JP2007021771A - Vapor deposition polyamide resin laminated film roll and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a biaxially oriented vapor deposition polyamide resin laminated film roll having high gas barrier properties, capable of being smoothly subjected to bag making processing by virtue of lamination in a good yield and capable of efficiently obtaining a package free from an S-shaped curl. <P>SOLUTION: In the vapor deposition polyamide resin laminated film roll, a first sample cutting part is provided within a 2m range from the winding completion of a film roll formed by taking up a film before vapor deposition while a final cutting part is provided within a 2m range from the winding start of the film and, in a case that sample cutting parts are provided at every about 100 m from the first sample cutting part, physical properties such as a boiling water shrinkage factor, surface roughness, a refractive index in a thickness direction, etc., are adjusted with respect to all samples cut from the respective cutting parts so as to fall within a predetermined range of fluctuation width. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a high-quality film roll having a uniform physical property 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 resin laminated | multilayer film roll with the favorable workability (especially workability under 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, when the lamination process is performed under high humidity such as in summer, the polyamide-based resin laminated film is placed on the roll of the laminating machine. It has been found that good slipperiness may not be exhibited, and good processing characteristics cannot always be obtained.

  In addition, the 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 to produce a polyamide-based resin film roll having a highly uniform gas barrier property and a production technique for making the polyamide-based resin film highly slippery under high humidity and having no fluctuation. As a result of diligent research and development on the production technology, the purpose is to eliminate the problems of conventional vapor-deposited polyamide resin laminated film rolls, extremely high gas barrier properties, and highly uniform. Biaxially oriented vapor-deposited polyamide-based resin laminated film roll that can be made smoothly by laminating without any problems even under high humidity such as summer, and can efficiently obtain a package without S-curls Is to provide. Another object of the present invention is to provide a biaxially oriented vapor-deposited polyamide-based 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 vapor deposition polyamide-type resin laminated | multilayer film roll efficiently.

Among the present inventions, the structure of the invention described in claim 1 is a polyamide system in which a plurality of polyamide-based resin layers are laminated and 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 polyamide-based resin laminate roll obtained by winding a vapor-deposited polyamide-based resin laminate film obtained by depositing an inorganic substance on at least one surface of a resin laminate film, and winding a polyamide-based resin laminate film before vapor deposition The laminated film roll is provided with a first sample cutout portion within 2 m from the end of winding of the film, and a final cutout portion within 2 m from the start of film winding, and every about 100 m from the first sample cutout portion. When the sample cutout portion is provided, the following requirements (1) to (5) are satisfied.
(1) For each sample cut out from each cutout part, when measuring the maximum boiling water shrinkage, which is the maximum value of the boiling water shrinkage in all directions, the average is the average value of the maximum boiling water shrinkage The boiling water shrinkage is 2% to 6%, and the variation rate of the maximum boiling water shrinkage of all the samples is within a range of ± 2% to ± 10% with respect to the average boiling water shrinkage (2) For each sample cut out from each cut-out part, 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 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 shrinkage. Within ± 2% to ± 30% of the rate direction difference (3) When the three-dimensional surface roughness in the winding direction is measured for each sample cut out from each cut-out portion, the average surface roughness, which is an average value of the three-dimensional surface roughness, is 0. The variation rate of the three-dimensional surface roughness of all the samples is in the range of ± 5% to ± 20% with respect to the average surface roughness (4) When measuring the haze of each sample cut out from each cut-out portion, the average haze, which is the average value of those hazes, is in the range of 1.0 to 4.0, and the haze variation of all the samples. The rate is in the range of ± 2% to ± 15% with respect to the average haze. (5) The variation rate of the thickness over the entire length in the longitudinal direction of the wound roll is ± 2% to the average thickness. Within ± 10%

The structure of the invention described in claim 2 is the invention described in claim 1, wherein the first sample cutout portion is within 2 m from the end of winding of the film roll after vapor deposition, and 2 m from the start of winding of the film. When the sample cut-out portion is provided at intervals of about 100 m from the first sample cut-out portion and 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 50 ml / m ² · MPa · day or less, and the variation rate of the oxygen permeability of all the samples is ± 2 with respect to the average oxygen permeability. % To ± 20%.

  The structure of the invention described in claim 3 is the invention described in claim 1, wherein the polyamide-based resin laminated film roll formed by winding up the polyamide-based resin laminated film before vapor deposition is cut out from each of the cutout portions. For each sample, when the dynamic friction coefficient was measured in an atmosphere of 80% RH at 23 ° C., the average dynamic friction coefficient, which is the average value of the dynamic friction coefficients, was in the range of 0.3 to 0.8, 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.

  According to a fourth aspect of the present invention, in the first aspect of the invention, a polyamide-based resin laminated film roll formed by winding a polyamide-based resin laminated film before vapor deposition is cut out from each of the cutout portions. For each sample, when the content of the inorganic particles was measured, the average content, which is the average value of the inorganic particle content, was in the range of 0.01 to 0.5% by weight, and all the samples The variation rate of the inorganic particle content is in the range of ± 2% to ± 10% with respect to the average content.

  According to a fifth aspect of the present invention, in the first aspect of the invention, a polyamide-based resin laminated film roll formed by winding a polyamide-based resin laminated film before vapor deposition is cut out from each of the cutout portions. Further, when the refractive index in the thickness direction was measured for each sample, the average refractive index, which is the average value of the refractive indexes, was 1.500 or more and 1.520 or less, and the variation rate of the refractive index of all the samples. Is within a range of ± 2% with respect to the average refractive index.

  The structure of the invention described in claim 6 is the inorganic particle in which the polyamide resin laminated film roll formed by winding the polyamide resin laminated film before vapor deposition in the invention described in claim 1 is included in the core layer. The average particle diameter is to be equal to or greater than the thickness of the skin layer.

  The structure of the invention described in claim 7 is that, in the invention described in claim 1, the main component of the polyamide constituting the polyamide-based resin laminated film other than the inorganic substance is nylon 6.

  The structure of the invention described in claim 8 is the deposition according to the invention described in claim 1, wherein an inorganic substance is deposited on a polyamide-based resin laminated film formed from a mixture of two or more different polyamide-based resins. It is that the polyamide-based resin laminated film is wound up.

  The structure of the invention described in claim 9 is that, in the invention described in claim 1, the vapor-deposited polyamide-based resin laminated film is laminated with the polyolefin-based resin film.

  The structure of the invention described in claim 10 is the non-oriented structure obtained in the invention described in claim 1 by extruding the melted polyamide-based resin from the T-die and bringing it into contact with a metal roll and cooling it. That is, an inorganic substance is vapor-deposited on a polyamide-based resin laminated film obtained by biaxially stretching a sheet-like material.

  The structure of the invention described in claim 11 is that, in the invention described in claim 1, an inorganic substance is vapor-deposited and wound on a polyamide-based resin laminated film stretched by a tenter stretching method.

  The structure of the invention described in claim 12 is that, in the invention described in claim 1, an inorganic substance is vapor-deposited and wound up on a polyamide-based resin laminated film that is successively biaxially stretched.

  The structure of the invention described in claim 13 is the invention described in claim 1, in which an inorganic substance is vapor-deposited and wound on a polyamide-based resin laminated film stretched biaxially in the longitudinal direction and the transverse direction. It is to be.

  The structure of the invention described in claim 14 is the invention described in claim 1, wherein the sheet-like material made of a substantially unoriented polyamide resin is more than the glass transition temperature + 20 ° C. of the polyamide resin. After stretching in the longitudinal direction in at least two stages so that the magnification is 3 times or more at high temperature, an inorganic substance is deposited on the polyamide-based resin laminated film that is stretched in the transverse direction so that the magnification is 3 times or more. It is to have been rolled up.

  The structure of the invention described in claim 15 is the invention described in claim 1, in which an inorganic substance is vapor-deposited and wound on a polyamide-based resin laminated film that has been heat-set after the final stretching treatment. It is to be.

  The structure of the invention described in claim 16 is that in the invention described in claim 1, an inorganic substance is vapor-deposited and wound on a polyamide-based resin laminated film that has been subjected to relaxation treatment after heat setting. is there.

  In the invention described in claim 17, in the invention described in claim 1, in the polyamide resin laminate film other than the inorganic substance of the polyamide resin laminate film deposited polyamide resin laminate film wound up, That is, at least one of a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a light resistance agent and an impact resistance improver is added.

  The structure of the invention described in claim 18 is that, in the invention described in claim 1, inorganic particles are added to the polyamide resin laminated film other than the inorganic substance of the wound polyamide resin laminated film wound up. There is in being.

  The structure of the invention described in claim 19 is that, in the invention described in claim 18, the inorganic particles are silica particles having an average particle diameter of 0.5 to 5.0 μm.

  According to a twentieth aspect of the invention, in the invention described in the first aspect, a higher fatty acid is added to a polyamide-based resin laminated film other than the inorganic substance of the wound-up vapor-deposited polyamide-based resin laminated film. There is in being.

The structure of the invention described in claim 21 is as follows.
It is a manufacturing method for manufacturing the vapor deposition polyamide-type resin laminated | multilayer film roll described in Claim 1, Comprising: A polyamide-type resin is melt-extruded from several extruders by a coextrusion method, A some polyamide-type resin layer A film forming step for forming an unstretched laminated sheet laminated with a biaxially stretching step for biaxially stretching the unstretched laminated sheet obtained in the filming step in the longitudinal and transverse directions, and a biaxially stretched film. The process includes a roll forming process for winding and a vapor deposition process for depositing an inorganic substance on at least one surface of the wound film, and the following requirements (a) to (f) are satisfied.
(A) The film forming step uses a high-concentration raw material chip to laminate a skin layer added with 0.05 to 2.0% by weight of inorganic particles on the core layer (b) In the biaxial stretching process, the stretching is performed in two stages in the longitudinal direction and then in the transverse direction, and the first stretching ratio in the two-stage stretching in the longitudinal direction is set higher than the stretching ratio in the second stage. (C) In the film forming step, each of the extrusions is performed after mixing a chip made of a polyamide resin having the largest use amount with one or more other polyamide resin chips having a composition different from that of the polyamide resin chip. The shape of each polyamide-based resin chip used is melt-extruded from a machine to form an unstretched laminated sheet, and the shape of each polyamide-based resin chip is an elliptical column having an elliptical cross section having a major axis and a minor axis In addition, the polyamide resin chips other than the polyamide resin chips that are used in the largest amount are each ± 20 relative to the average major axis, average minor axis, and average chip length of the polyamide resin chips that are used the most. (D) a plurality of extrusions provided with a funnel-shaped hopper as a raw material chip supply section, being adjusted to have an average major axis, an average minor axis and an average chip length included in the range of A step of melt-extruding using a machine, and all the inclination angles of the funnel-shaped hopper are adjusted to 65 degrees or more, and the moisture content of the polyamide-based resin chip before being supplied to the funnel-shaped hopper Is adjusted to 800 ppm or more and 1000 ppm or less, and the temperature of the polyamide resin chip before being supplied to the funnel-shaped hopper is 80 ° C. (E) The film forming step includes a step of cooling the melt-extruded unstretched laminated sheet by bringing it into contact with a cooling roll, and in the cooling step, The portion in contact with the surface of the cooling roll is sucked in the direction opposite to the winding direction by the suction device over the entire width of the molten resin. (F) The vapor deposition step is performed by laminating a metal or metal oxide with a polyamide resin laminate. The film should be deposited on at least one side of the film to have a thickness of 5.0 nm to 200 nm.

  The structure of the invention described in claim 22 is that, in the invention described in claim 21, the high-concentration raw material chip used in the film-forming step is a polyamide to which inorganic particles are added in an amount of 5 wt% or more and less than 20 wt%. It is based on a resin chip.

  The structure of the invention described in claim 23 is that, in the invention described in claim 21, in the film forming step, the inorganic particles added to the polyamide-based resin laminate sheet laminated on the outermost layer have a pore volume. The average particle size is 0.5 to 2.0 ml / g and the average particle size is 1.0 to 5.0 μm.

  The structure of the invention described in claim 24 is that, in the invention described in claim 21, the inorganic substance is a metal or a metal oxide.

  The structure of the invention described in claim 25 includes, in the invention described in claim 21, 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 resin laminated film roll of the present invention, it has a high gas barrier property, and can be smoothly made into a bag by laminating without any trouble even under high humidity such as in summer. It is possible to efficiently obtain a package without any defects. 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 resin laminated film roll of the present invention is used, the bag for food packaging after the bag forming process by lamination has a high and uniform gas barrier property, and is tough and pinhole resistant. Even better.

  In addition, according to the method for producing a vapor-deposited polyamide-based resin laminated film roll of the present invention, a vapor-deposited polyamide-based resin laminated film roll having high gas barrier properties and good laminating property even under high humidity is inexpensive, and It can be obtained very efficiently.

  The vapor-deposited polyamide-based resin laminated film roll of the present invention is the maximum value of the boiling water shrinkage in all directions for all samples when the polyamide-based resin laminated film roll before vapor deposition is cut out by the method described later. When the maximum boiling water shrinkage is measured, the average boiling water shrinkage, which is the average value of the maximum boiling water shrinkage, is adjusted to be 3% or more and 6% or less.

  Moreover, when the polyamide-based resin laminated film roll before vapor deposition cuts out the sample by the method described later, the vapor-deposited polyamide-based resin laminated film roll of the present invention has boiling water in the +45 degree direction with respect to the longitudinal direction for all the samples. When the boiling water shrinkage direction difference, which is the absolute value of the difference between the shrinkage rate and the boiling water shrinkage in the direction of -45 degrees with respect to the longitudinal direction, is obtained, the average boiling water shrinkage rate is the average value of the boiling water shrinkage direction differences. The direction difference is adjusted to 1.5% or less.

  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. For each of the cut samples, the boiling water shrinkage rate (hereinafter referred to as BS), the maximum boiling water shrinkage rate (hereinafter referred to as BSx), the average boiling water shrinkage rate (hereinafter referred to as BSax), and the boiling water shrinkage direction in the following manner. A difference (hereinafter referred to as BSd) and an average boiling water shrinkage direction difference (hereinafter referred to as BSad) are measured.

[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 biaxially oriented film cut out from each cut-out portion of the polyamide-based 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

  In addition, the BSx value of the film constituting the polyamide-based resin laminated film 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, and the film It is important for improving its own toughness and pinhole resistance. If the BSx value is less than 2%, the toughness and pinhole resistance will be insufficient. On the other hand, if it exceeds 6%, a laminate failure will occur. Or the heat resistant laminate strength at the time of hot water treatment is not preferable. 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 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 easier the bag to bend and the curling become remarkable. Is controlled to 2.0% or less, preferably 1.5% or less, and more preferably 1.2% or less, the bag warpage during boiling water treatment is suppressed as much as possible, and the occurrence of S-curl phenomenon is prevented. It becomes possible to prevent.

  In the vapor-deposited polyamide-based resin laminated film roll of the present invention, the variation rate of the maximum boiling water shrinkage (BSx) of all samples cut out from the polyamide-based resin laminated film roll before vapor deposition is the average boiling water shrinkage (BSa). It is necessary to adjust to be within a range of ± 2% to ± 10% (± 2% or more and ± 10% or less). 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 resin laminated film roll before vapor deposition, when the boiling water shrinkage rate of samples (1) to (6) is Xn (n = 1 to 6), the maximum value Xmax of Xn and the average boiling water shrinkage rate. This means that both the difference from (BSax) and the difference between the minimum value Xmin and the average boiling water shrinkage (BSax) must be within ± 10%. That is, BSax-Xn | (where || indicates an absolute value) is required to be 10% or less.

  The polyamide-based resin laminated film roll before vapor deposition is preferably such that the variation rate of the maximum boiling water shrinkage rate (BSx) of all the cut out samples is within a range of ± 9% of the average boiling water shrinkage rate (BSa), More preferably within the range of ± 8%, and even more preferably within the range of ± 7%.

  In addition, the polyamide-based 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. I think the degree is the limit.

  Moreover, the vapor-deposited polyamide resin laminated film of the present invention has a variation rate of the boiling water shrinkage direction difference (BSd) of all samples cut out from the polyamide resin laminated film roll before vapor deposition, and the average boiling water shrinkage direction difference (BSad). ) Of ± 2% to ± 30% (± 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 resin laminated film roll before vapor deposition, when the boiling water shrinkage direction difference of the samples (1) to (6) is Yn (n = 1 to 6), the maximum value Ymax of Yn and the average boiling water The difference between the difference in shrinkage direction (BSad) and the difference between the minimum value Ymin and the average boiling water shrinkage direction difference (BSad) must be within ± 30%. In other words, | BSad-Yn | (where || indicates an absolute value) is required to be 10% or less.

  In addition, as for the polyamide-type resin laminated | multilayer film roll before vapor deposition, the fluctuation rate of the boiling water shrinkage | contraction rate direction difference (BSd) of all the cut-out samples exists in the range within +/- 20% of the average boiling water shrinkage rate direction difference (BSad). More preferably, it is in a range within ± 15%, more preferably in a range within ± 10%, and further preferably in a range within ± 8%.

  In addition, the polyamide resin laminated film roll before vapor deposition is preferable as the fluctuation rate of the boiling water shrinkage direction difference (BSd) of all the cut out samples is smaller, but the lower limit of the fluctuation rate is 2 in consideration of measurement accuracy. % Is considered the limit.

Moreover, the vapor deposition polyamide-type resin laminated | multilayer film roll of this invention is the average surface roughness ( SRa ) which is an average value of the three-dimensional surface roughness (SRa) of all the samples cut out from the polyamide-type resin laminated | multilayer film roll before vapor deposition. Is preferably in the range of 0.01 to 0.06 μm, and more preferably in the range of 0.02 to 0.05 μm (Note that in the Examples, an example of a method for measuring three-dimensional surface roughness is used. explain). 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.

  Moreover, as for the vapor deposition polyamide-type resin laminated | multilayer film roll of this invention, the variation rate of the three-dimensional surface roughness (SRa) of all the samples cut out from the polyamide-type resin laminated | multilayer film roll before vapor deposition is average surface roughness (SRaa). It is necessary to adjust so that it may be in the range of ± 5% to ± 20% (± 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 resin laminated film roll 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 This means that both the difference from the surface roughness (SRaa) and the difference between the minimum value SRmin and the average surface roughness must be within ± 20%, in other words, | SRaa -SRn | (where || indicates an absolute value) is required to be 20% or less.

  In addition, it is preferable that the polyamide-based resin laminated film roll before vapor deposition has a variation rate of the three-dimensional surface roughness (SRa) of all cut out samples within a range of ± 15% of the average surface roughness (SRaa). , More preferably within a range of ± 10%, and even more preferably within a range of ± 8%. In addition, the polyamide-based resin laminated film roll before vapor deposition is preferable as the variation rate of the three-dimensional surface roughness (SRa) of all the cut out samples is smaller, but the lower limit of the variation rate is 5 in consideration of measurement accuracy. % Is considered the limit.

  Moreover, the vapor deposition polyamide-type resin laminated | multilayer film roll of this invention has the average haze which is the average value of the haze of all the samples cut out from the polyamide-type resin laminated | multilayer film roll before vapor deposition in the range of 1.0-4.0. It is more 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 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 ± 5% (± 2% or more and ± 5% or less) of the average haze. It is necessary to be adjusted as follows. 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 resin laminated film roll before vapor deposition, when the haze of the samples (1) to (6) is Hn (n = 1 to 6), the difference between the maximum value Hmax of Hn and the average haze. And the difference between the minimum value Hmin and the average haze (Han) is required to be within ± 15%, in other words, | Han−Hn | | Indicates an absolute value), both of which are required to be 5% or less.

  In addition, the polyamide-based resin laminated film roll before vapor deposition preferably has a variation rate of haze of all cut out samples within a range of ± 10% of the average haze, and more preferably within a range of ± 8%. . In addition, the polyamide-based 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. thinking.

  In the vapor-deposited polyamide-based resin laminated film roll of the present invention, the variation rate of the thickness over the entire length in the longitudinal direction of the polyamide-based resin laminated film roll before vapor deposition is ± 2% to ± 10% (± 2) with respect to the average thickness. % Or more and ± 10% or less) is required to be adjusted. 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 resin laminated film roll before vapor deposition, the difference between the maximum thickness Tmax and the average thickness (average thickness Ta over the entire length in the longitudinal direction), the minimum value Tmin and the average thickness (Ta) ) Is required to be within ± 10%.

  In addition, the polyamide-based 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%. More preferred.

  In addition, the polyamide-based 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% in view of the performance of the film forming apparatus. I believe.

  On the other hand, the vapor-deposited polyamide resin laminated film roll of the present invention has an average dynamic friction coefficient 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 resin laminated film roll before vapor deposition. (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-based 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% or more and ± 30% or less) of the average dynamic friction coefficient. It is preferable to adjust 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 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 ± 20%. In other words, | μda−μn | (where || Indicates an absolute value) is preferably 20% or less.

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

  On the other hand, the vapor-deposited polyamide resin laminated film roll of the present invention has an average content of 0.01 to 0.00, which is the average value of the inorganic particle contents of all the samples cut out from the polyamide resin laminated film roll before vapor deposition. It is preferably in the range of 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 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 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% (± 5% or more and ± 20% or less) of the average content. It is preferable to adjust 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 resin laminated film roll before vapor deposition, when the content of the inorganic particles of the samples (1) to (6) is Cn (n = 1 to 6), the maximum value Cmax and the average of Cn are averaged. The difference between the content (Ca) and the difference between the minimum value Cmin and the average content is preferably within ± 10%. In other words, | Ca-Cn | , || represents an absolute value) is preferably 10% or less.

  In addition, the polyamide-based resin laminated film roll before vapor deposition is 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. In addition, the polyamide-based 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 limited to about 2% in consideration of measurement accuracy. I believe that.

Further, when the vapor-deposited polyamide-based resin laminated film roll of the present invention is cut out by the same method as described above, when the oxygen permeability is determined for each sample cut out from each cut-out portion, preferably the average oxygen permeability is the average value of the oxygen permeability is not more than ^{50ml / m 2 · MPa · day} , more preferably it is not more than ^{40ml / m 2 · MPa · day} , 30ml / m 2 · MPa · It is particularly preferable that it is not more than day.

  Further, in the vapor-deposited polyamide resin laminated film roll of the present invention, the variation rate of oxygen permeability from the polyamide resin laminated film roll before vapor deposition is ± 2% to ± 20% (± 2%) with respect to the average oxygen permeability. It is preferable that it is adjusted to be within the range of ± 20% or less. 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 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 value Pmin and the average oxygen permeability Pa are all. It is required to be within ± 20%.

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

  In addition, the vapor-deposited polyamide-based resin laminated film roll of the present invention is preferable as the fluctuation rate of the oxygen permeability is small, but the lower limit of the fluctuation rate is considered to be about 2% in view of the performance of the film forming apparatus. ing.

Furthermore, the polyamide-based resin laminated film roll of the present invention is a polyamide-based resin laminated film roll before vapor deposition. When the refractive index (Nz) in the thickness direction is obtained, the average refractive index (Nza), which is the average value of the refractive indexes, is preferably 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 film which comprises the polyamide-type resin film roll before vapor deposition has big influence on film quality, such as laminate strength and thickness spots. 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 polyamide-based resin laminated film. 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.

  In addition, the polyamide-based resin laminated film roll before vapor deposition has a variation rate of refractive index (Nz) of all cut out samples of ± 2% relative to the average value of the refractive indexes (hereinafter referred to as average refractive index). It is preferable to adjust so that it may become in the range. 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 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, That is, the difference between the minimum value Nzmin of Nz1 to Nz6 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 resin laminated | multilayer film roll before vapor deposition, it is more preferable that the variation 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 resin film roll obtained by winding the polyamide-based resin film before vapor deposition is preferably as small as the variation rate of the refractive index (Nz) of all the cut out samples, but the lower limit of the variation rate is the measurement accuracy. In terms of machine accuracy, about 0.1% is considered the limit.

  As described above, the maximum boiling water shrinkage rate, boiling water shrinkage direction difference, surface roughness, etc. in one polyamide-based resin laminated film roll before vapor deposition are adjusted to values within a predetermined range, and their maximum boiling water shrinkage rate By reducing fluctuations in boiling water shrinkage direction difference, surface roughness, etc., it is possible to uniformly deposit on the film surface, reduce variation in oxygen permeability, and in bag making and laminating processes Deterioration of the appearance can be prevented, and smooth processing can be performed with high yield even under high humidity.

  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 the polyamide-based resin laminated film roll before vapor deposition of the present invention is produced, the above 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.

  An inorganic vapor deposition layer is laminated on the polyamide-based resin laminated film. This inorganic vapor deposition layer imparts high gas barrier properties to the resulting polyamide-based resin 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 resin laminated film or heating and cooling the polyamide-based 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 resin film as needed.

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

  The polyamide-based resin laminated film needs to 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). It is. 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 the two-type two-layer configuration is referred to as a core layer. And the outermost layer (ie, 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 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 a two-type two-layer configuration is referred to as a skin layer.

  The thickness ratio of each layer of the polyamide-based 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%, and particularly preferably 12 to 18%. is there. 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 produce the laminated film as described above, a substantially unoriented polyamide sheet having the layer structure of A / B, A / B / A, or A / B / C is formed. 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 obtain a substantially unoriented polyamide sheet (so-called co-extrusion). Extrusion method) can be suitably employed.

  As a result of examining the thickness variation in the vertical direction of the film roll before vapor deposition (thickness variation over the entire length of the film roll), fluctuations in physical properties such as the boiling water shrinkage, and variations, the present inventors have found that It has been found that fluctuations and variations in physical properties 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 supplied to a funnel-shaped popper directly connected to the extruder (hereinafter simply referred to as a hopper) is low or the moisture content of the resin supplied to the hopper is high, the thickness in the longitudinal direction of the unstretched film It was found that the spots became larger, and the fluctuations and variations in physical properties of 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) Uniformity of resin chip shape (2) Optimization of hopper shape (3) Reduction of moisture content when resin chip is dried (4) Temperature retention when resin is supplied to hopper (5) Molten resin to metal roll Suction at the time of contact (6) Optimization of stretching conditions (7) Use of high-concentration raw material chips (8) Adjustment of properties of inorganic particles (9) Adjustment of film lamination mode Each of the above-described means will be described in turn below. .

(1) Uniformization of resin chip shape In the case of adopting a blend method in the production of a polyamide-based resin laminated film roll before vapor deposition, a plurality of raw material polyamide resin chips having different compositions are blended in a hopper and then melted. They are kneaded and extruded from an extruder to form a film (in the production of the film roll of the present invention, a plurality of extruders are used as described above). For example, when there are three types of polyamide as the raw material, the respective polyamide resin chips are supplied to three hoppers in a continuous or intermittent manner, and finally through the buffer hopper as needed, finally before the extruder Alternatively, while mixing three types of polyamide resin chips in a hopper directly above (hereinafter referred to as “final hopper”), raw material chips are quantitatively supplied to the extruder according to the extrusion amount of the extruder 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 the remaining amount of chips in the final hopper is small, the material segregation phenomenon, that is, from the final hopper to the extruder. A phenomenon occurs in which the composition of the supplied chip is different. Further, such segregation phenomenon appears particularly prominent when the shape or specific gravity of the chip is different. Further, due to such segregation phenomenon, when a long film is produced, the maximum boiling water shrinkage rate, the boiling water shrinkage direction difference, the film thickness, and the refractive index in the thickness direction vary.

  That is, if there is a difference in the size of the chips, when the mixture of chips falls in the final hopper, small chips tend to fall first, so if the remaining amount of chips in the final hopper decreases, This increases the ratio of this, which causes segregation of raw materials. Therefore, in order to obtain a film roll with little variation in physical properties, the shape of multiple types of polyamide resin chips to be used is matched, and the phenomenon of raw material segregation in the final hopper (each final hopper supplied to each extruder) is reduced. It is necessary to deter.

  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. Here, as a result of examining the relationship between the shape of the polymer chip and the raw material segregation, the average major axis (mm), the average minor axis (mm) of the cross-sectional ellipse of the other polyamide chips mixed with the polyamide chip with the largest amount of use, The average tip length (mm) is ± 20% relative to the average major axis (mm), average minor axis (mm), and average tip length (mm) of the cross-sectional ellipse of the polyamide material chip with the largest use amount, respectively. The raw material segregation can be reduced by adjusting within the above range. The average major axis, average minor axis, and average tip length of the elliptical cross section of the polyamide chip other than the polyamide chip with the largest amount of use are respectively shown in FIG. Adjustment to a range within ± 15% with respect to the diameter and average chip length is more preferable because the effect of preventing segregation becomes extremely remarkable.

(2) Optimizing the hopper shape By using a funnel-shaped hopper as the final hopper and making its inclination angle 65 ° or more, large chips can be easily dropped as well as small chips. Since it descends while maintaining a horizontal plane, it is effective in reducing raw material segregation. A more preferable inclination angle is 70 ° 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, and more preferably 70 ° or more.

  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 the 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.

  In addition, as a means for reducing raw material segregation in the hopper, it is also a preferable means to optimize the capacity of the hopper used. Here, the proper capacity of the 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% by weight with respect to the discharge amount per hour of the extruder. It is more preferable that it is within the range.

  As a method of mixing two or more kinds of polyamide raw material chips having different compositions, a method of mixing while continuously feeding each raw material to the extruder with a hopper (final hopper) directly above the extruder is most preferable. It is also possible to feed a final hopper and an extruder through several intermediate hoppers (buffer hoppers) after previously mixing a raw material chip size controlled within the aforementioned range. When mixing multiple types of raw materials, use a method of mixing raw materials chips continuously while quantitatively supplying multiple types of raw materials into a hopper, or using a blender, paddle dryer, etc. However, when using the latter, it is preferable to reduce the raw material chip size so that the raw material segregation does not occur when the mixture is discharged.

(3) Reduction of moisture content during resin chip drying Chips supplied into the hopper are usually heated by a device such as a blender to reduce moisture. 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 the study by the present inventors, in the production of a polyamide-based resin laminated film roll, it is difficult to stretch simply by reducing the moisture content during drying, and a film roll having uniform physical properties can be obtained. It was found that a film roll with uniform physical properties can be obtained 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. did. That is, in order to obtain the film roll of the present invention, it is necessary to control the moisture content of the 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.

(4) Maintaining temperature when resin is supplied to the 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 allowed to stand until the temperature reaches room temperature (room temperature). When it is supplied to the hopper after being lowered, a film roll with uniform physical properties cannot be obtained. In other words, in order to obtain a film roll having highly uniform physical properties, it is necessary to supply chips that have been heat-dried with a blender or the like to a hopper (each final hopper supplied to each extruder) while maintaining a high temperature. It is. Specifically, the chips dried by heating with a blender need to be supplied to the hopper while being maintained at 80 ° C. or higher, and more preferably supplied to the hopper while being maintained at 90 ° C. or higher. If the temperature of the chip supplied to the hopper is lower than 80 ° C., the resin will be poorly bitten, resulting in vertical thickness unevenness, physical property fluctuations and variations, and a film roll with highly uniform physical properties 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.

(5) Suction when the molten resin is brought into contact with a metal roll When an unstretched film is obtained by melting and extruding a chip, the chip is melted at a temperature of 200 to 300 ° C. by each extruder and extruded from a T die. After forming (i.e., casting) into a laminated film shape (laminated sheet shape), the film is rapidly cooled by a method of winding around a cooling roll such as a metal roll cooled to a predetermined temperature. In addition, from the viewpoint of vertical thickness variation, physical property fluctuations, and variations, a preferable melt extrusion temperature is 240 ° C. to 290 ° C. 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. At the same time, using a suction device such as a vacuum box (vacuum chamber) having a wide suction port, the part contacting the surface of the molten resin and 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. In this case, the suction air speed 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 the film roll of the present invention, it is necessary to suppress the variation in the suction wind speed of the vacuum box within ± 20% of the average suction wind speed (set value), and more preferably within ± 10%. . 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.

  Moreover, in order to obtain the film roll of the present invention, when the molten resin is wound around the cooling roll, a DC negative charge of 90 to 105 mA is applied to the molten resin sheet at 2 to 15 kv from the needle electrode, It is necessary to continuously contact and quench 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. Further, in order to obtain the film roll of the present invention, it is necessary to suppress the variation of the DC negative charge to be applied within an average negative charge (set value) of ± 20%, more preferably within ± 10%. .

(6) 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 the film roll of the present invention, it is necessary to adopt 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. And in order to obtain the film roll of this invention, when performing longitudinal-longitudinal-lateral stretching mentioned above, it is necessary to make the longitudinal stretch ratio of the 1st stage higher than the longitudinal stretch ratio of the 2nd stage. 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. Further, when a polyamide-based resin laminated film roll is produced by such a longitudinal-longitudinal-lateral stretching method, not only the thickness variation in the longitudinal direction, the variation in physical properties and the variation are reduced, but also the variation in physical properties in the lateral direction Variations can also be reduced. 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, the thickness of the film constituting the vapor-deposited polyamide-based resin laminated film roll of the present invention is not particularly limited. For example, the packaging polyamide-based film is preferably 8 to 50 μm, and more preferably 10 to 30 μm. .

  In addition, in polyamide-based resin laminated films other than vapor-deposited layers, lubricants, anti-blocking agents, thermal stabilizers, antioxidants, antistatic agents, light-proofing agents, impact resistance-improving agents can be used as long as the properties are not impaired. It is also possible to contain various additives such as. 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 resin laminated film before vapor deposition can be subjected to heat treatment or humidity control treatment in order to improve dimensional stability according to 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.

(7) 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.

(8) 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, it is also possible to measure from the particles before adding to the polyamide-based resin, It is also possible to measure from particles deposited by dissolving a polyamide-based 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.

(9) Adjustment of film lamination mode As described above, by adding inorganic particles in the polyamide-based resin and forming irregularities on the surface of the film, it becomes possible to express slipperiness. 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 (9) described above, and 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 (9) does not effectively contribute to the reduction of the physical property variation of the film roll, and the means (1) to (9) 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. . Properties of raw material chips A to E used in Examples and Comparative Examples, composition of raw material chips used in Examples and Comparative Examples, and film forming conditions of film rolls in Examples and Comparative Examples are shown in Tables 1 to 3, respectively. Show. In addition, chip A is nylon 6 (relative viscosity = 2.8, Tg = 41 ° C.) 94.85% by weight, polymetaxylylene adipamide (relative viscosity = 2.1) 5.00% by weight, ethylenebisstearin The chip B is composed of 99.85% by weight of nylon 6 (same physical properties as the chip A) and 0.15% by weight of ethylene bis-stearic acid amide. Chips C and E are both nylon particles (same physical properties as chip A) 85.00% by weight, average particle size 2.0 μm, pore volume 1.2 ml / g silica particles 15.0% The tip D is 95.00% by weight of nylon 6 (same physical properties as chip A), 5.0% by weight of silica particles having an average particle diameter of 2.0 μm and a pore volume of 1.6 ml / g. %. In addition, the shapes of the chips A to E are all elliptic cylinders, and the chips A to D have the same cross-sectional major axis, cross-sectional minor axis, and chip length.

[Example 1]
Using a co-extrusion method, a polyamide resin is melt-extruded from three extruders (first to third extruders) (laminated in a die and extruded), and rotated at 17 ° C. By being wound around and rapidly cooled, 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 resin laminated sheet (that is, the surface of the third layer is a metal roll contact surface).

-Formation of first layer (outer layer) Chips A and C 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 and C was 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.

  Thereafter, the chips A and C in each blender were continuously and separately supplied to the hopper directly above the extruder (first extruder) with a metering screw feeder. The supply amount of chip A was 99.5% by weight, and the supply amount of chip C was 0.5% by weight. 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 and C were supplied into the hopper, they were supplied to the hopper within a short time after drying so that the temperature of the chip in each blender would not become too low. The temperatures of chips A and C immediately before being supplied to the hopper were both about 91 ° C. Then, the supplied chips A and C were mixed in a hopper and melt-extruded from a T die at 270 ° C. by a single-screw first extruder.

・ Formation of second layer (intermediate layer) Chips A and C in each blender dried as described above are continuously supplied separately to the hopper directly above the extruder (second extruder) with a fixed screw feeder. did. The supply amount of chip A was 99.97% by weight, and the supply amount of chip C was 0.03% by weight. 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 and C were supplied into the hopper, they were supplied to the hopper within a short time after drying so that the temperature of the chip in each blender would not become too low. The temperatures of chips A and C immediately before being supplied to the hopper were both about 91 ° C. Then, the supplied chips A and C were mixed in a hopper, and melt-extruded from a T die at 270 ° C. by a single-screw second extruder.

-Formation of third layer (inner layer) Chips A and C in each blender dried as described above were continuously and separately supplied to the hopper directly above the extruder (third extruder) with a quantitative screw feeder. . The supply amount of chip A was 99.5% by weight, and the supply amount of chip C was 0.5% by weight. 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 and C were supplied into the hopper, they were supplied to the hopper within a short time after drying so that the temperature of the chip in each blender would not become too low. The temperatures of chips A and C immediately before being supplied to the hopper were both about 91 ° C. Then, the supplied chips A and C were mixed in a hopper, and melt-extruded from a T die at 270 ° C. with a single-screw third extruder.

  In each extruder of Example 1, the average major axis, the average minor axis, and the average chip length of the polyamide resin chips (Chip C) other than the polyamide resin chip having the largest usage amount are the most used. The average major axis, average minor axis, and average chip length of the polyamide-based resin chip (Chip A) are each 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-based 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). In the following BS (boiling water shrinkage), BSx (maximum boiling water shrinkage), BSd (boiling water shrinkage direction difference), and refractive index measurement, the first sample cut-out portion is within 2 m from the end of film winding. The second to tenth sample cutout portions are provided approximately every 100 m from the first sample cutout portion, and the eleventh sample cutout portion is provided within 2 m from the beginning of winding of the film. A sample film was cut out from each of the sample cutout portions. Further, using a polyamide-based resin film roll after composite vapor deposition (that is, 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), refractive index, and thickness variation were measured to evaluate the laminate processability. The evaluation results are shown in Tables 4-8. 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 polyamide-based resin laminated film (sample film) cut out from each cut-out part of the slit roll was cut into a square shape with a side of 21 cm and left for 2 hours or more in an atmosphere of 23 ° C. and 65% RH. 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]
For the surface of the biaxially oriented polyamide-based resin laminated film (sample film) cut out from each cut-out part of the slit roll, a stylus type three-dimensional surface roughness meter (SE-3AK, manufactured by Kosaka Laboratory Ltd.) was used. Under the conditions of a needle radius of 2 μm, a load of 30 mg, and a needle speed of 0.1 mm / s, the film was measured over a measurement length of 1 mm with a cutoff value of 0.25 mm in the longitudinal direction of the film 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 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]
The weight of the residue when the biaxially oriented film cut out from each cutout part of the slit roll is burned at 800 ° C. is calculated, and the ratio (percentage) of the residue weight to the film weight before burning is calculated as the content of inorganic particles. did. 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. In addition, the average average refractive index of all sample films is calculated to calculate the difference between the maximum or minimum Nz and the average refractive index in all samples, and the ratio of the difference to the average refractive index is calculated as the variation rate. did.

[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.

[Oxygen permeability]
After the film cut out from each cut-out part of the film roll was subjected to oxygen substitution for 2 days in an atmosphere of humidity 65% RH and temperature 25 ° C., in accordance with JIS-K-7126 (Method B), It measured using the oxygen permeability measuring apparatus (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 resin laminated film, an LDPE (15 μm thick) using a single test laminator device manufactured by Modern Machinery Co., Ltd. Low-density polyethylene) film is extruded at 315 ° C., and a 40 μm-thick LLDPE (linear low-density polyethylene) film is continuously laminated thereon to form a three-layer laminated structure of polyamide resin / LDPE / LLDPE A laminate film roll 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 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 to make a test piece, and a “Tensilon UMT-II-500 type” manufactured by Toyo Baldwin was used. The peel strength between the vapor-deposited polyamide-based resin laminated film layer and the LDPE layer was measured under the condition 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.

[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 the formation of the first layer and the third layer, when the chips A and C in each blender are supplied to the hopper immediately above the first extruder and the third extruder, the supply amount of the chip A is 99.0% by weight. And the amount of chips C supplied is 1.0% by weight, and when the chips A and C in each blender are supplied to the hopper directly above the second extruder in the formation of the second layer, The supply amount was 99.94% by weight, and the supply amount of chip C was 0.06% by weight. Other than that was carried out similarly to Example 1, and obtained the polyamide-type 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 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 4-8.

[Example 3]
When the raw material chips are melt extruded from the first to third extruders, the thickness ratio of the first layer / second layer / third layer is 1/13/1 so that the thickness ratio of the first to third extruders becomes 1/13/1. A polyamide-based resin laminated film roll was obtained in the same manner as in Example 1 except that the discharge amount 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 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 4-8.

[Example 4]
A polyamide-based resin laminated film roll was obtained in the same manner as in Example 1 except that instead of the raw material chip A, the raw material chip B was used (that is, in Example 4, the first to third layers were formed). Polyamide resin does not contain polymetaxylene dipamide). 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 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 4-8.

[Example 5]
When forming an unstretched laminated resin sheet, adjust the discharge rate of the first and third extruders so that the third layer is not formed and the thickness ratio of the first layer / second layer is 2/13. A polyamide-based resin laminated film roll was obtained in the same manner as in Example 1 except that. 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 (outer layer) and the second layer (inner layer) were about 2 μm, about It was 13 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 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 4-8.

[Example 6]
The raw material chip D is used instead of the raw material chip C as a raw material for forming the first layer and the third layer, and the chip A to the first extruder and the third extruder in the formation of the first layer and the third layer is used. The supply amount is 94.0% by weight, the supply amount of chip D is 6.0% by weight, the supply amount of chip A to the second extruder in the formation of the second layer is 99.6% by weight, The supply amount of chip C was set to 0.4% by weight. Other than that was carried out similarly to Example 1, and obtained the polyamide-type 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 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 4-8.

[Example 7]
An unstretched film (laminated 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, Longitudinal stretching (second longitudinal stretching) was performed about 1.5 times at a stretching temperature of about 70 ° C. by a ceramic roll. 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 biaxially stretched film was slit and wound in the same manner as in Example 1 to obtain a polyamide-based 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 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 4-8.

[Example 8]
An unstretched film (laminated film) obtained in the same manner as in Example 1 was 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 biaxially stretched film was slit and wound in the same manner as in Example 1 to obtain a polyamide-based 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 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 4-8.

[Example 9]
A polyamide-based resin laminated film roll was obtained in the same manner as in Example 1 except that when the raw material chips in the blender were supplied to the hoppers directly above the first to third extruders, the inclination angle of each hopper was changed to 65 °. 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 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 4-8.

[Comparative Example 1]
When forming an unstretched resin sheet, a single-layer structure is formed without forming the second layer and the third layer, and only the raw material chip A is used as a raw material for forming the first layer. Thus, a polyamide resin 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 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 4-8.

[Comparative Example 2]
A polyamide-based resin laminated film roll was obtained in the same manner as in Example 1 except that the raw material chip E was used instead of the raw material chip C. In Comparative Example 2, the average major axis and the average chip length of the polyamide resin chip (chip E) other than the polyamide resin chip having the largest use amount are the polyamide resin chips (chip A) having the largest use amount. The average major axis and the average chip length are not included within the 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 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 4-8.

[Comparative Example 3]
A polyamide-based resin laminated film roll was obtained in the same manner as in Example 1 except that when the raw material chips in the blender were supplied to the hoppers immediately above the first to third extruders, the inclination angle of the hopper was changed to 45 °. 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 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 4-8.

[Comparative Example 4]
The raw material chips A and C were preliminarily dried and then supplied to the hoppers immediately above the first to third extruders, and then left in each blender for about 5 hours, as in Example 1. A polyamide-based resin laminated film roll was obtained. The moisture content of the chips A and C immediately before being supplied to each hopper was 800 ppm, and the temperature of the chips A and C immediately before being supplied to each hopper was both about 30 ° 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 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 4-8.

[Comparative Example 5]
A polyamide-based resin laminated film roll was obtained in the same manner as in Example 1, except that the preliminary drying conditions of the raw material chips A and C were changed to a method of heating to about 100 ° C. over about 4.0 hours. . After pre-drying, a predetermined amount of each chip was sampled from the blender and the moisture content was measured. As a result, the moisture content of each of the chips A and C was 1500 ppm, and the chips A and C immediately before being supplied to the hopper The temperatures were all 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 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 4-8.

[Comparative Example 6]
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 obtained film was slit and wound in the same manner as in Example 1 to obtain a polyamide-based resin laminated film roll. 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 types of vapor-deposited polyamide-based resin laminated film rolls were obtained. Got. 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.

[Effects of Example Film]
From Tables 4 to 8, the film rolls before vapor deposition in the examples all have very small vertical thickness variation throughout the roll, and have physical properties such as boiling water shrinkage, refractive index, and dynamic friction coefficient under high humidity. It can be seen that the fluctuation of is small. In addition, it can be seen that all of the film rolls of the examples with small variations in physical properties such as boiling water shrinkage rate and refractive index do not cause the S-curl phenomenon and have good laminate processability even under high humidity. . In addition, it can be seen that the film constituting the film roll before vapor deposition in Examples has good impact strength (toughness and pinhole resistance) and good laminating properties. And the vapor deposition film roll which vapor-deposited the film roll of an Example with such a small fluctuation | variation of physical properties, such as a boiling water shrinkage | contraction rate, a refractive index, and a dynamic friction coefficient under high humidity, has low oxygen permeability (gas barrier property). It is understood 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 of the comparative example has a large variation in physical properties such as longitudinal thickness unevenness over the entire roll, boiling water shrinkage rate, refractive index, dynamic friction coefficient under high humidity, and poor laminating workability. It can be seen that the haze is extremely large and the S-curl phenomenon is observed. And the vapor deposition film roll which vapor-deposited the film roll of the comparative example with such a large physical property fluctuation | variation, such as boiling water shrinkage | contraction rate, refractive index, and a dynamic friction coefficient under high humidity, has a large fluctuation | variation of oxygen permeability. It can be seen that the laminate processability is poor.

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

Claims (25)

A vapor-deposited polyamide-based resin laminated film obtained by laminating a plurality of polyamide-based resin layers and depositing an inorganic substance on at least one side of a polyamide-based resin laminated film having a width of 0.2 m to 3.0 m and a length of 300 m to 30000 m. It is a vapor deposition polyamide-based resin laminated film roll formed by winding
A polyamide-based resin laminated film roll formed by winding a polyamide-based 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 resin laminated film roll characterized by satisfying the following requirements (1) to (5).
(1) For each sample cut out from each cutout part, when measuring the maximum boiling water shrinkage, which is the maximum value of the boiling water shrinkage in all directions, the average is the average value of the maximum boiling water shrinkage The boiling water shrinkage is 2% to 6%, and the variation rate of the maximum boiling water shrinkage of all the samples is within a range of ± 2% to ± 10% with respect to the average boiling water shrinkage (2) For each sample cut out from each cut-out part, 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 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 shrinkage. Within ± 2% to ± 30% of the rate direction difference (3) When the three-dimensional surface roughness in the winding direction is measured for each sample cut out from each cut-out portion, the average surface roughness, which is an average value of the three-dimensional surface roughness, is 0. The variation rate of the three-dimensional surface roughness of all the samples is in the range of ± 5% to ± 20% with respect to the average surface roughness (4) When measuring the haze of each sample cut out from each cut-out portion, the average haze, which is the average value of those hazes, is in the range of 1.0 to 4.0, and the haze variation of all the samples. The rate is in the range of ± 2% to ± 15% with respect to the average haze. (5) The variation rate of the thickness over the entire length in the longitudinal direction of the wound roll is ± 2% to the average thickness. Within ± 10% 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 vapor-deposition polyamide-based resin laminated film roll according to claim 1, 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. A polyamide-based resin laminated film roll formed by winding a polyamide-based 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 vapor-deposited polyamide according to claim 1, wherein the dynamic friction coefficient of all samples is within a range of ± 5% to ± 30% with respect to the average dynamic friction coefficient. -Based resin laminated film roll. A polyamide-based resin laminated film roll formed by winding a polyamide-based 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% The vapor deposition polyamide system according to claim 1, wherein 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. Resin laminated film roll. A polyamide-based resin laminated film roll formed by winding a polyamide-based 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-based resin laminated film roll according to claim 1, wherein a variation rate of a refractive index of the sample is within a range of ± 2% with respect to the average refractive index. A polyamide-based resin laminated film roll formed by winding a polyamide-based resin laminated film before vapor deposition,
The vapor-deposited polyamide-based resin laminated film roll according to claim 1, wherein the average particle diameter of the inorganic particles contained in the core layer is equal to or greater than the thickness of the skin layer.   The vapor-deposited polyamide-based resin laminated film roll according to claim 1, wherein the main component of polyamide constituting the polyamide-based resin laminated film other than the inorganic substance is nylon 6.   2. The laminated polyamide-based resin laminated film formed by vapor-depositing an inorganic substance on a polyamide-based resin laminated film formed from a mixture of two or more different polyamide-based resins. Vapor deposition polyamide resin laminated film roll.   The vapor-deposited polyamide resin laminate film roll according to claim 1, wherein the wound vapor-deposition polyamide resin laminate film is laminated with a polyolefin resin film.   The molten polyamide resin is extruded from a T-die, brought into contact with a metal roll and cooled, and an inorganic substance is deposited on a polyamide resin laminated film obtained by biaxially stretching an unoriented sheet-like material and wound. The vapor-deposited polyamide-based resin laminated film roll according to claim 1, wherein the film-laminated film roll is a film roll.   The vapor-deposited polyamide-based resin laminated film roll according to claim 1, wherein the polyamide-based resin laminated film stretched by a tenter stretching method is an inorganic substance deposited and wound up.   The vapor-deposited polyamide resin laminated film roll according to claim 1, wherein the polyamide resin laminated film sequentially biaxially stretched is an inorganic substance deposited and wound.   The vapor-deposited polyamide-based resin laminate film roll according to claim 1, wherein the polyamide-based resin laminate film stretched biaxially in the longitudinal direction and the transverse direction is obtained by depositing and winding an inorganic substance.   A sheet-like material composed of a substantially unoriented polyamide resin was stretched in the longitudinal direction in at least two stages so that the glass transition temperature of the polyamide resin + 20 ° C. and a magnification of 3 times or more. 2. The vapor-deposited polyamide system according to claim 1, wherein an inorganic substance is vapor-deposited and wound on a polyamide-based resin laminated film that has been stretched in the lateral direction so as to have a magnification of 3 times or more. Resin laminated film roll.   The vapor-deposited polyamide resin laminate film roll according to claim 1, wherein the polyamide resin laminate film heat-fixed after being subjected to a final stretching treatment is an inorganic substance deposited and wound up.   The vapor-deposited polyamide resin laminate film roll according to claim 1, wherein the polyamide resin laminate film subjected to relaxation treatment after heat setting is obtained by depositing and winding an inorganic substance.   In the polyamide-based resin laminated film other than the inorganic substance of the wound vapor-deposited polyamide-based resin laminated film, a lubricant, an anti-blocking agent, a thermal stabilizer, an antioxidant, an antistatic agent, a light resistance agent, an impact resistance improving agent At least 1 sort (s) of them is added, The vapor deposition polyamide-type resin laminated film roll of Claim 1 characterized by the above-mentioned.   The vapor-deposited polyamide resin laminated film roll according to claim 1, wherein inorganic particles are added to the polyamide-based resin laminated film other than the inorganic substance of the wound vapor-deposited polyamide-based resin laminated film.   The vapor deposition polyamide resin laminated film roll according to claim 18, wherein the inorganic particles are silica particles having an average particle diameter of 0.5 to 5.0 μm.   The vapor-deposited polyamide resin laminate film roll according to claim 1, wherein higher fatty acid is added to the polyamide resin laminate film other than the inorganic substance of the wound vapor-deposition polyamide resin laminate film. It is a manufacturing method for manufacturing the vapor deposition polyamide-type resin laminated | multilayer film roll described in Claim 1,
A film forming step of forming an unstretched laminated sheet in which a plurality of polyamide resin layers are laminated by melt-extruding a polyamide resin from a plurality of extruders by a coextrusion method;
A biaxial stretching step of biaxially stretching the unstretched laminated sheet obtained in the film forming step in the longitudinal 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 vapor deposition polyamide-type resin laminated | multilayer film roll characterized by satisfy | filling the following requirements (a)-(f).
(A) The film forming step uses a high-concentration raw material chip to laminate a skin layer added with 0.05 to 2.0% by weight of inorganic particles on the core layer (b) In the biaxial stretching process, the stretching is performed in two stages in the longitudinal direction and then in the transverse direction, and the first stretching ratio in the two-stage stretching in the longitudinal direction is set higher than the stretching ratio in the second stage. (C) In the film forming step, each of the extrusions is performed after mixing a chip made of a polyamide resin having the largest use amount with one or more other polyamide resin chips having a composition different from that of the polyamide resin chip. The shape of each polyamide-based resin chip used is melt-extruded from a machine to form an unstretched laminated sheet, and the shape of each polyamide-based resin chip is an elliptical column having an elliptical cross section having a major axis and a minor axis In addition, the polyamide resin chips other than the polyamide resin chips that are used in the largest amount are each ± 20 relative to the average major axis, average minor axis, and average chip length of the polyamide resin chips that are used the most. (D) a plurality of extrusions provided with a funnel-shaped hopper as a raw material chip supply section, being adjusted to have an average major axis, an average minor axis and an average chip length included in the range of A step of melt-extruding using a machine, and all the inclination angles of the funnel-shaped hopper are adjusted to 65 degrees or more, and the moisture content of the polyamide-based resin chip before being supplied to the funnel-shaped hopper Is adjusted to 800 ppm or more and 1000 ppm or less, and the temperature of the polyamide resin chip before being supplied to the funnel-shaped hopper is 80 ° C. (E) The film forming step includes a step of cooling the melt-extruded unstretched laminated sheet by bringing it into contact with a cooling roll, and in the cooling step, the molten resin and The portion in contact with the surface of the cooling roll is sucked in the direction opposite to the winding direction by the suction device over the entire width of the molten resin. (F) The vapor deposition step is performed by laminating a metal or metal oxide with a polyamide resin laminate. The film should be deposited on at least one side of the film to have a thickness of 5.0 nm to 200 nm.   The vapor-deposited polyamide-based resin laminated film according to claim 21, 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, the inorganic particles added to the polyamide-based resin laminate 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 method for producing a vapor-deposited polyamide-based resin laminated film roll according to claim 21, wherein the method is a product.   The method for producing a vapor-deposited polyamide resin laminated film roll according to claim 21, wherein the inorganic substance is a metal or a metal oxide. 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 resin laminated | multilayer film roll of Claim 21.