WO2017126636A1

WO2017126636A1 - Laminate film

Info

Publication number: WO2017126636A1
Application number: PCT/JP2017/001822
Authority: WO
Inventors: 陽祐早川; 哲也小尻; 山下　孝典; 山下　力也; かおる宮崎
Original assignee: 大日本印刷株式会社
Priority date: 2016-01-19
Filing date: 2017-01-19
Publication date: 2017-07-27
Also published as: CN108472923B; CN111497380A; CN108472923A; CN111497380B

Abstract

Provided is a laminate film in which curl is suppressed and that is easily positioned in a mold during molding. The laminate film is formed from at least a laminated body of a support and a resin layer formed from a resin. The laminate film has an absolute value |B-A| of a difference between a spectral intensity ratio A obtained by dividing the spectral intensity, which is measured by Raman spectroscopy in one direction of the resin layer, of a crystal portion of the resin by the spectral intensity of an amorphous portion, and a spectral intensity ratio B obtained by dividing the spectral intensity, which is measured by Raman spectroscopy in another direction of the resin layer orthogonal to the one direction, of a crystal portion of the resin by the spectral intensity of an amorphous portion, in the range of 0.00 or more to 0.70 or less.

Description

Laminated film

The present invention relates to a laminated film.

Conventionally, a laminated film in which a resin layer is laminated on a support such as a base material layer or a barrier 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 cold forming for the purpose of forming a space for containing contents. Exists.

A laminated film subjected to cold forming is usually produced as a belt-like laminated film, and is used for various purposes by cutting into an appropriate size. In the laminated film after being cut, a phenomenon called curl in which the laminated film is curved may occur. When the curl is generated in the laminated film, it is difficult to position the mold when the laminated film is molded, and there is a problem that the yield cannot be achieved because the film cannot be molded with a desired accuracy. There is also a problem that the efficiency of the forming process of the laminated film is lowered.

Also, in the laminated film used for cold forming, 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 cold forming. 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 cold forming, 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 during 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

Under such circumstances, the main object of the invention according to the first aspect of the present invention is to provide a laminated film in which curling is suppressed and the mold can be easily positioned during molding.

Further, as described above, a lubricant may be blended or coated on the surface of the resin layer of the laminated film subjected to cold forming. 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 depending on the storage environment from the production of the laminated film to the time 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 invention according to the second aspect of the present invention exhibits stable moldability by suppressing a significant change in the amount of the lubricant present on the surface of the resin layer. The main object is to provide a laminated film in which lump adhesion is effectively suppressed.

The present inventors have intensively studied to solve the above problems. As a result, the spectrum of the crystal part of the resin measured by Raman spectroscopy in one direction on the resin layer plane in a laminated film composed of at least a support and a resin layer formed of resin. The spectral intensity ratio A obtained by dividing the intensity by the spectral intensity of the amorphous part, and the crystalline part of the resin measured by Raman spectroscopy in the other direction on the same plane orthogonal to the one direction of the resin layer. When the absolute value | BA | of the difference from the spectral intensity ratio B obtained by dividing the spectral intensity by the spectral intensity of the amorphous part is in the range of 0.00 to 0.70, It was found that curling is suppressed and positioning of the mold during molding becomes easy.

That is, the invention according to the first aspect of the present invention provides the following aspects of the invention.
Item 1A. At least a laminated film composed of a laminate of a support and a resin layer formed of a resin,
The spectral intensity ratio A obtained by dividing the spectral intensity of the crystal part of the resin measured by Raman spectroscopy in one direction on the plane of the resin layer by the spectral intensity of the amorphous part, and the one direction of the resin layer The absolute value of the difference from the spectral intensity ratio B obtained by dividing the spectral intensity of the crystalline part of the resin by the spectral intensity of the amorphous part measured by Raman spectroscopy in the other direction on the same plane perpendicular to | B-A | is a laminated film having a range of 0.00 to 0.70.
Item 2A. The laminated film having a length of 90 mm in one direction and a length of 150 mm in the other direction is prepared, and in the center of the laminated film, on the two lines connecting the diagonals of the laminated film, the thickness direction of the laminated film Two cuts with a length of 100 mm with the center being the center are made from the side of the support and placed on a horizontal surface so that the support is on the bottom, and at 8 ° C. The laminated film according to Item 1A, wherein the maximum distance h is 30 mm or less when the maximum distance h between the horizontal plane and the center is measured in a direction perpendicular to the horizontal plane after standing for a time.
Item 3A. Item 2. The laminated film according to Item 1A or 2A, wherein the resin layer is made of polyolefin.
Item 4A. Item 3. The laminated film according to any one of Items 1A to 3A, wherein the sum (A + B) of the spectral intensity ratio A and the spectral intensity ratio B is in the range of 1.95 to 2.66.
Item 5A. Item 4. The laminated film according to any one of Items 1A to 4A, wherein the support has a barrier layer.
Item 6A. The support has a base material layer and a barrier layer,
Item 4. The laminated film according to any one of Items 1A to 4A, wherein the resin layer is laminated on a side of the barrier layer opposite to the base material layer.
Item 7A. Item 6. The laminated film according to Item 6A, wherein the base material layer has a multilayer structure composed of a laminate of a polyester film and a nylon film.
Item 8A. Item 6. The laminated film according to Item 6A, wherein the base material layer is made of a polyester film.
Item 9A. Item 6. The laminated film according to Item 6A, wherein the base material layer is made of a nylon film.
Item 10A. Item 10. The laminated film according to any one of Items 1A to 9A, which is used as a packaging material.
Item 11A. Item 10. The laminated film according to any one of Items 1A to 10A, which is a laminated film subjected to cold forming.

In addition, the present inventors, at least in the laminated film composed of a laminate of a support and a resin layer formed of a resin, the resin measured by Raman spectroscopy in one direction on the resin layer plane The spectral intensity ratio A obtained by dividing the spectral intensity of the crystal part by the spectral intensity of the amorphous part and the Raman spectrum measured in the other direction on the same plane orthogonal to the one direction of the resin layer The sum of the spectral intensity ratio B obtained by dividing the spectral intensity of the crystal part of the resin by the spectral intensity of the amorphous part is in the range of 1.95 or more and 2.66 or less, so that it exists on the surface of the resin layer. It has been found that a significant change in the amount of lubricant can be suppressed and that stable moldability can be exhibited even in cold forming (molding depth of 4.0 mm or more).

That is, the invention according to the second aspect of the present invention provides the following aspects of the invention.
Item 1B. At least a laminated film composed of a laminate of a support and a resin layer formed of a resin,
The spectral intensity ratio A obtained by dividing the spectral intensity of the crystal part of the resin measured by Raman spectroscopy in one direction on the plane of the resin layer by the spectral intensity of the amorphous part, and the one direction of the resin layer And the spectral intensity ratio B obtained by dividing the spectral intensity of the crystal part of the resin measured by Raman spectroscopy in the other direction on the same plane orthogonal to the spectral intensity of the amorphous part is 1. A laminated film in the range of 95 to 2.66.
Item 2B. The laminated film according to Item 1B, wherein the resin layer includes a lubricant.
Item 3B. Item 3. The laminated film according to Item 1B or 2B, wherein the absolute value | BA | of the difference between the spectral intensity ratio A and the spectral intensity ratio B is in the range of 0.00 to 0.70.
Item 4B. The laminated film having a length of 90 mm in one direction and a length of 150 mm in the other direction is prepared, and in the center of the laminated film, on the two lines connecting the diagonals of the laminated film, the thickness direction of the laminated film Two cuts with a length of 100 mm with the center being the center are made from the side of the support and placed on a horizontal surface so that the support is on the bottom, and at 8 ° C. After standing for a time, when the maximum distance h between the horizontal plane and the center is measured in a direction perpendicular to the horizontal plane, the maximum distance h is 30 mm or less. The laminated film as described.
Item 5B. Item 4. The laminated film according to any one of Items 1B to 4B, wherein the resin layer is made of polyolefin.
Item 6B. Item 6. The laminated film according to any one of Items 1B to 5B, wherein the support has a barrier layer.
Item 7B. The support has a base material layer and a barrier layer,
Item 6. The laminated film according to any one of Items 1B to 5B, wherein the resin layer is laminated on the opposite side of the barrier layer from the base material layer.
Item 8B. Item 8. The laminated film according to Item 7B, wherein the base material layer has a multilayer structure composed of a laminate of a polyester film and a nylon film.
Item 9B. The laminated film according to Item 7B, wherein the base material layer is formed of a polyester film.
Item 10B. The laminated film according to Item 7B, wherein the base material layer is made of a nylon film.
Item 11B. Item 11. The laminated film according to any one of Items 1B to 10B, which is used as a packaging material.
Item 12B. Item 12. The laminated film according to any one of Items 1B to 11B, which is a laminated film subjected to cold forming.

The laminated film according to the first aspect of the present invention has a spectral intensity obtained by dividing the spectral intensity of the crystal part of the resin measured by Raman spectroscopy in one direction on the resin layer plane by the spectral intensity of the amorphous part. Spectral intensity obtained by dividing the spectral intensity of the crystal part of the resin measured by Raman spectroscopy in the other direction on the same plane orthogonal to the one direction of the resin layer A by the spectral intensity of the amorphous part When the absolute value | BA− of the difference from the ratio B is in the range of 0.00 to 0.70, curling of the laminated film is suppressed and positioning of the mold during molding becomes easy. For this reason, a laminated film can be shape | molded with a desired precision and a yield can be improved. Moreover, the efficiency of the forming process of the laminated film can be improved.

In addition, the laminated film according to the second aspect of the present invention is obtained by dividing the spectral intensity of the crystalline part of the resin measured by Raman spectroscopy in one direction on the resin layer plane by the spectral intensity of the amorphous part. Obtained by dividing the spectral intensity of the crystal part of the resin measured by Raman spectroscopy in the other direction on the same plane orthogonal to the one direction of the resin layer by the spectral intensity of the amorphous part. When the sum of the spectral intensity ratio B is in the range of 1.95 or more and 2.66 or less, a significant change in the amount of the lubricant present on the surface of the resin layer is suppressed, and cold forming (for example, the forming depth is 4). 0.0 mm or more), stable moldability can be exhibited.

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 first aspect of the present invention is a laminated film composed of at least a support and a resin layer formed of a resin, and Raman spectroscopy in one direction on the resin layer plane The spectral intensity ratio A obtained by dividing the spectral intensity of the crystal part of the resin measured by the method by the spectral intensity of the amorphous part, and Raman in the other direction on the same plane perpendicular to the one direction of the resin layer The absolute value | BA | of the difference from the spectral intensity ratio B obtained by dividing the spectral intensity of the crystalline part of the resin by the spectral intensity of the amorphous part measured by spectroscopy is 0.00 or more and 0.00. It is characterized by being in the range of 70 or less. The above spectral intensity usually shows the absolute value | BA− of the difference at orthogonal positions in MD and TD (described later) on the same plane of the resin layer. It is not limited to.

Further, the laminated film of the second aspect of the present invention is a laminated film composed of at least a support and a resin layer formed of a resin, and is unidirectional on the resin layer plane ( For example, the spectral intensity ratio obtained by dividing the spectral intensity of the crystal part of the resin measured by Raman spectroscopy in MD (Machine Direction), which is the flow direction when forming the resin layer, by the spectral intensity of the amorphous part A and the spectral intensity of the crystal part of the resin measured by Raman spectroscopy in the other direction (for example, TD: Transverse Direction) on the same plane orthogonal to the one direction of the resin layer. The sum of the spectral intensity ratio B obtained by dividing by the intensity is in the range of 1.95 to 2.66. .

Hereinafter, the laminated film of the present invention will be described in detail. In addition, in this specification, about the matter which is different between the laminated film of the first aspect and the laminated film of the second aspect, it is clearly shown which aspect is concerned, and the laminated film of the first aspect The matters common to the laminated film of the second aspect are the descriptions of the laminated film of the present invention. Moreover, the code | symbol in drawing was used in common with the 1st aspect and the 2nd aspect. For example, in the following description, the base film 21, the barrier layer 22, the adhesive layer A, and the adhesive layer B of the support 2 are common to the laminated film of the first aspect and the second aspect.

In the claims and the description, the symbol “˜” is used as the notation of the numerical range. For example, the meaning of the numerical range “the value X is A1 to A2” means “A1 ≦ X ≦ A2 "means. As for MD and TD of the laminated film, for example, when a barrier layer 22 described later is made of an aluminum foil, the rolling direction of the aluminum foil is MD, and the direction perpendicular to the same plane as MD is TD. The rolling direction of the aluminum foil can be confirmed by the rolling trace of the aluminum foil.

Laminated Structure of Laminated Film The laminated film of the present invention (first aspect and second aspect) is formed by laminating a support 2 and a resin layer 1 as shown in FIG. 1, for example. 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 barrier 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 barrier layer 22, the laminated | multilayer film of this invention are laminated | stacked in order of the base material layer 21, the barrier layer 22, and the resin layer 1, as FIG. 1 shows. It is preferable. When the support 2 has the base material layer 21 and the barrier layer 22, for the purpose of improving the adhesiveness between the base material layer 21 and the barrier 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 barrier 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 heat-fusible resin layer. The heat-fusible resin layer is a layer that constitutes the innermost layer of the packaging material when the contents are sealed with the packaging material. When sealing the contents, the surfaces of the heat-fusible resin layer 1 can be brought into contact with each other, and the contacted parts can be heat-sealed to seal the contents.

As described above, a laminated film is usually produced as a strip-like laminate and is used for various applications as described later by cutting into an appropriate size. In the laminated film 10 after being cut, a phenomenon called curl in which the laminated film is curved may occur. When the curl is generated in the laminated film, it is difficult to position the mold when the laminated film is molded, and there is a problem that the yield cannot be achieved because the film cannot be molded with a desired accuracy. There is also a problem that the efficiency of the forming process of the laminated film is lowered.

On the other hand, in the laminated film 10 of the first aspect, the resin measured by Raman spectroscopy in one direction of the resin layer 1 (for example, MD which is the flow direction when forming the resin layer 1). Raman intensity in the spectral intensity ratio A (crystal part / amorphous part) between the crystal part and the amorphous part and the other direction orthogonal to the one direction of the resin layer 1 (for example, TD which is the perpendicular direction of MD in the same plane) The absolute value | BA | of the difference between 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 0.00 to 0.70. It is in. In the laminated film 10 of the first aspect, the absolute value of the difference between the spectral intensity ratio A and the spectral intensity ratio B of the resin layer 1 is in such a range, so that curling of the laminated film is suppressed and molding is performed. The positioning of the mold at the time becomes easy. The details of this mechanism can be considered as follows. That is, in the resin layer 1, although there are a crystalline part and an amorphous part of the resin, the absolute value | BA | of the difference between the spectral intensity ratio A and the spectral intensity ratio B is small as described above (for example, The difference between the ratio of the crystal part and the amorphous part in MD and the ratio of the crystal part and the amorphous part in TD is small), so the ratio of the crystal part in one direction and the other direction orthogonal to the one direction is It is considered that the distortion of the shape of the laminated film based on the difference is suppressed, and as a result, 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 10. For measurement of the curl amount h, as shown in the schematic diagram of FIG. 2, a laminated film 10 having a length of 90 mm in one direction and a length of 150 mm in the other direction orthogonal to the one direction is prepared. Next, at the center P of the laminated film 10, the length from which the center is the center from the support side so as to penetrate in the thickness direction of the laminated film on two lines connecting the respective diagonals of the laminated film 10. Two cuts (through the laminated film) with a thickness of 100 mm are made. Next, the laminated film with the cuts is placed on the horizontal surface 30 so that the support is on the lower side, and allowed to stand at 20 ° C. for 8 hours. Next, in the direction perpendicular to the horizontal plane 30 of the laminated film, the distance between the apex (center P) of the four surfaces raised by curling and the horizontal plane 30 is measured, and the largest value is set as the maximum distance h. Let the amount be h. The curl amount h can be measured using a height gauge manufactured by Mitutoyo Corporation.

The absolute value of the difference between the spectral intensity ratio A and the spectral intensity ratio B from the viewpoint of further reducing the curl amount h of the laminated film 10 of the first embodiment and further facilitating the positioning of the mold during molding. | BA is preferably about 0.00 to 0.66, more preferably about 0.00 to 0.51, still more preferably about 0.00 to 0.43, and still more preferably 0.00 to About 0.33, more preferably about 0.00 to 0.27, more preferably about 0.00 to 0.15, more preferably about 0.00 to 0.10, and still more preferably 0.00 to 0.00. The range is about 08, particularly preferably about 0.00 to 0.05. From the same viewpoint, the spectral intensity ratio A is preferably about 0.90 to 1.17, more preferably about 0.90 to 1.15, still more preferably about 0.92 to 1.07, The range of about 0.99 to 1.05 is particularly preferable, and the spectral intensity ratio B is preferably about 0.90 to 1.66, more preferably about 0.90 to 1.51, and still more preferably. Is about 1.00 to 1.43, more preferably about 1.00 to 1.25, and particularly preferably about 1.00 to 1.10.

The curl amount h of the laminated film 10 of the present invention is preferably about 30 mm or less, more preferably about 29 mm or less, further preferably about 28 mm or less, more preferably about 27 mm or less, still more preferably 25 mm or less, more preferably about about 20 mm or less, More preferably, about 10 mm or less, More preferably, about 5 mm or less is mentioned. A preferred lower limit of the curl amount h is 0 mm.

In the resin layer 1 of the laminated film 10 of the present invention, the spectral intensity ratio A in one direction (for example, TD which is the vertical direction of the same plane as MD) and the other direction (for example, MD) orthogonal to the one direction. Is a spectral intensity ratio B in TD, which is the vertical direction of the same plane, respectively, using a microscope laser Raman spectrometer (for example, LabRAM HR-800 manufactured by HORIBA JOBIN YVON) It is a value measured under the following measurement conditions and analysis conditions.
In the measurement of the spectral intensity A in the MD, a Raman spectrum is measured so that the MD and the incident laser polarization plane are parallel, and in the measurement of the spectral intensity B in the TD, the TD and the incident laser polarization plane are parallel. Measure the Raman spectrum.
Measurement conditions: excitation laser wavelength 633 nm, exposure time 15 seconds, objective lens 50 times, number of integrations 8 times, confocal hole diameter φ0.1 mm, grating 800 L / mm
Analysis conditions:
(1) The average value of the scattering intensity at a Raman shift of 600 to 700 cm −1 is taken as the baseline value.
(2) The peak value at 809 cm−1 is obtained by subtracting the baseline value from the maximum value of the scattering intensity in the range of Raman shift 809 ± 2 cm−1.
(3) The peak value at 842 cm−1 is obtained by subtracting the baseline value from the maximum value of the scattering intensity in the range of Raman shift 842 ± 2 cm−1.
(4) The spectral intensity ratios A and B are calculated using the peak intensities in (2) and (3) above.

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 near the Raman shift 809 cm−1, and the peak of the amorphous part is observed near the Raman shift 842 cm−1. As described above, since the peak of the spectrum is usually observed at a different position between the crystal part and the amorphous part of the resin, the crystal in one direction (for example, MD) and the other direction (for example, TD) orthogonal to the one. The peak intensity of the part and the amorphous part are measured, and the spectrum intensity ratio A and the spectrum intensity ratio B can be calculated from the obtained values.

Moreover, in the laminated film 10 of the first aspect, the spectral intensity ratio A of the crystal part and the amorphous part in one direction (for example, MD which is the flow direction when forming the resin layer 1) is orthogonal to this. The sum (A + B) of the spectral intensity ratio B of the crystal part and the amorphous part in the other direction (for example, TD which is the vertical direction of MD in the same plane) may be in the range of 1.95 to 2.66. preferable. 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 a temperature change or the like when the sum of the ratio of the amorphous part and the crystal part of the resin in the one direction and the other direction is in the above-mentioned predetermined range. And the amount of lubricant transferred from the surface of the resin layer 1 to the inside can be made constant. As a result, a significant change in the amount of lubricant present on the surface of the resin layer 1 is suppressed, the laminated film 10 of the first aspect exhibits stable moldability, and adhesion of the lubricant mass to the mold is effective. It is thought that it is suppressed.

In the laminated film 10 of the first aspect, the spectral intensity ratio A in one direction (for example, MD which is the flow direction when forming the resin layer 1) and the other direction orthogonal to the spectral intensity ratio A (for example, MD are the same). The sum of the spectral intensity ratios B in the vertical direction of the plane (TD) may be within the above range, but it suppresses a significant change in the amount of the lubricant present on the surface of the resin layer 1 and can also be used in cold forming. From the viewpoint of exhibiting stable moldability and suppressing adhesion of a lump of lubricant to the mold, it is preferably about 1.95 to 2.66, more preferably about 1.95 to 2.60, More preferably, about 1.95 to 2.51, more preferably about 1.95 to 2.41, more preferably about 1.95 to 2.35, still more preferably about 1.95 to 2.10, and still more preferably. Is 1 About 99 to 2.09, and particularly preferably include a range of about 2.00 to 2.07.

Further, in the laminated film 10 of the second aspect, the resin crystal part measured by Raman spectroscopy in one direction of the resin layer 1 (for example, MD which is the flow direction when forming the resin layer 1) Raman spectroscopy in the spectral intensity ratio A (crystal part / amorphous part) of the amorphous part and the other direction orthogonal to the one direction of the resin layer 1 (for example, TD which is the vertical direction of the same plane as MD) The sum (A + B) of the spectrum intensity ratio B (crystal part / amorphous part) of the crystal part and the amorphous part of the resin to be measured is in the range of 1.95 to 2.66. In the laminated film 10 of the second aspect, 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 lubricant present on the surface of the resin layer 1. It is possible to effectively suppress adhesion of a lump of lubricant to the mold while exhibiting stable moldability. 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 a temperature change or the like when the sum of the ratio of the amorphous part and the crystal part of the resin in the one direction and the other direction is in the above-mentioned predetermined range. And the amount of lubricant transferred from the surface of the resin layer 1 to the inside can be made constant. 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.

Moreover, in the laminated film 10 of the second aspect, the spectral intensity ratio A in one direction (for example, MD, which is the flow direction when forming the resin layer 1), and the other direction (for example, MD) orthogonal to this. The sum of the spectral intensity ratios B in TD, which is the vertical direction of the same plane, may be in the above range, but suppresses a significant change in the amount of lubricant present on the surface of the resin layer 1 and is cold formed. However, from the viewpoint of exhibiting stable moldability and suppressing adhesion of a lump of lubricant to the mold, it is preferably about 1.95 to 2.60, more preferably 1.95 to 2.51. More preferably, about 1.95 to 2.41, more preferably about 1.95 to 2.35, more preferably about 1.95 to 2.10, more preferably about 1.99 to 2.09, Especially preferred The range of about 2.00 to 2.07, and the like. From the same viewpoint, the spectral intensity ratio A is preferably about 0.90 to 1.17, more preferably about 0.90 to 1.15, still more preferably about 0.92 to 1.07, The range of about 0.99 to 1.05 is particularly preferable, and the spectral intensity ratio B is preferably about 0.90 to 1.66, more preferably about 0.90 to 1.51, and still more preferably. Is about 1.00 to 1.43, more preferably about 1.00 to 1.25, and particularly preferably about 1.00 to 1.10.

In addition, in the laminated film 10 of the second aspect, the spectral intensity ratio A between the crystal part and the amorphous part in one direction (for example, MD which is the flow direction when forming the resin layer 1), and the one direction The absolute value | B−A | of the difference between the spectral intensity ratio B of the crystal part and the amorphous part in the other orthogonal direction (for example, TD which is the vertical direction of the same plane as MD) is 0.00-0. It is preferable to be in the range of 70. When the absolute value | BA | of the difference between the spectral intensity ratio A and the spectral intensity ratio B is in such a range, the curl amount h of the laminated film 10 of the second aspect can be reduced. . The above spectral intensity usually shows the absolute value | BA− of the difference at orthogonal positions in MD and TD (described later) on the same plane of the resin layer. It is not limited to.

As described above, the laminated film 10 is usually produced 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 second embodiment, the absolute value | BA− 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. In this case, it is possible to easily position the mold when forming, and to efficiently perform the forming process of the laminated film of the second aspect.

In the laminated film 10 of the second aspect, the difference between the spectral intensity ratio A between the crystal part and the amorphous part in one direction and the spectral intensity ratio B between the crystal part and the amorphous part in the other direction orthogonal to the one direction. The mechanism that can reduce the curl amount h of the laminated film 10 by the absolute value | BA | being in the above range can be considered as follows. That is, in the resin layer 1, although there are a crystalline part and an amorphous part of the resin, the absolute value | BA | of the difference between the spectral intensity ratio A and the spectral intensity ratio B is small as described above (for example, , The difference between the ratio of the crystal part and the amorphous part in MD and the ratio of the crystal part and the amorphous part in TD is small), so the ratio of the crystal part in one direction and the other direction orthogonal to the one direction The distortion of the shape of the laminated film based on the difference is suppressed, and as a result, it is considered that the curl amount h of the laminated film 10 of the second aspect can be reduced.

From the viewpoint of further reducing the curl amount h of the laminated film 10 of the second embodiment, the absolute value | BA | of the difference between the spectral intensity ratio A and the spectral intensity ratio B is more preferably 0.00. About 0.66, more preferably about 0.00 to 0.51, more preferably about 0.00 to 0.43, more preferably about 0.00 to 0.33, and still more preferably 0.00 to 0. About 27, more preferably about 0.00 to 0.15, more preferably about 0.00 to 0.10, still more preferably about 0.00 to 0.08, and particularly preferably 0.00 to 0.05. A range of degrees is mentioned.

In the laminated film 10 of the present invention, the resin constituting the resin layer 1 is not particularly limited, but the resin layer 1 is preferably formed of a 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 (for example, 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, 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.

Carboxylic acid-modified polyolefin is a polymer obtained by modifying polyolefin with 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 or graft polymerization of an unsaturated carboxylic acid or acid anhydride thereof. 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, in the first embodiment, by setting the absolute value of the difference between the spectral intensity ratio A and the spectral intensity ratio B in the above range, the curl amount h of the laminated film 10 is further increased. From the viewpoint of reducing the size and further facilitating the positioning of the mold during molding, preferably polyolefin, cyclic polyolefin, and blended polymers thereof; more preferably polyethylene, polypropylene, a copolymer of ethylene and norbornene, and Among these, two or more kinds of blend polymers are listed. Also in the second aspect, 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 cold forming, these resins are preferable from the viewpoint of exhibiting stable formability and suppressing adhesion of a lump of lubricant to the mold.

As a method of setting the sum and difference of the spectral intensity ratio A and the spectral intensity ratio B in the above numerical range, for example, as the resin constituting the resin layer 1, the resin exemplified above is used, The method of setting the temperature of the chill roll cooled at the time of formation of the resin layer 1 to 10 degreeC or more and less than 50 degreeC is mentioned, for example. When the said temperature is less than 10 degreeC, the peelability of the chill roll surface and the resin layer deteriorates, and tearing 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 temperature of the chill roll for setting the sum and difference of the spectral intensity ratio A and the spectral intensity ratio B within the above numerical range is preferably about 10 to 50 ° C., more preferably about 15 to 48 ° C. Preferably, it is about 15 to 33 ° C, more preferably about 15 to 31 ° C, more preferably about 15 to 28 ° C, and particularly preferably about 25 to 28 ° C.

The resin layer 1 may be formed of only one type of resin component or may be formed of a blend polymer that is a combination of two or more types of resin components. 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 usually 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 a method for causing a lubricant to be present on the surface of the resin layer 1 include a method of coating the lubricant on the surface of the resin layer 1 and a method of blending a 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 moving a part of the lubricant from the surface to the inside. 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 several hours to 3 days to facilitate the bleeding out. 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.

Although it does not restrict | limit especially as a kind of lubricant, By setting the sum (A + B) of said spectrum intensity ratio A and spectrum intensity ratio B to said range, the amount of lubricant which exists in the resin layer 1 surface is large. From the viewpoint of suppressing changes, exhibiting stable moldability even in cold forming, and suppressing adhesion of a lump of lubricant to the mold, amide-based lubricants are preferably used.

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 palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide 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. And 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′-distearyl isophthalic acid amide and the like.

When the resin layer 1 contains a 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, further preferably 700 to 2500 ppm on a mass basis. The level is particularly preferably about 1200 to 2000 ppm. 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.

The thickness of the resin layer 1 is not particularly limited, but is preferably about 5 to 500 μm, for example, from the viewpoint of further reducing the curl amount h of the laminated film 10 and making it easier to position the mold during molding. Is about 5 to 200 μm. In addition, the thickness of the resin layer 1 can be measured from the cross section of the thickness direction of a laminated | multilayer film.

[Support 2]
As a layer which comprises the support body 2, the base material layer 21, the barrier 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 barrier 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 barrier layer 22, and the resin layer 1. FIG. When the support 2 has the base material layer 21 and the barrier layer 22, for the purpose of improving the adhesiveness between the base material layer 21 and the barrier 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 barrier 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 a copolymer of nylon 6 and nylon 66; terephthalic acid and / or isophthalic acid Nylon 6I, Nylon 6T, Nylon 6IT, Nylon 6I6T (I represents isophthalic acid, T represents terephthalic acid) and the like, and polymetaxylylene azide Polyamide containing aromatics such as Pamide (MXD6); Alicyclic polyamides such as Polyaminomethylcyclohexyl Adipamide (PACM6); and Lactam components and isocyanate components such as 4,4′-diphenylmethane-diisocyanate are copolymerized 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, the resin film forming the base layer 21 is preferably nylon or polyester, more preferably biaxially stretched nylon, biaxially stretched polyester, and particularly preferably biaxially stretched nylon.

The base material layer 21 can be laminated with resin films of different materials in order to improve the pinhole resistance of the laminated film 10. 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 lamination method, a sandwich lamination method, or a thermal lamination 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. Furthermore, the adhesive 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 curable type, an ultraviolet curable type, 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 silicone resins can be used.

The thickness of the base material layer 21 is not particularly limited, but can be, for example, about 5 to 50 μm, preferably about 10 to 30 μm.

(Barrier layer 22)
In the laminated film 10, the barrier 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 barrier layer 22 include aluminum, stainless steel, and titanium, and preferably aluminum. The barrier layer 22 can be formed of, for example, a metal foil, a metal vapor-deposited film, an inorganic oxide vapor-deposited film, a carbon-containing inorganic oxide vapor-deposited film, a film provided with these vapor-deposited films, etc. Is preferable, and it is more preferable to form with an aluminum alloy foil. From the viewpoint of preventing the generation of wrinkles and pinholes in the barrier layer 22 during the production of the laminated film, the barrier layer is made of, for example, annealed aluminum (JIS H4160: 1994 A8021H-O, JIS H4160: 1994 A8079H). -O, JIS H4000: 2014 A8021P-O, JIS H4000: 2014 A8079P-O) and the like are more preferable.

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

The barrier 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 barrier layer. As the chemical conversion treatment, for example, chromate treatment using a chromium compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromic acid acetyl acetate, chromium chloride, potassium sulfate chromium; Phosphoric acid treatment using a phosphoric acid compound such as sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid; an aminated phenol polymer having a repeating unit represented by the following general formulas (1) to (4) is used And chromate treatment.

In the 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, Examples thereof include a linear or branched alkyl group having 1 to 4 carbon atoms such as a tert-butyl group. 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 a repeating unit 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 barrier 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 barrier layer 22 by performing a baking treatment at 150 ° C. or higher is 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 processing 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, a chromate treatment, a chemical conversion treatment combining a chromium compound, a phosphate compound, and an aminated phenol polymer are preferable. Of the chromium compounds, chromic acid compounds are preferred.

The amount of the acid-resistant film formed on the surface of the barrier layer 22 in the chemical conversion treatment is not particularly limited. For example, in the case of performing the above chromate treatment, the chromium compound is chromium per 1 m ² of the surface of the barrier layer 22. About 0.5 to 50 mg in terms of conversion, preferably about 1.0 to 40 mg, about 0.5 to 50 mg, preferably about 1.0 to 40 mg in terms of phosphorus, and about 1.0 to 40 mg of aminated phenol polymer. It is desirable that it is contained in a proportion of about 200 mg, preferably about 5.0 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 barrier layer by a bar coating method, a roll coating method, a gravure coating method, a dipping method, etc., and then the temperature of the barrier layer is 70. It is carried out by heating so as to reach about 200 ° C to 200 ° C. Further, before the chemical conversion treatment is performed on the barrier layer, the barrier 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 process in this manner, it is possible to more efficiently perform the chemical conversion process on the surface of the barrier 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 barrier layer 22.

The adhesive layer A is formed of an adhesive capable of adhering the base material layer 21 and the barrier 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; amino resin such as urea resin and melamine resin; chloroprene rubber, nitrile rubber, steel Silicone resin; - down rubber such as butadiene rubber 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, extensibility, durability under high humidity conditions, anti-hypertensive action, thermal deterioration-preventing action during heat sealing, etc. are excellent, and a decrease in laminate strength between the base material layer 21 and the barrier layer 22 is suppressed. 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.

Also, 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 laminate strength between the base material layer 21 and the barrier layer 22, the adhesive component disposed on the base material layer 21 side is changed to the base material layer 21. It is preferable to select a resin excellent in adhesiveness and to select an adhesive component excellent in adhesiveness to the barrier layer 22 as an adhesive component disposed on the barrier layer 22 side. When the adhesive layer A is multilayered with different adhesive components, specifically, the adhesive component disposed on the barrier 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.

The thickness of the adhesive layer A is, for example, about 2 to 50 μm, preferably about 3 to 25 μm.

(Adhesive layer B)
In the laminated film 10, adhesion between the support 2 (for example, the base material layer 21 and the barrier 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 barrier 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 for forming the adhesive layer B include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, copolymer polyester, and other polyester resins; polyethers 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 to 40 μm, for example, and more preferably about 2 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 barrier layer 22, the laminated film 10 is obtained by the following laminating process. First, the base material layer 21 and the barrier 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. Further, as a method of laminating the base material layer 21 and the barrier layer 22, a method of extruding and forming a resin that forms the base material layer 21 on the surface of the barrier layer 22, or a metal on one surface of the base material layer 21. A method of forming the barrier layer 22 by vapor-depositing the material is also included. Next, the resin layer 1 is laminated on the barrier 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 barrier layer 22 and the resin layer 1, if necessary, an adhesive component for forming the adhesive layer B is applied on the barrier layer 22, dried, and then from above 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 adhesion 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 enhance the adhesion 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 peak temperature of the resin layer 1. The temperature at this time is preferably the melting peak temperature of the resin layer 1 + 5 ° C. or higher and the melting peak temperature + 100 ° C. or lower, more preferably the melting peak temperature + 10 ° C. or higher and the melting peak temperature + 80 ° C. or lower. In the present invention, the melting peak temperature of the resin layer 1 refers to the endothermic peak temperature in the differential scanning calorimetry of the resin component constituting the resin layer 1. The heating in the aging treatment and the heating above the melting peak temperature of the resin layer 1 can be performed by, for example, a hot roll contact method, a hot air method, a near or far infrared method, and the like.

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.

Use of Laminate Film As described above, the laminate film 10 of the present invention is usually produced as a strip-like laminate 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 cold forming, in particular, having a forming depth of 0.5 mm or more, and 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 to 16 and Comparative Example 1>
[Manufacture of laminated film]
On the base material layer 21 having the configuration described later, a barrier layer 22 made of an aluminum foil (thickness: 40 μm) subjected to chemical conversion treatment on both surfaces was laminated by a dry laminating method. Specifically, a two-component urethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of the aluminum foil, and an adhesive layer A (thickness 4 μm) was formed on the barrier layer 22. Next, after the adhesive layer A and the base material layer 21 on the barrier layer 22 are pressure-heated and bonded, an aging treatment is performed to support the base material layer 21 / adhesive layer A / barrier layer 22 laminated in order. Got the body. In addition, the chemical conversion treatment of the aluminum foil used as the barrier 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 mass). The coating was performed on both surfaces of the aluminum foil and baked.

The structure of the base material layer 21 used in Examples and Comparative Examples is as follows.
Examples 1 and 2: A laminate of PET film (12 μm) / adhesive layer (3 μm) / nylon film (15 μm) (nylon is on the barrier layer side)
Example 3: PET (5 μm) / nylon (20 μm) two-layer coextruded film (nylon is on the barrier layer side)
Example 4: Three-layer coextruded film of PET (5 μm) / thermoplastic polyester elastomer (1 μm) / nylon (20 μm) (nylon is on the barrier layer side)
Examples 5 and 6: PET film (12 μm) monolayer Examples 7 to 16 and Comparative Example 1: Nylon film (25 μm) monolayer “PET” means “polyethylene terephthalate”.

Next, in Examples 1 to 11 and Comparative Example 1, a resin A (carboxylic acid-modified polypropylene, melting peak temperature 160 ° C.) and a resin B (fatty acid amide-based lubricant) that form the resin layer 1 on the barrier layer 22 side of the support. The resin layer 1 (thickness 25 μm / 25 μm, resin B is the innermost layer side) was laminated on the barrier layer 22 by coextrusion of polypropylene containing, melting peak temperature 140 ° C.) in the molten state (250 ° C.). Thus, the laminated films of Examples 1 to 11 and Comparative Example 1 in which the base layer 21 / adhesive layer A / barrier layer 22 / resin layer 1 were laminated in order were 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.

In Examples 12 and 13, a two-component urethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to the barrier layer 22 side to form an adhesive layer B (thickness 4 μm). Next, unstretched polypropylene film (3-layer extruded product, propylene-ethylene random copolymer (resin B, 4 μm) containing fatty acid amide-based lubricant / propylene-ethylene block copolymer (22 μm) / propylene-ethylene random copolymer (4 μm), resin B Are bonded together to form a resin layer 1. Thus, laminated films of Examples 12 and 13 in which the base material layer 21 / adhesive layer A / barrier layer 22 / adhesive layer B / resin layer 1 were laminated in order were obtained.

In Example 14, a resin composed of acid-modified polypropylene as a main agent and methylene diisocyanate as a curing agent was applied to the barrier layer 22 side to form a resin layer B (thickness 1 μm). In Example 15, a resin composed of acid-modified polypropylene as a main agent and methylene diisocyanate as a curing agent was applied to the barrier layer 22 side to form a resin layer B (thickness 3 μm). In Example 16, a resin composed of an acid-modified polypropylene as a main component and an epoxy resin (weight average molecular weight 500) as a curing agent was applied to the barrier layer 22 side to form a resin layer B (thickness 1 μm). Next, in Examples 14 to 16, unstretched polypropylene film (3-layer extruded product, propylene-ethylene random copolymer (resin B, 4 μm) containing fatty acid amide-based lubricant / propylene-ethylene block copolymer (22 μm) / propylene- An ethylene random copolymer (4 μm) and the resin B is the innermost layer side) were bonded together to form a resin layer 1. Thus, laminated films of Examples 14, 15, and 16 in which the base layer 21 / adhesive layer A / barrier layer 22 / adhesive layer B / resin layer 1 were laminated in order were obtained. In Examples and Comparative Examples, the amount of the fatty acid amide lubricant contained in the resin B is as shown in Tables 1 and 2.

<Measurement of spectral intensities A and B by Raman spectroscopy>
About the resin layer of the laminated film obtained above, the spectral intensity ratio A in one direction (MD) and the spectral intensity ratio B in the other direction (TD) orthogonal to the one direction are respectively measured using Raman spectroscopy. The measurement was performed using the following measuring equipment, measurement conditions, and analysis conditions. The results are shown in Tables 1 and 2.
Measuring instrument: LabRAM HR-800 manufactured by HORIBA JOBIN YVON
In the measurement of the spectral intensity A in the MD, a Raman spectrum is measured so that the MD and the incident laser polarization plane are parallel, and in the measurement of the spectral intensity B in the TD, the TD and the incident laser polarization plane are parallel. Raman spectrum was measured.
Measurement conditions: excitation laser wavelength 633 nm, exposure time 15 seconds, objective lens 50 times, number of integrations 8 times, confocal hole diameter φ0.1 mm, grating 800 L / mm
Analysis conditions:
(1) The average value of the scattering intensity at a Raman shift of 600 to 700 cm −1 is taken as the baseline value.
(2) The peak value at 809 cm−1 is obtained by subtracting the baseline value from the maximum value of the scattering intensity in the range of Raman shift 809 ± 2 cm−1.
(3) The peak value at 842 cm−1 is obtained by subtracting the baseline value from the maximum value of the scattering intensity in the range of Raman shift 842 ± 2 cm−1.
(4) The spectral intensity ratios A and B are calculated using the peak intensities in (2) and (3) above. As described above, when polypropylene is used as the resin for forming the resin layer 1, the peak of the crystal part of the resin is observed in the vicinity of 809 cm-1 in the spectrum measurement by Raman spectroscopy, and the peak of the amorphous part is 842 cm. Observed around -1. As described above, since the peak of the spectrum is usually observed at different positions between the crystal part and the amorphous part of the resin, the crystal part and the amorphous part in one direction (MD) and the other direction (TD) orthogonal thereto are observed. The spectral intensity ratio A and the spectral intensity ratio B can be calculated from the obtained values.

<Measurement of curl amount h>
Using the laminated film obtained above, each diagonal of the laminated film is set at the center of the laminated film having a length of 90 mm in one direction (MD) and a length of 150 mm in the other direction (TD) perpendicular to the one direction. Two cuts (cuts that penetrate the laminated film) having a length of 100 mm are provided from the support side so as to penetrate the laminated film in the thickness direction of the laminated film. The substrate was placed on a horizontal surface with the support on the lower side and allowed to stand at 20 ° C. for 8 hours. Next, as shown in FIG. 2, in the direction perpendicular to the horizontal plane, the distance between the apex (center P) of the four surfaces raised by the curl and the horizontal plane 30 is measured using a height gauge (made by Mitutoyo Corporation). The largest value was taken as the maximum distance h. 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, then cut, and a strip of 120 mm × 80 mm was produced as a test sample. Next, a straight mold composed of a 30 mm × 50 mm rectangular male mold and a female mold with a clearance of 0.5 mm between the male mold is used, and on the female mold so that the resin layer 1 side is located 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.
A: No adhesion of lubricant to the mold after 5000 moldings B: Adhesion of lubricant to the mold was confirmed after 5000 moldings, but there was no effect on the molding state C: Lubricant adhered to the molds after 5000 moldings Causes indentations in molded samples

As shown in Table 1, the absolute value of the difference between the spectral intensity ratio A in one direction (MD) in the resin layer and the spectral intensity ratio B in the other direction (TD) orthogonal to the one direction | BA In the laminated films of Examples 1 to 8 and 12 to 16 in which | is 0.01 to 0.66, the curl amount h can be suppressed to about 30 mm or less. It was easy to perform positioning. In addition, in the laminated films of Examples 1 to 8 and 12 to 16 in which the sum (A + B) of the spectrum intensity ratio A and the spectrum intensity ratio B is in the range of 2.06 to 2.66, the result of the lubricant deposition evaluation Was good. In contrast, the absolute value | BA− of the difference between the spectral intensity ratio A in one direction in the resin layer and the spectral intensity ratio B in the other direction orthogonal to the one direction is a large comparison of 0.73. In the laminated film of Example 1, the curl amount h was 37 mm, and it was difficult to position the mold. Moreover, in the laminated | multilayer film of the comparative example 1 whose sum (A + B) of the spectral intensity ratio A and the spectral intensity ratio B is 2.77, the result of lubricant precipitation evaluation was inferior.

<Lubricant precipitation evaluation 2>
After storing the laminated films of Examples 1, 2, 6, 7, 9 to 16 and Comparative Example 1 obtained above at the respective storage temperatures shown in Table 2 (5 ° C., 20 ° C., 40 ° C.) for 1 week. Cut into 120 mm × 80 mm strips to prepare test samples. Next, a straight mold composed of a 30 mm × 50 mm rectangular male mold and a female mold with a clearance of 0.5 mm between the male mold is used, and on the female mold so that the resin layer 1 side is located 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.
A: No adhesion of lubricant to the mold after 5000 moldings B: Adhesion of lubricant to the mold was confirmed after 5000 moldings, but there was no effect on the molding state C: Lubricant adhered 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.
A: No pinhole generation B: Pinhole generation rate 10% or less C: Pinhole generation rate 11% or more

As shown in Table 2, the absolute value of the difference between the spectral intensity ratio A in one direction (MD) in the resin layer and the spectral intensity ratio B in the other direction (TD) orthogonal to the one direction | BA In the laminated films of Examples 1, 2, 6, 7, and 9 to 16 in which | is 0.05 to 0.66, curling can be suppressed. It was easy to do. In the laminated films of Examples 1, 2, 6, 7, and 9 to 16, the sum of the spectral intensity ratio A and the spectral intensity ratio B (A + B) is in the range of 1.99 to 2.66. The result of precipitation evaluation was good and the moldability was also excellent. In contrast, the absolute value | BA− of the difference between the spectral intensity ratio A in one direction in the resin layer and the spectral intensity ratio B in the other direction orthogonal to the one direction is a large comparison of 0.73. In the laminated film of Example 1, the curl was large and it was difficult to position the mold. Moreover, in the laminated | multilayer film of the comparative example 1 whose sum (A + B) of the spectral intensity ratio A and the spectral intensity ratio B is 2.77, the result of lubricant precipitation evaluation was inferior.

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

Claims

At least a laminated film composed of a laminate of a support and a resin layer formed of a resin,
The spectral intensity ratio A obtained by dividing the spectral intensity of the crystal part of the resin measured by Raman spectroscopy in one direction on the plane of the resin layer by the spectral intensity of the amorphous part, and the one direction of the resin layer The absolute value of the difference from the spectral intensity ratio B obtained by dividing the spectral intensity of the crystalline part of the resin by the spectral intensity of the amorphous part measured by Raman spectroscopy in the other direction on the same plane perpendicular to | B-A | is a laminated film having a range of 0.00 to 0.70.
At least a laminated film composed of a laminate of a support and a resin layer formed of a resin,
The spectral intensity ratio A obtained by dividing the spectral intensity of the crystal part of the resin measured by Raman spectroscopy in one direction on the plane of the resin layer by the spectral intensity of the amorphous part, and the one direction of the resin layer And the spectral intensity ratio B obtained by dividing the spectral intensity of the crystal part of the resin measured by Raman spectroscopy in the other direction on the same plane orthogonal to the spectral intensity of the amorphous part is 1. A laminated film in the range of 95 to 2.66.
The laminated film according to claim 2, wherein the resin layer contains a lubricant.
The laminated film according to claim 2 or 3, wherein the absolute value | BA of the difference between the spectral intensity ratio A and the spectral intensity ratio B is in the range of 0.00 to 0.70.
The laminated film having a length of 90 mm in one direction and a length of 150 mm in the other direction is prepared, and in the center of the laminated film, on the two lines connecting the diagonals of the laminated film, the thickness direction of the laminated film Two cuts with a length of 100 mm with the center being the center are made from the side of the support and placed on a horizontal surface so that the support is on the bottom, and at 8 ° C. The maximum distance h is 30 mm or less when the maximum distance h between the horizontal plane and the center is measured in a direction perpendicular to the horizontal plane after standing for a period of time. The laminated film as described.
The laminated film according to any one of claims 1 to 5, wherein the resin layer is made of polyolefin.
The laminated film according to any one of claims 1 to 6, wherein the sum (A + B) of the spectral intensity ratio A and the spectral intensity ratio B is in the range of 1.95 or more and 2.66 or less.
The laminated film according to any one of claims 1 to 7, wherein the support has a barrier layer.
The support has a base material layer and a barrier layer,
The laminated film according to any one of claims 1 to 7, wherein the resin layer is laminated on a side of the barrier layer opposite to the base material layer.
The laminate film according to claim 9, wherein the base material layer has a multilayer structure composed of a laminate of a polyester film and a nylon film.
The said base material layer is a laminated | multilayer film of Claim 10 comprised by the polyester film.
The laminated film according to claim 10, wherein the base material layer is made of a nylon film.
The laminated film according to any one of claims 1 to 12, which is used as a packaging material.
The laminated film according to any one of claims 1 to 13, which is a laminated film subjected to cold forming.