JP2007015353A - Vapor deposition polyamide-based mixed resin-laminated film roll and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vapor deposition polyamide-based mixed resin-laminated film roll having high gas barrier properties, capable of being smoothly subjected to bag-making process due to lamination in a good yield and capable of efficiently obtaining a package free from an S-shaped curl. <P>SOLUTION: The vapor deposition polyamide-based mixed resin-laminated film roll is constituted so that a first sample cutting part is provided within 2 m range from the winding completion of the film roll formed by taking up a film before vapor deposition, a final cutting part is provided within 2 m range from the winding start of the film and, in a case that sample cutting parts are provided every about 100 m from the first sample cutting part, physical properties such as the content of an elastomer, tensile elastic modulus, thickness irregularity in a longitudinal direction, etc. are adjusted so as to become a predetermined range of fluctuation width with respect to all samples cut from the respective cutting parts. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a high-quality film roll having uniform physical properties over a long length obtained by winding a polyamide-based resin film on which an inorganic substance is deposited. Specifically, the present invention relates to a retort food by laminating with a polyolefin-based resin film. It is related with the vapor deposition polyamide type mixed resin laminated | multilayer film roll with the favorable workability (especially workability in high humidity) at the time of using for packaging.

  Nylon-based biaxially oriented polyamide resin film is tough and has excellent gas barrier properties, pinhole resistance, transparency, printability, etc., so it can be used for various liquid foods, water-containing foods, frozen foods, retort It has been widely put into practical use as a packaging material for various foods such as foods, pasty foods, livestock and fishery products, and in recent years, it has been widely used for packaging retort foods. Such a polyamide-based resin film is laminated with, for example, a polyolefin-based resin film such as polyethylene or polypropylene, folded in two parallel to the flow direction, then heat-sealed on three sides, and opened on one side. The three-side sealed bag is in a state, filled with various foods and the like, sealed, and then heat-sterilized in boiling water for market.

  However, when a biaxially oriented polyamide-based resin film is used, there is a phenomenon in which the corners of the packaging bag are warped after heat sterilization and the four sides curl into an S shape (hereinafter referred to as an S-curl phenomenon). It may occur and the appearance as a packaged product may be remarkably deteriorated. Therefore, as a method of reducing such curling phenomenon, as in Patent Document 1, the product of boiling water shrinkage strain rate and change rate of molecular orientation angle in the film width direction in a biaxially oriented polyamide resin film is adjusted to a specific value. In order to improve dimensional stability during boiling water treatment, it is necessary to extremely increase the temperature during heat setting or excessively perform relaxation heat treatment after stretching. Therefore, there arises a problem that the toughness and pinhole resistance of the obtained film are impaired.

  Therefore, as described in Patent Document 2, the applicants adjust the boiling water shrinkage and refractive index of the film to a specific numerical range, thereby reducing the S-curl phenomenon without reducing toughness and pinhole resistance. Invented and proposed a method for obtaining a biaxially oriented polyamide-based resin film that does not cause the problem.

Japanese Patent Laid-Open No. 4-103335 JP-A-8-174663

  According to the method of Patent Document 2 described above, it is possible to obtain a biaxially oriented polyamide-based resin film that is tough and excellent in pinhole resistance and does not cause an S-curl phenomenon. However, in the bag making process by lamination, the conditions such as pressure and time when heat-sealing are finely adjusted for each film roll used, so the boiling water shrinkage and refractive index of the film wound around the film roll Even in the case where the average value of physical property values such as is within the range of Patent Document 2, if the amount of fluctuation in one film roll is large, there is a wrinkle between the films when laminating in the bag making process. And troubles such as poor yield are likely to occur.

  On the other hand, in the manufacturing method of a biaxially stretched film roll for winding a biaxially stretched film after mixing and extruding a mixture of a plurality of resins, the applicants as raw material chips Proposed a method for reducing the segregation of the raw material by making the shape of the same and increasing the inclination angle of the funnel-like hopper which is a raw material supply unit to the extruder (Japanese Patent Laid-Open No. 2004-181777). However, this method is not necessarily a definitive method as a method for suppressing fluctuations and variations in physical properties such as boiling water shrinkage and refractive index of a film wound on a film roll.

  Therefore, as a result of earnestly examining the production technology for producing highly uniform biaxially stretched film rolls, the applicants have highly uniform physical properties such as film thickness, boiling water shrinkage rate and refractive index, The inventors have invented a polyamide-based resin film roll that can be formed with a high yield without causing wrinkles between the films when laminating (Japanese Patent Application No. 2004-262922).

  According to the polyamide resin film roll having highly uniform physical properties such as film thickness, boiling water shrinkage and refractive index as described above, the S-curl phenomenon is maintained without deteriorating the good toughness and pinhole resistance of the polyamide resin film. The processability at the time of laminating can be made good without causing the above. However, even if the polyamide-based resin film roll has a highly uniform physical property as described above, the polyamide-based resin laminated film is good on the roll of the laminating machine when laminating under high humidity such as summer. As a result, it was found that good processing characteristics cannot always be obtained.

  In addition, a film made only of a polyamide-based resin has a limit in pinhole resistance, and is not necessarily suitable for food packaging applications containing a large amount of water such as liquid soup. As a means for improving the pinhole resistance of a polyamide-based resin film, a method of filling an elastomer into a polyamide-based resin as a film raw material is known, but in such a mixed resin film roll, It is not possible to obtain good processability at the time of laminating by simply reducing the fluctuations in physical properties such as boiling water shrinkage and refractive index, and there is variation in pinhole resistance in each laminated three-sided seal bag. End up.

  On the other hand, a polyamide-based resin film alone has a limit in gas barrier properties and is not necessarily suitable for packaging applications such as fresh food products. Further, as a means for improving the gas barrier property of the polyamide resin film, a method of depositing a metal or the like on the surface of the polyamide resin film is known, but if the physical properties of the polyamide resin film are non-uniform, The thickness of the metal vapor deposition layer and the adhesive strength with the metal vapor deposition layer will vary, and the gas barrier property will also be non-uniform.

  The present invention is a high-performance biaxially stretched mixed resin film made of a mixed resin of a polyamide resin and an elastomer. As a result of earnest research and development, the production technology for making the material uniform and the production technology for producing a vapor-deposited polyamide-based mixed resin laminated film roll having a highly uniform gas barrier property have been achieved. Its purpose is to eliminate the problems of conventional polyamide resin film rolls, and it can be used for packaging applications that require extremely high pinhole resistance, and has extremely high gas barrier properties and is highly uniform. In addition, it is a vapor-deposited biaxially oriented polyamide resin that can be processed smoothly with a laminate even under high humidity, such as in summer, and can efficiently produce a package without S-curls. It is to provide a laminated film roll. Another object of the present invention is to provide a vapor-deposited biaxially oriented polyamide-based mixed resin laminated film roll capable of obtaining a processed product with a high yield in post-processing such as bag making. In addition, it is providing the manufacturing method which can manufacture such a biaxially oriented polyamide type mixed resin laminated | multilayer film roll efficiently.

Among the present inventions, the configuration of the invention described in claim 1 is a polyamide-based mixed resin laminated film substrate formed by laminating a plurality of polyamide-based resin layers made of a mixed resin of a polyamide-based resin and a thermoplastic elastomer. Vapor-deposited polyamide-based mixed resin laminate film obtained by winding a vapor-deposited polyamide-based mixed resin laminate film having an inorganic substance deposited on at least one side so that the width is from 0.2 m to 3.0 m and the length is from 300 m to 30000 m A polyamide-based mixed resin laminated film roll, which is a film roll and wound up of a polyamide-based mixed resin laminated film before vapor deposition, has a first sample cut-out portion within 2 m from the end of film winding, A final cutout is provided within 2 m from the beginning, and about 100 from the first sample cutout. When the sample cutout portion is provided in each is to satisfy the following requirements (1) and (2).
(1) When the content of the thermoplastic elastomer component is measured for each sample cut out from each cut-out portion and the average content rate, which is the average value of the content rates, is calculated, the thermoplasticity of all the samples The variation rate of the content of the elastomer component is within a range of ± 10% with respect to the average content rate. (2) The variation rate of the thickness over the entire length in the longitudinal direction of the wound roll is ± with respect to the average thickness. Within 2% to ± 10%

The structure of the invention described in claim 2 is that an inorganic substance is formed on at least one surface of a polyamide-based mixed resin laminated film substrate formed by laminating a plurality of polyamide-based resin layers made of a mixed resin of a polyamide-based resin and a thermoplastic elastomer. A vapor-deposited polyamide-based mixed resin laminated film roll obtained by winding the vapor-deposited polyamide-based mixed resin laminated film so that the width is 0.2 m or more and 3.0 m or less and the length is 300 m or more and 30000 m or less, The polyamide-based mixed resin laminated film roll formed by winding the polyamide-based mixed resin laminated film before vapor deposition has the first sample cutout portion within 2 m from the end of film winding, and the final within 2 m from the beginning of film winding. A sample cutout is provided every 100m from the first sample cutout When the provided is to satisfy the following requirement (3).
(3) For each sample cut out from each cut-out part, when the tensile elastic modulus in the winding direction of the film was measured, the average tensile elastic modulus, which is the average value of the tensile elastic modulus, was 1.30 GPa or more 2 Less than 50 GPa, and the variation rate of the tensile modulus of elasticity of all the samples is within ± 10% of the average tensile modulus.

According to a third aspect of the present invention, there is provided an inorganic substance on at least one surface of a polyamide-based mixed resin laminated film substrate formed by laminating a plurality of polyamide-based resin layers made of a mixed resin of a polyamide-based resin and a thermoplastic elastomer. A vapor-deposited polyamide-based mixed resin laminated film roll obtained by winding the vapor-deposited polyamide-based mixed resin laminated film so that the width is 0.2 m or more and 3.0 m or less and the length is 300 m or more and 30000 m or less, A first sample cutout is provided within 2 m from the end of film winding, a final cutout is provided within 2 m from the start of film winding, and a sample cutout is provided approximately every 100 m from the first sample cutout. Is to satisfy the following requirement (4).
(4) For each sample cut out from each cut-out part, the number of pinholes when a 3000-cycle bending test was continuously performed at a rate of 40 cycles per minute using a gelbo flex tester, All are 10 or less

The structure of the invention described in claim 4 is the invention described in any one of claims 1 to 3, wherein the first sample cutout portion is formed within 2 m from the end of winding of the film roll after vapor deposition, and the film When the final cutout portion is provided within 2 m from the beginning of winding and the sample cutout portion is provided at intervals of about 100 m from the first sample cutout portion, the oxygen permeability is measured for each sample cut out from each cutout portion. When obtained, the average oxygen permeability, which is the average value of the oxygen permeability, is 50 ml / m ² · MPa · day or less, and the variation rate of the oxygen permeability of all the samples is the average oxygen permeability. Lies in the range of ± 2% to ± 20%.

  The structure of the invention described in claim 5 is that, in the invention described in any one of claims 1 to 3, the inorganic substance is a metal or a metal oxide.

  The structure of the invention described in claim 6 is the invention described in any one of claims 1 to 3, wherein the polyamide-based mixed resin laminated film roll formed by winding the polyamide-based mixed resin laminated film before vapor deposition, For each sample cut out from each cut-out part, when measuring the maximum boiling water shrinkage, which is the maximum value of the boiling water shrinkage in all directions, the average boiling water shrinkage is the average of those maximum boiling water shrinkage Is 2% to 6%, and the variation rate of the maximum boiling water shrinkage of all the samples is in the range of ± 2% to ± 10% with respect to the average boiling water shrinkage.

  The structure of the invention described in claim 7 is the invention described in any one of claims 1 to 3, wherein the polyamide-based mixed resin laminated film roll formed by winding the polyamide-based mixed resin laminated film before vapor deposition, For each sample cut out from each cutout section, the boiling water shrinkage direction difference, which is the absolute value of the difference between the boiling water shrinkage rate in the +45 degree direction with respect to the longitudinal direction and the boiling water shrinkage ratio in the −45 degree direction with respect to the longitudinal direction, is calculated. When obtained, the average boiling water shrinkage direction difference, which is the average value of the boiling water shrinkage direction differences, is 2.0% or less, and the variation rate of the boiling water shrinkage direction difference of all the samples is the average boiling water difference. The difference is in the range of ± 2% to ± 30% with respect to the shrinkage rate direction difference.

The structure of the invention described in claim 8 is the invention described in any one of claims 1 to 3, wherein the polyamide-based mixed resin laminated film roll formed by winding the polyamide-based mixed resin laminated film before vapor deposition, Each sample cut out from each cut-out part satisfies the following requirement (5) and the following requirement (6).
(5) When measuring the three-dimensional surface roughness in the winding direction, the average surface roughness, which is the average value of the three-dimensional surface roughness, is in the range of 0.01 to 0.06 μm, and all The variation rate of the three-dimensional surface roughness of the sample is in the range of ± 5% to ± 20% with respect to the average surface roughness. (6) When haze is measured, the average value of those hazes A certain average haze is in the range of 1.0 to 4.0, and the haze variation rate of all the samples is in the range of ± 2% to ± 15% with respect to the average haze.

  The structure of the invention described in claim 9 is the invention described in any one of claims 1 to 3, wherein the polyamide-based mixed resin laminated film roll formed by winding up the polyamide-based mixed resin laminated film before vapor deposition, About each sample cut out from each said cut-out part, when measuring a dynamic friction coefficient in the atmosphere of 80% RH at 23 degreeC, the average dynamic friction coefficient which is the average value of those dynamic friction coefficients is 0.3-0.8. And the variation rate of the dynamic friction coefficient of all the samples is in the range of ± 5% to ± 30% with respect to the average dynamic friction coefficient.

  The structure of the invention described in claim 10 is the invention described in any one of claims 1 to 3, wherein the polyamide-based mixed resin laminated film roll formed by winding the polyamide-based mixed resin laminated film before vapor deposition, About each sample cut out from each said cut-out part, when content of an inorganic particle is measured, the average content which is the average value of those inorganic particle content is in the range of 0.01 to 0.5 weight% And the variation rate of the inorganic particle content of all the samples is in the range of ± 2% to ± 10% with respect to the average content.

  The structure of the invention described in claim 11 is the invention described in any one of claims 1 to 3, wherein the polyamide-based mixed resin laminated film roll formed by winding up the polyamide-based mixed resin laminated film before vapor deposition, For each sample cut out from each cutout portion, when the refractive index in the thickness direction was measured, the average refractive index, which is the average value of those refractive indexes, was 1.500 or more and 1.520 or less, and all The variation rate of the refractive index of the sample is within a range of ± 2% with respect to the average refractive index.

  The structure of the invention described in claim 12 is a polyamide-based mixed resin laminated film roll formed by winding the polyamide-based mixed resin laminated film before vapor deposition in the invention described in any of claims 1 to 3. The polyamide-based mixed resin laminated film is made by reducing the average particle diameter of the inorganic particles in 1/3 of the total thickness of the front and back surfaces to be smaller than the average particle diameter of the inorganic particles in the portions other than the surface layers. There is to be.

  The structure of the invention described in claim 13 is that, in the invention described in any one of claims 1 to 3, the main component of the polyamide constituting the polyamide-based mixed resin laminated film other than the inorganic substance is nylon 6. It is in.

  The structure of the invention described in claim 14 is the inorganic substance added to the polyamide-based mixed resin laminated film formed from a mixture of two or more different polyamide-based resins in the invention described in any one of claims 1 to 3. In other words, a vapor-deposited polyamide-based mixed resin laminated film is wound up.

  The structure of the invention described in claim 15 is that, in the invention described in any one of claims 1 to 3, the wound-up deposited polyamide-based mixed resin laminated film is laminated with a polyolefin-based resin film. It is in.

  According to a sixteenth aspect of the present invention, in the invention according to any one of the first to third aspects, the molten polyamide-based mixed resin is extruded from a T-die and brought into contact with a metal roll to be cooled. That is, an inorganic substance is vapor-deposited and wound on a polyamide-based mixed resin laminated film obtained by biaxially stretching the obtained unoriented sheet-like material.

  The structure of the invention described in claim 17 is the invention described in any one of claims 1 to 3, wherein an inorganic substance is vapor-deposited and wound on a polyamide-based mixed resin laminated film stretched by a tenter stretching method. It is to be.

  The structure of the invention described in claim 18 is the invention described in any one of claims 1 to 3, in which an inorganic substance is vapor-deposited and wound up on a polyamide-based mixed resin laminated film that is sequentially biaxially stretched. There is to be.

  According to a nineteenth aspect of the present invention, in the invention described in any of the first to third aspects, an inorganic substance is deposited on a polyamide-based mixed resin laminated film stretched biaxially in the longitudinal direction and the transverse direction. It is to have been rolled up.

  According to a twentieth aspect of the present invention, in the invention according to any one of the first to third aspects, a sheet-like material made of a substantially unoriented polyamide resin is replaced with a glass transition of the polyamide resin. A polyamide-based mixed resin laminated film formed by stretching in the longitudinal direction in at least two stages so as to obtain a magnification of 3 times or more at a temperature higher than temperature + 20 ° C. and then stretching in the transverse direction so as to obtain a magnification of 3 times or more. It is that the inorganic substance is deposited and wound up.

  The structure of the invention described in claim 21 is the invention described in any one of claims 1 to 3, wherein an inorganic substance is vapor-deposited on a polyamide-based mixed resin laminated film that is heat-set after the final stretching treatment. It is to have been rolled up.

  The structure of the invention described in claim 22 is the invention described in any one of claims 1 to 3, wherein an inorganic substance is vapor-deposited and wound on a polyamide-based mixed resin laminated film that has been subjected to relaxation treatment after heat setting. It is to be a thing.

  According to a twenty-third aspect of the present invention, in the invention according to any one of the first to third aspects, in the polyamide-based mixed resin laminated film other than the inorganic substance of the wound vapor-deposited polyamide-based mixed resin laminated film In addition, at least one of a lubricant, an anti-blocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a light resistance agent, and an impact resistance improvement agent is added.

  According to a twenty-fourth aspect of the present invention, in the invention according to any one of the first to third aspects, in the polyamide-based mixed resin laminated film other than the inorganic substance of the wound vapor-deposited polyamide-based mixed resin laminated film In addition, inorganic particles are added.

  The structure of the invention described in claim 25 is that, in the invention described in claim 24, the inorganic particles are silica particles having an average particle diameter of 0.5 to 5.0 μm.

  According to a twenty-seventh aspect of the present invention, in the invention according to any one of the first to third aspects, in the polyamide-based mixed resin laminated film other than the inorganic substance of the wound vapor-deposited polyamide-based mixed resin laminated film In addition, higher fatty acids are added.

According to a twenty-seventh aspect of the present invention, there is provided a manufacturing method for manufacturing the vapor-deposited polyamide-based mixed resin laminated film roll according to the first aspect, wherein the mixed resin comprises a polyamide-based resin and a thermoplastic elastomer. A film forming step for forming an unstretched polyamide-based mixed resin laminated sheet by melt extrusion from a plurality of extruders by a co-extrusion method, and an unstretched polyamide-based mixed resin laminated sheet obtained in the film forming step A biaxial stretching step of biaxially stretching in the longitudinal direction and the transverse direction, a roll-up step of winding up the biaxially stretched film, and a vapor deposition step of depositing an inorganic substance on at least one side of the wound up film. And satisfying the following requirements (a) to (g).
(A) In the film forming step, the polyamide resin chip and the thermoplastic elastomer chip are mixed and then melt-extruded, and the mixture of the polyamide resin chip and the thermoplastic elastomer chip is sublimated and segregated. (B) A polyamide-based mixed resin in which the film forming step is performed by mixing a polyamide-based resin chip and a thermoplastic elastomer chip and adding 0.1 to 2.0% by weight of inorganic particles. (C) The biaxial stretching step involves stretching in two stages in the longitudinal direction and then stretching in the transverse direction, and the first stage in the two-stage stretching in the longitudinal direction. (D) The film forming step includes a polyamide resin chip and a thermoplastic resin. It is melt extruded from each extruder after mixing with a steamer chip, and the shape of each chip used is an elliptical cylinder having an elliptical cross section having a major axis and a minor axis, and a thermoplastic elastomer The tip is adjusted to have an average major axis, an average minor axis, and an average tip length that are included within ± 25% of the average major axis, average minor axis, and average tip length of the polyamide resin chip, respectively. (E) The film forming step includes a step of melt extrusion using a plurality of extruders provided with a funnel-shaped hopper as a raw material chip supply unit, and all the inclination angles of the funnel-shaped hopper are 65 degrees or more. The moisture content of the polyamide resin chip before being supplied to the funnel-shaped hopper is 800 ppm or more and 1000 ppm or less. The temperature of the polyamide-based resin chip before being supplied to the funnel-shaped hopper is adjusted to 80 ° C. or higher. (F) The film forming step is performed simultaneously from the plurality of extruders. It includes a step of cooling by winding the polyamide-based mixed resin laminated sheet melt-extruded by an extrusion method around a cooling roll, and in that cooling step, the contact between the polyamide-based mixed resin laminated sheet and the surface of the cooling roll The portion is sucked by the suction device in the direction opposite to the winding direction over the entire width of the polyamide-based mixed resin laminated sheet. (G) The vapor deposition step is performed by metal or metal oxidation on at least one surface of the wound film. The material is deposited so as to have a thickness of 5.0 nm to 200 nm.

  According to a 28th aspect of the present invention, in the invention described in the 27th aspect, the film forming step uses a high-concentration raw material chip, whereby 0.05 to 2.0% by weight of inorganic particles are obtained. 27. The method for producing a vapor-deposited polyamide-based resin laminated film roll according to claim 26, wherein the added skin layer is laminated on the core layer.

  The structure of the invention described in claim 29 is the polyamide according to the invention described in claim 27, wherein the high-concentration raw material chip used in the film forming step is added with 5% by weight or more and less than 20% by weight of inorganic particles. It is based on a resin chip.

  The structure of the invention described in claim 30 is the invention described in claim 27, wherein, in the film forming step, the inorganic particles added to the polyamide-based resin sheet laminated on the outermost layer have a pore volume of 0. The average particle size is 1.0 to 5.0 μm at a rate of 0.5 to 2.0 ml / g.

  The structure of the invention described in claim 31 in the invention described in claim 27 includes a preheating step performed before the longitudinal stretching step and a heat treatment step performed after the longitudinal stretching step. The fluctuation range of the surface temperature of the film at an arbitrary point in the longitudinal stretching step, the preheating step, and the heat treatment step is adjusted within the range of the average temperature ± 1 ° C. over the entire length of the film. .

  According to the vapor-deposited polyamide-based mixed resin laminated film roll of the present invention, the bag-making process of a three-side sealed bag for packaging liquid soup or the like that requires high gas barrier properties and high pinhole resistance is performed in summer and the like. Even when the process is performed under high humidity, the bag-making process can be smoothly performed by laminating with almost no trouble, and a package without S-curls can be efficiently obtained. Further, in post-processing such as bag making processing, a processed product can be obtained with a high yield. In addition, if the vapor-deposited polyamide-based mixed resin laminated film roll of the present invention is used, the food packaging bag after the bag-making process by lamination has a very high pinhole resistance and a very high gas barrier property. In addition, variations in pinhole resistance and gas barrier properties for each bag are reduced.

  In addition, according to the method for producing a vapor-deposited lyamide-based mixed resin laminated film roll of the present invention, it has extremely high pinhole resistance and high gas barrier property, and also has good lamination processability under high humidity. A polyamide-based mixed resin film roll can be obtained inexpensively and very efficiently.

  The polyamide-based mixed resin laminated film roll of the present invention is a polyamide-based mixed resin laminated film roll before vapor deposition, cut out the sample by the following method, and for each sample cut out, measure the content of the thermoplastic elastomer component, When calculating the average content rate, which is the average value of those content rates, the variation rate of the content of the thermoplastic elastomer component of all the samples may be within a range of ± 10% with respect to the average content rate. It is necessary (Claim 1).

  In the cutting of the sample in the present invention, first, the first sample cutting portion is provided within 2 m from the end of winding of the film, and the final cutting portion is provided within 2 m from the beginning of winding of the film. A sample cut-out section is provided every about 100 m. Note that “about every 100 m” means that the sample may be cut out at about 100 m ± 1 m.

  More specifically, the cutting of the above sample will be described. For example, when a polyamide-based film having a length of 498 m is wound around a roll, the first sample (1) is taken within 2 m from the end of winding of the film. cut out. For convenience, the sample is cut out in a rectangular shape so as to have a side along the longitudinal direction of the film and a side along the direction orthogonal to the longitudinal direction (not cut diagonally). Subsequently, the second sample (2) is cut away from the cut portion at a distance of 100 m from the winding start side. In the same manner, the third sample (3) is separated to the winding start side of 200 m, the fourth sample (4) is separated to the winding start side of 300 m, and the fifth sample is separated to the winding start side of 400 m. Cut out (5). When the sample is cut out in this way, the remainder becomes shorter than 100 m, so the sixth (final) sample (6) cuts out any portion within 2 m from the start of film winding.

  And about each sample cut out as mentioned above, when the content of the thermoplastic elastomer component is quantitatively analyzed, and the average content rate that is the average value of those content rates is calculated, the thermoplastic elastomer component of all the samples That is, it is necessary that the fluctuation rate of the content of is within a range of ± 10% with respect to the average content. Here, the variation rate of the thermoplastic elastomer component content of all the samples is the maximum / minimum of the thermoplastic elastomer component content (measured value) of all the samples. It means the ratio of the difference with respect to the average content when the difference between the average content and the one with the larger difference from the average content is obtained. As will be described later, the content of the thermoplastic elastomer component is sliced perpendicular to the surface to form an ultrathin piece, and the elastomer component is dyed with a specific substance to occupy the entire dyed portion. It can be measured by a method of calculating the area ratio, or can be measured by other methods such as infrared analysis and NMR analysis focusing on a peak peculiar to the elastomer.

  The polyamide-based mixed resin laminated film roll of the present invention has a fluctuation rate of the elastomer component content of all samples cut out from the polyamide-based mixed resin laminated film roll before vapor deposition within ± 9% of the average content. It is preferably within the range, more preferably within the range of ± 8%, and further preferably within the range of ± 7%.

  In addition, the polyamide-based mixed resin laminated film roll before vapor deposition is preferably as small as the variation rate of the elastomer component content of all cut out samples, but the lower limit of the variation rate is about 2% in consideration of measurement accuracy. Is the limit.

Moreover, the polyamide-based mixed resin laminated film roll of the present invention has a tensile elastic modulus when the tensile elastic modulus is measured for each sample cut from each cut-out portion of the polyamide-based mixed resin laminated film roll before vapor deposition. The average tensile modulus of elasticity is 1.30 GPa (1300 N / mm ² ) or more and less than 2.50 GPa (2500 N / mm ² ), and the variation rate of the tensile modulus of all samples is the average tensile elasticity. It is necessary to adjust within a range of ± 10% with respect to the rate (Claim 2). Here, the fluctuation rate of the tensile modulus of elasticity of all the samples is the maximum / minimum of the tensile modulus of elasticity of all the samples, and the larger of the difference between the average tensile modulus of the maximum / minimum It means the ratio of the difference to the average tensile elastic modulus when the difference from the average tensile elastic modulus is obtained.

  In addition, the tensile elastic modulus of the film constituting the polyamide-based mixed resin laminated film roll before vapor deposition is important for enhancing the toughness and pinhole resistance of the film itself, and when the tensile elastic modulus is less than 1.30 GPa, On the other hand, if the toughness and pinhole resistance are insufficient, and if it exceeds 2.50 GPa, tearing properties are deteriorated when a three-side sealed bag is formed, it is not preferable. A more preferable range of the tensile elastic modulus is 1.50 GPa to 2.30 GPa in order to enhance toughness / pinhole resistance and tearability when forming a three-side sealed bag.

  In addition, the polyamide-based mixed resin laminated film roll before vapor deposition is preferably such that the variation rate of the tensile elastic modulus of all the cut out samples is within ± 9% of the average tensile elastic modulus, and is within ± 8%. More preferably, it is more preferably within the range of ± 7%.

  In addition, the polyamide-based mixed resin laminated film roll before vapor deposition is preferable as the variation rate of the tensile elastic modulus of all the cut out samples is smaller, but the lower limit of the variation rate is about ± 2% in consideration of measurement accuracy. I think it is the limit.

  The vapor-deposited polyamide-based mixed resin laminated film roll of the present invention is a gelbo flex tester for each sample cut out from the film roll after vapor deposition by the same method as the above-described sample cutting method. It is necessary that the number of pinholes in the case where the bending test of 3000 cycles is continuously performed at a rate of 40 cycles per minute is adjusted to be 10 or less (claims) Item 3).

[Measurement method of pinhole resistance]
A film cut to a predetermined size (20.3 cm × 27.9 cm) by laminating with a polyolefin film or the like, and a film cut to a predetermined size (20.3 cm × 27.9 cm) to a predetermined temperature / humidity After conditioning for a predetermined time below, the rectangular test film is wound into a cylindrical shape of a predetermined length. Then, both ends of the cylindrical film are fixed to the outer periphery of the disk-shaped fixed head of the gel bow flex tester and the outer periphery of the disk-shaped movable head, respectively, and the movable heads are parallel to the direction of the fixed head. Rotate a predetermined angle (440 °) while approaching a predetermined length (7.6 cm) along the axis, and then proceed straight ahead for a predetermined length (6.4 cm) without rotating, then reverse their movements A one-cycle bending test in which the movable head is returned to the initial position by being executed in the direction is continuously repeated for a predetermined cycle (3000 cycles) at a predetermined speed (40 cycles per minute). Thereafter, the number of pinholes generated in a predetermined range (497 cm ² ) excluding a fixed portion of the tested film and a portion fixed to the outer periphery of the movable head is measured.

  In addition, the polyamide-based mixed resin laminated film roll of the present invention is omnidirectional by the following method for all samples when the samples are cut out from the polyamide-based mixed resin laminated film roll before vapor deposition by the above-described method. When the maximum boiling water shrinkage, which is the maximum value of the boiling water shrinkage, is measured, the average boiling water shrinkage, which is the average of the maximum boiling water shrinkage, is adjusted to be 2% or more and 6% or less. And preferred.

  In addition, the polyamide-based mixed resin laminated film roll of the present invention has a longitudinal direction in which all samples are cut in the longitudinal direction by the following method when the samples are cut out from the polyamide-based mixed resin laminated film roll before vapor deposition by the method described above. On the other hand, when the boiling water shrinkage direction difference, which is the absolute value of the difference between the boiling water shrinkage rate in the + 45 ° direction and the boiling water shrinkage rate in the −45 ° direction with respect to the longitudinal direction, is obtained, the average value of the boiling water shrinkage direction differences. It is preferable that the average boiling water shrinkage direction difference is adjusted to be 2.0% or less.

[Measuring method of boiling water shrinkage (BS), maximum boiling water shrinkage (BSx), average boiling water shrinkage (BSax), boiling water shrinkage direction difference (BSd), average boiling water shrinkage direction difference (BSad)]
The film cut out from each cut-out portion of the polyamide-based mixed resin laminated film roll is cut into a square shape and left in an atmosphere of 23 ° C. and 65% RH for 2 hours or more. A circle (about 20 cm in diameter) centered on the center of this sample is drawn, and a straight line passing through the center of the circle in the direction of 0 to 165 ° clockwise at 15 ° intervals, with the vertical direction (film drawing direction) being 0 °. Pull, measure the diameter in each direction, and make it the length before processing. The cut sample was then heat-treated in boiling water for 30 minutes, then removed and wiped off the moisture adhering to the surface, air-dried, and left in an atmosphere of 23 ° C. and 65% RH for 2 hours or more, as described above. The length of the straight line drawn in each diametric direction is measured and set as the length after treatment. BS (boiling water shrinkage), BSx (maximum boiling water shrinkage), BSax (average boiling water shrinkage), BSd (boiling water shrinkage direction difference) and BSad (average boiling water shrinkage direction difference) are calculated.
BS = [(length before processing−length after processing) / length before processing] × 100 (%)... 1
BSx = Maximum shrinkage rate (%) measured in 0 to 165 ° direction at 15 ° intervals 2
BSax = sum of BSx of all samples / number of samples 3
BSd = | (BS in 45 ° direction) − (BS in 135 ° direction) |
BSad = sum of BSd of all samples / number of samples 5

  The BSx value of the film constituting the polyamide-based mixed resin laminated film roll ensures heat resistance (also referred to as laminate strength or heat-resistant laminate strength) when the film is formed into a bag shape and subjected to hot water treatment. It is important to improve the toughness and pinhole resistance of the film itself. If the BSx value is less than 2%, the toughness and pinhole resistance will be insufficient. Or the heat-resistant laminate strength at the time of hot water treatment becomes insufficient. The range of BSx that is more preferable for enhancing toughness, pinhole resistance, laminating properties, and heat-resistant laminating strength is 3.5 to 5.0%.

  In addition, the BSd value of the film constituting the polyamide-based mixed resin laminated film roll has a great influence on the curling phenomenon that occurs during the boiling water treatment, and the larger the BSd value, the more easily the bag is bent and the curling becomes remarkable. If BSd is suppressed to 2.0% or less, preferably 1.5% or less, more preferably 1.2% or less, the bag warp during boiling water treatment is suppressed as much as possible, and the occurrence of S-curl phenomenon occurs. Can be prevented.

  In addition, in the polyamide-based mixed resin laminated film roll before vapor deposition, the variation rate of the maximum boiling water shrinkage (BSx) of all the cut out samples is ± 2% to ± 10% (± 2) of the average boiling water shrinkage (BSa). % Or more and ± 10% or less) is preferably adjusted. Here, the variation rate of the maximum boiling water shrinkage (BSx) of all the samples is the maximum / minimum of the maximum boiling water shrinkage (BSx) of all the samples, and the average boiling water shrinkage of those maximum / minimum. It means the ratio of the difference with respect to the average boiling water shrinkage when the difference between the one with the larger difference between the ratio and the average boiling water shrinkage is obtained.

  That is, in the polyamide-based mixed resin laminated film roll before vapor deposition, when the boiling water shrinkage rate of the samples (1) to (6) is Xn (n = 1 to 6), the maximum value Xmax of Xn and the average boiling water shrinkage. That is, it is preferable that the difference between the rate (BSax) and the difference between the minimum value Xmin and the average boiling water shrinkage (BSax) are within ± 10%, in other words, | BSax−Xn It is preferable that all of | (where || represents an absolute value) is 10% or less.

  In addition, the polyamide-based mixed resin laminated film roll before vapor deposition has a variation rate of the maximum boiling water shrinkage (BSx) of all the cut out samples within a range of ± 9% of the average boiling water shrinkage (BSa). Preferably, it is more preferably within a range of ± 8%, and particularly preferably within a range of ± 7%.

  In addition, the polyamide-based mixed resin laminated film roll before vapor deposition is preferable as the variation rate of the maximum boiling water shrinkage (BSx) of all the cut out samples is smaller, but the lower limit of the variation rate is 2 in consideration of measurement accuracy. % Is considered the limit.

  In addition, in the polyamide-based mixed resin laminated film roll before vapor deposition, the fluctuation rate of the boiling water shrinkage direction difference (BSd) of all the cut out samples is ± 2% to ± 30% of the average boiling water shrinkage direction difference (BSad). It is preferable to adjust to be within a range of (± 2% or more and ± 30% or less). Here, the fluctuation rate of the boiling water shrinkage direction difference (BSd) of all the samples is the maximum / minimum in the boiling water shrinkage direction difference (BSd) of all the samples, and the average of these maximum / minimum values. When the difference between the larger difference between the boiling water shrinkage direction difference and the average boiling water shrinkage direction difference is obtained, it means the ratio of the difference to the average boiling water shrinkage direction difference.

  That is, in the polyamide-based mixed resin laminated film roll before vapor deposition, when the boiling water shrinkage direction difference of samples (1) to (6) is Yn (n = 1 to 6), the maximum value Ymax of Yn and the average That is, it is preferable that the difference between the boiling water shrinkage direction difference (BSad) and the difference between the minimum value Ymin and the average boiling water shrinkage direction difference (BSad) are within ± 30%, in other words. For example, | BSad-Yn | (where || indicates an absolute value) is preferably 30% or less.

  In addition, in the polyamide-based mixed resin laminated film roll before vapor deposition, the fluctuation rate of the boiling water shrinkage direction difference (BSd) of all the cut out samples is within a range of ± 20% of the average boiling water shrinkage direction difference (BSad). More preferably, it is more preferably within the range of ± 15%, even more preferably within the range of ± 10%, and particularly preferably within the range of ± 8%.

  In addition, the polyamide-based mixed resin laminated film roll before vapor deposition is preferable as the fluctuation rate of the boiling water shrinkage direction difference (BSd) of all cut out samples is smaller, but the lower limit of the fluctuation rate is based on measurement accuracy. We think about 2% is the limit.

Moreover, the vapor deposition polyamide type mixed resin laminated | multilayer film roll of this invention is the average surface roughness (average value of the three-dimensional surface roughness (SRa) of all the samples cut out from the polyamide type mixed resin laminated film roll before vapor deposition. SRa ) is preferably in the range of 0.01 to 0.06 μm, more preferably in the range of 0.02 to 0.05 μm (in addition, an example of a method for measuring the three-dimensional surface roughness will be described in Examples). To do). If the average surface roughness is less than 0.01 μm, good slipperiness under high humidity cannot be obtained, and on the contrary, if the average surface roughness is more than 0.06 μm, when laminating, Since adhesiveness with films, such as polyolefin, will fall, it is not preferred.

  In addition, the polyamide-based mixed resin laminated film roll before vapor deposition had a variation rate of the three-dimensional surface roughness (SRa) of all the cut out samples within ± 5% to ± 20% of the average surface roughness (SRaa) (± It is preferable to adjust to be within a range of 5% or more and ± 20% or less. Here, the variation rate of the three-dimensional surface roughness (SRa) of all samples is the maximum / minimum of the three-dimensional surface roughness (SRa) of all samples, and the average of the maximum / minimum values. It means the ratio of the difference to the average surface roughness when the difference between the larger surface roughness and the average surface roughness is obtained.

  That is, in the polyamide-based mixed resin laminated film before vapor deposition, when the three-dimensional surface roughness of the samples (1) to (6) is SRn (n = 1 to 6), the SRn maximum value SRmax and the average That is, the difference between the surface roughness (SRaa) and the difference between the minimum value SRmin and the average surface roughness is preferably within ± 20%. In other words, | SRaa−SRn | ( Note that || indicates an absolute value) is preferably 20% or less.

  In addition, as for the polyamide-type mixed resin laminated | multilayer film roll before vapor deposition, when the fluctuation rate of the three-dimensional surface roughness (SRa) of all the cut-out samples is in the range within ± 15% of average surface roughness (SRaa). More preferably, it is more preferably within the range of ± 10%, and particularly preferably within the range of ± 8%. In addition, the polyamide-based mixed resin laminated film roll before vapor deposition is preferable as the variation rate of the three-dimensional surface roughness (SRa) of all cut out samples is smaller, but the lower limit of the variation rate is based on measurement accuracy. We think about 5% is the limit.

  Moreover, as for the vapor deposition polyamide type mixed resin laminated | multilayer film roll of this invention, the average haze which is an average value of the haze of all the samples cut out from the polyamide type mixed resin laminated film roll before vapor deposition is the range of 1.0-4.0. It is preferable that it is in the range of 1.5 to 3.0. If the average haze is more than 4.0, it is not preferable because the appearance of the formed bag is deteriorated when the bag making process is performed. Although the average haze is preferably as small as possible, the lower limit of the average haze is considered to be about 1.0 when the measurement accuracy is taken into consideration.

  Moreover, as for the polyamide-type mixed resin laminated | multilayer film roll before vapor deposition, the fluctuation rate of the haze of all the cut-out samples is in the range of ± 2% to ± 15% (± 2% or more and ± 15% or less) of the average haze. It is preferable to adjust so as to be. Here, the haze variation rate of all samples is the maximum / minimum of all samples in the haze, and the difference between the average haze and the larger of the maximum / minimum average hazes It refers to the ratio of the difference to the average haze when obtained.

  That is, in the polyamide-based mixed resin laminated film roll before vapor deposition, when the haze of the above samples (1) to (6) is Hn (n = 1 to 6), the maximum value Hmax of Hn and the average haze The difference and the difference between the minimum value Hmin and the average haze (Han) are preferably within ± 15%. In other words, | Han−Hn | (where || It is preferable that all of them are 15% or less.

  In addition, the polyamide-based mixed resin laminated film roll before vapor deposition is more preferable when the fluctuation rate of the haze of all the cut out samples is within a range of ± 10% of the average haze, and within a range of ± 8%. Further preferred. In addition, the polyamide-based mixed resin laminated film roll before vapor deposition is preferable as the haze fluctuation rate of all the cut out samples is smaller, but the lower limit of the fluctuation rate is about 2% in consideration of measurement accuracy. I believe.

  Moreover, as for the vapor deposition polyamide type mixed resin laminated | multilayer film roll of this invention, the fluctuation rate of the thickness over the longitudinal direction full length of the polyamide type mixed resin laminated film roll before vapor deposition is +/- 2%-+/- 10% with respect to average thickness ( It is necessary to adjust to be within a range of ± 2% or more and ± 10% or less. Here, the variation rate of the thickness over the entire length in the longitudinal direction is the maximum / minimum of the thickness over the entire length in the longitudinal direction, and the difference between the average thickness of the maximum / minimum average thickness and the average thickness It means the ratio of the difference to the average thickness when the difference is obtained.

  That is, in the polyamide-based mixed resin laminated film roll before vapor deposition, the difference between the maximum value Tmax of the thickness over the entire length in the longitudinal direction and the average thickness (the average thickness Ta over the entire length in the longitudinal direction), the minimum value Tmin, and the average thickness ( This means that any difference from Ta) must be within ± 10%.

  In addition, the polyamide-based mixed resin laminated film roll before vapor deposition preferably has a variation rate of thickness over the entire length in the longitudinal direction within a range of ± 8% of the average thickness (Ta), and within a range of ± 6%. And more preferred.

  In addition, the polyamide-based mixed resin laminated film roll before vapor deposition is preferable as the variation rate of the thickness over the entire length in the longitudinal direction is smaller. However, the lower limit of the variation rate is about 2% from the viewpoint of the performance of the film forming apparatus. I think there is.

  On the other hand, the vapor-deposited polyamide-based mixed resin laminated film roll of the present invention is an average which is an average value of the dynamic friction coefficient (μd) at 23 ° C. × 80% RH of all samples cut out from the polyamide-based mixed resin laminated film roll before vapor deposition. The dynamic friction coefficient (μda) is preferably in the range of 0.3 to 0.8, and more preferably in the range of 0.4 to 0.6. When the average dynamic friction coefficient at 23 ° C. × 80% RH is less than 0.3, film misalignment occurs on the roll at the time of bag-making processing, which is not preferable, and conversely, the average dynamic friction coefficient is 0.8. Above the range, it is not preferable because good slipperiness under high humidity cannot be obtained.

  In addition, the polyamide mixed resin laminated film roll before vapor deposition has a variation rate of the dynamic friction coefficient (μd) of all the cut out samples within ± 5% to ± 30% (± 5% to ± 30% or less) of the average dynamic friction coefficient ) Is preferably adjusted so as to be within the range. Here, the fluctuation rate of the dynamic friction coefficient (μd) of all the samples is the maximum / minimum of the dynamic friction coefficients (μd) of all the samples, and is the difference between the average dynamic friction coefficient of the maximum / minimum. When the difference between the larger one and the average dynamic friction coefficient is obtained, it means the ratio of the difference to the average dynamic friction coefficient.

  That is, in the polyamide-based mixed resin laminated film roll before vapor deposition, when the dynamic friction coefficient of the samples (1) to (6) is μn (n = 1 to 6), the maximum value μmax of μn and the average dynamic friction coefficient (Μda) and the difference between the minimum value μmin and the average dynamic friction coefficient are preferably within ± 30%. In other words, | μda−μn | | Indicates an absolute value) is preferably 30% or less.

  In addition, it is more preferable that the fluctuation rate of the dynamic friction coefficient (μd) of all cut out samples in the polyamide-based mixed resin laminated film roll before vapor deposition is within ± 20% of the average dynamic friction coefficient, and within ± 15%. Is more preferably in the range of ± 10%, and particularly preferably in the range of ± 10%. In addition, the polyamide-based mixed resin laminated film roll before vapor deposition is preferably as small as the variation rate of the dynamic friction coefficient (μd) of all the cut out samples, but the lower limit of the variation rate is about 5% in consideration of measurement accuracy. Is the limit.

  On the other hand, the vapor-deposited polyamide-based mixed resin laminated film roll of the present invention has an average content that is an average value of the content of inorganic particles of all the samples cut out from the polyamide-based mixed resin laminated film roll before vapor deposition. It is preferably in the range of 0.5% by weight and more preferably in the range of 0.05 to 0.3% by weight (an example of a method for measuring the content of inorganic particles will be described in the examples). If the average content is less than 0.01% by weight, it is not preferable because good slipperiness under high humidity cannot be obtained. Conversely, if the average content exceeds 0.5% by weight, it is deleted in the manufacturing process. It is not preferable because it is difficult to recover and reuse the polyamide resin.

  Moreover, the polyamide-based mixed resin laminated film roll before vapor deposition has a variation rate of the inorganic particle content of all cut out samples within ± 2% to ± 10% (± 2% or more and ± 10% or less) of the average content. It is preferable to adjust so as to be within the range. Here, the fluctuation rate of the inorganic particle content of all the samples is the maximum or minimum of the inorganic particle content of all the samples, and the difference between the average content of the maximum and minimum is the larger The ratio of the difference to the average content when the difference between the average content and the average content is obtained.

  That is, in the polyamide-based mixed resin laminated film roll before vapor deposition, when the content of inorganic particles in the samples (1) to (6) is Cn (n = 1 to 6), the maximum value Cmax of Cn is That is, the difference between the average content (Ca) and the difference between the minimum value Cmin and the average content is preferably within ± 10%, in other words, | Ca-Cn | ( Note that || indicates an absolute value) is preferably 10% or less.

  In addition, the polyamide-based mixed resin laminated film roll before vapor deposition is more preferably such that the variation rate of the inorganic particle content of all cut out samples is within ± 8% of the average content, and within ± 6%. More preferably, it is in the range. In addition, the polyamide-based mixed resin laminated film roll before vapor deposition is preferably as small as the variation rate of the inorganic particle content of all cut out samples, but the lower limit of the variation rate is about 2% in consideration of measurement accuracy. I think it is the limit.

Moreover, when the vapor-deposited polyamide-based mixed resin laminated film roll of the present invention cuts out a sample by the same method as described above, when the oxygen permeability is determined for each sample cut out from each cut-out portion, The average oxygen permeability, which is the average value of the oxygen permeability, is preferably 50 ml / m ² · MPa · day or less, more preferably 40 ml / m ² · MPa · day or less, and 30 ml / m ² · MPa or less. -It is especially preferable that it is below day.

  In the vapor-deposited polyamide-based mixed resin laminated film roll of the present invention, the fluctuation rate of oxygen permeability is within a range of ± 2% to ± 20% (± 2% to ± 20%) with respect to the average oxygen permeability. It is preferable that the adjustment is performed. Here, the fluctuation rate of oxygen permeability is the maximum / minimum of oxygen permeability, and the difference between the average oxygen permeability and the larger of the maximum / minimum average oxygen permeability It means the ratio of the difference in the average oxygen permeability when obtained.

  That is, in the vapor-deposited polyamide-based mixed resin laminated film roll of the present invention, both the difference between the maximum oxygen permeability Pmax and the average oxygen permeability Pa and the difference between the minimum Pmin and the average oxygen permeability Pa are both. Is required to be within ± 20%.

  In the vapor-deposited polyamide-based mixed resin laminated film roll of the present invention, the variation rate of the oxygen permeability is preferably within ± 15% of the average oxygen permeability (Pa), and is within ± 10%. And more preferred.

  In addition, the vapor deposition polyamide-based mixed resin laminated film roll of the present invention is preferably as the fluctuation rate of oxygen permeability is small, but the lower limit of the fluctuation rate is about 2% in terms of the performance of the film forming apparatus. thinking.

Furthermore, the vapor-deposited polyamide-based mixed resin laminated film roll of the present invention has a refractive index (Nz) in the thickness direction for all samples when the samples are cut out from the polyamide-based mixed resin laminated film roll before vapor deposition by the above method. When obtained, it is preferable that the average refractive index (Nza), which is the average value of these refractive indexes, is adjusted to be 1.500 or more and 1.520 or less. The average refractive index is calculated by the following formula 6.
Nza = total Nz of all samples / number of samples 6

  In addition, the value of Nz of the biaxially oriented film constituting the polyamide-based mixed resin laminated film roll has a great influence on the film quality such as laminate strength and thickness unevenness. Therefore, the requirement that the average refractive index is 1.500 or more and 1.520 or less is an essential requirement when the biaxially oriented film is laminated with a polyolefin resin film. When Nz is less than 1.500, the laminate strength with the polyolefin resin film or the like becomes insufficient, and peeling between the laminate base material is likely to occur due to boiling water treatment after bag making. On the other hand, this Nz gradually decreases in the process of biaxially stretching an unstretched film (sheet). In other words, Nz can also be considered as one of the indices of stretching, and a large Nz indicates that stretching is insufficient. If Nz exceeds 1.520, it is due to insufficient biaxial stretching. Thick spots and the like appear remarkably, and satisfactory film quality cannot be obtained. Considering both the laminate strength and the film quality, a particularly preferable range of Nz is in the range of 1.507 to 1.516.

  Further, in the polyamide-based mixed resin laminated film roll before vapor deposition, the variation rate of the refractive index (Nz) of all the cut out samples is ± 2 with respect to the average value of the refractive indexes (hereinafter referred to as the average refractive index). It is preferable to adjust so that it may become in the range within%. Here, the variation rate of the refractive index (Nz) of all the samples is the maximum / minimum of the refractive indexes (Nz) of all the samples, and the difference between the average refractive index of the maximum / minimum values. When the difference between the larger one and the average refractive index is obtained, it means the ratio of the difference to the average refractive index.

  That is, in the polyamide-based mixed resin laminated film roll before vapor deposition, when the refractive indexes of the samples (1) to (6) are Nz1 to Nz6, the difference between the maximum value Nzmax of Nz1 to Nz6 and the average refractive index , Nz1 to Nz6, and the difference between the minimum value Nzmin and the average refractive index is preferably within ± 2%, in other words, | average refractive index−Nz1 | ˜ | average refractive index. -Nz6 | is preferably 2% or less. Moreover, as for the polyamide-type mixed resin laminated | multilayer film roll before vapor deposition, it is more preferable that the fluctuation rate of the refractive index (Nz) of all the cut-out samples exists in the range within +/- 1% with respect to an average refractive index.

  In addition, the polyamide-based mixed resin laminated film roll before vapor deposition is preferable as the variation rate of the refractive index (Nz) of all the cut out samples is smaller. However, the lower limit of the variation rate is from the viewpoint of measurement accuracy and mechanical accuracy. About 0.1% is considered the limit.

  As described above, physical properties such as boiling water shrinkage and tensile elastic modulus of one polyamide-based mixed resin laminated film roll before vapor deposition are adjusted to values within a predetermined range, and the boiling water shrinkage and tensile elastic modulus thereof are adjusted. By reducing fluctuations in physical properties such as the content of the elastomer and the content of the elastomer, uniform deposition on the film surface is possible, variation in oxygen permeability can be reduced, the content of the thermoplastic elastomer, By reducing fluctuations in physical properties such as tensile elastic modulus, it is possible to prevent deterioration of the appearance in bag making and laminating, and it is possible to process smoothly with high yield even under high humidity, making bag making Each bag afterwards has extremely high pinhole resistance and gas barrier properties and no variation.

  Examples of the polyamide resin used in the present invention include nylon 6 using ε-caprolactam as a main raw material. Examples of other polyamide resins include polyamide resins obtained by polycondensation of lactams having three or more members, ω-amino acids, dibasic acids and diamines. Specifically, as lactams, in addition to the aforementioned ε-caprolactam, enantolactam, capryllactam, lauryllactam, and ω-amino acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9- Examples include aminononanoic acid and 11-aminoundecanoic acid. Dibasic acids include adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecadioic acid, hexadecadioic acid, eicosandioic acid, eicosadienedioic acid, 2 2,4-trimethyladipic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and xylylenedicarboxylic acid. Furthermore, as diamines, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, pentamethylenediamine, undecamethylenediamine, 2,2,4 (or 2,4,4) -trimethylhexamethylenediamine, cyclohexane Examples thereof include diamine, bis- (4,4′-aminocyclohexyl) methane, and metaxylylenediamine. And polymers obtained by polycondensation of these or copolymers thereof, such as nylon 6, 7, 11, 12, 6.6, 6.9, 6.11, 6.12, 6T, 6I, MXD6 (Metaxylene dipanamid 6), 6 / 6.6, 6/12, 6 / 6T, 6 / 6I, 6 / MXD6, and the like can be used. In addition, when producing the polyamide-based mixed resin laminated film roll of the present invention, the above-mentioned polyamide resins can be used alone or in admixture of two or more.

  Of the polyamide-based resins, those having a relative viscosity in the range of 2.0 to 3.5 are particularly preferable in the present invention. The relative viscosity of the polyamide-based resin affects the toughness and spreadability of the resulting biaxially stretched film. If the relative viscosity is less than 2.0, the impact strength tends to be insufficient. This is because, if it exceeds 3.5, the biaxial stretchability tends to deteriorate with increasing stretching stress. In addition, the relative viscosity in this invention means the value at the time of measuring at 25 degreeC using the solution which melt | dissolved 0.5g of polymers in 50 ml of 97.5% sulfuric acid.

Examples of the thermoplastic elastomer used in the present invention include a polyamide such as a block or random copolymer of a polyamide-based resin such as nylon 6 or nylon 12 and PTMG (polytetramethylene glycol) or PEG (polyethylene glycol). It is preferable to use a polyolefin-based elastomer, an ethylene-methacrylic acid copolymer, a copolymer of ethylene and butene, a polyolefin-based elastomer such as a copolymer of styrene or butadiene, or an ionomer of an olefin-based resin such as an ethylene-based ionomer. it can.

  Further, the amount of the thermoplastic elastomer added to the polyamide resin is not particularly limited, but the lower limit of the addition amount is preferably 1% by weight or more, more preferably 2% by weight or more. More preferably, it is at least wt%. On the other hand, the upper limit of the addition amount is preferably 15% by weight or less, more preferably 10% by weight or less, and further preferably 6% by weight or less. If the added amount of the thermoplastic elastomer is less than 1% by weight, it is not preferable because good pinhole resistance cannot be obtained. Conversely, if the added amount of the thermoplastic elastomer exceeds 15% by weight, the toughness of the film is reduced. It is not preferable because it is damaged.

  An inorganic vapor deposition layer is laminated on the polyamide-based mixed resin laminated film. This inorganic vapor deposition layer provides a high gas barrier property to the obtained polyamide-based mixed resin laminated film. Examples of the material for the inorganic vapor deposition layer having such an action include metals such as Al, Si, Ti, Zn, Zr, Mg, Sn, Cu, and Fe, and oxides, nitrides, fluorides, and sulfides of these metals. Specifically, SiOx (x = 1.0-2.0), alumina, magnesia, zinc sulfide, titania, zirconia, cerium oxide, or a mixture thereof is exemplified. The inorganic vapor deposition layer may be a single layer or a laminate of two or more layers.

  The thickness of the inorganic vapor deposition layer is preferably 5 to 500 nm, more preferably 5 to 200 nm. When the film thickness is less than 5 nm, there is a possibility that sufficient gas barrier properties may not be obtained. On the other hand, when the thickness exceeds 500 nm, the corresponding effect is not achieved, the bending resistance is lowered, and the manufacturing cost is disadvantageous, which is not preferable.

  As the method for forming the inorganic vapor deposition layer, a known method, for example, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method or an ion plating method, a chemical vapor deposition method such as PECVD, or the like is employed.

  In the vacuum deposition method, the deposition material is a metal such as aluminum, silicon, titanium, magnesium, zirconium, cerium, or zinc, SiOx (x = 1.0 to 2.0), alumina, magnesia, zinc sulfide, titania, Compounds such as zirconia and mixtures thereof are used. As the heating method, resistance heating, induction heating, electron beam heating or the like is employed. Alternatively, reactive vapor deposition using oxygen, nitrogen, hydrogen, argon, carbon dioxide, water vapor, or the like as a reactive gas, or using means such as ozone addition or ion assist may be employed. Furthermore, a method of applying a bias to the polyamide-based mixed resin laminated film or heating and cooling the polyamide-based mixed resin laminated film may be employed. The vapor deposition material, reaction gas, bias application, and heating / cooling can also be employed in the sputtering method and the CVD method. In addition, it is also possible to provide an anchor coat layer between a metal vapor deposition layer and a polyamide-type mixed resin laminated film as needed.

  Next, the preferable manufacturing method for obtaining the vapor deposition polyamide type mixed resin laminated | multilayer film roll of this invention is demonstrated. The vapor-deposited polyamide-based mixed resin laminated film roll of the present invention is a longitudinal direction (longitudinal direction) and a lateral direction of an unstretched film (unstretched laminated film) obtained by melt-extruding a raw material polyamide resin chip and a thermoplastic elastomer chip. It is produced by depositing an inorganic substance on the surface of the biaxially stretched film after being biaxially stretched in the method (width direction) and then wound up into a roll.

  The polyamide-based mixed resin laminated film may have a configuration of A / B (two types and two layers), A / B / A (two types and three layers), or A / B / C (three types and three layers). is necessary. From the viewpoint of curling, an A / B / A configuration that is a symmetrical layer configuration is preferable. In the following description, among the layers constituting the laminated film, the central layer not located on the outermost side (that is, the B layer in the case of the A / B / A or A / B / C layer configuration) A thick layer (that is, a B layer in the case of an A / B layer configuration of a thin A layer and a thick B layer) in the case of a two-type two-layer configuration is referred to as a core layer. Further, the outermost layers (that is, the A and B layers in the case of the A / B layer structure, the A and C layers in the case of the A / B / A or A / B / C layer structure), and two A thin layer (that is, an A layer in the case of an A / B layer configuration of a thin A layer and a thick B layer) in the case of the seed two-layer configuration is referred to as a skin layer.

  The thickness ratio of each layer of the polyamide-based mixed resin laminated film is preferably 5 to 50% of the A layer or the A layer and the C layer, more preferably 10 to 20%, particularly preferably 12 to 18%. It is. In the case of the A / B / A configuration of two types and three layers, the thickness ratio of the A layer of the surface layer described above means the sum of the thickness ratios of both surface layers, and in the case of the A / B / C configuration of the three types and three layers Means the sum of the thickness ratios of the two surface layers. If the thickness ratio of the A layer, or the A layer and the C layer is less than 5%, the variation rate of the turbidity due to the thickness unevenness becomes large, which is not preferable. On the other hand, if the thickness ratio of the A layer or the A layer and the C layer exceeds 30%, the bending fatigue resistance deteriorates, the number of pinholes increases, and the transparency deteriorates, which is not preferable.

  In order to manufacture the laminated film as described above, a substantially unoriented polyamide-based mixed resin sheet having a layer configuration of A / B, A / B / A, or A / B / C is manufactured. In forming a film, the polymer constituting each layer is melted using a separate extruder, co-extruded, cast onto a rotating drum from a die, and rapidly cooled and solidified to solidify substantially unoriented polyamide mixed resin sheet. A method (so-called coextrusion method) for obtaining the above can be suitably employed.

  As a result of examining the thickness variation in the vertical direction of the film roll (thickness variation over the entire length of the film roll) and variation in physical properties such as boiling water shrinkage rate and variations, the present inventors have found that the thickness variation in the vertical direction and the variation in physical properties. It has been found that variations and variations are largely influenced by various factors in the casting process in which a molten resin is converted into an unstretched film. That is, if the temperature of the resin when supplying to a funnel-shaped popper directly connected to each extruder (hereinafter simply referred to as a hopper) is low or the moisture content of the resin supplied to the hopper is high, the longitudinal direction of the unstretched film It was found that the thickness unevenness increased and the physical property variation and variation in the biaxially stretched film increased. In addition, when the resin extruded from the T die is wound around a metal roll, even if the contact point between the resin and the metal roll is disturbed, the thickness unevenness in the longitudinal direction in the unstretched film becomes large, and the physical properties in the biaxially stretched film It was found that the fluctuation and variation of Furthermore, it was also found that if the stretching conditions in the biaxial stretching process are inappropriate, the thickness unevenness in the longitudinal direction of the unstretched film is amplified, which promotes fluctuations and variations in physical properties.

Furthermore, as a result of intensive studies based on the above-mentioned facts, the present inventors have taken the following measures to produce a film roll, which has little fluctuation in physical properties and maintains good slipperiness even under high humidity. I found out that I could get
(1) Uniform shape of polyamide resin chip and elastomer chip (2) Reduction of moisture content when resin chip is dried (3) Temperature retention when resin is supplied to hopper (4) Optimization of hopper shape (5) Resin Addition of segregation inhibitor during mixing (6) Removal of adverse effects due to addition of segregation inhibitor (7) Optimization of stretching conditions (8) Use of high-concentration raw material chips (9) Adjustment of properties of inorganic particles (10) Film Adjustment of Laminate Mode Hereinafter, each of the above-described means will be sequentially described.

(1) Unification of the shape of polyamide resin chip and elastomer chip In the production of a polyamide-based mixed resin laminated film roll before vapor deposition, the raw material polyamide resin chip and elastomer chip are blended in a hopper, and then a plurality of extrusions are performed. It is melt-kneaded in a machine (extruder for forming each layer of the laminated film) and melt-extruded to form a film (so-called blend method). That is, the polyamide-based resin chip and the elastomer chip are supplied continuously or intermittently in separate hoppers, and finally passed through a buffer hopper as needed, and finally, a hopper immediately before or immediately above each extruder (hereinafter referred to as a hopper) , Referred to as “final hopper”), while mixing the polyamide resin chip and the elastomer chip, the raw material chips are quantitatively supplied to the extruder according to the extrusion amount to form a film.

  However, depending on the capacity or shape of the final hopper, when the amount of chips in the final hopper is large and when the remaining amount of chips in the final hopper is small, the material segregation phenomenon, that is, from the final hopper to each extruder. A phenomenon occurs in which the composition of the supplied chips is different. Further, such segregation phenomenon appears particularly prominent when the shape or specific gravity of the chip is different. Furthermore, due to such segregation phenomenon, when a long film is produced, the tensile elastic modulus, pinhole resistance, maximum boiling water shrinkage rate, boiling water shrinkage direction difference, film thickness, and refractive index in the thickness direction vary.

  That is, if there is a difference between the size of the polyamide resin chip and the size of the elastomer chip, when the mixture of chips falls in the final hopper, small chips tend to fall first, so that the chip residue in the final hopper remains. As the amount decreases, the ratio of large chips increases, which causes raw material segregation. Therefore, in order to obtain a film roll with little variation in physical properties, it is necessary to match the shapes of the polyamide resin chip and the elastomer chip to suppress the phenomenon of raw material segregation in the final hopper.

  Polyamide raw material chips are usually formed in a molten state after polymerization in the form of strands from a polymerization apparatus, immediately cooled with water, and then cut with a strand cutter. For this reason, the polyamide chip has an elliptical column shape with an elliptical cross section. On the other hand, elastomer raw material chips are often formed in a disk shape having an elliptical cross section, and as a result of examining the relationship between the shape of polyamide chips and elastomer chips and raw material segregation, The average major axis (mm), average minor axis (mm), and average chip length (mm) are the average major axis (mm), average minor axis (mm), and average chip length of the cross-sectional ellipse of the polyamide resin raw material chip, respectively. The raw material segregation can be reduced by adjusting the thickness (mm) within a range of ± 25%. The average major axis, average minor axis, and average chip length of the cross-sectional ellipse of the elastomer chip are within ± 20% of the average major axis, average minor axis, and average chip length of the cross-sectional ellipse of the polyamide resin chip, respectively. Adjusting to the range is more preferable because the effect of preventing segregation becomes extremely remarkable.

(2) Moisture reduction at the time of resin chip drying The chip | tip supplied into each hopper is normally heated by apparatuses, such as a blender, and a water | moisture content is reduced. When drying such a chip, in the production of a polyester film roll or a polypropylene film roll, it is generally considered that the lower the moisture content during drying, the less hydrolysis in the extrusion process and the better the film roll is obtained. ing. However, as a result of studies by the present inventors, in the production of a polyamide-based mixed resin laminated film roll, it is difficult to stretch simply by reducing the moisture content at the time of drying, and a film roll having uniform physical properties can be obtained. It is not possible to obtain a film roll with uniform physical properties by controlling the moisture content within a predetermined range and securing a certain amount of moisture, so that it is appropriately plasticized without being hydrolyzed in the extrusion process. found. That is, in order to obtain a film roll having highly uniform physical properties, it is necessary to control the moisture content of the polyamide resin chip and the thermoplastic elastomer chip to 800 ppm or more and 1000 ppm or less. When the moisture content of the chip exceeds 1000 ppm, hydrolysis is promoted when it is melted, the viscosity is lowered, the thickness unevenness in the longitudinal direction of the unstretched film is deteriorated, and the thickness unevenness in the longitudinal direction of the biaxially stretched film is deteriorated. Increase, fluctuations in physical properties and variations. On the contrary, if the moisture content of the chip is less than 800 ppm, the viscosity when melted becomes too high, and the film-forming property (easy to stretch) deteriorates. In addition, the optimal moisture content of the chip | tip supplied into a hopper is 850 ppm or more and 950 ppm or less.

(3) Temperature maintenance at the time of resin supply to each hopper As described above, even when the moisture content of the chip is adjusted to 800 ppm or more and 1000 ppm or less, the chip after heating and drying is left to stand at room temperature (room temperature). When the film is supplied to each hopper after lowering the thickness, a film roll having uniform physical properties cannot be obtained. That is, in order to obtain a film roll having highly uniform physical properties, it is necessary to supply chips that have been heat-dried by a blender or the like to each hopper that communicates with each extruder while maintaining a high temperature. Specifically, the chips heated and dried by the blender need to be supplied to each hopper while being maintained at 80 ° C. or higher, and more preferably supplied to each hopper while being maintained at 90 ° C. or higher. When the temperature of the chip supplied to each hopper is lower than 80 ° C., the resin bite becomes worse, causing vertical thickness variation, physical property fluctuations and variations, and the film roll of the present invention cannot be obtained. In addition, when drying a chip | tip with apparatuses, such as a blender, it is necessary to adjust drying temperature to 150 degrees C or less. If the drying temperature exceeds 150 ° C., hydrolysis may occur during drying, which is not preferable. In addition, when the temperature of the chip heat-dried by the blender falls below 80 ° C., it is necessary to reheat the chip to 80 ° C. or higher and supply it to the hopper.

(4) Optimization of hopper shape By using a funnel-shaped hopper as the final hopper communicated with each extruder and making the inclination angle 65 ° or more, large chips can be easily dropped as well as small chips. Since the upper end of the contents descends while maintaining a horizontal plane, it is effective in reducing raw material segregation. A more preferable inclination angle is 70 ° or more, and a more preferable inclination angle is 75 ° or more. The inclination angle of the hopper is an angle between the funnel-shaped hypotenuse and the horizontal line segment. A plurality of hoppers may be used upstream of the final hopper. In this case, in any hopper, the inclination angle needs to be 65 ° or more, more preferably 70 ° or more, and further preferably 75 °. That's it.

  It is also preferable to reduce the ratio of the fine powder generated due to the cutting of the raw material chips used in order to suppress fluctuations in the boiling water shrinkage rate. Since the fine powder promotes the occurrence of raw material segregation, it is preferable to remove the fine powder generated in the process and reduce the ratio of the fine powder contained in each hopper. The ratio of the fine powder contained is preferably within 1% by weight and more preferably within 0.5% by weight throughout the entire process until the raw material chips enter the extruder. As a specific method for reducing the fine powder ratio, the fine powder is removed by passing a sieve at the time of chip formation with a strand cutter or by passing a cyclone air filter when the raw material chips are air-fed. The method of doing can be mentioned.

(5) Addition of anti-segregation agent during resin mixing Furthermore, as a means of reducing raw material segregation in each hopper, a sublimation anti-segregation agent is added in the mixing of polyamide resin and elastomer in each hopper. It is also preferable to do. As such a sublimation segregation preventing agent, a low boiling glycol can be used, and among them, polyoxyethylene / polyoxypropylene glycol can be suitably used. The amount of the sublimation segregation inhibitor added to the polyamide resin raw material chip and the elastomer raw material chip is in the range of 0.02% to 2.00% with respect to the total weight of the polyamide resin and the elastomer. It is preferable to do this. If it is less than 0.02%, it is not preferable because a sufficient segregation preventing effect cannot be obtained. On the other hand, if it is 2.00% or more, there is a possibility that it cannot be completely sublimated.

  In addition, as a means for reducing the raw material segregation in each hopper, it is also a preferable means to optimize the capacity of the hopper used. Here, the proper capacity of each hopper is in the range of 15 to 120% by weight with respect to the discharge amount per hour of the extruder, and 20 to 100 weight with respect to the discharge amount per hour of the extruder. % Is more preferable.

  In addition, as a method of mixing the raw material chip of polyamide resin and the raw material chip of elastomer, it is also possible to supply to the final hopper and each extruder through an intermediate hopper (buffer hopper) for mixing.

  In addition, when mixing multiple types of raw materials, each as polyamide-based resin and elastomer, mixing is performed while quantitatively supplying multiple types of raw materials into each hopper from a device that continuously supplies quantitative raw material chips. Or a method of mixing in advance using a blender or paddle dryer, etc., but when using the latter, the raw material chip size is set so that the raw material segregation does not occur when the mixture is discharged. Is preferably reduced.

(6) Elimination of adverse effects due to addition of segregation inhibitor (suction when molten resin contacts metal roll)
When an unstretched film is obtained by melt-extrusion of the chip, the film is formed by melting the chips at a temperature of 200 to 300 ° C. with each extruder using a coextrusion method, laminating them, and extruding them from a T die. After forming (i.e., casting) into a laminated sheet form, it is rapidly cooled by a method of winding around a cooling roll such as a metal roll cooled to a predetermined temperature. In addition, the preferable melt extrusion temperature is 240 degreeC-290 degree | times from a viewpoint of the thickness variation of a vertical direction, the fluctuation | variation of physical properties, and dispersion | variation. In order to obtain a film roll with highly uniform physical properties, the air gap (that is, the vertical distance from the exit of the T die lip to the chill roll surface) is adjusted to 20 to 60 mm when the molten resin is wound around a metal roll. In addition, using a suction device such as a vacuum box (vacuum chamber) having a wide suction port, the contact portion between the molten resin and the surface of the cooling roll is opposite to the winding direction over the entire width of the molten resin. It is preferable that the molten resin is forcibly adhered to the metal roll by suction in the direction.

  And in that case, in order to prevent the situation where the sublimation segregation preventing agent described above impedes the adhesion of the molten resin to the cooling roll, the suction air velocity at the suction port is set to 2.0 to 7.0 m / sec. Need to be adjusted to 2.5 to 5.5 m / sec. It is more preferable to adjust to. Furthermore, the vacuum box may have a series of suction ports, but the suction ports are divided into a predetermined number of sections in the lateral direction in order to facilitate adjustment of the suction air velocity at the suction ports. It is preferable that the suction air speed can be adjusted for each section. Further, when the casting speed is increased, an accompanying flow is generated with the rotation of the metal roll, and the adhesion of the molten resin to the metal roll is hindered. In order to improve the degree of adhesion of the metal roll to the metal roll, a wide shield plate made of a soft material such as Teflon (registered trademark) is installed on the upstream side adjacent to the suction device (the metal roll rotates relative to the suction device). It is preferable to install on the side opposite to the direction) to block the accompanying flow. Furthermore, in order to obtain a film roll having highly uniform physical properties, it is necessary to suppress the variation in the suction air speed of the vacuum box within ± 20% of the average suction air speed (set value), and within ± 10%. And more preferred. In addition, it is preferable to adjust the suction force by providing a filter in the vacuum box and feeding back the differential pressure before and after the filter so that the suction wind speed of the vacuum box does not fluctuate due to oligomer dust or the like.

  In order to obtain a film roll having highly uniform physical properties, when a molten resin is wound around a cooling roll, a negative DC charge of 90 to 105 mA is applied to the molten resin sheet at 2 to 15 kv from a needle electrode. Thus, it is necessary to continuously and rapidly cool the metal roll while glow discharge. In this case, it is preferable to adjust the DC negative charge to be applied in the range of 7 to 14 kv because vertical thickness variation, physical property fluctuations and variations are reduced. In addition, in order to obtain a film roll having highly uniform physical properties, it is necessary to suppress the variation of the applied DC negative charge within an average negative charge (set value) of ± 20%, and within ± 10%. And more preferred.

(7) Optimization of stretching conditions As a method of biaxially stretching an unstretched film, the unstretched film is stretched in the longitudinal direction with a roll-type stretching machine and stretched in the transverse direction with a tenter-type stretching machine, followed by heat setting treatment and relaxation. It is necessary to employ a longitudinal / lateral stretching method for performing the treatment. Furthermore, in order to obtain a film roll having highly uniform physical properties, it is necessary to employ a so-called longitudinal-longitudinal-lateral stretching method as a biaxial stretching method. The longitudinal-longitudinal-lateral stretching method means that, in longitudinal stretching of a substantially unoriented polyamide film, the first-stage stretching is performed, and the second-stage stretching is continuously performed without cooling to Tg or less. Thereafter, it is a method of transverse stretching at a magnification of 3.0 times or more, preferably 3.5 times or more, and further heat setting. In order to obtain a film roll having highly uniform physical properties, it is necessary to make the first-stage longitudinal stretch ratio higher than the second-stage longitudinal stretch ratio when performing the longitudinal-longitudinal-lateral stretching described above. is there. That is, by making the first stage longitudinal draw ratio higher than the second stage longitudinal draw ratio, it is possible to obtain a film roll with good physical properties such as boiling water shrinkage and few variations in those physical properties. It becomes. In addition, when performing longitudinal-longitudinal-lateral stretching, it is usually easier to make the first-stage longitudinal stretching ratio lower than the second-stage longitudinal stretching ratio without causing sticking to the roll during the first-stage stretching. However, by using a special roll such as a Teflon (registered trademark) roll, even if the longitudinal stretch ratio of the first stage is higher than the longitudinal stretch ratio of the second stage, it causes sticking to the roll. It becomes possible to stretch easily.

  When performing longitudinal-longitudinal-lateral stretching as described above, the first-stage longitudinal stretching is preferably stretched about 2.0 to 2.4 times at a temperature of 80 to 90 ° C. When the draw ratio at the first stage is out of the above range and becomes high, the thickness unevenness in the vertical direction becomes large, which is not preferable. In addition, the longitudinal stretching in the second stage is preferably stretched about 1.3 to 1.7 times at a temperature of 65 to 75 ° C. If the draw ratio of the second stage falls outside the above range, it becomes unfavorable because the boil distortion increases and becomes unpractical.On the other hand, if the draw ratio of the second stage goes out of the above range, it becomes high. The strength in the direction (such as strength at 5% elongation) becomes low and becomes unpractical.

  Moreover, when performing longitudinal-longitudinal-lateral stretching as described above, hot roll stretching, infrared radiation stretching, or the like can be employed as the longitudinal stretching method. In addition, when a film roll is produced by such a longitudinal-longitudinal-lateral stretching method, not only the thickness unevenness in the vertical direction, fluctuations in physical properties and variations are reduced, but also variations in physical properties and variations in the horizontal direction are reduced. be able to. In the case of longitudinal-longitudinal-lateral stretching, the total longitudinal stretching condition is preferably 3.0 to 4.5 times.

  Moreover, when performing longitudinal-longitudinal-lateral stretching, it is preferable to stretch the lateral stretching at a temperature of 120 to 140 ° C. by about 4.0 to 5.5 times. If the transverse stretching ratio falls outside the above range, the transverse strength (5% elongation strength, etc.) becomes low and impractical, which is not preferable. Conversely, the transverse stretching ratio falls within the above range. If the deviation is high, the thermal contraction rate in the lateral direction is increased, which is not preferable. On the other hand, if the transverse stretching temperature falls outside the above range, it becomes unpreferable because the boil distortion becomes large and becomes impractical, and conversely, if the transverse stretching temperature rises outside the above range, It is not preferable because the strength (strength at 5% elongation, etc.) decreases and becomes impractical.

  Furthermore, in order to obtain a film roll having highly uniform physical properties, it is preferable to perform the heat setting treatment after longitudinal-longitudinal-lateral stretching at a temperature of 180 to 230 ° C. If the temperature of the heat setting treatment falls outside the above range, the heat shrinkage rate in the longitudinal direction and the transverse direction increases, which is not preferable. On the contrary, if the temperature of the heat setting treatment rises outside the above range, biaxial stretching Since the impact strength of a film becomes low, it is not preferable.

  In addition, in order to obtain a film roll having highly uniform physical properties, it is preferable to relax the relaxation treatment after heat setting by 2 to 10%. If the rate of relaxation treatment falls outside the above range, the thermal contraction rate in the longitudinal direction and the transverse direction increases, which is not preferable. Conversely, if the rate of relaxation treatment falls outside the above range, the longitudinal direction and the width direction The strength (such as strength at 5% elongation) becomes low and becomes unpractical.

  Further, the width of the film roll before and after vapor deposition is not particularly limited, but from the viewpoint of ease of handling, the lower limit of the width of the film roll is preferably 0.35 m or more, and is 0.50 m or more. And more preferred. On the other hand, the upper limit of the width of the film roll is preferably 2.5 m or less, more preferably 2.0 m or less, and further preferably 1.5 m or less. In addition, the winding length of the film roll is not particularly limited, but the lower limit of the winding length of the film roll is preferably 500 m or more and more preferably 1,000 m or more from the viewpoint of ease of winding and handling. . On the other hand, the upper limit of the roll length of the film roll is preferably 2,5000 m or less, more preferably 20,000 m or less, and further preferably 15,000 m or less. In addition, when a film thickness is about 15 micrometers, it is especially preferable in it being 12000 m or less. In addition, as the winding core, usually, paper of 3 inches, 6 inches, 8 inches, etc., a plastic core or a metal core can be used.

  On the other hand, although the thickness of the film which comprises the film roll of this invention is not specifically limited, For example, as a polyamide-type film for packaging, 8-50 micrometers is preferable and 10-30 micrometers is more preferable.

  In addition, the polyamide-based mixed resin laminated film constituting the film roll before vapor deposition has a lubricant, an anti-blocking agent, a thermal stabilizer, an antioxidant, an anti-static agent, a light-proofing agent, a light-proofing agent, as long as the properties are not impaired. It is also possible to contain various additives such as impact modifiers. In particular, it is preferable to contain various inorganic particles for the purpose of improving the slipperiness of the biaxially stretched film. Moreover, it is preferable to add an organic lubricant such as ethylenebisstearic acid that exhibits the effect of reducing the surface energy because the slipping property of the film constituting the film roll becomes excellent.

  Furthermore, the polyamide-based mixed resin laminated film constituting the film roll before vapor deposition can be subjected to heat treatment or humidity control treatment in order to improve dimensional stability depending on the application. In addition, in order to improve the adhesion of the film surface, corona treatment, coating treatment, flame treatment, etc., and processing such as printing, vapor deposition and the like can be performed.

(8) Use of high-concentration raw material chip As described above, in order to improve the slipperiness of the biaxially oriented film under high humidity, various inorganic particles are contained in the polyamide-based resin, and the surface roughness of the film is increased. It is preferable to adjust, but in that case, good slipperiness under high humidity can be expressed by adding inorganic particles by a specific addition method. That is, when adding inorganic particles to a polyamide-based resin, a master batch in which high-concentration inorganic particles are added in advance to a polyamide-based resin, rather than adding powdered inorganic particles into an extruder and kneading. It is preferable to employ a method in which a polymer chip is prepared and the master chip (high-concentration raw material chip) is blended and diluted with a polyamide-based resin not containing inorganic particles. By adopting such means, the dispersibility of the inorganic particles is improved by rubbing the inorganic particles in the melt line, and as a result, it is considered to have a positive effect on the slipperiness under high humidity. .

  Moreover, when manufacturing a high concentration raw material chip | tip, it is preferable that the addition amount of the inorganic particle in a polyamide-type resin shall be 5-20 weight%, and it is more preferable to set it as 10-15 weight%. When the added amount of the inorganic particles exceeds 20% by weight, the dispersibility of the inorganic particles is lowered, and foreign matter may be formed in the film, which is not preferable. On the other hand, if the amount of inorganic particles added exceeds 5% by weight, it is not preferable because economic efficiency deteriorates. In addition, when preparing such a high-concentration raw material chip, the polyamide resin is previously powdered by a method such as pulverization in a cooled state, and then kneaded with inorganic particles, whereby the inorganic particle resin The dispersibility to the inside is improved, which is preferable.

(9) Adjustment of properties of inorganic particles When inorganic particles are added to the polyamide-based resin, the properties of the inorganic particles to be added to the polyamide resin constituting the skin layer are specified, so that the properties can be increased under high humidity. It is possible to exhibit good slipperiness. That is, as the inorganic particles to be added, those having an average particle size (that is, average particle size) of 0.5 to 5.0 μm are preferable, and silica particles are particularly preferable. If the average particle size is less than 0.5 μm, good slipperiness will not be obtained. Conversely, if the average particle size is more than 5.0 μm, transparency will be poor or so-called “missing” will occur during printing. This is not preferable. In addition, the measurement of the average particle diameter can employ a method of calculating the weight average diameter from the particle size distribution obtained by a Coulter counter, and can be measured from the particles before being added to the polyamide resin. It is also possible to measure from particles precipitated by dissolving the system mixed resin laminated film with an acid. The inorganic particles preferably have a pore volume of 0.5 to 2.0 ml / g, and more preferably 0.8 to 1.5 ml / g. When the pore volume is less than 0.5 ml / g, the transparency of the film deteriorates, which is not preferable. When the pore volume exceeds 2.0 ml / g, the slipperiness of the film deteriorates, which is not preferable. In addition, not only adding inorganic particles to the polyamide resin constituting the skin layer, but also adding a small amount of 0.001 to 0.005% by weight inorganic particles to the polyamide resin constituting the core layer, It is preferable because the slipperiness under humidity is significantly improved, and it is more preferable to add 0.002 to 0.004% by weight of inorganic particles. Moreover, it is preferable to make the particle diameter of the inorganic particles added to the core layer larger than the thickness of the skin layer because the slipping property under high humidity becomes more stable. The reason why the slipperiness under high humidity is stabilized is not clear, but the undulation action of the film surface by the inorganic particles in the core layer has a positive effect on the slipperiness under high humidity. I believe that.

(10) Adjustment of film lamination mode As described above, inorganic particles are added to the polyamide-based resin, and unevenness is formed on the surface of the film. In addition, by adjusting the lamination mode of the film, it is possible to exhibit good slipperiness even under high humidity. That is, in the production of the film roll of the present invention, a laminated film (laminated sheet) having a plurality of layer structures is formed by melt extrusion from a plurality of extruders using the coextrusion method as described above. However, at this time, it is preferable to adjust the discharge amount of the resin to be melt-extruded as a skin layer so that the final thickness of the skin layer after stretching is 0.5 to 4.0 μm. It is more preferable to adjust to 0.0 μm.

  In addition, at the time of formation of an unstretched laminated film, by using the means (1) to (5) and (7) to (10) described above, by using the means (6) in the stretching process of the unstretched laminated film, It becomes possible to reduce the uneven thickness of each layer constituting the laminated film, and consequently reduce the uneven thickness of the entire laminated film. And it is thought that it becomes possible to reduce the physical property fluctuation | variation of a film roll very efficiently resulting from that. In addition, any one of the above-described means (1) to (10) does not effectively contribute to the reduction of the physical property fluctuation of the film roll, and the means (1) to (10) are combined. Therefore, it is considered that the change in physical properties of the film roll can be reduced very efficiently.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the embodiments of the examples, and can be appropriately changed without departing from the spirit of the present invention. . Tables 1 to 4 show the properties of the raw material chips A to I used in the examples and comparative examples, the compositions of the raw material chips A to I, and the film roll film formation conditions in the examples and comparative examples, respectively. The chip A is composed of 99.85% by weight of nylon 6 (relative viscosity = 2.8, Tg = 41 ° C.) and 0.15% by weight of ethylene bis stearic acid amide. Also, nylon 6 (same physical properties as chip A) is 85.00% by weight, 15.0% by weight of silica particles having an average particle diameter of 2.0 μm and a pore volume of 0.8 ml / g. In addition, the shapes of the chips A to C are all elliptic cylinders, and the chips A and B have the same cross-sectional major axis, cross-sectional minor axis, and chip length. Chips D and I are made of a copolymer of nylon 12 and PTMG (polytetramethylene glycol) (relative viscosity = 2.0), and chip E is made of nylon 6 and PEG (polyethylene glycol). The chip F is made of an ethylene / methacrylic acid copolymer (MFR (Melt Flow Rate) at 190 ° C. = 2.4 g / 10 minutes). Chip G is made of an ethylene / butene copolymer (MFR = 2.0 g / 10 minutes), and Chip H is made of an ethylene ionomer (MFR = 2.4 g / 10 minutes). is there. In addition, the shapes of the chips D to I are all elliptic cylinders, and the chips D to H have the same cross sectional major axis, sectional minor axis, and chip length.

[Example 1]
Using a co-extrusion method, a polyamide-based mixed resin is melt-extruded (laminated in a die and extruded) from three extruders (first to third extruders), and turned to a rotating metal roll cooled to 17 ° C. By winding and quenching, an unstretched film (polyamide-based resin laminated sheet) having a thickness of 257 μm and a two-layer / three-layer structure was obtained. The method for forming each layer of the unstretched film (steps until melt extrusion) is as follows. In the following description, the first layer, the second layer, and the third layer are referred to in order from the surface layer of the polyamide-based mixed resin laminated sheet (that is, the surface of the third layer is a metal roll contact surface).

-Formation of first layer (outer layer) The chips A, B and D described above were separately dried using a 15 kl blender apparatus while heating to about 120 ° C for about 8.0 hours. When a predetermined amount of each chip was collected from the blender and the moisture content was measured, the moisture content of chips A, B, and D were all 800 ppm. The moisture content was measured using a Karl Fischer moisture meter (MKC-210 manufactured by KYOTO Electronics) under the conditions of a sample weight of 1 g and a sample heating temperature of 230 ° C.

  And each chip | tip in each blender after preliminary drying was continuously supplied separately into the mixing mixer with the fixed screw feeder. The supply amount of chip A was 96.5% by weight, the supply amount of chip B was 0.5% by weight, and the supply amount of chip D was 3.0% by weight. In addition, polyoxyethylene / polyoxypropylene glycol (Newpol PE-64 manufactured by Sanyo Chemical Co., Ltd.) is used as the sublimation segregation preventing agent in the hopper to which the chips A and B are supplied. It added so that it might become 1000 ppm with respect to the total weight of.

  Thereafter, the mixed raw materials of chips A, B, and D mixed in the mixing mixer as described above were continuously and separately supplied to the hopper immediately above the extruder (first extruder) with a quantitative screw feeder. The hopper had a capacity of 150 kg of raw material chips. The inclination angle of the hopper was adjusted to 70 °.

  Further, when the chips A, B, and D were supplied into the hopper via the mixing mixer, they were supplied to the hopper within a short time after drying so that the temperature of each chip would not be too low. The temperatures of chips A, B, and D immediately before being supplied to the hopper were all about 91 ° C. Then, the supplied chips A, B, and D (mixed ones) were melt-extruded from a T die at 270 ° C. by a single-screw first extruder.

-Formation of second layer (intermediate layer) Chips A, B, and D in each blender dried as described above were continuously and separately fed into the mixing mixer with a quantitative screw feeder. The supply amount of chip A was 96.97% by weight, the supply amount of chip B was 0.03% by weight, and the supply amount of chip D was 3.0% by weight. In addition, polyoxyethylene / polyoxypropylene glycol (Newpol PE-64 manufactured by Sanyo Chemical Co., Ltd.) is used as the sublimation segregation preventing agent in the hopper to which the chips A and B are supplied. It added so that it might become 1000 ppm with respect to the total weight of.

  Thereafter, the mixed raw materials of chips A, B, and D mixed in the mixing mixer as described above were continuously and separately supplied to the hopper immediately above the extruder (second extruder) with a quantitative screw feeder. The hopper had a capacity of 150 kg of raw material chips. The inclination angle of the hopper was adjusted to 70 °.

  Further, when the chips A, B, and D were supplied into the hopper via the mixing mixer, they were supplied to the hopper within a short time after drying so that the temperature of each chip would not be too low. The temperatures of chips A, B, and D immediately before being supplied to the hopper were all about 91 ° C. Then, the supplied chips A, B, and D (mixed ones) were melt-extruded from a T die at 270 ° C. by a single-screw second extruder.

-Formation of third layer (inner layer) Chips A, B, and D in each blender dried as described above were continuously and separately fed into the mixing mixer with a quantitative screw feeder. The supply amount of chip A was 96.5% by weight, the supply amount of chip B was 0.5% by weight, and the supply amount of chip D was 3.0% by weight. In addition, polyoxyethylene / polyoxypropylene glycol (Newpol PE-64 manufactured by Sanyo Chemical Co., Ltd.) is used as the sublimation segregation preventing agent in the hopper to which the chips A and B are supplied. It added so that it might become 1000 ppm with respect to the total weight of.

  Thereafter, the mixed raw materials of chips A, B, and D mixed in the mixing mixer as described above were continuously and separately supplied to the hopper immediately above the extruder (third extruder) with a quantitative screw feeder. The hopper had a capacity of 150 kg of raw material chips. The inclination angle of the hopper was adjusted to 70 °.

  Further, when the chips A, B, and D were supplied into the hopper via the mixing mixer, they were supplied to the hopper within a short time after drying so that the temperature of each chip would not be too low. The temperatures of chips A, B, and D immediately before being supplied to the hopper were all about 91 ° C. Then, the supplied chips A, B and D (mixed ones) were melt-extruded from a T die at 270 ° C. by a single-screw third extruder.

  In each extruder of Example 1, the average major axis, average minor axis, and average chip length of the thermoplastic elastomer chip (Chip D) are the average major axis and average of each polyamide-based resin chip (Chips A and B). Each of the minor diameter and the average chip length is included within a range of ± 20%. Moreover, the discharge amount of the 1st-3rd extruder in formation of an unstretched film was adjusted so that the thickness ratio of 1st layer / 2nd layer / 3rd layer might be 2/11/2.

  In addition, the air gap when the molten resin is wound around the metal roll is adjusted to 40 mm, and by applying a negative DC charge of 100 mA at 11 ± 1.1 kv from the needle electrode to the molten film, glow discharge is performed. The molten resin was electrostatically adhered to a metal roll. Further, when the molten resin is wound around the metal roll, the portion where the molten resin comes into contact with the metal roll is opposite to the direction in which the resin is wound using the vacuum box over the entire width of the molten resin. By attracting in the direction, adhesion of the molten resin to the metal roll was promoted. The suction air velocity of the vacuum box is 5.0 ± 0.5 m / sec. Over the entire width of the suction port (that is, the entire width of the molten resin). It adjusted so that it might become.

  Thereafter, the obtained unstretched film was longitudinally stretched (first longitudinal stretching) about 2.1 times at a stretching temperature of about 85 ° C. by a Teflon (registered trademark) roll, and then stretched at a stretching temperature of about 70 by a ceramic roll. Longitudinal stretching (second longitudinal stretching) was performed at 1.6 ° C. at about 1.6 times. Further, the longitudinally stretched sheet is continuously led to a tenter, stretched by 4.0 times at about 130 ° C, heat-set at about 210 ° C, subjected to 5.0% lateral relaxation treatment, and then cooled. By cutting and removing both edges, a biaxially stretched film of about 15 μm was continuously formed over 2000 m to produce a mill roll. When the obtained biaxially stretched laminated film was sliced thinly in the thickness direction and observed with an electron microscope, the thicknesses of the first layer, the second layer, and the third layer were about 2 μm, about 11 μm, It was about 2 μm.

  In addition, the fluctuation range of the film surface temperature when the film is continuously produced 2000 m is the average temperature ± 0.8 ° C. in the preheating step, the average temperature ± 0.6 ° C. in the stretching step, and the average temperature ± 0.5 ° C. in the heat treatment step. It was in the range. Further, while rolling the obtained mill roll, it was slit into a width of 400 mm and a length of 1000 m, and wound around a 3 inch paper tube to obtain six polyamide mixed resin laminated film rolls (slit rolls). Thereafter, various metals or metal oxides were vapor-deposited on the obtained slit roll by the following method.

[Aluminum deposition]
On the surface of the polyamide-based mixed resin film constituting the polyamide-based mixed resin film roll obtained as described above, particulate aluminum having a size of about 8 to 10 mm (purity 99.9%) is used as a deposition source. An aluminum thin film was formed by an electron beam evaporation method. An electron gun (hereinafter referred to as an EB gun) was used as a heating source, and the emission current was set to 0.5A. The film feed rate was 130 m / min, and a film with a thickness of 50 nm was formed. Moreover, the pressure at the time of vapor deposition was adjusted to 1 × 10 ⁻² Pa. Moreover, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 degreeC.

[Aluminum oxide deposition]
As a vapor deposition source, particulate Al ₂ O _{3 having} a size of about 3 to 5 mm (purity 99.9%) was used, and the polyamide-based mixed resin film constituting the polyamide-based mixed resin film roll obtained as described above was used. An aluminum oxide thin film was formed on the surface by electron beam evaporation. An EB gun was used as the heating source, and the emission current was 1.3A. The film feed rate was 130 m / min, and a 20 nm thick film was formed. Moreover, the pressure at the time of vapor deposition was adjusted to 1 × 10 ⁻² Pa. Moreover, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 degreeC.

[Silicon oxide deposition]
As the evaporation source, the size particulate Si (99.99% purity) of about 3~5mm and using SiO ₂ (purity 99.9%), constituting the polyamide-based mixed resin film roll obtained as above A silicon oxide thin film was formed on the surface of the polyamide-based mixed resin film to be formed by electron beam evaporation. The vapor deposition material was divided into two without being mixed. An EB gun was used as a heating source, and each of Si and SiO ₂ was heated in a time-sharing manner. Each material was heated so that the emission current of the EB gun at that time was 0.8 A and the composition ratio of Si and SiO ₂ was 1: 9. The film feed rate was 130 m / min, and a 20 nm thick film was formed. Moreover, the pressure at the time of vapor deposition was adjusted to 1 × 10 ⁻² Pa. Moreover, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 degreeC.

[Composite deposition]
Using a particulate SiO ₂ (purity 99.9%) and Al ₂ O ₃ (purity 99.9%) of about 3 mm to 5 mm as a deposition source, a polyamide-based mixed resin film roll obtained as described above is constructed. A mixed thin film of aluminum oxide and silicon dioxide was formed on the surface of the polyamide-based mixed resin film by electron beam evaporation. The vapor deposition material was divided into two without being mixed. An EB gun was used as a heating source, and each of Al ₂ O ₃ and SiO ₂ was heated in a time division manner. At that time, each material was heated so that the emission current of the EB gun was 1.2 A and the composition ratio of Al ₂ O ₃ and SiO ₂ was 3: 7. The film feed rate was 130 m / min, and a 20 nm thick film was produced. Moreover, the pressure at the time of vapor deposition was adjusted to 1 × 10 ⁻² Pa. Moreover, the temperature of the roll for cooling the film at the time of vapor deposition was adjusted to -10 degreeC.

  And the characteristic was evaluated by the following method using each slit roll before vapor deposition (namely, what was obtained from the same mill roll). The following BS (boiling water shrinkage), BSx (maximum boiling water shrinkage), BSd (boiling water shrinkage direction difference), surface roughness, dynamic friction coefficient, haze, inorganic particle content, elastomer content, impact strength In the measurement of refractive index, etc., the first sample cutout part is provided within 2 m from the end of winding of the film, and the second to tenth sample cutout parts are provided about every 100 m from the first sample cutout part. An eleventh sample cutout portion was provided within 2 m from the beginning of winding, and a sample film was cut out from each of the first to eleventh sample cutout portions. Further, using a polyamide-based resin film roll after composite vapor deposition (that is, one obtained from the same mill roll), a sample film is cut out from each cutout portion by the same method as the above method, BS (boiling water shrinkage rate), BSx (maximum boiling water shrinkage), BSd (boiling water shrinkage direction difference), surface roughness, dynamic friction coefficient, haze, inorganic particle content, elastomer content, impact strength, oxygen permeability, refractive index are measured. The thickness unevenness and laminate processability were evaluated. The evaluation results are shown in Tables 5-10. When showing the evaluation results, for the impact strength and the laminate strength, the measured average values of the sample samples and the fluctuation range of the values of the sample samples were shown. For S-curl, the number of sample samples at each evaluation level and the overall evaluation level of all sample samples are shown.

[Boiling water shrinkage]
A biaxially oriented film (sample film) cut out from each cut-out portion of the slit roll was cut into a square shape with a side of 21 cm and left in an atmosphere of 23 ° C. and 65% RH for 2 hours or more. Draw a circle with a diameter of 20 cm centered on the center of the sample, draw a straight line passing through the center of the circle in the direction of 0 to 165 ° clockwise at 15 ° intervals, with the vertical direction (film drawing direction) being 0 °. The diameter in the direction was measured and taken as the length before treatment. The cut sample was then heat-treated in boiling water for 30 minutes, then removed and wiped off the moisture adhering to the surface, air-dried, and left in an atmosphere of 23 ° C. and 65% RH for 2 hours or more, as described above. The length of the straight line drawn in each diametric direction is measured and set as the length after treatment, and BS (boiling water shrinkage rate), BSx (maximum boiling water shrinkage rate), BSax (average boiling water shrinkage rate), BSd (boiling water shrinkage direction difference) and BSad (average boiling water shrinkage direction difference) were calculated.

  Then, the maximum / minimum in the maximum boiling water shrinkage (BSx) of all the samples is obtained, and the difference between the larger one of the maximum / minimum average boiling water shrinkage (BSax) and the average boiling water shrinkage And the ratio (%) of the difference to the average boiling water shrinkage (BSax) was calculated to obtain the variation rate of the maximum boiling water shrinkage (BSx) with respect to the average boiling water shrinkage (BSax). In addition, the maximum / minimum difference in boiling water shrinkage direction difference (BSd) of all samples is obtained, and the difference between the maximum / minimum average boiling water shrinkage direction difference (BSad) and the average boiling water shrinkage rate. The difference in boiling water shrinkage direction difference (BSd) with respect to the average boiling water shrinkage direction difference (BSad) is calculated by calculating the ratio (%) of the difference to the average boiling water shrinkage direction difference (BSad). The rate was determined.

[Three-dimensional surface roughness]
About the surface of the biaxially oriented film (sample film) cut out from each cut-out part of the slit roll, using a stylus type three-dimensional surface roughness meter (SE-3AK, manufactured by Kosaka Laboratory Ltd.), Under the conditions of a radius of 2 μm, a load of 30 mg, and a needle speed of 0.1 mm / s, the film was measured in the longitudinal direction with a cut-off value of 0.25 mm over a measurement length of 1 mm, and divided into 500 points at intervals of 2 μm. In the width direction of the film, it was measured over a measurement length of 0.3 mm under the same conditions as described above, and was divided into 150 points at intervals of 2 μm. The three-dimensional height of each of the obtained dividing points is analyzed using a three-dimensional roughness analyzer (manufactured by Kosaka Laboratory Ltd., TDA-21), and the three-dimensional average surface roughness (nm). )

[Dynamic friction coefficient in high humidity μd]
Using the biaxially oriented film cut out from each cut-out part of the slit roll, the dynamic friction coefficient between the outer layers was evaluated according to the following conditions in accordance with JIS-C2151.
Measurement atmosphere: 23 ° C., 80% RH
-Test piece: width 130mm, length 250mm
・ Test speed: 150mm / min

[Haze]
About each biaxially oriented film cut out from each cutout part of a slit roll, based on JISK7136, it measured using the haze meter (Nippon Denshoku Industries Co., Ltd. make, 300A). In addition, the measurement was performed twice and the average value was calculated | required.

[Content of inorganic particles]
Obtaining the weight of the residue when the biaxially oriented film cut out from each cut-out part of the slit roll is burned at 800 ° C., the ratio (percentage) of the residue weight with respect to the film weight before burning contains inorganic particles (silica) Calculated as a quantity. In the measurement of the content of the inorganic particles, the weight of the residue when the biaxially oriented film cut out from each cut-out portion is dissolved in a solvent such as sulfuric acid is obtained, and the ratio of the residue weight to the initial film weight ( It is also possible to employ a method of calculating (percentage).

[Vertical thickness unevenness]
The slit roll was slit to a width of about 3 cm over the entire length in the longitudinal direction to prepare a slit roll for thickness spot measurement. Thereafter, an average thickness, a maximum thickness, and a minimum thickness over the entire length in the longitudinal direction were determined using a thickness spot measuring device (wide range high sensitivity electronic micrometer K-313A) manufactured by Anritsu Corporation. And by calculating the difference between the average thickness and the larger one of the maximum thickness and the minimum thickness among the maximum thickness and the minimum thickness, and calculating the ratio (%) of the difference to the average thickness by the following formula 7. The variation rate of thickness over the entire length in the longitudinal direction was calculated.
Variation rate of thickness = | maximum thickness or minimum thickness−average thickness | / average thickness 7

[Refractive index]
Using an “Abbe refractometer 4T type” manufactured by Atago Co., Ltd., each sample film cut out from each sample cut-out part was left in an atmosphere of 23 ° C. and 65% RH for 2 hours or more, and then the refractive index in the thickness direction ( Nz) was measured. Also, the average average refractive index of all sample films is calculated, and as shown in Table 6, the difference between the maximum or minimum Nz and the average refractive index in all samples is calculated, and the ratio of the difference to the average refractive index is calculated. Was calculated as the rate of change.

[Impact strength]
Each sample film cut out from each cut-out part was allowed to stand in an atmosphere of 23 ° C. and 65% RH for 2 hours or more, and then a “film impact tester TSS type” manufactured by Toyo Seiki Seisakusho was used. The breaking strength was measured with a hemispherical impactor to determine the impact strength. The average impact strength of all sample films was also calculated.

[Content of elastomer component]
Each sample film cut out from each cut-out section is cut perpendicularly to the surface and perpendicular to the winding direction to produce an ultrathin section, and dyed with phosphotungstic acid and ruthenium oxide by the ultrathin piece method The sample was prepared. Thereafter, an electron micrograph (thickness direction: about 160 mm × winding direction: about 220 mm) was taken with a transmission electron microscope (JEM2010) manufactured by JEOL Ltd. at a magnification of 10,000 times. And the ratio which occupies for the whole area of the elastomer part dye | stained with phosphotungstic acid and ruthenium oxide using the image processing apparatus (analySIS) by JEOL Ltd. was computed as a content rate of an elastomer component.

[Tensile modulus]
Each sample film cut out from each cut-out part was sampled to a length of 150 mm and a width of 15 mm, and conditioned for 24 hours in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%. Then, under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, in accordance with JIS K-7127, using an autograph AG-100E type manufactured by Shimadzu Corp. The tensile modulus was calculated as the ratio of the tensile stress within the tensile proportional limit and the corresponding strain.

[Oxygen permeability]
The film cut out from each cut-out part was oxygen-substituted for 2 days in an atmosphere of humidity 65% RH and temperature 25 ° C., and then the oxygen permeability according to JIS-K-7126 (Method B). The measurement was performed using a measuring device (OX-TRAN 2/20: manufactured by MOCOM).

[Lamination workability]
Vapor water shrinkage, longitudinal thickness unevenness, refractive index, slit roll after vapor deposition that is different from the slit roll whose impact strength was measured (obtained from the same mill roll), vapor deposition constituting the slit roll After applying a urethane AC agent (“EL443” manufactured by Toyo Morton Co., Ltd.) to a biaxially oriented polyamide-based mixed resin laminated film, an LDPE having a thickness of 15 μm is then formed using a single test laminator device manufactured by Modern Machinery. (Low-density polyethylene) film is extruded at 315 ° C, and a 40 μm-thick LLDPE (linear low-density polyethylene) film is continuously laminated thereon, and a three-layer laminate composed of polyamide resin / LDPE / LLDPE A laminated film roll having a structure was obtained. Moreover, the laminated film roll was obtained by laminating the LDPE film by the method similar to the above to the vapor deposition biaxially oriented polyamide type mixed resin laminated film which comprises the slit roll using the slit roll before vapor deposition. And the workability at the time of manufacturing a laminate film roll was evaluated in the following three steps.
○: No wrinkle on the roll and condition adjustment is not required. Δ: Roll wrinkle is eliminated by condition adjustment. ×: No matter how the condition is adjusted, wrinkle is generated on the roll.

[Lamination strength]
In addition, the laminate film cut out from the laminate film roll was cut out into a width of 15 mm and a length of 200 mm as a test piece, and “Tensilon UMT-II-500 type” manufactured by Toyo Baldwin Co., Ltd. was used. The peel strength between the polyamide-based mixed resin laminated film layer and the LDPE layer was measured under conditions of a humidity of 65%. The tensile rate was 10 cm / min, the peel angle was 180 degrees, and water was added to the peeled portion for measurement. The laminate strength is measured by cutting out the first sample piece within 2 m from the end of winding of the laminate film roll, and cutting out the second to tenth sample pieces every about 100 m from the cut out portion of the first sample piece. The eleventh sample piece was cut out within 2 m from the beginning of winding of the film, and the measurement was performed on each of the first to eleventh sample pieces. Moreover, the average of those measured values was also calculated.

[Pinhole resistance]
The laminated film cut out from the laminated film roll was cut into a size of 20.3 cm (8 inches) × 27.9 cm (11 inches), and the rectangular test film (laminated film) after the cutting was cut at a temperature of 23 ° C. Condition under a condition of 50% relative humidity for 24 hours or longer. Thereafter, the rectangular test film is wound into a cylindrical shape having a length of 20.32 cm (8 inches). Then, one end of the cylindrical film is fixed to the outer periphery of a disk-shaped fixing head of a gel bow flex tester (manufactured by Rigaku Kogyo Co., Ltd., NO.901 type) (conforming to the standard of MIL-B-131C). The other end of the tester is fixed to the outer periphery of a disc-shaped movable head of a tester facing the fixed head with a distance of 17.8 cm (7 inches). Then, the movable head is rotated 440 ° while approaching the fixed head in the direction of 7.6 cm (3.5 inches) along the axis of both heads opposed in parallel, and then 6.4 cm (without rotation) 2.5-inch) A one-cycle bending test in which the movement is performed in the reverse direction and the movable head is returned to the initial position is performed continuously for 3000 cycles at a rate of 40 cycles per minute. repeat. After that, the number of pinholes generated in the portion within 17.8 cm (7 inches) × 27.9 cm (11 inches) excluding the portion fixed to the outer periphery of the fixed head and movable head of the tested film is measured (ie, The number of pinholes per 497 cm ² (77 square inches) is measured).

[S-curl phenomenon]
The laminate film wound up as a laminate film roll as described above is folded into two parallel to the winding length direction using a test sealer manufactured by Seibu Machinery Co. Then, 10 mm in the vertical direction was intermittently heat-sealed at intervals of 150 mm to obtain a semi-finished product having a width of 200 mm. This was cut in the winding length direction and both edges were cut so that the seal portion was 10 mm, and then cut at the boundary of the seal portion in the direction perpendicular to this to produce a three-side seal bag (seal width: 10 mm). . From these three-sided sealing bags, a three-sided sealing bag made from a portion within 2 m from the end of winding of the laminate film roll is selected as the first sample, and about 100, 200, ... 800, 900 m three-way seal bags made from parts separated from each other are selected as the second to tenth samples, respectively, and 3 made from parts within 2 m from the start of the lamination film roll. A side seal bag was selected as the 11th sample. And after heat-treating those 11 three-way seal bags in boiling water for 30 minutes, hold them in an atmosphere of 23 ° C. and 65% RH all day and night. A load of 1 kg was applied to the entire surface of the bag, and the bag was removed after being held for a whole day and night, and the degree of bag curl (S-curl) was evaluated as follows.
◎: No warping at all. ○: Slight warping is observed. X: Warping is clearly observed. XX: Warping is remarkable.

[Example 2]
In forming the first layer and the third layer, when the chips A, B, and D in each blender are supplied to the hopper immediately above the first extruder and the third extruder through the mixing mixer, The supply amount is 96.0% by weight, the supply amount of the chip B is 1.0% by weight, the supply amount of the chip D is 3.0% by weight, and the chips in each blender are formed in the formation of the second layer. When A, B, and D are supplied to the hopper immediately above the second extruder via the mixing mixer, the supply amount of chip A is 96.94% by weight, and the supply amount of chip B is 0.06% by weight. And the supply amount of the chip D was set to 3.0% by weight. Other than that was carried out similarly to Example 1, and obtained the polyamide-type mixed resin laminated | multilayer film roll. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Example 3]
When the raw material is melt-extruded from the first to third extruders to form an unstretched laminated sheet, the first layer / second layer / third layer has a thickness ratio of 1/13/1. A polyamide-based mixed resin laminated film roll was obtained in the same manner as in Example 1 except that the discharge amount of the third extruder was adjusted. When the obtained biaxially stretched laminated film was sliced thinly in the thickness direction and observed with an electron microscope, the thicknesses of the first layer, the second layer, and the third layer were about 1 μm, about 13 μm, It was about 1 μm. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Example 4]
An unstretched film obtained in the same manner as in Example 1 was longitudinally stretched (first longitudinal stretching) about 2.2 times at a stretching temperature of about 90 ° C. by a Teflon (registered trademark) roll, and then by a ceramic roll. The film was stretched longitudinally (second longitudinal stretching) about 1.5 times at a stretching temperature of about 70 ° C. Further, similarly to Example 1, the longitudinally stretched sheet was continuously led to a stenter, transversely stretched 4.0 times at about 130 ° C., and heat-set at about 210 ° C. to be 5.0% transverse After the relaxation treatment, the film was cooled and both edges were cut and removed to continuously form a biaxially stretched film of about 15 μm over 2000 m. The fluctuation range of the film surface temperature when the film was continuously produced was the same as in Example 1. The obtained film was slit and wound in the same manner as in Example 1 to obtain a polyamide-based mixed resin laminated film roll. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Example 5]
The unstretched film obtained in the same manner as in Example 1 was longitudinally stretched in two stages in the same manner as in Example 1. After that, the longitudinally stretched sheet is continuously guided to a stenter, transversely stretched 3.6 times at about 130 ° C., heat fixed at about 215 ° C. and subjected to 3.0% lateral relaxation treatment. By cooling and cutting and removing both edges, a biaxially stretched film of about 15 μm was continuously formed over 2000 m. The fluctuation range of the film surface temperature when the film was continuously produced was the same as in Example 1. The obtained film was slit and wound in the same manner as in Example 1 to obtain a polyamide-based mixed resin laminated film roll. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Example 6]
The polyamide system was the same as in Example 1 except that the raw material chips in the blender were supplied to the hoppers directly above the respective extruders (first to third extruders) except that the inclination angle of each hopper was changed to 65 °. A mixed resin laminated film roll was obtained. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Example 7]
In forming the first layer and the third layer, when the chips A, B, and D in each blender are supplied to the hopper immediately above the first extruder and the third extruder through the mixing mixer, The supply amount is 89.5% by weight, the supply amount of chip B is 0.5% by weight, the supply amount of chip D is 10.0% by weight, and the chips in each blender are formed in the formation of the second layer. When A, B, and D are supplied to the hopper immediately above the second extruder through the mixing mixer, the supply amount of chip A is 89.97% by weight, and the supply amount of chip B is 0.03% by weight. The supply amount of chip D was 10.0% by weight. Other than that was carried out similarly to Example 1, and obtained the polyamide-type mixed resin laminated | multilayer film roll. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Example 8]
In the formation of the first to third layers, the raw material chip E was used instead of the raw material chip D. In forming the first layer and the third layer, the chips A, B, and E in each blender are supplied to the hopper directly above the first extruder and the third extruder via the mixing mixer. The supply amount of A is 94.5% by weight, the supply amount of chip B is 0.5% by weight, the supply amount of chip E is 5.0% by weight, and in each blender, the second layer is formed. When the chips A, B, and E are supplied to the hopper immediately above the second extruder through the mixing mixer, the supply amount of the chip A is 94.97% by weight and the supply amount of the chip B is 0.03. The supply amount of chip D was 5.0% by weight. Other than that was carried out similarly to Example 1, and obtained the polyamide-type mixed resin laminated | multilayer film roll. In each extruder of Example 8, the average major axis, average minor axis, and average chip length of the thermoplastic elastomer chip (Chip E) are the average major axis and average of each polyamide-based resin chip (Chips A and B). Each of the minor diameter and the average chip length is included within a range of ± 20%. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Example 9]
A polyamide-based mixed resin laminated film roll was obtained in the same manner as in Example 8 except that the raw material chip F was used instead of the raw material chip E. In each extruder of Example 9, the average major axis, average minor axis, and average chip length of the thermoplastic elastomer chip (Chip F) are the average major axis and average of each polyamide resin chip (Chip A, B). Each of the minor diameter and the average chip length is included within a range of ± 20%. And the characteristic of the obtained film roll was evaluated by the method similar to Example 1. FIG. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Example 10]
A polyamide-based mixed resin laminated film roll was obtained in the same manner as in Example 8 except that the raw material chip G was used instead of the raw material chip E. In each extruder of Example 10, the average major axis, average minor axis, and average chip length of the thermoplastic elastomer chip (chip G) are the average major axis and average of each polyamide-based resin chip (chips A and B). Each of the minor diameter and the average chip length is included within a range of ± 20%. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Example 11]
A polyamide-based mixed resin laminated film roll was obtained in the same manner as in Example 8 except that the raw material chip H was used instead of the raw material chip E. In each extruder of Example 11, the average major axis, average minor axis, and average chip length of the thermoplastic elastomer chip (Chip H) are the average major axis and average of each polyamide-based resin chip (Chips A and B). Each of the minor diameter and the average chip length is included within a range of ± 20%. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Comparative Example 1]
When forming an unstretched resin sheet, a single layer structure is formed without forming the first layer and the third layer, and in the formation of the second layer, chips A, B, and D in each blender are mixed with a mixing mixer. The supply amount of chip A is 96.5% by weight, the supply amount of chip B is 0.5% by weight, and the supply amount of chip D is 3. 0% by weight. Other than that was carried out similarly to Example 1, and obtained the polyamide-type mixed resin laminated | multilayer film roll. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Comparative Example 2]
A polyamide-based mixed resin laminated film roll was obtained in the same manner as in Example 1 except that the raw material chip C was used instead of the raw material chip B. In Comparative Example 2, the average long diameter and average chip length of the thermoplastic elastomer chip (chip D) are ± 20 with respect to the average long diameter and average chip length of one polyamide resin chip (chip C), respectively. Not included in the range. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Comparative Example 3]
A polyamide-based mixed resin laminated film roll was obtained in the same manner as in Example 1 except that the raw material chip I was used instead of the raw material chip D. In Comparative Example 3, the average major axis and average chip length of the thermoplastic elastomer chip (Chip I) are ±± with respect to the average major axis and average chip length of each polyamide-based resin chip (Chips A and B). It is not included in the range within 20%. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Comparative Example 4]
The polyamide system was the same as in Example 1 except that the raw material chips in the blender were supplied to the hoppers directly above the respective extruders (first to third extruders) except that the inclination angle of each hopper was changed to 45 °. A mixed resin laminated film roll was obtained. And the characteristic of the obtained film roll was evaluated by the method similar to Example 1. FIG. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Comparative Example 5]
Example 1 except that the raw material chips A, B and D were pre-dried and then left for about 5 hours in each blender before being fed to the hopper directly above each extruder via a mixing mixer. Similarly, a polyamide-based mixed resin laminated film roll was obtained. The moisture content of chips A, B, and D immediately before being supplied to each hopper is 800 ppm, and the temperature of chips A, B, and D immediately before being supplied to each hopper is about 30 ° C. It was. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Comparative Example 6]
A polyamide-based mixed resin laminated film roll in the same manner as in Example 1 except that the pre-drying conditions of the raw material chips A, B, and D were changed to a method of heating to about 100 ° C. over about 4.0 hours. Got. After preliminary drying, a predetermined amount of each chip was collected from each blender and the moisture content was measured. The moisture content of chips A, B, and D was all 1500 ppm, and each extruder was fed through a mixing mixer. The temperatures of chips A, B, and D immediately before being supplied to the hopper immediately above were about 85 ° C. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Comparative Example 7]
When supplying the raw material chips A, B, and D to the hopper immediately above each extruder through the mixing mixer, except that the segregation preventing agent was not added in each hopper, the same as in Example 1, A polyamide-based mixed resin laminated film roll was obtained. Then, using the obtained polyamide-based mixed resin film roll, aluminum vapor deposition, aluminum oxide vapor deposition, silicon oxide vapor deposition, and composite vapor deposition were performed under the same conditions as in Example 1, and four kinds of vapor-deposited polyamide-based mixed resin laminated films were obtained. Got a roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 4-8. The evaluation results are shown in Tables 5-10.

[Comparative Example 8]
The unstretched film obtained in the same manner as in Example 1 was longitudinally stretched (first longitudinal stretching) by about 1.5 times at a stretching temperature of about 90 ° C. with a Teflon (registered trademark) roll, and then with a ceramic roll. The film was stretched longitudinally (second longitudinal stretching) about 2.2 times at a stretching temperature of about 70 ° C. Furthermore, the longitudinally stretched sheet is continuously guided to a stenter, and is stretched in the same manner as in Example 1, and is subjected to a lateral relaxation treatment by heat fixing and then cooled, and both edges are cut and removed. A biaxially stretched film of about 15 μm was continuously formed over 2000 m. The fluctuation range of the film surface temperature when the film was continuously produced was the same as in Example 1. Thereafter, the resulting film was slit and wound in the same manner as in Example 1 to obtain a polyamide-based mixed resin laminated film roll. Then, the resulting film roll, by was slit and winded up in the same manner as in Example 1, after the slit roll, under the same conditions as in Example 1, the composite deposited with SiO ₂ and Al ₂ O ₃ It performed and obtained the vapor deposition polyamide type mixed resin laminated | multilayer film roll. And the characteristic of the film roll before and behind obtained vapor deposition was evaluated by the method similar to Example 1. FIG. The evaluation results are shown in Tables 5-10.

[Effects of Example Film]
From Tables 5 to 10, the film rolls before vapor deposition of the examples all have very small thickness unevenness in the longitudinal direction over the entire roll, the elastomer content, tensile elastic modulus, boiling water shrinkage, refractive index, high It can be seen that the variation in physical properties such as the dynamic friction coefficient under humidity is small. In addition, the film rolls of the examples with small variations in physical properties such as the elastomer content and the tensile elastic modulus do not cause the S-curl phenomenon and can be laminated even under high humidity (75% RH). It is clear that the variation in pinhole resistance is small. Furthermore, it can be seen that the film constituting the film roll before vapor deposition of the example has extremely high pinhole resistance, impact strength (toughness), and laminate strength. And as for the vapor deposition film roll which vapor-deposited the film roll before vapor deposition of the Example whose physical property fluctuations, such as an elastomer content rate and a tensile elasticity modulus, are small, all have low oxygen permeability (high gas barrier property). It can be seen that the variation is small and the laminating property is good as in the film roll before vapor deposition. On the other hand, the film roll before vapor deposition of the comparative example has a thickness variation in the vertical direction over the entire roll, the content of the elastomer, the tensile elastic modulus, the boiling water shrinkage, the refractive index, the coefficient of dynamic friction under high humidity, etc. It can be seen that the fluctuations in the physical properties of the film are large, the variation in pinhole resistance is large, the S-curl phenomenon is observed, and the laminate processability is poor. And the vapor deposition film roll which vapor-deposited the film roll of the comparative example with such a large fluctuation | variation of physical properties, such as an elastomer content rate and a tensile elasticity modulus, as for all, the fluctuation | variation of oxygen permeability is large, and laminating workability is bad. It turns out that it is.

Since the vapor-deposited polyamide-based mixed resin laminated film roll of the present invention has excellent processing characteristics as described above, it can be suitably used for food retort processing and the like.

Claims (31)

A vapor-deposited polyamide-based mixed resin laminated film obtained by depositing an inorganic substance on at least one surface of a polyamide-based mixed resin laminated film base material obtained by laminating a plurality of polyamide-based resin layers made of a mixed resin of a polyamide-based resin and a thermoplastic elastomer, A vapor-deposited polyamide-based mixed resin laminated film roll wound up to have a width of 0.2 m to 3.0 m and a length of 300 m to 30000 m,
A polyamide-based mixed resin laminated film roll formed by winding a polyamide-based mixed resin laminated film before vapor deposition,
A first sample cutout is provided within 2 m from the end of film winding, a final cutout is provided within 2 m from the start of film winding, and a sample cutout is provided approximately every 100 m from the first sample cutout. A vapor-deposited polyamide-based mixed resin laminated film roll characterized by satisfying the following requirements (1) and (2).
(1) When the content of the thermoplastic elastomer component is measured for each sample cut out from each cut-out portion and the average content rate, which is the average value of the content rates, is calculated, the thermoplasticity of all the samples The variation rate of the content of the elastomer component is within a range of ± 10% with respect to the average content rate. (2) The variation rate of the thickness over the entire length in the longitudinal direction of the wound roll is ± with respect to the average thickness. Within 2% to ± 10% A vapor-deposited polyamide-based mixed resin laminated film obtained by depositing an inorganic substance on at least one surface of a polyamide-based mixed resin laminated film base material obtained by laminating a plurality of polyamide-based resin layers made of a mixed resin of a polyamide-based resin and a thermoplastic elastomer, A vapor-deposited polyamide-based mixed resin laminated film roll wound up to have a width of 0.2 m to 3.0 m and a length of 300 m to 30000 m,
A polyamide-based mixed resin laminated film roll formed by winding a polyamide-based mixed resin laminated film before vapor deposition,
A first sample cutout is provided within 2 m from the end of film winding, a final cutout is provided within 2 m from the start of film winding, and a sample cutout is provided approximately every 100 m from the first sample cutout. A vapor-deposited polyamide-based mixed resin laminated film roll characterized by satisfying the following requirement (3).
(3) For each sample cut out from each cut-out part, when the tensile elastic modulus in the winding direction of the film was measured, the average tensile elastic modulus, which is the average value of the tensile elastic modulus, was 1.30 GPa or more 2 Less than 50 GPa, and the variation rate of the tensile modulus of elasticity of all the samples is within ± 10% of the average tensile modulus. A vapor-deposited polyamide-based mixed resin laminated film obtained by depositing an inorganic substance on at least one surface of a polyamide-based mixed resin laminated film base material obtained by laminating a plurality of polyamide-based resin layers made of a mixed resin of a polyamide-based resin and a thermoplastic elastomer, A vapor-deposited polyamide-based mixed resin laminated film roll wound up to have a width of 0.2 m to 3.0 m and a length of 300 m to 30000 m,
A first sample cutout is provided within 2 m from the end of film winding, a final cutout is provided within 2 m from the start of film winding, and a sample cutout is provided approximately every 100 m from the first sample cutout. A vapor-deposited polyamide-based mixed resin laminated film roll characterized by satisfying the following requirement (4).
(4) For each sample cut out from each cut-out part, the number of pinholes when a 3000-cycle bending test was continuously performed at a rate of 40 cycles per minute using a gelbo flex tester, All are 10 or less The first sample cut-out portion is provided within 2 m from the end of winding of the film roll after vapor deposition, and the final cut-out portion is provided within 2 m from the start of film winding, and samples are sampled about every 100 m from the first sample cut-out portion. When a cutout is provided,
For each sample cut out from each cut-out part, when the oxygen permeability was determined, the average oxygen permeability, which is the average value of the oxygen permeability, was 50 ml / m ² · MPa · day or less, and all The vaporized polyamide system according to any one of claims 1 to 3, wherein a variation rate of oxygen permeability of the sample is within a range of ± 2% to ± 20% with respect to the average oxygen permeability. Mixed resin laminated film roll.   The vapor-deposited polyamide-based mixed resin laminated film roll according to any one of claims 1 to 3, wherein the inorganic substance is a metal or a metal oxide. A polyamide-based mixed resin laminated film roll formed by winding a polyamide-based mixed resin laminated film before vapor deposition,
For each sample cut out from each cut-out part, when measuring the maximum boiling water shrinkage, which is the maximum value of the boiling water shrinkage in all directions, the average boiling water shrinkage is the average of those maximum boiling water shrinkage Is 2% to 6%, and the variation rate of the maximum boiling water shrinkage rate of all the samples is within a range of ± 2% to ± 10% with respect to the average boiling water shrinkage rate. The vapor deposition polyamide type mixed resin laminated | multilayer film roll in any one of 1-3. A polyamide-based mixed resin laminated film roll formed by winding a polyamide-based mixed resin laminated film before vapor deposition,
For each sample cut out from each cutout section, the boiling water shrinkage direction difference, which is the absolute value of the difference between the boiling water shrinkage rate in the +45 degree direction with respect to the longitudinal direction and the boiling water shrinkage ratio in the −45 degree direction with respect to the longitudinal direction, is calculated. When obtained, the average boiling water shrinkage direction difference, which is the average value of the boiling water shrinkage direction differences, is 2.0% or less, and the variation rate of the boiling water shrinkage direction difference of all the samples is the average boiling water difference. The vapor-deposited polyamide-based mixed resin laminated film roll according to any one of claims 1 to 3, wherein the difference is within a range of ± 2% to ± 30% with respect to a shrinkage rate direction difference. A polyamide-based mixed resin laminated film roll formed by winding a polyamide-based mixed resin laminated film before vapor deposition,
The vapor-deposited polyamide-based mixed resin laminated film roll according to any one of claims 1 to 3, wherein each sample cut out from each cut-out portion satisfies the following requirement (5) and the following requirement (6).
(5) When measuring the three-dimensional surface roughness in the winding direction, the average surface roughness, which is the average value of the three-dimensional surface roughness, is in the range of 0.01 to 0.06 μm, and all The variation rate of the three-dimensional surface roughness of the sample is in the range of ± 5% to ± 20% with respect to the average surface roughness. (6) When haze is measured, the average value of those hazes A certain average haze is in the range of 1.0 to 4.0, and the haze variation rate of all the samples is in the range of ± 2% to ± 15% with respect to the average haze. A polyamide-based mixed resin laminated film roll formed by winding a polyamide-based mixed resin laminated film before vapor deposition,
About each sample cut out from each said cut-out part, when measuring a dynamic friction coefficient in the atmosphere of 80% RH at 23 degreeC, the average dynamic friction coefficient which is the average value of those dynamic friction coefficients is 0.3-0.8. The dynamic friction coefficient of all the samples is within a range of ± 5% to ± 30% with respect to the average dynamic friction coefficient. The vapor-deposited polyamide-based mixed resin laminated film roll described in 1. A polyamide-based mixed resin laminated film roll formed by winding a polyamide-based mixed resin laminated film before vapor deposition,
About each sample cut out from each said cut-out part, when content of an inorganic particle is measured, the average content which is the average value of those inorganic particle content is in the range of 0.01 to 0.5 weight% And the variation rate of the inorganic particle content of all the samples is within a range of ± 2% to ± 10% with respect to the average content. The vapor-deposited polyamide-based mixed resin laminated film roll described. A polyamide-based mixed resin laminated film roll formed by winding a polyamide-based mixed resin laminated film before vapor deposition,
For each sample cut out from each cutout portion, when the refractive index in the thickness direction was measured, the average refractive index, which is the average value of those refractive indexes, was 1.500 or more and 1.520 or less, and all The vapor deposition polyamide type mixed resin laminated film roll according to any one of claims 1 to 3, wherein a variation rate of a refractive index of the sample is within a range of ± 2% with respect to the average refractive index.   The polyamide-based mixed resin laminated film constituting the polyamide-based mixed resin laminated film roll formed by winding the polyamide-based mixed resin laminated film before vapor deposition is an average of the inorganic particles in 1/3 of the total thickness of the front and back surfaces. The vapor-deposited polyamide-based mixed resin laminated film roll according to any one of claims 1 to 3, wherein the particle size is smaller than the average particle size of the inorganic particles in the portion other than the surface layer.   The vapor-deposited polyamide-based mixed resin laminated film roll according to any one of claims 1 to 3, wherein the main component of polyamide constituting the polyamide-based mixed resin laminated film other than the inorganic substance is nylon 6.   2. A vapor-deposited polyamide-based mixed resin laminated film formed by vapor-depositing an inorganic substance on a polyamide-based mixed resin laminated film formed from a mixture of two or more different polyamide-based resins. The vapor deposition polyamide type mixed resin laminated | multilayer film roll in any one of -3.   The vapor-deposited polyamide mixed resin laminated film roll according to any one of claims 1 to 3, wherein the wound vapor-deposited polyamide mixed resin laminated film is laminated with a polyolefin resin film.   An inorganic substance is applied to a polyamide-based mixed resin laminated film obtained by biaxially stretching a non-oriented sheet-like material obtained by extruding a melted polyamide-based mixed resin from a T-die and bringing it into contact with a metal roll and cooling it. The vapor-deposited polyamide-based mixed resin laminated film roll according to any one of claims 1 to 3, wherein the roll is vapor-deposited by winding.   The vapor-deposited polyamide-based mixed resin laminated film roll according to any one of claims 1 to 3, wherein an inorganic substance is vapor-deposited and wound on a polyamide-based mixed resin laminated film stretched by a tenter stretching method.   The vapor-deposited polyamide-based mixed resin laminated film roll according to any one of claims 1 to 3, wherein an inorganic substance is vapor-deposited on a polyamide-based mixed resin laminated film that has been successively biaxially stretched.   The vapor-deposited polyamide system according to any one of claims 1 to 3, wherein an inorganic substance is vapor-deposited and wound on a polyamide-based mixed resin laminated film stretched biaxially in the longitudinal direction and the transverse direction. Mixed resin laminated film roll.   After stretching a sheet-like material composed of a substantially unoriented polyamide resin in the longitudinal direction in at least two stages so as to obtain a magnification of 3 times or more at a temperature higher than the glass transition temperature + 20 ° C. of the polyamide resin, The inorganic material is vapor-deposited and wound on a polyamide-based mixed resin laminated film formed by stretching in the transverse direction so as to have a magnification of 3 times or more. Vapor deposition polyamide-based mixed resin laminated film roll.   The vapor-deposited polyamide system according to any one of claims 1 to 3, wherein an inorganic substance is vapor-deposited and wound on a polyamide-based mixed resin laminated film that is heat-set after the final stretching treatment. Mixed resin laminated film roll.   The vapor-deposited polyamide-based mixed resin laminated film according to any one of claims 1 to 3, wherein the polyamide-based mixed resin laminated film that has been subjected to relaxation treatment after heat setting is obtained by vapor-depositing an inorganic substance. roll.   In the polyamide-based mixed resin laminated film other than inorganic substances of the wound vapor-deposited polyamide-based mixed resin laminated film, lubricant, anti-blocking agent, thermal stabilizer, antioxidant, antistatic agent, light resistance agent, impact resistance improvement At least 1 sort (s) of the agent is added, The vapor deposition polyamide type mixed resin laminated film roll in any one of Claims 1-3 characterized by the above-mentioned.   The vapor-deposited polyamide according to any one of claims 1 to 3, wherein inorganic particles are added to the polyamide-based mixed resin laminated film other than the inorganic substance of the wound vapor-deposited polyamide-based mixed resin laminated film. -Based mixed resin laminated film roll.   25. The vapor-deposited polyamide-based mixed resin laminated film roll according to claim 24, wherein the inorganic particles are silica particles having an average particle size of 0.5 to 5.0 [mu] m.   The vapor-deposited polyamide according to any one of claims 1 to 3, wherein a higher fatty acid is added to the polyamide-based mixed resin laminated film other than the inorganic substance of the wound vapor-deposited polyamide-based mixed resin laminated film. -Based mixed resin laminated film roll. A production method for producing the vapor-deposited polyamide-based mixed resin laminated film roll according to claim 1,
A film forming step of forming an unstretched polyamide-based mixed resin laminate sheet by melt-extruding a mixed resin composed of a polyamide-based resin and a thermoplastic elastomer from a plurality of extruders by a coextrusion method;
A biaxial stretching step of biaxially stretching the unstretched polyamide-based mixed resin laminate sheet obtained in the film-forming step in the machine direction and the transverse direction;
A roll forming step of winding a biaxially stretched film;
A vapor deposition step of depositing an inorganic substance on at least one surface of the wound film,
The manufacturing method of the polyamide-type mixed resin laminated | multilayer film roll characterized by satisfy | filling the following requirements (a)-(g).
(A) In the film forming step, the polyamide resin chip and the thermoplastic elastomer chip are mixed and then melt-extruded, and the mixture of the polyamide resin chip and the thermoplastic elastomer chip is sublimated and segregated. (B) A polyamide-based mixed resin in which the film forming step is performed by mixing a polyamide-based resin chip and a thermoplastic elastomer chip and adding 0.1 to 2.0% by weight of inorganic particles. (C) The biaxial stretching step involves stretching in two stages in the longitudinal direction and then stretching in the transverse direction, and the first stage in the two-stage stretching in the longitudinal direction. (D) The film forming step includes a polyamide resin chip and a thermoplastic resin. It is melt extruded from each extruder after mixing with a steamer chip, and the shape of each chip used is an elliptical cylinder having an elliptical cross section having a major axis and a minor axis, and a thermoplastic elastomer The tip is adjusted to have an average major axis, an average minor axis, and an average tip length that are included within ± 25% of the average major axis, average minor axis, and average tip length of the polyamide resin chip, respectively. (E) The film forming step includes a step of melt extrusion using a plurality of extruders provided with a funnel-shaped hopper as a raw material chip supply unit, and all the inclination angles of the funnel-shaped hopper are 65 degrees or more. The moisture content of the polyamide resin chip before being supplied to the funnel-shaped hopper is 800 ppm or more and 1000 ppm or less. The temperature of the polyamide-based resin chip before being supplied to the funnel-shaped hopper is adjusted to 80 ° C. or higher. (F) The film forming step is performed simultaneously from the plurality of extruders. It includes a step of cooling by winding the polyamide-based mixed resin laminated sheet melt-extruded by an extrusion method around a cooling roll, and in that cooling step, the contact between the polyamide-based mixed resin laminated sheet and the surface of the cooling roll The portion is sucked by the suction device in the direction opposite to the winding direction over the entire width of the polyamide-based mixed resin laminated sheet. (G) The vapor deposition step is performed by metal or metal oxidation on at least one surface of the wound film. The material is deposited so as to have a thickness of 5.0 nm to 200 nm.   28. The film forming step is characterized by laminating a skin layer added with 0.05 to 2.0% by weight of inorganic particles on a core layer by using a high-concentration raw material chip. The manufacturing method of the vapor deposition polyamide-type resin laminated | multilayer film roll of description.   28. The vapor-deposited polyamide-based resin laminated film according to claim 27, wherein the high-concentration raw material chip used in the film forming step is a polyamide-based resin chip to which inorganic particles are added in an amount of 5 wt% to less than 20 wt%. A method for manufacturing a roll.   In the film forming step, inorganic particles added to the polyamide resin sheet laminated on the outermost layer have a pore volume of 0.5 to 2.0 ml / g and an average particle size of 1.0 to 5.0 μm. The manufacturing method of the vapor deposition polyamide-type resin laminated | multilayer film roll of Claim 27 characterized by the above-mentioned. A preheating step that is performed before the longitudinal stretching step, and a heat treatment step that is performed after the longitudinal stretching step,
The fluctuation range of the surface temperature of the film at an arbitrary point in the longitudinal stretching step, the preheating step, and the heat treatment step is adjusted within a range of an average temperature ± 1 ° C. over the entire length of the film. The manufacturing method of the vapor deposition polyamide type mixed resin laminated | multilayer film roll of Claim 27.