Resin films, laminated films, packaging materials, packaging bags and packaging bodies

Abstract

To provide a resin film that can achieve both antistatic and hygroscopic properties. [Solution] The present disclosure provides a resin film having a first resin layer and a second resin layer, wherein the first resin layer contains a hygroscopic agent, the second resin layer contains a polyolefin resin and a polymer-based antistatic agent, the second resin layer is located on the outermost surface, the second resin layer has a first region containing the polyolefin resin and a second region containing the polymer-based antistatic agent, the second region has a striated structure, and when one direction in the planar direction of the second resin layer is defined as the first direction, in a cross section parallel to the first direction and the thickness direction of the second resin layer, the ratio of the autocorrelation length in the first direction to the autocorrelation length in the thickness direction of the second resin layer is 4 or more in the striated structure.

Description

Technical Field

[0001] The present disclosure relates to a resin film, a laminated film, a packaging material, a packaging bag, and a package using the same.

Background Art

[0002] For packaging materials for packaging electronic components such as wafers and electronic parts, antistatic properties are required to protect the electronic components from static electricity. Conventionally, as a packaging material provided with antistatic properties, a resin film in which an antistatic agent is kneaded into a resin has been used.

[0003] Also, it is important to protect electronic components from humidity so as to suppress deterioration of the electronic components and maintain their functions and properties. Conventionally, a desiccant has been enclosed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] As an antistatic agent, a surfactant-type antistatic agent is common. However, the surfactant-type antistatic agent has a reduced function under low humidity conditions. In addition, the surfactant-type antistatic agent is likely to bleed out and elute ionic components, so the surface of the electronic component is contaminated. Therefore, it is not practical. The applicant of the present application has been developing a resin film having good antistatic properties and hygroscopic properties as described in Patent Documents 1 and 2, and has focused on polymer-based antistatic agents.

[0006] This disclosure is made in view of the above circumstances and aims to provide a resin film that can achieve both antistatic and hygroscopic properties. [Means for solving the problem]

[0007] One embodiment of the present disclosure provides a resin film having a first resin layer and a second resin layer, wherein the first resin layer contains a hygroscopic agent, the second resin layer contains a polyolefin resin and a polymer-based antistatic agent, the second resin layer is located on the outermost surface, the second resin layer has a first region containing the polyolefin resin and a second region containing the polymer-based antistatic agent, the second region has a striated structure, and when one direction in the planar direction of the second resin layer is defined as the first direction, in a cross section parallel to the first direction and the thickness direction of the second resin layer, the ratio of the autocorrelation length in the first direction to the autocorrelation length in the thickness direction of the second resin layer is 4 or more in the striated structure.

[0008] Another embodiment of the present disclosure provides a laminated film having a barrier substrate layer and the above-mentioned resin film, wherein the second resin layer of the resin film is located on the outermost surface.

[0009] Other embodiments of the present disclosure provide a packaging material comprising the laminated film described above.

[0010] Another embodiment of the present disclosure provides a packaging bag comprising the laminated film described above.

[0011] Another embodiment of the present disclosure provides a package comprising the above-described packaging bag and an object to be packaged contained within the packaging bag. [Effects of the Invention]

[0012] The resin film in this disclosure has the effect of achieving both antistatic and hygroscopic properties. [Brief explanation of the drawing]

[0013] [Figure 1] This is a schematic cross-sectional view illustrating a resin film in this disclosure. [Figure 2] This is a schematic cross-sectional view illustrating the second resin layer in this disclosure. [Figure 3] This is a schematic cross-sectional view illustrating the second resin layer in this disclosure. [Figure 4] This is a schematic cross-sectional view illustrating a resin film in this disclosure. [Figure 5] This is a schematic cross-sectional view illustrating a laminated film in this disclosure. [Figure 6] This is a schematic cross-sectional view illustrating a laminated film in this disclosure. [Modes for carrying out the invention]

[0014] Embodiments of this disclosure will be described below with reference to drawings and other figures. However, this disclosure can be implemented in many different ways and should not be interpreted as being limited to the embodiments described below. In addition, the drawings may be schematically represented in terms of width, thickness, shape, etc. of each part compared to the actual form in order to make the explanation clearer, but these are merely examples and should not limit the interpretation of this disclosure. Furthermore, in this specification and each figure, elements similar to those described above with respect to previously shown figures will be denoted by the same reference numerals, and detailed explanations may be omitted as appropriate.

[0015] In this specification, when describing a configuration in which one member is placed on top of another member, unless otherwise specified, the terms "on top" or "below" include both cases: one in which the other member is placed directly above or below the other member so as to be in contact with it, and another in which the other member is placed above or below the other member via yet another member. Similarly, when describing a configuration in this specification in which one member is placed on the surface of another member, unless otherwise specified, the terms "on the surface" or "on the surface" include both cases: one in which the other member is placed directly above or below the other member so as to be in contact with it, and another in which the other member is placed above or below the other member via yet another member.

[0016] The resin films, laminated films, packaging materials, packaging bags, and packaging bodies described herein will be explained in detail below.

[0017] A. Resin film The resin film in this disclosure is a resin film having a first resin layer and a second resin layer, wherein the first resin layer contains a hygroscopic agent, the second resin layer contains a polyolefin resin and a polymer-based antistatic agent, the second resin layer is located on the outermost surface, the second resin layer has a first region containing the polyolefin resin and a second region containing the polymer-based antistatic agent, the second region has a striated structure, and when one direction in the planar direction of the second resin layer is defined as the first direction, in a cross section parallel to the first direction and the thickness direction of the second resin layer, the ratio of the autocorrelation length in the first direction to the autocorrelation length in the thickness direction of the second resin layer is 4 or more in the striated structure.

[0018] Figure 1 is a schematic cross-sectional view illustrating a resin film in this disclosure. As shown in Figure 1, the resin film 10 has a first resin layer 1 containing a hygroscopic agent and a second resin layer 2 containing a polyolefin resin and a polymer-based antistatic agent, with the second resin layer 2 located on the outermost surface.

[0019] Figure 2 is a schematic cross-sectional view illustrating a second resin layer in this disclosure. In the second resin layer 2, the polyolefin resin and the polymer antistatic agent are in phase separation, and the second resin layer 2 has a first region 11 containing the polyolefin resin and a second region 12 containing the polymer antistatic agent, the second region 12 having a striated structure. When the planar direction of the second resin layer 2 is defined as the first direction D1, in a cross-section parallel to the first direction D1 and the thickness direction Dt of the second resin layer, the ratio L1 / L2 of the autocorrelation length L1 in the first direction D1 to the autocorrelation length L2 in the thickness direction Dt of the second resin layer 2 is greater than or equal to a predetermined value.

[0020] In image processing, autocorrelation is a measure of how well an image matches an image with its own coordinates shifted. Simply put, the autocorrelation function finds the area where an image overlaps with an image with its own coordinates shifted. A larger overlap results in a higher autocorrelation. Conversely, a smaller overlap results in a lower autocorrelation.

[0021] For example, consider the case where the second region 12 has a striated structure, as shown in Figure 2. When the image is shifted in the first direction D1, the overlapping area is large, and the shape does not change unless the amount of shift is large, so the autocorrelation function does not decay easily. On the other hand, when the image is shifted in the thickness direction Dt of the second resin layer 2, the overlapping area is small, and the shape changes significantly even with a small amount of shift, so the autocorrelation function decays quickly.

[0022] The autocorrelation length L1 in the first direction D1 is the longest distance in the first direction D1 ± 30° where, when the image of the cross-section parallel to the first direction D1 and the thickness direction Dt of the second resin layer 2 is shifted in the first direction D1 ± 30°, and the maximum value of the autocorrelation function is set to 1, the autocorrelation function decays and "falls below" the specified value s (s=0.8) for the first time. As described above, when the image is shifted in the first direction D1, the overlapping portion is large, and the shape does not change unless the amount of shift is large, so the autocorrelation function does not decay easily. For this reason, the autocorrelation length L1 in the first direction D1 is relatively large. Also, the longer the length of the striated structure in the second region 12, the larger the autocorrelation length L1 in the first direction D1 becomes.

[0023] The autocorrelation length L2 in the thickness direction Dt of the second resin layer 2 is the longest distance in the thickness direction Dt ± 30° at which the autocorrelation function decays to the point where it "first falls below" the specified value s (s=0.8) when the image of the cross-section parallel to the first direction D1 and the thickness direction Dt of the second resin layer is shifted in the thickness direction Dt ± 30°, with the maximum value of the autocorrelation function being set to 1. As described above, when the image is shifted in the thickness direction Dt, the overlapping area is small, and even a small amount of shift causes a large change in shape, so the autocorrelation function decays quickly. For this reason, the autocorrelation length L2 in the thickness direction Dt of the second resin layer 2 is relatively small.

[0024] As described above, the longer the length of the striated structure in the second region 12, the larger the autocorrelation length L1 in the first direction D1. Therefore, the longer the length of the striated structure in the second region 12, the larger the ratio L1 / L2 of the autocorrelation length L1 in the first direction D1 to the autocorrelation length L2 in the thickness direction Dt of the second resin layer 2.

[0025] In this disclosure, the ratio L1 / L2 of the autocorrelation length L1 in the first direction D1 to the autocorrelation length L2 in the thickness direction Dt of the second resin layer 2 is greater than or equal to a predetermined value and is relatively large. Therefore, it can be said that the length of the striated structure in the second region 12 is relatively long. Since the second region 12 is a region containing a polymer-based antistatic agent, it is thought that conductive paths are easily formed due to the relatively long length of the striated structure in the second region 12. Thus, the antistatic properties can be improved.

[0026] Furthermore, low-molecular-weight antistatic agents, such as surfactants, may lose their antistatic properties when used in combination with hygroscopic agents. In contrast, this disclosure uses polymer-based antistatic agents. Polymer-based antistatic agents can maintain both hygroscopic and antistatic properties without losing their antistatic properties, even when used in combination with hygroscopic agents.

[0027] The composition of the resin film in this disclosure will be described below.

[0028] 1.Second resin layer In the resin film of this disclosure, the second resin layer is located on the outermost surface. The second resin layer contains a polyolefin resin and a polymer-based antistatic agent, and has a first region containing the polyolefin resin and a second region containing the polymer-based antistatic agent, the second region having a striated structure.

[0029] (1) Area 1 and Area 2 In the second resin layer of this disclosure, the polyolefin resin and the polymer-based antistatic agent are in phase separation, and the second resin layer has a first region containing the polyolefin resin and a second region containing the polymer-based antistatic agent, the second region having a striated structure. Specifically, the first region containing the polyolefin resin is a continuous phase, and the second region containing the polymer-based antistatic agent exists in a striated manner within the first region containing the polyolefin resin.

[0030] In this disclosure, when the planar direction of the second resin layer is defined as the first direction D1, in a cross section parallel to the first direction D1 and the thickness direction Dt of the second resin layer, the ratio L1 / L2 of the autocorrelation length L1 in the first direction D1 to the autocorrelation length L2 in the thickness direction Dt of the second resin layer is 4 or more, may be 5 or more, may be 7 or more, or may be 10 or more. As described above, when L1 / L2 is relatively large within the above range, the length of the striated structure of the second region 12 containing the polymer-based antistatic agent is relatively long. Therefore, conductive paths are more easily formed, and antistatic properties can be improved. On the other hand, L1 / L2 may be, for example, 20 or less, 15 or less, or 12 or less. By keeping L1 / L2 below a predetermined value, the decrease in heat sealability due to the second region can be suppressed. Specifically, L1 / L2 may be between 4 and 20, between 4 and 15, between 5 and 15, or between 5 and 12.

[0031] Figure 3 is a schematic cross-sectional view illustrating the second resin layer in this disclosure. For example, as shown in Figure 2, when the second region 12 has a striated structure, and the second region 12 is present in a striated manner along the first direction D1, the striated structure of the second region 12 should be difficult to observe in the second direction D2, which is perpendicular to the first direction D2, as shown in Figure 3.

[0032] Therefore, when the second direction D2 is defined as the direction perpendicular to the first direction D1 in the planar direction of the second resin layer, in a cross section parallel to the second direction D2 and the thickness direction Dt of the second resin layer, the ratio L3 / L4 of the autocorrelation length L3 in the second direction D2 to the autocorrelation length L4 in the thickness direction Dt of the second resin layer is preferably 2 or less, may be 1.5 or less, or 1.2 or less. A relatively small L3 / L4 within the above range makes it easier for the second region to form a striated structure. On the other hand, the lower limit of L3 / L4 is not particularly limited, but may be 0.5 or more, 0.7 or more, or 0.9 or more. By having L3 / L4 above a predetermined value, it is possible to suppress the thinning of the thickness of the striated structure in the second region 12 and to suppress the difficulty in forming conductive paths in the three-dimensional direction. As a result, deterioration of antistatic properties can be suppressed. Specifically, L3 / L4 may be between 0.5 and 2, between 0.7 and 1.5, or between 0.9 and 1.2.

[0033] Furthermore, the ratio of L1 / L2 to L3 / L4 ([L1 / L2] / [L3 / L4]) is preferably 4 or greater, but may also be 5 or greater, 7 or greater, or 10 or greater. As mentioned above, it is preferable that L1 / L2 be relatively large and L3 / L4 be relatively small. Therefore, when [L1 / L2] / [L3 / L4] is relatively large as in the above range, the second region tends to form a striated structure, and conductive paths are more easily formed. On the other hand, [L1 / L2] / [L3 / L4] may be, for example, 20 or less, 15 or less, or 12 or less. By keeping [L1 / L2] / [L3 / L4] below a predetermined value, the decrease in heat sealability due to the second region can be suppressed. Specifically, [L1 / L2] / [L3 / L4] may be 4 or more and 20 or less, 4 or more and 15 or less, 5 or more and 15 or less, or 5 or more and 12 or less.

[0034] The autocorrelation function is determined by first preparing a section of the resin film at a predetermined cross-section, then capturing an image of the predetermined cross-section using a scanning electron microscope (SEM), and finally using an image processing program on the obtained image.

[0035] Sections of the cross-section are prepared by the following method. First, the resin film is cut into strips, the resin film is embedded in resin, and the resin-embedded resin film is cut with an ultramicrotome to prepare sections of the desired cross-section. Staining may be performed to enhance the contrast between the first and second regions.

[0036] When acquiring SEM images, the observation conditions are as follows: acceleration voltage: 30.0kV, emission current: 10μA, WD: 8mm, detector: TE.

[0037] The autocorrelation function is determined by the following method. First, using an image processing program such as the OpenCV library in Python, the autocorrelation length is calculated according to the following procedure and input parameters in accordance with JIS B0681-2:2018. 1) Extract an 880-pixel square area from the measurement image, excluding the scale bar. 2) Use the equalizeHist function from the OpenCV library to equalize the contrast. 3) For each coordinate (x,y) of the image, the following autocorrelation function f ACF Calculate. The autocorrelation function is a measure of how well an image whose coordinates have been shifted matches the original image, and t x , t y These represent the amounts moved in the x and y directions, respectively.

[0038]

number

[0039] 4) When considering the movement of an image in a specific angle θ direction, t x , t y Each is t x =r·cosθ, t y = r·sinθ. The autocorrelation length in the θ direction is obtained when θ is fixed and r is increased, f ACF We define it as the smallest r for which the first time is less than 0.8, and let this be R(θ). 5) With the horizontal direction of the sample film surface defined as θ=0 degrees, the autocorrelation length R(θ) is calculated in 1-degree increments from θ=0 degrees to θ=360 degrees. 6) Smooth R(θ) using the Savitzky-Golay filter (order=1, filter size=15) from the scipy library. Replace the 15 points with linearly fitted points. 7) Of R(θ), the maximum value at 60° < θ < 120° is defined as the autocorrelation length in the Y-axis direction, and the maximum value at 150° < θ < 210° is defined as the autocorrelation length in the X-axis direction.

[0040] The autocorrelation function is measured twice, and the average of the two measurements is used.

[0041] The autocorrelation length L1 in the first direction D1 is the longest distance in the first direction D1±30° where, when the cross-sectional image of the second resin layer 2, parallel to the first direction D1 and the thickness direction Dt of the second resin layer 2, is shifted by the first direction D1±30°, the autocorrelation function, with its maximum value set to 1, decays and "falls below" the specified value s (s=0.8) for the first time.

[0042] The autocorrelation length L2 in the thickness direction Dt of the second resin layer 2 is the longest distance in the thickness direction Dt ± 30° at which the autocorrelation function decays and "falls below" the specified value s (s=0.8) for the first time, when the cross-sectional images of the second resin layer 2, which are parallel to the first direction D1 and the thickness direction Dt of the second resin layer, are shifted by Dt ± 30° in the thickness direction, with the maximum value of the autocorrelation function being set to 1.

[0043] The autocorrelation length L3 in the second direction D2 is the longest distance in the second direction D2 ± 30° at which, when the cross-sectional image of the second resin layer 2, parallel to the second direction D2 and the thickness direction Dt of the second resin layer 2, is shifted by the second direction D2 ± 30°, the autocorrelation function, with its maximum value set to 1, decays and "falls below" the specified value s (s=0.8) for the first time.

[0044] The autocorrelation length L4 in the thickness direction Dt of the second resin layer 2 is the longest distance in the thickness direction Dt ± 30° at which the autocorrelation function decays and "falls below" the specified value s (s=0.8) for the first time, when the cross-sectional image of the second resin layer 2, which is parallel to the second direction D2 and the thickness direction Dt of the second resin layer, is shifted by Dt ± 30° in the thickness direction, with the maximum value of the autocorrelation function being set to 1.

[0045] The first direction D1 is the planar direction of the second resin layer. When any direction in the planar direction of the second resin layer is set to θ1 = 0 degrees, the autocorrelation function is calculated for cross-sections parallel to the thickness direction Dt of the second resin layer in 1-degree increments from θ1 = 0 degrees to θ1 = 90 degrees. If L1 / L2 is 4 or more at any of the θ1 values, the result is included in this embodiment.

[0046] Methods for creating a striated structure in the second region and setting L1 / L2 to a predetermined value or higher include, for example, adjusting the MFR (melt mass flow rate) of the composition for the second resin layer used in forming the second resin layer, adjusting the MFR of the polyolefin resin, adjusting the melting point of the polyolefin resin, adjusting the molding method of the second resin layer, adjusting the molding conditions of the second resin layer, and adjusting the composition of the second resin layer. When the MFR of the composition for the second resin layer is large, the fluidity of the composition for the second resin layer improves, so the second region tends to form a striated structure and L1 / L2 tends to increase. When both the MFR of the polyolefin resin and the MFR of the second resin layer composition are large, and the MFR of the polyolefin resin is smaller than the MFR of the second resin layer composition, and the difference between the MFR of the polyolefin resin and the MFR of the second resin layer composition is small, the fluidity of the second resin layer composition and the fluidity of the polyolefin resin constituting the first region of the continuous phase improve, so the second region tends to form a striated structure and L1 / L2 tends to increase. When the fluidity of the second resin layer composition is good, and the melting point of the polyolefin resin is low, during melt molding, the fluidity of the second resin layer composition and the fluidity of the polyolefin resin constituting the first region of the continuous phase improve, so the second region tends to form a striated structure and L1 / L2 tends to increase. When the molding method for the second resin layer is extrusion molding, L1 / L2 tends to increase. If the molding temperature of the second resin layer is set to a temperature 20 degrees or more higher than the melting point of the composition for the second resin layer and the melting point of the polyolefin resin, sufficient fluidity can be obtained, making it easier to form a striated structure, and the L1 / L2 ratio tends to increase. Regarding the composition of the composition for the second resin layer, as will be described later, if the content of the polymer-based antistatic agent in the second resin layer is within a predetermined range, the L1 / L2 ratio tends to increase.

[0047] The second resin layer preferably has multiple striated structures in the second region. Furthermore, it is more preferable that the striated structures in the second region are located on the outermost surface of the second resin layer and inside the second resin layer. For example, if there is only one striated structure, and the striated structure in the second region is located on the outermost surface of the second resin layer, the antistatic performance will be sufficiently exhibited, but the sealing strength may decrease. On the other hand, if there is only one striated structure, and the striated structure in the second region is located inside the second resin layer, it is expected that the charge will not flow easily, and sufficient antistatic performance will not be exhibited. Therefore, by having multiple striated structures in the second region of the second resin layer, and by having multiple striated structures in the second region located on the outermost surface of the second resin layer and inside the second resin layer, both sealing performance and antistatic performance can be achieved.

[0048] (2) Material of the second resin layer The second resin layer contains a polyolefin resin and a polymer-based antistatic agent.

[0049] (a) Polyolefin resins Examples of polyolefin resins contained in the second resin layer include polyethylene resins and polypropylene resins.

[0050] The polyethylene-based resin may be a homopolymer of ethylene or a copolymer of ethylene and a monomer other than ethylene. The ethylene copolymer may be a copolymer of ethylene and an α-olefin. Examples of the α-olefin include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. The α-olefin may be used alone or in combination of two or more. Examples of the ethylene copolymer include ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, and ethylene-propylene copolymer. Examples of the polyethylene-based resin include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), etc. The polyethylene-based resin may be used alone or in combination of two or more.

[0051] The polypropylene-based resin may be a homopolymer of propylene or a copolymer of propylene and a monomer other than propylene. The propylene copolymer may be a copolymer of propylene and an α-olefin. Examples of the α-olefin include 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. The α-olefin may be used alone or in combination of two or more.

[0052] Among them, the polyethylene-based resin is preferred because of its excellent heat sealability. The polyethylene-based resin is preferably linear low-density polyethylene (LLDPE), more preferably linear low-density polyethylene (LLDPE) which is a copolymer of ethylene and an α-olefin, and even more preferably linear low-density polyethylene (LLDPE) which is a copolymer of ethylene and 1-hexene.

[0053] The density of the polyethylene-based resin is, for example, 0.880 g / cm 3 or more and 0.930 g / cm 3The following is preferable: When the density of the polyethylene resin is within the above range, it is easy to process and obtain sufficient heat sealability. The density of the polyethylene resin is measured by Method B: liquid pycnometer method in accordance with JIS K7112-1:2023.

[0054] The melt mass flow rate (MFR) of the polyethylene resin may be, for example, 0.5 g / 10 min to 20 g / 10 min, 1 g / 10 min to 10 g / 10 min, or 1.2 g / 10 min to 5 g / 10 min. Good film-forming and adhesive properties can be obtained if the MFR of the polyethylene resin is within the above range. Furthermore, by adjusting the MFR of the polyethylene resin within the above range, phase separation between the polyethylene resin and the polymer-based antistatic agent can be controlled, making it easier to form a second region of the striated structure containing the polymer-based antistatic agent.

[0055] The MFR of polyethylene resins shall be measured in accordance with Method A of JIS K7210-1:2014. The measurement conditions shall be a temperature of 190°C and a load of 2.16 kg.

[0056] The melting point of the polyethylene resin may be, for example, 80°C to 130°C, 85°C to 125°C, or 90°C to 110°C. If the melting point of the polyethylene resin is within the above range, good film-forming properties and adhesive properties can be obtained. Furthermore, by adjusting the melting point of the polyethylene resin within the above range, the phase separation between the polyethylene resin and the polymer-based antistatic agent can be controlled, making it easier to form a second region of the striated structure containing the polymer-based antistatic agent.

[0057] The melting point of polyethylene resins is measured in accordance with JIS K7121:2012 by input-compensated differential scanning calorimetry (input-compensated DSC), and the melting peak temperature (Tpm) is defined as the melting point.

[0058] The second resin layer contains polyethylene resin as its main component. The main component is the component that is present in the largest quantity in the second resin layer. The polyethylene resin content in the second resin layer is preferably 60% by mass or more and 95% by mass or less, and more preferably 70% by mass or more and 85% by mass or less.

[0059] (b) Polymer-based antistatic agents Any of the following polymer-based antistatic agents can be used: anionic antistatic agents, cationic antistatic agents, amphoteric antistatic agents, and nonionic antistatic agents.

[0060] Anionic antistatic agents are polymer-based antistatic agents that form anions when dissolved in water. Examples include antistatic agents containing compounds having anionic groups such as sulfonic acid bases, sulfate ester bases, phosphate ester bases, and phosphonic acid bases. Anionic antistatic agents may be polymer compounds that form cations, or they may be polymer compounds to which anion-forming additives have been added.

[0061] Cationic antistatic agents are polymeric antistatic agents that form cations when dissolved in water. Examples include antistatic agents containing compounds having cationic groups such as quaternary ammonium salts, pyridinium salts, and primary to tertiary amino groups. Cationic antistatic agents may be polymeric compounds that form cations, or they may be polymeric compounds to which cation-forming additives have been added.

[0062] Amphoteric antistatic agents are polymer-based antistatic agents that, when dissolved in water, form anions in alkaline environments and cations in acidic environments. Examples include amino acid-based and aminosulfate ester-based antistatic agents.

[0063] Nonionic antistatic agents are polymer-based antistatic agents that do not ionize when dissolved in water. Examples include amino alcohol-based, glycerin-based, polyethylene glycol-based, polyether ester amide type, polyether ester type, polyethylene glycol methacrylate copolymer, and ethylene oxide-epichlorohydrin type antistatic agents.

[0064] In particular, polymer-based antistatic agents are preferably anionic, cationic, or nonionic antistatic agents, with nonionic antistatic agents being more preferred. In the case of nonionic antistatic agents, the elution of ionic components can be suppressed.

[0065] Nonionic antistatic agents preferably contain polyethylene oxide chains, and more preferably are hydrophilic polymers with polyethylene oxide chains as conductive units. In particular, nonionic antistatic agents preferably contain at least one selected from the group consisting of polyether ester amides, polyether esters, and polyethylene glycol methacrylate copolymers, because this facilitates the formation of the second region of the striated structure.

[0066] The content of the polymer-based antistatic agent in the second resin layer is preferably 10% by mass or more, more preferably 12% by mass or more, and even more preferably 15% by mass or more. When the content of the polymer-based antistatic agent is 15% by mass or more, the dispersion of the polymer-based antistatic agent into the polyolefin resin before it can form a striated structure is suppressed, and the L1 / L2 ratio tends to increase, resulting in good antistatic properties. On the other hand, the content of the polymer-based antistatic agent in the second resin layer is preferably 50% by mass or less, more preferably 49% by mass or less, even more preferably 45% by mass or less, and particularly preferably 35% by mass or less. When the content of the polymer-based antistatic agent is within the above range, it is possible to suppress a decrease in seal strength while maintaining antistatic properties. Specifically, the content of the polymer-based antistatic agent in the second resin layer is preferably 10% to 50% by mass, preferably 10% to 49% by mass, more preferably 12% to 45% by mass, and even more preferably 15% to 35% by mass. If the content of the polymer-based antistatic agent is within the above range, sufficient antistatic properties, as well as good film-forming properties and heat-sealing properties can be obtained.

[0067] The antistatic agent may be directly mixed and melt-kneaded with the polyolefin resin, but it is preferable to first mix the antistatic agent with a thermoplastic resin at a high concentration, then melt-knead (melt blend) to prepare a masterbatch, and then mix and melt-knead this masterbatch with the polyolefin resin. This so-called masterbatch method improves the dispersibility of the polymer-based antistatic agent in the second resin layer. By adopting the masterbatch method, even when using polymer-based antistatic agents that are prone to aggregation, the polymer-based antistatic agent can be efficiently and homogeneously dispersed in the second resin layer. Furthermore, using a masterbatch allows for stable mixing of the polyolefin resin and the antistatic agent.

[0068] Any thermoplastic resin can be used as the masterbatch, as long as it does not significantly affect the heat sealability, film-forming properties, and hygroscopicity of the entire resin film. In particular, a resin that has high compatibility with the above-mentioned polyolefin resin and has a similar density and heat sealability is preferred, and may be the same as or different from the above-mentioned polyolefin resin. Examples of thermoplastic resins used in the masterbatch include polyolefin resins such as polyethylene, polypropylene, methylpentene polymer, and acid-modified polyolefin resins. These may be used individually or as a mixture of two or more.

[0069] The mass ratio of antistatic agent to thermoplastic resin in the masterbatch is not particularly limited, but is preferably 20 / 80 or more and 80 / 20 or less, and more preferably 30 / 70 or more and 70 / 30 or less. Known or conventional mixing methods can be applied to mix the antistatic agent and the thermoplastic resin.

[0070] (c) Other ingredients The second resin layer may contain a desiccant, to the extent that it does not impair antistatic properties and heat sealability. The desiccant is the same as that described in the section on the first resin layer below.

[0071] Furthermore, the second resin layer may contain other resins or additives, provided that they do not impair the antistatic properties and heat sealability. Examples of additives include antiblocking agents, slip agents, and antioxidants.

[0072] Antiblocking agents can enhance the blocking resistance of resin films. Zeolites, spherical silica, needle-shaped silica, talc, PMMA, and the like are preferably used as antiblocking agents. The content of the antiblocking agent in the second resin layer is preferably, for example, 0.1% to 5.0% by mass, and more preferably 0.5% to 2.0% by mass. Sufficient blocking resistance can be obtained if the antiblocking agent content is within the above range.

[0073] (3) Other aspects of the second resin layer The thickness of the second resin layer is preferably, for example, 3 μm to 40 μm, more preferably 5 μm to 30 μm, and even more preferably 8 μm to 20 μm. If the thickness of the second resin layer is within the above range, sufficient antistatic properties and good heat sealability can be obtained.

[0074] 2.First resin layer The first resin layer in this disclosure contains a resin and a desiccant.

[0075] (1) Material of the first resin layer (a) Desiccant The desiccant is not particularly limited, and for example, both inorganic and organic desiccant can be used. The desiccant may be used alone or in combination of two or more types.

[0076] The inorganic desiccant is not particularly limited, and general desiccants can be used, such as oxides, metal salts, clay-based desiccants, hydrotalcite, activated carbon, and metal-organic frameworks (MOFs). Examples of oxides include alumina, calcium oxide, magnesium oxide, barium oxide, zeolite, and silica gel. Examples of metal salts include calcium chloride, magnesium chloride, magnesium sulfate, copper sulfate, and calcium carbonate. Examples of clay-based desiccants include bentonite and montmorillonite. These may be in hydrated or anhydrous form.

[0077] Examples of organic desiccants include superabsorbent polymers (SAPs). Examples of superabsorbent polymers include cellulose-based superabsorbent polymers, polyvinyl alcohol-based superabsorbent polymers, and (meth)acrylic acid-based superabsorbent polymers.

[0078] Among these, inorganic desiccants are preferred because they have good thermal and chemical stability. The inorganic desiccant is preferably at least one selected from the group consisting of calcium oxide, magnesium oxide, hydrophilic zeolite, calcium chloride, magnesium chloride, clay-based desiccants, hydrotalcite, activated carbon, and metal-organic frameworks (MOFs).

[0079] Hydrophilic zeolites can be preferably used because their hygroscopic effect is maintained even when exposed to temperatures above 230°C. Due to their hydrophilic nature, hydrophilic zeolites readily adsorb highly polar water molecules and other substances, while having low affinity for low-polarity organic gases, as well as other low-polarity gas components, hydrophobic gases, and lipophilic gases (including solvent-based gases), making them difficult to adsorb. In other words, they excel in their ability to not adsorb gas components that do not have functional groups.

[0080] The desiccant can take any shape, such as spherical, rod-shaped, or elliptical. The desiccant may also be in powder, lump, or granular form, but a powder form is preferred from the viewpoint of uniform dispersibility in the resin, kneading characteristics, and film-forming properties.

[0081] The average particle size of the desiccant is appropriately selected depending on the application, but is preferably 0.01 μm to 15 μm, and more preferably 1 μm to 12 μm. When the average particle size of the desiccant is above a predetermined value, aggregation of the desiccant is less likely to occur, and dispersibility is improved. Furthermore, when the average particle size of the desiccant is below a predetermined value, film-forming properties are improved, and sufficient hygroscopicity is obtained.

[0082] The average particle size of the desiccant is defined as the average value of 20 desiccant particles observed by transmission electron microscope (TEM) images of the cross-section of the first resin layer.

[0083] In the case of inorganic desiccants, the D50 of the desiccant is appropriately selected depending on the application, but is preferably 0.01 μm to 15 μm, and more preferably 1 μm to 12 μm. When the D50 of the desiccant is above a predetermined value, aggregation of the desiccant is less likely to occur and dispersibility improves. Conversely, when the D50 of the desiccant is below a predetermined value, film-forming properties improve and sufficient hygroscopicity is obtained.

[0084] D50 represents the median of the particle size distribution. The D50 of a desiccant is measured by laser diffraction. To measure the D50 of a desiccant, the first resin layer is taken from the resin film, and then the first resin layer is calcined to remove the resin components and separate the desiccant. Ethanol, for example, can be used as the dispersion medium when measuring D50.

[0085] The desiccant may be directly mixed and melt-blended with other components, but it is preferable to first mix the desiccant with a thermoplastic resin at a high concentration, then melt-blend it to create a masterbatch, and then mix and melt-blend this masterbatch with other components. This so-called masterbatch method improves the dispersibility of the desiccant in the first resin layer. By adopting the masterbatch method, even when using a desiccant that is prone to aggregation, the desiccant can be efficiently and homogeneously dispersed in the first resin layer.

[0086] Any thermoplastic resin can be used for the masterbatch, as long as it does not significantly affect the heat sealability, film-forming properties, and hygroscopicity of the entire resin film. In particular, a resin that has high compatibility with other resins such as polyolefin resins contained in the first resin layer and has a similar density and heat sealability is preferred, and it may be the same as or different from these other resins. Examples of thermoplastic resins used for the masterbatch include polyolefin resins such as polyethylene, polypropylene, methylpentene polymer, and acid-modified polyolefin resins. These may be used individually or as a mixture of two or more.

[0087] The MFR of the thermoplastic resin used in the masterbatch is preferably, for example, 0.2 g / 10 min or more and 10 g / 10 min or less. If the MFR of the thermoplastic resin is within the above range, melt mixing with the desiccant is easy, the desiccant is easily dispersed in the first resin layer, and the film-forming properties of the first resin layer are easily maintained.

[0088] The mass ratio of the desiccant / thermoplastic resin in the masterbatch is not particularly limited, but is preferably 20 / 80 or more and 90 / 10 or less, and more preferably 30 / 70 or more and 80 / 20 or less. Known or conventional mixing methods can be applied as the method for mixing the desiccant and thermoplastic resin.

[0089] The content of the desiccant in the first resin layer is preferably, for example, 10% by mass or more and 60% by mass or less, and more preferably 30% by mass or more and 50% by mass or less. If the content of the desiccant is within the above range, sufficient hygroscopicity can be obtained, as well as good film-forming properties, adhesion, and heat-sealing properties.

[0090] (b) Resin The first resin layer contains a resin that disperses a desiccant. Examples of the resin include thermoplastic resins. Among these, polyolefin resins are preferred, and polyethylene resins are more preferred. The details regarding polyolefin resins and polyethylene resins are the same as those described in the section on the second resin layer above.

[0091] The polyolefin resin contained in the first resin layer and the polyolefin resin contained in the second resin layer may be the same or different. Furthermore, the polyethylene resin contained in the first resin layer and the polyethylene resin contained in the second resin layer may be the same or different.

[0092] In the first resin layer, the lower the density of the polyolefin resin and the thinner the thickness of the second resin layer, the faster moisture can be absorbed.

[0093] The content of polyolefin resin in the first resin layer is preferably 40% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 70% by mass or less. If the content of polyolefin resin is within the above range, sufficient strength can be obtained and the content of the desiccant can be ensured.

[0094] (c) Other ingredients The first resin layer may contain an antistatic agent, to the extent that it does not impair hygroscopicity. The antistatic agent is preferably a polymer-based antistatic agent. The details regarding the polymer-based antistatic agent are the same as those described in the section on the second resin layer above.

[0095] Furthermore, the first resin layer may contain additives, provided that they do not impair its hygroscopic properties. Examples of additives include antiblocking agents, slip agents, and antioxidants. The antiblocking agents are the same as those described in the section on the second resin layer above.

[0096] (2) Other aspects of the first resin layer The thickness of the first resin layer is preferably 5 μm to 55 μm, more preferably 10 μm to 50 μm, and even more preferably 20 μm to 45 μm, in order to exhibit good hygroscopic properties.

[0097] 3.Third resin layer The resin film in this disclosure may have a third resin layer 3 on the side of the first resin layer 1 opposite to the second resin layer 2, as shown in Figure 4, for example.

[0098] Examples of resins contained in the third resin layer include thermoplastic resins. Among these, polyolefin resins are preferred, and polyethylene resins are more preferred. The details regarding polyolefin resins and polyethylene resins are the same as those described in the section on the second resin layer above.

[0099] The polyolefin resin contained in the third resin layer and the polyolefin resin contained in the second resin layer may be the same or different. Furthermore, the polyethylene resin contained in the third resin layer and the polyethylene resin contained in the second resin layer may be the same or different.

[0100] The third resin layer may contain an antistatic agent, to the extent that it does not impair the heat sealability. The antistatic agent is preferably a polymer-based antistatic agent. The details regarding the polymer-based antistatic agent are the same as those described in the section on the second resin layer above.

[0101] Furthermore, the third resin layer may contain additives, provided that they do not impair the heat sealability. Examples of additives include antiblocking agents, slip agents, and antioxidants. The antiblocking agents are the same as those described in the section on the second resin layer above.

[0102] The thickness of the third resin layer is preferably 3 μm to 40 μm, more preferably 5 μm to 30 μm, and even more preferably 8 μm to 25 μm, in order to have a good balance of adhesion, heat sealability, and rigidity. If the thickness of the third resin layer is within the above range, sufficient adhesion and heat sealability can be obtained while preventing the rigidity from becoming too high.

[0103] 4.Adhesive layer In the resin film of this disclosure, each layer may be laminated with an adhesive layer in between.

[0104] The adhesive (adhesive composition) used in the adhesive layer may be thermosetting, ultraviolet curing, or electron beam curing, and may be aqueous, solution, emulsion, or dispersion type. Furthermore, its properties may be in the form of a film, sheet, powder, or solid. The bonding mechanism may be a chemical reaction, solvent evaporation, thermal melting, or hot-pressure bonding.

[0105] Examples of adhesives include polyvinyl acetate adhesives such as polyvinyl acetate and vinyl acetate-ethylene copolymers, polyacrylic acid adhesives consisting of copolymers of polyacrylic acid and polystyrene, polyester, polyvinyl acetate, etc., cyanoacrylate adhesives, ethylene copolymer adhesives consisting of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, and methacrylic acid, polyurethane adhesives, polyester adhesives, polyimide adhesives, polyolefin adhesives, amino resin adhesives consisting of urea resin or melamine resin, phenolic resin adhesives, epoxy adhesives, reactive (meth)acrylic adhesives, elastomer adhesives consisting of chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc., silicone adhesives, and inorganic adhesives consisting of alkali metal silicates, low-melting-point glass, etc. Among these, polyurethane adhesives are preferred.

[0106] The adhesive layer may be made of any of the following: a dry laminating adhesive, a non-solvent laminating adhesive, or the like.

[0107] Furthermore, the adhesive layer may be formed by sand lamination. First, a thermoplastic resin is heated and melted, then expanded and stretched in the required width direction using a T-die or the like to extrude it in a curtain-like shape, and allowed to flow down onto the layer to be bonded. By sandwiching it between a rubber roll and a cooled metal roll, the adhesive layer is formed, and adhesion and lamination to the layer to be bonded are performed simultaneously. In this case, any resin that can be heated and melted and applied in an extruder can be used for the adhesive layer. Specifically, the resins listed above as thermoplastic resins having heat-sealing properties can be preferably used.

[0108] When using a dry laminating adhesive, the adhesive, dispersed or dissolved in a solvent, is applied to one film and allowed to dry. After layering the other film on top, the adhesive is cured and bonded by aging at a temperature between 30°C and 120°C for several hours to several days, allowing the films to be laminated.

[0109] When using a non-solvent laminate adhesive, the adhesive itself is applied to the layer to be bonded without dispersion or dissolution in a solvent, dried, and then the film forming the other layer is layered on top. Finally, the adhesive is cured by aging at 30°C to 120°C for several hours to several days to complete the lamination.

[0110] Adhesives for dry lamination or non-solvent lamination can be applied using, for example, roll coating, gravure roll coating, or kiss coating. The application amount is, for example, 0.1 g / m² in a dry state. 2 More than 10g / m 2 The following is preferable: Good adhesion is obtained.

[0111] 5. Anchor Coat Layer In the resin film of this disclosure, an anchor coat layer may be placed at the interface between each layer and the adhesive layer in order to improve adhesion.

[0112] Any anchor coating agent can be used as the anchor coating layer. Examples of anchor coating agents include organic titanium-based, isocyanate (urethane-based), polyethyleneimine-based, acid-modified polyethylene-based, polybutadiene-based, polyacrylic-based, polyester-based, epoxy-based, polyvinyl acetate-based, and others.

[0113] 6. Physical properties of resin films The surface resistivity of the second resin layer surface of the resin film in this disclosure is 1 × 10⁻⁶ 7 Ω / □ or more 1×10 12 Preferably, Ω / □ is less than or equal to 1 × 10 8 Ω / □ or more 1×10 11 A value less than Ω / □ is preferable. If the surface resistivity is within the above range, sufficient static protection can be obtained. In addition, a decrease in heat sealability and an increase in cost can be suppressed.

[0114] When the resin film in this disclosure is used, for example, as a packaging material for electronic components, it is preferable that it has a low content of eluting ions in order to suppress ionic contamination of the electronic components. Specifically, Li in the resin film + na + , K + Mg 2+ Ca 2+ NH4 + F - Cl - , NO 2 - , Br - NO3 - SO4 2- and PO4 2- The content of each ion is preferably 100 ppb or less, and more preferably 50 ppb or less.

[0115] The content of elutable ions in the resin film is measured by the following method. First, the resin film is cut into 10cm x 20cm pieces, folded in half, and heat-sealed on three sides to create small pouches, and the weight of the pouches is measured. Next, 100mL of ultrapure water is placed in the pouches and heat-sealed. The heat-seal width is 2cm. The pouches containing the ultrapure water are rotated 20 times to allow the ultrapure water to permeate the entire pouch and to dissolve the ionic components to obtain a sample solution. 5mL of this sample solution is taken, and the concentration of each ion in the sample solution is measured using ion chromatography, and the content of each ion in the resin film is calculated.

[0116] Regarding the hygroscopicity of the resin film in this disclosure, the amount of moisture absorbed after being left standing for 11 days in an environment of 40°C and 90% RH was 1 g / m². 2 More than 15g / m 2 The following is preferable: 2 g / m 2 More than 10g / m 2 The following is more preferable: If the amount of moisture absorbed is above a predetermined value, the packaged items can be sufficiently dried. Also, if the amount of moisture absorbed is below a predetermined value, it is possible to prevent the amount of desiccant from becoming excessive, thereby suppressing a decrease in seal strength and an increase in costs.

[0117] 7. Method for manufacturing resin film The film formation and lamination of each layer constituting the resin film are not particularly limited, and known or conventional film formation and lamination methods can be applied. For example, any method such as wet lamination, dry lamination, solvent-free dry lamination, extrusion lamination, T-die co-extrusion molding, co-extrusion lamination, inflation lamination, and others can be used.

[0118] Resin films can also be subjected to secondary processing to impart various surface functions such as chemical, electrical, magnetic, mechanical, friction / abrasion / lubrication, optical, thermal, and biocompatibility. Examples of secondary processing include embossing, painting, bonding, printing, metallizing (plating, etc.), machining, and surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.).

[0119] B. Laminated film The laminated film in this disclosure is a laminated film having a barrier substrate layer and the resin film described above, wherein the second resin layer of the resin film is located on the outermost surface.

[0120] Figure 5 is a schematic cross-sectional view illustrating a laminated film in this disclosure. As shown in Figure 5, the laminated film 20 has a barrier substrate layer 21 and a resin film 10, with the second resin layer 2 of the resin film 10 located on the outermost surface. In Figure 5, the substrate layer 21 has a base layer 22 and a barrier layer 23.

[0121] The following describes the various components of the laminated film in this disclosure.

[0122] 1. Resin film The resin film is the same as described in section "A. Resin Film" above. In the laminated film of this disclosure, the second resin layer of the resin film is located on the outermost surface.

[0123] 2.Base material layer The substrate layer in this disclosure has barrier properties. The substrate layer may consist of a single layer such as a barrier resin film having barrier properties and self-supporting properties, or it may be a multilayer structure including a substrate layer and a barrier layer. In particular, it is preferable that the substrate layer has a substrate layer and a barrier layer.

[0124] The thickness of the base layer is preferably, for example, 5 μm to 50 μm, and more preferably 7 μm to 25 μm. If the thickness of the base layer is above the predetermined value, sufficient rigidity and barrier properties can be obtained. If the thickness of the base layer is below the predetermined value, workability can be improved.

[0125] (1) Substrate layer For example, a resin substrate or a paper substrate can be used as the base layer. The base layer may consist of a single layer, or it may be a multilayer structure including two or more layers with the same or different compositions.

[0126] As the resin substrate, a film made of thermoplastic resin can be used. Preferably, the resin substrate is a thermoplastic resin film that has excellent chemical or physical strength, can withstand the conditions for forming a metal or metal oxide vapor-deposited film as a barrier layer, and can maintain the properties of those vapor-deposited films well without impairing them.

[0127] Examples of resins used in resin substrates include polyolefin resins such as polyethylene resins and polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), poly(meth)acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, polyurethane resins, acetal resins, and polyamide resins. Among these, polyester resins and polyolefin resins are preferred, and polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polypropylene (PP) are particularly preferred.

[0128] Various additives can be added to the resin substrate for the purpose of improving or modifying properties such as processability, heat resistance, weather resistance, mechanical properties, dimensional stability, oxidation resistance, slipperiness, release properties, flame retardancy, mold resistance, electrical properties, and strength. Examples of additives include lubricants, crosslinking agents, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins. The content of additives in the resin substrate can be arbitrarily adjusted from trace amounts to tens of percent by mass, depending on the purpose.

[0129] The thickness of the substrate layer varies depending on the material. The thickness of the resin substrate is preferably 5 μm to 50 μm, and more preferably 10 μm to 30 μm.

[0130] Thermoplastic resins used in resin substrates can be formed into films using various film-forming methods. For example, a film can be formed using one type of resin with film-forming methods such as extrusion, casting, T-die, cutting, or inflation; a multilayer co-extrusion film can be formed using two or more types of resins; and two or more types of resins can be mixed before film formation and then formed using the above film-forming methods. Furthermore, films can be formed by stretching in one or two axes using methods such as the tenter method or tubular method. In addition, one or more types of resins can be applied to other resin substrates and dried to form laminates, or molten resins can be laminated using methods such as the T-die method.

[0131] The resin substrate is preferably a polyester film, polyamide film, or polyolefin film, and more preferably a biaxially oriented PET film, biaxially oriented PBT film, biaxially oriented polyamide film, or biaxially oriented PP film.

[0132] (2) Barrier layer The barrier layer may be an inorganic film or an organic film. Examples of inorganic films include metal foils and vapor-deposited films containing metal or metal oxides. Examples of organic films include barrier resin films and coatings containing barrier resins. The barrier layer may also be a laminate having a resin substrate and a vapor-deposited film containing metal or metal oxides. Furthermore, the barrier layer may have one or more of the above-mentioned inorganic films, organic films, and laminates.

[0133] Aluminum foil is preferably used as the metal foil. The thickness of the metal foil is preferably, for example, 3 μm to 15 μm.

[0134] Examples of vapor-deposited films containing metal or metal oxide include aluminum vapor-deposited films, silica vapor-deposited films, and aluminum oxide vapor-deposited films.

[0135] As the barrier resin film, any resin film having barrier properties can be used. Preferably, the barrier resin film is made of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, or polyimide.

[0136] As a barrier resin coating, a coating containing a sol-gel hydrolyzed polycondensate formed from a metal alkoxide and a water-soluble polymer is preferred.

[0137] In a laminate having a resin substrate and a vapor-deposited film containing a metal or metal oxide, the vapor-deposited film containing the metal or metal oxide is the same as the vapor-deposited film described above. Examples of the resin substrate include polyethylene terephthalate film. The laminate can be bonded to other layers using a dry laminate adhesive. Alternatively, the substrate layer described above may be used as the resin substrate of the laminate.

[0138] (3) Surface layer The barrier substrate layer may have a surface layer containing an antistatic agent on the outermost surface opposite to the resin film. This can suppress quality deterioration during packaging due to static electricity generation. In Figure 6, the substrate layer 21 has a barrier layer 23, a base layer 22, and a surface layer 24 in that order from the resin film 10 side, with the surface layer 24 located on the outermost surface of the substrate layer 21 opposite to the resin film 10.

[0139] The surface layer preferably contains a resin and an antistatic agent, more preferably a conductive polymer or metal oxide as the antistatic agent, and even more preferably a conductive polymer as the antistatic agent. In other words, the surface layer preferably contains a resin and a conductive polymer or metal oxide, and more preferably a resin and a conductive polymer.

[0140] (a) resin The resin is not particularly limited, but it is preferably a highly polar resin, i.e., a water-based resin. Specifically, acrylic resins, epoxy resins, polyester resins, or urethane resins are preferred.

[0141] Examples of acrylic resins include acrylic resins obtained by polymerizing one type of monomer containing a hydroxyl group, monomer containing an amide group, monomer containing a carboxyl group, or other monomers, or by copolymerizing two or more types, and crosslinked acrylic resins obtained by crosslinking these resins with a crosslinking agent. Examples of monomers containing a hydroxyl group include 2-hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate. Examples of monomers containing an amide group include acrylamide and N-methylolacrylamide. Examples of monomers containing a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, and maleic anhydride. Examples of other monomers include methyl acrylate, ethyl acrylate, N-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate. Examples of crosslinking agents include melamine-based crosslinking agents, urea-based crosslinking agents, epoxy-based crosslinking agents, isocyanate-based crosslinking agents, aziridine-based crosslinking agents, ethyleneimine-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, and silane coupling agents. In particular, from the viewpoint of mechanical properties, water resistance, and adhesion, acrylic resins having carboxyl groups, or crosslinked acrylic resins in which acrylic resins having carboxyl groups are crosslinked with aziridine-based crosslinking agents, are preferred. Acrylic resins may be used individually or in combination of two or more types.

[0142] Examples of epoxy resins include bixylenol-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AF-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol novolac-type epoxy resin, phenol novolac-type epoxy resin, tert-butyl-catechol-type epoxy resin, naphthalene-type epoxy resin, naphthol-type epoxy resin, anthracene-type epoxy resin, glycidylamine-type epoxy resin, glycidyl ester-type epoxy resin, cresol novolac-type epoxy resin, biphenyl-type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro-ring-containing epoxy resin, cyclohexanedimethanol-type epoxy resin, naphthylene ether-type epoxy resin, trimethylol-type epoxy resin, and tetraphenylethane-type epoxy resin. Epoxy resins may be used individually or in combination of two or more types.

[0143] Polyester resins are composed of a polycarboxylic acid component and a polyol component. The polycarboxylic acid component includes at least one of aromatic dicarboxylic acids and aliphatic dicarboxylic acids. The aromatic dicarboxylic acid includes, for example, at least one component selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid, diphenic acid, naphthalic acid, 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. The aliphatic dicarboxylic acid may be linear, branched, or alicyclic. Aliphatic dicarboxylic acids include, for example, at least one component selected from the group consisting of oxalic acid, malonic acid, succinic acid, maleic acid, itaconic acid, glutaric acid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, diglycolic acid, and thiodipropionic acid. Polyol components include, for example, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2,2,4-trimethyl-1,6-hexanediol, It contains at least one component selected from the group consisting of 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-dihydroxybiphenol, 4,4'-methylenediphenol, 1,5-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), and bisphenol S.Polyethylene glycol includes, for example, at least one component selected from the group consisting of diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, and octaethylene glycol. Polypropylene glycol includes, for example, at least one component selected from the group consisting of dipropylene glycol, tripylene glycol, and tetrapropylene glycol.

[0144] The resin content in the surface layer is preferably 45% by mass or more, and more preferably 60% by mass or more. On the other hand, the resin content is preferably 98% by mass or less, and more preferably 95% by mass or less. That is, the resin content is preferably 45% by mass or more and 98% by mass or less, and more preferably 60% by mass or more and 95% by mass or less. If the resin content is too low, the surface layer may peel off easily. On the other hand, if the resin content is too high, the content of the antistatic agent and the specific additives described later will be relatively low, which may make it difficult for the antistatic agent and specific additives to exert their full effect.

[0145] (b) Antistatic agent As described above, the surface layer preferably contains a conductive polymer or a metal oxide as an antistatic agent, and more preferably contains a conductive polymer. Furthermore, the surface layer may also contain both a conductive polymer and a metal oxide as antistatic agents.

[0146] (i) Conductive polymer In this specification, "conductive polymer" refers to polymers that exhibit conductivity in themselves, such as polythiophene, as described later.

[0147] Examples of conductive polymers include polythiophene, polyaniline, polypyrrole, polyacetylene, poly(p-phenylene), polyphenylenevinylene, and polyvinylcarbazole.

[0148] In particular, the conductive polymer is preferably one or more selected from the group consisting of polythiophene, polyaniline, and polypyrrole. This is because the polymer itself exhibits conductivity, and therefore sufficient antistatic properties can be obtained regardless of humidity. As polythiophene, for example, PEDOT / PSS((poly(3,4-ethylenedioxythiophene)) / polystyrene sulfonic acid) is preferably used. As polyaniline, for example, sulfonated polyaniline is preferably used. With a surface layer containing these conductive polymers, a low surface resistivity can be obtained even if the thickness is thin.

[0149] The content of the conductive polymer in the surface layer should be such that a predetermined surface resistivity is obtained. The content of the conductive polymer is preferably 5% by mass or more, and more preferably 7% by mass or more. On the other hand, the content of the conductive polymer is preferably 15% by mass or less, and more preferably 12% by mass or less. In other words, the content of the conductive polymer is preferably 5% by mass or more and 15% by mass or less, and more preferably 7% by mass or more and 12% by mass or less. If the content of the conductive polymer is too low, the antistatic effect may not be easily achieved. On the other hand, if the content of the conductive polymer is too high, the dispersibility may be poor, and the adhesion, optical properties, and mechanical properties may be inferior.

[0150] (ii) metal oxides Examples of metal oxides include antimond-doped tin oxide (ATO), fluorine-doped tin oxide, phosphorus-doped tin oxide (PTO), aluminum-doped tin oxide, niobium-doped tin oxide, tantalum-doped tin oxide, tungsten-doped tin oxide, indium-doped tin oxide, tin oxide, tin-doped indium oxide (ITO), fluorine-doped indium oxide, cadmium-doped indium oxide, indium-doped zinc oxide, fluorine-doped zinc oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, magnesium-doped zinc oxide, silicon-doped zinc oxide, tin-doped zinc oxide, boron-doped zinc oxide, zinc oxide, zinc antimonate (AZO), niobium-doped titanium oxide, and the like. Metal oxides may be used individually or in combination of two or more. From the viewpoint of stabilizing the surface resistivity, antimond-doped tin oxide, tin-doped indium oxide, phosphorus-doped tin oxide, tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, and zinc antimonate are preferred.

[0151] The shape of the metal oxide may be spherical, needle-shaped, or layered, but from the viewpoint of surface resistivity and dispersibility, spherical and needle-shaped are preferred. The average particle size of the metal oxide is, for example, 0.01 μm or more and 1 μm or less, and may be 0.01 μm or more and 0.5 μm or less.

[0152] The amount of metal oxide in the surface layer should be such that the surface resistivity is within a predetermined range, for example, 30% by mass or more and 70% by mass or less.

[0153] (iii) Other antistatic agents The surface layer may contain an antistatic agent other than conductive polymers and metal oxides. Other antistatic agents include surfactants. Surfactants include cationic, anionic, and nonionic types.

[0154] (c) Specific additives The surface layer preferably contains a polyetheramine-type surfactant or a polymer compound having a long-chain alkyl group in its side chain. In this specification, polyetheramine-type surfactants and polymer compounds having a long-chain alkyl group in their side chain may be referred to as specific additives. This is because the inclusion of specific additives in the surface layer makes it easier to obtain the desired surface resistivity. Furthermore, the inclusion of specific additives can improve the slipperiness of the surface layer, thereby suppressing blocking. In addition, it can suppress wear of the surface layer due to friction with the equipment.

[0155] (i) Polyetheramine-type surfactants Examples of polyetheramine-type surfactants include polyoxyalkylene alkylamines. Examples of polyoxyalkylene alkylamines include polyoxyethylene alkylamines. Examples of polyoxyethylene alkylamines include polyoxyethylene laurylamine, polyoxyethylene alkyl(coconut)amine, polyoxyethylene beef tallow alkylamine, polyoxyethylene stearylamine, polyoxyethylene oleylamine, and polyoxyethylene alkylpropylenediamine. Polyetheramine-type surfactants may be used individually or in combination of two or more types.

[0156] In polyoxyalkylene alkylamines, the number of carbon atoms in the alkyl group may be, for example, 10 or more, and may be 12 or more. Alternatively, the number of carbon atoms in the alkyl group may be, for example, 20 or less, and may be 18 or less. That is, the number of carbon atoms in the alkyl group may be, for example, 10 to 20, and 12 to 18. This is because if the number of carbon atoms in the alkyl group is within the above range, it is easier to adjust the HLB value, as described later, to fall within a preferred range.

[0157] Furthermore, in polyoxyalkylene alkylamines, examples of oxyalkylene groups include oxyethylene groups and oxypropylene groups. Among these, oxyethylene groups are preferred because they are easier to adjust so that the HLB value, as described later, falls within a desirable range.

[0158] Furthermore, in polyoxyalkylene alkylamines, the number of moles of alkylene oxide added is, for example, 1 to 10, or 1 to 5. This is because if the number of moles added is within the above range, it is easier to adjust the HLB value, which will be described later, to be within a preferred range.

[0159] In polyoxyalkylene alkylamines, the number of carbon atoms in the alkyl group, the oxyalkylene group, and the number of added moles of alkylene oxide are analyzed by gas chromatography-mass spectrometry (GC-MS).

[0160] The HLB value (Hydrophilic-Lipophilic Balance) of the polyetheramine-type surfactant is preferably between 3 and 7. Generally, a higher HLB value is assumed to result in higher hydrophilicity and better compatibility with the resin. By keeping the HLB value of the polyetheramine-type surfactant below a predetermined value, the compatibility with the resin does not become too good, and the polyetheramine-type surfactant is more likely to localize on the surface of the surface layer. Therefore, the blocking resistance can be improved. If the HLB value of the polyetheramine-type surfactant is high and the compatibility with the resin is too good, the polyetheramine-type surfactant may dissolve or disperse well in the resin in the surface layer, making it difficult to bleed onto the surface layer. Furthermore, by keeping the HLB value of the polyetheramine-type surfactant above a predetermined value, the compatibility with the resin is improved, and dispersibility can be enhanced.

[0161] In this specification, the HLB value represents the degree of affinity of a surfactant to water and oil, and takes a value from 0 to 20, with a value closer to 0 indicating higher lipophilicity and a value closer to 20 indicating higher hydrophilicity. The HLB value is calculated by the Griffin method and is determined by the following formula. HLB value = 20 × sum of formula weights of hydrophilic parts / molecular weight

[0162] The content of the polyetheramine-type surfactant in the surface layer is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the total of the resin and antistatic agent. Furthermore, the content of the polyetheramine-type surfactant is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of the total of the resin and antistatic agent. In other words, the content of the polyetheramine-type surfactant is preferably 5 parts by mass or more and 30 parts by mass or less, more preferably 8 parts by mass or more and 25 parts by mass or less, and even more preferably 10 parts by mass or more and 20 parts by mass or less, per 100 parts by mass of the total of the resin and antistatic agent. If the content of the polyetheramine-type surfactant is too low, the effect of improving antiblocking properties may not be sufficiently obtained. On the other hand, if the content of the polyetheramine-type surfactant is too high, the antistatic performance may decrease.

[0163] (ii) Polymer compounds having long-chain alkyl groups in their side chains Polymeric compounds having long-chain alkyl groups in their side chains are used as release agents to improve blocking resistance. Hereinafter, polymeric compounds having long-chain alkyl groups in their side chains may be referred to as long-chain alkyl group-containing polymeric compounds.

[0164] In a long-chain alkyl group-containing polymer compound, the long-chain alkyl group is either a linear or branched alkyl group. The number of carbon atoms in the long-chain alkyl group is preferably 6 or more, more preferably 8 or more, even more preferably 12 or more, and particularly preferably 15 or more. Furthermore, the number of carbon atoms in the long-chain alkyl group is preferably 30 or less, and more preferably 25 or less. When the number of carbon atoms is above a predetermined value, the long-chain alkyl group in the long-chain alkyl group-containing polymer compound is more likely to orient itself to the surface of the surface layer or to bleed, thereby improving blocking resistance. Furthermore, when the number of carbon atoms is below a predetermined value, compatibility with the resin is improved, and dispersibility can be enhanced. In addition, a decrease in antistatic performance can be suppressed. Examples of long-chain alkyl groups include hexyl group, octyl group, decyl group, lauryl group, octadecyl group, behenyl group, myristyl group, palmityl group, stearyl group, oleyl group, elaidyl group, erucyl group, zomaryl group, lylyl group, lylyl group, eleostearyl group, and lysylyl group.

[0165] In long-chain alkyl group-containing polymer compounds, the basic structure of the main chain is not particularly limited and is appropriately selected depending on the synthesis method. Examples of basic structures of the main chain include polyester, polyamide, polyurethane, acrylic polymer, methacrylic polymer, acrylic acid ester copolymer, acrylamide copolymer, polyvinyl alcohol, polyethyleneimine, polyethyleneamine, and the like.

[0166] Long-chain alkyl group-containing polymer compounds can be obtained by reacting a polymer compound having a reactive group with a compound having an alkyl group that can react with the reactive group. Examples of the reactive group include hydroxyl groups, amino groups, carboxyl groups, and acid anhydrides. Examples of polymer compounds having a reactive group include polyvinyl alcohol, saponified vinyl acetate polymer, saponified vinyl acetate-ethylene copolymer, saponified vinyl acetate-acrylic acid copolymer, polyethyleneimine, polyethyleneamine, reactive group-containing polyester resin, and reactive group-containing poly(meth)acrylic resin. Among these, polyvinyl alcohol, saponified vinyl acetate polymer, saponified vinyl acetate-ethylene copolymer, and saponified vinyl acetate-acrylic acid copolymer are preferred considering release properties and ease of handling. The degree of saponification of the saponified vinyl acetate polymer is preferably 50% or more, and more preferably 60% or more. Furthermore, the degree of saponification of the saponified vinyl acetate polymer is preferably 90% or less, and more preferably 80% or less. In other words, the degree of saponification of the vinyl acetate polymer saponified product is preferably 50% to 90%, and more preferably 60% to 80%.

[0167] Compounds having alkyl groups that can react with the above-mentioned reactive group include, for example, long-chain alkyl group-containing isocyanates, long-chain alkyl group-containing acid chlorides, long-chain alkyl group-containing amines, and long-chain alkyl group-containing alcohols. Examples of long-chain alkyl group-containing isocyanates include hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, octadecyl isocyanate, and behenyl isocyanate. Examples of long-chain alkyl group-containing acid chlorides include hexyl chloride, octyl chloride, decyl chloride, lauryl chloride, octadecyl chloride, and behenyl chloride. Among these, long-chain alkyl group-containing isocyanates are preferred, and octadecyl isocyanate is particularly preferred, considering release properties and ease of handling.

[0168] Furthermore, long-chain alkyl group-containing polymer compounds can also be obtained by polymerization of long-chain alkyl (meth)acrylates or copolymerization of long-chain alkyl (meth)acrylates with other vinyl group-containing monomers. Examples of long-chain alkyl (meth)acrylates include hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, and behenyl (meth)acrylate.

[0169] In particular, the long-chain alkyl group-containing polymer compound is a reaction product of a vinyl acetate polymer saponified with a degree of saponification of 50% to 90%, especially 60% to 80%, and a long-chain alkyl group-containing isocyanate, and it is preferable that the long-chain alkyl group has 20 to 25 carbon atoms.

[0170] In long-chain alkyl group-containing polymer compounds, the degree of polymerization of the main chain is, for example, 200 to 6000.

[0171] The number of carbon atoms in the long-chain alkyl group, the basic structure of the main chain, the degree of polymerization of the main chain, and whether the long-chain alkyl group-containing polymer compound is a reaction product of vinyl acetate polymer saponification and long-chain alkyl group-containing isocyanate are analyzed by Fourier transform infrared spectroscopy (FT-IR).

[0172] The content of the long-chain alkyl group-containing polymer compound in the surface layer is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and even more preferably 50 parts by mass or more, per 100 parts by mass of the total of the resin and the antistatic agent. Furthermore, the content of the long-chain alkyl group-containing polymer compound is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 80 parts by mass or less, per 100 parts by mass of the total of the resin and the antistatic agent. In other words, the content of the long-chain alkyl group-containing polymer compound is preferably 30 parts by mass or more and 100 parts by mass or less, more preferably 40 parts by mass or more and 90 parts by mass or less, and even more preferably 50 parts by mass or more and 80 parts by mass or less, per 100 parts by mass of the total of the resin and the antistatic agent. If the content of the long-chain alkyl group-containing polymer compound is too low, the effect of improving blocking resistance may not be sufficiently obtained. On the other hand, if the content of the long-chain alkyl group-containing polymer compound is too high, the blocking resistance may decrease.

[0173] (d) Additives The surface layer may contain additives as needed. Examples of additives include fillers.

[0174] (e) Thickness and method of forming the surface layer The thickness of the surface layer is, for example, 0.02 μm to 3 μm. If the thickness of the surface layer is within the above range, antistatic properties can be imparted to the substrate layer having barrier properties.

[0175] As a method for forming the surface layer, for example, a method is used in which a surface layer composition is obtained by dispersing or dissolving a resin, an antistatic agent, and specific additives in a solvent, and the surface layer composition is applied and dried. Known application methods for the surface layer composition include air doctor, blade coat, knife coat, rod coat, bar coat, direct roll coat, reverse roll coat, gravure coat, and slide coat.

[0176] (4) Other layers In a substrate layer having barrier properties, adhesive layers may be placed between each layer or between other layers to improve adhesion, or each layer may be surface-treated. Examples of surface treatments include corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, and oxidation treatment using chemicals. In addition, various coating layers such as a primer coating layer, undercoat layer, anchor coating layer, adhesive layer, and vapor-deposited anchor coating layer may be placed on the surface of each layer. For the above-mentioned various coating layers, for example, resin compositions in which polyester resins, polyurethane resins, epoxy resins, phenolic resins, (meth)acrylic resins, polyvinyl acetate resins, polyolefin resins such as polyethylene or polypropylene or their copolymers or modified resins, and cellulose resins can be used as the main components of the vehicle.

[0177] C. Packaging materials The packaging material in this disclosure is a packaging material composed of the laminated film described above.

[0178] Since the laminated film described above has antistatic and hygroscopic properties, the packaging material is preferably a packaging material for electronic components and electronic / electrical products. It can protect against static electricity and moisture. Examples of electronic components include wafers, wiring boards, circuit boards, semiconductor packages, and electronic components such as semiconductor elements, ICs, and capacitors. Examples of electronic / electrical products include batteries, solar cells, organic light-emitting diodes, wavelength conversion sheets, and display devices.

[0179] Furthermore, since the laminated film described above has hygroscopic and antistatic properties, the packaging material may also be used for packaging powders or granules. Adhesion of powders and granules can be suppressed. Examples of powders and granules that can be packaged include food products, pharmaceuticals (quasi-drugs), cleaning agents, cosmetics, and chemicals.

[0180] D. Packaging bag The packaging bag in this disclosure comprises the laminated film described above. The packaging bag in this disclosure is obtained by overlapping two laminated films so that the second resin layer of the resin film faces each other, or by folding one laminated film so that the second resin layer of the resin film faces inward, and then forming the bag by heat sealing.

[0181] Specific examples of packaging bags include pillow packaging bags and gusset packaging bags. Examples of sealing types include side seals, two-side seals, three-side seals, four-side seals, envelope seals, gusset seals (pillow seals), pleated seals, flat-bottom seals, square-bottom seals, and gusset seals.

[0182] Examples of heat sealing methods include bar seals, rotary roll seals, belt seals, impulse seals, high-frequency seals, and ultrasonic seals.

[0183] E. Packaging The packaging in this disclosure comprises the above-described packaging bag and the packaged item contained within the packaging bag.

[0184] The contents to be packaged are the same as those described in the section on packaging materials above. Preferably, the contents to be packaged are electronic components. Specifically, an example of the contents to be packaged is a dedicated wafer carrier case in which multiple wafers are housed.

[0185] This disclosure is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of this disclosure and achieves similar effects is included within the technical scope of this disclosure. [Examples]

[0186] Examples and comparative examples are shown below to further illustrate this disclosure.

[0187] [material] Details of the materials used in the examples are as follows.

[0188] (1) Polyolefin resins • Polyethylene resin A: Linear low-density polyethylene, a copolymer of ethylene and 1-hexene. "Kernel KF260T" manufactured by Nippon Polyethylene Co., Ltd. Density 0.901 g / cm³ 3 MFR 2.0g / 10 minutes (190℃, 2.16kg) • Polypropylene resin A: Metallocene polypropylene, manufactured by Nippon Polypropylene Co., Ltd., "Wintech WFX4M" • Polyethylene resin B: Linear low-density polyethylene, "Harmolex NF444" manufactured by Nippon Polyethylene Co., Ltd., density 0.912 g / cm³ 3 MFR 2.0g / 10 minutes (190℃, 2.16kg) • Polyethylene resin C: Linear low-density polyethylene, "Ultzex ​​2021L" manufactured by Prime Polymer, density 0.918 g / cm³ 3 MFR 2.1g / 10 min (190℃, 2.16kg)

[0189] (2) Desiccant Masterbatch • Dehumidifying masterbatch A A desiccant masterbatch A was prepared by melt-kneading calcium oxide and low-density polyethylene (LC602A, manufactured by Nippon Polyethylene Co., Ltd.) according to the following formulation. Calcium oxide 70 parts by mass Low-density polyethylene 30 parts by mass • Desiccant Masterbatch B A desiccant masterbatch containing calcium oxide with the following formulation (Sasaki Chemical Co., Ltd.'s "S-KID PES-60-FL T3") was prepared. Calcium oxide 60 parts by mass Low-density polyethylene 40 parts by mass • Dehumidifying agent masterbatch C A desiccant masterbatch C was prepared by melt-kneading a metal-organic frame (MOF) (BASF "A520", average particle size 5 μm, primary particle size 50 nm) and low-density polyethylene (Nippon Polyethylene Co., Ltd. "LC602A") according to the following formulation. Metal-organic framework (MOF) 60 parts by mass Low-density polyethylene 40 parts by mass • Dehumidifying agent Masterbatch D A desiccant masterbatch D was prepared by melt-kneading nanozeolite 4A (manufactured by Nakamura Choko Co., Ltd., average particle size 50 nm) and low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., "LC602A") according to the following formulation. Nanozeolite 10 parts by mass Low-density polyethylene 90 parts by mass • Desiccant Masterbatch E A desiccant masterbatch E was prepared by melt-kneading hydrotalcite (DHT-4C, manufactured by Kyowa Chemical Co., Ltd.) and low-density polyethylene (LC602A, manufactured by Nippon Polyethylene Co., Ltd.) according to the following formulation. Hydrotalcite 50 parts by mass Low-density polyethylene 50 parts by mass

[0190] (3) Antistatic masterbatch • Antistatic masterbatch A A polyether polyamide-type polymer antistatic agent (Pelektron PVL, manufactured by Sanyo Chemical Industries, Ltd., melting point 135°C) and low-density polyethylene (LC602A, manufactured by Nippon Polyethylene Co., Ltd.) were melt-kneaded together to prepare an antistatic agent masterbatch A. The MFR of antistatic agent masterbatch A at 190°C and 2.16 kg was 15 g / 10 min. Antistatic agent 60 parts by mass Low-density polyethylene 40 parts by mass • Antistatic masterbatch B A polymer-based antistatic agent having a polyether, polyamide, or polypropylene skeleton (Sanyo Chemical Industries' "Perestat RS230" with a melting point of 135°C) was melt-kneaded with low-density polyethylene (Nippon Polyethylene Co., Ltd.'s "LC602A") in the following formulation to prepare an antistatic agent masterbatch B. The MFR of antistatic agent masterbatch B at 190°C and 2.16 kg was 15 g / 10 min. Antistatic agent 60 parts by mass Low-density polyethylene 40 parts by mass • Antistatic Masterbatch C A masterbatch containing a lithium salt-containing polyether polymer-type polymer-based antistatic agent (Sanko Chemical Industry Co., Ltd.'s "Sankonol TBX-310," melting point 135°C) was prepared. • Antistatic Masterbatch D A polyether polyamide-type polymer antistatic agent (Pelektron PVL, manufactured by Sanyo Chemical Industries, Ltd., melting point 135°C) and low-density polyethylene (LJ802, manufactured by Nippon Polyethylene Co., Ltd.) were melt-kneaded together to prepare an antistatic agent masterbatch D. The MFR of antistatic agent masterbatch D at 190°C and 2.16 kg was 23 g / 10 min. Antistatic agent 60 parts by mass Low-density polyethylene 40 parts by mass • Antistatic Masterbatch E A nonionic surfactant antistatic masterbatch (Riken Vitamin Co., Ltd.'s "Rikemaster MPE-3") was prepared. • Antistatic Masterbatch F A polymer-based antistatic agent having polyether, polyamide, and polypropylene skeletons (Sanyo Chemical Industries, Ltd.'s "Perestat 201," melting point 168°C) and low-density polyethylene (Nippon Polyethylene Co., Ltd.'s "LC602A") was melt-kneaded to prepare an antistatic agent masterbatch E. The MFR of antistatic agent masterbatch F at 190°C and 2.16 kg was 2.6 g / 10 min. Antistatic agent 70 parts by mass Low-density polyethylene 30 parts by mass

[0191] [Example 1] (1) Preparation of resin film A polyethylene resin C was used as the composition for the third resin layer. A composition was prepared for the first resin layer by mixing 42% by mass of a hygroscopic masterbatch A and 58% by mass of polyethylene resin A. A composition was prepared for the second resin layer by mixing 65% by mass of polyethylene resin B and 35% by mass of antistatic masterbatch A. A resin film having the third resin layer, the first resin layer, and the second resin layer in order was formed by multilayer melt extrusion at a processing temperature of 170°C. The thickness of each layer was 30 μm for the third resin layer, 50 μm for the first resin layer, and 15 μm for the second resin layer.

[0192] (2) Preparation of laminated film The surface of the third resin layer of the resin film was corona-treated. A biaxially oriented polyester film (Toyobo Co., Ltd. "E5100", 25 μm thick) corona-treated on both sides was used as the substrate layer. A surface layer composition (Arakawa Chemical Co., Ltd. Alacote AS601D / CL910 (mass ratio) = 10 / 1, solution solids content 1.5 wt%) containing poly-3,4-ethylenedioxythiophene (PEDOT) as a conductive polymer and aziridine as a curing agent) was applied to the substrate layer to form a surface layer with a thickness of 0.05 μm. Aluminum foil (Toyo Aluminum Co., Ltd. "A8079 foil", 7 μm thick) was prepared as the barrier layer, and a biaxially oriented nylon film (Unitika Corporation "ON-BC", 25 μm thick) corona-treated on both sides was prepared as the intermediate layer.

[0193] A two-component urethane adhesive (manufactured by Rock Paint Co., Ltd., main component: RU-77T, hardener: H-7) was applied to the corona-treated surface of the substrate layer to a thickness of 3 μm and bonded to the barrier layer. Next, adhesive was applied to the non-laminate surface of the barrier layer and bonded to the intermediate layer. Then, adhesive was applied to the non-laminate surface of the intermediate layer and bonded to the surface of the third resin layer of the resin film to produce a laminated film.

[0194] [Examples 2-12 and Comparative Examples 1-4] Compositions for each layer were prepared according to the formulations shown in Tables 1 and 2 below, and resin films and laminated films were manufactured in the same manner as in Example 1 at the processing temperatures shown in Tables 1 and 2 below.

[0195] [evaluation] (1) Moisture absorption A resin film was cut to dimensions of 100 mm x 100 mm and left standing for 11 days in an environment with a temperature of 40°C and a humidity of 90% RH. The amount of moisture absorbed was determined from the change in the weight of the resin film. Moisture absorption amount = [Weight after moisture absorption (g) - Initial weight (g)] / 0.01(m 2 )

[0196] (2) Moisture absorption rate A 500mm x 500mm three-sided sealed pouch was fabricated using laminated film. KN Laboratories' "Hygrochron" was placed inside the pouch, the air was removed, and it was heat-sealed. The pouch was left standing for 72 hours at a temperature of 23°C and a humidity of 50%RH. After that, the pouch was opened, the Hygrochron was removed, data was extracted, and the change in humidity was checked.

[0197] (3) Surface resistivity Using a resistivity meter ("Highresist-UX MCP-HT800" manufactured by Nitto Seiko Analytech Co., Ltd.), the surface resistivity of the second resin layer of the resin film was measured with an applied voltage of 1,000V and a measurement time of 30 seconds.

[0198] (4) Autocorrelation length As a pretreatment, the resin film was cut into strips and embedded in a thermosetting resin at 60°C for 120 hours. Sections of a predetermined cross-section with a thickness of 0.5 μm were prepared from the resin-embedded resin film using an ultramicrotome (diamond knife). Subsequently, ruthenium staining was performed using an aqueous ruthenium tetroxide solution for 12 hours. After that, sections of a predetermined cross-section with a thickness of 80 nm were prepared from the ruthenium-stained sections using an ultramicrotome (diamond knife). The cross-sectional sections were prepared so that cross-sections parallel to the MD direction and thickness direction of the second resin layer, and cross-sections parallel to the TD direction and thickness direction of the second resin layer were obtained. Then, the cross-section of the second resin layer was observed using a scanning electron microscope (Hitachi High-Technologies Corporation "S-4800 TYPE I+II") under observation conditions of acceleration voltage: 30.0 kV, emission current: 10 μA, WD: 8 mm, detector: TE).

[0199] The autocorrelation function was calculated using the OpenCV library in Python, an image processing program, following the procedure and input parameters described in the section on the second resin layer above, to determine the autocorrelation lengths L1 to L4 in a given cross-section.

[0200] (5) Leaching ion content First, the laminated film was cut into 10cm x 20cm sections, folded in half, and heat-sealed on three sides to create small pouches, and the weight of each pouch was measured. Next, 100mL of ultrapure water was placed in each pouch and heat-sealed. The heat-seal width was 2cm. The pouch containing the ultrapure water was rotated 20 times to distribute the ultrapure water throughout the pouch and to dissolve the ionic components, thereby obtaining a sample solution. 5mL of this sample solution was taken and analyzed. Using a Thermo Fisher Scientific ion chromatograph "DIONEX ICS-3000," the concentrations of the following anions and cations in the sample solution were measured, and the content of anions and cations in the resin film was calculated. Anion type: F - Cl - , NO 2 - , Br- NO3 - SO4 2- , PO4 2- Cation species: Li + na + , K + Mg 2+ Ca 2+ NH4 +

[0201] [Table 1]

[0202] [Table 2]

[0203] In the resin films of Examples 1 to 12, polymer-based antistatic agents were used, and the L1 / L2 ratio was above a predetermined value, resulting in good antistatic and hygroscopic properties. In particular, in Examples 1 to 11, the relatively low content of the antistatic agent in polymer form suppressed the elution of ionic components. On the other hand, in Comparative Example 1, a surfactant-based antistatic agent was used, making it impossible to measure the autocorrelation length, and there was significant elution of ionic components. In Comparative Examples 2 to 4, although polymer-based antistatic agents were used, the L1 / L2 ratio was low, resulting in poor antistatic properties.

[0204] This disclosure provides, for example, the following inventions. [1] A resin film having a first resin layer and a second resin layer, The above-mentioned first resin layer contains a desiccant, The above-mentioned second resin layer contains a polyolefin resin and a polymer-based antistatic agent. The above-mentioned second resin layer is located on the outermost surface. The above-mentioned second resin layer has a first region containing the above-mentioned polyolefin resin and a second region containing the above-mentioned polymer-based antistatic agent, and the second region has a striated structure. A resin film in which, when the planar direction of the second resin layer is defined as the first direction, in a cross-section parallel to the first direction and the thickness direction of the second resin layer, the ratio of the autocorrelation length in the first direction to the autocorrelation length in the thickness direction of the second resin layer is 4 or more in the striated structure. [2] The resin film according to [1], wherein the polymer-based antistatic agent is a nonionic antistatic agent. [3] The resin film according to [2], wherein the above-mentioned nonionic antistatic agent comprises polyethylene oxide chains. [4] The resin film according to [2] or [3], wherein the above-mentioned nonionic antistatic agent comprises at least one selected from the group consisting of polyether ester amide, polyether ester, and polyethylene glycol methacrylate copolymer. [5] The resin film according to any one of [1] to [4], wherein the content of the polymer-based antistatic agent in the second resin layer is 10% by mass or more and 50% by mass or less. [6] The resin film according to any one of [1] to [4], wherein the polyolefin resin contained in the second resin layer is a polyethylene resin. [7] The surface resistivity of the surface of the second resin layer described above is 1 × 10⁻⁶ 7 Ω / □ or more 1×10 12 A resin film described in any of [1] to [4], having a coefficient of less than Ω / □. [8] Li in the above resin film + na + , K + Mg 2+ Ca 2+ NH4 + F - Cl - , NO 2 - , Br - NO3 - SO4 2- and PO4 2-A resin film according to any of [1] to [4], wherein the content of each ion is 100 ppb or less. [9] A resin film according to any one of [1] to [4], wherein the thickness of the second resin layer is 5 μm or more and 20 μm or less.

[10] A resin film according to any one of [1] to [4], wherein the first resin layer contains a polyolefin resin.

[11] The resin film according to

[10] , wherein the polyolefin resin contained in the first resin layer is a polyethylene resin.

[12] A resin film according to any one of [1] to [4], having a third resin layer on the side of the first resin layer opposite to the second resin layer.

[13] The resin film according to

[12] , wherein the third resin layer contains a polyolefin resin.

[14] The resin film according to

[13] , wherein the polyolefin resin contained in the third resin layer is a polyethylene resin.

[15] A laminated film having a barrier substrate layer and a resin film according to any one of [1] to

[14] , A laminated film in which the second resin layer of the above-mentioned resin film is located on the outermost surface.

[16] The laminated film according to

[15] , wherein the above-mentioned base material layer has a surface layer containing an antistatic agent on the outermost surface opposite to the above-mentioned resin film.

[17] A packaging material comprising the laminated film described in

[15] or

[16] .

[18] A packaging bag comprising the laminated film described in

[15] or

[16] .

[19] A packaging body comprising a packaging bag as described in

[18] and an item to be packaged contained within the packaging bag. [Explanation of Symbols]

[0205] 1...First resin layer 2...Second resin layer 3...Third resin layer 10… Resin film 11 … 1st area 12…Second area 20… Laminated film 21 … Barrier-type substrate layer 24 … surface layer

Claims

1. A resin film having a first resin layer and a second resin layer, The first resin layer contains a desiccant, The second resin layer contains a polyolefin resin and a polymer-based antistatic agent. The second resin layer is located on the outermost surface, The second resin layer has a first region containing the polyolefin resin and a second region containing the polymer-based antistatic agent, and the second region has a striated structure. A resin film in which, when one direction in the planar direction of the second resin layer is defined as the first direction, in a cross section parallel to the first direction and the thickness direction of the second resin layer, the ratio of the autocorrelation length in the first direction to the autocorrelation length in the thickness direction of the second resin layer is 4 or more and 20 or less in the striated structure.

2. A resin film having a first resin layer and a second resin layer, The first resin layer contains a desiccant, The second resin layer contains a polyolefin resin and a polymer-based antistatic agent. The second resin layer is located on the outermost surface, The second resin layer has a first region containing the polyolefin resin and a second region containing the polymer-based antistatic agent, and the second region has a striated structure. When one direction in the planar direction of the second resin layer is defined as the first direction, in a cross-section parallel to the first direction and the thickness direction of the second resin layer, the ratio of the autocorrelation length in the first direction to the autocorrelation length in the thickness direction of the second resin layer is 4 or more in the striated structure. A resin film in which the striated structure exists on the outermost surface of the second resin layer and inside the second resin layer.

3. The resin film according to claim 1 or claim 2, wherein the polymer-based antistatic agent is a nonionic antistatic agent.

4. The resin film according to claim 3, wherein the nonionic antistatic agent comprises polyethylene oxide chains.

5. The resin film according to claim 3, wherein the nonionic antistatic agent comprises at least one selected from the group consisting of polyether ester amide, polyether ester, and polyethylene glycol methacrylate copolymer.

6. The resin film according to claim 1 or claim 2, wherein the content of the polymer-based antistatic agent in the second resin layer is 10% by mass or more and 50% by mass or less.

7. The resin film according to claim 1 or claim 2, wherein the polyolefin resin contained in the second resin layer is a polyethylene resin.

8. The surface resistivity of the surface of the second resin layer is 1 × 10 ７ Ω / □ or more 1×10 １２ A resin film according to claim 1 or claim 2, wherein the Ω / □ is less than Ω.

9. Li in the resin film ＋ , Na ＋ , K ＋ , Mg ２＋ , Ca ２＋ , NH ４ ＋ , F － , Cl － , NO₂⁻, Br － , NO ３ － , SO ４ ２－ and PO ４ ２－ The resin film according to claim 1 or claim 2, wherein the content of each of the ions of is 100 ppb or less.

10. The resin film according to claim 1 or claim 2, wherein the thickness of the second resin layer is 5 μm or more and 20 μm or less.

11. The resin film according to claim 1 or claim 2, wherein the first resin layer contains a polyolefin resin.

12. The resin film according to claim 11, wherein the polyolefin resin contained in the first resin layer is a polyethylene resin.

13. The resin film according to claim 1 or claim 2, wherein the first resin layer has a third resin layer on the side of the first resin layer opposite to the second resin layer.

14. The resin film according to claim 13, wherein the third resin layer contains a polyolefin resin.

15. The resin film according to claim 14, wherein the polyolefin resin contained in the third resin layer is a polyethylene resin.

16. A laminated film comprising a substrate layer having barrier properties and a resin film according to claim 1 or claim 2, A laminated film in which the second resin layer of the aforementioned resin film is located on the outermost surface.

17. The laminated film according to claim 16, wherein the base layer has a surface layer containing an antistatic agent on the outermost surface opposite to the resin film.

18. A packaging material comprising the laminated film described in claim 16.

19. A packaging bag comprising the laminated film described in claim 16.

20. A packaging body comprising a packaging bag according to claim 19 and an object to be packaged contained within the packaging bag.

Images