JP2016068495A - Laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film which suppresses a significant change in a lubricant amount existing on the surface of a resin layer, thereby exhibits stable moldability, and effectively suppresses deposition of a lump of a lubricant onto a die.SOLUTION: There is provided a laminated film 10 formed by laminating at least a support body 2 and a resin layer 1 formed of a resin in which a sum (A+B) of a spectrum intensity ratio A (crystal portion/amorphous portion) of a crystal portion and an amorphous portion of the resin in an MD direction of the resin layer 1 that is measured by a Raman spectroscopy and a spectrum intensity ratio B (crystal portion/amorphous portion) of a crystal portion and an amorphous portion of the resin in a TD direction of the resin layer 1 that is measured by the Raman spectroscopy is in a range of 1.95 to 2.60.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminated film that exhibits stable moldability by suppressing a significant change in the amount of lubricant present on the surface of a resin layer, and effectively prevents adhesion of a lump of lubricant to a mold.

  Conventionally, a laminated film in which a resin layer is laminated on a support such as a base material layer or a metal layer has been widely used in various fields such as packaging materials (Patent Document 1). Some laminated films used as packaging materials, such as battery packaging materials, are used for deep drawing for the purpose of forming a space for containing contents. Exists.

  In a laminated film used for deep drawing, there is a problem that cracks and pinholes are likely to occur in the flange portion of the mold by stretching the laminated film during deep drawing. In order to solve such problems, a lubricant is coated on the resin layer surface of the laminated film, or a lubricant is blended into the resin forming the resin layer, and the lubricant is bleeded out on the resin layer surface before being used for molding. There is known a method of improving the slipperiness of the resin layer surface by, By adopting such a method, at the time of deep drawing, the laminated film is easily drawn into the mold, and cracks and pinholes in the laminated film can be suppressed.

  However, if the amount of the lubricant present on the surface of the resin layer is too large, there is a problem that the lubricant adheres to the mold and becomes a lump and contaminates the mold. When another laminated film is molded while the mold is contaminated, a lump of lubricant adhered to the mold adheres to the surface of the laminated film. When a lump of lubricant adheres to the surface of the laminated film, how to melt the part to which the lubricant has adhered, such as when the resin layers of the two laminated films after molding are heat-sealed to form a packaging material Is non-uniform, which causes a problem that a seal failure is likely to occur. Further, it is necessary to perform cleaning for removing the lump of lubricant adhering to the mold, and the efficiency of the molding process is lowered.

  On the other hand, when the amount of the lubricant present on the surface of the resin layer is too small at the time of molding, there is a problem that the slipperiness of the laminated film is lowered and the moldability of the laminated film is lowered.

JP 2008-287971 A

  As described above, the resin layer of the laminated film subjected to deep drawing may be mixed with a lubricant or may be coated on the surface. However, even when the lubricant to be coated on the surface of the resin layer and the lubricant to be blended in the resin layer are set to a predetermined amount, when the laminated film is molded, if the lubricant adheres to the mold, Cracks and pinholes may occur. Specifically, in both cases where a lubricant is blended and coated in the resin layer, the lubricant located on the surface of the resin layer by a storage ring or the like from the production of the laminated film until it is used for molding. The amount of the resin may change greatly, and the lubricant may adhere to the mold during molding, or the moldability may deteriorate. For example, when the laminated film is stored at a high temperature, the lubricant easily enters the resin layer. As a result, the slipperiness of the resin layer is lowered, and the moldability is easily lowered. On the other hand, when the laminated film is stored at a low temperature below room temperature, the saturation solubility of the lubricant inside the resin layer decreases, the amount of lubricant located on the surface of the resin layer increases, and the mold is contaminated. It becomes easy.

  Under such circumstances, the present invention exerts stable moldability by suppressing a significant change in the amount of lubricant present on the surface of the resin layer, and effectively suppresses adhesion of the lubricant mass to the mold. The main object is to provide a laminated film.

  The present inventor has intensively studied to solve the above problems. As a result, at least in the laminated film in which the support and the resin layer formed of the resin are laminated, the spectral intensity of the crystal part and the amorphous part of the resin measured by Raman spectroscopy in the MD direction of the resin layer The sum of the ratio A (crystal part / amorphous part) and the spectral intensity ratio B (crystal part / amorphous part) of the crystal part and the amorphous part of the resin measured by Raman spectroscopy in the TD direction of the resin layer By setting (A + B) in the range of 1.95 to 2.60, a significant change in the amount of lubricant present on the resin layer surface is suppressed, and in deep drawing (molding depth is 4.0 mm or more) It was also found that stable moldability can be exhibited.

That is, this invention provides the invention of the aspect hung up below.
Item 1. At least a laminated film in which a support and a resin layer formed of a resin are laminated,
Spectral intensity ratio A (crystal part / amorphous part) of crystal part and amorphous part of the resin measured by Raman spectroscopy in the MD direction of the resin layer, and measurement by Raman spectroscopy in the TD direction of the resin layer A laminated film in which the sum (A + B) of the spectral intensity ratio B (crystal part / amorphous part) of the crystal part and amorphous part of the resin is in the range of 1.95 to 2.60.
Item 2. Item 2. The laminated film according to Item 1, wherein the resin layer contains a lubricant.
Item 3. Item 3. The laminated film according to Item 1 or 2, which is a laminated film subjected to deep drawing.
Item 4. Item 4. The laminated film according to any one of Items 1 to 3, wherein an absolute value | B-A | of a difference between the spectral intensity ratio A and the spectral intensity ratio B is in a range of 0.00 to 0.60.
Item 5. In the center of the laminated film having a length of 90 mm in the MD direction and a width of 150 mm in the TD direction, two cuts having a length of 100 mm having the center as the center are formed on two lines connecting the respective diagonals of the laminated film. Item 1 is placed on a horizontal plane and allowed to stand at 20 ° C. for 8 hours. The maximum distance h between the horizontal plane and the center is in the range of 0 to 30 mm in a direction perpendicular to the horizontal plane. Laminated film in any one of -4.
Item 6. Item 6. The laminated film according to any one of Items 1 to 5, wherein the resin layer is formed of polyolefin.
Item 7. Item 7. The laminated film according to any one of Items 1 to 6, wherein the support has a metal layer.
Item 8. In the laminated film, the support has at least a base material layer and a metal layer,
Item 8. The laminated film according to any one of Items 1 to 7, wherein the resin layer is laminated on the opposite side of the metal layer from the base material layer.
Item 9. Item 9. The laminated film according to any one of Items 1 to 8, which is used as a packaging material.

  The laminated film of the present invention includes a spectral intensity ratio A (crystal part / amorphous part) of a resin crystal part and an amorphous part measured by Raman spectroscopy in the MD direction of the resin layer, and Raman in the TD direction of the resin layer. The sum (A + B) of the spectral intensity ratio B (crystal part / amorphous part) of the crystal part and the amorphous part of the resin measured by spectroscopy is in the range of 1.95 to 2.60. A significant change in the amount of lubricant present on the surface of the layer is suppressed, and stable moldability can be exhibited even in deep drawing (molding depth of 4.0 mm or more).

It is typical sectional drawing which shows the laminated structure of the laminated | multilayer film of this invention. It is a schematic diagram for demonstrating the curl amount of the laminated | multilayer film of this invention. It is a schematic diagram which shows the spectrum at the time of measuring the spectral intensity ratio (crystal part / amorphous part) of the crystalline part of a resin, and an amorphous part about the resin layer formed with the polypropylene using Raman spectroscopy.

  The laminated film of the present invention is a laminated film in which at least a support and a resin layer formed of a resin are laminated, and the resin crystal part measured by Raman spectroscopy in the MD direction of the resin layer; Spectral intensity ratio A (crystal part / amorphous part) of the amorphous part and spectral intensity ratio B (crystal part / non-crystalline part) of the resin part measured by Raman spectroscopy in the TD direction of the resin layer The sum (A + B) with the crystal part) is in the range of 1.95 to 2.60. Hereinafter, the laminated film of the present invention will be described in detail.

Laminated Structure of Laminated Film The laminated film of the present invention is formed by laminating a support 2 and a resin layer 1 as shown in FIG. The resin layer 1 may be composed of only one layer, or may be composed of a plurality of layers.

  Moreover, as a layer which comprises the support body 2, the base material layer 21, the metal layer 22, etc. are mentioned, for example. The support 2 may be composed of only one layer or may be composed of a plurality of layers. Moreover, when the support body 2 has the base material layer 21 and the metal layer 22, the laminated | multilayer film of this invention are laminated | stacked in order of the base material layer 21, the metal layer 22, and the resin layer 1, as FIG. 5 shows. It is preferable. When the support 2 has the base material layer 21 and the metal layer 22, for the purpose of improving the adhesiveness between the base material layer 21 and the metal layer 22, an adhesive layer A is provided between these layers as necessary. (Not shown) may be provided. Moreover, between these layers (for example, between the base material layer 21 and the resin layer 1, between the metal layer 22 and the resin layer 1, for the purpose of improving the adhesiveness of the support body 2 and the resin layer 1, etc. An adhesive layer B (not shown) may be provided as needed.

Configuration of each layer of laminated film [resin layer 1]
In the laminated film 10, the resin layer 1 is made of resin and is laminated on the support 2. As will be described later, when the laminated film 10 of the present invention is used as a packaging material or the like, the resin layer 1 can be a sealant layer. The sealant layer is a layer constituting the innermost layer of the packaging material when the contents are sealed with the packaging material. When sealing the contents, the surfaces of the sealant layer 1 can be brought into contact with each other, and the contacted portions can be heat-sealed to seal the contents.

  In the laminated film 10, the spectral intensity ratio A (crystal part / crystal part / crystal part) of the resin is measured by Raman spectroscopy in the MD direction of the resin layer 1 (flow direction when forming the resin layer 1). (Amorphous part) and the spectral intensity ratio B (crystalline part / non-crystalline part) of the resin part 1 measured by Raman spectroscopy in the TD direction of the resin layer 1 (perpendicular to the MD direction). (A + B) is in the range of 1.95 to 2.60. In the laminated film 10, the sum of the spectral intensity ratio A and the spectral intensity ratio B is within such a range, thereby suppressing a significant change in the amount of the lubricant present on the surface of the resin layer 1 and stable moldability. It is possible to effectively suppress adhesion of a lump of lubricant to the mold while exhibiting the above. The details of this mechanism can be considered as follows. That is, in the resin layer 1, there are a crystal part and an amorphous part of the resin, but when a lubricant is contained inside the resin layer 1, the lubricant is present in the amorphous part of the resin. Therefore, the amount of lubricant bleed-out from the inside of the resin layer 1 to the surface due to temperature change and the like by the sum of the ratios of the amorphous part and the crystal part of the resin in the MD / TD direction being in the above certain range, It becomes possible to make constant the amount of lubricant transferred from the surface of the resin layer 1 to the inside. As a result, a significant change in the amount of the lubricant present on the surface of the resin layer 1 is suppressed, the laminated film 10 exhibits a stable moldability, and adhesion of the lubricant mass to the mold is effectively suppressed. It is thought that there is.

  In the resin layer 1 of the laminated film 10, the spectral intensity ratio A in the MD direction and the spectral intensity ratio B in the TD direction are values measured using JOBIN YVON manufactured by HORIBA, respectively, with a laser wavelength of 633 nm. is there.

For example, as will be described later, when polypropylene is used as the resin for forming the resin layer 1, in the spectrum measurement by Raman spectroscopy, as shown in the schematic diagram of FIG. Is observed at 809 cm ^−1, and the peak of the amorphous part is observed at 842 cm ⁻¹ . Thus, since the peak of the spectrum is usually observed at different positions between the crystal part and the amorphous part of the resin, the peak intensities of the crystal part and the amorphous part in the MD direction and the TD direction are measured and obtained. From the obtained values, the spectrum intensity ratio A and the spectrum intensity ratio B can be calculated.

  The sum of the spectral intensity ratio A in the MD direction and the spectral intensity ratio B in the TD direction may be in the above range, but a significant change in the amount of lubricant present on the surface of the resin layer 1 is suppressed, Also in the draw molding, from the viewpoint of exhibiting stable moldability and suppressing adhesion of a lump of lubricant to the mold, it is preferably in the range of 1.95 to 2.40, more preferably 1.95 to A range of 2.35 is mentioned.

  In the laminated film 10, the absolute value | B−A | of the difference between the spectral intensity ratio A between the crystal part and the amorphous part in the MD direction and the spectral intensity ratio B between the crystal part and the amorphous part in the TD direction is 0. It is preferable to be in the range of 0.05 to 0.60. When the absolute value | B−A | of the difference between the spectral intensity ratio A and the spectral intensity ratio B is within such a range, the curl amount h of the laminated film 10 can be reduced. In the present invention, the curl amount h of the laminated film 10 is an index indicating the degree of curvature of the laminated film, and as shown in the schematic diagram of FIG. 2, the MD direction has a length of 90 mm and the TD direction has a width of 150 mm. At the center P of the laminated film 10, two cuts (penetrating the laminated film) having a length of 100 mm with the center being the center are made on two lines connecting the diagonals of the laminated film 10. Is placed on the horizontal plane 30 and allowed to stand at 20 ° C. for 8 hours, and is the maximum distance h between the horizontal plane 30 and the center P in a direction perpendicular to the horizontal plane 30. The maximum distance h is measured using a Mitutoyo height gauge.

  The laminated film 10 is usually manufactured as a belt-like laminated film, and is used for various applications as described later by cutting into an appropriate size. In the laminated film 10 after being cut, when the curl amount h is large, it is difficult to position the mold when molding. In the laminated film 10 of the present invention, when the absolute value | B−A | of the difference between the spectral intensity ratio A and the spectral intensity ratio B is in the above range, and the curl amount h is in the following range, for example. Since the mold can be easily positioned when molding, the molding process of the laminated film can be performed efficiently.

  In the laminated film 10, the absolute value | B−A | of the difference between the spectral intensity ratio A of the crystal part and the amorphous part in the MD direction and the spectral intensity ratio B of the crystal part and the amorphous part in the TD direction is By being in the range, the mechanism that can reduce the curl amount h of the laminated film 10 can be considered as follows. That is, in the resin layer 1, there are a crystal part and an amorphous part of the resin, but the absolute value | B−A | of the difference between the spectral intensity ratio A and the spectral intensity ratio B is small as described above (MD The difference between the ratio between the crystal part and the amorphous part in the direction and the ratio between the crystal part and the amorphous part in the TD direction is small), so the laminated film based on the difference in the ratio of the crystal part in the MD direction and the TD direction As a result, it is considered that the curl amount h of the laminated film 10 can be reduced.

  From the viewpoint of further reducing the curl amount h of the laminated film 10, the absolute value | BA of the difference between the spectral intensity ratio A and the spectral intensity ratio B is more preferably 0.00 to 0.50. A range, more preferably a range of 0.00 to 0.30.

  The curl amount h of the laminated film 10 is preferably about 0 to 50 mm, more preferably about 0 to 40 mm, and still more preferably about 0 to 30 mm.

  Although it does not restrict | limit especially as resin which comprises the resin layer 1, It is preferable that the resin layer 1 is formed with the thermoplastic resin. Examples of the thermoplastic resin include polyolefin, cyclic polyolefin, carboxylic acid-modified polyolefin, carboxylic acid-modified cyclic polyolefin, and the like.

  Specific examples of polyolefins include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, polypropylene block copolymers (for example, block copolymers of propylene and ethylene), polypropylene Crystalline or amorphous polypropylene such as random copolymers (eg, random copolymers of propylene and ethylene); ethylene-butene-propylene terpolymers, and the like. Among these polyolefins, polyethylene and polypropylene are preferable, and polypropylene is particularly preferable.

  Cyclic polyolefin is a copolymer of olefin and cyclic monomer. Examples of the olefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, and isoprene. Examples of the cyclic monomer include cyclic alkenes such as norbornene; cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, norbornadiene, and the like. Among these polyolefins, a cyclic alkene is preferable, and norbornene is more preferable.

  A carboxylic acid-modified polyolefin is a polymer obtained by modifying a polyolefin with a carboxylic acid. Examples of the carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like.

  The carboxylic acid-modified cyclic polyolefin is a copolymer obtained by copolymerizing a part of the monomer constituting the cyclic polyolefin in place of the α, β-unsaturated carboxylic acid or its acid anhydride, or α, β with respect to the cyclic polyolefin. -A polymer obtained by block polymerization or graft polymerization of an unsaturated carboxylic acid or its acid anhydride. The cyclic polyolefin to be modified with carboxylic acid can be the same as the above cyclic polyolefin. The carboxylic acid used for modification can be the same as that used for modification of the acid-modified cycloolefin copolymer.

  Among these thermoplastic resins, by setting the sum of the spectral intensity ratio A and the spectral intensity ratio B within the above range, a significant change in the amount of lubricant present on the surface of the resin layer 1 is suppressed, Also in drawing molding, from the viewpoint of exhibiting stable moldability and suppressing adhesion of a lump of lubricant to the mold, preferably polyolefin, cyclic polyolefin, and blended polymers thereof; more preferably polyethylene, polypropylene , Copolymers of ethylene and norbornene, and blend polymers of two or more of these.

  As a method of setting the sum of the spectral intensity ratio A and the spectral intensity ratio B within the above numerical range, for example, the resin exemplified above is used as the resin constituting the resin layer 1, and the resin layer The method of setting the temperature of the chill roll cooled at the time of formation of 1 to 10 or more and less than 50 degreeC is mentioned, for example. When the temperature is less than 10 ° C., the peelability between the film and the resin layer is deteriorated, and tearing or the like occurs when peeling. On the other hand, when the temperature is 50 ° C. or higher, the ratio of the crystal part is increased, the amount of the lubricant deposited at the time of forming the laminated film is excessively increased, and stable moldability is hardly exhibited.

  The resin layer 1 may be formed from only one type of resin component, or may be formed from a blend polymer in which two or more types of resin components are combined. Furthermore, as described above, the resin layer 1 may be formed of only one layer, or may be formed of two or more layers using the same or different resin components.

  When the laminated film 10 is subjected to molding, a lubricant is present on the surface of the resin layer 1. Thereby, the slipperiness of the surface of the resin layer 1 is improved, and the moldability of the laminated film is enhanced. Since the lubricant easily moves in a resin such as a polyolefin resin forming the resin layer 1, the resin layer 1 can be used when a lubricant is blended in the resin layer 1 or immediately after the surface of the resin layer 1 is coated with the lubricant. Even when only one of the lubricants is included, the lubricant moves over time, and the lubricant exists on both the surface and the inside of the resin layer 1. That is, in the laminated film 10, a lubricant may be included in the resin layer 1 in advance, or after the production of the laminated film 10, the surface of the resin layer 1 may be coated before molding.

  Examples of the method for allowing the lubricant to be present on the surface of the resin layer 1 include a method in which the surface of the resin layer 1 is coated with a lubricant, or a method of blending the lubricant with the polyolefin forming the resin layer 1. As described above, even when a lubricant is blended with the polyolefin forming the resin layer 1, the lubricant can be present on the surface of the resin layer 1 by bleeding out the lubricant on the surface of the resin layer 1. . On the other hand, when a lubricant is coated on the surface of the resin layer 1, the lubricant can be present inside the resin layer 1 by transferring a part of the lubricant from the surface to the inside. In addition, as a method of bleeding out the lubricant on the surface of the resin layer 1, it is general to age the laminated film at a slightly high temperature of about 30 to 50 ° C. for about several hours to 3 days to promote bleeding. It is. The movement of the lubricant between the inside and the surface of the resin layer 1 as described above is a phenomenon that is particularly likely to occur in the amide-based lubricant described later.

  The type of lubricant is not particularly limited, but by setting the sum of the spectral intensity ratio A and the spectral intensity ratio B in the above range, a significant change in the amount of lubricant present on the surface of the resin layer 1 is suppressed. Even in deep drawing, an amide-based lubricant is preferably used from the viewpoints of exhibiting stable moldability and suppressing adhesion of a lump of lubricant to the mold.

  The amide-based lubricant is not particularly limited as long as it has an amide group, and preferred examples include fatty acid amides and aromatic bisamides. An amide type lubricant may be used individually by 1 type, and may be used in combination of 2 or more types.

  Examples of fatty acid amides include saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylol amides, saturated fatty acid bisamides, and unsaturated fatty acid bisamides. Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic acid amide and the like. Specific examples of the unsaturated fatty acid amide include oleic acid amide and erucic acid amide. Specific examples of the substituted amide include N-oleyl palmitate, N-stearyl stearate, N-stearyl oleate, N-oleyl stearate, N-stearyl erucamide, and the like. Specific examples of methylolamide include methylol stearamide. Specific examples of saturated fatty acid bisamides include methylene bis stearamide, ethylene biscapric amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bishydroxy stearic acid amide, ethylene bisbehenic acid amide, hexamethylene bis stearic acid amide. Examples include acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl sebacic acid amide, and the like. Specific examples of unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide Etc. Specific examples of the fatty acid ester amide include stearoamidoethyl stearate. Specific examples of the aromatic bisamide include m-xylylene bis stearic acid amide, m-xylylene bishydroxy stearic acid amide, N, N′-cysteallyl isophthalic acid amide and the like.

  When the resin layer 1 contains an amide-based lubricant, the content of the lubricant present on the surface and inside of the resin layer 1 is preferably 700 ppm or more, more preferably about 700 to 3000 ppm, more preferably 700 on a mass basis. About 2,500 ppm is mentioned. In addition, these values mean content when the lubricant which exists in the surface and the inside of the resin layer 1 exists in the resin layer 1 altogether.

Although it does not restrict | limit especially as thickness of the resin layer 1, For example, about 5-500 micrometers, Preferably about 5-200 micrometers is mentioned.
[Support 2]
As a layer which comprises the support body 2, the base material layer 21, the metal layer 22, etc. are mentioned, for example. The support 2 may be composed of only one layer or may be composed of a plurality of layers. When the support body 2 has the base material layer 21 and the metal layer 22, it is preferable to laminate | stack so that the layer structure of the laminated | multilayer film 10 may become the order of the base material layer 21, the metal layer 22, and the resin layer 1. FIG. When the support 2 has the base material layer 21 and the metal layer 22, for the purpose of improving the adhesiveness between the base material layer 21 and the metal layer 22, an adhesive layer A is provided between these layers as necessary. May be provided. Moreover, between these layers (for example, between the base material layer 21 and the resin layer 1, between the metal layer 22 and the resin layer 1, for the purpose of improving the adhesiveness of the support body 2 and the resin layer 1, etc. The adhesive layer B may be provided as needed. Hereinafter, these layers will be described in detail.

(Base material layer 21)
In the laminated film 10, the base material layer 21 that can be included as the support 2 is a layer that is provided as necessary and serves as the base material of the laminated film 10. The material for forming the base material layer 21 is not particularly limited. Specific examples of the material for forming the base material layer 21 include, for example, polyester, polyamide, epoxy, acrylic, fluorine resin, polyurethane, silicon resin, phenol, polyetherimide, polyimide, and mixtures and copolymers thereof. Resin.

  Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, copolymerized polyester mainly composed of ethylene terephthalate, butylene terephthalate as a repeating unit. Examples thereof include a copolymer polyester mainly used. The copolymer polyester mainly composed of ethylene terephthalate is a copolymer polyester that polymerizes with ethylene isophthalate mainly composed of ethylene terephthalate (hereinafter, polyethylene (terephthalate / isophthalate)). Abbreviated), polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sodium sulfoisophthalate), polyethylene (terephthalate / sodium isophthalate), polyethylene (terephthalate / phenyl-dicarboxylate) And polyethylene (terephthalate / decanedicarboxylate). In addition, as a copolymer polyester mainly composed of butylene terephthalate as a repeating unit, specifically, a copolymer polyester that polymerizes with butylene isophthalate having butylene terephthalate as a repeating unit (hereinafter referred to as polybutylene (terephthalate / isophthalate)). For example), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene naphthalate and the like. These polyesters may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of polyamides include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and copolymers of nylon 6 and nylon 6,6; terephthalic acid and / or Nylon 6I, Nylon 6T, Nylon 6IT, Nylon 6I6T (I represents isophthalic acid, T represents terephthalic acid) and the like, which include a structural unit derived from isophthalic acid, Aromatic polyamides such as silylene adipamide (MXD6); alicyclic polyamides such as polyaminomethylcyclohexyl adipamide (PACM6); and lactam components and isocyanate components such as 4,4′-diphenylmethane-diisocyanate. Polymerized polyamide, co-weight Polyester amide copolymer and polyether ester amide copolymer is a copolymer of polyamide and polyester and polyalkylene ether glycol; copolymers thereof, and the like. These polyamides may be used individually by 1 type, and may be used in combination of 2 or more type. The stretched polyamide film is excellent in stretchability, can prevent whitening due to resin cracking of the base material layer 21 during molding, and is suitably used as a material for forming the base material layer 21.

  The base material layer 21 may be formed of a uniaxially or biaxially stretched resin film, or may be formed of an unstretched resin film. Among them, a uniaxially or biaxially stretched resin film, in particular, a biaxially stretched resin film has improved heat resistance due to orientation crystallization, and thus is suitably used as the base material layer 21.

  Among these, as a resin film which forms the base material layer 21, Preferably nylon and polyester, More preferably, biaxially stretched nylon, biaxially stretched polyester, Most preferably, biaxially stretched nylon is mentioned.

  In order to improve the pinhole resistance of the laminated film 10, the base material layer 21 can also be laminated with resin films of different materials. Specific examples include a multilayer structure in which a polyester film and a nylon film are laminated, and a multilayer structure in which a biaxially stretched polyester and a biaxially stretched nylon are laminated. When making the base material layer 21 into a multilayer structure, each resin film may be adhere | attached through an adhesive agent, and may be laminated | stacked directly without an adhesive agent. In the case of bonding without using an adhesive, for example, a method of bonding in a hot melt state such as a co-extrusion method, a sand lamination method, or a thermal laminating method can be mentioned. Moreover, when making it adhere | attach through an adhesive agent, the adhesive agent to be used may be a two-component curable adhesive, or a one-component curable adhesive. Further, the bonding mechanism of the adhesive is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, an electron beam curing type such as UV and EB, and the like. As an adhesive component, polyester resin, polyether resin, polyurethane resin, epoxy resin, phenol resin resin, polyamide resin, polyolefin resin, polyvinyl acetate resin, cellulose resin, (meth) acrylic resin Resins, polyimide resins, amino resins, rubbers, and silicon resins can be used.

Although the thickness in particular of the base material layer 21 is not restrict | limited, For example, about 5 micrometers-50 micrometers, Preferably it can be set as about 12 micrometers-30 micrometers.
(Metal layer 22)
In the laminated film 10, the metal layer 22 that can be included as the support 2 is a layer provided as necessary. For example, when the laminated film 10 is used as a packaging material or the like, in addition to improving the strength, it functions as a barrier layer for preventing water vapor, oxygen, light, etc. from entering the inside sealed by the laminated film 10. Specific examples of the metal constituting the metal layer 22 include aluminum, stainless steel, and titanium, and preferably aluminum. The metal layer 22 can be formed by metal foil, metal vapor deposition, or the like, preferably by metal foil, and more preferably by aluminum foil. From the viewpoint of preventing wrinkles and pinholes from being generated in the metal layer 22 when the laminated film 10 is manufactured, for example, it is formed of a soft aluminum foil such as annealed aluminum (JIS A8021P-O, JIS A8079P-O). More preferably.

  The thickness of the metal layer 22 is not particularly limited, but can be, for example, about 10 μm to 200 μm, preferably about 20 μm to 100 μm.

  The metal layer 22 is preferably subjected to chemical conversion treatment on at least one surface, preferably both surfaces, for the purpose of stabilizing adhesion, preventing dissolution and corrosion, and the like. Here, the chemical conversion treatment refers to a treatment for forming an acid-resistant film on the surface of the metal layer. As the chemical conversion treatment, for example, chromate chromate using chromic acid compounds such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromic acetyl acetate, chromium chloride, potassium sulfate chromium, etc. Treatment; Phosphoric acid chromate treatment using a phosphoric acid compound such as sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid; aminated phenol having a repeating unit represented by the following general formulas (1) to (4) Examples include chromate treatment using a polymer.

In general formulas (1) to (4), X represents a hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group. R ¹ and R ² are the same or different and each represents a hydroxyl group, an alkyl group, or a hydroxyalkyl group. In the general formulas (1) to (4), examples of the alkyl group represented by X, R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, C1-C4 linear or branched alkyl groups, such as a tert- butyl group, are mentioned. Examples of the hydroxyalkyl group represented by X, R ¹ and R ² include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 3- C1-C4 straight or branched chain in which one hydroxy group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group is substituted An alkyl group is mentioned. In the general formulas (1) to (4), the alkyl group and hydroxyalkyl group represented by X, R ¹ and R ² may be the same or different. In the general formulas (1) to (4), X is preferably a hydrogen atom, a hydroxyl group or a hydroxyalkyl group. The number average molecular weight of the aminated phenol polymer having the repeating units represented by the general formulas (1) to (4) is preferably, for example, 500 to 1,000,000, more preferably about 1,000 to 20,000. preferable.

  Further, as a chemical conversion treatment method for imparting corrosion resistance to the metal layer 22, a phosphoric acid is coated with a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide, or barium sulfate fine particles dispersed therein, A method of forming a corrosion-resistant treatment layer on the surface of the metal layer 22 by performing a baking treatment at 150 ° C. or higher can be mentioned. Further, a resin layer obtained by crosslinking a cationic polymer with a crosslinking agent may be further formed on the corrosion-resistant treatment layer. Here, examples of the cationic polymer include polyethyleneimine, an ionic polymer complex composed of a polymer having polyethyleneimine and a carboxylic acid, a primary amine graft acrylic resin obtained by graft polymerization of a primary amine on an acrylic main skeleton, and polyallylamine. Or the derivative, aminophenol, etc. are mentioned. As these cationic polymers, only one type may be used, or two or more types may be used in combination. Examples of the crosslinking agent include a compound having at least one functional group selected from the group consisting of an isocyanate group, a glycidyl group, a carboxyl group, and an oxazoline group, and a silane coupling agent. As these crosslinking agents, only one type may be used, or two or more types may be used in combination.

  As the chemical conversion treatment, only one type of chemical conversion treatment may be performed, or two or more types of chemical conversion treatment may be performed in combination. Furthermore, these chemical conversion treatments may be carried out using one kind of compound alone, or may be carried out using a combination of two or more kinds of compounds. Among the chemical conversion treatments, chromic acid chromate treatment, chromate treatment combining a chromic acid compound, a phosphoric acid compound, and an aminated phenol polymer are preferable.

The amount of the acid-resistant film formed on the surface of the metal layer 22 in the chemical conversion treatment is not particularly limited. For example, in the case of performing the above chromate treatment, a chromic acid compound is present per 1 m ² of the surface of the metal layer 22. About 0.5 mg to about 50 mg, preferably about 1.0 mg to about 40 mg in terms of chromium, about 0.5 mg to about 50 mg, preferably about 1.0 mg to about 40 mg in terms of phosphorus, and aminated phenol weight It is desirable that the coalescence is contained at a ratio of about 1 mg to about 200 mg, preferably about 5.0 mg to 150 mg.

In the chemical conversion treatment, a solution containing a compound used for forming an acid-resistant film is applied to the surface of the metal layer by a bar coating method, a roll coating method, a gravure coating method, an immersion method, or the like, and then the temperature of the metal layer is 70. It is carried out by heating so as to have a temperature of from about 0C to about 200C. Further, before the chemical conversion treatment is performed on the metal layer, the metal layer may be previously subjected to a degreasing treatment by an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or the like. By performing the degreasing treatment in this way, it becomes possible to more efficiently perform the chemical conversion treatment on the surface of the metal layer.
(Adhesive layer A)
In the laminated film 10, the adhesive layer A that can be included in the support 2 is a layer provided as necessary for the purpose of increasing the adhesive strength between the base material layer 21 and the metal layer 22.

  The adhesive layer A is formed of an adhesive that can bond the base material layer 21 and the metal layer 22. The adhesive used for forming the adhesive layer A may be a two-component curable adhesive or a one-component curable adhesive. Further, the adhesive mechanism of the adhesive used for forming the adhesive layer A is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, and the like.

  Specific examples of the resin component of the adhesive that can be used to form the adhesive layer A include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, and copolyester. Resin; Polyether adhesive; Polyurethane adhesive; Epoxy resin; Phenol resin resin; Polyamide resin such as nylon 6, nylon 66, nylon 12, copolymer polyamide; polyolefin, acid-modified polyolefin, metal-modified polyolefin, etc. Polyolefin resin; polyvinyl acetate resin; cellulose adhesive; (meth) acrylic resin; polyimide resin; urea resin, melamine resin and other amino resins; chloroprene rubber, nitrile rubber, styrene - rubbers such as butadiene rubber, silicone resin; fluorinated ethylene propylene copolymer, and the like. These adhesive components may be used individually by 1 type, and may be used in combination of 2 or more type. The combination mode of two or more kinds of adhesive components is not particularly limited. For example, as the adhesive component, a mixed resin of polyamide and acid-modified polyolefin, a mixed resin of polyamide and metal-modified polyolefin, polyamide and polyester, Examples thereof include a mixed resin of polyester and acid-modified polyolefin, and a mixed resin of polyester and metal-modified polyolefin. Among these, it has excellent spreadability, durability under high humidity conditions, anti-hypertensive action, heat deterioration-preventing action during heat sealing, etc., and suppresses a decrease in lamination strength between the base material layer 21 and the metal layer 22. From the viewpoint of effectively suppressing the occurrence of delamination, a polyurethane two-component curable adhesive; polyamide, polyester, or a blended resin of these with a modified polyolefin is preferable.

  Further, the adhesive layer A may be multilayered with different adhesive components. When the adhesive layer A is multilayered with different adhesive components, from the viewpoint of improving the lamination strength between the base material layer 21 and the metal layer 22, the adhesive component disposed on the base material layer 21 side is used as the base material layer 21. It is preferable to select a resin having excellent adhesion to the metal layer 22 and selecting an adhesive component having excellent adhesion to the metal layer 22 as the adhesive component disposed on the metal layer 22 side. When the adhesive layer A is multilayered with different adhesive components, specifically, the adhesive component disposed on the metal layer 22 side is preferably an acid-modified polyolefin, a metal-modified polyolefin, a polyester and an acid-modified polyolefin. And a resin containing a copolyester.

About the thickness of the contact bonding layer A, about 2-50 micrometers is mentioned, for example, Preferably about 3-25 micrometers is mentioned.
(Adhesive layer B)
In the laminated film 10, adhesion between the support 2 (for example, the base material layer 21 and the metal layer 22) and the resin layer 1 is performed for the purpose of firmly bonding the support 2 and the resin layer 1. Layer B may be further provided.

  The adhesive layer B is formed of an adhesive component capable of bonding the base material layer 21, the metal layer 22, and the like that can be included as the support 2 and the resin layer 1. The adhesive used for forming the adhesive layer B may be a two-component curable adhesive or a one-component curable adhesive. Further, the adhesion mechanism of the adhesive component used for forming the adhesive layer B is not particularly limited, and examples thereof include a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.

  Specific examples of the adhesive component that can be used to form the adhesive layer B include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, and copolyester; polyether Polyurethane adhesives; epoxy resins; phenol resin resins; polyamide resins such as nylon 6, nylon 66, nylon 12, copolymer polyamides; polyolefins such as polyolefins, carboxylic acid modified polyolefins, metal modified polyolefins Resin, polyvinyl acetate resin; cellulose adhesive; (meth) acrylic resin; polyimide resin; urea resin, melamine resin and other amino resins; chloroprene rubber, nitrile rubber, - styrene rubbers such as butadiene rubber; and silicone resins. These adhesive components may be used alone or in combination of two or more.

  The thickness of the adhesive layer B is not particularly limited, but is preferably about 1 μm to 40 μm, for example, and more preferably about 2 μm to 30 μm.

  It should be noted that each layer constituting the laminated film 10 may be subjected to corona treatment, in order to improve or stabilize the film forming property, lamination processing, suitability for final product secondary processing (pouching, embossing), etc. Surface activation treatment such as blast treatment, oxidation treatment, and ozone treatment may be performed.

Manufacturing method of laminated film The laminated film 10 of this invention can be manufactured by laminating | stacking the support body 2 and the resin layer 1, Specifically, the following manufacturing methods can be illustrated, for example.

  For example, if the support 2 has the base material layer 21 and the metal layer 22, the laminated film 10 is obtained by the following laminating steps. First, the base material layer 21 and the metal layer 22 are laminated. This lamination can be performed by, for example, a dry lamination method using the above-described adhesive component that forms the adhesive layer A or the like. Moreover, as a method of laminating the base material layer 21 and the metal layer 22, a method of extruding a resin for forming the base material layer 21 on the surface of the metal layer 22, or a metal on one surface of the base material layer 21. The method etc. which form the metal layer 22 by vapor-depositing can also be mentioned. Next, the resin layer 1 is laminated on the metal layer 22. The resin layer 1 can be formed by, for example, melt extrusion of a thermoplastic resin or a dry lamination method. For the purpose of increasing the adhesive strength between the metal layer 22 and the resin layer 1, if necessary, an adhesive component for forming the adhesive layer B is applied on the metal layer 22 and dried. The resin layer 1 may be formed. When the resin layer 1 is formed of a plurality of layers, the resin layer 1 formed of a plurality of layers can be laminated by a known method such as a coextrusion method.

  In order to improve the adhesiveness of each layer in the obtained laminated film 10, an aging treatment or the like may be performed. The aging treatment can be performed, for example, by heating the laminated film 10 at a temperature of about 30 to 100 ° C. for 1 to 200 hours. Furthermore, in order to further improve the adhesiveness of each layer in the obtained laminated film, the obtained laminated film 10 may be heated at a temperature equal to or higher than the melting point of the resin layer 1. The temperature at this time is preferably the melting point of the resin layer 1 + 5 ° C. or higher and the melting point + 100 ° C. or lower, more preferably the melting point + 10 ° C. or higher and the melting point + 80 ° C. or lower. In the present invention, the melting point of the resin layer 1 refers to an endothermic peak temperature in differential scanning calorimetry of the resin component constituting the resin layer 1. Heating in the aging treatment and heating above the melting point of the resin layer 1 can be performed by a method such as a hot roll contact method, a hot air method, a near or far infrared method, respectively.

  It should be noted that each layer constituting the laminated film may be subjected to corona treatment, blasting, or the like to improve or stabilize film forming properties, lamination processing, suitability for final product secondary processing (pouching, embossing), etc., as necessary. Surface activation treatment such as treatment, oxidation treatment, and ozone treatment may be performed.

Application of Laminated Film As described above, the laminated film 10 of the present invention is usually produced as a belt-like laminated film, and is used for various applications by cutting into an appropriate size. In addition, the laminated film 10 of the present invention can be suitably used as a laminated film that is used for deep drawing, in particular, having a molding depth of 0.5 mm or more, preferably about 4.0 to 7.0 mm. Although it does not restrict | limit especially as a specific use of the laminated | multilayer film 10, For example, a packaging material etc. are mentioned. For example, when the laminated film 10 is used as a packaging material, the packaging material can be used for packaging various contents such as medicines, cosmetics, foods, and electrolytic solutions. That is, the packaging material of the present invention is suitably used as a pharmaceutical packaging material, a cosmetic packaging material, a food packaging material, a battery packaging material, and the like. In addition, the packaging material can be deformed according to the shape of the contents, and can be a package that accommodates the contents.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the examples.

<Examples 1-11 and Comparative Examples 1-2>
[Manufacture of laminated film]
On a base material layer 21 made of a stretched nylon film (thickness 25 μm), a metal layer 22 made of aluminum foil (thickness 40 μm) subjected to chemical conversion treatment on both surfaces was laminated by a dry lamination method. Specifically, a two-component urethane adhesive (polyol compound and aromatic isocyanate compound) was applied to one surface of the aluminum foil to form an adhesive layer A (thickness 4 μm) on the metal layer 22. Next, after bonding the adhesive layer A and the base material layer 21 on the metal layer 22 under pressure and heating, by performing an aging treatment at 40 ° C. for 24 hours, the base material layer 21 / adhesive layer A / metal layer 22 is obtained. A laminate A was prepared. In addition, the chemical conversion treatment of the aluminum foil used as the metal layer 22 is performed by rolling a treatment liquid composed of a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m ² (dry weight). The coating was applied to both surfaces of the aluminum foil and baked for 20 seconds under the condition that the film temperature was 180 ° C. or higher.

  Next, a resin component (a carboxylic acid-modified cyclic polyolefin containing a fatty acid amide-based lubricant) that forms the resin layer 1 on the metal layer 22 side of the laminate A is extruded in a molten state (250 ° C.). Resin layer 1 (thickness 50 μm) was laminated. Thus, a laminated film in which the base material layer 21 / adhesive layer A / metal layer 22 / resin layer 1 were laminated in order was obtained. In addition, the temperature of the chill roll which cools a laminated body after laminating | stacking the resin layer 1 was made into the temperature of Table 1 and Table 2, respectively.

<Measurement of spectral intensities A and B by Raman spectroscopy>
About the resin layer of the laminated | multilayer film obtained above, the said spectral intensity ratio A in MD direction and the spectral intensity ratio B in TD direction were each measured with the following measuring instruments and measurement conditions using the Raman spectroscopy. . The results are shown in Tables 1 and 2.
Measuring equipment: JOBIN YVON made by HORIBA
Measurement conditions: laser wavelength 633 nm, measurement time 15 seconds, microscope magnification 50 times <measurement of curl amount h>
Using the laminated film obtained above, at the center of the laminated film having a length of 90 mm in the MD direction and a width of 150 mm in the TD direction, the length having the center as the center on the two lines connecting the respective diagonals of the laminated film Two cuts having a thickness of 100 mm (cuts penetrating the laminated film) were made, placed on a horizontal surface, and allowed to stand at 20 ° C. for 8 hours. Next, as shown in FIG. 2, the maximum distance h between the horizontal plane and the center was measured in a direction perpendicular to the horizontal plane using a height gauge (manufactured by Mitsuto Corporation). The results are shown in Tables 1 and 2.

<Lubricant precipitation evaluation 1>
The laminated film obtained above was stored at 20 ° C. for 1 week and then cut to prepare a 120 × 80 mm strip piece as a test sample. Next, a straight mold comprising a 30 × 50 mm rectangular male mold and a female mold with a clearance of 0.5 mm between the male mold is used, and the resin layer 1 side is positioned on the male mold side. The above test samples are placed, and 5000 pieces (5000 shots) of each test sample are pressed with a presser pressure (surface pressure) of 0.1 MPa so that the forming depth is 4.0 mm, and cold forming ( Pulling in one step). The lubricant precipitation of the test sample at this time was evaluated according to the following criteria. The results are shown in Table 1.
○: No adhesion of lubricant to the mold after 5000 moldings Δ: Adhesion of lubricant to the mold was confirmed after 5000 moldings, but there was no effect on the molding state ×: Adhesion of lubricant to the molds after 5000 moldings Causes indentations in molded samples

  As shown in Table 1, Example 1 in which the sum (A + B) of the spectral intensity ratio A in the MD direction and the spectral intensity ratio B in the TD direction in the resin layer is in the range of 2.06 to 2.51. In the laminated films of -8, the result of the lubricant deposition evaluation was good. Furthermore, in the laminated films of Examples 1 to 6 and 8 in which the absolute value | B−A | of the difference between the spectral intensity ratio A and the spectral intensity ratio B is as small as 0.06 to 0.32, the curl amount h is set to 30 mm. It was able to be suppressed to the extent. In contrast, the laminated film of Comparative Examples 1 and 2 in which the sum (A + B) of the spectral intensity ratio A in the MD direction in the resin layer and the spectral intensity ratio B in the TD direction is 2.71 or 2.75. The results of the lubricant deposition evaluation were inferior.

<Lubricant precipitation evaluation 2>
The laminated films of Examples 1, 2, 6, 7, 9, 10, 11, and Comparative Examples 1 and 2 obtained above were 1 at each storage temperature (5 ° C., 20 ° C., 40 ° C.) described in Table 2. After storing for a week, it cut | judged and produced the strip piece of 120x80 mm, and made it the test sample. Next, a straight mold comprising a 30 × 50 mm rectangular male mold and a female mold with a clearance of 0.5 mm between the male mold is used, and the resin layer 1 side is positioned on the male mold side. The above test samples are placed, and 5000 pieces (5000 shots) of each test sample are pressed with a presser pressure (surface pressure) of 0.1 MPa so that the forming depth is 4.0 mm. Inter-molding (retraction one-stage molding) was performed. The lubricant precipitation of the test sample at this time was evaluated according to the following criteria. The results are shown in Table 2. The curl amount is a value measured in the same manner as in the above <Measurement of curl amount h> for any test sample stored at each temperature.
○: No adhesion of lubricant to the mold after 5000 moldings Δ: Adhesion of lubricant to the mold was confirmed after 5000 moldings, but there was no effect on the molding state ×: Adhesion of lubricant to the molds after 5000 moldings Causes indentations in molded samples

<4.0 mm formability evaluation>
In the same manner as the lubricant deposition evaluation 2 described above, cold forming was performed on each of 5000 test samples so as to determine whether or not pinholes were generated, so that the forming depth was 4.0 mm. Formability was evaluated according to the following criteria. The results are shown in Table 2.
○: No pinhole occurrence △: Pinhole generation rate 10% or less ×: Pinhole generation rate 11% or more

DESCRIPTION OF SYMBOLS 1 ... Resin layer 2 ... Support body 21 ... Base material layer 22 ... Metal layer 10 ... Laminated film 30 ... Horizontal surface

Claims (9)

At least a laminated film in which a support and a resin layer formed of a resin are laminated,
Spectral intensity ratio A (crystal part / amorphous part) of crystal part and amorphous part of the resin measured by Raman spectroscopy in the MD direction of the resin layer, and measurement by Raman spectroscopy in the TD direction of the resin layer A laminated film in which the sum (A + B) of the spectral intensity ratio B (crystal part / amorphous part) of the crystal part and amorphous part of the resin is in the range of 1.95 to 2.60.   The laminated film according to claim 1, wherein the resin layer contains a lubricant.   The laminated film according to claim 1, which is a laminated film subjected to deep drawing.   The laminated film according to any one of claims 1 to 3, wherein an absolute value | B-A | of a difference between the spectral intensity ratio A and the spectral intensity ratio B is in a range of 0.00 to 0.60. .   In the center of the laminated film having a length of 90 mm in the MD direction and a width of 150 mm in the TD direction, two cuts having a length of 100 mm having the center as the center are formed on two lines connecting the respective diagonals of the laminated film. And after placing it on a horizontal plane and leaving it at 20 ° C. for 8 hours, the maximum distance h between the horizontal plane and the center is in the range of 0 to 30 mm in a direction perpendicular to the horizontal plane. The laminated film in any one of 1-4.   The laminated film according to claim 1, wherein the resin layer is made of polyolefin.   The laminated film according to claim 1, wherein the support has a metal layer. In the laminated film, the support has at least a base material layer and a metal layer,
The laminated film according to any one of claims 1 to 7, wherein the resin layer is laminated on the opposite side of the metal layer from the base material layer.   The laminated film according to any one of claims 1 to 8, which is used as a packaging material.