WO2013099698A1 - Easy-to-tear laminated film and easy-to-tear packaging bag - Google Patents

Easy-to-tear laminated film and easy-to-tear packaging bag Download PDF

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Publication number
WO2013099698A1
WO2013099698A1 PCT/JP2012/082785 JP2012082785W WO2013099698A1 WO 2013099698 A1 WO2013099698 A1 WO 2013099698A1 JP 2012082785 W JP2012082785 W JP 2012082785W WO 2013099698 A1 WO2013099698 A1 WO 2013099698A1
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film
mxd6
raw material
easily tearable
biaxially stretched
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PCT/JP2012/082785
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French (fr)
Japanese (ja)
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真男 高重
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出光ユニテック株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/04—4 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/46—Bags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to an easily tearable laminate film and an easily tearable packaging bag using the film.
  • Biaxially stretched nylon film (hereinafter also referred to as ONy film) is excellent in strength, impact resistance, pinhole resistance, etc., so it is used for packaging materials for various foods such as retort foods, packaging materials for pharmaceuticals, and electronic components. It is used in very wide fields such as packaging materials.
  • the packaging ONy film used in each field described above is required to have a cutting property that can be easily opened at the time of opening, in addition to the strength required for conveyance and heat treatment. So far, an easily tearable ONy film using a mixed resin made of nylon 6 (Ny6) and metaxylylene adipamide (MXD6) as a raw material is known (see Patent Documents 1 and 2).
  • Patent Document 1 and Patent Document 2 gives a surface base material excellent in linear cut property, and even when used as a laminate film, the excellent straight cut property can be maintained. Practical value as a sex bag.
  • a biaxially stretched film made of a blend resin of Ny6 and MXD6 may cause so-called delamination within the layer of the biaxially stretched film if it is placed under harsh conditions after forming a laminate film. is there. When such delamination occurs, the strength of the laminate film becomes unstable, causing a practical problem when a bag is constructed.
  • the easy tearability of the easy tearable ONy film alone is good, and even if the laminate strength is high, the tearability after lamination (particularly the straight cut property) may not be exhibited. Furthermore, after forming a packaging bag, a so-called mouth curl phenomenon in which an unsealed end (mouth) curls may occur.
  • the present invention uses a raw material obtained by adding a heat history product of the resin to a mixed resin composed of Ny6 and MXD6, and improves the thickness accuracy (thickness accuracy) of the obtained stretched film.
  • the laminate film is excellent in laminating strength, is not easily peeled in the layer of the stretched film, is easily tearable (straight cut property), and is easily peelable after the bag is formed.
  • An object of the present invention is to provide an easily tearable packaging bag using
  • the present invention provides the following easily tearable laminate film and easily tearable packaging bag.
  • MXD6 metaxylylene adipamide
  • the biaxially stretched film obtained by further laminating is a biaxially stretched film according to the above (1), or Ny6, MXD6, and ethylene vinyl alcohol.
  • An easily tearable laminate film which is a biaxially stretched film made from a polymer, polyester (PET, PBT, etc.), polyolefin, polystyrene, or polycarbonate.
  • the biaxially stretched film obtained by further laminating and the biaxially stretched film described in (1) above are coextrusion multilayer stretched.
  • a mixed resin composed of Ny6 and MXD6 is used with a raw material in which a heat history product of the resin is further added, and the thickness accuracy (thickness accuracy) of the obtained stretched film is improved, and the sealant film
  • the laminate film is excellent in laminating strength, is not easily peeled in the layer of the stretched film, is easily tearable (straight cut property), and is easily peelable after the bag is formed.
  • An easily tearable packaging bag can be provided.
  • FIG. 1 Schematic of the biaxial stretching apparatus which manufactures the ONy film which concerns on embodiment.
  • a biaxially stretched nylon film (hereinafter also simply referred to as “ONy film”), which is a component of the easily tearable laminate film of the present invention, will be described, and then the easily tearable laminate film and easily tearable.
  • the packaging bag will be described.
  • a virgin raw material and a heat history product in which Ny6 and MXD6 are melt-kneaded at the same ratio as the virgin raw material to have a melting point of MXD6 of 233 ° C. or higher and 238 ° C. or lower.
  • the blending ratio of the heat history product is 5% by mass or more and 40% by mass or less based on the total amount of raw materials.
  • the chemical formula of Ny6 is shown in the following formula (1)
  • the chemical formula of MXD6 is shown in the following formula (2).
  • the above-mentioned virgin raw material usually means a raw material that is not a mixed raw material having a history in which Ny6 and MXD6 are mixed and melt-kneaded.
  • Ny6 and MXD6 have a history of being melt-kneaded independently (for example, recycled products), they are virgin raw materials when they are not mixed and melt-kneaded.
  • Ny6 and MXD6 have a history of being mixed and melt-kneaded with each other, the kneading is weak, so MXD6 does not have much melting point drop, and if it exceeds 238 ° C., these Ny6 and MXD6 are still It constitutes a virgin raw material, not a heat history product. That is, in this embodiment, three (or two) who added heat history products to Ny6 and MXD6 constituting the virgin raw material are so-called dry blended and then melt-kneaded to constitute an ONy film.
  • the above-mentioned heat history product is a blended product of Ny6 and MXD6, which has passed through the extruder once.
  • the melting point of MXD6 resin is 233 ° C. or higher and 238 by a scanning scanning calorimeter (DSC). The one kept in the range of °C or less is used.
  • Ny6 is 40 parts by mass or more and 85 parts by mass or less
  • MXD6 is 15 parts by mass or more and 60 parts by mass or less
  • Ny6 is 60 parts by mass or more and 85 parts by mass or less
  • MXD6 is 15 parts by mass or more and 40 parts by mass or less.
  • the ratio of Ny6 and MXD6 is the ratio for the raw material consisting of both the virgin raw material and the heat history product. When the ratio of Ny6 and MXD6 in the raw material is within this range, not only the tearability (particularly, the straight cut property) is excellent, but also the thickness accuracy of the film after biaxial stretching is extremely excellent.
  • the melting point of MXD6 in the heat history product is 233 ° C. or higher and 238 ° C. or lower, preferably 235 ° C. or higher and 237 ° C. or lower.
  • the melting point of MXD6 in the heat history product is less than 233 ° C., the linear cut property and impact strength of the ONy film are lowered.
  • the melting point of MXD6 in the heat history product exceeds 238 ° C., the thickness accuracy deteriorates.
  • the melting point of MXD6 in the heat history product is further lowered.
  • the melting point of MXD6 in the heat history product refers to a melting point measured in a state before being melt-kneaded with the virgin raw material. Since the ONy film of this embodiment is used as a surface base material of an easily tearable laminate film (and also an easily tearable packaging bag) as described later, from the viewpoint of easy tearing, either the MD direction or the TD direction. Also in this direction, the tear strength is preferably 70 N / cm or less.
  • the blending ratio of the heat history product is 5% by mass or more and 40% by mass or less, preferably 15% by mass or more and 30% by mass or less based on the total amount of raw materials.
  • in-layer peeling refers to a phenomenon that causes peeling in an ONy film (nylon layer) when the ONy film is laminated with an appropriate sealant film and used under severe conditions. The mechanism of delamination is not necessarily clear, but it is considered that Ny6 and MXD6 are oriented in layers in the ONy film, and delamination occurs at the interface.
  • the ONy film of this embodiment can be suitably manufactured by a simultaneous biaxial stretching method using a tubular method. Specifically, it can be produced as follows. First, in an extrusion process, a raw material including a virgin raw material and a heat history product is melted and kneaded at 270 ° C., and then the melt is extruded from a die as a cylindrical film (melting raw material). Next, in the cooling step, the molten original fabric is quenched with water to obtain an original fabric film. Next, in the stretching step, as shown in FIG.
  • each draw ratio of MD direction and TD direction is 2.8 times or more. If the draw ratio is less than 2.8 times, the impact strength may be reduced, causing a problem in practicality.
  • the stretched film is placed in a tenter heat treatment furnace (not shown) and heat-set at 160 to 210 ° C., whereby the ONy film 18 of the present embodiment can be obtained.
  • a required additive can be suitably added to an ONy film.
  • antiblocking agents such as inorganic fillers
  • water repellents such as ethylene bis stearamide
  • lubricants such as magnesium stearate
  • the easily tearable laminate film in this embodiment has a configuration in which a seal layer (sealant film (SL)) is laminated on an ONy film via an adhesive layer (AD) as follows.
  • various resin films can be used depending on applications. For example, for retort, it is preferable to use a commercially available retort CPP film. Moreover, it is preferable to use linear low density polyethylene (LLDPE) for heavy goods packaging.
  • LLDPE linear low density polyethylene
  • this adhesive layer is required to have a dynamic elastic modulus E ′ at 25 ° C. satisfying the following formula [A].
  • LogE ′ ⁇ 7.7 [A] (Log is a common logarithm.) If LogE ′ is less than 7.7, even if the laminate strength is high, tearability cannot be obtained when the laminate film (packaging bag) is cut (opened). Specifically, the ONy film and the seal layer are so-called pulled (a phenomenon in which the ONy film and the sealant film extend and cannot be cut cleanly) at the time of cutting, and good openability (straight cut performance) is obtained. Disappear.
  • E ′ can be measured, for example, by the following method.
  • the elastic modulus E ′ is obtained.
  • the measurement temperature is 25 ° C.
  • the thickness accuracy of the film is excellent. This thickness accuracy is important because it affects printing suitability and laminate suitability when producing a laminate film.
  • the laminate film is excellent in the strength of lamination with the sealant film, and is difficult to cause in-layer peeling of the stretched film. In addition, the curl of the mouth is less likely to occur after bag making.
  • the ONy film as the front substrate is used as a single layer.
  • a biaxially stretched film or an unstretched film may be further laminated.
  • the same film as the above-mentioned ONy film may be used, such as Ny6, MXD6, ethylene vinyl alcohol copolymer (EVOH), polyester (PET, PBT, etc.), polyolefin, polystyrene, polycarbonate, etc. May be used as a raw material.
  • Ny6, MXD6 ethylene vinyl alcohol copolymer
  • PET PET, PBT, etc.
  • polyolefin polystyrene
  • polycarbonate etc.
  • the following configuration may be used.
  • a laminate film was prepared by dry laminating the stretched film 18 (surface base film) and a sealant film (CPP film for retort [Unilux RT680 manufactured by Idemitsu Unitech Co., Ltd., thickness 60 ⁇ m]). Details of the agent are shown in Examples and Comparative Examples described later and Table 1.
  • the laminated film after dry lamination was aged at 40 ° C. for 3 days.
  • a strip-shaped test piece having a width of 15 mm was cut out from the above-mentioned laminate film, and the end thereof was subjected to interfacial peeling by several cm by hand to separate the surface base film (stretched film 18) and the sealant film.
  • each film piece was set in a tensile tester (Instron universal tester 1123 type), a peel test of the laminate portion was performed at a speed of 300 mm / min, and the laminate strength was measured (90 degree peel).
  • the laminate strength (peel strength) of 5 N / m or more was evaluated as A, less than 5 N / m, 3 N / m or more as B, and less than 3 N / m as C.
  • the peel strength sharply decreases. Therefore, it can be determined whether or not such peeling has occurred, depending on whether or not such behavior has occurred. For example, at the start of the peel test, if the peel strength was about 7 N / m, but it suddenly decreased to about 1 to 2 N / m during the peel test, it can be determined that in-layer peel occurred. And the thing which did not show the behavior of peeling in a layer inside a surface base film, and the thing which showed the behavior of peeling in a layer were evaluated as B.
  • FIG. 4 shows a packaging bag 42 in which the opening 41 faces the TD direction of the laminate film 18.
  • the size of this packaging bag 42 is 150 mm (length) x 130 mm (width), and the seal width is 10 mm.
  • the mouth curl of the packaging bag 42 was measured and evaluated as follows. That is, as shown in FIG. 5, the packaging bag 42 was left in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% for 3 hours, and the thickness L of the opening 41 due to the mouth curl was measured. And when the average value of the thickness L of the opening part 41 of 10 packaging bags 42 was less than 2 mm, the case where it was 2 mm or more and less than 4 mm was evaluated as B and the case where it was 4 mm or more as C did.
  • Example 1 Manufacture of stretched film
  • a heat history product that has been melt-mixed and pelletized once at this blending ratio with respect to a virgin raw material obtained by mixing 70 parts by mass of Ny6 pellets and 30 parts by mass of MXD6 pellets (with a melting point of MXD6 of 236 ° C.) 20% by mass based on the total amount of raw materials (based on the total amount of virgin raw materials and heat history products).
  • this dry blend product was melt-kneaded at 270 ° C. in an extruder, the melt was extruded as a cylindrical film from a die and then rapidly cooled with water (15 ° C.) to produce a raw film.
  • the melting point of MXD6 was measured by increasing the temperature from 50 ° C. to 280 ° C. at a temperature increase rate of 10 ° C./min using a differential scanning calorimeter (DSC) manufactured by PerkinElmer. In any case, the peak value in the first run was taken as the melting point.
  • the heat history product was heat-treated at 270 ° C. for 10 minutes.
  • the raw film 11 is inserted between a pair of nip rolls 12, and then heated with a heater 13 (set temperature 310 ° C.) while a gas is being pressed into the film 11.
  • Air 15 is blown from the air ring 14 with an air volume of 15 m 3 / min to be expanded into a bubble 16 and taken up by a pair of downstream nip rolls 17 to perform simultaneous biaxial stretching in the MD direction and the TD direction by the tubular method. It was. The magnification during this stretching was 3.0 times in the MD direction and 3.2 times in the TD direction. The stretch moldability was good.
  • the thickness precision was measured by the above-mentioned method.
  • dry lamination was performed using the ONy film as a front substrate to produce a laminate film.
  • Takelac A-615 / A-65 (mixing ratio 16: 1) manufactured by Mitsui Chemicals was used.
  • Examples 2 to 8, Comparative Examples 1 to 11 Except for changing the resin / layer structure of the surface base material, the blending amount of the heat history product, the melting point of the heat history product, and the type of adhesive (logE ') used for lamination with the sealant as shown in Table 1.
  • An ONy film was produced in the same manner as in Example 1.
  • the heat history products are all manufactured by melt-kneading using virgin products at the same Ny6 / MXD blend ratio as the virgin products.
  • the surface base material was coextruded (total film thickness was 25 ⁇ m, and the thickness of each layer was 8 ⁇ m / 9 ⁇ m / 8 ⁇ m).
  • Example 6 and Comparative Example 6 a polyester film (PET film 12 ⁇ m thickness) was dry laminated on the ONy surface. The thickness of each layer is 12 ⁇ m / 3 ⁇ m / 15 ⁇ m.
  • the same adhesive as that used for the laminate of ONy and sealant was used under the same conditions.
  • the surface base material was manufactured and evaluated by coextrusion multilayer stretching of PET / AD / (Ny6 + MXD6).
  • Comparative Example 7 since no heat history product was blended and the log E ′ of the adhesive was as small as 7.4, an in-layer peeling phenomenon occurred, the thickness accuracy was poor, and the tearability was poor. In Comparative Example 8, since the log E ′ of the adhesive is as small as 7.4, the tearability is poor. In Comparative Example 9, only Ny6 is used as a raw material, and MXD6 is not blended, so that easy tearing does not occur. In addition, the mouth curl of the packaging bag is large, and it is predicted that trouble will occur during filling. In Comparative Example 10, since the amount of MXD6 blended is small and there is no blend of heat history products, in-layer peeling is likely to occur, and easy tearability is poor. Also, the film thickness accuracy is poor.
  • the mouth curl of the packaging bag is also large.
  • the amount of MXD6 blended is too large, while no heat history product is blended. Therefore, delamination is likely to occur and the tearability is poor. Furthermore, the thickness accuracy of the film is very poor.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Bag Frames (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

An easy-to-tear laminated film comprising: a biaxially stretched film which is produced using a raw material comprising a virgin raw material and a heat history product, wherein the virgin raw material comprises 40 to 85 parts by mass inclusive of Ny6 and 15 to 60 parts by mass inclusive of MXD6, the heat history product is produced by melt-kneading Ny6 with MXD6 at the same ratio as that employed in the virgin raw material until the melting point of MXD6 becomes 233 to 238˚C inclusive, and the content ratio of the heat history product is 5 to 40 mass% inclusive in terms of raw material content; an adhesive layer of which the dynamic elastic modulus (E') at 25˚C fulfills formula [A] shown below; and a seal layer. LogE' ≥ 7.7 [A]

Description

易裂性ラミネートフィルムおよび易裂性包装袋Easy tear laminate film and easy tear packaging bag
　本発明は、易裂性ラミネートフィルム、および当該フィルムを用いてなる易裂性包装袋に関する。 The present invention relates to an easily tearable laminate film and an easily tearable packaging bag using the film.
　二軸延伸ナイロンフィルム（以後、ＯＮｙフィルムとも言う）は、強度や耐衝撃性、耐ピンホール性等に優れるため、レトルト食品等の各種食品用の包装材料、医薬品用包装材料、および電子部品用包装材料など非常に広い分野で使用されている。
　一方、上述した各分野で用いられる包装用ＯＮｙフィルムには、搬送時や熱処理時等に必要な強度のほか、開封時に容易に開封することができるカット性が求められている。これまで、ナイロン６（Ｎｙ６）とメタキシリレンアジパミド（ＭＸＤ６）からなる混合樹脂を原料とする易裂性ＯＮｙフィルムが知られている（特許文献１、２参照）。 Biaxially stretched nylon film (hereinafter also referred to as ONy film) is excellent in strength, impact resistance, pinhole resistance, etc., so it is used for packaging materials for various foods such as retort foods, packaging materials for pharmaceuticals, and electronic components. It is used in very wide fields such as packaging materials.
On the other hand, the packaging ONy film used in each field described above is required to have a cutting property that can be easily opened at the time of opening, in addition to the strength required for conveyance and heat treatment. So far, an easily tearable ONy film using a mixed resin made of nylon 6 (Ny6) and metaxylylene adipamide (MXD6) as a raw material is known (see Patent Documents 1 and 2).
　特許文献１や特許文献２に記載された易裂性ＯＮｙフィルムは、直線カット性に優れた表基材を与え、ラミネートフィルムとした時でも、その優れた直線カット性を維持できるため、易裂性袋として実用上の価値が高い。しかしながら、Ｎｙ６とＭＸＤ６とのブレンド樹脂からなる二軸延伸フィルムは、ラミネートフィルムを構成した後に、過酷な条件下に置かれると、二軸延伸フィルムの層内で、いわゆる層内剥離を引き起こす恐れがある。このような、層内剥離が起こると、ラミネートフィルムの強度が不安定となり、袋を構成した場合に実用上の問題が生ずる。そこで、Ｎｙ６とＭＸＤ６樹脂からなる混合樹脂（バージン樹脂）に対し、Ｎｙ６とＭＸＤ６を溶融混練して、ＭＸＤ６の融点を２３３～２３８℃とした熱履歴品を添加することにより、層内剥離性を改善した易裂性ＯＮｙフィルムが提案されている（特許文献３参照）。 The easily tearable ONy film described in Patent Document 1 and Patent Document 2 gives a surface base material excellent in linear cut property, and even when used as a laminate film, the excellent straight cut property can be maintained. Practical value as a sex bag. However, a biaxially stretched film made of a blend resin of Ny6 and MXD6 may cause so-called delamination within the layer of the biaxially stretched film if it is placed under harsh conditions after forming a laminate film. is there. When such delamination occurs, the strength of the laminate film becomes unstable, causing a practical problem when a bag is constructed. Therefore, by mixing Ny6 and MXD6 into a mixed resin (virgin resin) composed of Ny6 and MXD6 resin and adding a heat history product in which the melting point of MXD6 is 233 to 238 ° C., the in-layer peelability is improved. An improved easily tearable ONy film has been proposed (see Patent Document 3).
特開平５－２２０８３７号公報Japanese Patent Laid-Open No. 5-220837 特開平５－２００９５８号公報Japanese Patent Laid-Open No. 5-200958 特開２００７－３９６６４号公報JP 2007-39664 A
　特許文献３のように、Ｎｙ６とＭＸＤ６を溶融混練してなる熱履歴品を添加した原料を用いてチューブラー法による二軸延伸を行うと、バブルが安定せず横揺れを起こしたり、時にはバブルが破裂するという製造上の問題がある。また、このように成形安定性が低下すると、結果としてフィルムの厚み精度（偏肉精度）も低下するという問題も生じる。
　一方、易裂性ＯＮｙフィルムのような表基材は、裏基材（シーラントフィルム）とラミネートした後に包装袋として用いられる。その際、易裂性ＯＮｙフィルム単体での易裂性がよく、さらにラミネート強度が高くても、ラミネート後の易裂性（特に直線カット性）が発揮できないことがある。さらに、包装袋とした後に、開封端（口元）がカールしてしまういわゆる口元カール現象が生じる場合もある。 As in Patent Document 3, biaxial stretching by the tubular method using a raw material added with a heat history product obtained by melt-kneading Ny6 and MXD6 causes bubbles to become unstable and sometimes roll, There is a manufacturing problem that ruptures. Further, when the molding stability is lowered in this way, there arises a problem that the thickness accuracy (thickness accuracy) of the film is also lowered as a result.
On the other hand, a front substrate such as an easily tearable ONy film is used as a packaging bag after being laminated with a back substrate (sealant film). At that time, the easy tearability of the easy tearable ONy film alone is good, and even if the laminate strength is high, the tearability after lamination (particularly the straight cut property) may not be exhibited. Furthermore, after forming a packaging bag, a so-called mouth curl phenomenon in which an unsealed end (mouth) curls may occur.
　そこで、本発明は、Ｎｙ６とＭＸＤ６からなる混合樹脂に対し、さらに当該樹脂の熱履歴品を添加した原料を用い、得られた延伸フィルムの厚み精度（偏肉精度）を向上させるとともに、シーラントフィルムとのラミネート強度に優れ、延伸フィルムの層内剥離も生じにくく、ラミネートフィルムの易裂性（直線カット性）に優れ、さらには製袋後に口元カールが生じにくい易裂性ラミネートフィルム、および当該フィルムを用いてなる易裂性包装袋を提供することを目的とする。 Therefore, the present invention uses a raw material obtained by adding a heat history product of the resin to a mixed resin composed of Ny6 and MXD6, and improves the thickness accuracy (thickness accuracy) of the obtained stretched film. The laminate film is excellent in laminating strength, is not easily peeled in the layer of the stretched film, is easily tearable (straight cut property), and is easily peelable after the bag is formed. An object of the present invention is to provide an easily tearable packaging bag using
　前記課題を解決すべく、本発明は、以下のような易裂性ラミネートフィルムおよび易裂性包装袋を提供するものである。
（１）ナイロン６（Ｎｙ６）を４０質量部以上８５質量部以下と、メタキシリレンアジパミド（ＭＸＤ６）を１５質量部以上６０質量部以下とからなる（ただし、Ｎｙ６＋ＭＸＤ６＝１００重量部）バージン原料と、Ｎｙ６およびＭＸＤ６を前記バージン原料と同じ割合で溶融混練してＭＸＤ６の融点を２３３℃以上２３８℃以下とした熱履歴品とを含み、前記熱履歴品の配合割合が原料全量基準で５質量％以上４０質量％以下である原料を用いてなる二軸延伸フィルムと、２５℃における動的弾性率Ｅ’が下記式〔Ａ〕を満たす接着層と、シール層とを備えることを特徴とする易裂性ラミネートフィルム。
　　　　　　　　　　ＬｏｇＥ’≧７．７　　　　　〔Ａ〕
（２）上述した本発明の易裂性ラミネートフィルムにおいて、二軸延伸フィルムあるいは無延伸フィルムをさらに積層してなることを特徴とする易裂性ラミネートフィルム。
（３）上述した本発明の易裂性ラミネートフィルムにおいて、前記さらに積層してなる二軸延伸フィルムが、上述の（１）に記載の二軸延伸フィルム、または、Ｎｙ６、ＭＸＤ６、エチレンビニルアルコール共重合体、ポリエステル（ＰＥＴ、ＰＢＴ等）、ポリオレフィン、ポリスチレンおよびポリカーボネートのいずれかを原料とした二軸延伸フィルムであることを特徴とする易裂性ラミネートフィルム。
（４）上述した本発明の易裂性ラミネートフィルムにおいて、前記さらに積層してなる二軸延伸フィルムと、上述の（１）に記載の二軸延伸フィルムとが、共押出多層延伸されたものであることを特徴とする易裂性ラミネートフィルム。
（５）上述した本発明の易裂性ラミネートフィルムを用いて製袋されてなることを特徴とする易裂性包装袋。 In order to solve the above-mentioned problems, the present invention provides the following easily tearable laminate film and easily tearable packaging bag.
(1) 40 to 85 parts by mass of nylon 6 (Ny6) and 15 to 60 parts by mass of metaxylylene adipamide (MXD6) (where Ny6 + MXD6 = 100 parts by weight) virgin And a heat history product in which the melting point of MXD6 is 233 ° C. or more and 238 ° C. or less by melting and kneading Ny6 and MXD6 at the same ratio as the virgin material, and the blending ratio of the heat history product is 5 on the basis of the total amount of the material A biaxially stretched film using a raw material that is not less than 40% by mass and not more than 40% by mass, an adhesive layer having a dynamic elastic modulus E ′ at 25 ° C. satisfying the following formula [A], and a seal layer, Easy tearable laminate film.
LogE ′ ≧ 7.7 [A]
(2) The easily tearable laminate film of the present invention described above, which is obtained by further laminating a biaxially stretched film or an unstretched film.
(3) In the easily tearable laminate film of the present invention described above, the biaxially stretched film obtained by further laminating is a biaxially stretched film according to the above (1), or Ny6, MXD6, and ethylene vinyl alcohol. An easily tearable laminate film, which is a biaxially stretched film made from a polymer, polyester (PET, PBT, etc.), polyolefin, polystyrene, or polycarbonate.
(4) In the easily tearable laminate film of the present invention described above, the biaxially stretched film obtained by further laminating and the biaxially stretched film described in (1) above are coextrusion multilayer stretched. An easily tearable laminate film characterized by being.
(5) An easily tearable packaging bag formed by using the above easily tearable laminate film of the present invention.
　本発明によれば、Ｎｙ６とＭＸＤ６からなる混合樹脂に対し、さらに当該樹脂の熱履歴品を添加した原料を用い、得られた延伸フィルムの厚み精度（偏肉精度）を向上させるとともに、シーラントフィルムとのラミネート強度に優れ、延伸フィルムの層内剥離も生じにくく、ラミネートフィルムの易裂性（直線カット性）に優れ、さらには製袋後に口元カールが生じにくい易裂性ラミネートフィルム、および当該フィルムを用いてなる易裂性包装袋を提供することができる。 According to the present invention, a mixed resin composed of Ny6 and MXD6 is used with a raw material in which a heat history product of the resin is further added, and the thickness accuracy (thickness accuracy) of the obtained stretched film is improved, and the sealant film The laminate film is excellent in laminating strength, is not easily peeled in the layer of the stretched film, is easily tearable (straight cut property), and is easily peelable after the bag is formed. An easily tearable packaging bag can be provided.
実施形態に係るＯＮｙフィルムを製造する二軸延伸装置の概略図。Schematic of the biaxial stretching apparatus which manufactures the ONy film which concerns on embodiment. 実施例において直線カット性の評価方法を示す図。The figure which shows the evaluation method of linear cut property in an Example. 実施例において包装袋の製造方法を示す図。The figure which shows the manufacturing method of a packaging bag in an Example. 実施例における包装袋の正面図。The front view of the packaging bag in an Example. 実施例において口元カールの測定方法を示す図。The figure which shows the measuring method of a mouth curl in an Example.
　以下に、本発明を実施するための一形態について詳述する。具体的には、本発明の易裂性ラミネートフィルムの構成要素である二軸延伸ナイロンフィルム（以下、単に「ＯＮｙフィルム」ともいう。）について説明し、その後に易裂性ラミネートフィルムおよび易裂性包装袋について説明する。
〔ＯＮｙフィルムの構成〕
　本実施形態に係るＯＮｙフィルムは、ナイロン６（Ｎｙ６）を４０質量部以上８５質量部以下と、メタキシリレンアジパミド（ＭＸＤ６）を１５質量部以上６０質量部以下とからなる（ただし、Ｎｙ６＋ＭＸＤ６＝１００重量部）バージン原料と、Ｎｙ６およびＭＸＤ６を前記バージン原料と同じ割合で溶融混練してＭＸＤ６の融点を２３３℃以上２３８℃以下とした熱履歴品とを含む。また、前記熱履歴品の配合割合は、原料全量基準で５質量％以上４０質量％以下である。
　ここで、Ｎｙ６の化学式を下記式（１）に示し、ＭＸＤ６の化学式を下記式（２）に示す。 Hereinafter, an embodiment for carrying out the present invention will be described in detail. Specifically, a biaxially stretched nylon film (hereinafter also simply referred to as “ONy film”), which is a component of the easily tearable laminate film of the present invention, will be described, and then the easily tearable laminate film and easily tearable. The packaging bag will be described.
[Configuration of ONy film]
The ONy film according to this embodiment includes nylon 6 (Ny6) in a range of 40 parts by mass to 85 parts by mass and metaxylylene adipamide (MXD6) in a range of 15 parts by mass to 60 parts by mass (provided that Ny6 + MXD6 = 100 parts by weight) A virgin raw material, and a heat history product in which Ny6 and MXD6 are melt-kneaded at the same ratio as the virgin raw material to have a melting point of MXD6 of 233 ° C. or higher and 238 ° C. or lower. The blending ratio of the heat history product is 5% by mass or more and 40% by mass or less based on the total amount of raw materials.
Here, the chemical formula of Ny6 is shown in the following formula (1), and the chemical formula of MXD6 is shown in the following formula (2).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　上述のバージン原料とは、通常は、Ｎｙ６とＭＸＤ６とが互いに混合され溶融混練された履歴を持つ混合原料ではない状態の原料を意味する。例えば、Ｎｙ６やＭＸＤ６が各々単独で溶融混練された履歴があっても（例えばリサイクル品）、これらが混合され溶融混練されていない場合は、バージン原料である。ただし、ＯＮｙフィルムとなったときの物性の面からは、リサイクル回数のできるだけ少ないバージン原料を用いることが好ましい。なお、Ｎｙ６とＭＸＤ６とが互いに混合され溶融混練された履歴を持っていても、その混練が弱いため、ＭＸＤ６の融点降下があまりなく、２３８℃を超えていれば、これらのＮｙ６とＭＸＤ６は依然としてバージン原料を構成するものであって、熱履歴品を構成するものではない。
　すなわち、本実施形態では、バージン原料を構成するＮｙ６とＭＸＤ６に熱履歴品を加えた三者（あるいは二者）がいわゆるドライブレンドされた後に溶融混練されてＯＮｙフィルムを構成する。
　上述の熱履歴品とは、Ｎｙ６とＭＸＤ６の配合品で、一度押出機を通過したものをいい、本発明については、示査走査熱量計（ＤＳＣ）でＭＸＤ６樹脂の融点が２３３℃以上、２３８℃以下の範囲に保持されたものを用いる。 The above-mentioned virgin raw material usually means a raw material that is not a mixed raw material having a history in which Ny6 and MXD6 are mixed and melt-kneaded. For example, even if Ny6 and MXD6 have a history of being melt-kneaded independently (for example, recycled products), they are virgin raw materials when they are not mixed and melt-kneaded. However, from the viewpoint of physical properties when it becomes an ONy film, it is preferable to use a virgin raw material with as few times of recycling as possible. Even if Ny6 and MXD6 have a history of being mixed and melt-kneaded with each other, the kneading is weak, so MXD6 does not have much melting point drop, and if it exceeds 238 ° C., these Ny6 and MXD6 are still It constitutes a virgin raw material, not a heat history product.
That is, in this embodiment, three (or two) who added heat history products to Ny6 and MXD6 constituting the virgin raw material are so-called dry blended and then melt-kneaded to constitute an ONy film.
The above-mentioned heat history product is a blended product of Ny6 and MXD6, which has passed through the extruder once. In the present invention, the melting point of MXD6 resin is 233 ° C. or higher and 238 by a scanning scanning calorimeter (DSC). The one kept in the range of ℃ or less is used.
　本実施形態のＯＮｙフィルムは、原料として、Ｎｙ６が４０質量部以上８５質量部以下、ＭＸＤ６が１５質量部以上６０質量部以下であり、好ましくは、Ｎｙ６が６０質量部以上８５質量部以下、ＭＸＤ６が１５質量部以上４０質量部以下である。このＮｙ６とＭＸＤ６の割合は、バージン原料と熱履歴品の双方からなる原料についての割合である。
　原料におけるＮｙ６とＭＸＤ６の割合がこの範囲であると、易裂性（特に直線カット性）に優れるだけでなく、二軸延伸後のフィルムの厚み精度に極めて優れる。 In the ONy film of this embodiment, Ny6 is 40 parts by mass or more and 85 parts by mass or less, and MXD6 is 15 parts by mass or more and 60 parts by mass or less, preferably Ny6 is 60 parts by mass or more and 85 parts by mass or less, and MXD6. Is 15 parts by mass or more and 40 parts by mass or less. The ratio of Ny6 and MXD6 is the ratio for the raw material consisting of both the virgin raw material and the heat history product.
When the ratio of Ny6 and MXD6 in the raw material is within this range, not only the tearability (particularly, the straight cut property) is excellent, but also the thickness accuracy of the film after biaxial stretching is extremely excellent.
　また、熱履歴品におけるＭＸＤ６の融点は２３３℃以上、２３８℃以下であり、好ましくは２３５℃以上、２３７℃以下である。熱履歴品におけるＭＸＤ６の融点が２３３℃未満になると、ＯＮｙフィルムの直線カット性と衝撃強度が低下する。一方、熱履歴品におけるＭＸＤ６の融点が２３８℃を超えると厚み精度が悪化する。
　なお、熱履歴品が製造される過程で、混練時の温度や圧力が高いと熱履歴品中のＭＸＤ６の融点はより大きく下がる。
　ここで、熱履歴品におけるＭＸＤ６の融点とは、バージン原料と溶融混練される前の状態で測定された融点をいう。
　本実施形態のＯＮｙフィルムは、後述するように易裂性ラミネートフィルム（さらには易裂性包装袋）の表基材として使用されるので、易裂性の観点より、ＭＤ方向およびＴＤ方向のいずれの方向についても引裂強度が７０Ｎ／ｃｍ以下であることが好ましい。 Further, the melting point of MXD6 in the heat history product is 233 ° C. or higher and 238 ° C. or lower, preferably 235 ° C. or higher and 237 ° C. or lower. When the melting point of MXD6 in the heat history product is less than 233 ° C., the linear cut property and impact strength of the ONy film are lowered. On the other hand, when the melting point of MXD6 in the heat history product exceeds 238 ° C., the thickness accuracy deteriorates.
In addition, when the temperature and pressure at the time of kneading are high in the process of manufacturing a heat history product, the melting point of MXD6 in the heat history product is further lowered.
Here, the melting point of MXD6 in the heat history product refers to a melting point measured in a state before being melt-kneaded with the virgin raw material.
Since the ONy film of this embodiment is used as a surface base material of an easily tearable laminate film (and also an easily tearable packaging bag) as described later, from the viewpoint of easy tearing, either the MD direction or the TD direction. Also in this direction, the tear strength is preferably 70 N / cm or less.
　本実施形態のＯＮｙフィルムでは、熱履歴品の配合割合は、原料全量基準で５質量％以上４０質量％以下であり、好ましくは１５質量％以上３０質量％以下である。
　熱履歴品の配合割合が５質量％以上であると、ＯＮｙフィルムを過酷な条件下で使用しても層内剥離を起こしにくい。
　ここで、層内剥離とは、ＯＮｙフィルムを適当なシーラントフィルムとラミネートした後に過酷な条件で使用すると、ＯＮｙフィルム（ナイロン層）内で剥離を引き起こす現象をいう。層内剥離の機構は必ずしも明確ではないが、ＯＮｙフィルム内では、Ｎｙ６とＭＸＤ６が層状に配向しており、その界面で剥離が起こるものと考えられる。
　このような層内剥離が起こると、ラミネートフィルムの強度が不安定となり、袋を構成した場合に過酷な使用条件下では破袋等の問題を生ずるおそれがある。このような過酷な使用条件は、例えば、ラミネートフィルムのラミネート強度（剥離強度）を測定する試験により再現することができる。
　また、熱履歴品の配合割合が５質量％未満では、二軸延伸後のフィルムの厚み精度が悪化する。一方、熱履歴品の配合割合が４０質量％を超えると易裂性が低下する。 In the ONy film of this embodiment, the blending ratio of the heat history product is 5% by mass or more and 40% by mass or less, preferably 15% by mass or more and 30% by mass or less based on the total amount of raw materials.
When the blending ratio of the heat history product is 5% by mass or more, even if the ONy film is used under severe conditions, it is difficult to cause delamination within the layer.
Here, in-layer peeling refers to a phenomenon that causes peeling in an ONy film (nylon layer) when the ONy film is laminated with an appropriate sealant film and used under severe conditions. The mechanism of delamination is not necessarily clear, but it is considered that Ny6 and MXD6 are oriented in layers in the ONy film, and delamination occurs at the interface.
When such delamination occurs, the strength of the laminate film becomes unstable, and there is a risk of problems such as broken bags under severe use conditions when a bag is constructed. Such severe use conditions can be reproduced by, for example, a test for measuring the laminate strength (peel strength) of the laminate film.
Moreover, if the mixing ratio of the heat history product is less than 5% by mass, the thickness accuracy of the film after biaxial stretching deteriorates. On the other hand, if the blending ratio of the heat history product exceeds 40% by mass, the easy tearability is lowered.
〔ＯＮｙフィルムの製造方法〕
　本実施形態のＯＮｙフィルムは、チューブラー法による同時二軸延伸法により好適に製造できる。具体的には、以下のようにして製造できる。
　まず、押出工程において、バージン原料と熱履歴品を含む原料を２７０℃で溶融混練した後、溶融物をダイスから円筒状のフィルム（溶融原反）として押し出す。次いで、冷却工程において、溶融原反を水で急冷して原反フィルムとする。
　次に延伸工程において、図１に示すように、上述の原反フィルム１１を一対のニップロール１２間に挿通した後、中に気体を圧入しながらヒータ１３で加熱すると共に、延伸開始点にエアーリング１４よりエアー１５を吹き付けてバブル１６に膨張させ、下流側の一対のニップロール１７で引き取ることにより、チューブラー法によるＭＤ方向およびＴＤ方向の同時二軸延伸を行う。この際、ＭＤ方向およびＴＤ方向のそれぞれの延伸倍率が２．８倍以上であることが好ましい。延伸倍率が２．８倍未満である場合、衝撃強度が低下して実用性に問題が生ずるおそれがある。 [ONy film manufacturing method]
The ONy film of this embodiment can be suitably manufactured by a simultaneous biaxial stretching method using a tubular method. Specifically, it can be produced as follows.
First, in an extrusion process, a raw material including a virgin raw material and a heat history product is melted and kneaded at 270 ° C., and then the melt is extruded from a die as a cylindrical film (melting raw material). Next, in the cooling step, the molten original fabric is quenched with water to obtain an original fabric film.
Next, in the stretching step, as shown in FIG. 1, after the raw film 11 is inserted between a pair of nip rolls 12, it is heated by a heater 13 while a gas is being pressed into it, and an air ring is formed at the stretching start point. The air 15 is blown from 14 to be expanded into a bubble 16 and taken up by a pair of nip rolls 17 on the downstream side, thereby performing simultaneous biaxial stretching in the MD direction and the TD direction by the tubular method. Under the present circumstances, it is preferable that each draw ratio of MD direction and TD direction is 2.8 times or more. If the draw ratio is less than 2.8 times, the impact strength may be reduced, causing a problem in practicality.
　上述の延伸工程後、延伸されたフィルムをテンター式熱処理炉（図示せず）に入れ、１６０～２１０℃で熱固定を施すことにより、本実施形態のＯＮｙフィルム１８を得ることができる。
　なお、ＯＮｙフィルムには、必要な添加剤を適宜添加することができる。このような添加剤として、例えばアンチブロッキング剤（無機フィラー等）、はっ水剤（エチレンビスステアリン酸アミド等）、滑剤（ステアリン酸マグネシウム等）を挙げることができる。 After the above-described stretching step, the stretched film is placed in a tenter heat treatment furnace (not shown) and heat-set at 160 to 210 ° C., whereby the ONy film 18 of the present embodiment can be obtained.
In addition, a required additive can be suitably added to an ONy film. Examples of such additives include antiblocking agents (such as inorganic fillers), water repellents (such as ethylene bis stearamide), and lubricants (such as magnesium stearate).
〔易裂性ラミネートフィルムの構成〕
　本実施形態における易裂性ラミネートフィルムは、以下のようにＯＮｙフィルムに接着層（ＡＤ）を介してシール層（シーラントフィルム（ＳＬ））がラミネートされた構成を備えている。
　　　ＯＮｙ（Ｎｙ６＋ＭＸＤ６）／ＡＤ／ＳＬ
　シーラントフィルムとしては、用途により種々の樹脂フィルムを用いることができる。例えば、レトルト用であれば、市販のレトルト用ＣＰＰフィルムを用いることが好ましい。また、重量物包装用であれば、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）を用いることが好ましい。 [Composition of easily tearable laminate film]
The easily tearable laminate film in this embodiment has a configuration in which a seal layer (sealant film (SL)) is laminated on an ONy film via an adhesive layer (AD) as follows.
ONy (Ny6 + MXD6) / AD / SL
As the sealant film, various resin films can be used depending on applications. For example, for retort, it is preferable to use a commercially available retort CPP film. Moreover, it is preferable to use linear low density polyethylene (LLDPE) for heavy goods packaging.
　ここで、上記接着層にはいわゆるドライラミネート用の接着剤を用いることが好ましい。ただし、この接着層は、２５℃における動的弾性率Ｅ’が下記式〔Ａ〕を満たすことが必要である。
　　　　　　　ＬｏｇＥ’≧７．７　　　　　〔Ａ〕
　　　　　　（Ｌｏｇは常用対数である。）
　ＬｏｇＥ’が７．７未満であると、例えラミネート強度が高くても、ラミネートフィルム（包装袋）をカット（開封）した際に易裂性が得られない。具体的には、カット時にＯＮｙフィルムと、シール層とがいわゆる引きつり（ＯＮｙフィルムとシーラントフィルムが延びてしまい、きれいに切断できなくなる現象）を生じ、良好な開封性（直線カット性）が得られなくなる。
　このようなＥ’は、例えば、以下のような方法で測定することができる。接着剤の主剤と硬化剤を調合後、平坦なガラス板の表面に流して薄膜を形成し、この薄膜から試験片を切り取り、試験機（バイブロン）によりこの試験片に繰り返し振動を与えて動的弾性率Ｅ’を求める。測定温度は、２５℃である。 Here, it is preferable to use an adhesive for so-called dry lamination for the adhesive layer. However, this adhesive layer is required to have a dynamic elastic modulus E ′ at 25 ° C. satisfying the following formula [A].
LogE ′ ≧ 7.7 [A]
(Log is a common logarithm.)
If LogE ′ is less than 7.7, even if the laminate strength is high, tearability cannot be obtained when the laminate film (packaging bag) is cut (opened). Specifically, the ONy film and the seal layer are so-called pulled (a phenomenon in which the ONy film and the sealant film extend and cannot be cut cleanly) at the time of cutting, and good openability (straight cut performance) is obtained. Disappear.
Such E ′ can be measured, for example, by the following method. After mixing the main agent and curing agent of the adhesive, it flows on the surface of a flat glass plate to form a thin film, and a test piece is cut out from this thin film, and this test piece (vibron) is repeatedly vibrated to give dynamic vibration. The elastic modulus E ′ is obtained. The measurement temperature is 25 ° C.
　上述した実施形態によれば、所定の原料構成を有する二軸延伸ナイロンフィルムを用いているので、当該フィルムの厚み精度に優れる。この厚み精度は、印刷適性やラミネートフィルムを製造する際のラミネート適性に影響を与えるので重要である。
　また、上述の二軸延伸ナイロンフィルムを表基材として、所定の接着剤によりシーラントフィルムをラミネートしているので、シーラントフィルムとのラミネート強度に優れ、延伸フィルムの層内剥離も生じにくく、ラミネートフィルムの直線カット性に優れ、さらには製袋後に口元カールが生じにくい。 According to the above-described embodiment, since the biaxially stretched nylon film having a predetermined raw material configuration is used, the thickness accuracy of the film is excellent. This thickness accuracy is important because it affects printing suitability and laminate suitability when producing a laminate film.
In addition, since the above biaxially stretched nylon film is used as a front substrate and the sealant film is laminated with a predetermined adhesive, the laminate film is excellent in the strength of lamination with the sealant film, and is difficult to cause in-layer peeling of the stretched film. In addition, the curl of the mouth is less likely to occur after bag making.
〔本発明における他の構成〕
　上述の実施形態では、表基材としてのＯＮｙフィルムを単層として用いたが、本発明では、二軸延伸フィルムあるいは無延伸フィルムをさらに積層してもよい。このような二軸延伸フィルムとしては、例えば、上述したＯＮｙフィルムと同じフィルムでもよく、Ｎｙ６、ＭＸＤ６、エチレンビニルアルコール共重合体（ＥＶＯＨ）、ポリエステル（ＰＥＴ、ＰＢＴ等）、ポリオレフィン、ポリスチレンおよびポリカーボネートなどを原料としたものでもよい。
　例えば、以下のような構成としてもよい。なお、上述した実施形態における二軸延伸フィルムを単に「Ｎｙ６＋ＭＸＤ６」と表記する。
　　（Ｎｙ６＋ＭＸＤ６）／ＭＸＤ６／（Ｎｙ６＋ＭＸＤ６）／ＡＤ／ＳＬ
　　（Ｎｙ６＋ＭＸＤ６）／ＥＶＯＨ／（Ｎｙ６＋ＭＸＤ６）／ＡＤ／ＳＬ
　　ＰＥＴ／ＡＤ／（Ｎｙ６＋ＭＸＤ６）／ＡＤ／ＳＬ
　これらの中で、（Ｎｙ６＋ＭＸＤ６）／ＭＸＤ６／（Ｎｙ６＋ＭＸＤ６）や（Ｎｙ６＋ＭＸＤ６）／ＥＶＯＨ／（Ｎｙ６＋ＭＸＤ６）については、対応する原料を用いて共押出を行い、得られた原反を共延伸することで二軸延伸フィルムとすればよい。
　なお、これらの積層品は、接着剤等を利用したドライラミネート品でもよいし、多層延伸品でもよい。 [Other Configurations in the Present Invention]
In the above-described embodiment, the ONy film as the front substrate is used as a single layer. However, in the present invention, a biaxially stretched film or an unstretched film may be further laminated. As such a biaxially stretched film, for example, the same film as the above-mentioned ONy film may be used, such as Ny6, MXD6, ethylene vinyl alcohol copolymer (EVOH), polyester (PET, PBT, etc.), polyolefin, polystyrene, polycarbonate, etc. May be used as a raw material.
For example, the following configuration may be used. In addition, the biaxially stretched film in embodiment mentioned above is only described with "Ny6 + MXD6."
(Ny6 + MXD6) / MXD6 / (Ny6 + MXD6) / AD / SL
(Ny6 + MXD6) / EVOH / (Ny6 + MXD6) / AD / SL
PET / AD / (Ny6 + MXD6) / AD / SL
Among these, for (Ny6 + MXD6) / MXD6 / (Ny6 + MXD6) and (Ny6 + MXD6) / EVOH / (Ny6 + MXD6), co-extrusion is carried out using the corresponding raw materials, and the obtained raw fabric is co-stretched. What is necessary is just to set it as an axial stretched film.
In addition, these laminated products may be a dry laminate product using an adhesive or the like, or may be a multilayer stretched product.
　次に、実施例および比較例により本発明をさらに詳細に説明する。ただし、本発明はこれらの例によって何等限定されるものではない。 Next, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples.
［評価方法］
　各種の原料を用いて、図１の装置によりチューブラー二軸延伸を行い、さらに、得られたＯＮｙフィルムからラミネートフィルムを製造して以下に示す評価を行った。二軸延伸方法等の詳細は後述する。原料構成および結果を表１に示す。 [Evaluation methods]
Using various raw materials, tubular biaxial stretching was performed using the apparatus shown in FIG. 1, and a laminate film was produced from the obtained ONy film and evaluated as follows. Details of the biaxial stretching method and the like will be described later. The raw material composition and results are shown in Table 1.
（厚み精度）
　延伸フィルム１８の幅方向に１ｃｍごとに厚みを測定し、下記式で厚み精度（％）を求めた。
　（（フィルム最大厚み－フィルム最小厚み）／２／フィルム平均厚み）×１００％
　そして、この式で求めた厚み精度（％）に基づき、以下の基準で評価した。
　　Ａ：４％以下
　　Ｂ：４％を超え、６％以下
　　Ｃ：６％を超える (Thickness accuracy)
The thickness was measured every 1 cm in the width direction of the stretched film 18, and the thickness accuracy (%) was determined by the following formula.
((Film maximum thickness−film minimum thickness) / 2 / film average thickness) × 100%
And based on the thickness accuracy (%) calculated | required by this type | formula, it evaluated by the following references | standards.
A: 4% or less B: Over 4%, 6% or less C: Over 6%
（ラミネート強度および層内剥離）
　延伸フィルム１８（表基材フィルム）と、シーラントフィルム（レトルト用ＣＰＰフィルム〔出光ユニテック製　ユニラックスＲＴ６８０、厚さ６０μｍ〕とをドライラミネートしてラミネートフィルムを作成した。用いた表基材フィルムや接着剤の詳細については、後述する実施例・比較例および表１に示す。なお、ドライラミネート後のラミネートフィルムは、４０℃で３日間エージングを行った。
　上述のラミネートフィルムから１５ｍｍ幅の短冊状試験片を切り出し、その端部を手で数ｃｍほど界面剥離を行い、表基材フィルム（延伸フィルム１８）とシーラントフィルムとに分離した。その後、各々のフィルム片を引張試験機（インストロン万能試験機　１１２３型）にセットして、３００ｍｍ／ｍｉｎの速度でラミネート部分の剥離試験を行い、ラミネート強度を測定した（９０度剥離）。
　このラミネート強度（剥離強度）が５Ｎ／ｍ以上のものをＡ、５Ｎ／ｍ未満３Ｎ／ｍ以上のものをＢ、３Ｎ／ｍ未満のものをＣとして評価した。 (Lamination strength and delamination in the layer)
A laminate film was prepared by dry laminating the stretched film 18 (surface base film) and a sealant film (CPP film for retort [Unilux RT680 manufactured by Idemitsu Unitech Co., Ltd., thickness 60 μm]). Details of the agent are shown in Examples and Comparative Examples described later and Table 1. The laminated film after dry lamination was aged at 40 ° C. for 3 days.
A strip-shaped test piece having a width of 15 mm was cut out from the above-mentioned laminate film, and the end thereof was subjected to interfacial peeling by several cm by hand to separate the surface base film (stretched film 18) and the sealant film. Thereafter, each film piece was set in a tensile tester (Instron universal tester 1123 type), a peel test of the laminate portion was performed at a speed of 300 mm / min, and the laminate strength was measured (90 degree peel).
The laminate strength (peel strength) of 5 N / m or more was evaluated as A, less than 5 N / m, 3 N / m or more as B, and less than 3 N / m as C.
　剥離試験の最中に表基材フィルム内部で層内剥離が生ずると剥離強度が急激に減少するため、そのような挙動が発現したか否かで層内剥離発生の有無を判別できる。例えば、剥離試験の開始時は、剥離強度が７Ｎ／ｍ程度であったものが、剥離試験の途中で急激に１～２Ｎ／ｍ程度に減少すれば、層内剥離が生じたと判断できる。
　そして、表基材フィルム内部で層内剥離の挙動を示さないものＡ、層内剥離の挙動を示したものをＢとして評価した。 In the middle of the peel test, if peeling inside the surface substrate film occurs, the peel strength sharply decreases. Therefore, it can be determined whether or not such peeling has occurred, depending on whether or not such behavior has occurred. For example, at the start of the peel test, if the peel strength was about 7 N / m, but it suddenly decreased to about 1 to 2 N / m during the peel test, it can be determined that in-layer peel occurred.
And the thing which did not show the behavior of peeling in a layer inside a surface base film, and the thing which showed the behavior of peeling in a layer were evaluated as B.
（易裂性）
　直線カット性により評価した。具体的には以下の通りである。
　図２に示すように、２０ｃｍ幅のラミネートフィルム１８’に２ｃｍ間隔で切れ目２１を入れ、これらの切れ目２１に沿ってラミネートフィルム１８’を引き裂いた後、フィルム片１８Ａの他端の幅Ｗeを測定し、元の間隔Ｗsとの偏差αを下記の通り求める。
　　α＝｜〔（Ｗs－Ｗe）／Ｗs〕｜×１００
　この測定を１０枚のフィルム片１８Ａに対して行い、その平均値のα（％）が３０％以下のものをＡ（直線カット性が良好）、α（％）が３０％を越えるものをＢ（直線カット性が不良）として評価した。α（％）が３０％を越えるとフィルムを真っ直ぐに切ることが困難になる。 (Easily tearable)
Evaluation was made by straight-line cut ability. Specifically, it is as follows.
As shown in FIG. 2, cuts 21 are made at intervals of 2 cm in a laminate film 18 'having a width of 20 cm, the laminate film 18' is torn along these cuts 21, and the width We of the other end of the film piece 18A is measured. The deviation α from the original interval Ws is obtained as follows.
α = | [(Ws−We) / Ws] | × 100
This measurement is performed on 10 pieces of film 18A, the average value α (%) of which is 30% or less is A (good linear cut property), and α (%) is more than 30% of B. (Evaluation was poor). When α (%) exceeds 30%, it becomes difficult to cut the film straight.
（口元カール）
　図３に示すように、製袋する際、ラミネートフィルム１８’に対して、袋の開口部の向きがこのラミネートフィルム１８’のＴＤ方向となる（横取り）ようにして２丁取りした。図４に、開口部４１がラミネートフィルム１８のＴＤ方向を向いた包装袋４２を示す。なお、この包装袋４２のサイズは、１５０ｍｍ（長さ）×１３０ｍｍ（幅）であり、シール幅は１０ｍｍである。次に、この包装袋４２の口元カールを下記のように測定して評価した。
　即ち、図５に示すように、前記包装袋４２を温度２３℃、相対湿度５０％の雰囲気に３時間放置して口元カールによる開口部４１の厚さＬを測定した。そして、１０枚の包装袋４２の開口部４１の厚さＬの平均値が２ｍｍ未満であった場合をＡ、２ｍｍ以上４ｍｍ未満であった場合をＢ、４ｍｍ以上であった場合をＣとして評価した。 (Mouth curl)
As shown in FIG. 3, when making a bag, two pieces were taken with respect to the laminate film 18 ′ so that the direction of the opening of the bag was the TD direction of the laminate film 18 ′ (horizontal orientation). FIG. 4 shows a packaging bag 42 in which the opening 41 faces the TD direction of the laminate film 18. In addition, the size of this packaging bag 42 is 150 mm (length) x 130 mm (width), and the seal width is 10 mm. Next, the mouth curl of the packaging bag 42 was measured and evaluated as follows.
That is, as shown in FIG. 5, the packaging bag 42 was left in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% for 3 hours, and the thickness L of the opening 41 due to the mouth curl was measured. And when the average value of the thickness L of the opening part 41 of 10 packaging bags 42 was less than 2 mm, the case where it was 2 mm or more and less than 4 mm was evaluated as B and the case where it was 4 mm or more as C did.
［実施例１］
（延伸フィルムの製造）
　Ｎｙ６ペレット７０質量部と、ＭＸＤ６ペレット３０質量部を混合してなるバージン原料に対して、すでに一度、この配合比で溶融混合してペレット化した熱履歴品（ＭＸＤ６の融点が２３６℃のもの）を原料全量基準（バージン原料と熱履歴品の合計量基準）で２０質量％配合した。
　このドライブレンド品を押出機中、２７０℃で溶融混練した後、溶融物をダイスから円筒状のフィルムとして押し出し、引き続き水（１５℃）で急冷して原反フィルムを作製した。なお、ＭＸＤ６の融点は、パーキンエルマー社製示差走査熱量測定装置（ＤＳＣ）を用い、昇温速度１０℃／ｍｉｎで５０℃から２８０℃まで昇温を行って測定した。いずれもファーストランにおけるピーク値を融点とした。なお、熱履歴品は、２７０℃で１０分間熱処理を行ったものである。
　Ｎｙ６として使用したものは、宇部興産（株）製ナイロン６〔ＵＢＥナイロン　１０２２ＦＤ（商品名）、相対粘度　ηｒ＝３．６〕であり、ＭＸＤ６として使用したものは、三菱ガス化学（株）製メタキシリレンジアジパミド〔ＭＸナイロン　６００７（商品名）、相対粘度　ηｒ＝２．７〕である。 [Example 1]
(Manufacture of stretched film)
A heat history product that has been melt-mixed and pelletized once at this blending ratio with respect to a virgin raw material obtained by mixing 70 parts by mass of Ny6 pellets and 30 parts by mass of MXD6 pellets (with a melting point of MXD6 of 236 ° C.) 20% by mass based on the total amount of raw materials (based on the total amount of virgin raw materials and heat history products).
After this dry blend product was melt-kneaded at 270 ° C. in an extruder, the melt was extruded as a cylindrical film from a die and then rapidly cooled with water (15 ° C.) to produce a raw film. The melting point of MXD6 was measured by increasing the temperature from 50 ° C. to 280 ° C. at a temperature increase rate of 10 ° C./min using a differential scanning calorimeter (DSC) manufactured by PerkinElmer. In any case, the peak value in the first run was taken as the melting point. The heat history product was heat-treated at 270 ° C. for 10 minutes.
Ny6 used was Ube Industries' nylon 6 [UBE nylon 1022FD (trade name), relative viscosity ηr = 3.6], and MXD6 used was made by Mitsubishi Gas Chemical Co., Ltd. It is xylylene adipamide [MX nylon 6007 (trade name), relative viscosity ηr = 2.7].
　次に、図１に示すように、この原反フィルム１１を一対のニップロール１２間に挿通した後、中に気体を圧入しながらヒータ１３（設定温度　３１０℃）で加熱すると共に、延伸開始点にエアーリング１４よりエアー１５を１５ｍ３／分の風量で吹き付けてバブル１６に膨張させ、下流側の一対のニップロール１７で引き取ることにより、チューブラー法によるＭＤ方向およびＴＤ方向の同時二軸延伸を行った。この延伸の際の倍率はＭＤ方向で３．０倍、ＴＤ方向で３．２倍とした。延伸成形性は良好であった。
　得られたＯＮｙフィルムについて、上述の方法により厚み精度を測定した。また、ＯＮｙフィルムを表基材としてドライラミネートを行い、ラミネートフィルムを製造した。ラミネート用の接着剤としては、三井化学製　タケラック　Ａ－６１５／Ａ－６５（調合比　１６：１）を用いた。 Next, as shown in FIG. 1, the raw film 11 is inserted between a pair of nip rolls 12, and then heated with a heater 13 (set temperature 310 ° C.) while a gas is being pressed into the film 11. Air 15 is blown from the air ring 14 with an air volume of 15 m 3 / min to be expanded into a bubble 16 and taken up by a pair of downstream nip rolls 17 to perform simultaneous biaxial stretching in the MD direction and the TD direction by the tubular method. It was. The magnification during this stretching was 3.0 times in the MD direction and 3.2 times in the TD direction. The stretch moldability was good.
About the obtained ONy film, the thickness precision was measured by the above-mentioned method. Also, dry lamination was performed using the ONy film as a front substrate to produce a laminate film. As an adhesive for laminating, Takelac A-615 / A-65 (mixing ratio 16: 1) manufactured by Mitsui Chemicals was used.
［実施例２～８、比較例１～１１］
　表基材の樹脂・層構成、熱履歴品の配合量、熱履歴品の融点、およびシーラントとのラミネートに用いた接着剤の種類（ｌｏｇＥ’）を表１の通りに変更した以外は、実施例１と同様にしてＯＮｙフィルムを製造した。なお、熱履歴品は、いずれもバージン品を用いて、バージン品と同じＮｙ６／ＭＸＤ配合比で溶融混練して製造したものである。
　なお、実施例５、７、比較例５、７は、表基材を共押出成形（フィルム総厚みは２５μｍであり、各層の厚みは８μｍ／９μｍ／８μｍである。）したものであり、実施例６、比較例６、はＯＮｙ面にポリエステルフィルム（ＰＥＴフィルム　１２μｍ厚み）をドライラミネートしたものである。各層の厚みは１２μｍ／３μｍ／１５μｍである。
ＯＰＥＴとＯＮｙとのラミネートには、ＯＮｙとシーラントとのラミネートに用いたのと同じ接着剤を同じ条件で用いた。
　実施例８と比較例８は、表基材を、ＰＥＴ／ＡＤ／（Ｎｙ６＋ＭＸＤ６）の共押出多層延伸により製造して評価したものである。 [Examples 2 to 8, Comparative Examples 1 to 11]
Except for changing the resin / layer structure of the surface base material, the blending amount of the heat history product, the melting point of the heat history product, and the type of adhesive (logE ') used for lamination with the sealant as shown in Table 1. An ONy film was produced in the same manner as in Example 1. The heat history products are all manufactured by melt-kneading using virgin products at the same Ny6 / MXD blend ratio as the virgin products.
In Examples 5 and 7 and Comparative Examples 5 and 7, the surface base material was coextruded (total film thickness was 25 μm, and the thickness of each layer was 8 μm / 9 μm / 8 μm). In Example 6 and Comparative Example 6, a polyester film (PET film 12 μm thickness) was dry laminated on the ONy surface. The thickness of each layer is 12 μm / 3 μm / 15 μm.
For the laminate of OPET and ONy, the same adhesive as that used for the laminate of ONy and sealant was used under the same conditions.
In Example 8 and Comparative Example 8, the surface base material was manufactured and evaluated by coextrusion multilayer stretching of PET / AD / (Ny6 + MXD6).
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
１）三井化学製　タケラック　Ａ－６１５／Ａ－６５（調合比　１６：１）
２）東洋モートン製　ＡＤ５９０／ＣＡＴ５６（調合比　１００：１６）
３）三井化学製　タケラック　ＡＤ５９０＋ＣＡＴ５６（調合比　１００：１６）
４）三井化学製　タケラック　Ａ－５２０／Ａ－４０（調合比　　６：１）
５）三井化学製　タケラック　Ａ－６１５／Ａ－６５（調合比　５：１）
６）東洋モートン製　ＡＤ５９０＋ＣＡＴ５６（調合比　１６：１）
７）三井化学製　タケラック　Ａ－５２０／Ａ－４０（調合比　６：１）
８）東洋モートン製　ＡＤ５９０＋ＣＡＴ５６（調合比　１００：１６）
９）三井化学製　タケラック　Ａ９７５／Ａ－３（調合比　７：１）
１０）三井化学製　タケラック　Ａ－６１５／Ａ－６５（調合比　１６：１）
１１）三井化学製　タケラック　Ａ－６１５／Ａ－６５（調合比　１６：１）
１２）三井化学製　タケラック　Ａ－６１５／Ａ－６５（調合比　１６：１）
１３）三井化学製　タケラック　Ａ－６１５／Ａ－６５（調合比　１６：１） 
１４）大日本インキ化学製　ＬＸ－７５／ＫＷ－４０（調合比　５：１）
１５）大日本インキ化学製　ＬＸ－７５／ＫＷ－４０（調合比　５：１）
１６）大日本インキ化学製　ＬＸ－７５／ＫＷ－４０（調合比　５：１）
１７）三井化学製　タケラック　Ａ－６１５／Ａ－６５（調合比　１６：１）
１８）三井化学製　タケラック　Ａ－６１５／Ａ－６５（調合比　１６：１）
１９）大日本インキ化学製　ＬＸ－７５／ＫＷ‐４０（調合比　５：１） 1) Takelac A-615 / A-65 (Mixing ratio 16: 1) manufactured by Mitsui Chemicals
2) Toyo Morton AD590 / CAT56 (mixing ratio 100: 16)
3) Takelac AD590 + CAT56 (mixing ratio 100: 16) manufactured by Mitsui Chemicals
4) Takelac A-520 / A-40 (mixing ratio 6: 1) manufactured by Mitsui Chemicals
5) Takelac A-615 / A-65 (Mitsui ratio 5: 1) manufactured by Mitsui Chemicals
6) Toyo Morton AD590 + CAT56 (mixing ratio 16: 1)
7) Takelac A-520 / A-40 (mixing ratio 6: 1) manufactured by Mitsui Chemicals
8) Toyo Morton AD590 + CAT56 (mixing ratio 100: 16)
9) Takelac A975 / A-3 (mixing ratio 7: 1) manufactured by Mitsui Chemicals
10) Takelac A-615 / A-65 (Mixing ratio 16: 1) manufactured by Mitsui Chemicals
11) Takelac A-615 / A-65 (Mixing ratio 16: 1) manufactured by Mitsui Chemicals
12) Takelac A-615 / A-65 (Mixing ratio 16: 1) manufactured by Mitsui Chemicals
13) Mitsui Chemicals Takerak A-615 / A-65 (mixing ratio 16: 1)
14) Dainippon Ink & Chemicals LX-75 / KW-40 (mixing ratio 5: 1)
15) Dainippon Ink & Chemicals LX-75 / KW-40 (mixing ratio 5: 1)
16) Dainippon Ink & Chemicals LX-75 / KW-40 (mixing ratio 5: 1)
17) Takelac A-615 / A-65 (Mixing ratio 16: 1) manufactured by Mitsui Chemicals
18) Takelac A-615 / A-65 (Mixing ratio 16: 1) manufactured by Mitsui Chemicals
19) Dainippon Ink & Chemicals LX-75 / KW-40 (mixing ratio 5: 1)
［評価結果］
　表１の各実施例からわかるように、所定の原料から得られたフィルム１８は厚み精度に優れ、また、ラミネートフィルム１８’は、ラミネート強度や易裂性（直線カット性）にも優れていた。さらにラミネートフィルム１８’は、層内剥離を起こさず、口元カールもほとんど無かった。また、延伸成形性はいずれも良好であった。
　一方、比較例１では、接着剤のｌｏｇＥ’が７．４と小さいため、易裂性（直線カット性）に劣る。比較例２では、熱履歴品が配合されていないため、層内剥離現象が起こり、また、フィルムの厚み精度も悪く二次加工に適さない。比較例３では、熱履歴品の配合量が多すぎるため、易裂性が劣る。比較例４では、熱履歴品の融点が低すぎるので、易裂性が劣り、包装袋の口元カールも大きい。比較例５では、熱履歴品が配合されていないため、層内剥離現象が起こり、フィルムの厚み精度も悪く二次加工に適さない。比較例６では、接着剤のｌｏｇＥ’が７．４と小さいため、易裂性（直線カット性）に劣る。 [Evaluation results]
As can be seen from each example in Table 1, the film 18 obtained from a predetermined raw material was excellent in thickness accuracy, and the laminate film 18 ′ was also excellent in laminate strength and easy tearability (straight cut property). . Furthermore, the laminate film 18 ′ did not cause delamination within the layer and had almost no curl at the mouth. In addition, the stretch moldability was good.
On the other hand, in Comparative Example 1, since the log E ′ of the adhesive is as small as 7.4, it is inferior in easy tearability (straight cut property). In Comparative Example 2, since the heat history product is not blended, an in-layer peeling phenomenon occurs, and the film thickness accuracy is poor and is not suitable for secondary processing. In the comparative example 3, since there are too many compounding quantities of a heat history goods, easy tearability is inferior. In Comparative Example 4, since the melting point of the heat history product is too low, the tearability is poor and the mouth curl of the packaging bag is large. In Comparative Example 5, since no heat history product is blended, an in-layer peeling phenomenon occurs, the film thickness accuracy is poor, and it is not suitable for secondary processing. In Comparative Example 6, since the log E ′ of the adhesive is as small as 7.4, the tearability (straight cut property) is poor.
　比較例７では、熱履歴品が配合されておらず、接着剤のｌｏｇＥ’も７．４と小さいため、層内剥離現象が起こり、厚み精度も悪く、また易裂性にも劣る。比較例８では、接着剤のｌｏｇＥ’が７．４と小さいため、易裂性に劣る。また、比較例９では、原料としてＮｙ６だけを用い、ＭＸＤ６が配合されていないので易裂性が発現しない。また、包装袋の口元カールが大きく、充填時にトラブルを生じることが予測される。比較例１０では、ＭＸＤ６の配合量が少なく、さらに熱履歴品の配合もないため、層内剥離を起こしやすく、易裂性も劣る。また、フィルムの厚み精度も悪い。さらに、包装袋の口元カールも大きい。比較例１１では、ＭＸＤ６の配合量が多すぎ、一方、熱履歴品が配合されていない。それ故、層内剥離が起こりやすく、易裂性も劣る。さらに、フィルムの厚み精度も非常に劣る。 In Comparative Example 7, since no heat history product was blended and the log E ′ of the adhesive was as small as 7.4, an in-layer peeling phenomenon occurred, the thickness accuracy was poor, and the tearability was poor. In Comparative Example 8, since the log E ′ of the adhesive is as small as 7.4, the tearability is poor. In Comparative Example 9, only Ny6 is used as a raw material, and MXD6 is not blended, so that easy tearing does not occur. In addition, the mouth curl of the packaging bag is large, and it is predicted that trouble will occur during filling. In Comparative Example 10, since the amount of MXD6 blended is small and there is no blend of heat history products, in-layer peeling is likely to occur, and easy tearability is poor. Also, the film thickness accuracy is poor. Furthermore, the mouth curl of the packaging bag is also large. In Comparative Example 11, the amount of MXD6 blended is too large, while no heat history product is blended. Therefore, delamination is likely to occur and the tearability is poor. Furthermore, the thickness accuracy of the film is very poor.
１１・・・原反フィルム
１２・・・ニップロール
１３・・・ヒータ
１４・・・エアーリング１５・・・エアー
１６・・・バブル
１７・・・ニップロール
１８・・・延伸フィルム
１８’・・・ラミネートフィルム
１８Ａ・・・フィルム片
２１・・・切れ目
４１・・・開口部
４２・・・包装袋 11 ... Raw film 12 ... Nip roll 13 ... Heater 14 ... Air ring 15 ... Air 16 ... Bubble 17 ... Nip roll 18 ... Stretched film 18 '... Laminate Film 18A ... Film piece 21 ... Cut 41 ... Opening 42 ... Packaging bag

Claims (5)

  1. 　ナイロン６を４０質量部以上８５質量部以下と、メタキシリレンアジパミドを１５質量部以上６０質量部以下とからなり、Ｎｙ６＋ＭＸＤ６＝１００重量部、ただし、Ｎｙ６はナイロン６、ＭＸＤはメタキシリレンアジパミドであるバージン原料と、ナイロン６およびメタキシリレンアジパミドを前記バージン原料と同じ割合で溶融混練してメタキシリレンアジパミドの融点を２３３℃以上２３８℃以下とした熱履歴品とを含み、前記熱履歴品の配合割合が原料全量基準で５質量％以上４０質量％以下である原料を用いてなる第一の二軸延伸フィルムと、
    　２５℃における動的弾性率Ｅ’が下記式〔Ａ〕を満たす接着層と、
    　　　　　　　　　　　ＬｏｇＥ’≧７．７　　　　　〔Ａ〕
    　シール層とを備える
    　ことを特徴とする易裂性ラミネートフィルム。     Nylon 6 consists of 40 parts by weight to 85 parts by weight and metaxylylene adipamide 15 parts by weight to 60 parts by weight. Ny6 + MXD6 = 100 parts by weight, where Ny6 is nylon 6 and MXD is metaxylylene. A heat history product in which the melting point of metaxylylene adipamide is 233 ° C. or higher and 238 ° C. or lower by melting and kneading nylon 6 and metaxylylene adipamide at the same ratio as the virgin raw material, virgin raw material that is adipamide A first biaxially stretched film using a raw material in which the blending ratio of the heat history product is 5% by mass or more and 40% by mass or less based on the total amount of the raw material,
    An adhesive layer having a dynamic elastic modulus E ′ at 25 ° C. satisfying the following formula [A]:
    LogE ′ ≧ 7.7 [A]
    An easily tearable laminate film comprising a sealing layer.
  2. 　請求項１に記載の易裂性ラミネートフィルムにおいて、
    　第二の二軸延伸フィルムあるいは無延伸フィルムをさらに積層してなる
    　ことを特徴とする易裂性ラミネートフィルム。     In the easily tearable laminate film according to claim 1,
    An easily tearable laminate film characterized by further laminating a second biaxially stretched film or an unstretched film.
  3. 　請求項２に記載の易裂性ラミネートフィルムにおいて、
    　前記第二の二軸延伸フィルムが、前記第一の二軸延伸フィルム、または、ナイロン６、メタキシリレンアジパミド、エチレンビニルアルコール共重合体、ポリエステル、ポリオレフィン、ポリスチレンおよびポリカーボネートのいずれかを原料とした二軸延伸フィルムである
    　ことを特徴とする易裂性ラミネートフィルム。     In the easily tearable laminate film according to claim 2,
    The second biaxially stretched film is made from the first biaxially stretched film or any of nylon 6, metaxylylene adipamide, ethylene vinyl alcohol copolymer, polyester, polyolefin, polystyrene and polycarbonate. An easily tearable laminate film characterized by being a biaxially stretched film.
  4. 　請求項３に記載の易裂性ラミネートフィルムにおいて、
    　前記第二の二軸延伸フィルムと、前記第一の二軸延伸フィルムとが、共押出多層延伸されたものである
    　ことを特徴とする易裂性ラミネートフィルム。     In the easily tearable laminate film according to claim 3,
    The easily tearable laminate film, wherein the second biaxially stretched film and the first biaxially stretched film are coextrusion multilayer stretched.
  5. 　請求項１から請求項４までのいずれか１項に記載の易裂性ラミネートフィルムを用いて製袋されてなる
    　ことを特徴とする易裂性包装袋。     A bag that is made using the easily tearable laminate film according to any one of claims 1 to 4. An easily tearable packaging bag.
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JPH0948101A (en) * 1995-08-09 1997-02-18 Idemitsu Petrochem Co Ltd Easy tearing laminated film, easy tearing bag and production thereof
JP2007039664A (en) * 2005-06-27 2007-02-15 Idemitsu Unitech Co Ltd Easily tearable oriented film, easily tearable laminate film, easily tearable bag, and process for producing the easily tearable oriented film
JP2008024744A (en) * 2006-07-18 2008-02-07 Idemitsu Unitech Co Ltd Easily tearable shrink film, easily tearable laminated film, easily tearable bag and process for producing easily tearable shrink film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0948101A (en) * 1995-08-09 1997-02-18 Idemitsu Petrochem Co Ltd Easy tearing laminated film, easy tearing bag and production thereof
JP2007039664A (en) * 2005-06-27 2007-02-15 Idemitsu Unitech Co Ltd Easily tearable oriented film, easily tearable laminate film, easily tearable bag, and process for producing the easily tearable oriented film
JP2008024744A (en) * 2006-07-18 2008-02-07 Idemitsu Unitech Co Ltd Easily tearable shrink film, easily tearable laminated film, easily tearable bag and process for producing easily tearable shrink film

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