CN108472923B

CN108472923B - Laminated film

Info

Publication number: CN108472923B
Application number: CN201780007282.XA
Authority: CN
Inventors: 早川阳祐; 小尻哲也; 山下孝典; 山下力也; 宫崎薰
Original assignee: Dai Nippon Printing Co Ltd
Current assignee: Dai Nippon Printing Co Ltd
Priority date: 2016-01-19
Filing date: 2017-01-19
Publication date: 2020-12-18
Anticipated expiration: 2037-01-19
Also published as: CN111497380A; CN111497380B; CN108472923A; WO2017126636A1

Abstract

The invention provides a laminated film which is restrained from curling and easy to position a die during molding. The laminated film is composed of a laminate of at least a support and a resin layer formed from a resin, wherein an absolute value | B-A | of a difference between a spectral intensity ratio A, which is a spectral intensity ratio obtained by dividing a spectral intensity of a crystalline portion of the resin measured in one direction of the resin layer by a spectral intensity of an amorphous portion, and a spectral intensity ratio B, which is a spectral intensity ratio obtained by dividing a spectral intensity of a crystalline portion of the resin measured in the other direction orthogonal to the one direction of the resin layer by a spectral intensity of an amorphous portion, is in a range of 0.00 to 0.70.

Description

Laminated film

Technical Field

The present invention relates to a laminated film.

Background

Conventionally, a laminate film in which a resin layer is laminated on a support such as a base layer or a barrier layer has been widely used in various fields such as packaging materials (patent document 1). Among laminated films used as packaging materials, there are films that are provided in cold molding for forming a space for storing contents, such as a battery packaging material.

Laminated films for cold forming are generally produced into a tape-shaped laminated film, and are used for various applications by being cut into an appropriate size. In the cut laminated film, a phenomenon called curl of the laminated film may occur. If the laminated film is largely curled, positioning of a mold becomes difficult when the laminated film is molded, and there is a problem that the required precision and yield cannot be obtained by molding. Further, there is a problem that the efficiency of the molding process of the laminated film is lowered.

Further, in the laminated film to be cold-formed, since the laminated film is stretched at the time of cold forming, there is a problem that cracks and pinholes are likely to occur in the flange portion of the mold. To solve such a problem, there are known: a method of improving the sliding property of the surface of the resin layer by applying a lubricant to the surface of the resin layer of the laminate film, blending a lubricant into the resin forming the resin layer, and allowing the lubricant to bleed out onto the surface of the resin layer before molding. By adopting such a method, the laminated film is easily drawn into a mold during cold forming, 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, the lubricant adheres to the mold and agglomerates to contaminate the mold. When molding another laminated film in a state where the mold is contaminated, a lubricant lump adhering to the mold adheres to the surface of the laminated film. If a slip agent lump adheres to the surface of the laminate film, there is a problem that sealing failure is likely to occur due to uneven melting of the portion to which the slip agent adheres in the case of forming a packaging material by thermally fusing the resin layers of 2 laminate films to each other after molding. In addition, the lubricant cake adhered to the mold needs to be cleaned to remove the lubricant cake, and thus the efficiency of the molding process is reduced.

On the other hand, if the amount of the lubricant present on the surface of the resin layer is too small during molding, the lubricity of the laminated film is lowered, and thus there is a problem that the moldability of the laminated film is lowered.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2008-287971

Disclosure of Invention

Technical problem to be solved by the invention

Under such circumstances, a main object of the invention according to a first aspect of the present invention is to provide a laminated film in which curling is suppressed and positioning of a mold at the time of molding is easy.

As described above, a lubricant may be mixed into the resin layer of the laminated film for cold forming or a lubricant may be applied to the surface of the resin layer. However, although the lubricant applied to the surface of the resin layer and the lubricant blended in the resin layer are set to predetermined amounts, the lubricant may adhere to the mold and cracks or pinholes may be generated in the laminated film during the molding of the laminated film. Specifically, in both the case where the lubricant is blended in the resin layer and the case where the lubricant is applied, the amount of the lubricant on the surface of the resin layer greatly changes due to a storage environment or the like provided until molding after the production of the laminated film, and the lubricant may adhere to a mold during molding, thereby deteriorating moldability. For example, when the laminate film is stored at a high temperature, the lubricant easily enters the inside of the resin layer, and 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 of room temperature or lower, the saturated solubility of the lubricant in the resin layer is lowered, the amount of the lubricant on the surface of the resin layer is increased, and the mold is easily contaminated.

Under such circumstances, a main object of the invention according to a second aspect of the present invention is to provide a laminated film which can exhibit stable moldability by suppressing a large change in the amount of a lubricant present on the surface of a resin layer, and which can effectively suppress adhesion of a lubricant cake to a mold.

Technical solution for solving technical problem

The present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, it has been found that a multilayer film comprising at least a laminate of a support and a resin layer formed from a resin, wherein the absolute value | B-a | of the difference between a spectral intensity ratio a, which is a spectral intensity ratio obtained by dividing the spectral intensity of a crystalline portion of the resin measured in one direction of the plane of the resin layer by the spectral intensity of an amorphous portion, and a spectral intensity ratio B, which is a spectral intensity ratio obtained by dividing the spectral intensity of a crystalline portion of the resin measured in another direction of the same plane of the resin layer orthogonal to the one direction by the spectral intensity of an amorphous portion, is suppressed in curling and positioning of a mold at the time of molding is facilitated.

That is, the invention according to the first aspect of the present invention provides the inventions of the following embodiments.

The laminated film according to item 1a is a laminated film including at least a support and a resin layer formed of a resin, wherein an absolute value | B-a | of a difference between a spectral intensity ratio a, which is a spectral intensity ratio obtained by dividing a spectral intensity of a crystalline portion of the resin measured in one direction of a plane of the resin layer by a spectral intensity of an amorphous portion, and a spectral intensity ratio B, which is a spectral intensity ratio obtained by dividing a spectral intensity of a crystalline portion of the resin measured in another direction of the same plane of the resin layer orthogonal to the one direction by a spectral intensity of an amorphous portion, is in a range of 0.00 to 0.70.

The laminated film according to item 2a to item 1A, wherein the laminated film having a length in the one direction of 90mm and a length in the other direction of 150mm is prepared, 2 slits having a length of 100mm and centered on the center are cut into the laminated film from the support body side on 2 lines connecting each pair of corners of the laminated film so as to penetrate the thickness direction of the laminated film, the laminated film is placed on a horizontal plane with the support body as the lower side, and after standing at 20 ℃ for 8 hours, the maximum distance h between the horizontal plane and the center is measured in a direction perpendicular to the horizontal plane, and the maximum distance h is 30mm or less.

The laminate film according to item 3a or item 1A or 2A, wherein the resin layer is made of polyolefin.

The laminated film according to any one of items 1A to 3A, wherein a sum (a + B) of the spectral intensity ratio a and the spectral intensity ratio B is in a range of 1.95 to 2.66.

The laminated film according to any one of items 1A to 4A, wherein the support has a barrier layer.

The laminated film according to any one of items 1A to 4A, wherein the support has a base material layer and a barrier layer,

the resin layer is laminated on the side of the barrier layer opposite to the base layer.

The laminated film according to item 7a or 6A, wherein the base layer has a multilayer structure comprising a laminate of a polyester film and a nylon film.

The laminated film according to item 8a or 6A, wherein the base layer is formed of a polyester film.

The laminated film according to item 9a or 6A, wherein the base layer is a nylon film.

The laminate film according to any one of items 10a and 1A to 9A, which is used as a packaging material.

The laminated film according to any one of items 1A to 10A, which is provided for cold forming.

Further, the present inventors have found that a laminate film in which a large change in the amount of a slip agent present on the surface of a resin layer is suppressed, thereby, stable moldability can be exhibited even in cold molding (molding depth of 4.0mm or more), and the laminated film is composed of a laminate of at least a support and a resin layer formed of a resin, wherein the sum of the spectral intensity ratio A and the spectral intensity ratio B is in the range of 1.95 to 2.66, the spectral intensity ratio A is a spectral intensity ratio obtained by dividing the spectral intensity of the crystalline portion of the resin measured in one direction of the plane of the resin layer by the spectral intensity of the amorphous portion by Raman spectroscopy, the spectral intensity ratio B is a spectral intensity ratio obtained by dividing the spectral intensity of the crystalline portion of the resin by the spectral intensity of the amorphous portion, which is measured by raman spectroscopy in another direction on the same plane orthogonal to the one direction of the resin layer.

That is, the invention according to the second aspect of the present invention provides the inventions of the following embodiments.

The laminated film according to item 1B is a laminated film including at least a support and a resin layer formed of a resin, wherein a sum of a spectral intensity ratio a, which is a spectral intensity ratio obtained by dividing a spectral intensity of a crystalline portion of the resin measured by raman spectroscopy in one direction of a plane of the resin layer by a spectral intensity of an amorphous portion, and a spectral intensity ratio B, which is a spectral intensity ratio obtained by dividing a spectral intensity of a crystalline portion of the resin measured by raman spectroscopy in another direction of the same plane of the resin layer orthogonal to the one direction by a spectral intensity of an amorphous portion, is in a range of 1.95 or more and 2.66 or less.

The laminate film according to item 2B or 1B, wherein the resin layer contains a slip agent.

The laminated film according to item 3B, item 1B or item 2B, 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 0.70.

The laminated film according to any one of claims 1B to 3B, wherein the laminated film having a length in one direction of 90mm and a length in the other direction of 150mm is prepared, 2 slits having a length of 100mm and centered on the center are cut from the support body side at the center of the laminated film so as to penetrate the thickness direction of the laminated film on 2 lines connecting each pair of corners of the laminated film, the laminated film is placed on a horizontal plane with the support body as the lower side, and after standing at 20 ℃ for 8 hours, the maximum distance h between the horizontal plane and the center is 30mm or less when measured in the vertical direction to the horizontal plane.

The laminate film according to any one of claims 1B to 4B, wherein the resin layer is made of polyolefin.

The laminated film according to any one of items 1B to 5B, wherein the support has a barrier layer.

The laminated film according to any one of items 7B and 1B to 5B, wherein the support has a base material layer and a barrier layer,

The laminated film according to item 8B or 7B, wherein the base layer has a multilayer structure of a laminate of a polyester film and a nylon film.

The laminated film according to item 9B or 7B, wherein the base layer is formed of a polyester film.

The laminated film according to item 10B or 7B, wherein the base layer is a nylon film.

The laminate film according to any one of items 11B and 1B to 10B, which is used as a packaging material.

The laminated film according to any one of items 1B to 11B, which is a laminated film for cold forming.

Effects of the invention

In the laminated film according to the first aspect of the present invention, the absolute value | B-a | of the difference between the spectral intensity ratio a, which is a spectral intensity ratio obtained by dividing the spectral intensity of the crystalline portion of the resin measured in one direction of the plane of the resin layer by the spectral intensity of the amorphous portion by raman spectroscopy, and the spectral intensity ratio B, which is a spectral intensity ratio obtained by dividing the spectral intensity of the crystalline portion of the resin measured in the other direction of the same plane of the resin layer orthogonal to the one direction by the spectral intensity of the amorphous portion by raman spectroscopy, is in the range of 0.00 to 0.70, thereby suppressing curling of the laminated film and facilitating positioning of the mold during molding. Therefore, the laminated film can be molded with required accuracy, and the yield can be improved. In addition, the efficiency of the molding process of the laminated film can be improved.

In addition, the multilayer film according to the second aspect of the present invention can suppress a large change in the amount of lubricant present on the surface of the resin layer, and can exhibit stable moldability even at the time of cold press molding (for example, molding depth of 4.0mm or more) because the sum of the spectral intensity ratio a of the spectral intensity of the crystalline portion of the resin measured in one direction of the plane of the resin layer by raman spectroscopy divided by the spectral intensity of the amorphous portion and the spectral intensity ratio B of the spectral intensity of the crystalline portion of the resin measured in another direction on the same plane of the resin layer orthogonal to the one direction divided by the spectral intensity of the amorphous portion is 1.95 or more and 2.66 or less.

Drawings

Fig. 1 is a schematic cross-sectional view showing a laminated structure of the laminated film of the present invention.

Fig. 2 is a schematic view for explaining the amount of curling of the laminated film of the present invention.

Fig. 3 is a schematic diagram showing a spectrum when the spectral intensity ratio (crystalline portion/amorphous portion) of the crystalline portion and the amorphous portion of the resin is measured by raman spectroscopy for a resin layer formed of polypropylene.

Detailed Description

A laminated film according to a first aspect of the present invention is a laminated film including at least a support and a resin layer formed of a resin, the laminated film including: an absolute value | B-A | of a difference between a spectral intensity ratio A, which is a spectral intensity ratio obtained by dividing a spectral intensity of a crystal portion of the resin measured in one direction of the plane of the resin layer by a spectral intensity of an amorphous portion, and a spectral intensity ratio B, which is a spectral intensity ratio obtained by dividing a spectral intensity of a crystal portion of the resin measured in another direction of the same plane of the resin layer orthogonal to the one direction by a spectral intensity of an amorphous portion, is in a range of 0.00 to 0.70. The spectral intensity is usually the maximum absolute value | B-a | of the difference between the orthogonal positions of MD and TD (described later) on the same plane of the resin layer, but is not limited to the positional relationship.

A laminated film according to a second aspect of the present invention is a laminated film comprising at least a support and a resin layer formed of a resin, the laminated film comprising: the sum of a spectral intensity ratio A obtained by dividing the spectral intensity of the crystalline portion of the resin by the spectral intensity of the amorphous portion measured by Raman spectroscopy in one Direction of the plane of the resin layer (for example, MD: Machine Direction, which is the flow Direction when the resin layer is formed) and a spectral intensity ratio B obtained by dividing the spectral intensity of the crystalline portion of the resin measured by Raman spectroscopy in the other Direction (for example, TD: Transverse Direction) of the same plane of the resin layer, which is orthogonal to the one Direction, by the spectral intensity ratio of the amorphous portion is in a range of 1.95 to 2.66.

The laminated film of the present invention will be described in detail below. In the present specification, the description will be given of which embodiment is the case for the different matters in the laminated film of the first embodiment and the laminated film of the second embodiment, and the matters common to the laminated film of the first embodiment and the laminated film of the second embodiment will be the description of the laminated film of the present invention. In the drawings, reference numerals are used in common for the first and second embodiments. For example, in the following description, the substrate layer 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 embodiment and the laminated film of the second embodiment.

In the claimed range and specification, "-" is used as the expression of the numerical range, and a numerical range such as "the value X is A1 to A2" means "A1. ltoreq. X. ltoreq.A 2". In the MD and TD of the laminated film, for example, when the 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 the 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

For example, as shown in fig. 1, the laminated film of the present invention (first and second embodiments) is formed by laminating a support 2 and a resin layer 1. The resin layer 1 may be formed of only one layer or may be formed of a plurality of layers.

Examples of the layer constituting the support 2 include a base layer 21 and a barrier layer 22. The support body 2 may be formed of only one layer or may be formed of a plurality of layers. When the support 2 has the base layer 21 and the barrier layer 22, the multilayer film of the present invention preferably includes the base layer 21, the barrier layer 22, and the resin layer 1 stacked in this order as shown in fig. 1. When the support 2 includes the base material layer 21 and the barrier layer 22, an adhesive layer a (not shown) may be provided between these layers as necessary for the purpose of improving the adhesiveness between the base material layer 21 and the barrier layer 22, and the like. For the purpose of improving the adhesion between the support 2 and the resin layer 1, an adhesive layer B (not shown) may be provided between these layers (for example, between the base layer 21 and the resin layer 1, between the barrier layer 22 and the resin layer 1, and the like) as needed.

Constitution of each layer of laminated film

[ resin layer 1]

In the laminated film 10, the resin layer 1 is formed of a resin and is laminated on the support 2. As 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 constituting the innermost layer of the packaging material when the contents are sealed with the packaging material. When the contents are sealed, the surfaces of the thermally fusible resin layers 1 are brought into contact with each other, and the contacted portions are thermally fused, whereby the contents can be sealed.

As described above, the laminated film is generally produced as a tape-shaped laminate, and is used for various applications as described later by being cut into an appropriate size. In the cut laminated film 10, a phenomenon called curling may occur in which the laminated film is bent. If the laminated film is largely curled, positioning of a mold becomes difficult when the laminated film is molded, and there is a problem that the required precision cannot be obtained and the yield is lowered. Further, there is a problem that the efficiency of the molding process of the laminated film is lowered.

In contrast, in the laminated film 10 of the first embodiment, an absolute value | B-a | of a difference between a spectral intensity ratio a (crystalline portion/amorphous portion) of a crystalline portion and an amorphous portion of the resin measured by raman spectroscopy in one direction of the resin layer 1 (for example, a flow direction MD when the resin layer 1 is formed) and a spectral intensity ratio B (crystalline portion/amorphous portion) of the resin measured by raman spectroscopy in another direction orthogonal to the one direction of the resin layer 1 (for example, a direction TD perpendicular to the MD on the same plane) is in a range of 0.00 to 0.70. In the laminated film 10 of the first embodiment, when 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, curling of the laminated film is suppressed, and positioning of the mold at the time of molding becomes easy. Details of this mechanism are considered as follows. That is, it is considered that, although the resin layer 1 has the crystalline portion and the amorphous portion of the resin, 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 (for example, the difference between the ratio of the crystalline portion to the amorphous portion in MD and the ratio of the crystalline portion to the amorphous portion in TD is small), and therefore, the shape deformation of the laminated film due to the difference in the ratio of the crystalline portion in one direction and the ratio of the crystalline portion in the other direction orthogonal to the one direction is suppressed, and as a result, the amount of curling 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 bending of the laminated film 10. For measuring the curl amount h, as shown in the schematic view of fig. 2, a laminated film 10 having a length of 90mm in one direction and a length of 150mm in the other direction orthogonal to the one direction was prepared. Next, 2 slits (penetrating the laminated film) having a length of 100mm and centered on the center P of the laminated film 10 were cut from the support side so as to penetrate the laminated film in the thickness direction thereof on 2 lines connecting the respective corners of the laminated film 10. Next, the slit-cut laminate film was placed on a horizontal surface 30 with the support on the lower side, and allowed to stand at 20 ℃ for 8 hours. Next, the distance from the top surface (center P) of 4 surfaces standing up due to curling to the horizontal surface 30 in the direction perpendicular to the horizontal surface 30 of the laminated film was measured, and the maximum value thereof was defined as the maximum distance h and this was defined as the curl amount h. The curl amount h can be measured using a height gauge manufactured by MITUTOYO corporation, or the like.

From the viewpoint of reducing the curl amount h of the laminated film 10 of the first embodiment and facilitating the positioning of the mold during molding, the absolute value | B-a | of the difference between the spectral intensity ratio a and the spectral intensity ratio B is preferably about 0.00 to 0.66, more preferably about 0.00 to 0.51, even more preferably about 0.00 to 0.43, even more preferably about 0.00 to 0.33, even more preferably about 0.00 to 0.27, even more preferably about 0.00 to 0.15, even more preferably about 0.00 to 0.10, even more preferably about 0.00 to 0.08, and 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, further preferably about 0.92 to 1.07, and particularly preferably about 0.99 to 1.05, and the spectral intensity ratio B is preferably about 0.90 to 1.66, more preferably about 0.90 to 1.51, further preferably about 1.00 to 1.43, further 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 30mm or less, more preferably about 29mm or less, further preferably about 28mm or less, further preferably about 27mm or less, further preferably about 25mm or less, further preferably about 20mm or less, further preferably about 10mm or less, and further preferably about 5mm or less. Further, a preferable 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, the direction TD perpendicular to the MD in the same plane) and the spectral intensity ratio B in the other direction (for example, the direction TD perpendicular to the MD in the same plane) orthogonal to the one direction are values measured under the following measurement conditions and analysis conditions using a microscope laser raman spectroscopy apparatus (for example, LabRAM HR-800 manufactured by HORIBA JOBIN YVON corporation).

In the measurement of the spectral intensity a in the MD, the raman spectrum is measured so that the MD is parallel to the incident laser polarization plane, and in the measurement of the spectral intensity B in the TD, the raman spectrum is measured so that the TD is parallel to the incident laser polarization plane.

The measurement conditions were as follows: laser wavelength for excitation of 633nm, exposure time of 15 s, 50 times of objective lens, cumulative frequency of 8 times, aperture of confocal point

The grating is 800L/mm.

Analysis conditions were as follows:

(1) shifting by Raman frequency 600-700 cm^－1The average value of the scattering intensities of (a) is taken as a baseline value.

(2) Frequency shift from Raman 809 + -2 cm^－1The maximum value of the scattering intensity in the range of (1) was subtracted from the above baseline value to obtain the value at 809cm^－1Peak intensity of (a).

(3) From Raman frequency shift 842 + -2 cm^－1The maximum value of the scattering intensity in the range of (3) is subtracted from the above-mentioned baseline value to obtain the value at 842cm^－1Peak intensity of (a).

(4) The spectral intensity ratio A, B was calculated using the peak intensities of (2) and (3) above.

For example, when polypropylene is used as the resin forming the resin layer 1 as described later, the raman shift at 809cm is measured in the spectrum measurement by raman spectroscopy as shown in the schematic diagram of fig. 3^－1The peak of the crystal part of the resin was observed in the vicinity of the peak, and the Raman shift was 842cm^－1A peak in an amorphous part was observed in the vicinity. Since peaks of spectral lines are observed at different positions in the crystalline portion and the amorphous portion of the resin, the peak intensities of the crystalline portion and the amorphous portion in one direction (for example, MD) and the other direction (for example, TD) orthogonal thereto are measured, and the spectral intensity ratio a and the spectral intensity ratio B can be calculated from the obtained values.

In the multilayer film 10 of the first aspect, the sum (a + B) of the spectral intensity ratio a of the crystalline portion to the amorphous portion in one direction (for example, the flow direction MD when the resin layer 1 is formed) and the spectral intensity ratio B of the crystalline portion to the amorphous portion in another direction orthogonal to the one direction (for example, the direction TD perpendicular to the same plane as the MD) is preferably in the range of 1.95 to 2.66. In the multilayer film 10, when the sum of the spectral intensity ratio a and the spectral intensity ratio B falls within such a range, a large change in the amount of the lubricant present on the surface of the resin layer 1 is suppressed, and thus stable moldability is exhibited and adhesion of lubricant lumps to a mold can be effectively suppressed. Details of the mechanism are as follows. That is, in the resin layer 1, there are a crystalline portion and an amorphous portion of the resin, but when the lubricant is contained in the resin layer 1, the lubricant is present in the amorphous portion of the resin. Therefore, when the total ratio of the amorphous portion to the crystalline portion of the resin in the one direction and the other direction is within the above-described fixed range, the amount of the lubricant oozing out from the inside of the resin layer 1 to the surface and the amount of the lubricant moving from the surface of the resin layer 1 to the inside can be fixed due to a temperature change or the like. As a result, it is considered that a large change in the amount of the lubricant present on the surface of the resin layer 1 is suppressed, and the laminated film 10 of the first embodiment can exhibit stable moldability and effectively suppress adhesion of the lubricant cake to the mold.

In the laminated film 10 of the first embodiment, the sum of the spectral intensity ratio a in one direction (for example, the flow direction MD in forming the resin layer 1) and the spectral intensity ratio B in the other direction (for example, the direction TD perpendicular to the same plane as the MD) orthogonal thereto may be within the above range, and from the viewpoint of suppressing a large change in the amount of the lubricant present on the surface of the resin layer 1, exhibiting stable moldability even in cold molding, and suppressing adhesion of the lubricant cake to the mold, there may be mentioned a range of preferably about 1.95 to 2.66, more preferably about 1.95 to 2.60, still more preferably about 1.95 to 2.51, still more preferably about 1.95 to 2.41, still more preferably about 1.95 to 2.35, still more preferably about 1.95 to 2.10, still more preferably about 1.99 to 2.09, and particularly preferably about 2.00 to 2.07.

In the laminated film 10 of the second embodiment, the sum (a + B) of the spectral intensity ratio a (crystalline/amorphous) of the crystalline portion to the amorphous portion of the resin measured by raman spectroscopy in one direction of the resin layer 1 (for example, the flow direction MD in the case of forming the resin layer 1) and the spectral intensity ratio B (crystalline/amorphous) of the crystalline portion to the amorphous portion of the resin measured by raman spectroscopy in another direction orthogonal to the one direction of the resin layer 1 (for example, the direction TD perpendicular to the MD in the same plane) is in the range of 1.95 to 2.66. In the laminated film 10 of the second embodiment, when the sum of the spectral intensity ratio a and the spectral intensity ratio B falls within such a range, a large change in the amount of the lubricant present on the surface of the resin layer 1 is suppressed, and stable moldability is exhibited, and adhesion of the lubricant cake to the mold can be effectively suppressed. Details of the mechanism are as follows. That is, although the resin layer 1 includes a crystalline portion and an amorphous portion of the resin, when the lubricant is contained in the resin layer 1, the lubricant is present in the amorphous portion of the resin. Therefore, when the total ratio of the amorphous portion to the crystalline portion of the resin in the one direction and the other direction is within the above-described fixed range, the amount of the lubricant oozing out from the inside of the resin layer 1 to the surface due to temperature variation or the like and the amount of the lubricant moving from the surface of the resin layer 1 to the inside can be fixed. As a result, it is considered that a large change in the amount of the lubricant present on the surface of the resin layer 1 is suppressed, the laminated film 10 can exhibit stable moldability, and adhesion of the lubricant cake to the mold is effectively suppressed.

In the laminated film 10 of the second embodiment, the sum of the spectral intensity ratio a in one direction (for example, the flow direction MD in forming the resin layer 1) and the spectral intensity ratio B in the other direction (for example, the direction TD perpendicular to the same plane as the MD) orthogonal thereto may be within the above range, and from the viewpoint of suppressing a large change in the amount of the lubricant present on the surface of the resin layer 1, exhibiting stable moldability even in cold molding, and suppressing adhesion of the lubricant cake to the mold, there may be mentioned a range of preferably about 1.95 to 2.60, more preferably about 1.95 to 2.51, further preferably about 1.95 to 2.41, further preferably about 1.95 to 2.35, further preferably about 1.95 to 2.10, further preferably about 1.99 to 2.09, and particularly preferably about 2.00 to 2.07. 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, and particularly preferably about 0.99 to 1.05, and the spectral intensity ratio B is preferably about 0.90 to 1.66, more preferably about 0.90 to 1.51, still more preferably about 1.00 to 1.43, still more preferably about 1.00 to 1.25, and particularly preferably about 1.00 to 1.10.

In the multilayer film 10 of the second embodiment, an absolute value | B-a | of a difference between a spectral intensity ratio a of a crystalline portion and an amorphous portion in one direction (for example, a flow direction MD when the resin layer 1 is formed) and a spectral intensity ratio B of a crystalline portion and an amorphous portion in another direction orthogonal to the one direction (for example, a direction TD perpendicular to the same plane as the MD) is preferably in a range of 0.00 to 0.70. When the absolute value | B-a | 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 multilayer film 10 of the second embodiment can be reduced. The spectral intensity is usually the maximum absolute value | B-a | of the difference between the orthogonal positions of MD and TD (described later) on the same plane of the resin layer, but is not limited to the positional relationship.

As described above, the laminated film 10 is generally produced as a band-shaped laminated film, and is used for various applications described later by being cut into an appropriate size. If the above-mentioned curl amount h is large in the cut laminated film 10, it becomes difficult to position the mold at the time of molding. In the laminated film 10 of the second embodiment, when the absolute value | B-a | of the difference between the spectral intensity ratio a and the spectral intensity ratio B is within the above range and the curl amount h is within a range as described below, for example, positioning of a mold can be easily performed at the time of molding, and the molding process of the laminated film of the second embodiment can be efficiently performed.

In the multilayer film 10 of the second embodiment, the absolute value | B-a | of the difference between the spectral intensity ratio a of the crystalline portion and the amorphous portion in one direction and the spectral intensity ratio B of the crystalline portion and the amorphous portion in the other direction orthogonal to the one direction is in the above range, and thus the amount of curling h of the multilayer film 10 can be considered as follows. That is, it is considered that, although the resin layer 1 has a crystalline portion and an amorphous portion of the resin, 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 (for example, the difference between the ratio of the crystalline portion to the amorphous portion in MD and the ratio of the crystalline portion to the amorphous portion in TD is small), and therefore, deformation of the shape of the laminated film due to the difference in the ratio of the crystalline portion in one direction and the ratio of the crystalline portion in the other direction orthogonal to the one direction is suppressed, and as a result, the amount of curling h of the laminated film 10 according to the second aspect can be reduced.

From the viewpoint of further reducing the amount of curl h of the laminated film 10 of the second embodiment, the absolute value | B-a | of the difference between the spectral intensity ratio a and the spectral intensity ratio B is more preferably about 0.00 to 0.66, still more preferably about 0.00 to 0.51, still more preferably about 0.00 to 0.43, still more preferably about 0.00 to 0.33, still more preferably about 0.00 to 0.27, still more preferably about 0.00 to 0.15, still more preferably about 0.00 to 0.10, still more preferably about 0.00 to 0.08, and particularly preferably about 0.00 to 0.05.

In the laminated film 10 of the present invention, the resin constituting the resin layer 1 is not particularly limited, and the resin layer 1 is preferably formed of a thermoplastic resin. Examples of the thermoplastic resin include polyolefin, cyclic polyolefin, carboxylic acid-modified polyolefin, and carboxylic acid-modified cyclic polyolefin.

Specific examples of the polyolefin include: polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; crystalline or amorphous polypropylene such as homopolypropylene, a block copolymer of polypropylene (for example, a block copolymer of propylene and ethylene), a random copolymer of polypropylene (for example, a random copolymer of propylene and ethylene), and the like; terpolymers of ethylene-butene-propylene, and the like. Of these polyolefins, polyethylene and polypropylene are preferred, and polypropylene is particularly preferred.

Cyclic polyolefins are copolymers of olefins with cyclic monomers. Examples of the olefin include ethylene, propylene, 4-methyl-1 pentene, butadiene, and isoprene. Examples of the cyclic monomer include: cyclic olefins such as norbornene; cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene and norbornadiene. Among these polyolefins, cyclic olefins are preferable, and norbornene is more preferable.

The carboxylic acid-modified polyolefin refers to 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, and itaconic anhydride.

The carboxylic acid-modified cyclic polyolefin is a polymer obtained by copolymerizing a part of monomers constituting the cyclic polyolefin with an α, β -unsaturated carboxylic acid or an anhydride thereof, or block-polymerizing or graft-polymerizing the cyclic polyolefin with an α, β -unsaturated carboxylic acid or an anhydride thereof. The cyclic polyolefin subjected to carboxylic acid modification can be the same as the above-mentioned cyclic polyolefin. The carboxylic acid used for the modification may be the same as the carboxylic acid used for the modification of the acid-modified cycloolefin copolymer.

Among these thermoplastic resins, in the first aspect, from the viewpoint of further reducing the amount of curling h of the laminated film 10 and facilitating the positioning of the mold at the time of molding by setting the absolute value of the difference between the spectral intensity ratio a and the spectral intensity ratio B to the above range, preferred are: polyolefins, cyclic polyolefins, and polymer blends of these; further preferred are polyethylene, polypropylene, copolymers of ethylene and norbornene, and polymer blends of 2 or more of these. In the second aspect, these resins are also preferable from the viewpoint of suppressing a large change in the amount of the lubricant present on the surface of the resin layer 1, exhibiting stable moldability even in cold molding, and suppressing adhesion of the lubricant cake to the mold by setting the sum of the spectral intensity ratio a and the spectral intensity ratio B to the above range.

As a method of setting the difference between the sum of the spectral intensity ratio a and the spectral intensity ratio B to the numerical range, for example, the above-exemplified resin is used as the resin constituting the resin layer 1, and the temperature of a cooling roll for cooling when the resin layer 1 is formed is set to, for example, 10 ℃ or higher and lower than 50 ℃. When the temperature is less than 10 ℃, the releasability between the surface of the cooling roll and the resin layer is deteriorated, and breakage occurs when peeling is performed. On the other hand, when the temperature is 50 ℃ or higher, the proportion of the crystal portion becomes large, and the amount of slip agent deposited at the time of molding of the multilayer film becomes too large, and stable moldability is difficult to develop. The temperature of the cooling roll for setting the sum and difference of the spectral intensity ratio a and the spectral intensity ratio B to the above numerical range is preferably about 10 to 50 ℃, more preferably about 15 to 48 ℃, further preferably about 15 to 33 ℃, further preferably about 15 to 31 ℃, further preferably about 15 to 28 ℃, and particularly preferably about 25 to 28 ℃.

The resin layer 1 may be formed of only 1 resin component, or may be formed of a polymer blend in which 2 or more resin components are combined. Further, as described above, the resin layer 1 may be formed of only 1 layer, or may be formed of 2 or more layers of the same or different resin layers.

When the laminate film 10 is provided for molding, a lubricant is usually present on the surface of the resin layer 1. This improves the smoothness of the surface of the resin layer 1, and improves the moldability of the laminate film. However, since the lubricant easily migrates in the resin such as polyolefin resin forming the resin layer 1, even when the lubricant is mixed into the resin layer 1 or when the lubricant is contained only in one of the resin layers 1 immediately after the lubricant is applied to the surface of the resin layer 1, the lubricant migrates with time and the lubricant exists on both the surface and the inside of the resin layer 1. That is, in the laminated film 10, the lubricant may be contained in the resin layer 1 in advance, or the lubricant may be applied to the surface of the resin layer 1 before molding after the laminated film 10 is manufactured.

Examples of the method of allowing the lubricant to be present on the surface of the resin layer 1 include a method of applying the lubricant to the surface of the resin layer 1 and a method of blending the lubricant with polyolefin or the like forming the resin layer 1. In addition, as described above, when a lubricant is blended with polyolefin or the like forming the resin layer 1, the lubricant can be made to exist on the surface of the resin layer 1 by bleeding the lubricant to the surface of the resin layer 1. On the other hand, when the lubricant is applied to the surface of the resin layer 1, a part of the lubricant moves from the surface to the inside, so that the lubricant can be present inside the resin layer 1. Among them, as a method for bleeding the lubricant to the surface of the resin layer 1, there is generally a method of aging the laminate film at a slightly high temperature of about 30 to 50 ℃ for about several hours to 3 days to promote bleeding. The movement of the lubricant in the inside and the surface of the resin layer 1 as described above is a phenomenon which is likely to occur particularly in an amide-based lubricant described later.

The type of the lubricant is not particularly limited, and an amide-based lubricant is preferably used from the viewpoint of suppressing a large change in the amount of the lubricant present on the surface of the resin layer 1 by setting the sum (a + B) of the spectral intensity ratio a and the spectral intensity ratio B to the above range, exhibiting stable moldability even at the time of cold molding, and suppressing adhesion of a lubricant cake to a mold.

The amide-based lubricant is not particularly limited as long as it has an amide group, and preferably includes a fatty acid amide and an aromatic bisamide. The amide slip agent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Examples of the fatty acid amide 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 amide include lauramide, palmitamide, stearamide, behenamide, and hydroxystearamide. Specific examples of the unsaturated fatty amide include oleamide and erucamide. Specific examples of the substituted amide include N-oleyl palmitamide, N-stearyl stearamide, N-stearyl oleamide, N-oleyl stearamide, N-stearyl erucamide and the like. Specific examples of the methylolamide include methylolstearylamide and the like. Specific examples of the saturated fatty acid bisamide include methylene bisstearamide, ethylene biscapramide, ethylene bislauramide, ethylene bisstearamide, ethylene bishydroxystearamide, ethylene bisbehenamide, hexamethylene bisstearamide, hexamethylene bisbehenamide, hexamethylene hydroxystearamide, N '-distearyldiadipamide, N' -distearyldisebacamide, and the like. Specific examples of the unsaturated fatty acid bisamide include ethylene bisoleamide, ethylene biserucamide, hexamethylene bisoleamide, N '-dioleyl adipamide, N' -dioleyl sebacamide, and the like. Specific examples of the fatty acid ester amide include stearamide ethyl stearate. Specific examples of the aromatic bisamide include m-xylylene bisstearamide, m-xylylene bishydroxystearamide, and N, N' -distearyl isophthalamide.

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 700ppm or more, more preferably about 700 to 3000ppm, further preferably about 700 to 2500ppm, and particularly preferably about 1200 to 2000ppm on a mass basis. Here, these values mean the contents when it is assumed that all of the slip agents present on the surface and inside of the resin layer 1 are present in the resin layer 1.

The thickness of the resin layer 1 is not particularly limited, and from the viewpoint of further reducing the curl amount h of the laminated film 10 and further facilitating the positioning of the mold at the time of molding, for example, the thickness is about 5 to 500 μm, and preferably about 5 to 200 μm. The thickness of the resin layer 1 can be measured from a cross section of the laminated film in the thickness direction.

[ support 2]

Examples of the layer constituting the support 2 include a base layer 21 and a barrier layer 22. The support body 2 may be formed of only one layer or may be formed of a plurality of layers. When the support 2 has the base material layer 21 and the barrier layer 22, the layer structure of the multilayer film 10 is preferably laminated so as to include the base material layer 21, the barrier layer 22, and the resin layer 1 in this order. When the support 2 includes the base material layer 21 and the barrier layer 22, an adhesive layer a may be provided between these layers as needed for the purpose of improving the adhesion between the base material layer 21 and the barrier layer 22. In addition, for the purpose of improving the adhesion between the support 2 and the resin layer 1, an adhesive layer B may be provided 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, and the like) as necessary. These layers are explained in detail below.

(substrate layer 21)

In the laminated film 10, the base layer 21 that can be included as the support 2 is a layer that is provided as necessary and serves as a base of the laminated film 10. The raw material for forming the base material layer 21 is not particularly limited. Specific examples of the material for forming the base layer 21 include resins such as polyester, polyamide, epoxy, acrylic, fluororesin, polyurethane, silicon-containing resin, phenol, polyetherimide, polyimide, and a mixture or copolymer thereof.

Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, a copolyester mainly composed of ethylene terephthalate and a copolyester mainly composed of butylene terephthalate. Specific examples of the copolyester mainly composed of ethylene terephthalate as a repeating unit include a copolyester polymerized with ethylene isophthalate mainly composed of ethylene terephthalate as a repeating unit (hereinafter, the notation of "polyethylene (terephthalate/isophthalate)" is omitted), polyethylene (terephthalate/isophthalate), polyethylene (terephthalate/adipate), polyethylene (terephthalate/sodium sulfoisophthalate), polyethylene (terephthalate/sodium isophthalate), polyethylene (terephthalate/phenyl dicarboxylate), and polyethylene (terephthalate/decanedicarboxylate). Specific examples of the copolyester mainly composed of a butylene terephthalate as a repeating unit include a copolyester polymerized with a butylene isophthalate mainly composed of a butylene terephthalate as a repeating unit (hereinafter, the notation of "polybutylene (terephthalate/isophthalate)" is omitted), polybutylene (terephthalate/adipate), polybutylene (terephthalate/sebacate), and polybutylene naphthalate. These polyesters may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Further, as the polyamide, specifically, there can be mentioned: aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and copolymers of nylon 6 and nylon 66; aromatic-containing polyamides such as hexamethylenediamine-isophthalic acid-terephthalic acid copolyamides including terephthalic acid-and/or isophthalic acid-derived constituent units such as nylon 6I, nylon 6T, nylon 6IT, and nylon 6I6T (I represents isophthalic acid and T represents terephthalic acid), and polyamides such as polymetaxylylene adipamide (MXD 6); alicyclic polyamides such as polyaminomethylcyclohexyl adipamide (PACM 6); a polyamide obtained by copolymerizing a lactam component and an isocyanate component such as 4, 4' -diphenylmethane-diisocyanate, a polyester amide copolymer or a polyether ester amide copolymer which is a copolymer of a copolymerized polyamide and a polyester or a polyalkylene ether glycol; copolymers of the above and the like. These polyamides may be used alone in 1 kind, or 2 or more kinds may be used in combination. The stretched polyamide film is excellent in stretchability, can prevent occurrence of whitening due to resin fracture of the base material layer 21 during molding, and is suitable for use as a material for forming the base material layer 21.

The base material layer 21 may be formed of a resin film that has been uniaxially or biaxially stretched, or may be formed of an unstretched resin film. Among them, a uniaxially or biaxially stretched resin film, particularly a biaxially stretched resin film, is improved in heat resistance due to oriented crystallization, and is therefore suitable for use as the substrate layer 21.

Among these, as the resin film forming the base layer 21, nylon and polyester are preferable, biaxially stretched nylon and biaxially stretched polyester are more preferable, and biaxially stretched nylon is particularly preferable.

In the base material layer 21, resin films made of different materials may be laminated to improve the pinhole resistance of the laminated film 10. Specifically, a multilayer structure in which a polyester film and a nylon film are laminated, a multilayer structure in which a biaxially stretched polyester and a biaxially stretched nylon are laminated, and the like can be cited. When the substrate layer 21 has a multilayer structure, the resin films may be bonded with an adhesive, or may be directly laminated without an adhesive. When the bonding is not performed by an adhesive, for example, a method of bonding in a hot-melt state such as a coextrusion lamination method, an interlayer lamination method, or a heat lamination method can be mentioned. In the case of bonding with an adhesive, the adhesive used may be a 2-liquid curable adhesive or a 1-liquid curable adhesive. The bonding mechanism of the adhesive is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a hot-melt type, a hot-press type, an electron beam curing type, an ultraviolet curing type, and the like. Examples of the component of the adhesive include polyester-based resins, polyether-based resins, polyurethane-based resins, epoxy-based resins, phenol-based resins, polyamide-based resins, polyolefin-based resins, polyvinyl acetate-based resins, cellulose-based resins, (meth) acrylic resins, polyimide-based resins, amino resins, rubbers, and silicone-based resins.

The thickness of the base material layer 21 is not particularly limited, and may 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 needed. For example, when the laminated film 10 is used as a packaging material or the like, the laminated film functions as a barrier layer for preventing water vapor, oxygen, light, or the like from entering the inside sealed by the laminated film 10, in addition to improving strength. Specific examples of the metal constituting the barrier layer 22 include aluminum, stainless steel, and titanium, and aluminum is preferably used. 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, or the like, and is preferably formed of a metal foil, and more preferably an aluminum alloy foil. In the production of the laminated film, from the viewpoint of preventing the occurrence of wrinkles and pinholes in the barrier layer 22, the barrier layer is more preferably formed of a soft aluminum alloy foil such as annealed aluminum (JIS H4160: 1994A 8021H-O, JIS H4160: 1994A 8079H-O, JIS H4000: 2014A 8021P-O, JIS H4000: 2014A 8079P-O).

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

In the barrier layer 22, at least one surface, preferably both surfaces, are preferably chemically surface-treated for stabilization of adhesion, prevention of dissolution, corrosion, and the like. Here, the chemical surface treatment refers to a treatment for forming an acid-resistant coating film on the surface of the barrier layer. Examples of the chemical surface treatment include: chromate treatment using chromium compounds such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium dihydrogen phosphate, chromic acid acetoacetate, chromium chloride, and chromium potassium sulfate; phosphoric acid treatment using a phosphoric acid compound such as sodium phosphate, potassium phosphate, ammonium phosphate, or polyphosphoric acid; chromate treatment using an aminated phenol polymer having repeating units represented by the following general formulae (1) to (4).

In the general formulae (1) to (4), X represents a hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group. In addition, R¹And R²Each of which is the same or different, represents a hydroxyl group, an alkyl group or a hydroxyalkyl group. X, R in the general formulae (1) to (4)¹And R²Examples of the alkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. In addition, as X, R¹And R²Examples of the hydroxyalkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms, such as a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, or 4-hydroxybutyl group, substituted with 1 hydroxyl group. X, R in the general formulae (1) to (4)¹And R²The alkyl group and the hydroxyalkyl group may be the same or different. In the general formulae (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 formulae (1) to (4) is preferably, for example, 500 to 100 ten thousand, and more preferably 1000 to 2 ten thousand or so.

As a chemical surface treatment method for imparting corrosion resistance to the barrier layer 22, there is a method in which a substance in which fine particles of a metal oxide such as alumina, titanium oxide, cerium oxide, or tin oxide or barium sulfate are dispersed in phosphoric acid is applied, and then baking treatment is performed at 150 ℃. Further, a resin layer obtained by crosslinking the cationic polymer with a crosslinking agent may be further formed on the corrosion-resistant layer. Examples of the cationic polymer include polyethyleneimine, an ionic polymer complex comprising polyethyleneimine and a polymer having a carboxylic acid, a primary amine-grafted acrylic resin obtained by graft-polymerizing a primary amine onto an acrylic main skeleton, polyallylamine or a derivative thereof, and aminophenol. As such cationic polymers, only 1 kind may be used, or 2 or more kinds may be used in combination. Examples of the crosslinking agent include compounds 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 silane coupling agents. These crosslinking agents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The chemical surface treatment may be performed by only 1 kind of chemical surface treatment, or may be performed by combining 2 or more kinds of chemical surface treatments. These chemical surface treatments may be carried out using 1 compound alone or 2 or more compounds in combination. Among the chemical surface treatments, chromate treatment, chemical surface treatment combining a chromium compound, a phosphoric acid compound and an aminated phenol polymer, and the like are preferable. Among the chromium compounds, a chromic acid compound is preferable.

The amount of the acid-resistant coating film formed on the surface of the barrier layer 22 in the chemical surface treatment is not particularly limited, and for example, in the case of performing the chromate treatment, it is preferable that the surface of the barrier layer 22 is coated every 1m²The components are as follows: the chromium compound is about 0.5 to 50mg, preferably about 1.0 to 40mg, in terms of chromium; the phosphorus compound is about 0.5 to 50mg, preferably about 1.0 to 40mg, in terms of phosphorus; and the aminated phenol polymer is about 1.0 to 200mg, preferably about 5.0 to 150 mg.

The chemical surface treatment is carried out by: after a solution containing a compound for forming an acid-resistant coating 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, or the like, the solution is heated so that the temperature of the barrier layer is about 70 to 200 ℃. Before the barrier layer is subjected to the chemical surface treatment, the barrier layer may be subjected to degreasing treatment by an alkali immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or the like. By performing such degreasing treatment, chemical surface treatment of the surface of the barrier layer can be performed more efficiently.

(adhesive layer A)

The adhesive layer a that can be included in the support 2 in the laminated film 10 is a layer provided as needed for the purpose of improving the adhesive strength between the base layer 21 and the barrier layer 22.

The adhesive layer a is formed of an adhesive capable of bonding the base layer 21 and the barrier layer 22. The adhesive used for forming the adhesive layer a may be a 2-liquid curing adhesive, or may be a 1-liquid curing adhesive. The adhesive mechanism of the adhesive for forming the adhesive layer a is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a hot melt type, a hot press type, and the like.

As the resin component of the adhesive that can be used for forming the adhesive layer a, specifically, there can be mentioned: polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, and copolyester; a polyether adhesive; a polyurethane adhesive; an epoxy resin; a phenolic resin-based resin; polyamide resins such as nylon 6, nylon 66, nylon 12, and copolyamide; polyolefin resins such as polyolefin, acid-modified polyolefin, and metal-modified polyolefin; polyvinyl acetate resin; a cellulose-based binder; (meth) acrylic resins; a polyimide-based resin; amino resins such as urea resins and melamine resins; rubbers such as chloroprene rubber, nitrile rubber, and styrene-butadiene rubber; a silicone resin; fluorinated ethylene propylene copolymers and the like. These adhesive components may be used alone in 1 kind, or may be used in combination of 2 or more kinds. The combination of 2 or more adhesive components is not particularly limited, and examples of the adhesive component include a mixed resin of polyamide and acid-modified polyolefin, a mixed resin of polyamide and metal-modified polyolefin, a mixed resin of polyamide and polyester, a mixed resin of polyester and acid-modified polyolefin, and a mixed resin of polyester and metal-modified polyolefin. Among these, polyurethane-based 2-liquid curable adhesives are preferred from the viewpoint that they are excellent in ductility, durability under high humidity conditions, strain suppression effect, thermal degradation suppression effect during heat sealing, and the like, and can suppress a decrease in lamination strength between the base material layer 21 and the barrier layer 22, thereby effectively suppressing the occurrence of delamination; polyamide, polyester or their blend resins with modified polyolefin.

The adhesive layer a may be multilayered with different adhesive components. In the case where the adhesive layer a is multilayered using different adhesive components, it is preferable to select a resin having excellent adhesion to the substrate layer 21 as the adhesive component disposed on the substrate layer 21 side and an adhesive component having excellent adhesion to the barrier layer 22 as the adhesive component disposed on the barrier layer 22 side, from the viewpoint of improving the lamination strength between the substrate layer 21 and the barrier layer 22. When the adhesive layer a is multilayered with different adhesive components, specifically, the adhesive component disposed on the barrier layer 22 side preferably includes a resin containing an acid-modified polyolefin, a metal-modified polyolefin, a mixed resin of a polyester and an acid-modified polyolefin, a copolyester, or the like.

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 multilayer film 10, an adhesive layer B may be further provided between the support 2 (for example, the base layer 21, the barrier layer 22, and the like) and the resin layer 1 for the purpose of firmly bonding the support 2 and the resin layer 1, and the like.

The adhesive layer B is formed of an adhesive component capable of bonding the resin layer 1 with the substrate layer 21, the barrier layer 22, and the like included as the support 2. The adhesive used for forming the adhesive layer B may be a 2-liquid curing adhesive or a 1-liquid curing adhesive. The bonding mechanism of the adhesive component for forming the adhesive layer B is not particularly limited, and examples thereof include a chemical reaction type, a solvent volatilization type, a hot melt type, and a hot press type.

Specific examples of the adhesive component that can be used for forming the adhesive layer B include: polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, and copolyester; a polyether adhesive; a polyurethane adhesive; an epoxy resin; a phenolic resin-based resin; polyamide resins such as nylon 6, nylon 66, nylon 12, and copolyamide; polyolefin resins such as polyolefin, carboxylic acid-modified polyolefin, and metal-modified polyolefin, and polyvinyl acetate resins; a cellulose-based binder; (meth) acrylic resins; a polyimide-based resin; amino resins such as urea resins and melamine resins; rubbers such as chloroprene rubber, nitrile rubber, and styrene-butadiene rubber; silicone resins, and the like. These adhesive components may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

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

Each layer constituting the laminated film 10 may be subjected to surface activation treatment such as corona discharge treatment, sandblasting treatment, oxidation treatment, or ozone treatment as necessary for improving or stabilizing film formability, lamination processing, secondary processing (packaging, embossing) suitability of a final product, or the like.

Method for producing laminated film

The laminated film 10 of the present invention can be produced by laminating the support 2 and the resin layer 1, and specifically, for example, the following production method can be exemplified.

For example, when the support 2 includes the base layer 21 and the barrier layer 22, the multilayer film 10 can be obtained by the following lamination process. First, the base layer 21 and the barrier layer 22 are laminated. The lamination can be performed by, for example, a dry lamination method using the adhesive component or the like for forming the adhesive layer a. Further, as a method of laminating the substrate layer 21 and the barrier layer 22, a method of extruding a resin forming the substrate layer 21 on the surface of the barrier layer 22, a method of forming the barrier layer 22 by depositing metal on one surface of the substrate layer 21, and the like can be cited. 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 improving the adhesive strength between the barrier layer 22 and the resin layer 1, an adhesive component for forming the adhesive layer B may be applied to the barrier layer 22, dried, and then the resin layer 1 may be formed thereon, as necessary. When the resin layer 1 is formed of a plurality of layers, the resin layer 1 formed of a plurality of layers by a known method such as co-extrusion may be laminated.

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

Each layer constituting the laminate film may be subjected to surface activation treatment such as corona discharge treatment, sandblast treatment, oxidation treatment, or ozone treatment as necessary for improving or stabilizing film formability, lamination processing, secondary processing (packaging, embossing) suitability of the final product, and the like.

Use of laminated film

As described above, the laminated film 10 of the present invention is generally produced as a tape-shaped laminated film, and is used for various applications by being cut into an appropriate size. The laminated film 10 of the present invention is particularly suitable for use as a cold-formed laminated film having a forming depth of 0.5mm or more, preferably about 4.0 to 7.0 mm. Specific applications of the laminated film 10 are not particularly limited, and examples thereof include packaging materials and the like. 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 electrolytes. That is, the packaging material of the present invention is suitably used as a packaging material for pharmaceuticals, a packaging material for cosmetics, a packaging material for foods, a packaging material for batteries, and the like. The packaging material can be deformed to conform to the shape of the contents to produce a package for storing the contents.

Examples

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

< examples 1 to 16 and comparative example 1 >

[ production of laminated film ]

A barrier layer 22 comprising an aluminum foil (thickness: 40 μm) chemically surface-treated on both surfaces thereof was laminated on a base material layer 21 having a configuration described later by a dry lamination method. In particular toOn one surface of the aluminum foil, 2-liquid type urethane adhesive (polyol compound and aromatic isocyanate compound) was applied to form an adhesive layer a (thickness 4 μm) on the barrier layer 22. Next, the adhesive layer a on the barrier layer 22 and the base layer 21 were bonded together by heating under pressure, and then subjected to a curing treatment to obtain a support body in which the base layer 21/the adhesive layer a/the barrier layer 22 were sequentially stacked. The chemical surface treatment of the aluminum foil used as the barrier layer 22 was carried out by applying a treatment liquid containing a phenol resin, a chromium fluoride compound and phosphoric acid in an amount of 10mg/m in terms of the amount of chromium applied²The method (dry mass) was performed by coating both surfaces of the aluminum foil by roll coating and baking.

The substrate layer 21 used in examples and comparative examples had the following structure.

Examples 1, 2: lamination of PET film (12 μm)/adhesive layer (3 μm)/nylon film (15 μm) (nylon is the barrier layer side)

Example 3: 2-layer coextruded film of PET (5 μm)/nylon (20 μm) (nylon is the barrier layer side)

Example 4: 3-layer coextruded film of PET (5 μm)/thermoplastic polyester elastomer (1 μm)/nylon (20 μm) (nylon is the barrier layer side)

Examples 5, 6: monolayer of PET film (12 μm)

Examples 7 to 16 and comparative example 1: nylon film (25 μm) single layer

Herein, "PET" means "polyethylene terephthalate".

In examples 1 to 11 and comparative example 1, the resin layer 1 (thickness 25 μm/25 μm, resin B on the innermost layer side) was laminated on the barrier layer 22 by coextruding the resin a (carboxylic acid-modified polypropylene, melting peak temperature 160 ℃) and the resin B (polypropylene containing a fatty amide-based lubricant, melting peak temperature 140 ℃) which form the resin layer 1 on the barrier layer 22 side of the support in a molten state (250 ℃). Thus, the multilayer films of examples 1 to 11 and comparative example 1, in which the base layer 21, the adhesive layer a, the barrier layer 22 and the resin layer 1 were sequentially laminated, were obtained. The temperatures of the cooling rolls for cooling the laminate after laminating the resin layers 1 were set to the temperatures shown in tables 1 and 2, respectively.

In examples 12 and 13, 2-liquid polyurethane adhesive (polyol compound and aromatic isocyanate compound) was applied to the side of the barrier layer 22 to form an adhesive layer B (thickness 4 μm). Next, an unstretched polypropylene film (3-layer extrusion product, propylene-ethylene random copolymer containing fatty amide based lubricant (resin B, 4 μm)/propylene-ethylene block copolymer (22 μm)/propylene-ethylene random copolymer (4 μm) with resin B being the innermost layer side) was laminated to form a resin layer 1. Thus, each of the multilayer films of examples 12 and 13, in which the base layer 21, the adhesive layer a, the barrier layer 22, the adhesive layer B, and the resin layer 1 were sequentially stacked, was obtained.

In example 14, a resin layer B (thickness 1 μm) was formed by applying a resin containing acid-modified polypropylene as a main agent and methylene diisocyanate as a curing agent to the barrier layer 22 side. In example 15, a resin layer B (thickness 3 μm) was formed by applying a resin containing acid-modified polypropylene as a main agent and methylene diisocyanate as a curing agent to the barrier layer 22 side. In example 16, a resin layer B (thickness 1 μm) was formed by applying a resin containing acid-modified polypropylene as a main agent and an epoxy resin (weight average molecular weight 500) as a curing agent to the barrier layer 22 side. In examples 14 to 16, an unstretched polypropylene film (3-layer extrusion product, propylene-ethylene random copolymer containing fatty amide based lubricant (resin B, 4 μm)/propylene-ethylene block copolymer (22 μm)/propylene-ethylene random copolymer (4 μm), resin B being the innermost layer side) was laminated to form a resin layer 1. Thus, laminated films of examples 14, 15 and 16 were obtained, in which the base layer 21, the adhesive layer a, the barrier layer 22, the adhesive layer B and the resin layer 1 were sequentially laminated. In the examples and comparative examples, the amount of the fatty amide based lubricant contained in the resin B is shown in tables 1 and 2.

< determination of spectral intensity A, B by Raman Spectroscopy >

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 were measured by raman spectroscopy using the following measurement equipment, measurement conditions, and analysis conditions for the resin layers of the obtained laminated film. The results are shown in tables 1 and 2.

Measurement equipment: LabRAM HR-800, manufactured by HORIBA JOBIN YVON, measures the Raman spectrum so that the MD is parallel to the polarization plane of the incident laser light in the measurement of the spectral intensity A in the MD, and measures the Raman spectrum so that the TD is parallel to the polarization plane of the incident laser light in the measurement of the spectral intensity B in the TD.

The grating is 800L/mm.

Analysis conditions were as follows:

(2) Frequency shift from Raman 809 + -2 cm^－1The maximum value of the scattering intensity in the range of (1) was subtracted from the above baseline value to obtain the value at 809cm^－1The peak intensity of (c).

(3) From Raman frequency shift 842 + -2 cm^－1The maximum value of the scattering intensity in the range of (3) is subtracted from the above-mentioned baseline value to obtain the value at 842cm^－1The peak intensity of (c).

(4) The spectral intensity ratio A, B was calculated using the peak intensities of (2) and (3) above. As described above, when polypropylene was used as the resin forming the resin layer 1, the peak of the crystal part of the resin was 809cm in the spectrum measurement by Raman spectroscopy^－1The vicinity was observed, and the peak of the amorphous part was 842cm^－1A vicinity is observed. Since peaks of spectral lines are observed at different positions in the crystalline portion and the amorphous portion of the resin, the peak intensities of the crystalline portion and the amorphous portion in one direction (MD) and the other direction (TD) orthogonal thereto are measured, and 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, 2 slits (slits through the laminated film) having a length of 100mm from the center were cut from the support side so as to penetrate the thickness direction of the laminated film on 2 lines connecting each pair of corners of the laminated film at the center of the laminated film having a length of 90mm in one direction (MD) and a length of 150mm in another direction (TD) orthogonal to the one direction, and the laminated film was placed on a horizontal plane so that the support was on the lower side and left to stand at 20 ℃ for 8 hours. Next, as shown in fig. 2, the distance from the apex (center P) of the 4 surfaces standing by curling to the horizontal surface 30 in the direction perpendicular to the horizontal surface was measured by a height gauge (manufactured by MITUTOYO corporation), and the maximum value thereof was defined as the maximum distance h. The results are shown in tables 1 and 2.

< evaluation of lubricant precipitation 1 >

The laminated film obtained above was stored at 20 ℃ for 1 week and then cut to prepare a rectangular sheet of 120mm × 80mm as a test sample. Next, using a straight mold including a rectangular male mold of 30mm × 50mm and a female mold having a clearance of 0.5mm from the male mold, the test samples were placed on the female mold so that the resin layer 1 side was positioned on the male mold side, and 5000 (5000) test samples were pressed at a pressing pressure (surface pressure) of 0.1MPa so that the molding depth was 4.0mm, respectively, to perform cold molding (pull-in 1-stage molding). The lubricant deposition of the test sample at this time was evaluated according to the following criteria. The results are shown in Table 1.

A: the lubricant did not adhere to the mold after 5000 molding times.

B: the adhesion of the lubricant to the mold was confirmed 5000 times of molding, but the molding state was not affected.

C: the formed sample was indented by the adhesion of the lubricant to the mold at 5000 times of molding.

[ Table 1]

As shown in Table 1, in the laminated films of examples 1 to 8 and 12 to 16 in which the absolute value | B-A | of the difference between the spectral intensity ratio A in one direction (MD) of the resin layer and the spectral intensity ratio B in the other direction (TD) orthogonal to the one direction is 0.01 to 0.66, the curl amount h can be suppressed to about 30mm or less, and the positioning of the mold can be easily performed as compared with comparative example 1. Further, the results of evaluation of lubricant deposition were good in the laminated films of examples 1 to 8 and 12 to 16 in which the sum (A + B) of the spectral intensity ratio A and the spectral intensity ratio B was in the range of 2.06 to 2.66. On the other hand, in the multilayer film of comparative example 1 in which the absolute value | B-a | of the difference between the spectral intensity ratio a in one direction of the resin layer and the spectral intensity ratio B in the other direction orthogonal to the one direction was 0.73, the curl amount h was 37mm, and positioning of the mold was difficult. In addition, the result of evaluation of lubricant deposition was poor in the multilayer film of comparative example 1 in which the sum of the spectral intensity ratio a and the spectral intensity ratio B (a + B) was 2.77.

< evaluation of lubricant precipitation 2 >

The laminated films of examples 1, 2, 6, 7, 9 to 16 and comparative example 1 obtained above were stored at storage temperatures (5 ℃, 20 ℃ and 40 ℃) shown in table 2 for one week and then cut to prepare rectangular pieces of 120mm × 80mm as test samples. Next, using a straight mold including a rectangular male mold of 30mm × 50mm and a female mold having a clearance of 0.5mm from the male mold, the test samples were placed on the female mold so that the resin layer 1 side was positioned on the male mold side, and 5000 (5000) test samples were pressed at a pressing pressure (surface pressure) of 0.1MPa so that the molding depth was 4.0mm, respectively, to continuously perform cold molding (drawing 1 molding). The lubricant deposition 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 the measurement of the above-described < curl amount h > for an arbitrary test sample stored at each temperature.

A: the lubricant did not adhere to the mold after 5000 molding times.

Formability evaluation of < 4.0mm >

In the same manner as in the above lubricant precipitation evaluation 2, 5000 test samples were cold-formed so that the molding depth was 4.0mm, and whether or not pinholes were generated was confirmed. Moldability was evaluated according to the following criteria. The results are shown in Table 2.

A: no pinhole is generated

B: the generation rate of pinholes is less than 10%

C: the pinhole generation rate is more than 11%

[ Table 2]

As shown in table 2, the multilayer films of examples 1, 2, 6, 7, 9 to 16, in which the absolute value | B-a | of the difference between the spectral intensity ratio a in one direction (MD) of the resin layer and the spectral intensity ratio B in the other direction (TD) orthogonal to the one direction was 0.05 to 0.66, could suppress curling, and the positioning of the mold was easier than that of comparative example 1. In addition, in the laminated films of examples 1, 2, 6, 7, 9 to 16 in which the sum (A + B) of the spectral intensity ratio A and the spectral intensity ratio B was in the range of 1.99 to 2.66, the evaluation result of the lubricant deposition was good and the moldability was also excellent. On the other hand, in the multilayer film of comparative example 1 in which the absolute value | B-a | of the difference between the spectral intensity ratio a in one direction of the resin layer and the spectral intensity ratio B in the other direction orthogonal to the one direction was 0.73, curling was large, and positioning of the mold was difficult. In addition, the result of evaluation of lubricant deposition was poor in the multilayer film of comparative example 1 in which the sum of the spectral intensity ratio a and the spectral intensity ratio B (a + B) was 2.77.

Description of the symbols

1 … resin layer

2 … support body

21 … base material layer

22 … Barrier layer

10 … laminated film

30 … horizontal plane

Claims

1. A laminated film characterized by:

which comprises a laminate of at least a support and a resin layer formed of a resin,

wherein the resin layer contains a slip agent, and the content of the slip agent present on the surface and inside of the resin layer is 700 to 3000ppm by mass,

the lubricant is an amide lubricant,

an absolute value | B-A | of a difference between a spectral intensity ratio A, which is a spectral intensity ratio obtained by dividing a spectral intensity of a crystal portion of the resin measured in one direction of a plane of the resin layer by a spectral intensity of an amorphous portion, and a spectral intensity ratio B, which is a spectral intensity ratio obtained by dividing a spectral intensity of a crystal portion of the resin measured in another direction of the same plane of the resin layer orthogonal to the one direction by a spectral intensity of an amorphous portion, is in a range of 0.05 to 0.51.

2. A laminated film characterized by:

the lubricant is an amide lubricant,

the absolute value | B-A | of the difference between the spectral intensity ratio A and the spectral intensity ratio B is in the range of 0.05 to 0.51,

the sum of the spectral intensity ratio A and the spectral intensity ratio B is in the range of 2.05 to 2.51,

the spectral intensity ratio a is a spectral intensity ratio obtained by dividing a crystalline portion spectral intensity of the resin measured in one direction of the plane of the resin layer by an amorphous portion spectral intensity by raman spectroscopy, and the spectral intensity ratio B is a spectral intensity ratio obtained by dividing a crystalline portion spectral intensity of the resin measured in another direction on the same plane of the resin layer orthogonal to the one direction by an amorphous portion spectral intensity by raman spectroscopy.

3. The laminate film as claimed in claim 1 or 2, wherein:

the laminated film having a length in the one direction of 90mm and a length in the other direction of 150mm is prepared, 2 slits having a length of 100mm and a center of the laminated film are cut from the support so as to penetrate the thickness direction of the laminated film at 2 lines connecting the respective corners of the laminated film, the laminated film is placed on a horizontal plane with the support as the lower side, and after standing at 20 ℃ for 8 hours, the maximum distance h between the horizontal plane and the center is 30mm or less when measured in the vertical direction to the horizontal plane.

4. The laminate film as claimed in claim 1 or 2, wherein:

the resin layer is composed of polyolefin.

5. The laminate film as claimed in claim 1 or 2, wherein:

the support has a barrier layer.

6. The laminate film as claimed in claim 1 or 2, wherein:

the support body is provided with a base material layer and a barrier layer,

the resin layer is laminated on the side of the barrier layer opposite to the base material layer.

7. The laminate film as claimed in claim 6, wherein:

the base material layer has a multilayer structure formed by a laminate of a polyester film and a nylon film.

8. The laminate film as claimed in claim 6, wherein:

the base material layer is formed of a polyester film.

9. The laminate film as claimed in claim 6, wherein:

the substrate layer is composed of a nylon film.

10. The laminate film as claimed in claim 1 or 2, wherein:

it is used as a packaging material.

11. The laminate film as claimed in claim 1 or 2, wherein:

which is a laminated film provided for cold forming.