine group or the like can be used as a group capable of changing to a hydrophilic group. The water-dispersible property of the grafted polyester can be controlled by grafting the hydrophilic group to the polyester. Among the above hydrophilic groups, since the carboxyl group is used in the technical field, the well-known acid value can correctly determine the amount of introduction of the grafted polyester-50-200927788, and in order to control the dispersibility of the grafted polyester to water, It is better. As the carboxyl group-containing radical polymerizable monomer, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or the like can be used, and carboxy can be easily produced by using contact water/amine. Acid maleic anhydride, itaconic anhydride, methacrylic anhydride, and the like. Preferred carboxyl group-containing radical polymerizable monomers are acrylic anhydride, methacrylic anhydride, and maleic anhydride. In addition to the above-mentioned carboxyl group-containing radically polymerizable monomer, it is preferred to copolymerize at least one radical polymerizable monomer having no hydrophilic group. In the case of a monomer having a hydrophilic group of 0, since the grafting of the polyester main chain cannot be smoothly produced, it is difficult to obtain a good copolymerized polyester aqueous dispersion. By copolymerizing at least one radical polymerizable monomer having no hydrophilic group, efficient grafting can be achieved. As the radical polymerizable monomer which does not contain a hydrophilic group, one or a combination of one or more monomers having an ethylenically unsaturated bond and not containing the hydrophilic group as described above can be used. Examples of such a monomer include acrylic acid, methyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, C) 2-hydroxyethyl acrylate, hydroxypropyl acrylate, and the like. Ester; methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, lauryl methacrylate, methacrylic acid a methacrylate such as 2-hydroxyethyl ester or hydroxypropyl methacrylate; an acrylic acid or methacrylic acid derivative such as acrylamide, N-methylol acrylamide or diacetone acrylamide; acrylonitrile; Nitriles such as methacrylonitrile; vinyl acetate, vinyl propionate: vinyl esters such as vinyl benzoate: vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether Vinyl ketones, vinyl-51- 200927788 vinyl ketones such as hexyl ketone, methyl isopropyl ketone; N-vinyl pyrrole, N-vinyl carbazole 'N-vinyl fluorene, N-vinyl compound such as N-vinylpyrrolidone; chlorine Halogenated ethylene such as olefin, vinylidene chloride, vinyl bromide or vinyl fluoride; aromatic vinyl compound such as styrene, α-methylstyrene, t-butylstyrene, vinyltoluene or vinylnaphthalene . These monomers may be used alone or in combination of two or more. The ratio of use of the hydrophilic group-containing monomer to the non-hydrophilic group-containing monomer is determined by considering the amount of the hydrophilic group introduced into the graft polyester, usually weight-to-weight ratio (monomer containing hydrophilic group: not The hydrophilic group-containing monomer is 95:5 to 5:95, preferably 90:10 to 10:90, and 80:20 to 40:60 for a more ambiguous range. When a single system containing a hydrophilic group uses a carboxyl group-containing monomer, the total acid value of the grafted polyester is 600-40 〇〇eq. N〇6g, with 700-3000eq. /106g is better, with 800-2500eq. /106g is the best. The acid price is 600eq. When the grafted polyester is dispersed in water, it is difficult to obtain a copolymerized aqueous polyester dispersion having a small particle diameter, and the dispersion stability of the copolymerized polyester aqueous dispersion is lowered. The acid price is 4000eq. When the amount is /106 g or more, the water resistance of the adhesive modified film formed of the copolymerized polyester aqueous dispersion is lowered. The weight ratio of the polyester main chain to the grafted portion of the grafted polyester (polyester: radical polymerizable monomer) is 40: 60 to 95: 5, preferably 55: 45 to 93: 7 60: 40 to 90: The range of 10 is better. When the weight ratio of the polyester main chain is 40% by weight or less, the excellent properties of the base polyester which have been described, that is, high workability, excellent water resistance, and excellent adhesion to various substrates cannot be sufficiently exerted, and conversely Undesirable properties of acrylic resin, that is, low processability, gloss, water resistance, and the like, may be added. -52- 200927788 The weight ratio of polyester is 95% by weight. When /〇 is above, the hydrophilicity of the graft portion of the additive is insufficient, and it is not possible to disperse. (Solvent of Grafting Reaction) The solvent of the grafting reaction is preferably constituted by a boiling point of 50 to a solvent. Here, the solubility of the aqueous organic solvent 1 is at least 1 g/L or more, preferably an organic solvent. The aqueous organic solvent having a boiling point of more than 250 ° C is slow, and it is not suitable to be dried at a high temperature by the coating film after the formation of the coating film. Further, when the boiling point is 50 ° C, when the grafting reaction is carried out as a solvent, the decomposition at a temperature of 50 ° C or lower becomes a risk of an increase in radicals, which is not preferable. An aqueous organic solvent (first group) containing a carboxyl group-containing polymerizable monomer, which contains a carboxyl group-containing polymerizable compound, and a ketone such as methyl ethyl ketone, can be preferably dissolved in a good manner. Methyl isobutyl ethers such as tetrahydrofuran, dioxane and (dioxolan); glycol ethers such as ethylene glycol diether ether, propylene glycol propyl ether, ethylene glycol ethyl ether and alcohols, for example a lower ester of methyl carbitol, ethyl carbitol or glycol ether, such as ethylene glycol ethyl ether acetate; a ketone alcohol such as diacetone alcohol such as dimethylformamide, two Methylacetamide and N· relatively, the polyester which is hardly dissolved and contains the hydrophilicity of the grafted polyester to a good aqueous content of -250 ° C means that the water is at 20 ° C A solvent of 20 g / liter or more, because of the evaporation rate 穹 can not fully remove the aqueous organic solvent, because it must be used in the agent, the handling of hazardous groups, especially the polymerizable monomer and its poly vinegar , for example, ethyl ketone acetate and cyclohexanone; cyclo1,3-dioxalanyl methyl ether, propylene glycol Glycol butyl 醆; card and butyl carbitol; Gan and ethylene glycol diacetate; N-acyl substituted amines, like methyl pyrrolidone. The hydrophilic group, in particular, -53-200927788 is an aqueous organic solvent (second group) capable of dissolving a polymerizable monomer containing a carboxyl group-containing polymerizable monomer and a polymer thereof in a relatively good manner, and examples thereof include water and a lower alcohol. Classes, lower glycols, lower carboxylic acids, lower amines, etc. It is preferred to use alcohols and glycols having 1 to 4 carbon atoms. When the grafting reaction is carried out in a single solvent, one of the first group of aqueous organic solvents can be used. When it is carried out in a mixed solvent, at least one of a plurality of the first group of aqueous organic solvents or at least one of the first group of aqueous organic solvents and at least one of the second group of aqueous organic solvents can be used.接枝 can be grafted in a single solvent from the first group of aqueous organic solvents and in a mixed solvent composed of one of the first group and the second group of aqueous organic solvents. reaction. However, the behavior of the grafting reaction, the appearance of the grafting reaction product, and the subsequent introduction of the aqueous dispersing agent, the properties, properties, and the like are each composed of one of the first group and the second group of aqueous organic solvents. A mixed solvent is preferred. This reason is due to the grafting reaction of the polyester, and the system is liable to cause gelation due to cross-linking between the polyester molecules. As described below, gelation can be prevented by using a mixed solvent. In the solvent of the first group, the polyester molecular chain expands to have a large chain elongation state. On the other hand, in the mixed solvent of the first group/second group, the polyester molecular chain system expands and has a small The spheroidal state of the filament can be confirmed by measuring the viscosity of the polyester in the solutions. When the polyester molecular chain is in a state of elongation, since all the reaction points in the polyester main chain can contribute to the grafting reaction, the grafting ratio of the polyester becomes high, and the rate of cross-linking between molecules becomes high. . On the other hand, when the polyester molecular chain is expanded to become a small spheroidal entangled state, the reaction point inside the spheroid does not contribute to the grafting reaction, and the rate of cross-linking between molecules is also lowered. Therefore, the state of the polyester molecule can be adjusted by selecting the type of the solvent -54 - 200927788, whereby the intermolecular crosslinking caused by the grafting reaction grafting reaction can be adjusted. Both high grafting ratio and gelation inhibition can be achieved by mixing and dissolving. The optimum mixing ratio of the first group/second group of mixed solvent is obtained by changing the solubility of the polyester used, etc., usually the weight ratio of the first group/second mixed solvent is 95: 5 to 10: 90, 90: 10 to 80 is better, with a range of 85: 15 to 30: 70 is better. (Radical Polymerization Initiator and Other Additives) 〇 As the radical polymerization initiator which can be used in the present invention, such well-known organic peroxides or organic azo compounds can be used. Examples of the organic peroxide include peroxybenzamide, tributyl peroxydicarboxylate, and an organic azo compound: 2,2'-azobisisobutyl 2,2'-azobis (2) , 4-dimethylvaleronitrile) and the like. The use of the radical polymerization initiator for carrying out the grafting reaction is at least 0. More than 2% by weight, more preferably 5% by weight or more. Q In addition to the polymerization initiator, for example, octanol, mercaptoethanol, 3-tert-butyl-4-hydroxyanisole or the like may be used as necessary. In this case, the radical polymerizable monomer is added in the range of 5% by weight to 5% by weight (grafting reaction), and the graft portion is formed by radical polymerization of the above-mentioned polyester by saturated double bond and the above radical polymerization. The polymerization of the monomer and/or the reaction of the polymerizable unsaturated double bond with the polymerizable terminal of the above radical polymerizable monomer is carried out. The reaction product after the grafting reaction, in addition to the target grafted polyester, also contains a polyester having no graft portion and a catalyst system according to the group 20: the manufacturer's acetonitrile, the amount system. 5 heavy base sulfur, good. The ratio of the grafting polyester in the reaction product of the reaction product of the polyester-free graft polymerizable monomer is low, and has no graft portion. When the ratio of the polymer of the polyester and the ungrafted radically polymerizable monomer is high, a dispersion having good stability cannot be obtained. In general, the grafting reaction can be carried out by adding the above-mentioned radical polymerizable monomer and a radical initiator to the solution containing the above polyester under heating, or by dropwise addition for a certain period of time, and then The reaction was carried out by heating under stirring for a certain period of time. Or, if necessary, first add a portion of the radical polymerizable monomer, and then add the residual radical polymerizable monomer and the polyinitiator to each other for a certain period of time, and then continue to heat under stirring for a certain period of time. It is allowed to react to carry out a grafting reaction. The weight ratio of the polyester to the solvent can be selected in consideration of the reactivity of the polyester and the radical polymerizable monomer and the solvent solubility of the polyester to uniformly carry out the reaction in the polymerization step. Usually 70: 30~1〇: 90, 50: 50~15: The range of 85 is better. (Water Dispersion of Grafted Polyester) 接枝 The grafted polyester which can be used in the present invention can be dispersed in water by being discharged into a water-based medium by using a solid medium or a hydrophilic solvent. In particular, in the case of a radically polymerizable gastric body having a hydrophilic group, when a monomer having an acidic group such as a sulfonic acid group or a carboxyl group is used, it is easy to neutralize the grafted polyacetate from the test compound. The polyester aqueous dispersion was copolymerized by dispersing fine particles having a polyH average particle diameter of 500 nm or less in water. When the basic compound is formed by a coating film, or when the following compound is formulated, a compound which volatilizes during baking hardening is preferable. This test -56- 200927788 is better than ammonia, organic amines and so on. The organic amines may, for example, be triethylamine, hydrazine, hydrazine-diethylethanolamine, hydrazine, hydrazine-dimethylethanolamine, aminoethanolamine, hydrazine-methyl-hydrazine, hydrazine-diethanolamine, isopropylamine or imino group. Dipropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, second butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyliminodipropylamine , 3-methoxypropylamine, ethanolamine, diethanolamine and triethanolamine. The basic compound is used in an amount such that the carboxyl group contained in the graft portion is at least partially neutralized or completely neutralized so that the pH of the aqueous dispersion is 5. 0 Ο~9. The amount of the range of 0 is preferred. The method of preparing a copolymerized polyester aqueous dispersion obtained by neutralizing a basic compound can be melted by removing the solvent from the reaction liquid by an extruder or the like under a reduced pressure after completion of the grafting reaction. Or a solid (particles, powder, etc.), and then, it is put into an alkaline compound aqueous solution and heated and stirred, or the alkaline compound aqueous solution is put into the reaction liquid immediately after the completion of the grafting reaction, and the heating and stirring are continued. Pot method) to prepare the aqueous dispersion. In terms of convenience, a one-pot method is preferred. In this case, when the boiling point of the solvent used in the grafting reaction is 1 〇〇 ° C or less, part or all of the solvent can be easily removed by distillation. (Coating of Adhesive Modification Resin) The polyamido film-based laminate of the present invention can be used as an adhesive-modified resin on at least one side of a polyamide film substrate, and can be used on a polyimide film substrate. A coating agent containing the above-mentioned copolymerized polyester aqueous dispersion is applied to form a preferred film. The above-mentioned copolymerized polyester aqueous dispersion can be used as a coating agent to form an adhesive modified film, and a crosslinking agent (curing resin) -57-200927788 can be further cured and cured to impart an adhesive modified film. Highly resistant to cross-linking agents, it is possible to use alkylated phenols, cresols and other phenol formaldehyde resins with formaldehyde; adducts of urea, melamine, benzoguanamine, etc., from these adducts and carbon atoms An amine-based resin such as an alcohol-based ether compound of 1 to 6; a polyfunctional epoxy compound; a isocyanate compound; a blocked isocyanate compound; a polyfunctional propane compound; a Bazozoline compound. Examples of the phenol formaldehyde resin include alkylated (methyl, ethyl, fluorene) isopropyl or butyl) phenol, p-third amyl phenol, 4,4'- phenol, and tert-butyl phenol. O-, m-p-cresol, p-cyclohexylphenol-isopropylidenephenol, p-nonylphenol, p-octylphenol, 3-pentadecanol, phenol, phenyl o-cresol, p-phenylphenol and dimethyl a condensate of phenol and the like with formaldehyde. The amine-based resin may, for example, be methoxylated methylol urea, methoxymethyl N,N-extended ethyl urea, methoxylated hydroxymethyldicyanodiamine-modified methylol melamine, A Oxylated methylol benzoguanamine, Q-hydroxymethyl melamine, butylated hydroxymethyl benzoguanamine, etc. 'Methylated melamine, butoxylated methylol melamine and hydroxybenzopyrene Amines and the like are preferred. The polyfunctional epoxy compound may, for example, be a bicyclic ether of bisphenol A and an oligomer thereof, a diepoxypropyl ether of hydrogenated bisphenol A, and a low diglycidyl phthalate or isodecanoic acid. Glycidyl propyl ester, p-nonanoic acid diester, diglycidyl hydroxybenzoate, diglycidyl dihydrogenate diglycidyl hydride, diglycidyl succinate, adipic acid Ester, diglycidyl sebacate, ethylene glycol diepoxypropyl _, propylene water. Condensation and formaldehyde alkyl polyfunctional oxime cyclopropyl, dibutylene, 4,4, alkane, phenolic hydroxy group of benzene, methoxybutoxy group with methoxymethylated oxypropyl polymer, Glycidyl propyl ester, hexa-epoxypropylene glycol di-58- 200927788 epoxy propyl ether, 1,4-butanediol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether and polycondensation Alkyl glycol diepoxypropyl ethers, 1,2,4-benzenetricarboxylic acid triglycidyl ester, triepoxypropyl trimeric isocyanate, 1,4-diepoxypropoxybenzene, bicyclo Oxidylpropyl propyl urea, glycerol triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, neopentyl alcohol triepoxypropyl ether, glycerol alkylene oxide adduct Ether and the like. As the polyfunctional isocyanate compound, a low molecular or high molecular aromatic, aliphatic diisocyanate or a trivalent or higher polyisocyanate can be used. The polyisocyanate is tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, phenyl diisocyanate, hydrogenation Terephthalic acid diisocyanate, isophorone diisocyanate and terpolymer of the isocyanate compounds. Further, low molecular activity such as an excess amount of the isocyanate compound and ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine or the like can be mentioned. A compound containing an isocyanate group at the terminal obtained by reacting a hydrogen compound or a stilbene active hydrogen compound such as a polyester polyol, a polyether polyol or a polydecylamine. The blocked isocyanate can be prepared by reacting the above-mentioned isocyanate compound with a blocking agent by a suitable method known in the art to prepare an 'isocyanate blocking agent, for example, phenol, cresol, xylene oxime, resorcinol. , phenols such as nitrophenol and chlorophenol; thiophenols such as benzene-sulfur and methylthiobenzene; moon bows such as acetone oxime, methyl ethyl ketone oxime, and cyclohexanone; Alcohols such as ethanol, propanol and butanol; halogen-substituted alcohols such as ethyl chlorohydrin and 1,3-dichloro-2-propanol; third butanol, third pentanol-59-200927788, etc. Tertiary alcohols; indoleamines such as ε-caprolactam, 5-valeroinamide, butyrolactam, /3-propionalamine; aromatic amines; quinone imines; Active methylene compounds such as acetaminophen, acetamidine acetate, ethyl malonate; mercaptans; imines; ureas; diaryl compounds; sodium hydrogen sulfite. These crosslinking agents may be used singly or in combination of two or more kinds. The amount of the crosslinking agent is preferably from 5% by weight to 40% by weight based on the grafted polyester. The method for formulating the ruthenium crosslinking agent can be carried out by using (1) a crosslinking agent which is water-soluble, which is directly dissolved or dispersed in an aqueous dispersion, or (2) a crosslinking reaction when the crosslinking agent is oil-soluble. After completion, a crosslinking agent is added before or after the water dispersion to coexist the core with the polyester. These methods can be appropriately selected depending on the type and properties of the crosslinking agent. Further, the crosslinking agent may be used in combination with a hardener or an accelerator. In the coating agent which can be used in the present invention, an additive such as an antistatic agent, an inorganic slip agent or an organic slip agent can be further blended in a range which does not impair the effects of the present invention. In the case of applying the adhesive-modified resin of the present invention, it is possible to further contain an additive such as an antistatic agent, an inorganic slip agent or an organic slip agent in a range that does not impair the effects of the present invention, and these are contained in the coating agent. And it is given on the surface of the substrate. In order to form an adhesive modified film, a coating agent containing a copolymerized polyester aqueous dispersion is applied to a polyimide film substrate, and a gravure method, a reverse roll method, a die method, a rod method, a dipping method, or the like can be used. A well known coating method. -60- 200927788 The coating amount of the coating agent is 0. 01~1 g / m ^ 2 as a solid component. 02~0. The coating method of 5 g / m ^ 2 is better, the coating amount is less than 〇.  When 〇 1 g/m 2 , the adhesive modified film and the other layer cannot obtain sufficient adhesive strength, which is not preferable. When it is larger than 1 g/m2, it is problematic because it causes sticking. The application of the coating adhesive-modified resin can be carried out, for example, by applying a coating agent to a biaxially stretched polyimide film substrate or by applying a coating agent to a polyimide film substrate which is not stretched or uniaxially stretched. Dry and modulate as necessary with uniaxial extension or biaxial extension heat fixation. The drying temperature after application of the coating agent is dried and heat-set at 15 (TC or more, preferably 200 ° C or more, and the coating film becomes firm and can improve the adhesion of the adhesive modified film to the polyimide film substrate. When stretching is performed after coating, in order not to impair the elongation of the coated film, drying after coating is performed to control the moisture content of the coated film to 0. A range of 1 to 2% is preferred. The extension is dried and heat-set at 200 ° C or higher, and the coating film becomes firm, and the adhesion of the adhesive modified film to the polyimide film substrate is dramatically improved. In the present invention, it is preferred to apply a coating modified agent containing a copolymerized polyester aqueous dispersion containing particles of a grafted polyester and an aqueous solvent, and grafting the adhesive modified resin. The polyester is preferably a graft portion having a polyester main chain and a radical polymerizable monomer (containing a radical polymerizable monomer having a hydrophilic group). Further, when laminating is performed using the polyamido resin-based laminated film roll of the present invention obtained as described above, for example, the following ink layer, adhesive layer, and sealing layer can be provided. -61 - 200927788 (Ink Layer) In the polyamide film-based laminate of the present invention, the ink layer can be laminated on the adhesion improving film formed on the polyimide film substrate. The printing ink forming the ink layer can mainly use an ink having a cellulose derivative as a binder or a gravure ink using a synthetic resin as a binder. In particular, in the case where water resistance is required, it is possible to add a curing agent to an ink which is a binder of vinyl chloride, polyester, polyether or polyhydric alcohol having a hydroxyl group at the terminal of the polymer chain. The ink layer is formed on the adhesive modified film into a full or partial or arbitrary pattern. (Adhesive layer) In the polyamidide-based film laminate of the present invention, an adhesive is laminated on the ink cartridge. The thickness of the adhesive layer is usually 0. 1 micron to 10 micron. The sealing layer laminated on the adhesive layer is laminated by extrusion lamination, and the adhesive forming the adhesive layer is preferably an isocyanate-based adhesive. As the isocyanate-based pressure-sensitive adhesive, a single-liquid type can be, for example, a reaction product of a diisocyanate and a polyol, and a polyurethane or polyurethane prepolymer having an isocyanate group at a molecular terminal. Alternatively, it is also possible to use a two-liquid type in which a polyol and a polyurethane prepolymer having a hydroxyl group at a molecular terminal are mixed immediately before use. The sealing layer laminated on the adhesive layer is layered by dry lamination. In the case of the adhesive, an ethylene-based, acrylic-based, polyamidiamine-based, epoxy-based, or urethane-based adhesive known to those skilled in the art can be used. Among these, a two-liquid type in which a polyol and a polyurethane prepolymer having a hydroxyl group at a molecular terminal are mixed immediately before use is preferred. The adhesive layer can be formed by applying a liquid adhesive to the ink layer by a method well known to the manufacturer. (Sealing layer) In the polyamidide-based film laminate of the present invention, a sealing layer is laminated on the above-mentioned adhesive layer. The thickness of the sealing layer is usually from 20 μm to 100 μm. The sealing layer can be extruded by a synthetic resin such as low density polyethylene (LDPE), ethylene-vinyl acetate copolymer (EVA), ionic polymer, polypropylene (PP), etc., and laminated or dry laminated. form. The adhesive modified film is located on the outermost surface of at least one side of the polyamidiminated biaxially stretched film of the present invention, and the ink layer, the adhesive layer and the sealing layer are preferably disposed on the adhesive modified film. . Further, an inorganic vapor deposited film can also be formed on the above polyimide-based thin film. The inorganic vapor deposition film can impart high gas barrier properties to the obtained polyamidated layered biaxially stretched film. Examples of the material of the inorganic deposited film having such an action include a metal or a non-metal such as Al, Si, Ti, Zn, Zr, Mg, Ce, Sn, Cu, Fe, or the like, or an oxide of the metal or non-metal. , nitrides, fluorides, sulfides, etc. Specifically, SiOx (x=1. 0~ Ο 2. 0), alumina, magnesia, zinc sulfide, titanium dioxide, zirconium oxide, cerium oxide or a mixture of these. The inorganic vapor film may be a laminate of 1 or more layers. The film thickness of the inorganic deposited film is preferably from 5 to 500 nm, more preferably from 5 to 2 nm. When the film thickness is less than 5 nm, there is a possibility that sufficient gas barrier properties cannot be obtained, which is not preferable. On the other hand, when it is more than 500 nm, it is impossible to achieve the same effect, and the bending fatigue resistance is lowered, and it is unfavorable in terms of manufacturing cost. The method of forming the inorganic vapor-deposited film can be carried out by a well-known method of -63-200927788, for example, a physical vapor deposition method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method such as PECVD. In the vacuum evaporation method, the vapor deposition material can be a metal or a non-metal such as aluminum, tantalum, titanium, magnesium, pin, bismuth, or zinc, or si〇x (x=1〇~2〇), oxidized, magnesium oxide. , a compound such as zinc sulfide 'titanium dioxide, an oxidation pin, and the like. The heating method may be resistance heating, induction heating, electron beam heating or the like. Further, the reaction gas may be introduced into a reactive vapor deposition method such as oxygen, nitrogen, hydrogen, argon, carbon dioxide gas, water vapor or the like, or by means of a method of adding ozone or an ionic auxiliary agent. Further, a method of applying a bias to the polyimide film or heating and cooling the polyimide film may be employed. The vapor deposition material, the reaction gas, the bias voltage, the heating, and the cooling can also be used in the sputtering method or the CVD method. Further, between the inorganic material vapor-deposited film and the polyimide resin-based resin, an undercoat layer may be provided as necessary. The vapor deposited film of the vapor-deposited polyamine-based laminated resin film of the present invention may be formed on at least one side of a polyamide-based bilayer-stretched film which is preferably used as a substrate, but is formed in an aliphatic polyfluorene. The surface of the film on the side of the resin layer (B) of the amine resin is preferred. The laminated film of the vapor-deposited polyamine-based laminated resin film of the present invention and a polyethylene film having a thickness of 40 μm has an oxygen permeability of 50 ml/m 2 · 24 hours at a temperature of 23 ° C and a relative humidity of 65%. . Below MPa is preferred. When the oxygen permeability is in the above range, the vapor-deposited polyamine-based laminated resin film of the present invention can effectively exhibit deterioration in the quality of the contents when the gas barrier packaging material obtained by using the gas barrier packaging material is stored for a long period of time. effect. The oxygen permeability is preferably 4 Gml/m 2 · 24 hours · Mpa or less, and particularly preferably 30 ml / m 2 · 24 hours · Mpa or less. -64 - 200927788 A laminate film obtained by laminating a vapor-deposited polyamine-based laminated resin film of the present invention and a polyethylene film having a thickness of 40 μm is used in an environment of a temperature of 23 t and a relative humidity of 50%. In the following method, a bending fatigue tester is used, and when the bending test of 2000 cycles is continuously performed at an average speed of 40 cycles per minute, the number of pinholes is preferably 10 or less, and of course, the optimum is one. The method for measuring the number of pinholes described above is as follows. It will be laminated with polyolefin and cut into a specified size (2 0. 3 cm X27. The film of 9 cm) is adjusted to a predetermined length of the cylindrical film after being adjusted for a predetermined period of time at a predetermined temperature. Subsequently, both ends of the cylindrical film are respectively fixed to the outer circumference of the disc-shaped fixed head of the bending fatigue tester and the outer circumference of the disc-shaped movable head, and the movable head is placed in the direction of the fixed head. , along the axes of the two heads that are parallel and opposite each other, making them close to the specified length (7. During the period of 6 cm), the specified angle (440°) is rotated, and then it is linearly advanced by a predetermined length without being rotated (6. After 4 cm), the movement of the movable head back to the first position is referred to as one-cycle bending measurement, and the calibration cycle is continuously repeated at a predetermined speed (40 cycles per minute). 2000 cycles). Subsequently, the number of pinholes generated in the predetermined range (49 7 cm 2 ) of the film after the test was fixed except for the portions fixed to the outer periphery of the fixed head and the movable head. When the number of the pinholes is in the above range, the vapor-deposited polyamine-based laminated resin film of the present invention can effectively exhibit breakage due to vibration or impact when the gas barrier packaging material obtained by using the gas barrier packaging material is transported or The effect of leakage or deterioration of quality caused by tiny holes. It is more preferable that the number of pinholes is 8 or less, and it is particularly preferable to be 6 or less. In order to make the number of pinholes of the vapor-deposited polyamine-based laminated resin film of the present invention from -65 to 200927788 to 10 or less, as described above, it is possible to use a metaxylylene group-containing polyamine polymer as The resin layer (layer A) of the main component is as thin as possible, and is formed by appropriately including a thermoplastic elastomer in a resin layer (layer B) containing an aliphatic polyamine resin as a main component. A method for laminating a vapor-deposited polyaniline-based laminated resin film of the present invention and a polyethylene film having a thickness of 40 μm to have an oxygen permeability of 50 ml/m 2 *24 hours·MPa or less, as described above. The thickness ratio of the resin layer (layer A) having a metaxylylene group-containing polyamine polymer as a main component can be increased as much as possible, and the thickness ratio of the layer A is appropriately adjusted to be the total film thickness. It is achieved by forming an inorganic vapor deposition film in a range of 10 to 30% of the thickness. 1 In a resin having a high gas barrier property such as a metaxylylene-containing polyamine polymer, when a resin having a lower gas barrier property such as an aliphatic polyamine resin is mixed, The progress of the resin dispersion and homogenization has a hindrance to the formation of an effective gas barrier structure, and the more the mixing ratio is increased, the higher the degree of mixing and homogenization is, the more the gas barrier property tends to decrease. . Further, when the single layer of the gas barrier resin and the single layer of the other resin are laminated in an incompletely mixed state, the gas barrier property of the laminated film is optimal, but when the molten resin is laminated, it is actually The interface between the two types of resin layers causes a slight sway, and the gas barrier properties are also somewhat lowered. It is possible to prevent the ratio of other resins by using the polyether amine polymer containing the metaxylylene group as the main component, or to reduce the ratio of other resins as much as possible, by mixing as much as possible during melt extrusion. It is achieved by means of different resin blending methods or adjustment of mixing conditions. -66-200927788 The content of the packaging material using the polyamide film which is the object of the present invention, or the protection against impact, bending, and vibration during transportation can be well balanced by use The polyamine-based laminated biaxially stretched film of the above characteristics is realized. Further, the laminated film of the vaporized polyamine-based laminated resin film of the present invention and the polyethylene film having a thickness of 40 μm was subjected to a bending fatigue tester (Gelbo-Flex Tester) in an environment of a temperature of 23 ° C and a relative humidity of 50%. When the bending test of 50 cycles was continuously performed at an average speed of 40 cycles per minute, the oxygen permeability at a helium temperature of 23 ° C and a relative humidity of 65% was 100 ml/m 2 .  MPa · day or less is preferred. The gas barrier property is deteriorated, and the bending fatigue causes pinholes and the inorganic vapor deposited film in the bent portion is broken. On the other hand, the bending fatigue resistance can suppress the occurrence of pinholes or the breakage of the inorganic vapor deposition film by plasticity, and can suppress the deterioration of the barrier property of the damaged portion of the inorganic vapor deposition film by the gas barrier property of the resin. Achieved. The vapor-deposited polyamine-based laminated resin film of the present invention is excellent in elastic resilience at normal temperature or low temperature, and exhibits excellent properties such as impact resistance and bending fatigue resistance, and processing suitability such as printability or lamination. Also good, as a suitable laminate film for various packaging materials. The thickness of the vapor-deposited polyamine-based laminated resin film of the present invention is not particularly limited. It is usually preferably 8 to 50 μm as the packaging material, and more preferably 10 to 30 μm. (Here, although the thickness of the vaporized polyamine-based laminated resin film of the present invention means the thickness of the entire film including the vapor-deposited film', but since the thickness of the deposited film is much thinner than the thickness of the substrate film of -67 to 200927788 The thickness of the base film is not substantially different. When the vapor-deposited polyamine-based resin film of the present invention is laminated with another film such as polyolefin to produce a laminate film, at least steam is formed. It is preferable to laminate other films on the surface of the plating film. [Examples] Next, the present invention will be described in more detail by way of examples (each experimental example), but the present invention is not limited to the following examples. Further, the evaluation of the film was carried out in accordance with the following measurement methods. First, the measurement method of the characteristics of the substance constituting the adhesive 0-modified film applied to the film is as follows. In addition, in the following description, regarding the mixing or composition, etc., it is abbreviated as "parts" which means heavy 〇 , 馆 Γ 〇 „ „.  Y玄圭5宙昼〇/„. [Weight average molecular weight] will be 0. 03 g of the polymer was dissolved in 10 ml of tetrahydrofuran, and was measured using a GPC-LALLS apparatus-low angle light scattering photometer LS-8000 (manufactured by TOSOH Co., Ltd., tetrahydrofuran solvent, reference: polystyrene). [Grafting efficiency of polyester]

The product obtained by the grafting reaction was measured for 1H-NMR (220 MHz, measurement solvent CDCI3/DMSO) from the proton of the double bond containing double bond component in the polyester using UNITY 500 (manufactured by VARIAN Co., Ltd.). -d6), and based on the change in the intensity of the signal, the grafting efficiency was calculated using the following formula 1. Grafting efficiency of polyester = (1 - (relative strength of signal from double bond containing double bond component in grafted polyester / relative intensity of signal from double bond containing double bond component in raw polyester) )) χ100 (%). · ·1 Further, the relative intensity is calculated by comparing the signal strength of the internal memory of the reference signal to -68-200927788. [Measurement of Weight Average Molecular Weight of Graft Portion] The hydrolysis of the polyester was carried out by refluxing the grafted polyester in a KOH/water-methanol solution. The product was decomposed by extraction under acidic conditions using THF, and purified by reprecipitating the graft portion from the extract with hexane. The polymer obtained was measured for molecular weight using a GPC apparatus (manufactured by Shimadzu Corporation, tetrahydrofuran solvent, converted to polystyrene), and the weight average molecular weight of the graft portion was calculated. ® [particle size of aqueous dispersion] The aqueous dispersion was prepared by using ion-exchanged water to prepare a solid content of concentrated N4 (manufactured by Coulter Co., Ltd.), and the particle diameter was measured at 20 °C. [B-type viscosity of aqueous dispersion] The viscosity of the aqueous dispersion was measured at 25 ° C using a rotary viscometer (manufactured by Tokyo Keiki Co., Ltd., EM type). [Measurement of the half-inch amplitude of the signal of 13C-NMR] Ο The aqueous dispersion was weighted so that the solid content concentration was 20% by weight.

The water was diluted, and then DSS was added thereto to prepare a sample for measurement. Using UNITY 500 (manufactured by VARIAN Co., Ltd.), the measurement conditions were set such that the signal of DSS was 5 Hz or less at 25 ° C, and then 13 C-NMR (125 MHZ) of the sample was measured, and the transfer curve was performed without adding a weighting function. The signal of the carbonyl carbon of the obtained polyester main chain and the half enthalpy of the signal of the carbonyl carbon of the grafted portion were each measured. [Glass Transfer Point (Tg)] The aqueous dispersion was coated on a glass plate, followed by drying at 170 ° C to obtain -69-200927788 to the polyester solid content. The solid content of the polyester was 10 mg as a sample, and the Tg was measured by scanning at a rate of 10 ° C/min using a differential scanning calorimeter. On the other hand, the film was evaluated in accordance with the following evaluation method. [Relative Viscosity (RV)] 0.25 g of the sample was dissolved in 25 ml of 96% sulfuric acid, and 10 ml of the solution was used, and the number of seconds at 20 ° C was measured by an Oswald viscometer, and was calculated according to the following formula. Relative viscosity.

Where to: the number of seconds of the drop of the solvent, t: the number of seconds of the drop of the sample solution. [Anab] ) After the film test piece was placed in an environment of 23 ° C and 65% RH for 2 hours or more, the Abbé refractometer 4T type manufactured by ATAG0 Co., Ltd. was used to measure the winding direction of the film to be taken up. The refractive index (na) of the direction constituting the angle of 45 degrees and the direction of the angle of the angle of 13 degrees with the winding direction of the wound film (that is, the direction of the angle of 90 degrees with the direction of the above 45 degrees) Rate (nb). Then, the absolute 値 of the difference between the two refractive indexes is calculated as Δ nab . The absolute enthalpy of the difference between the two refractive indexes is defined as A nab, and is calculated in accordance with Δ nab = 丨na - nb |. Δ nab was measured at both end edges of the film roll, and any larger one was used as the Δ nab of the present invention. [The heat shrinkage rate of the film] The position in the width direction of the film containing the Anab is 0.003 or more and 0.013 or less is 80 centimeters or more, and the width direction is uniformly divided into five, and the sample is cut out from the center of the portion. After air drying for 30 minutes in 50% of the environment, the heat shrinkage rate of the film winding direction after the heating at 160 °C for 10 -70 to 200927788 minutes is taken as HS 160. The sample having a width of 20 mm and a length of 250 mm in the longitudinal direction was drawn at intervals of 200 mm, and placed in a heating oven adjusted to 160 ° C. After taking out, the sample was taken at 23 ° C. After air drying for 30 minutes in a 50% environment, the heat shrinkage rate was measured for each film. The average heat shrinkage ratio of the film was calculated as the average enthalpy of the heat shrinkage rate of the five sample samples in the width direction. Further, the difference between the maximum enthalpy and the minimum enthalpy is taken as the difference in heat shrinkage rate. [Transmissibility of film] 0 Using a coater with a distance of 1,900 mm between two rolls, and setting the temperature to 160 °C and the furnace tension to 100 N, the ratio of Δη ab is 0.003 or more and 0.013 or less. The cut strips taken in the manner are heat treated. Then, the film was passed through a horizontally disposed roll having a roll interval of 2,000 mm under a tension of 98 N to evaluate the flatness of the film. Further, at the center position between the rolls having a roll interval of 2,000 mm, the iron rod is disposed such that the upper surface of the iron bar is located at a position of 30 mm from the common tangent line on the horizontally disposed roll, and the iron is passed when the film passes. When the rod does not touch the film, it is evaluated as Q, and when it is in contact with the iron, it is X. These steps are carried out continuously, and whether the film is in contact with the iron bar is visually observed. [Evaluation of wrinkles in the sealing portion of the bag] A film having a roll length of about 1,000 m was used, and an urethane-based AC agent was applied to the biaxially oriented polyamido resin film (manufactured by Toyo Morton Co., Ltd.) After "EL443"), a 15 micron LPDE (low density polyethylene) film was extruded at 315 ° C using a simple test laminator (SINGLE TEST LAMINATER) device manufactured by Modern Machinery Co., Ltd. A LLDPE (linear low-density polyethylene) film having a thickness of 40 micro-71 to 200927788 m is continuously laminated thereon to obtain a laminated film of a three-layer laminated structure composed of a polyamide resin/LDPE/LLDPE. . The laminate film which was taken up as a laminate film was subjected to a test sealing machine manufactured by Western Machinery Co., Ltd., and was folded in parallel in the longitudinal direction of the roll to form two layers, and heat-sealed continuously at 150 ° C in the longitudinal direction. Each of the two ends was 20 mm each, and 10 mm was intermittently heat-sealed at 550 mm intervals in a direction perpendicular thereto to obtain a semi-finished product having a width of 280 mm. The both edges were cut in the longitudinal direction of the wound so that the sealed portion became 10 mm, and then cut at the boundary of the sealing portion in the vertical direction to produce a three-way sealed bag (sealing width: 10 mm). After the three-party sealed bag was taken up, 10 bags were continuously sampled from the distance of 2 meters, and the sealing portion in the longitudinal direction was observed to evaluate whether or not the sealing portion was wrinkled. ◎: The bag with no wrinkles is 10 bags 〇: The bag with a little wrinkle is 1 to 3 bags X: The bag with a little crepe pattern is 4 bags or more XX: The bag with obvious wrinkles is 1 Above the bag Ο [Oxygen permeability (gas barrier property)] After the film is replaced by oxygen at 2 angels in an environment of humidity of 65% RH and a temperature of 25 °C, according to JIS-K-7126 (method B), Measurement using an oxygen permeability measuring device (OX-TRAN 2/2 0: manufactured by MOCOM Co., Ltd.) [Relative thickness unevenness] The film produced in the examples was produced in the range of the entire length in the longitudinal direction and cut into a width of 3 cm. A slit film for thickness unevenness measurement. Subsequently, an average thickness, maximum thickness, and minimum thickness of the length in the longitudinal direction of the range of -72 to 200927788 were obtained using a thickness unevenness measuring device manufactured by ANRITSU Co., Ltd. (Guang Fanyi high sensitivity electronic MICROMETERK-313A). Further, the difference between the maximum thickness and the minimum thickness and the average thickness among the maximum thickness and the minimum thickness is calculated according to the following formula, and the length is calculated by calculating the ratio (%) of the difference to the average thickness. The rate of change in thickness over the entire length of the direction. Change rate of thickness (%) = (I maximum thickness or minimum thickness - average thickness 丨 / average thickness) χ 100 [Production of laminated film] For the film produced in each experimental example, a polyester two-liquid type adhesive ( Made by MORTON Co., Ltd., TM590/CAT56=1 3/2 (parts by weight), coated with a coating amount of 3 g/m 2 , laminated with 40 μm linear low-density polyethylene film (L-LDPE film: Toyo Manufactured by the company, L16102), and aged for 3 days in an environment of 40 ° C to form a laminated film. [Pinhole resistance] The laminated film was cut into 20.3 cm (8 inches) χ 27·9 cm. The size of (1 1 inch) was adjusted by placing the cut rectangular test film (laminated film) at a temperature of 23 ° C and a relative humidity of 50% for 24 hours or more. The rectangular test film was wound into a cylindrical shape of 20.32 cm (8 inches). Then, one end of the cylindrical film was fixed to a bending fatigue tester (manufactured by Rigaku Corporation, model No. 901). (in accordance with the specifications of MIL-B-131C), the outer circumference of the disc-shaped fixed head, and will The other end of the tubular film is fixed to the outer circumference of the disc-shaped movable head of the tester which is 17.8 cm (7 inches) apart from the fixed head, and which will move the movable head in the direction of the fixed head. The axes of the two heads that are parallel and opposite each other are rotated 440° during the period of approaching 7.6 cm (3.5 inches), and then they are not rotated to make them straight forward 6.4 cm (2.5 inches) -73-200927788 The operation of returning the movable head to the first position in a reverse direction is called a one-cycle bending measurement, and the cycle is repeated for 2,000 cycles at a rate of 40 cycles per minute. Then, the cylindrical sample is taken from the head. After taking off, the rectangular film after the slit portion was cut was measured in the following manner, except for the portion fixed to the outer periphery of the fixed head and the movable head, at 17.8 cm (7 inches) x 27.9 cm (11 inches). The number of pinholes produced in the inner part (that is, the average number of pinholes measured at 497 square centimeters (77 square inches). The L-LDPE film side of the test film is taken as the bottom and placed on the filter paper) ( ADVANTEC, No. 50) above And the four-corner fixed to Adhesive cellophane tape (registered trademark). The ink (manufactured by PILOT ink (product number INK-3 50-blue) diluted 5 times with pure water) was applied to the test film, and the side was stretched with a rubber. After wiping the unnecessary ink, the test film is removed and the number of dots adhered to the ink of the filter paper is measured. [Oxygen permeability after bending treatment (oxygen barrier property)] (Measurement method for vapor deposited film) The same bending treatment as in the above item was applied to the above laminated film for 50 cycles, and then cut out from the central portion of the treated film. The sample was subjected to an oxygen permeability measuring device (〇x_TrAN2/20 according to JIS-K-7126 (method B) after being replaced by oxygen at 2 angels in an environment of humidity of 65% RH and a temperature of 25 °C. It is measured by MOCOM company. [Thickness of vapor-deposited film] (Measurement method of vapor-deposited film) A film sample having a vapor-deposited film was produced, and the thickness of the vapor-deposited film was measured by observing a photograph by a transmission electron microscope (TEM). [Peel Strength] The laminate film was cut into a width of 15 mm and a length of 200 mm as a test piece of -74 to 200927788, and a UMT-II-5 00 type manufactured by Toyo BALDWIN Co., Ltd. was used, and the temperature was set at a relative humidity of 23 ° C. Peel-strength biaxially stretched film and L-LDPE peel strength. Also, the extension speed is 10 cm/min. [Water-Release Strength] The laminate film was cut into a width of 15 mm, a long test piece, and a UMT-II-5 00 model manufactured by Toyo BALDWIN Co., Ltd. was used to condense the amide-based resin film at a temperature of 23 ° C and a relative humidity. Layer and L-LDPE film layering. Further, the stretching speed was 10 Å, minutes/min, and the peeling was carried out by measuring the water in the peeled portion. [Heat-resistant water peeling strength] The laminate film was immersed in hot water at 90 ° C for about 30 seconds at room temperature, and then cut into a width of 15 mm as a test piece, and used Toyo BALDWIN Co., Ltd.! The O UMT-II-500 type has a layer thickness of the amide-based resin film layer and the L-LDPE film at a temperature of 23 ° C and a relative humidity. Further, the stretching speed was 10 cm/min, and it was peeled off and measured by water in the peeled portion. [Storage stability test] (a) Manufacture of the packaging bag The above-mentioned laminated film was used, and the inner side of the linear low density was overlapped to produce an I-square sealed bag having an inner dimension of 15 cm in the lateral direction. "The TENSILON 65% condition is measured under the condition that the peeling angle between the layers of the film layer is 180 ° 200 mm." The peeling strength between the layers measured under the condition of TENSILON 6 5 % is 180 °' f 3 After 〇 minutes, the stripping strength between the layers measured under the condition of TENSILON 65% in meters and length of 200 millimeters is 180 degrees. Polyethylene film side to | 19 centimeters to 19 centimeters - 200927788 (b ) Production of coloring liquid To 7 parts by weight of water, 2,000 parts by weight of agar, 0.04 parts by weight of methylene blue, and dissolved in warm water at 95 ° C, and 1.2 parts by weight of hydrogen sulfite (Na2S204) was added under nitrogen atmosphere. And mixing to form a colorless solution. (c) Adding 250 ml of the coloring liquid produced in the above (b) to the three-way sealed bag manufactured in the above (a) under a nitrogen atmosphere, and removing the bag The inside of the bag seals the upper part of the bag and becomes a bag of 15 cm in the horizontal direction and 15 cm in the longitudinal direction. (d) The obtained bag is allowed to stand at room temperature for 3 hours to solidify the agar, at 4 Store at 0 °C, humidity 90%, and observe the bag after 2 weeks. The coloring state of the methylene blue-agar solution. The evaluation method is as follows, and the above is practically no problem. ◎: no discoloration 〇: very little turns blue △: some becomes blue X: turns blue [vibration endurance Sex test] The bags containing the methylene blue coloring liquid produced in the above (a) to (d) were used, and the shaking test was carried out by the following method. 20 pieces were placed in each corrugated box for the test. The bag was placed in an oscillation test apparatus and shaken for 24 hours at 23 ° C in a horizontal direction with a stroke width of 5 cm and an oscillation number of 120 times/min. Then, it was stored at 40 ° C and a humidity of 90%. The coloring state of the methylene blue-agar solution in the bag after 3 days was observed. The evaluation method was as follows, and there was no practical problem in the above. -76- 200927788 ◎: no discoloration 〇: very little turned blue △: several changes Blue X: turns blue [break-resistant bagging] The bag containing the methylene blue coloring liquid manufactured in the above (a) to (d) was used, and the bag breaking resistance test was carried out by the following method. Under conditions of 5 ° C and humidity of 40% Take 20 bags of bag as one unit and drop it from the height of 1 ft. to the floor of the steel. Treat it as one treatment and repeat it 20 times. Confirm the damage of the treated bag. There was a crack and a hole, and the contents leaked out as a broken bag. Moreover, no damage was observed for the appearance, but after storage for 3 days at 40 ° C and a humidity of 90%, the methylene blue-agar solution in the bag was significantly present. The color is also judged to be a broken bag. The evaluation method is as follows, and there is no problem in practical use. 〇: The bag breaking rate is less than 1 〇 % 〇 Δ: The bag breaking rate is 10% or more and less than 20% X: The bag breaking rate is 20% or more First, Experimental Examples 1 to 9 of the present invention are described. [Experimental Example 1] Unstretched sheets of the following constitution were obtained by using two types of three-layer co-extrusion T-die devices. The total thickness of the B layer/A layer/B layer and the unstretched sheet is 190 μm, and the thickness ratio of each layer with respect to the total thickness is b layer / A layer / B layer = 40% / 2 0 % / 4 0 %, the extrusion resin temperature of layer A is 270. (:, the extrusion resin temperature of layer B is 260 ° C. The composition constituting layer A: from poly-77-200927788 benzodimethyl hexamethyleneamine (Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = a composition composed of 100% by weight. A composition constituting the B layer: a polyamide-based block of 95% by weight of nylon 6 (manufactured by Toyobo Co., Ltd., RV = 2.8) and 5% by weight of a thermoplastic resin elastomer A composition of a copolymer (Nylon 12/polybutanediol copolymer, ARKEMA PEBAX403 3, RV = 2.0). The obtained unstretched sheet was longitudinally extended by a roll at an extension temperature of 85 ° C. 3 . 3 times, then extended by 3.7 times in the transverse direction by a tenter at an extension temperature of 120 ° C. And, by heat-fixing at a temperature of 215 ° C and applying 5% heat relaxation treatment, A biaxially stretched film having a thickness of 15 μm, and a corona discharge treatment was performed on the surface of the B layer on the dry lamination side of a 40 μm linear low-density polyethylene film (L-LDPE film: manufactured by Toyobo Co., Ltd., L6102). The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were further evaluated by The storage stability and vibration durability of the packaging bag produced by the biaxially stretched film are shown in Table 1. [Experimental Example 2] The description of Experimental Example 1 was changed to the following except The biaxially stretched film was obtained in the same manner as in Test Example 1. The composition constituting the B layer: a composition composed of 98% by weight of Nylon 6 and 2% by weight of a polyamido block copolymer. The oxygen permeability and the number of pinholes of the biaxially stretched film were measured. The storage stability and vibration durability of the package produced from the obtained biaxially stretched film were tested. The results are shown in Table 1. [Experimental Example 3] A biaxially stretched film was obtained by the same method as Experimental Example 1 except that the following was changed to the following: -78- 200927788 Composition constituting the B layer: resistant to 99% by weight Composition of nylon 6 and 1% by weight of polyamido block copolymer] The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the obtained biaxially stretched film was tested. Preservation stability and vibration of the manufactured bag The results are shown in Table 1. [Experimental Example 4] A biaxially stretched film was obtained by the same method as Experimental Example 1 except that the following was changed to the following. Composition of the layer: a composition composed of 98% by weight of nylon 6 and 2% by weight of a polyamine-based block copolymer. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 4 1 % /1 8 % / 4 1 %. The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the storage stability of the package made of the obtained biaxially stretched film was tested. Vibration durability. These results are shown in Table 1. [Experimental Example 5] 双 A biaxially stretched film was obtained by the same method as Experimental Example 1 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 97% by weight of nylon 6 and 3 parts by weight of ruthenium polyamine-based block copolymer. The thickness ratio of each layer with respect to the total thickness was B layer/A layer/B layer = 3 9% / 22% / 3 9% ° The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the storage stability and vibration durability of the packaging bag produced by the obtained biaxially stretched film were tested. These results are shown in Table 1. -79-200927788 [Experimental Example 6] A biaxially stretched film was obtained by the same method as Experimental Example 1 except that the following was changed to the following. The thickness ratio of each layer with respect to the total thickness was B layer/A layer/B layer = 4 3% / 14% / 4 3 % ° The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the storage stability and vibration durability of the packaging bag produced by the obtained biaxially stretched film were tested. These results are shown in Table 1. ® [Experimental Example 7] The biaxially stretched film was obtained by the same method as in Experiment 1, except that the description of Experimental Example 1 was changed to the following. The composition constituting the layer B: a composition composed of 98% by weight of nylon 6 and 2% by weight of a polyamine-based block copolymer. The thickness ratio of each layer with respect to the total thickness was B layer/A layer/B layer = 3 6% / 2 8% / 3 6% ° The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the test was carried out to test the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film. These results are shown in Table 1. [Experimental Example 8] A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 99% by weight of nylon 6 and 1% by weight of a polyamine-based block copolymer. The thickness ratio of each layer with respect to the total thickness is B layer/A layer/B layer=4 3 % /1 4 % / 4 3 0/〇° -80- 200927788 The oxygen permeability of the obtained biaxially stretched film is measured. , the number of pinholes. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 1. [Experimental Example 9] A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 93% by weight of nylon 6 and 7% by weight of a polyamine-based block copolymer. 0 The thickness ratio of each layer relative to the total thickness is B layer/A layer/B layer = 3 6%/28%/36%. The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 1. The following Experimental Example 1 〇~1 8 is a comparative example with respect to the above Experimental Examples 1 to 9. [Experimental Example 10] 0 A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 1% by weight of nylon 6. The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 1. [Experimental Example 11] A biaxially stretched film was obtained by the same method as that of the test example 1 of -81 - 200927788 except that the description of the experimental example 1 was changed. The thickness ratio of each layer with respect to the total thickness was B layer/A layer/B layer = 30%/40%/30% 〇 The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the storage stability and vibration durability of the packaging bag produced by the obtained biaxially stretched film were tested. These results are shown in Table 1. [Experimental Example 12] A biaxially stretched film was obtained by the same method as in Experimental Example 1, except that the following was changed to the following. The composition constituting the layer A: a composition composed of 80% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 20% by weight of nylon 6. The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 1. [Experimental Example 13] A biaxially stretched film was obtained by the same method as in Experimental Example 1, except that the following was changed to the following. The composition constituting the layer A: a composition composed of 80% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 20% by weight of nylon 6. The thickness ratio of each layer with respect to the total thickness was B layer/A layer/B layer = 2 0 〇 / 〇 / 6 0% / 20% ° The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 1. [Experimental Example 14] - 82 - 200927788 A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the following was changed to the following. The composition constituting the layer A: a composition composed of 80% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 20% by weight of nylon 6. The thickness ratio of each layer with respect to the total thickness was B layer/A layer/B layer = 30%/40%/3 0% ° The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the test was carried out to preserve the packaging bag produced by the obtained biaxially stretched film. © Stability and vibration durability. These results are shown in Table 1. [Experimental Example 15] A biaxially stretched film was obtained in the same manner as in Experimental Example 1 except that the following was changed to the following. The composition constituting the layer A: a composition composed of 90% by weight of poly-m-xylylene hexamethylenediamine and 10% by weight of a polyamine-based block copolymer. The composition constituting the layer B: a composition composed of 1% by weight of nylon 6. ¢) The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured and tested. The stability and vibration durability of the package produced by the obtained biaxially stretched film were measured. 1 is shown. [Experimental Example 16] A biaxially stretched film was obtained by the same method as Experimental Example 1 except that the following was changed to the following. The composition constituting the A layer was composed of 90% by weight of poly-m-xylylene hexamethyleneamine and 10% by weight. / 〇 nylon 6 composition of the composition. The composition constituting the B layer: consisting of 93 weights /. Nylon 6 and 7 wt% poly-83- 200927788 A composition composed of a guanamine-based block copolymer. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 15% / 70% / 1 5 %. The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 1. [Experimental Example 17] A biaxially stretched film was obtained by the same method as in Experimental Example 1, except that the following was changed to the following. The composition constituting the layer A: a composition composed of 96% by weight of nylon 6 and 4% by weight of a polyamine-based block copolymer. The composition constituting the B layer: a composition composed of 97% by weight of Nylon 6 and 3% by weight of poly-m-xylylene hexamethyleneamine. The thickness ratio of each layer with respect to the total thickness is B layer/A layer. /B layer = 1 5 % / 7 0 % /1 5 %. The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, 〇 was tested for the storage stability and vibration durability of the packaging bag produced by the obtained biaxially stretched film. These results are shown in Table 1. [Experimental Example 18] A biaxially stretched film was obtained by the same method as Experimental Example 1 except that the following was changed to the following. The composition constituting the layer A: a composition composed of 96% by weight of nylon 6 and 4% by weight of a polyamine-based block copolymer. The composition constituting the layer B: a composition composed of 90% by weight of poly-m-xylylene hexamethylenediamine and 1% by weight of nylon 6. -84- 200927788 The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 1 5% / 70% / 1 5%. The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured, and the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 1.

-85- 200927788 οο [15 Vibration durability ◎ ◎ ◎ ◎ ◎ 〇〇 ◎ X < 3 〇 XX 〇 X 〇 X Storage stability ◎ ◎ ◎ ◎ ◎ 〇 ◎ 〇 ◎ ◎ ◎ X ◎ < Ο ◎ X < pinhole resistance (4) wo 00 inch m 〇On b cs KT) tH 00 νο Formula 1 is established 〇〇〇〇〇〇〇〇〇〇〇XXXXX 1 X Type (I) Right ※ Μ >' < Os in Os m 1—^ κη oo 00 卜 as OO 卜 r- S Os v〇o Oxygen permeability (ml/m2 · 24 hours·MPa) 00 ON s 00 oo oc to •r·) Os 220 ο Oomm Thickness ratio B/A/B (%) 40/20/40 40/20/40 40/20/40 41/18/41 39/22/39 43/14/43 36/28/36 43/14/ 43 36/28/36 40/20/40 30/40/30 40/20/40 20/60/20 30/40/30 40/20/40 “15/70/15 15/70/15 15/70 /15 B-layer NY6/PA Elastomer = 95/5% NY6/PA Elastomer = 98/21⁄4 NY6/PA Elastomer = 99/1% ΝΥ 6/ΡΑ Elastomer = 98/2% NY6/PA Elastomer = 97 /3% NY6/PA Elastomer = 95/5% NY6/PA Elastomer = 98/2% NY6/PA Elastomer = 99/1% NY6/PA Elastomer = 93/7% NY6=100°/〇NY6 /PA Elastomer = 95/50/〇NY6/PA Elastomer = 95/5% Ν 6/ΡΑ Elastomer = 95/5% NY6/PA Elastomer = 95/50/〇NY6 -100% MXD6/PA Elastomer = 93/7% MXD6/NY6=3/97% MXD6/NY6=90/10 % A layer MXD6=100% MXD6=100% ! MXD6=100% MXD6=100% MXD6=100% MXD6=100°/〇MXD6=100°/〇MXD6=100°/〇MXD6=100% MXD6=100% MXD6=100% MXD6/NY6=80/20°/〇MXD6/NY6=80/20°/〇MXD6/NY6=80/20°/〇MXD6/PA Elastomer=90/10% 1 MXD6/NY6=90 /10°/〇NY6/ PA Elastomer=96/4% NY6/ PA Elastomer=96/4% Experimental Example 1 Experimental Example 2 Experimental Example 4 Experimental Example 5 Experimental Example ό Experimental Example 7 Experimental Example 8 Experimental Example 9 Experimental Example 10 Experimental Example 11 Experimental Example 12 Experimental Example 13 Experimental Example Μ Experimental Example 15 Experimental Example 16 Experimental Example 17 Experimental Example 18 9 Let: 9ΛΝ Dart unj slightly ffl-u擀酲 Step: 9axs -98 - [(ςΙο+χπο·ο)1]/ι>βαΗ(Ι)^:※laliM:lvd 200927788 Hereinafter, it is described that the peel strength described in the patent application range is 4.0 N/15 with respect to Experimental Examples 1 to 9. Experimental examples 19 to 30 of millimeters. [Experimental Example 19] Unstretched sheets having the following constitution were obtained by using two types of three-layer co-extrusion T-die devices. The total thickness of the B layer/A layer/B layer and the unstretched sheet is 190 μm, and the thickness ratio of each layer with respect to the total thickness is B layer/A layer/B layer=40%/20%/40%, A The extruded resin temperature of the layer was 270 ° C, and the extruded resin temperature of the B layer was 260 ° C. The composition constituting the layer A: a composition composed of poly(m-xylylene hexamethylenediamine) (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.6 5) = 1% by weight. The composition constituting the B layer: a polyamide-based block copolymer (Nylon 12/poly) composed of 88% by weight of nylon 6 (made by Toyobo Co., Ltd., RV = 2.8) and 5% by weight of a thermoplastic resin elastomer A composition comprising a butanediol copolymer, ARKEMA PEBAX403 3, RV = 2.0) and 6% by weight of poly-m-xylylene hexamethylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65). The obtained unstretched sheet was stretched 3.3 times in the longitudinal direction by a roll at an elongation temperature of 85 ° C, and then stretched by 3.7 times in the transverse direction by a stretching machine at an elongation temperature of 120 ° C. Further, a biaxially stretched film having a thickness of 15 μm was produced by heat-fixing at a temperature of 215 ° C and applying a heat relaxation treatment of 5%. Further, the surface of the layer B on the dry lamination side of a 40 μm linear low-density polyethylene film (L-LDPE film: manufactured by Toyobo Co., Ltd., L6 10 2) was subjected to corona discharge treatment. The oxygen permeability, the number of pinholes, and the peeling strength of the obtained biaxially stretched film were measured. Further, the packaging of the obtained biaxially stretched film was tested for its storage stability, vibration durability, and bag break resistance. These results are shown in Table 2. 87-200927788 [Experimental Example 20] The biaxially stretched film was obtained by the same method as Experimental Example 19 except that the description of Experimental Example 19 was changed. The composition constituting the layer B: a composition composed of 95% by weight of nylon 6, 2% by weight of a polyamine-based block copolymer, and 3% by weight of poly-m-xylylene dimethyl decylamine. The oxygen permeability, the number of pinholes, and the peeling strength of the obtained biaxially stretched film were measured. Further, the storage stability, vibration durability, and bag break resistance of the tantalum packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 2. [Experimental Example 21] A biaxially stretched film was obtained by the method of Experimental Example 19 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 97% by weight of nylon 6, 1% by weight of a polyamine-based block copolymer, and 2% by weight of poly-m-xylylene hexane dimethyl amide. 〇 The oxygen permeability, the number of pinholes, and the peel strength of the obtained biaxially stretched film were measured. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 2. [Experimental Example 22] A biaxially stretched film was obtained by the same method as Experimental Example 19 except that the following was changed to the following. The composition constituting the layer B consisted of a composition of -88 to 200927788 composed of 95% by weight of nylon 6, 2% by weight of a polyamine-based block copolymer, and 3% by weight of poly-m-xylylene hexane decylamine. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 4 1 % / 1 8% / 4 1 %. The oxygen permeability, the number of pinholes, and the peeling strength of the obtained biaxially stretched film were measured. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 2. [Experimental Example 23] 双 A biaxially stretched film was obtained by the same method as Experimental Example 19 except that the procedure of Experimental Example 19 was changed to the following. The composition constituting the layer B: a composition composed of 92% by weight of nylon 6, 3% by weight of a polyamine-based block copolymer, and 5% by weight of poly-m-xylylene dimethyl decylamine. The thickness ratio of each layer with respect to the total thickness is B layer/A layer/B layer=3 9%/22%/3 9% ° The oxygen permeability, the number of pinholes, and the peeling of the obtained biaxially stretched film are measured. ) from the strength. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 2. [Experimental Example 24] A biaxially stretched film was obtained by the same method as Experimental Example 19 except that the description of Experimental Example 19 was changed to the following. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 43% / 14% / 43%. The oxygen permeability, the number of pinholes, and the peeling-89- of the obtained biaxially stretched film were measured.

200927788 From the strength. Further, the test was carried out, and the storage stability, vibration durability, and bag break resistance of the obtained biaxially stretched thin packaging bag were as shown in Table 2. [Experimental Example 25] In the description of Experimental Example 19, a biaxially stretched film was obtained in the same manner as in the following except Example 1. The composition constituting the layer B was composed of a composition of 95% by weight of a nylon 6, 2 amine block copolymer and 3% by weight of poly(m-xylylene hexane). The thickness ratio of each layer with respect to the total thickness was B layer = 3 6% / 28% / 3 60 / 〇 ° The oxygen permeability and the separation strength of the obtained biaxially stretched film were measured. Further, the test was carried out, and the storage stability, vibration durability, and bag break resistance of the obtained biaxially stretched thin packaging bag were as shown in Table 2. [Experimental Example 26] In the description of Experimental Example 19, a biaxially stretched film was obtained in the same manner as in the following Test Example 19. The composition constituting the layer B was composed of a composition of 97% by weight of a nylon 6, an amine block copolymer and 2% by weight of poly-m-xylylene hexane. The thickness ratio of each layer with respect to the total thickness is B layer 4 3% / 14% / 43 0 / 〇. The oxygen permeability and the separation strength of the obtained biaxially stretched film were measured. Further, tests were carried out from the obtained biaxially stretched film. These results were produced by the number of pinholes and the number of pinholes formed by the actual weight % polydecylamine /A layer/B layer. These results are based on the storage stability of the package of -90-200927788, which is composed of the actual weight % polyamide, the number of pinholes of the A layer/B layer, and the peeling of the film, vibration durability, and bag break resistance. The system is shown in Table 2. [Experimental Example 27] In the description of Experimental Example 19, a biaxially stretched film was obtained in the same manner as in the following except Example 1. The composition constituting the layer B was composed of a composition of 83% by weight of a nylon 6,7-amine block copolymer and 10% by weight of poly-m-xylylene hexane. The thickness ratio of each layer with respect to the total thickness was B layer = 3 6% / 28% / 3 60 / 〇 ° The oxygen permeability and the separation strength of the obtained biaxially stretched film were measured. Further, the test was carried out, and the storage stability, vibration durability, and bag break resistance of the obtained biaxially stretched thin packaging bag were as shown in Table 2. [Experimental Example 28] A biaxially stretched film was obtained in the same manner as in Test Example 19 except that the following was changed to the following. The composition constituting the layer B was composed of a composition of 93% by weight of nylon 6, a amide-based block copolymer and 2% by weight of poly-m-xylylene hexane. The oxygen permeability and the separation strength of the obtained biaxially stretched film were measured. Further, the test was carried out, and the storage stability, vibration durability, and bag break resistance of the obtained biaxially stretched thin packaging bag were as shown in Table 2. [Experimental Example 29]. These results were produced by stripping the film with the actual weight % polydecylamine, the number of pinholes/ruthenium layers, and the film peeling. These results were produced by stripping the number of pinholes formed by the actual weight % polydecylamine. These results -91 - 200927788 The biaxially stretched film was obtained in the same manner as in the following Test Example 19 except that the following description was carried out. The composition constituting the layer B was composed of a composition of 84% by weight of a nylon 6,5-amine block copolymer and Η% by weight of poly-m-xylylene hexane. The oxygen permeability and the separation strength of the obtained biaxially stretched film were measured. Further, the test was carried out, and the storage stability, vibration durability, and bag break resistance of the obtained biaxially stretched thin packaging bag were as shown in Table 2. [Experimental Example 30] The biaxially stretched film was obtained in the same manner as in the following except as described in Experimental Example 19, except that the following description was carried out. The composition constituting the enamel layer was composed of a composition of 98% by weight of Nylon 6, 1 amine block copolymer and 1% by weight of poly-m-xylylene hexane. The oxygen permeability and the separation strength of the obtained biaxially stretched film were measured. Further, the test was carried out, and the storage stability and vibration durability of the obtained biaxially stretched thin packaging bag were shown in Table 2. The following Experimental Examples 31 to 42 are examples of Experimental Examples 19 to 30. [Experimental Example 31] In the description of Experimental Example 19, a biaxially stretched film was obtained in the same manner as in the following except Example 1. The composition constituting the enamel layer is made of 100% by weight of nylon 6 and is formed by the number of pinholes and the film formed by the solid weight % polyamine. These results were produced by stripping the number of pinholes formed by the actual weight % polydecylamine. A comparison experiment of these results was carried out by a group consisting of -92-200927788. The oxygen permeability, the number of pinholes, and the peeling strength of the obtained biaxially stretched film were measured. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 2. [Experimental Example 32] A biaxially stretched film was obtained by the same method as Experimental Example 19 except that the following was changed to the following. ^ The thickness ratio of each layer relative to the total thickness is B layer / A layer / B layer = 3 0 〇 / 〇 / 4 0 〇 / 〇 / 3 0 〇 / 〇. The oxygen permeability, the number of pinholes, and the peeling strength of the obtained biaxially stretched film were measured. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 2. [Experimental Example 33] A biaxially stretched film was obtained by the same method as in Practical Example C except that the following was changed to the following. The composition constituting the layer A: a composition composed of 80% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 20% by weight of nylon 6. The oxygen permeability, the number of pinholes, and the peeling strength of the obtained biaxially stretched film were measured. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 2. [Experimental Example 34] A biaxially stretched film was obtained by the same method as that of the test example No. 93-200927788 except the following. The composition constituting the layer A: a composition composed of 80% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 20% by weight of nylon 6. The thickness ratio of each layer with respect to the total thickness was B layer/A layer/B layer = 20%/60%/20% 〇 The oxygen permeability, the number of pinholes, and the peeling strength of the obtained biaxially stretched film were measured. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. The results are shown in Table 2. [Experimental Example 35] A biaxially stretched film was obtained by the same method as Experimental Example 19 except that the following was changed to the following. The composition constituting the layer A was composed of 80% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 20% by weight of nylon 6. The thickness ratio of each layer with respect to the total thickness is B layer/A layer/B layer=30%/40〇/〇/30〇/〇° 〇The oxygen permeability and the number of pinholes of the obtained biaxially stretched film are measured. Peel strength. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 2. [Experimental Example 36] A biaxially stretched film was obtained by the same method as Experimental Example 19 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 95% by weight of nylon 6 and 5% by weight of a polyamide-based block copolymer. -94- 200927788 The oxygen permeability, the number of pinholes, and the peeling strength of the obtained biaxially stretched film were measured. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 2. [Experimental Example 37] A biaxially stretched film was obtained by the same method as Experimental Example 19 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 99% by weight of nylon 6 and 1% by weight of a polyamine-based block copolymer. The oxygen permeability, the number of pinholes, and the peeling strength of the obtained biaxially stretched film were measured. Further, tests were carried out to obtain the stability, vibration durability and bag break resistance of the packaging bag produced from the obtained biaxially stretched film. These results are shown in Table 2. [Experimental Example 38] A biaxially stretched film was obtained by the same method as Experimental Example 19 except that the following was changed to the following.组成 The composition constituting the layer B: a composition composed of 95% by weight of nylon 6 and 5% by weight of poly-m-xylylene dimethyl decylamine. The oxygen permeability, the number of pinholes, and the peeling strength of the obtained biaxially stretched film were measured. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 2. [Experimental Example 39] A biaxially stretched film was obtained by the same method as Experimental Example 19 except that the following was changed to the following. -95- 200927788 Composition constituting the layer A: a composition composed of 90% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 10% by weight of a polyamine-based block copolymer. The composition constituting the layer B: a composition composed of 1% by weight of nylon 6. The oxygen permeability, the number of pinholes, and the peeling strength of the obtained biaxially stretched film were measured. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 2.实验 [Experimental Example 40] The description of Experimental Example 19 was changed to the following except that it was changed to the following. The same method was used to obtain a biaxially stretched film. Composition constituting the A layer: a composition composed of 90% by weight of poly-m-xylylene hexamethylenediamine and 1% by weight of nylon 6 constituting a composition of the B layer: 93% by weight of nylon 6 and A composition composed of 7 wt% polyamine-based block copolymer. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer 〇 =1 5% / 70% / 1 5%. The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 2. [Experimental Example 41] A biaxially stretched film was obtained by the same method as Experimental Example 19 except that the following was changed to the following. The composition constituting the layer A: a composition composed of 96% by weight of nylon 6 and 4% by weight of a polyamine-based block copolymer. -96- 200927788 Composition constituting the B layer: a composition composed of 97% by weight of nylon 6 and 3% by weight of poly-m-xylylene hexamethylenediamine. The thickness ratio of each layer with respect to the total thickness is B layer /A layer / B layer = 1 5 % / 7 0 % /1 5 %. The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 2. [Experimental Example 42]

In the case of Experimental Example 19, a biaxially stretched film was obtained by the same method as Experimental Example 19 except that the following was changed. The composition constituting the layer A: a composition composed of 96% by weight of nylon 6 and 4% by weight of a polyamine-based block copolymer. The composition constituting the layer B: a composition composed of 90% by weight of poly-m-xylylene hexamethylenediamine and 10% by weight of nylon 6. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 15% / 70% / 1 5 %. Q The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 2. -97- 200927788 €)〇<ΝΪ II 〇〇〇〇〇〇〇〇〇〇〇〇<〇〇< 〇XX <1 <1 X 〇< Vibration durability ◎ ◎ 〇◎ ◎ ◎ ◎ ◎ ◎ ◎ X <1 〇 XX ◎ ◎ X <3 X 〇X Storage stability ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ X ◎ ◎ ◎ ◎ < ◎ X Peel strength ( N/15mm) 00 *n 00 >ri Ο 卜 vi 00 VO — t> CN «〇sn Ό ui m «η »〇o 'sO r- ts (N 00 \d «r> m (S o *rl Pinhole resistance (a) — «Τ» Os inch ο Os 00 «Ν m 00 sn r—<00 (N — 00 00 Vi <N Formula (I) 〇〇〇〇〇〇〇〇 〇〇〇〇〇〇XXX 〇〇〇XX 1 X Type (I) Right ※ § <Ν ·«< P *r> s Art Ss • «4 OS s 〇§ Oxygen permeability (ml/m2 · 24 hours · MPa): ON v〇g ν〇ΓΟ v〇v〇o *n Os s »—>4 OS F-^ XTi o »·< s 00 〇\ s 00 00 〇om \nm Thickness ratio B/A/B (%) 40/20/40 | 40/20/40 40/20/40 41/18/41 1 39/22/3 9 : 1 43/14/43 1 [Ϊ6/28/36 | | 43/14/43 | 36/28/36 40/20/40 40/20/40 40/20/40 40/20/40 30/ 40/30 40/20/40 20/60/20 30/40/30 40/20/40 40/20/40 40/20/40 40/20/40 | 15/70/15 1 1 15/70/ 15 I 15/70/15 B layer composition VO $ SI 豳m S v〇$ »r> τ ν〇imm tUBL static; V〇(NT NO Q 1 幽 m sad. 静; VO >- (N la though Mv〇NY6/PA Elastomer 7MXD6=92/3/5% : w-» S έ S Miscellaneous a»LC! s? 1 i Miscellaneous Βϋ ΐ Static: VO s 1 l Q 1 Μ. Ό | S Ο I m emL; \〇(N $ l 0 1 twit % FH T mm 矣VO NY6/PA Elastomer/MXD6=98/l/l0/〇NY6 -100% 盈Q Ϊ mm Baa static; >< v〇 »r> sl Q 1 Miscellaneous m so )0 ί〇sla I m Biwl Static: VO in sl Q 1 幽m \D > IQ s: kmm _ NY6/PA Elastomer = 99/13⁄4 NY6 /MXD6=95/ 5% MXD6=100% MXD6/PA Elastomer=93/7% 1 MXD6/NY6=3/97% MXD6/NY6=90/10% A layer composition MXD6=100% MXD6=100% MXD6=100% MXD6- 100% MXD6=100% MXD6=100°/〇MXD6=100% MXD6-100% MXD6=100% MXD6-100% MXD6=100°/〇MXD6=100% MXD6=100% MXD6=100% MXD6/NY6= 80/20°/〇MXD6/NY6=80/20% MXD6/NY6=80/20% MXD6=100% MXD 6=100% MXD6=100% o T Weng mn〇L; V〇PX s MXD6/NY6=90/10% 1 m Bbh Song 2; % T turn m BDL Step > Experimental Example 19 Interest m Experimental Example 21 Experimental Example 22 Experimental Example 23 Experimental Example 24 Experimental Example 25 Experimental Example 26 Experimental Example 27 Experimental Example 28 Experimental Example 29 m K Experimental Example 31 Experimental Example 32 CO ΓΟ M mmm 1 Experimental Example 35 | Ό mm Interest u Experimental Example 37 Experimental Example 38 Experimental Example 39 1 Experimental Example 4〇 | Experimental Example 41 1 Experimental Example 42| -86-

9 Let: 9AN Distillation of MrasfrH擀酲 Step: 9QXH [(SId+xssdxl/lvBde^:※ 200927788 The following] shows the polyamide series that meet the Anab and the necessary conditions (4) and (5) described in the patent application scope. Experimental Examples 43 to 4 of the biaxially stretched film [Table 3] Manufacturing conditions of thin lining film thickness (micrometer) Dirty shielding condition of the shielding plate. Thermal fixation condition Experimental Example 43 Discontinuous A-state I Condition 15 Experimental example 44 discontinuous B-state II condition 15 experimental example 45 discontinuous A-state I condition 25 experimental example 46 discontinuous A-state I condition 15 experimental example 47 discontinuous A-state Ϊ condition 15 experimental example 48 unshielded plate without shading Plate III Condition 15 Experimental Example 49 No-shielded plate without shielding plate IV Condition 15 Experimental Example 50 No-shielded plate without shielding plate III Condition 25 [Experimental Example 43] Using two 3-layer co-extrusion T-shaped die devices, An unstretched sheet having the following constitution is obtained. The total thickness of the B layer/A layer/B layer and the unstretched sheet is 190 μm, and the thickness ratio of each layer with respect to the total thickness is B 〇 layer/A layer/B layer =40%/20°/./40%, the extrusion resin temperature of layer A is 270 ° C, the extrusion of layer B Resin temperature: 260 ° C. Composition constituting the A layer: a composition composed of poly-m-xylylene hexane decylamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. Composition of layer B: Polyamine-based block copolymer (Nylon 12/polybutylene) composed of 95% by weight of nylon 6 (made by Toyobo Co., Ltd., rv = 2.8) and 5% by weight of thermoplastic resin elastomer a composition of a diol copolymer, ARKEMA company PEBAX4033, RV = 2.0). The obtained unstretched sheet was extended 3.3 times in the longitudinal direction by a roll at an elongation temperature of 85 ° C, followed by a spreader. The elongation temperature at 120 °C was 3.7 times in the transverse direction -99-200927788. Moreover, by the method described later, 215. (: the temperature was thermally fixed and 6.7% lateral relaxation treatment was applied at 200 ° C, and the coil was wound into a roll. A biaxially stretched polyfluorene film (roll mill) having a width of 3,300 mm and a thickness of about 15 μm was produced. [Heat fixing treatment] The above heat setting treatment was as in the third The heat fixing device of the figure structure is carried out. The heat fixing device is divided into four heat fixing zones of the first to fourth zones, in the first Each of the 1 to 3 zones is provided with eight air supply passages a to X, and eight air supply passages are also provided in Fig. 4. Each of the air supply passages is disposed at an interval of 400 mm in a direction perpendicular to the progress direction of the film. The direction of the film is going up and down. Further, hot air is blown from the hot air blowing port (nozzle) of the air supply passages to the extended film. In Experimental Example 43, in the hot air blowing ports of the 15 air supply passages of a to ,, the discontinuous rod-shaped shielding plates S, S·· were attached as shown in Fig. 2 . Fig. 4 is a view showing the longitudinal direction of each of the shielding plates S, S··· 安装 which are provided with the shielding plates S, S·· in the hot air blowing ports of the air supply passages a to 〇 from the top. The center is set in such a manner as to substantially coincide with the width center of the film passing through the heat fixing device. Further, the length of each of the shielding plates s, s·· (the dimension in the width direction of the produced film) is adjusted so as to gradually become wider from the inlet to the outlet of the heat fixing device (that is, the manner of expansion). The shielding rate of the hot air blowing port of each of the air passages of a to ( (the shielding area of the hot air blowing port of the shielding plate/the area of the hot air blowing port) is as shown in Table 4. Further, the shielding pattern of the shielding plate of Experimental Example 43 was referred to as "a state". -100- 200927788

Q ο [inch 揪 遮蔽 遮蔽 遮蔽 遮蔽ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο α ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο Os Ό 〇 〇 〇 Ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο > Ό 〇 〇 〇 ^ ^ W W W W W W C C C C ο ο ο Q Q Q Q Q Q Q Q Q Q cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd cd Shielding state, Α Β Β Α 无 无 无 无 无 无 无 无 无 无 无 无 无 无Experimental Example 43 Experimental Example 441 Experimental Example 45 Experimental Example 46 Experimental Example 47 Experimental Example 48 Experimental Example 48 Experimental Example 48 Long 嗽 『0』K1 筚 I5S Right to destroy 200927788 Also, in Experimental Example 43, heat fixation and wind speed Further, in Table 4, the temperature conditions and the wind speed conditions in the fourth region of the experimental example 43 are both 25 ° C and the temperature in the first to fourth regions of the test example 43. The temperature of the 1st to 4th zones of the wind speed 1 ^ is less than the temperature m/s of the heat-fixed zone of the 1st to δth of the heat-fixing device. In addition, it will be "I condition".

-102- 200927788

Zone 4 wind speed (m/s) 00 11.0 〇〇 VO 00 νο 00 00 VO 11.0 00 vd Temperature ΓΟ 200 210 200 200 ! 200 | 200 200 200 3, 4 temperature difference X Wind speed difference (°C *m/ s) 〇〇〇〇〇〇〇ο Zone 3 wind speed (m/s) _1 00 11.0 〇〇00 00 VO 00 P 00 VO i Temperature ΓΟ _ 1 210 210 〇 (N 210 ! 210 214 214 214 2,3 Interval &S difference X Wind speed difference (°Cm/s) CS <N fS CS 〇ο ο Zone 2 wind speed (m/s) 15.9 27.0 15.9 15.9 15.9 00 ο »—Η 00 Temperature CC) 224 222 224 224 224 214 214 214 Temperature difference in interval 1, 2 Wind speed difference (°C *m/s) 〇〇〇ο ο Wind speed in zone 1 (m/s) 10.9 17.6 10.9 10.9 10.9 0〇c> οο Temperature CC) 〇<N (N 218 220 220 ! 220 214 214 214 Thermal fixation condition I Condition II Condition I Condition I Condition I Condition III Condition IV Condition III Condition Experimental Example 43 Experimental Example 44 Experimental Example 45 Experimental Example 46 Experimental Example 47 Experimental Example 48 Experimental Example 49 Experimental Example 50 200927788 [Evaluation of characteristics of film] The film obtained as described above was evaluated for characteristics according to the above method. The evaluation results are shown in Tables 6 and 7. [Experimental Example 4 4] In addition to increasing the amount of melt extrusion from the crucible extruder to increase the width of the unstretched film, the shielding plate attached to the hot air outlet of each air supply passage of the heat fixing device was changed to In the shielding rate of Table 4, the temperature and the wind speed in the first to fourth regions of the heat-fixing device were changed to the same as in Table 5, and the thickness was about 15 μm and the width was 5, 3 in the same manner as in Example 43). An unprocessed roll of a MM film taken up. Subsequently, the characteristics of the film were evaluated by the above method. The evaluation results are shown in Tables 6 and 7. Further, the shielding pattern of the shielding plate of Experimental Example 44 was referred to as "B aspect", and the temperature and wind speed in the first to fourth regions of Experimental Example 44 were referred to as "II conditions". [Experimental Example 45] The thickness of the film after heat fixation was changed to about 25 μm, except that the thickness of the unstretched film was increased to about 2 80 μm by increasing the amount of melt extrusion of the extruder. In the same manner as in Experimental Example 43, except that the stretching operation in the longitudinal direction was changed to 3.0 times, a raw roll obtained by winding a film having a thickness of about 25 μm and a width of 3,300 mm was obtained. Further, the characteristics of the film and the film roll were evaluated using the slits in the same position as Experimental Example 43. The evaluation results are shown in Tables 6 and 7. [Experimental Example 46] A biaxially stretched film was obtained by the same method as Experimental Example 43 except that the configuration of the unstretched sheet of Experimental Example 43 was changed as follows. The total thickness of the B layer/A layer/B layer and the unstretched sheet is 190 micro-104-200927788 meters, and the thickness ratio of each layer relative to the total thickness is B layer/A layer/B layer=40%/20% /4%, the extruded resin temperature of the layer A was 27 0 ° C, and the temperature of the extruded resin of the layer B was 260 °C. The composition constituting the layer A: polyamine-based block copolymerization of 95% by weight of poly-m-xylylene hexamethylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) and 5% by weight of a thermoplastic resin elastomer A composition of a material (Nylon 12/polybutanediol copolymer, ARKEMA PEBAX403 3, RV = 2.0). The composition constituting the B layer: a composition composed of 1% by weight of nylon 6 (manufactured by Toyobo Co., Ltd., RV = 2.8). Further, the characteristics of the film and the film roll were evaluated using the slits in the same position as Experimental Example 43. The evaluation results are shown in Tables 6 and 7. [Experimental Example 47] A biaxially stretched film was obtained by the same method as Experimental Example 43 except that the configuration of the unstretched sheet of Experimental Example 43 was changed as follows. Three types of 5-layer co-extrusion T-die devices were used to obtain unstretched sheets of the following constitution. The composition of the C layer/B layer/A layer/B layer/C layer and the total thickness of the unstretched sheet is 190 μm, and the thickness ratio of each layer with respect to the total thickness is C layer/B layer/A layer/B layer /C layer = 25% / 15% / 20% / 15% / 25%, the extruded resin temperature of the layer A was 270 ° C, and the temperature of the extruded resin of the layer B and the layer C was 260 °C. The composition constituting the layer A: polyamine-based block copolymerization of 95% by weight of poly-m-xylylene hexamethylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) and 5% by weight of a thermoplastic resin elastomer A composition of a material (Nylon 12/polybutanediol copolymer, ARKEMA PEBAX403 3, RV = 2.0). The composition constituting the B layer: 70% by weight of nylon 6 (made by Toyobo Co., Ltd., = 8), 25% by weight of poly-m-xylylene hexamethylenediamine (Mitsubishi Gas Chemical Co., Ltd., RV = 2_65) and 5% by weight of thermoplastic resin elastomer • 105- 200927788 Polyamide-based block copolymer (Nylon 12/polybutanediol copolymer, ARKEMA company PEBAX403 3, RV = 2.0) . The composition of the c layer was composed of 100% by weight of nylon 6 (manufactured by Toyobo Co., Ltd., RV = 2.8). Further, the characteristics of the film and the film roll were evaluated using the slits in the same position as Experimental Example 43. The evaluation results are shown in Tables 6 and 7. Hereinafter, Experimental Examples 48 to 50 are comparative examples of the above Experimental Examples 43 to 47.实验 [Experimental Example 48] In addition to the fact that the heat-blowing outlet of each air supply passage is not provided with a shield plate and is thermally fixed, the temperature and wind speed of the first to fourth zones of the heat-fixing device are changed as shown in Table 5, and Experimental Example 4 The same was done to obtain a raw roll of about 15 microns. Further, the temperature and the wind speed conditions in the first to fourth regions of Experimental Example 43 were referred to as "ΙΠ conditions". Further, the characteristics of the film and the film roll were evaluated using the cut rolls in the same position as Experimental Example 43. The evaluation results are shown in Tables 6 and 7.实验 [Experimental Example 49] The same procedure as in Experimental Example 44 except that the heat shield was not attached to the hot air outlet of each of the air supply passages, and the heat setting was performed, and the temperatures and wind speeds of the first to fourth regions of the heat fixing device were changed as shown in Table 5. The process was carried out to obtain a raw roll of about 15 microns. Further, the temperature and the wind speed conditions in the first to fourth regions of Experimental Example 49 were referred to as "IV conditions". Further, the characteristics of the film and the film roll were evaluated using the cut rolls in the same position as Experimental Example 44. The evaluation results are shown in Tables 6 and 7. [Experimental Example 50] -106-200927788 In addition to the heat-blowing outlet of each air supply passage, the shielding plate was not attached and heat-fixing was performed, and the temperature and wind speed of the first to fourth zones of the heat-fixing device were changed as shown in Table 5, and the experiment was performed. Example 43 was carried out in the same manner to obtain a raw roll of about 25 μm. Further, the temperature and the wind speed conditions in the first to fourth regions of Experimental Example 50 were referred to as "ΠΙ conditions". Further, the characteristics of the film and the film roll were evaluated using the cut rolls in the same position as Experimental Example 43. The evaluation results are shown in Tables 6 and 7. [Table 6] Δ nab HS160 (minimum 値 to maximum 値) The difference between the maximum 値 and the minimum HS of HS160 The wrinkle of the sealing portion of the bag is judged by the passability of the film % % Determination loot: 160 ° C Experimental Example 43 0.011 1.00 〜 1.10 0.10 ◎ 〇〇 Experimental Example 44 0.009 1.00 to 1.05 0.05 ◎ 〇〇 Experimental Example 45 0.010 0_95 ～ 1.05 0.10 ◎ 〇〇 Experimental Example 46 0.011 1.00 〜1.10 0.10 ◎ 〇〇 Experimental Example 47 0.011 [00~1.10 0.10 ◎ 〇〇 Experimental Example 48 0.011 0.80 1.00 1.00 0.20 XX 〇X Experimental Example 49 0.009 0.95 to 1.10 0.15 X 〇X Experimental Example 50 0.010 〇_85 〜1.10 0.25 X 〇X [Film effect of the experimental example] ❾ 得知 It is known from Table 6' In any of the films of Experimental Examples 43 to 47, the difference in the heat shrinkage ratio (i.e., the difference in heat shrinkage ratio) in the full width range of the roll was small, and the amount of change in the heat shrinkage rate in the longitudinal direction was also small, and the post processing was performed. Good pass-time can be suitable for post-processing. Moreover, the sealing portion is finished without a wrinkle when the bag is formed. On the other hand, it was found that the film of Experimental Examples 48 to 5 差异 had a large difference in heat shrinkage ratio over the full width range and the passability at the time of post-processing was not -107-200927788, and the seal portion was formed when the bag was formed. Wrinkles are not finished beautifully

-108- 200927788 〇ο 嗽 嗽 Vibration Durability ◎ ◎ ◎ X < ◎ ◎ ◎ Storage stability ◎ ◎ ◎ <l < ◎ ◎ ◎ Pinhole resistance (formation of side one-type (I)〇 〇〇〇〇〇〇〇 (I) Right ※ Μ s • n fS cs 0〇C\ 00 Oxygen permeability (ml/m2 · 24 hours · MPa) On σ\ π*ί m Thickness ratio B/A /B or C/B/A/B/C 40/20/40 40/20/40 40/20/40 40/20/40 25/15/20/15/25 40/20/40 40/20/ 40 40/20/40 C Layer III • NY6-100% IIIB Layer NY6/PA Elastomer = 95/5% NY6/PA Elastomer = 95/5% I : NY6/PA Elastomer = 95/5% I NY6 =lOO°/〇NY6/ MXD6 /PA Elastomer = 70/25/5% NY6/PA Elastomer = 95/5% NY6/PA Elastomer = 95/5% NY6/PA Elastomer = 95/5% A Layer MXD6=100°/〇MXD6=lOO°/〇MXD6=lOO°/〇MXD6/PA Elastomer=95/5% MXD6/PA Elastomer=95/5% MXD6=lOO°/〇I j MXD6=lOO °/〇I MXD6=l00% I_ Experimental Example 43 i Experimental Example 44 Experimental Example 45 Experimental Example 46 Experimental Example 47 Experimental Example 48 Experimental Example 49 Test Case 50 - 607

9 谨: 9AN 3⁄4 dart ussiu 擀酲 embedded: 90XS [(SI_o+XSIOd) l] / lvBd (I) 1 ^: ※ US - stupid ivd 200927788 The following is shown in relation to the experimental examples 43 to 47, the scope of patent application Experimental Examples 51 to 53 in which the peel strength also satisfies 4.0 N/15 mm or more are described. [Table 8] Fabrication of film roll Aberdeen film thickness (micrometer) Shape of shielding plate Masking condition Thermal fixation condition Experimental example 51 Non-leakage state I condition 15 Experimental example 52 Non-B-state II condition 15 Experimental example 53 Non-A A-state I condition 25 Experimental example 54 No-shielded plate without shielding plate II Condition 15 Experimental example 55 No-shielded plate without shielding plate IV Condition 15 Experimental Example 56 <> No-shielded plate without shielding plate ΙΠ Condition 25 [ Experimental Example 51] An unstretched sheet having the following constitution was obtained by using two types of three-layer co-extrusion T-die devices. The total thickness of the B layer/A layer/B layer and the unstretched sheet is 190 μm, and the thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 40% / 2 0 ° /. / 40%, the extruded resin temperature of layer A is 270 °C, and the temperature of extruded resin of layer B is 260 °C. The composition constituting the layer A: a composition composed of poly-m-xylylene dimethyl decylamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. Composition constituting the B layer: a polyamide-based block copolymer (Nylon 12/poly-stretch) composed of 89% by weight of nylon 6 (made by Toyobo Co., Ltd., RV = 2.8) and 3% by weight of a thermoplastic resin elastomer A composition of a butanediol copolymer, ARKEMA company PEBAX4033, RV = 2.0) and 2% by weight of poly-m-xylylene hexamethylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65). -110- 200927788 The obtained unstretched sheet was stretched 3.3 times in the longitudinal direction by a roll at an elongation temperature of 85 ° C, and then extended laterally by 3.7 times by a tenter at an extension temperature of 120 °C. Further, a biaxial stretching having a width of 3,300 mm and a thickness of about 15 μm was produced by heat-fixing at a temperature of 215 ° C by a method described later and applying a lateral relaxation treatment of 6.7% at 200 ° C, and winding into a roll shape. Polycrystalline film (unprocessed roll). [Heat-fixing treatment] The above-described heat-fixing treatment is carried out in a heat-fixing apparatus having a structure as shown in Fig. 3. The heat fixing device is divided into four heat fixing zones in the first to fourth zones, and eight air supply passages a to X are provided in the first to third zones, and eight air supply passages are also provided in the fourth drawing. Each of the air supply passages is disposed at an interval of 400 mm at a distance of 400 mm from the direction in which the film is oriented. Further, hot air is blown from the hot air blowing port (nozzle) of the air supply passages to the extended film. In Experimental Example 51, the hot air blowing ports of the 15 air supply passages of a to 安装 were attached with discontinuous rod-shaped shielding plates S, S·· as shown in Fig. 2 . The fourth drawing is a view of the longitudinal direction of each of the shielding plates s, S··· installed in the case where the hot air blowing ports of the air supply passages a to 〇 are provided with the shielding plates S, S·· from the top. The center is set in such a manner as to substantially coincide with the width center of the film passing through the heat fixing device. Further, the length of each of the shielding plates S, S·· (the dimension in the width direction of the film to be produced) is adjusted so as to gradually become wider from the inlet to the outlet of the heat fixing device (i.e., in a manner of expansion). The shielding rate of the hot air blowing port of each of the air passages of a to ( (the area of the shielding area of the hot air blowing port of the shielding plate/the area of the hot air blowing port) is as shown in Table 9. Further, the shielding pattern of the shielding plate of Experimental Example 51 was referred to as "a state". -111- 200927788

Q ο [6 peppers] The shielding rate (%) of the shielding plates set in the respective air supply passages (a to X) X Ο Ο Ο Ο ο ο Ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο 〇[ί ο ο ο ε ΓΛ S cn ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο -ΰ Ό ?; \η Ό ο ο ο b〇m »n ν〇ο ο ο S ϊ〇S ο ο ο <υ m *η ο ο ο Ο a\ CN ο ο ο ο ο (Ν Ό (N ΓΟ CN ο ο ο - Ω Ο ON ON ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο Experimental Example 52 Experimental Example 53 Experimental Example 54 Experimental Example 55 Experimental Example 56 's Tears "0" capsule - s Jean · 200927788 Further, in Experimental Example 51, the wind speed of the heat fixing device was adjusted as shown in Table 10. Further, in Experimental Example 51 Temperature conditions and wind speed conditions in ~4 zone Any one of the temperature difference between the mutual temperature and the wind speed is 25 ° C. The temperature of the first to fourth zones of the experimental example 51, the temperature of the first to fourth zones of the wind, and the first heat-fixing zone of the thermal fixture. • m/s or less. Also, it will be used as the “I condition”.

-113- 200927788 ο 〇oI^l Wind speed in Zone 4 (m/s) 00 \〇11.0 00 vd 00 11.0 00 Temperature (°C) 200 210 200 200 200 200 Temperature difference in section 3, 4 Wind speed difference 〇Cm /s) 〇〇ο ο ο ο Zone 3 wind speed (m/s) 00 11.0 00 00 vd 11.0 〇〇i Brewing (°C) 210 210 210 214 214 214 2, 3 temperature difference X Wind speed difference (° Cm/s) CN (Ν ON 127 ο ο ο Zone 2 wind speed (m/s) 15.9 27.0 15.9 00 ο 00 Temperature CC) 224 222 224 214 214 214 1,2 temperature difference X wind speed difference (°C * m/s) 〇〇ο ο ο Zone 1 wind speed (m/s) 10.9 17.6 10.9 00 ο 00 ν〇 temperature CC) 220 218 220 214 214 214 Thermal fixation condition I Condition II Condition I Condition III Condition IV Condition III Condition Experimental Example 51 Experimental Example 52 Experimental Example 53 Experimental Example 54 Experimental Example 55 Experimental Example 56 inch π. 200927788 [Characteristic evaluation of film] The film obtained as described above was evaluated for its characteristics in accordance with the above method. The evaluation results are shown in Tables 11 and 12. [Experimental Example 52] In addition to increasing the amount of melt extrusion from the extruder to increase the width of the unstretched film, the shielding plate attached to the hot air outlet of each air supply passage of the heat fixing device was changed as shown in Table 9. The shielding rate was changed to the temperature in the first to fourth regions of the heat-fixing device, and the wind speed was changed to the same as in the experimental example 5-1, and the thickness was about 15 μm and the width was 5, 3 . An unprocessed roll of 0 0 mm film taken up. Subsequently, the characteristics of the film were evaluated by the above method. The evaluation results are shown in Tables 11 and 5. In addition, the shielding state of the shielding plate of Experimental Example 52 was referred to as "B aspect", and the temperature and wind speed in the first to fourth regions of Experimental Example 52 were referred to as "II conditions". [Experimental Example 53] The thickness of the film after heat fixation was changed to about 25 μm, and the length was changed, except that the thickness of the unstretched film was increased to about 280 μm by increasing the amount of melt extrusion of the extruder. In the same manner as in Experimental Example 5, except that the stretching operation of the direction was changed to 3.0 times, an unprocessed roll obtained by winding a film having a thickness of about 25 μm and a width of 3,300 mm was obtained. Further, the characteristics of the film and the film roll were evaluated using the slits in the same position as Experimental Example 51. The evaluation results are shown in Tables 11 and 12. In the following, Comparative Experimental Examples 54 to 5 6 相对 [Experimental Example 54] with respect to Experimental Examples 51 to 53 are described. [Experimental Example 54] In addition to the fact that the shielding plate is not attached to the hot air outlet of each of the air supply passages, heat-fixing is performed at -115 to 200927788, and heat is fixed at the same time. The temperature and the wind speed in the first to fourth regions of the apparatus were changed in the same manner as in the experimental example 51 except that the temperature and the wind speed in the first to fourth regions of the apparatus were changed to obtain a raw roll of about 15 μm. Further, the temperature and the wind speed conditions in the first to fourth regions of Experimental Example 54 were referred to as "III conditions". Further, the characteristics of the film and the film roll were evaluated using a slit roll in the same position as Experimental Example 51. The evaluation results are shown in Tables 1 and 12. [Experimental Example 55] In the same manner as in Experimental Example 52, except that the heat-shield outlet of each of the air supply passages was not attached with a shield plate and heat-fixed, and the temperature and wind speed of the first to fourth regions of the heat-fixing device were changed as shown in Table 10. The process was carried out to obtain a raw roll of about 15 microns. Further, the temperature and the wind speed conditions in the first to fourth regions of Experimental Example 55 were referred to as "IV conditions". Further, the characteristics of the film and the film roll were evaluated using a slit roll in the same position as Experimental Example 51. The evaluation results are shown in Tables 1 and 12. [Experimental Example 56] Example 5 was carried out except that the temperature and the wind speed of the first to fourth zones of the heat fixing device were changed as shown in Table 1 except that the shielding plate was not attached to the hot air blowing port of each of the air supply passages. 1 was carried out in the same manner to obtain a raw roll of about 25 μm. Further, the temperature and the wind speed conditions in the first to fourth regions of Experimental Example 56 were referred to as "III conditions". Further, the characteristics of the film and the film roll were evaluated using a slit roll in the same position as Experimental Example 51. The evaluation results are shown in Tables 1 and 12. -116- 200927788 [Table 11]

△ nab HS160 (minimum 値 to maximum 値) difference between maximum 値 and minimum HS of HS160 皱 之 之 密封 密封 密封 密封 密封 袋 袋 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 〇〇 Experimental Example 52 0.009 1.00 to 1.05 0.05 ◎ 〇〇 Experimental Example 53 0.010 0.95 to 1.05 0.10 ◎ 〇〇 Experimental Example 54 0.011 0.80 1.00 1.00 0.20 XX 〇X Experimental Example 55 0.009 0.95~1_10 0.15 X 〇X Experimental Example 56 0.010 0.85 ~ 1.10 0.25 X 〇 X

[Film effect of the experimental example] From Table 11, it is found that any of the films of Experimental Examples 51 to 53 has a small difference in heat shrinkage ratio (that is, a difference in heat shrinkage ratio) over the full width of the wound, and is in the longitudinal direction. The amount of change in the heat shrinkage rate is also small, and the passability at the time of post-processing is good, and it can be suitable for post-processing. Moreover, there is no seal when the bag is made

Wrinkles are beautifully finished. On the other hand, it was found that the films of Experimental Examples 54 to 56 had a large difference in heat shrinkage ratio over the entire width range, and the passability at the time of post-processing was poor, and it was not good at the seal portion when the bag was formed. Completed 0 -117- 200927788 o 〇【ZI«】 Durable bag vibrating durability ◎ ◎ ◎ ◎ ◎ ◎ Storage I stability _I ◎ ◎ ◎ ◎ ◎ ◎ I Peel strength (N/ I5mm) ON wS ^£3 o \ό Pinhole resistance (set) Formula (I) is established (1) Right ※ 〇〇<N 00 <N 00 CN 00 <N Oxygen wear Permeability (ml/m2 · 24 hours·MPa) § v〇〇\ 00 S s Thickness ratio B/A/B(%) 40/20/40 40/20/40 40/20/40 40/20/40 40/20/40 40/20/40 B layer composition NY6/PA elastomer ΜΧΏδ=89/5/6% NY6/PA Elastomer/MXD6=89/5/6% NY6/PA Elastomer/MXD6=89/ 5/6% NY6/PA Elastomer/MXD6=89/5/6% NY6/PA Elastomer/MXD6=89/5/6% NY6/PA Elastomer/MXD6=89/5/6% Layer A Composition MXD6 =lOO°/〇MXD6=l00% MXD6=l00% MXD6=l00% MXD6=lOO°/〇j MXD6=l00% Experimental Example 5l Experimental Example 52 Experimental Example 53 Experiment Example 54 Experimental Example 55 Experimental Example 56 • OOII _ 9: 9AN3⁄4 crocodile uOJttlB-Ir^sff embedded: 9axs [(sro+xsloo)l]/lvBd(I)1^:※II hidden-w 200927788 Below, the system displays Experimental Examples 51 to 53 in which the thickness unevenness described in the patent application range also satisfies 3 to 10% of the polyamidominated biaxially stretched film. [Experiment 57] Two types of three-layer co-extruded T-shape were used. The die apparatus is used to obtain an unstretched sheet of the following constitution. The total thickness of the B layer/A layer/B layer and the unstretched sheet is 190 μm, and the thickness ratio of each layer with respect to the total thickness is B layer/A layer/B layer=40%/20%/40%, The extruded resin temperature of the layer A was 270 ° C, and the temperature of the extruded resin of the layer B was 260 ° C. The composition constituting the layer A: a composition composed of poly(m-xylylene dimethyl hexamethyleneamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. Composition constituting layer B: polyamine-based block copolymer composed of 95% by weight of nylon 6 (made by Toyobo Co., Ltd., RV = 2.8), 5% by weight of thermoplastic resin elastomer (Nylon 12/poly-stretching) The composition of the butanediol copolymer, ARKEMA company PEBAX4〇33, RV = 2.〇). The pulling speed of the unstretched sheet (rotation speed of the rolls) was about 66 meters/minute. At this time, the gap in which the molten resin was wound around the metal roll was adjusted to 40 mm, and the multi-needle electrode formed by the needle-like body of 1.5 mm φ was used to melt the resin with 11 〇l.lkv ( The sheet is applied with a DC negative charge of 10 mA, and the molten resin is electrostatically adhered to the metal roll by causing the flow to be photo-evaporated. Further, in the above-described flow photo-corona discharge, the wall member is used to surround the electrode and the periphery of the metal roller to block the outside, and the humidity around the multi-needle electrode is maintained at about 75% RH and the temperature around the multi-needle electrode is maintained at about 45. °C. Further, when the molten resin is wound around the metal roll, the portion where the molten resin is in contact with the metal roll is attracted to the entire width of the molten resin by the vacuum box in the opposite direction to the direction in which the resin is taken up, thereby promoting the molten resin. Adhered to the metal roll. Further, the suction wind speed of the vacuum box was adjusted in such a manner that the full width of the suction port -119 - 200927788 (i.e., the full width of the molten resin) was 5.0 ± 0.5 m / sec. Further, in the production of the above unstretched film, no oligomer was observed to adhere to the multi-needle electrode, and the electrostatic adhesion state was very stable. The obtained unstretched sheet was extended 3.3 times in the longitudinal direction by a roll at an elongation temperature of 85 ° C, and then stretched by 3.7 times in the transverse direction by a stretching machine at an elongation temperature of 120 ° C. Further, a biaxially stretched film having an average thickness of 15 μm was produced by heat-fixing at a temperature of 215 ° C and applying a heat relaxation treatment of 5%. Further, a surface of the layer B on the dry lamination side of a 40 μm linear low-density polyethylene film (L-LDPE film: © Toyobo Co., Ltd., L6 02) was subjected to corona discharge treatment. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, and thickness unevenness. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 13. [Experimental Example 58] A biaxially stretched film was obtained by the same method as Experimental Example 57 except that the following was changed to the following. Q The composition constituting the B layer: a composition composed of 98% by weight of nylon 6 and 2% by weight of a polyamidamide-based block copolymer. The oxygen permeability of the biaxially stretched film obtained by the measurement is measured. Uneven thickness. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 13. [Experimental Example 59] A biaxially stretched film was obtained by the same method as Experimental Example 57 except that the description of Experimental Example 57 was changed to the following. -120- 200927788 Composition constituting the B layer: a composition composed of 99% by weight of nylon 6 and 1% by weight of a polyamidamide-based block copolymer. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, and thickness unevenness. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 13. [Experimental Example 60] A biaxially stretched film was obtained in the same manner as in Practical Example 57 except that the procedure of Experimental Example 57 was changed to the following. The composition constituting the layer B: a composition composed of 98% by weight of nylon 6 and 2% by weight of a polyamine-based block copolymer. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 4 1% / 18% / 41%. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, and thickness unevenness. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 13. [Experimental Example 61] A biaxially stretched film was obtained by the same method as Experimental Example 57 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 97% by weight of nylon 6 and 3% by weight of a polyamine-based block copolymer. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 3 9% / 22% / 3 9%. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, and thickness -121 - 200927788 degree unevenness. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. The results are shown in Table 13. [Experimental Example 62] A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the following was carried out. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 43% / 14% / 43%. 〇 The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, and thickness unevenness. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 13. [Experimental Example 63] A biaxially stretched film was obtained by the same method as Experimental Example 57 except that the procedure of Experimental Example 57 was changed to the following. The composition constituting the layer B: a composition composed of 98% by weight of nylon 6 and 2% by weight of a polyfluorene) guanamine-based block copolymer. The thickness ratio of each layer with respect to the total thickness is Β layer/Α layer/Β layer=36%/28%/3 6% ° The oxygen permeability, pinhole number, and thickness unevenness of the obtained biaxially stretched film are measured. . Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 13. [Experimental Example 64] A biaxially stretched film was obtained in the same manner as in the test of Example No. 57-200927788 except the following. The composition constituting the layer B: a composition composed of 99% by weight of nylon 6 and 1% by weight of a polyamine-based block copolymer. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 4 3 % / 1 4 % / 4 3 %. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, and thickness unevenness. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 13. [Experimental Example 65] A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the procedure of Experimental Example 57 was changed to the following. The composition constituting the layer B: a composition composed of 93% by weight of nylon 6 and 7% by weight of a polyamine-based block copolymer. The thickness ratio of each layer with respect to the total thickness is B layer/A layer/B layer=3 6%/2 8%/3 6% ° 氧The oxygen permeability and pinhole number of the obtained biaxially stretched film are measured. Uneven thickness. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 13. Hereinafter, Comparative Experimental Examples 66 to Ί1 with respect to Experimental Examples 57 to 65 are described. [Experimental Example 66] A biaxially stretched film was obtained by the same method as Experimental Example 57 except that the procedure of Experimental Example 57 was changed to the following. -123- 200927788 Composition constituting layer B: a composition composed of 100% by weight of nylon 6. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, and thickness unevenness. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 13. [Experimental Example 67] A biaxially stretched film was obtained in the same manner as in Practical Example 57 except that the procedure of Experimental Example 57 was changed to the following. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 3 0% / 4 0% / 3 0%. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, and thickness unevenness. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 13. [Experimental Example 68] 双 A biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the procedure of Experimental Example 57 was changed to the following. The composition constituting the layer A was composed of 80% by weight of poly-m-xylylene hexamethylenediamine and 20% by weight of nylon 6. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, and thickness unevenness. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 13. [Experimental Example 69] -124-200927788 A biaxially stretched film was obtained by the same method as Experimental Example 57 except that the following was changed to the following. The composition constituting the layer A: a composition composed of 80% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 20% by weight of nylon 6. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 2 0% / 6 0% / 2 0 〇 / 〇. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, and thickness unevenness. Further, the storage stability and vibration durability of the tantalum packaging bag produced by the obtained biaxially stretched film were tested. The results are shown in Table 13. [Experimental Example 70] The biaxially stretched film was obtained in the same manner as in Experimental Example 57 except that the following was changed to the following. The composition constituting the layer A: a composition composed of 80% by weight of poly-m-xylylene hexamethylenediamine and 20% by weight of nylon 6. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer 〇 = 3 0% / 40% / 30%. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, and thickness unevenness. Further, the storage stability "vibration durability" of the packaging bag produced from the obtained biaxially stretched film was tested. These results are shown in Table 13. [Experimental Example 71] A biaxially stretched film was obtained by the same method as Experimental Example 57 except that the description of Experimental Example 57 was changed to the following. The composition constituting the enamel layer: a composition composed of 90% by weight of poly-m-xylylene hexamethylene oxime-125-200927788 amine and 1% by weight of polyamine-based block copolymer. The composition constituting the enamel layer: a composition composed of 100% by weight of nylon 6. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, and thickness unevenness. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Table 13. [Experimental Example 72] In the case of the experimental example 57, when the molten resin was electrostatically adhered to the metal roll, the rotation speed of the metal roll was maintained at about 66 meters/min in the same manner as in Experimental Example 57. The wire was changed to 55 mmφ, and a DC negative electric charge of 100 mA was applied to the molten resin at 11±1.1 Κν to cause glow discharge, and the same as in Experimental Example 5 except that suction was not performed using a vacuum chamber. The method is to obtain a biaxially stretched film. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, and thickness unevenness. Further, the storage stability and vibration durability of the tantalum packaging bag produced by the obtained biaxially stretched film were tested. These results are shown in Table 13. The temperature is not as good as -126-200927788 〇o [el撇] Vibration durability ◎ ◎ 〇 ◎ ◎ ◎ 〇〇 ◎ X <1 〇 XX 〇 ◎ Storage stability ◎ ◎ ◎ ◎ ◎ 〇 ◎ 〇 ◎ ◎ ◎ X ◎ <3 ◎ Formula (I) is established _1 〇〇〇〇〇〇〇〇〇〇〇XXXX 〇 (I) Right ※ Μ Τ—< f—Μ 00 呀rH 〇 \ in Os cn 00 卜 4Λ) 00 卜 Os 00 «•Η 卜r- On Vi pinhole resistance (a) Η oo to CO ο Ον 卜<Ν Τ-< 00 oxygen permeability (ml/m2 00 Os sg oo 00 00 Ό 1-^ (Ν O Os ui wn 220 〇m Ό ΟΟ 〇 〇 \ 1 thickness unevenness_1 «η «η cn \〇卜oo CO ΓΛ *η (N cn inch rn VO 00 irl VO (Ν 00 \6 οο ν〇 (Ν流光晕,vacuum: _1 shame W- W- glow discharge thickness ratio B/A/B(%) _1 40/20/ 40 40/20/40 40/20/40 41/18/41 39/22/39 43/14/43 36/28/36 43/14/43 36/28/36 40/20/40 30/40/ 30 40/20/40 20/60/20 30/40/30 40/20/40 40/20/40 B layer _ ____J ΝΥ6/ΡΑ Elastomer = 95/5% NY6/PA Elastomer = 98 /2% NY6/PA Elastomer = 99/1% NY6/PA Elastomer = 98/2% NY6/PA Elastomer = 97/3% NY6/PA Elastomer = 95/5% ΝΥ6/ΡΑ Elastomer = 98 /2% NY6/PA Elastomer = 99/1% NY6/PA Elastomer = 93/7% NY6=100% NY6/PA Elastomer = 95/5% ΝΥ6/ΡΑ Elastomer = 95/5% NY6/PA Elastomer = 95 / 5% ΝΥ 6 / 弹性 Elastomer = 95 / 5% ΝΥ 6 = 100% ΝΥ 6 / 弹性 Elastomer = 95 / 5% A layer __ _ ―.1 MXD6 = 100% MXD6 = 100% MXD6 = 100 % MXD6=100°/〇MXD6=100% MXD6=100% MXD6=100°/〇MXD6=100% MXD6=100% MXD6=100% MXD6=100% MXD6/NY6=80/20% MXD6/NY6=80 /20% MXD6/NY6=80/20% MXD6/PA Elastomer=90/10% MXD6=100°/〇1 Experimental Example 57 Experimental Example 5 Experimental Example e Experimental Example 60 Experimental Example 61 Experimental Example θ 丨 Experimental Example 63丨1 Experimental Example Μ Experimental Example 65 1 Experimental Example Θ Experimental Example Experimental Example 丨 Experimental Example θ Experimental Example 70 Experimental Example 71 Experimental Example 72 - ζζ»——Η— 5®: 9ΛΝw Luo HgsE-nMLSE Age: 9axs [(sro +XSIOds/I>ed(I)^:※ 200927788 In the following, the experimental examples 73 to 84 in which the peeling strength described in the patent application range is 4.0 N/15 mm or more are also shown with respect to the experimental examples 5 to 6 5 . [Experimental Example 73] Use Two 3-layer co-extruded T-shaped die devices were used to obtain unstretched sheets of the following constitution. The total thickness of the B layer/A layer/B layer and the unstretched sheet is 190 μm, and the thickness ratio of each layer with respect to the total thickness is b layer/A layer/B layer=40%/2 0%/40%, The extruded resin temperature of layer A (27, TC layer B, the temperature of the extruded resin is 260 ° C. The composition constituting the layer A: made of poly-m-xylylene hexamethylenediamine (Mitsubishi Gas Chemical Co., Ltd.) RV = 2.65) = 100% by weight of the composition. The composition constituting the three layers: 88% by weight of nylon 6 (made by Toyobo Co., Ltd., RV = 2.8), 5% by weight of thermoplastic resin elastomer Polyamide-based block copolymer (Nylon 12/polybutanediol copolymer, ARKEMA PEBAX4033, RV = 2.0) and 6% by weight of poly-m-xylylene hexane decylamine (Mitsubishi Gas Chemicals Co., Ltd.) The composition of the system, RV = 2.65). The pulling speed of the unstretched sheet (rotation speed of the roll) is about 66 meters / ϋ minute. At this time, the gap of the molten resin when wound around the metal roll is adjusted to 40. Millimeter, and a multi-needle electrode formed by a needle of 1.5 mm φ is applied with a DC negative charge of 100 mA to the molten resin (sheet) by ll±l.lkv And the molten resin is electrostatically adhered to the metal roll by causing the flow to be photo-foamed, and in the above-described flow photo-corona discharge, the wall member is used to surround the electrode and the metal roller to block the outside and maintain the multi-needle. The humidity around the electrode is about 75% RH and the temperature around the multi-needle electrode is maintained at about 45 C. Further, when the molten resin is wound around the metal roll, the portion where the molten resin is in contact with the metal roll is melted. The full width of the resin is attracted by the vacuum-128-200927788 box in the opposite direction of the direction in which the resin is taken up to promote the adhesion of the molten resin to the metal roll. Moreover, the suction speed of the vacuum box is at the full width of the suction port. (that is, the full width of the molten resin) was adjusted in a range of 5·0±0·5 m/sec. Further, in the production of the above unstretched film, no adhesion of the oligomer to the multi-needle electrode was observed. The state of electrostatic adhesion was very stable. The obtained unstretched sheet was extended 3.3 times in the longitudinal direction by a roll at an elongation temperature of 85 ° C, and then stretched by 3.7 times in the transverse direction by a stretching machine at an extension temperature of 120 ° C. And borrow A biaxially stretched film having an average thickness of 15 μm was produced by heat-fixing at a temperature of 215 ° C and applying 5% 5% thermal relaxation treatment at 200 ° C. Moreover, a linear low-density polyethylene film with a thickness of 40 μm (L) - LDPE film: manufactured by Toyobo Co., Ltd., L6 102) The surface of the B layer on the dry lamination side was subjected to corona discharge treatment. The oxygen permeability, pinhole number, peel strength, and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 1. [Experimental Example 74] 双 A biaxially stretched film was obtained by the same method as Experimental Example 713 except that the procedure of Experimental Example 73 was changed to the following. The composition constituting the layer B: a composition composed of 9.5 wt% of nylon 6, 2 wt% of a polyamine-based block copolymer, and 3% by weight of poly-m-xylylene hexane decylamine. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, peeling strength, and thickness unevenness. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 1. -129-200927788 [Experimental Example 75] A biaxially stretched film was obtained by the same method as Experimental Example 73 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 97% by weight of nylon 6, 1% by weight of a polyamine-based block copolymer, and 2% by weight of poly-m-xylylene hexane dimethyl amide. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, peeling strength, and thickness unevenness. Further, the storage stability, vibration durability, and bag break resistance of the packaging bag produced by the obtained biaxially stretched film were tested. These results are shown in Table 1. [Experimental Example 76] A biaxially stretched film was obtained by the same method as Experimental Example 73 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 95% by weight of a nylon 6' 2% by weight polyamine-based block copolymer and 3% by weight of poly-m-xylylene hexane decylamine. The thickness ratio of each layer with respect to the total thickness is B layer "layer / 8 〇 layer = 41% / 18% / 41. / 〇. The oxygen permeability, the number of pinholes, and the peeling strength of the obtained biaxially stretched film were measured. Further, the thickness of the package was measured by the obtained biaxially stretched film, and the storage stability, vibration durability, and bag break resistance were measured. The results are shown in Table 1. [Example 77 In the case of Experimental Example 73, a biaxially stretched film was obtained by the same method as Experimental Example 73 except that it was changed to the following. The composition constituting the B layer was composed of 92% by weight of nylon 6 and 3 parts by weight. Polyfluorene-130-200927788 A composition composed of an amine block copolymer and 5% by weight of poly-m-xylylene dimethyl decylamine. The thickness ratio of each layer relative to the total thickness is B layer / A layer / B layer =3 9%/22%/3 9% ° The oxygen permeability, the number of pinholes, the peel strength, and the thickness unevenness of the obtained biaxially stretched film were measured. Further, the test was carried out from the obtained biaxially stretched film. The storage bag has stability, vibration durability and bag break resistance. The results are shown in Table 1. Ο [Experiment In the case of Experimental Example 73, a biaxially stretched film was obtained by the same method as Experimental Example 73 except that the thickness ratio of each layer with respect to the total thickness was B layer/A layer/B layer = 43%/14%/43%. The oxygen permeability, the number of pinholes, the peel strength, and the thickness unevenness of the obtained biaxially stretched film were measured. Further, the test was performed on the package produced by the obtained biaxially stretched film. The storage stability, vibration durability, and bag break resistance of the bag were as follows. The results are shown in Table 1. [Experimental Example 79] The description of Experimental Example VII was changed to the following except for the following. 73. The same method was used to obtain a biaxially stretched film. Composition constituting the B layer: 95% by weight of nylon 6, 2% by weight of polyamido block copolymer and 3% by weight of poly-m-xylylene hexane dioxime A composition composed of an amine. The thickness ratio of each layer with respect to the total thickness is B layer/A layer/B layer=36%/28%/36% -131 - 200927788 The oxygen permeability of the obtained biaxially stretched film is measured. Rate, pinhole number, peel strength, thickness unevenness. Further, the test was carried out from the obtained biaxially stretched film. The storage bag of the manufactured packaging has stability, vibration durability, and bag breakage resistance. The results are shown in Table 1. [Experimental Example 80] In the description of Experimental Example 73, the experiment was carried out except for the following. The biaxially stretched film was obtained in the same manner as in Example 73. The composition constituting the B layer: 97% by weight of nylon 6, 1% by weight of polyamido block copolymer and 2% by weight of poly-m-xylylene A composition composed of diamine. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 43 0 / 〇 / 14% / 43%. The oxygen permeation of the obtained biaxially stretched film was measured. Permeability, pinhole number, peel strength, and thickness unevenness. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 1. [Experimental Example 81] A biaxially stretched film was obtained by the same method as Experimental Example 73 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 83% by weight of nylon 6, 7% by weight of a polyamine-based block copolymer, and 10% by weight of poly-m-xylylene dimethyl decylamine. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 3 6% / 2 8% / 3 60 / 〇. The oxygen permeability, the number of pinholes, and the peeling-132-200927788 peeling strength and thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging stability and vibration durability of the packaging bag produced by the obtained biaxially stretched film were tested. These results are shown in Table 1. [Experimental Example 82] A biaxially stretched film was obtained by the same method as Experimental Example 73 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 93% by weight of nylon 6, 5% by weight of a polyamine-based block copolymer, and 2% by weight of poly-m-xylylene hexane decylamine. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, peeling strength, and thickness unevenness. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 14. [Experimental Example 83] A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the procedure of Experimental Example 73 was changed to the following. Q A composition constituting the layer B: a composition composed of 84% by weight of nylon 6, 5% by weight of a polyamine-based block copolymer, and 11% by weight of poly-m-xylylene hexane decylamine. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, peeling strength, and thickness unevenness. Further, the results of the storage stability, the vibration durability, and the bag breakage resistance of the packaging bag produced by the obtained biaxially stretched film were measured as shown in Table 14. [Experimental Example 84] A biaxially stretched film was obtained in the same manner as in the test of Example 133-200927788 except the following. The composition constituting the layer B: a composition composed of 98% by weight of nylon 6'% by weight of a polyamine-based block copolymer and 1% by weight of poly-m-xylylene hexane decylamine. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, peeling strength, and thickness unevenness. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 14. In the following, Comparative Experimental Examples 85 to 94 ° with respect to Experimental Examples 73 to 84 are described. [Experimental Example 85] In the description of Experimental Example 73, a biaxial method was obtained by the same method as Experimental Example 73 except that the following was changed to the following. Extend the film. The composition constituting the layer B: a composition composed of 100% by weight of nylon 6 "The oxygen permeability, the number of pinholes, the peeling strength, and the thickness unevenness of the obtained biaxially stretched film were measured. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 14. [Experimental Example 86] A biaxially stretched film was obtained by the same method as Experimental Example 73 except that the procedure of Experimental Example 73 was changed to the following. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 3 0 〇 / 〇 / 4 0% / 3 0 〇 / 〇. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, peeling strength, and thickness unevenness. Further, the storage stability, the vibration durability, and the bag breakage resistance of the packaging bag produced by the obtained biaxially stretched film were measured. The results are shown in Table 14. [Experimental Example 87] A biaxially stretched film was obtained by the same method as Experimental Example 713 except that the following was changed to the following. The composition constituting the layer A: a composition composed of 80% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 20% by weight of nylon 6. 〇 The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, peel strength, and thickness unevenness. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 14. [Experimental Example 88] A biaxially stretched film was obtained in the same manner as in Experimental Example 73 except that the procedure of Experimental Example 73 was changed to the following. The composition constituting the layer A: a composition composed of 80% by weight of poly-m-xylylene hexamethylene phthalamide and 20% by weight of nylon 6. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 2 0% / 6 0% / 2 0%. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, peeling strength, and thickness unevenness. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 14. [Experimental Example 89] A biaxially stretched film was obtained in the same manner as in the test example 73 of 135-200927788 except that the description of the experimental example 73 was changed. The composition constituting the layer A: a composition composed of 80% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 20% by weight of nylon 6. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 3 0% / 4 0 〇 / 〇 / 3 0 〇 / 〇. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, peeling strength, and thickness unevenness. Further, the storage stability, the vibration durability, and the bag breakage resistance of the packaging bag produced by the obtained biaxially stretched film were measured. The results are shown in Table 14. [Experimental Example 90] A biaxially stretched film was obtained by the same method as Experimental Example 73 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 95% by weight of nylon 6 and 5% by weight of a polyamide-based block copolymer. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, peeling strength, and thickness unevenness. Further, the storage stability, vibration durability, and bag break resistance of the packaging bag produced by the obtained biaxially stretched film were tested. These results are shown in Table 14. [Experimental Example 91] A biaxially stretched film was obtained by the same method as Experimental Example 73 except that the procedure of Experimental Example 73 was changed to the following. The composition constituting the layer B: a composition composed of 99% by weight of nylon 6 and 1% by weight of a polyamine-based block copolymer. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, peeling strength, and thickness unevenness. Further, the storage stability and vibration durability of the packaging bag produced by the obtained biaxially stretched thin film -136-200927788 film were tested. These results are shown in Table 14. [Experimental Example 92] A biaxially stretched film was obtained by the same method as Experimental Example 713 except that the procedure of Experimental Example 73 was changed to the following. The composition constituting the layer B: a composition composed of 95% by weight of nylon 6 and 5% by weight of poly-m-xylylene dimethyl decylamine. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, peeling strength, and thickness unevenness. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. The results of this fundraising are shown in Table 14. [Experimental Example 93] A biaxially stretched film was obtained by the same method as Experimental Example 713 except that the procedure of Experimental Example 73 was changed to the following. The composition constituting the layer A: a composition composed of 90% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 10% by weight of a poly amide-based block copolymer. Q constitutes a composition of the B layer: a composition composed of 100% by weight of nylon 6. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, peeling strength, and thickness unevenness. Further, the packaging stability of the packaging bag produced by the obtained biaxially stretched film, vibration durability, and bag break resistance were tested. These results are shown in Table 14. [Experimental Example 94] In the case of the experimental example 73, when the molten resin was electrostatically adhered to the metal roll, the rotation speed of the metal roll was maintained at about -137 to 200927788 66 m/min in the same manner as in Experimental Example 73. In the state, the electrode was changed to a wire of 0.5 mm Φ and a DC negative charge of 100 mA was applied to the molten resin at 11 ± 1.1 Κν to cause glow discharge, and the same was carried out without using a vacuum box. The method to obtain a biaxially stretched film. The obtained biaxially stretched film was measured for oxygen permeability, pinhole number, peeling strength, and thickness unevenness. Further, the storage stability and vibration durability of the packaging bag produced by the obtained biaxially stretched film were tested. These results are shown in Table 14. 〇

-138 200927788 〇ο [inch i 5 resistance to bagging 〇〇〇〇〇〇〇〇〇〇〇〇<3 〇〇< 〇XX <1 < 〇vibration durability ◎ ◎ 〇◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ X <1 〇 XX ◎ ◎ X < ◎ Storage stability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ X ◎ < ◎ ◎ ◎ < ◎ Formula (I) 〇〇〇〇〇〇〇〇〇〇〇〇〇〇XXX 〇〇〇X 〇(I) Right ※00 2 2 (N *〇rn •1 2 \n 1 144 I Μ m 00 It? Si GO cn 〇\u-> 00 <s Peel strength (N/15mm) \ό 00 <〇00 vS 2 Bu wS 00 vb inch wS v〇wS ν〇ν〇wS CO v〇m iri o Bu (N fS Rn 00 V〇<r> mv〇 pinhole resistance () »/Ί ON inch oo 00 (S m 00 Ι/Ί »"<· 00 (S 00 oo v-> Oxygen penetration Rate (ml/m2 · 24 hours·MPa) a On s Ψ—4 v© cn so \oo ig s s \η α\ *η ο s 00 Os s 00 00 oa\ 00 Thickness unevenness 00 rS <N — CO VO cs mf〇»n <ri in cn — inch»Γϊ 卜rn v〇 \ό fS wS <s — CO in *ri •o VO 12.5 Flow Photovoltaic, Vacuum 蚺W- •Up Shame: Glow Discharge Thickness Ratio B/A/B (%) 40/20/40 I 40/20 /40| 40/20/40 I 41/18/411 1 39/22/391 I 43/14/431 I 36/28/361 | 43/14/431 1 36/28/36] 40/20/40 40/20/40 | 40/20/401 40/20/40 30/40/30 40/20/40 ; 20/60/20 | 30/40/301 40/20/40 40/20/40 | 40 /20/40 40/20/40 40/20/40 B layer composition NY6/PA elastomer/MXD6=89/5/6°/. NY6/PA Elastomer/MXD6=95/2/30/〇S? T v〇i Miscellaneous BW»1 s; v〇$ T v〇i Interest m ttnL; V〇NY6/PA Elastomer/MXD6=92 /3/5% NY6/PA Elastomer/MXD6=89/5/6% 5? Ci Os Q 1 豳mn〇L w, σ\ Q 1 豳ma pen v〇ο SS ι 1 豳MWtl Bt Dad g 1 Q 1 豳mav〇«Λί Ρ I m BBWlI song V〇:z * i XQ 1 豳m ML \o ΝΥ6=100% 00 l D 1 miscellaneous v〇〇〇l 0 1 Miscellaneous SR v〇>- 5 00 l Ο 1 Miscellaneous Bt tv〇00 l 1 Boat m BtnL Song SO NY6/PA Elastomer = 95/5% £ BUI St _ NY6/MXD6=95/5% NY6=100% NY6/PA Elastomer/MXD6 =89/5/6% A layer composition MXD6=100°/〇MXD6=100°/〇MXD6=100% MXD6=100°/〇MXD6=100% MXD6=100% MXD6=100% MXD6=100°/〇 MXD6=100% MXD6=100% MXD6=100% MXD6=100% MXD6=100% MXD6=100% MXD6/NY6-80/20% MXD6/NY6=80/20% MXD6/NY6=80/20% MXD6- 100% MXD6=100% MXD6=100°/〇0 § T Stupid: nnL sP; 1 MXD6=100% Experimental Example 73 Experimental Example 74 丨 Experimental Example 75 | 丨 Experimental Example 76 丨 Experimental Example 77 1 Experimental Example 78| 1 Experimental Example 79|Experimental Example 80 Experimental Example 81 Experimental Example 82 Experimental Example 83 Interested κ Experimental Example 85 Experimental Example 86 00 Interest Μ Experimental Example 88 Experimental Example 89 pmm 纒K Experimental Example 92 Experimental Example 93 Experimental Example 94 's, 9 let: 9ΛΝ [(sld+XSI0d]]/l>^I(I)^:※—Is Stupid: fMvd 200927788 In the following, Experimental Examples 95 to 97 in which the coating film was coated with a viscous modified coating film as described in the patent application were used. [Experimental Example 95] <Coating liquid for forming an adhesive modified film ( Adjustment of copolymerized polyester water system> In a non-autoclave equipped with a stirrer, a thermometer and a partial reflux cooler, 466 parts of dimethyl phthalate and 466 parts of neopentyl glycol isophthalate were added, 443 parts of ethylene glycol and 0.52 parts of tetra-n-butyl phthalate were subjected to transesterification at 160 to 220 ° C for 4 hours. Next, the reaction was carried out by adding a portion of fumaric acid and raising the temperature from 200 ° C to 220 ° C for 1 hour. Subsequently, the temperature was raised to 2 > 5 5 ° C, and the reaction system was slowly stirred under a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester. The obtained polyester was light yellow transparent and had a glass transition temperature of 60 ° C and a weight average molecular weight of 12,000. The composition according to NMR measurement or the like is as follows. Dicarboxylic acid component ζ) 酞 4 4 4 mol% isophthalic acid 4 8 mol% fumaric acid 4 mol% diol component neopentyl glycol 50 mol% ethylene glycol 5 0 mol% . A stirrer, a thermometer, a reflux device, and a dosing reactor were placed, and 75 parts of the above polyester resin, 56 parts of methyl ethyl ketone, and isopropyl alcohol were added, and the mixture was heated and stirred at 65 ° C to dissolve the resin. Resin complete agent dispersion) rust steel ester, ester, mouth 23 ester decompression should be set to 5: 19 after dissolution -140- 200927788, 17.5 parts of methacrylic acid and 7.5 parts of ethyl acrylate mixture A solution of 1.2 parts of azobisdimethylvaleronitrile dissolved in 25 parts of methyl ethyl ketone was added dropwise to the polyester solution at 0.2 ml/min, and stirring was continued for 2 hours after the completion of the dropwise addition. After the analysis sample (5 g) was used from the reaction solution, 300 parts of water and 25 parts of triethylamine were added to the reaction solution and stirred for 1 hour to prepare a dispersion of the grafted polyester. Subsequently, the temperature of the obtained dispersion was raised by 1 ° C, and methyl ethyl ketone, isopropyl alcohol and excess triethylamine were distilled off by distillation to obtain a copolymerized polyester aqueous dispersion. €) The resulting dispersion was white with an average particle size of 300 nm and a B-type viscosity of 50 cps at 25 °C. After 5 g of this dispersion was added with 1.25 g of heavy water to have a solid concentration of 20% by weight, D S S was added and 125 MHz l3C-NMR was measured. The half-turn amplitude of the signal (160-175 ppm) from the carbonyl carbon of the polyester backbone is 〇〇 (undetected signal), and the half-turn amplitude of the signal of the carbonyl carbon of the grafted portion of methacrylic acid (181-186 ppm) is 110Hz. The solution sampled at the end of the grafting reaction was dried at 100 ° C under vacuum for 8 hours, and the acid value of the solid component was measured, and the grafting efficiency (measurement of NMR) of the ruthenium polyester was measured and water was added. Decomposition to determine the molecular weight of the graft moiety. The acid value of the solid component was 2300 eq. / 106 g. In the measurement of 1H-NMR, since the signal derived from fumaric acid (5 = 6.8-6.9 ppm, doublet) was not detected at all, it was confirmed that the grafting efficiency of the polyester was 100%. The molecular weight of the graft portion was 10,000 by weight average molecular weight. Subsequently, the dispersion obtained above was diluted with water so that the solid content concentration was 5% to obtain a coating liquid (copolymerized polyester aqueous dispersion) A for forming an adhesive modified film. <Production of Polyamine-based Laminated Biaxially Stretched Film> -141 - 200927788 An unstretched sheet composed of τ was obtained by using two types of three-layer co-extruded T-shaped die equipment. The Β/Α/Β layer is composed of a total thickness of 210 μm, and the thickness ratio of each layer relative to the total thickness is b layer/A layer/B layer=40%/2 0%/40%, The extruded resin temperature of layer A was 2 70. (:, the extrusion resin temperature of layer B is 260 ° C. The composition constituting layer A: consisting of poly-m-xylylene hexane decylamine (Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100 weight Composition consisting of %. Composition constituting layer B: polyamine-based block copolymerization of 95% by weight of nylon 6 (made by Toyobo Co., Ltd., RV = 2_8) and 5% by weight of thermoplastic resin elastomeric steroid The composition of the product (Nylon 12/polybutylene glycol copolymer, ARKEMA company PEBAX4033, RV = 2.0). Subsequently, the obtained unstretched sheet was made of Teflon (registered trademark) roll. After stretching at a stretching temperature of 85 ° C for about 2.1 times in the longitudinal direction (first longitudinal extension), the ceramic roll is extended by about 1.6 times (2nd longitudinal extension) at an elongation temperature of about 70 ° C. Then, it is extended in the longitudinal direction. On the surface of the film, the coating liquid (copolymerized polyester aqueous dispersion) A for forming an adhesive modified film was continuously applied by a gravure method, and the coating liquid was dried on a roll C) adjusted to 150 ° C. . Further, the coating amount of the coating liquid was adjusted so as to form a 0.2 g/square-meter adhesive modified film. Further, the surface of the film which was longitudinally stretched as described above was coated with an adhesive modified film, and the longitudinally stretched sheet was continuously guided to a tenter and extended 4.0 times in the transverse direction at about 130 °C. Further, a biaxially stretched film of about 15 μm was produced by heat-fixing at a temperature of 210 ° C and applying a lateral relaxation treatment of 5.0%, followed by cooling and cutting off both edge portions. Further, the surface of the layer B on the dry lamination side of the 40 μm linear low-density polyethylene film (L-LDPE film: manufactured by Toyobo Co., Ltd., L6102) was subjected to a corona discharge -142 - 200927788. The oxygen permeability, the number of pinholes, and the peeling strength of the obtained biaxially stretched film were measured. Further, the storage stability and vibration durability of the packaging bag produced from the obtained biaxially stretched film were tested. These results are shown in Tables 15 to 16. [Experimental Example 96] <Adjustment of coating liquid for forming an adhesive modified film (copolymerized polyester aqueous dispersion)> In addition to changing to 90 parts of the polyester resin obtained in Experimental Example 95, 7.0 parts of methyl group A copolymerized polyester aqueous dispersion was obtained by the same preparation as Experimental Example 9.5 except for acrylic acid, 3.0 parts of ethyl acrylate, and 0.48 parts of azobisdimethylvaleronitrile. Subsequently, the dispersion was diluted with water at a solid concentration of 5% to obtain a coating liquid (copolymerized polyester aqueous dispersion) B for forming an adhesive modified film. Then, the polyimide liquid-coated biaxially stretched film of Experimental Example 96 was obtained in the same manner as in Experimental Example 9.5 except that the coating liquid applied to the sheet extending in the longitudinal direction was changed to the above-mentioned coating liquid B. Further, the properties of the obtained film were evaluated in the same manner as in Experimental Example 95. The evaluation results are shown in Tables 1 5 to 16. [Experimental Example 97] <Adjustment of coating liquid for forming an adhesive modified film (copolymerized polyester aqueous dispersion)> In addition to changing 'using 457 parts of dimethyl phthalate and 452 parts of dimethyl phthalate A polyester was obtained by the same method as Experimental Example 9.5 except for the ester and 7.4 parts of dimethyl 5-sodium sulfonate succinate. The obtained polyester was light yellow transparent and had a glass transition temperature of 62 ° C. The weight average molecular weight was 12 Å. The composition obtained by NMR measurement or the like according to -143-200927788 is as follows. Dicarboxylic acid component to citric acid 49 mol% isodecanoic acid 4 8.5 mol% 5-sodium sulfonate isophthalic acid 2.5 mol% diol component neopentyl glycol 5 0 mol% ethylene glycol 5 0 Moer%. In addition to adding 1 part of the polyester resin, and adding no methyl propyl acrylate and azobis dimethyl valeronitrile, the copolymerized polyester aqueous dispersion was obtained according to the experimental example. . Subsequently, the coating liquid (copolymerized polyester aqueous dispersion) C for forming a viscous film was obtained by diluting with water so that the solid content concentration was 5%. Subsequently, a polyimide-based biaxially stretched film of Experimental Example 97 was produced in the same manner as Experimental Example 95 except that the sheet coated in the longitudinal direction was applied as the above-mentioned coating liquid C. Further, the properties of the obtained film were evaluated in the same manner as in C). The evaluation is shown in Tables 1 5 to 16. Hereinafter, a comparative experimental example with respect to Experimental Examples 95 to 97 is described [Experimental Example 98] In Experimental Example 95, except for the step of omitting the film-coated modified film after the longitudinal stretching, the film was guided to a tenter to carry out lateral stretching for experiment. Example 95 was carried out in the same manner to obtain a polyamine biaxially stretched film of Experimental Example 98. Further, the characteristics of the film obtained were obtained in the same manner as in Experimental Example 95. The evaluation results are shown in Tables 15 to 16. The olefinic acid and hydrazine 95 were changed with the dispersion and the liquid was changed to obtain the photo and the actual result, and the layer was evaluated. -144- 200927788 〇ο [51撇] Heat-resistant water peeling strength (N/15mm) m Q Ο 耐 Water resistance 1 Peel strength (N/15mm) VO cn CN rn (N Relaxation treatment (%) O κη o Ο κη Heat fixation (°C) 〇V-Η (Ν 210 210 210 Lateral stretching ratio 〇oo ο ― Temperature. C ο m ^-Η 2nd longitudinal stretching ratio vq Temperature. C ο oo ο Coating solution for coating an adhesive film forming solution A Coating liquid B Coating liquid c Destroying the first longitudinal stretching ratio Η Temperature. C Vi 00 In 00 oo wn 00 Experimental Example 95 Experimental Example 96 Experimental Example 97 Experimental Example 98 -VOH — 200927788 ο 〇 [91嗽]

Vibration durability ◎ ◎ ◎ ◎ Storage stability ◎ ◎ ◎ ◎ Pinhole resistance (pieces) »—Η Formula (1) is established (I) Right side ※ 〇〇 inch 00 inch Η Oxygen permeability (ml /m2 · 24 hours.MPa) VO as VO 〇\ 〇\ 00 Os Thickness ratio B/A/B/(%) 40/20/40 40/20/40 40/20/40 40/20/40 B layer Composition NY6/PA Elastomer = 95/5% NY6/PA Elastomer = 95/5% NY6/PA Elastomer = 95/5% ΝΥ6/ΡΑ Elastomer = 95/5% A layer composition MXD6=100% MXD6= 100% i MXD6=100% 1 MXD6=100% Experimental Example 95 Experimental Example 96 Experimental Example 97 Experimental Example 98 5®: 9AN ^Dart ngsill^sff嵚: 9QXW [(no+XSIOds/I>ed(I)^: * 200927788 In the following, it is shown that the peeling strength described in the application specification is 4: ON / 1 5 mm or more in the experimental example 9 5 to 9 7 (Experimental Example 99) <Adhesiveness Coating liquid for forming a modified film (adjustment of copolymerized polyester water system) In the case of a non-autoclave equipped with a stirrer, a thermometer, and a partial reflux cooler, 466 parts of dimethyl phthalate and 466 parts of isononanoic acid were added. 401 parts of neopentyl glycol, 443 parts of ethylene glycol and 0.52 parts The tetra-n-butyl sulfonate was subjected to transesterification at 160 to 220 ° C for 4 hours. Then, the reaction was heated to 200 ° C to 220 ° C for 1 hour to evolve the reaction. At 25 ° C, the reaction was slowly carried out, and the system was stirred under a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester. The obtained polyester was light yellow transparent and the glass transfer temperature was 60 °. The weight average molecular weight of C ' is 12,000. The composition according to NMR measurement or the like is as follows. Dicarboxylic acid component 〇 〇 4 4 4 8 mol% isononanoic acid 4 8 mol% fumaric acid 4 mol % diol component Neopentyl glycol 50 mole % ethylene glycol 50 mole %. • Add 75 parts of the above polyester resin, 56 parts of methyl ethyl group with a stirrer, thermometer, reflux device and dosing retrofitting reactor Ketone: Isopropanol is heated and stirred at 65 °C to dissolve the resin. The resin is completely clean) 1 - Dispersion) Rusty steel ester, ester, P 23 ester decompression should be set to 5: 19 Dissolve After -147- 200927788, 17.5 parts of methacrylic acid and 7.5 parts of ethyl acrylate 1.2 parts of azobisdimethyl Carbonitrile was dissolved in 25 parts of methyl acetate was added dropwise to 0.2 ml / min to the polyester solution was added dropwise and stirring was continued for 2 hours. After the analysis was carried out for a month from the reaction solution, 300 parts of water and 25 parts of triethylamine were added to the reaction solution to prepare a dispersion of the grafted polyester. Subsequently, the obtained temperature was raised to 1 ° C, and methyl ether and excess triethylamine were distilled off to obtain a copolymerized polyester aqueous dispersion. The dispersion obtained was white and averaged. The B-type viscosity at 300 °C is 50 cps. After 5 g of this dispersion: heavy water and a solid concentration of 20% by weight, 125 MHZ13C-NMR was added. The enthalpy of the carbonyl group (160-175 ppm) from the polyester backbone was 〇〇 (undetected signal) and the signal of the carbonyl carbon of methacrylic acid (18 1-1 86 ppm) was 110 Hz. The mixture was dried under a vacuum sampled at the end of the grafting reaction for 8 hours, and the grafting efficiency (measurement of NMR) of the Q polyester and the molecular weight of the fraction by hydrolysis were measured for the solid content. When the acid value of the solid component was 2,300 eq./106, since the signal from the fumaric acid (5 = 6 doublet) was not detected at all, it was confirmed that the grafting efficiency of the polyester was a partial molecular weight, and the weight average molecular weight was 1 0000. Subsequently, the dispersion obtained above was diluted with water as a solid component to obtain an adhesive modified film (copolymerized polyester aqueous dispersion) A. Using two kinds of three-layer co-extruded T-shaped die equipment, the mixture and the base ketone were finished, and then the ketone of the dispersion (5 g) was stirred for 1 hour, and the ketone of isopropyl alcohol, Further, 1.2 5 g of DSS was added and the half-turn amplitude of the signal graft portion of carbon was measured at 100 ° C and the acid value was measured to determine the graft gram. 1 H-NMR .8 - 6 · 9 ppm, 100%. The coating liquid having a graft concentration of 5% was used to obtain an unstretched sheet composed of the following -148-200927788. The total thickness of the B layer/A layer/B layer and the unstretched sheet is 210 μm, and the thickness ratio of each layer with respect to the total thickness is b 'layer/A layer/B layer=40%/20%/40%, The extruded resin temperature of the layer A was 270 ° C, and the temperature of the extruded resin of the layer B was 260 ° C. Composition constituting the A layer • A composition composed of poly-m-xylylene hexamethylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. Composition constituting the B layer: a polyamide-based block copolymer (Nylon 12/poly-stretch) composed of 89% by weight of nylon 6 (made by Toyobo Co., Ltd., RV = 2.8) and 5% by weight of a thermoplastic resin elastomer A composition of a butanediol copolymer, 〇ARKEMA company PEBAX40 3 3, RV = 2.0) and 6 parts by weight of poly-m-xylylene hexane decylamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65). Subsequently, the obtained unstretched sheet was stretched by a roll made of Teflon (registered trademark) at a stretching temperature of 85 ° C for about 2.1 times in the longitudinal direction (first longitudinal extension). It is about 7 (the longitudinal extension of the TC is about 1.6 times (the second longitudinal extension). Subsequently, the coating liquid for forming the above-mentioned adhesive modified film is continuously applied by gravure on the surface of the film after the longitudinal stretching (copolymerization polymerization) The ester aqueous dispersion) A was dried on a roll adjusted to 150 ° C. Further, the coating amount of the coating liquid was adjusted so as to form a 0.2 g/m 2 adhesive modified film. Applying an adhesive modified film to the surface of the film extending in the longitudinal direction as described above continuously guides the longitudinally stretched sheet to a tenter and extends 4.0 times in the transverse direction at about 130 ° C. Also, by 2101 The temperature was thermally fixed and subjected to a lateral relaxation treatment of 5.0%, followed by cooling and cutting off both edge portions to produce a biaxially stretched film of about 15 μm. Moreover, a 40 μm linear low-density polyethylene film (L_LDPE film) The surface of the B layer on the dry lamination side of the company, manufactured by Toyobo Co., Ltd., 149-200927788, was subjected to corona discharge treatment. The oxygen permeability and the number of pinholes of the obtained biaxially stretched film were measured. The storage stability and vibration durability of the packaging bag produced by the biaxially stretched film are shown in Tables 17 to 18. [Experimental Example 100] <Coating liquid for forming an adhesive modified film (Adjustment of Copolymerized Polyester Water-Based Dispersion)> In addition to changing to 90 parts of the polyester obtained in Experimental Example 99, 7.0 parts of methyl hydrazine acrylate, 3.0 parts of ethyl acrylate, and 0.48 parts of azobisdimethyl valeronitrile In the same manner as in Experimental Example 99, a copolymerized polyester aqueous dispersion was obtained. Then, the dispersion was diluted with water so that the solid content concentration was 5% to obtain a coating liquid for forming an adhesive modified film. (Copolymerization of Polyester Water-Based Dispersion) B. The same procedure as in Experimental Example 99 was carried out except that the coating liquid applied to the sheet extending in the longitudinal direction was changed to the above-mentioned coating liquid B, and the polycondensation of Experimental Example 100 was obtained. Amine laminate The film was stretched by a shaft, and the properties of the obtained film were evaluated in the same manner as in Experimental Example 99. The evaluation results are shown in Tables 17 to 18. [Experimental Example 1 0 1 ] <Adhesive modified film Adjustment of Coating Liquid for Formation (Copolymerized Polyester Water-Based Dispersion)> In addition to changing, 45 7 parts of dimethyl phthalate, 452 parts of dimethyl isononate, and 7.4 parts of 5-sodium sulfonate were used. A polyester was obtained by the same method as Experimental Example 99 except for dimethyl decanoate. The obtained polyester was pale yellow and transparent, and had a glass transition temperature of 62 ° C and a weight average molecular weight of 12,000. According to -150-200927788 The composition obtained by NMR measurement or the like is as follows. Dicarboxylic acid component to citric acid 49 mol% isononanoic acid 4 8.5 mol% 5-sodium sulfonate isophthalic acid 2.5 mol% diol component neopentyl glycol 5 0 mol% ethylene glycol 50 mol %.共 A copolymerized polyester aqueous dispersion was obtained in accordance with the method necessary for the experiment, except that the polyester resin was added in an amount of 1 part, and ethyl methacrylate and azobisdimethylvaleronitrile were not added. Subsequently, the coating liquid (copolymerized polyester aqueous dispersion) C for forming a viscous film was obtained by diluting with water so that the solid content concentration was 5%. Subsequently, a polyimide-based biaxially stretched film of Experimental Example 101 was produced in the same manner as in Experimental Example 99 except that the sheet coated in the longitudinal direction was applied as the above-mentioned coating liquid C. Further, the properties of the obtained film were evaluated in the same manner as in Experimental Example 99. The evaluation is shown in Tables 1 7 to 18. In the following, a comparative experiment with respect to Experimental Examples 99 to 101 was described [Experimental Example 102] In Experimental Example 99, except for the step of omitting the film-coated modified film after the longitudinal stretching, the film was guided to the tenter to be laterally extended. Experimental Example 99 was carried out in the same manner to obtain a polyamine transaxially stretched film of Experimental Example 102. Further, the properties of the film obtained were obtained in the same manner as in Experimental Example 99. The evaluation results are shown in Tables 17 to 18. The olefinic acid, 99 and the dispersion change liquid change were obtained according to the valence result of the example 98 ° cloth adhesion, and the laminated layer was evaluated -151- 200927788 οο [Bu Yizhen] Heat-resistant water peeling strength (N/15mm) <;N (Ν ON ο ο 耐 耐 耐 耐 耐 耐 耐 耐Magnification ο — ο ο — ο 寸 · Temperature (.〇ο m 2nd longitudinal extension I 'sO vq Temperature (°c) ο ο ο ο Coating solution for coating a modified coating film A Coating liquid B Coating liquid C 壊The first longitudinal stretching ratio Η Η η Η temperature. C 00 00 00 00 Experimental Example 99 Experimental Example 100 Experimental Example ιοί Experimental Example 102 0, 200927788 〇❹ [81漱] Breaking bag 〇〇〇〇 J Vibration durability ◎ ◎ ◎ ◎ Storage stability ◎ ◎ ◎ ◎ Peel strength (N/15mm) w-ϊ \〇v〇ν〇\ό Pinhole resistance 14 (pieces) 1 Formula (I) is established (I) Right ※ 00 (N Η 00 (Ν 00 (N 00 (N oxygen penetration rate {ml/m2 · 24 hours · MPa) 00 00 00 οο 00 00 〇\ 00 Thickness ratio B/A/B(%) 40/20/40 40/20/40 40/20/40 ! ! 40/20/40 1 B layer composition ΝΥ6/ΡΑ Elastomer/MXD6 =89/5/6% ΝΥ6/ΡΑ Elastomer/MXD0=89/5/6% NY6/PA Elastomer/MXD6=89/5/6% 1 NY6/PA Elastomer/MXD6=89/5/6% A layer composition MXD6=100% MXD6=100% MXD6=100°/〇MXD6=100% Experimental Example 99 Experimental Example 100 Experimental Example 101 Experimental Example 102 9 Note: 9ΛΝ $0 Crocodile urasfrn Dripping: 9axw [(slo+elooxl /lvede^:※ ϊ»έ Flavor 3⁄4 crocodile inlay: difficult fflsvd 200927788 The following is a description of Experimental Example 1 0 3 to 1 1 1 for vapor deposition of a polyimide film. [Experimental Example 103] Using 2 A three-layer co-extrusion T-shaped die apparatus was used to obtain an unstretched sheet of the following constitution. The total thickness of the B layer/A layer/B layer and the unstretched sheet is 190 μm, and the thickness ratio of each layer with respect to the total thickness is B layer/A layer/B layer=40%/20%/40%, A The extruded resin temperature of the layer was 270 ° C, and the extruded resin temperature of the B layer was 2 60 ° C. The composition constituting the layer A: a composition composed of poly(m-xylylene dimethyl hexamethyleneamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65) = 100% by weight. Composition constituting the B layer: a polyamide-based block copolymer composed of 95% by weight of nylon 6 (manufactured by Toyobo Co., Ltd., RV = 2.8) and 5% by weight of a thermoplastic resin elastomer (Nylon 12/poly stretch) A composition of a butanediol copolymer, ARKEMA PEBAX4033, RV = 2.0). Subsequently, the obtained unstretched sheet was extended 3.3 times in the longitudinal direction by a roll at an elongation temperature of 85 ° C, and then stretched by 3.7 times in the transverse direction by a stretching machine at an elongation temperature of 120 ° C. Further, a biaxially stretched film having a thickness of 15 μm was produced by heat-fixing at a temperature of 215 ° C and applying a thermal relaxation treatment of ❹ 5 %. A vapor deposited film was produced by subjecting the obtained polyamine-based laminated biaxially stretched film to vapor deposition by the following method. [Alumina vapor deposition] The vapor deposition source is a granular Al 2 〇 3 (purity: 99.9%) having a size of about 3 to 5 mm, and is a polyamine-based resin film constituting the polyamido film roll obtained as described above. On the surface, an aluminum oxide film is formed by electron beam evaporation. The heating source used an EB gun and the emission current was 1·3 Α. A film having a thickness of 20 nm was produced at a film transport speed of 130 m/min. Further, the pressure at the time of vapor deposition of -154 - 200927788 was adjusted to lxlO_2Pa. Further, the temperature of the roller for cooling the film at the time of vapor deposition was adjusted to -10 °C. Further, a 40-micron linear low-density polyethylene film (L-LDPE film: manufactured by Toyobo Co., Ltd., L6102) was laminated on the vapor-deposited surface. The oxygen permeability of the obtained laminate film, the number of pinholes after the bending fatigue (Gelbo) treatment, and the oxygen permeability were measured. These results are shown in Table 19. [Experimental Example 104] A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the following description was carried out. The composition constituting the layer B: a composition composed of 98% by weight of nylon 6 and 2% by weight of a polyamine-based block copolymer. The obtained biaxially stretched film was subjected to vapor deposition by the following method to produce a vapor deposited film. [Oxide Oxidation] The vapor deposition source is a granular Si (purity: 99.99%) and Si〇2 (purity: 99.9%) having a size of about 3 to 5 mm, and the polyamine-based film-like film obtained as described above is formed. On the surface of the polyamine-based resin film, a ruthenium oxide film is formed by an electron beam evaporation method. The vapor deposition material was unmixed and placed in two compartments. The heating source uses an EB gun and heats each of Si and Si〇2 by time division. At this time, the emission current of the EB gun was set to 〇.8a, and each material was heated in such a manner that the composition ratio of Si to Si〇2 was 1:9. A film having a thickness of 20 nm was produced at a film transport speed of 130 m/min. In addition, the pressure at the time of vapor deposition was adjusted to 1×1 (T2Pa), and the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to −10° C. and the measurement was performed in the same manner as in Experimental Example 1 0 3 . Laminated film -155- 200927788 Oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability. The results are shown in Table 19. [Experimental Example 105] In Experimental Example 1〇3 It is described that a biaxially stretched film is obtained by the same method as Experimental Example 103 except that the composition is the same as that of Experimental Example 103. The composition constituting the B layer is composed of 99% by weight of nylon 6 and 1% by weight of polyamido block copolymerization. The composition of the object is formed by subjecting the obtained biaxially stretched film to vapor deposition to produce a vapor deposited film. [Composite vapor deposition] The vapor deposition source is used in a volume of 3 millimeters, and the size of the meter is about 5 mm. The granular SiO 2 (purity: 99.9%) and Al 2 〇 3 (purity: 9.9%) are vaporized by electron beam on the surface of the polyamido resin film constituting the polyamido film roll obtained as described above. The plating method forms a mixed film of alumina and cerium oxide. The vapor deposition material is unmixed and is divided into two. The heating source uses an EB gun and heats each of A1203 and SiO2 by time division. At this time, the 〇 current of the EB gun is 1.2A, and the composition ratio of AI2〇3 and SiO2 is 3:7. Each material was made to have a film conveying speed of 130 m/min to produce a film having a thickness of 20 nm. Further, the pressure at the steaming shovel was adjusted to lxl 〇 -2 Pa. And the roller which was used to cool the film during vapor deposition The temperature was adjusted to -1 (TC.) The oxygen permeability of the obtained laminate film, the number of pinholes after the bending fatigue treatment, and the oxygen permeability were measured in the same manner as in Experimental Example 031. In the case of the experimental example 103, the biaxially stretched film was obtained by the same method as the experimental example 103 of -156-200927788 except the following description. Composition: a composition composed of 98% by weight of nylon 6 and 2% by weight of a polyamido block copolymer. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 4 1% / 18%/41%. The obtained polyamidated biaxially stretched film was applied by the same method as Experimental Example 103. The vapor-deposited film was produced by vapor deposition. The oxygen permeation ratio of the obtained laminated film, the number of pinholes after bending fatigue treatment, and the oxygen permeability were measured in the same manner as in Experimental Example 103. [Experimental Example 107] In the case of Experimental Example 103, a biaxially stretched film was obtained by the same method as Experimental Example 103 except that the composition was changed to the following: The composition constituting the B layer: 97% by weight A composition composed of nylon 6 and 3% by weight of a polyamido block copolymer. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer ◎ = 3 9% / 22% / 3 9 % ° The obtained polyimide-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 104 to produce a vapor deposited film. The oxygen permeability of the obtained laminate film, the number of pinholes after the bending fatigue treatment, and the oxygen permeability were measured in the same manner as in Experimental Example 1 〇3. These results are shown in Table 19. [Experimental Example 1 〇 8] The biaxially stretched film was obtained by the same method as Experimental Example 103 except that the description of Experimental Example 103 was changed to the following. -157- 200927788 The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 4 3% / 14% / 43%. The obtained polyimide-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 105 to produce a vapor deposited film. The oxygen permeability of the obtained laminate film, the number of pinholes after the bending fatigue treatment, and the oxygen permeability were measured in the same manner as in Experimental Example 031. These results are shown in Table 19. [Experimental Example 109] 双 In the description of Experimental Example 103, a biaxially stretched film was obtained by the same method as Experimental Example 203 except that the following was changed. The composition constituting the layer B was a composition composed of 98% by weight of nylon 6 and 2% by weight of a polyamine-based block copolymer. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 3 6% / 2 80 / 〇 / 3 6%. The obtained polyimide-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 105 to produce a vapor deposited film. 〇 In the same manner as in Experimental Example 1 0 3, the oxygen permeability of the obtained laminate film, the number of pinholes after the bending fatigue treatment, and the oxygen permeability were measured. These results are shown in Table 19. [Experimental Example 110] A biaxially stretched film was obtained by the same method as Experimental Example 103 except that the description of Experimental Example 103 was changed to the following. The composition constituting the layer B was a composition composed of 99% by weight of nylon 6 and 1% by weight of a polyamine-based block copolymer. The thickness ratio of each layer with respect to the total thickness was B layer / A layer / B layer - 158 - 200927788 = 4 3 % / 1 4 % / 4 3 % ° The obtained polyfluorene was obtained by the same method as Experimental Example 105. The amine-based laminated biaxially stretched film was subjected to vapor deposition to produce a vapor deposited film. The oxygen permeability of the obtained laminate film, the number of pinholes after the bending fatigue treatment, and the oxygen permeability were measured in the same manner as in Experimental Example 1 〇3. These results are shown in Table 19. [Experimental Example 111] A biaxially stretched film was obtained by the same method as in Experimental Example 103 except that the description of Experimental Example 103 was changed to the following. The composition constituting the layer B was a composition composed of 93% by weight of nylon 6 and 7% by weight of a polyamine-based block copolymer. The thickness ratio of each layer with respect to the total thickness was B layer/A layer/B layer = 3 6% / 2 0 0 / 〇 / 3 6% ° The obtained polyamidamide system was obtained by the same method as Experimental Example 105. The laminated biaxially stretched film was subjected to vapor deposition to produce a vapor deposited film. The oxygen permeability of the obtained laminate film, the number of pinholes after the bending fatigue treatment, and the oxygen permeability were measured in the same manner as in Experimental Example 1 〇3. These results are shown in Table 19. In the following, a comparative experimental example 1 1 2 to 1 1 7 of the experimental example 1 03 to 1 1 1 is described. [Experimental Example 1 1 2] The description of Experimental Example 1〇3 is changed by the following except The biaxially stretched film was obtained in the same manner as in Experimental Example 103. Composition constituting the enamel layer: 1 〇〇% by weight of the composition of the nylon 6 composition. The obtained polyamidoline-159-200927788 layer biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 1 〇 5 to produce a vapor deposited film. In the same manner as in Experimental Example 1 〇 3, the oxygen permeability of the obtained laminate film, the number of pinholes after the bending fatigue treatment, and the oxygen permeability were measured. These results are shown in Table 19. [Experimental Example 113] A biaxially stretched film was obtained by the same method as Experimental Example 1 〇 3 except that the following was changed to the following. The thickness ratio of each layer with respect to the total thickness was B layer/A layer/B layer 〇=30%/40%/3 0% ° The obtained polyamidide double layer was obtained by the same method as Experimental Example 105. The shaft-extending film is subjected to vapor deposition to produce a vapor-deposited film. The results of measuring the oxygen permeability of the obtained laminate film, the number of pinholes after the bending fatigue treatment, and the oxygen permeability β were as shown in Table 19 in the same manner as in Experimental Example 1 〇 3 . [Experimental Example 1 14] A biaxially stretched film was obtained in the same manner as in Experimental Example 103 except that the following was changed to the following. The composition constituting the enamel layer: a composition composed of 80% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 20% by weight of nylon 6. The obtained polyimide-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 105 to produce a vapor deposited film. The oxygen permeability of the obtained laminate film, the number of pinholes after the bending fatigue treatment, and the oxygen permeability were measured in the same manner as in Experimental Example 1 〇3. These results are shown in Table 19. [Experimental Example 1 1 5] -160-200927788 The biaxially stretched film was obtained by the same method as Experimental Example 103 except that the description of the experimental example ι 3 was changed to the following. The composition constituting the layer A: a composition composed of 80% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 20% by weight of nylon 6. The thickness ratio of each layer with respect to the total thickness was B layer/A layer/B layer = 2 0 〇 / 〇 / 6 0% / 2 0% ° The obtained polyfluorene was obtained by the same method as Experimental Example 105. An amine-based laminated biaxially stretched film is subjected to steaming to produce a vaporized ore film.氧 The oxygen permeability of the obtained laminate film, the number of pinholes after the bending fatigue treatment, and the oxygen permeability were measured in the same manner as in Experimental Example 1 〇3. These results are as shown in Table 19. [Experimental Example 1 1 6] The biaxially stretched film was obtained by the same method as Experimental Example 103 except that the description of the experimental example was changed to the following. The composition constituting the enamel layer: a composition composed of 90% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 10% by weight of a polyamidamide-based block copolymer. G constitutes a composition of the B layer: a composition composed of 1 〇 〇% by weight of nylon 6. The obtained polyimide-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 1 to produce a vapor deposited film. The oxygen permeability of the obtained layered squeegee film, the number of pinholes after bending fatigue treatment, and the oxygen permeability were measured in the same manner as in Experimental Example 1 〇3. These results are shown in Table 19. [Experimental Example 11 7] A biaxially stretched film was obtained by the same method as that of Experimental Example 103 of -161 to 200927788 except that the description of Experimental Example 103 was changed to the following. The composition constituting the layer A: a composition composed of 95% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 5% by weight of a polyamine-based block copolymer. The obtained polyimide-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 105 to produce a vapor deposited film. In the same manner as in Experimental Example 103, the oxygen permeability of the obtained laminate film, the number of pinholes after the bending fatigue treatment, and the oxygen permeability were measured. These results are shown in Table 19. 〇

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[61嗽] ΓΤΤ11 OT Μ 11 ^ 1 Is ^ ? mm % 〇〇〇〇§ 00 VO (N 00 Os v〇κη 210 〇\ (N Η oo cn (N < N oxygen permeability (ml/ M2.24 hours.MPa) 〇00 00 (Ν ON (N in 00 (Ν cn (N pinhole resistance) (N vn 卜对对〇〇<Ν 1—^ CN Oxidation of alumina oxide film矽Composite composite alumina cerium oxide composite composite composite composite composite composite<ln thickness ratio B/A/B(%) 40/20/40 40/20/40 40/20/40 41/18/41 39/ 22/39 43/14/43 36/28/36 43/14/43 36/28/36 40/20/40 30/40/30 40/20/40 20/60/20 40/20/40 40/ 20/40 B layer composition NY6/PA Elastomer = 95/5% NY6/PA Elastomer = 98/2% NY6/PA Elastomer = 99/1 % NY6/PA Elastomer = 98/2% NY6/PA Elastic Body = 97/3% NY6/PA Elastomer = 95/5% NY6/PA Elastomer = 98/2% Price 6/? Into Elastomer = 99/1% ΝΥ 6/ΡΑ Elastomer = 93/7% NY6= 100% NY6/PA Elastomer = 95/5% 1 ΝΥ6/ΡΑ Elastomer = 95/5% NY6/PA Elastomer = 95/5% NY6=100°/〇NY6/PA Elastomer = 95/5% A Layer composition MXD6=100°/〇MXD6=100°/〇MXD6=100°/〇MXD6=100°/〇MXD6=100°/〇MX D6=100°/〇MXD6=100% MXD6=100°/〇MXD6=100% MXD6=100% MXD6=100% MXD6/NY6=80/20% MXD6/NY6=80/20% MXD6/PA Elastomer = 90/10% NY6/PA Elastomer=95/51⁄4 Experimental Example 103 Experimental Example 104 Experimental Example 105 Experimental Example 106 Experimental Example 107 Experimental Example 108 Experimental Example 109 Experimental Example 110 Experimental Example 111 Experimental Example 112 Experimental Example 113 Experimental Example 114 Experimental Example 115 Experimental Example 116 Experimental Example 117 «Hi 9 Let: 9AN & _ππ3»ϋ: Age: 9QXN -SI - 200927788 Hereinafter, with respect to Experimental Examples 103 to 111, it is described that the vapor deposition is described in the patent application scope. When the laminate film of the polyimide film and the polyethylene film having a thickness of 40 μm was peeled off between the layers, the test examples 118 to 129 having a peel strength of 4.0 N/15 mm or more were also satisfied. [Experimental Example 118] Unstretched sheets of the following constitution were obtained by using two types of three-layer co-extrusion T-die devices. The total thickness of the B layer/A layer/B layer and the unstretched sheet is 190 μm, and the thickness ratio of each layer with respect to the total thickness is B 〇 layer/A layer/B layer=40%/20%/4 0 %, the extruded resin temperature of the layer A was 270 ° C, and the temperature of the extruded resin of the layer B was 260 ° C. The composition constituting the layer A is a composition composed of poly-m-xylylene hexamethylenediamine (manufactured by R&S®Ring Chemical Co., Ltd., RV = 2.6 5) = 100% by weight. Composition constituting the B layer: a polyamide-based block copolymer (Nylon 12/poly-stretch) composed of 89% by weight of nylon 6 (made by Toyobo Co., Ltd., RV = 2.8) and 5% by weight of a thermoplastic resin elastomer Butanediol copolymer, ARKEMA company PEBAX 4033, RV = 2.0) and 6 weights of poly(m-xylylene hexamethylenediamine) (manufactured by Mitsubishi Gas Chemical Co., Ltd., RV = 2.65). Subsequently, the obtained unstretched sheet was extended by 3.3 times in the longitudinal direction by a roll at an elongation temperature of 85 ° C and then stretched by 3.7 times in the transverse direction by an extension temperature of the expander at 120 ° C. Further, a biaxially stretched film having a thickness of 15 μm was produced by heat-fixing at a temperature of 215 ° C and applying a heat relaxation treatment of 5%. A vapor deposited film was produced by subjecting the obtained polyamine-based laminated biaxially stretched film to vapor deposition by the following method. [Alumina vapor deposition] The vapor deposition source is a granular ammine 3 (purity -164 - 200927788 99.9%) having a size of about 3 to 5 mm, and a polyamine which constitutes the polyamine film-like film obtained as described above. On the surface of the resin film, an aluminum oxide film is formed by electron beam evaporation. The heating source used an EB gun and the emission current was 1.3 A. A film having a thickness of 20 nm was produced at a film transport speed of 130 m/min. Further, the pressure at the time of vapor deposition was adjusted to 1 χ 1 〇 _2 Pa. Further, the temperature of the roll was adjusted to -1 for the film at the time of vapor deposition. Further, a 40-micron linear low-density polyethylene film (L-LDPE film: manufactured by Toyobo Co., Ltd., L6102) was laminated on the vapor-deposited surface. The obtained ruthenium was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation. These results are shown in Table 20 。. [Experimental Example 9] A biaxially stretched film was obtained by the same method as Experimental Example 118 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 95% by weight of nylon 6, 2% by weight of a polyamine-based block copolymer, and 3% by weight of poly-m-xylylene hexane decylamine. The obtained biaxially stretched film was subjected to vapor deposition by the following method to produce a vapor deposited film. [The cerium oxide vapor deposition] The vapor deposition source is a granular Si (purity of 9 9.9 9%) and SiO 2 (purity of 9.9%) having a size of about 3 to 5 mm, and the polyamine film-like film obtained as described above is formed. On the surface of the polyamine-based resin film, a ruthenium oxide film is formed by an electron beam evaporation method. The vapor deposition material was unmixed and placed in two compartments. The heating source uses an EB gun and heats each of Si and SiO 2 -165 - 200927788 by time division. At this time, the emission current of the EB gun was set such that the composition ratio of 〇.8A SiO 2 was 1:9 to heat each material. A film having a thickness of 20 nm was produced at a thickness of 130 m/min. Further, the pressure was adjusted to lxl (Γ2 Pa. Further, the temperature of the rolled material was jg °C for the film at the time of vapor deposition. Further, in the same manner as in Experimental Example 1 18, the oxygen permeability of the obtained layer was measured, The number of pinholes, oxygen ionization strength, and falling body evaluation after bending fatigue treatment are shown in Table 20. 实验 [Experimental Example 120] In the case of Experimental Example 1 18, except that the following is changed to Experimental Example 1 8 The same method was used to obtain a biaxially stretched film. The composition constituting the layer B was composed of 97% by weight of a nylon 6, 1 amine block copolymer and 2% by weight of poly(m-xylylene hexane). The vapor-deposited film was produced by the following method on the obtained biaxially stretched film. 〇 [Composite vapor deposition] The vapor deposition source was 99.9%) and 8 12 〇3 (purity 99 9%) having a size of about 3 to 5 mm. On the surface of the polyamine-based resin film constituting the film roll as described above, a mixed film of alumina and ceria is formed by a steaming method. Steam and mix and divide into two. The heating source was heated by using an EB gun and cutting each of Al2〇3 and Si〇2. At this time, the EB flow was made 1.2 A' and the composition ratio of a12 〇 3 to SiO 2 was 3: 7 heat of each material. The film transport speed was 130 m/min, and the Si and film transport speeds were adjusted during the vapor deposition [adjusted to -10 pressure film to achieve penetration, stripping, by weight % polyamide Forming a row of vapor deposition, come

Si〇2 (purity obtained from polyelectronamine is not added by the electron emission of the time splitting gun [manufacturing a film of 20 nm-166-200927788 m thickness. Further, the pressure at the time of vapor deposition The temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 ° C. Further, in the same manner as in Experimental Example ,, the obtained laminated film was measured for oxygen permeability and bending. The number of pinholes, the oxygen permeability, the peeling strength, and the falling body evaluation after the fatigue treatment are shown in Table 20. [Experimental Example 121] In the case of Experimental Example 1 18, except for the following changes, A biaxially stretched film was obtained in the same manner as in Experimental Example 1 18. 组成 Composition constituting the enamel layer: 95% by weight of nylon 6, 2% by weight of polyamido block copolymer and 3% by weight of poly a composition composed of benzoyl hexamethylenediamine. The thickness ratio of each layer relative to the total thickness is Β layer/Α layer/Β layer = 4 1 % /1 8 % / 4 1 %. In the same manner as in Example 118, steaming was carried out on the obtained polyamidiminated biaxially oriented film to produce steam. In the same manner as in Experimental Example 1 18, the obtained laminate film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation. [Experimental Example 122] In the description of Experimental Example 118, a biaxially stretched film was obtained by the same method as Experimental Example 1 18 except that it was changed to the following. Compositions constituting the ruthenium layer: 92 A composition comprising a weight percent of nylon 6, 3% by weight of a polyamidoblock copolymer and 5% by weight of poly-m-xylylene hexamethylenediamine. The thickness ratio of each layer relative to the total thickness is Β layer / Α layer/Β layer-167- 200927788 = 3 9% / 22% / 3 9%. The obtained polyamidamide-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 119 to produce steam. The film was deposited in the same manner as in Experimental Example 8.1, and the obtained laminated film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation. (20) [Experimental Example 123] The description of Experimental Example 118 is changed to the following except A biaxially stretched film was obtained by the same method as in Experimental Example 1 18. The thickness ratio of each layer with respect to the total thickness was B layer/A layer/B layer = 4 3% / 14% / 43%. The obtained polyimide-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce a vapor-deposited film. The same procedure as in Experimental Example 8 was carried out to measure the oxygen permeability of the obtained laminated film. The number of the pinholes after the bending fatigue treatment, the oxygen permeability, the peeling strength, and the drop evaluation. The results are shown in Table 20. 〇 [Experimental Example 124] The description of Experimental Example 118 was changed to the following except A biaxially stretched film was obtained by the same method as Experimental Example 1 18. The composition constituting the layer B: a composition composed of 95% by weight of nylon 6, 2% by weight of a polyamine-based block copolymer, and 3% by weight of poly-m-xylylene dimethyl decylamine. The thickness ratio of each layer with respect to the total thickness was B layer/A layer/B layer = 3 6% / 2 0 0 / 〇 / 3 6% ° The obtained polyamidamide system was obtained by the same method as Experimental Example 120. The product -168- 200927788 layer biaxially stretched film was subjected to vapor deposition to produce a vapor deposited film. The obtained laminate film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation in the same manner as in Experimental Example 8.1. These results are shown in Table 20. [Experimental Example 125] A biaxially stretched film was obtained by the same method as Experimental Example 1 18 except that the following was changed to the following. The composition constituting the layer B: a composition comprising 97% by weight of nylon 6, 1% by weight of a polyfluorene-based amine block copolymer, and 2% by weight of poly-m-xylylene hexane dimethyl amide. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 4 3 % / 14% / 43%. A vapor deposited film was produced by subjecting the obtained polyamidated biaxially stretched film to vapor deposition in the same manner as in Experimental Example 1-20. The obtained laminate film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation in the same manner as in Experimental Example 181. These results are shown in Table 20. [Experimental Example 126] A biaxially stretched film was obtained by the same method as Experimental Example 118 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 83% by weight of nylon 6, 7% by weight of a polyamine-based block copolymer, and 10% by weight of poly-m-xylylene dimethyl decylamine. The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 3 6 0 / 〇 / 2 8% / 3 6%. -169-200927788 The obtained polyaniline-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce a vapor deposited film. The obtained laminate film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation in the same manner as in Experimental Example 1 1 8 . These results are shown in Table 20. [Experimental Example 127] In the description of Experimental Example 118, a biaxially stretched film was obtained by the same method as Experimental Example 1 18 except that it was changed to the following.组成 Composition constituting the enamel layer: 63% by weight of nylon 6, 5 by weight. /. A composition comprising a polyamine amine block copolymer and 2% by weight of poly-m-xylylene dimethyl decylamine. A vapor deposited film was produced by subjecting the obtained polyamidated biaxially stretched film to vapor deposition in the same manner as in Experimental Example 120. The obtained laminate film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation in the same manner as in Experimental Example 118. These results are shown in Table 20. [Experimental Example 128] A biaxially stretched film was obtained by the same method as Experimental Example 118 except that the description of Experimental Example 118 was changed to the following. The composition constituting the enamel layer was composed of 84% by weight of nylon 6, 5% by weight of a polyamine-based block copolymer, and 11% by weight of poly-m-xylylene hexamethyleneamine. The obtained polyimide-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 1 2 to produce a vapor deposited film. In the same manner as in Experimental Example 1 18, the obtained laminate film was subjected to measurement of oxygen-170-200927788 transmittance, pinhole number after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation. These results are shown in Table 20. In the following, the comparative experimental examples 13 to 1 3 9 » [Experimental Example 1 2 9 ] of the experimental examples 118 to 129 are described. The description of the experimental example 118 is the same as the experimental example 118 except that the following is changed. To obtain a biaxially stretched film. The composition constituting the layer B: a composition composed of 98% by weight of nylon 6, 1% by weight of a polyfluorene-based amine block copolymer, and 1% by weight of poly-m-xylylene hexane dimethyl amide. A polyimide-based biaxially stretched film obtained by the method of > was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce a vapor deposited film. In the same manner as in Experimental Example 1 18, the obtained laminated film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation. These results are shown in Table 20. [Experimental Example 1 3 0 ] 双 In the description of Experimental Example 118, a biaxially stretched film was obtained by the same method as Experimental Example 1 18 except that it was changed to the following. The composition constituting the layer B: a composition composed of 1% by weight of nylon 6. The obtained polyimide-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce a vapor deposited film. In the same manner as in Experimental Example 1 18, the obtained laminated film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation. These results are shown in Table 20. -171-200927788 [Experimental Example 131] The biaxially stretched film was obtained by the same method as Experimental Example 118 except that the description of Experimental Example 118 was changed to the following. The thickness ratio of each layer with respect to the total thickness was B layer / A layer / B layer = 30% / 40% / 3 0 ° / 〇 ° The obtained polyamidide layer was obtained by the same method as Experimental Example 120. The biaxially stretched film was subjected to vapor deposition to produce a vapor deposited film. In the same manner as in Experimental Example 1 18, the obtained laminate film was subjected to measurement of oxygen permeability, pinhole number after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation. These results are shown in Table 20. [Experimental Example 132] In the description of Experimental Example 118, a biaxially stretched film was obtained by the same method as Experimental Example 1 18 except that it was changed to the following. The composition constituting the layer A: a composition composed of 80% by weight of poly-m-xylylene dimethyl hexamethyleneamine and 20% by weight of nylon 6. The obtained polyamidominated bismuth layer biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce a vapor deposited film. The obtained laminate film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation in the same manner as in Experimental Example 1 1 8 . These results are shown in Table 20. [Experimental Example 133] A biaxially stretched film was obtained by the same method as Experimental Example 1 18 except that the description of Experimental Example I18 was changed to the following. The composition constituting the layer A: a composition composed of 80% by weight of poly-m-xylylene hexamethylenediamine and 20% by weight of ruthenium. -172- 200927788 The thickness ratio of each layer with respect to the total thickness is B layer / A layer / B layer = 2 0% / 6 0% / 2 0 ° / 〇 0 by the same method as Experimental Example 1 20 The polyamine-based laminated biaxially stretched film was subjected to vapor deposition to produce a vapor deposited film. The obtained laminate film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation in the same manner as in Experimental Example 8.1. These results are shown in Table 20. [Experimental Example 134] 双 In the description of Experimental Example 118, a biaxially stretched film was obtained by the same method as Experimental Example 1 18 except that it was changed to the following. The composition constituting the layer A: a composition composed of 80% by weight of poly-m-xylylene hexamethylenediamine and 20% by weight of nylon 6. The thickness ratio of each layer with respect to the total thickness was B layer/A layer/B layer = 30%/40%/3 0% ° The obtained polyamidene layer was biaxially obtained by the same method as Experimental Example 120. The stretched film is subjected to evaporation to produce a vaporized film. G In the same manner as in Experimental Example 1 18, the obtained laminated film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation. These results are shown in Table 20. [Experimental Example 135] A biaxially stretched film was obtained by the same method as Experimental Example 8 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 95% by weight of nylon 6 and 5% by weight of a polyamide-based block copolymer. A vapor deposited film was produced by subjecting the obtained polyamidoline-173-200927788 layer biaxially stretched film to vapor deposition in the same manner as in Experimental Example 120. In the same manner as in Experimental Example 1 18, the obtained laminated film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation. These results are shown in Table 20. - [Experimental Example 136] A biaxially stretched film was obtained by the same method as Experimental Example 118 except that the following was changed to the following. The composition constituting the layer B: a composition composed of 99% by weight of nylon 6 and 1% by weight of a polyamine-based block copolymer. The obtained polyimide-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce a vapor deposited film. In the same manner as in Experimental Example 1 18, the obtained laminated film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation. These results are shown in Table 20. [Experimental Example 137] In the description of Experimental Example 118, a biaxially stretched film was obtained by the same method as in Experimental Example 118 except that it was changed to the following. The composition constituting the layer B: a composition composed of 95% by weight of nylon 6 and 5% by weight of poly-m-xylylene dimethyl decylamine. The obtained polyimide-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 1 20 to produce a vapor deposited film. In the same manner as in Experimental Example 1 18, the obtained laminated film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation. These results are shown in Table 20. [Experimental Example 138] -174-200927788 A biaxially stretched film was obtained by the same method as Experimental Example 1 18 except that the following was changed to the following. The composition constituting the layer A: a composition composed of 90% by weight of poly-m-xylylene hexamethylenediamine and 10% by weight of a polyamine-based block copolymer. The composition constituting the layer B: a composition composed of 100% by weight of nylon 6. The obtained polyimide-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 1 20 to produce a vapor deposited film. 〇 In the same manner as in Experimental Example 1 18, the obtained laminate film was subjected to measurement of oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation. These results are shown in Table 20. [Experimental Example 139] In the description of Experimental Example 118, a biaxially stretched film was obtained by the same method as Experimental Example 1 1 8 except that the composition of the layer A was composed of 95% by weight of nylon. a composition composed of 6 and 5% by weight of a polyamidide-based block copolymer. 〇 Composition constituting the B layer: a composition composed of 95% by weight of nylon 6 and 5% by weight of a polyamido-based block copolymer The obtained polyaniline-based biaxially stretched film was subjected to vapor deposition in the same manner as in Experimental Example 120 to produce a vapor deposited film. The same procedure as in Experimental Example 1 1 8 was carried out. The film was measured for oxygen permeability, number of pinholes after bending fatigue treatment, oxygen permeability, peel strength, and drop evaluation. The results are shown in Table 20. -175- 200927788 〇ο 02:«] Evaluation ◎ ◎ 〇 ◎ ◎ ◎ 〇〇 ◎ ◎ ◎ ◎ XX <1 X < XXX < X Peel strength (Ν / 15 mm) \6 〇 <> Ο 00 uS 00 wS ON »〇W-&gt ; v〇v〇ιτί Ό »nm in cn v〇卜 in CN o ΓΛ ν〇<5 in \〇脚桃七一13⁄4 · ? L (N 00 00 SO s <〇00 m wj yn § 00 Ό o mouth in (N 00 VO VO Ό 00 Ό (Ν <N ms oxygen permeability (ml/m2 · 24 hours.MPa) Jn 00 m 〇〇(S rH rs 00 <N Os (N 00 (N <s os (N 00 (S oo (N CN Ό iN 艺(N ISi 1—* 1〇Os VO ο Os 卜 00 00 v〇 00 CN oo v〇cs 蒸 皮 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 in in in in in in in in in in in in in in in in in in in in in in in in ί ί ί ί ί ί ί ί ί ί ί ί ί /A/B(°/〇) 40/20/40 40/20/40 1 40/20/40 1 | 41/18/41 1 | 39/22/391 1 43/14/43 1 | 36/28 /36] 1 43/14/431 | 36/28/361 | 40/20/40 | 40/20/40 1 40/20/40 1 40/20/40 30/40/30 40/20/40 1 20/60/20 1 1 30/40/30 40/20/40 40/20/40 40/20/40 40/20/40 40/20/40 B layer composition\〇*〇1 Q 1 m CmL static ; Ό m $ 〇1 m BDL Ό 2 timm acyl v〇yn imm DQzL Ό gmim Sd BmL VO ϊ〇s I m #1 IML 〇v〇NY6/PA Elastomer/MXD6=95/2/3% s Q 1 Listen to m imL 陛: 1 Ό NY6/PA Elastomer / MXD6=83/7/10% gm T imm 11⁄2. Static: v〇NY6/PA Elastomer/MXD6=84/5/ll% Q 1 View m mnL Huan v〇NY6=100°/〇)〇»ns AQ 1 Acid m OBL Huan 1 Ό z | s QI m § SO £ v〇ΐ〇1 Ρ 1 mm tmrl Step 1 § 00 i I Forged i ίη T IS id ΠΜττΙ 征ν〇> NY6/PA Elastomer = 99/1% : NY6/MXD6=95/5% NY6= 100% T Listen m 11⁄2 Step A layer composition MXD6=100% MXD6=100% MXD6=100% MXD6=100°/〇MXD6=100% MXD6=100% MXD6=100% MXD6=100% MXD6=100% MXD6= 100% MXD6=100°/〇MXD6-100% MXD6=100% MXD6=100% ! MXD6/NY6=80/20% MXD6/NY6=80/20% 1 MXD6/NY6=80/20% MXD6=100% MXD6=100% MXD6=100% MXD6/PA Elastomer=90/10% T Listening to m got so S Experimental Example 118 Experimental Example 119 Experimental Example 120 Experimental Example 121 Experimental Example 122 Experimental Example 123 Experimental Example 124 Experimental Example 125 Experimental Example 126 丨 Experimental Example 7 Experimental Example 128 Experimental Example 129 Experimental Example 130 Experimental Example 131 1 Experimental Example 132 Experimental Example 133 Experimental Example 134 Experimental Example 135 Experimental Example 13 ό Experimental Example 137 1 Experimental Example 138 Experimental Example 139 9 Let: 9ΛΜ - is — 9/.I - 200927788 [Industrial Applicability] The polyamine-based laminated biaxially oriented film of the present invention The vapor-deposited laminated resin film has excellent oxygen barrier properties, and has good impact bending and fatigue resistance, and has the property of preventing deterioration or discoloration of contents in food packaging, and the like, and protecting contents from collision or vibration during transportation. Bending fatigue can be effectively used as various packaging materials. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory view of a masking pattern of a conventional shielding plate, (a is a hot ¢) a vertical section of a part of the fixing device, and b is mounted on the hot air blowing port of the air supply passage viewed from above The state of the shielding board). Fig. 2 is an explanatory view showing a shielding aspect of the shielding plate of the present invention, (a is a vertical cross section of a part of the heat fixing device, and b is a state in which a shielding plate is attached to a hot air blowing port of the air supply passage as viewed from above). Fig. 3 is an explanatory view showing the state of the heat fixing device used in the experimental example from the above. Fig. 4 is a view showing the shielding state of the shielding plate of Experimental Example 4 3, 5 1 . Fig. 5 is an explanatory view showing a state in which an electrode is disposed on a moving heat sink and a flow photo-wave discharge is performed. [Description of main component symbols] Heat fixing device Hot air blowing outlet a~X air supply passage Film shielding panel

1 2 3 F S 200927788 11 Extrusion die 12 Thin film melt 13 Cooling rotor 14 Unstretched film 15 Straight flow Local voltage 16 Electrode 17 Flow Corona discharge

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Claims (1)

200927788 X. Patent application scope: 1. - Polyurethane-based laminated biaxially stretched film characterized by m-xylylenediamine, or m-xylylenediamine and p-xylylenediamine The mixed dimethylenediamine is used as a main diamine component; and the α,ω-aliphatic dicarboxylic acid component having a carbon number of 6 to 12 is used as a main dicarboxylic acid component containing meta-xylylene poly a polyamide-based polymer bilayer-stretched film composed of at least one side of a resin layer (tantalum layer) as a main body, in which a resin 0 layer (8 layers) mainly composed of an aliphatic polyamide resin is laminated. The following requirements (1) to (3) are satisfied, and (1) the metaxylylene group-containing polyfluorene in the resin layer (ruthenium layer) mainly composed of a metaxylylene group-containing polyamine polymer a ratio of amine polymerization & 99% by weight or more and no addition or addition of a thermoplastic elastomer in a ratio of less than 1% by weight, (2) a polyamidominated biaxially stretched film and a polyethylene film having a thickness of 40 μm The laminated film is at a temperature of 2 3 . (:, under the environment of 50% relative humidity) Using a bending fatigue tester (Gelbo-Flex Tester), when the bending test of 2000 cycles is continuously performed at an average speed of 4 minutes, the number of pinholes is 10 or less. (3) The oxygen permeability at a temperature of 23 ° C and a relative humidity of 65% is 1 50 ml / m 2 · MPa. day or less. 2. The polyamine-based laminated biaxially stretched film of claim 1 is When the laminated film of the polyamine-based laminated biaxially stretched film and the polyethylene film having a thickness of 40 μm is peeled off between the layers, the peeling strength is 4·0Ν/15 -179-200927788 mm or more. 3. As claimed in the patent application The polyamide-based laminated biaxially stretched film of the first aspect, wherein the thermoplastic elastomer system has a mixing ratio of 0.5% by weight or more and 8.0% by weight or less in the resin layer (B layer) mainly composed of an aliphatic polyamide resin. 4. The method of adding a polyamine-based laminated biaxially stretched film according to the second aspect of the patent application, wherein the thermoplastic elastomer system is 0.5 in the resin layer (layer B) mainly composed of an aliphatic polyamide resin. More than weight%, 8.0 weight The amount of the polydecylamine polymer containing at least 5% by weight is added in a mixing ratio of 〇% by weight or more and 丨2.0% by weight or less. 5. If the scope of claim 1 or 2 is Polyimamine-based laminated biaxially stretched film, wherein the polyamine-based laminated biaxially stretched film satisfies the following formula (I), Pa<l/[t(〇.〇1 5x + 0.1 5)] (I) (where 'X represents the content (% by weight) of the metaxylylene-containing polyamine polymer in the film, and P a represents the oxygen permeation of the film at a temperature of 23 ° C and a relative humidity of 6 5 %. Rate (ml/m2 · MPa · day), t is the film thickness (mm). 6. Polyurethane-based laminated biaxially stretched film of claim 1 or 2 wherein the thickness of layer A is a 10% or more and 30% or less of the total thickness of the layer and the B layer. 7. The polyamine-based laminated biaxially stretched film of claim 1 or 2, which forms a 45-degree angle with the winding direction of the film. The refractive index of the direction 'and the direction of the 135 degree angle with the winding direction of the film -180- 200927788 The difference of the rate Anab is 0.003 or more, 0 0.001 or less, and the following requirements (4) and (5) are satisfied, (4) The film having a length of 80 cm or more in the width direction of the film is equally divided into 5 in the width direction of the film, and is divided into 5 pieces. Five samples of the obtained film in the central portion in the width direction were cut, and the heat shrinkage rate in the film winding direction after heating at 160 ° C for 10 minutes, that is, HS160 was determined. When the difference between the maximum 値 and the minimum _ is _ 0.1 5 % or less, ◎ (5) The HS160 series of all the five samples is 0.5% or more and 2.0% or less. 8. The polyamine-based laminate biaxially stretched film of claim 1 or 2, wherein the thickness is not in the range of 3 to 10%. 9. The polyamine-based laminated biaxially stretched film of the first or second aspect of the patent application is formed by coating an adhesive modified resin composed of a copolymerized polyester on the outermost surface of at least one surface of the film.蒸1〇· A vapor-deposited polyamine-based laminated resin film characterized by a mixed benzene composed of m-xylylenediamine, or m-xylylenediamine and p-xylylenediamine a methyl diamine as a main diamine component; and an α-aliphatic dicarboxylic acid component having 6 to 12 carbon atoms as a main dicarboxylic acid component, and a metaxylylene-containing polyamine polymer as a main resin At least one surface of the layer (anthracene layer) is formed by laminating at least one surface of a polyamine-based bilayer-stretched film composed of a resin layer (anthracene layer) mainly composed of an aliphatic polyamine resin, and depositing an inorganic substance. And satisfying the following requirements -181- 200927788 (9) to (10), (9) the isophthalic acid containing the metaxylylene-containing polyamine polymer as the main resin layer (layer A) a thermoplastic elastomer having a ratio of a methylpolyamine polymer of 99% by weight or more and no addition or addition of a ratio of less than 1% by weight, 〇 (10) A laminated film of the vapor-deposited polyamine-based laminated resin film and a polyethylene film having a thickness of 40 μm was at a temperature of 23. (: In a case where the relative humidity is 50%, the number of pinholes is 10 or less, using a bending fatigue tester (Gelbo-Flex Tester) to continuously perform a bending test of 20 cycles at an average speed of 40 cycles per minute. (11) The laminated film of the vapor-deposited polyamine-based laminated resin film and the polyethylene film having a thickness of 40 μm has an oxygen permeability of 5 0 ml/m 2 · MPa at a temperature of 23 ° C and a relative humidity of 65%. · Day or less, (12) The laminated film of the vapor-deposited polyamine-based laminated resin film and the polyethylene film having a thickness of 40 μm was used in a temperature of 23 ° C and a relative humidity of 50%, using a bending fatigue tester ( Gelbo-FlexTester), when the bending test is carried out continuously for 5 cycles at an average speed of 40 minutes per cycle, the oxygen permeability at a temperature of 23 ° C and a relative humidity of 65% is 100 ml/m 2 · MPa · day or less 11 The vapor-deposited polyamine-based laminated resin film of claim 10, wherein the laminated film of the vapor-deposited polyamine-based laminated resin film and the polyethylene film having a thickness of 40 μm is peeled off between the layers, and peeled off The strength is 4.0N/15mm or more. -182- 200927788 12. The vapor-deposited polyamine-based laminated resin film according to claim 10, wherein in the resin layer (layer B) mainly composed of an aliphatic polyamide resin, the thermoplastic elastomer system is 0.5% by weight or more and 8.0. The vapor-deposited polyamine-based laminated resin film of the eleventh aspect of the patent application, wherein the resin layer (layer B) mainly composed of an aliphatic polyamide resin is used. The thermoplastic elastomer system is added in an amount of 5% by weight or more and 8.0% by weight or less, and the metaxylylene group-containing polyamine polymer is added in a mixing ratio of 1.0% by weight or more and ❹ 12.0% by weight or less. 14. The vapor-deposited polyamine-based laminated resin according to the invention of claim 10 or 11, wherein the thickness of the layer A is 10% or more and 30% or less of the total thickness of the layer A and the layer B. The vapor-deposited polyamine-based laminated resin film according to claim 10 or 11, wherein the inorganic substance is selected from the group consisting of aluminum, bismuth, titanium, magnesium, cone, bismuth, tin, copper, iron and zinc or a plurality of metals or non-metals or metals Q or non-metallic oxides, nitrides, fluorines, sulfides. -183-