Packaging material, packaging bag, vacuum pack, method for preserving raw fish, and method for inspecting raw fish

Abstract

A packaging material (2) according to the present disclosure comprises a first base material layer (3), a barrier layer (4), and a sealant layer (5) in the stated order, the packaging material (2) being characterized in that: the first base material layer (3) contains a polyester-based resin; the barrier layer (4) is a vapor-deposited film of a metal oxide; the sealant layer (5) contains a heat-sealable resin; in order that the color tone in a CIE 1976 color space, as calculated from a reflection spectrum measured in conformance with JIS Z 8722:2009 under a D65 light source and a viewing angle of 2°, is comparable to the color tone of a specific packaging film used in the prior art, the color difference ΔE*ab from the color tone of the specific prior-art film within a specific numeric range or the color difference ΔE*ab from the color tone of the D65 light source is 1.20-1.80; and the oxygen permeability measured in conformance with JIS K 7126-2:2006 is 1.5 mL / m2⋅day⋅MPa or lower.

Description

Packaging materials, packaging bags, vacuum packs, methods for preserving raw fish, and methods for inspecting raw fish.

[0001] This disclosure relates to packaging materials, packaging bags, vacuum packs, methods for preserving raw fish, and methods for inspecting raw fish.

[0002] In the distribution of fresh fish, the fish is packaged in bags in its filleted state and transported while being kept chilled to prevent spoilage.

[0003] Important factors involved in the deterioration of raw fish include chemical changes such as oxidation, browning, and discoloration. Since oxygen is involved in these chemical changes, methods such as creating a vacuum inside the packaging bag and adjusting the gas concentration inside the bag are used to suppress deterioration of raw fish and maintain its quality (Non-Patent Literature 1).

[0004] As packaging materials for such packaging bags, laminated films of polyamide film and polyethylene film are frequently used due to their high transparency and ability to withstand not only vacuum packaging but also boiling. Commercially available laminated films include Sigma Tube (registered trademark, product number GT-1525, thickness 60 μm, manufactured by Chlorin Kasei Co., Ltd.), Kyobijin (product name, product number XS-1527, thickness 70 μm, size 150 mm x 270 mm, manufactured by Chlorin Kasei Co., Ltd.), and Nylon Poly TL Type 10-15 (product name, thickness 70 μm, size 100 mm x 150 mm, manufactured by Fukusuke Kogyo Co., Ltd.), and are used differently depending on the application. For example, Sigma Tube is often used in two-side seal type packaging bags, while Kyobijin and Nylon Poly TL Type 10-15 are often used in four-side seal type packaging bags.

[0005] However, laminated films of polyamide film and polyethylene film do not have excellent oxygen barrier properties, and oxygen entering from outside the packaging bag can cause raw fish inside the bag to spoil. Therefore, packaging materials with excellent oxygen barrier properties are sometimes used to make up the packaging bag. For example, Patent Document 1 describes a material with an oxygen permeability of 0.1 cc / m³ per day at 30°C and 70% relative humidity. ２ / atm (=1mL / m ２A discoloration-preventing packaging material comprising a film with a pressure of MPa or less is described.

[0006] Japanese Patent Publication No. 2022-148861, Japanese Patent Publication No. 2024-27765, Japanese Patent No. 7518522

[0007] Visual Guide to Fish Freshness - Commitment to Deliciousness and Safety, Seizando Shoten, December 18, 2007. Fish Freshness (K-value) Testing Method - High-Performance Liquid Chromatography Method, Japanese Agricultural Standards, established March 31, 2022.

[0008] In recent years, the Japanese Agricultural Standards (JAS) have established the K-value as an indicator of fish freshness (Non-Patent Literature 2). The K-value is an index based on the concentration ratio of ATP (adenosine triphosphate) decomposition products, and a smaller value indicates better fish freshness. Generally, fish with a K-value of 20% or less are considered suitable for raw consumption. Even when raw fish fillets are stored chilled in packaging bags made of conventional packaging materials, the K-value of the raw fish tends to rise in a short period (about 4 days), making it unsuitable for raw consumption. Furthermore, with the recent trend towards individual consumption, it has become common to process fish into fillets at the landing site, and then transport the raw fish fillets in packaging bags to the consumption area. As a result, the period during which raw fish is stored or transported in packaging bags has become longer, and there is a need to maintain the freshness of raw fish for a long period while it is in packaging bags.

[0009] Furthermore, since the K value is an index measured by destructive testing and is not suitable for 100% inspection, there is a need to estimate the K value of raw fish using non-destructive testing. For example, attempts have been made to measure the color tone of raw fish and estimate the K value from the color tone (Patent Documents 2 and 3). If raw fish is placed in a packaging bag using packaging material that has a significantly different color tone from conventional packaging materials, there is a concern that the K value of the raw fish cannot be accurately estimated from the color tone of the raw fish measured through the packaging bag. For this reason, the packaging bag that contains raw fish is required to have a color tone similar to that of the conventional packaging materials, namely Sigma Tube, Kyobijin, and Nylon Poly TL Type 10-15.

[0010] Therefore, the purpose of this disclosure is to provide a packaging material that can maintain the freshness of raw fish for a long period of time and is expected not to affect the measurement of the color of raw fish through the packaging bag. Another purpose of this disclosure is to provide a packaging bag, a vacuum pack, a method for preserving raw fish, and a method for inspecting raw fish using the packaging material.

[0011] The inventors have found that packaging bags made from a packaging material whose color difference from the above-mentioned Sigma Tube is within a specific range and whose oxygen permeability is below a certain level prevent the K value of raw fish from rising when stored chilled, and can maintain freshness suitable for raw consumption for 7 days. Furthermore, the inventors have found that packaging bags made from a packaging material whose color difference from the above-mentioned Nylon Poly TL Type 10-15 is within a specific range and whose oxygen permeability is below a certain level also prevent the K value of raw fish from rising when stored chilled, and can maintain freshness suitable for raw consumption for 7 days. Furthermore, the inventors have found that packaging bags made from a packaging material whose color difference from the color of a D65 light source is within a specific range and whose oxygen permeability is below a certain level also prevent the K value of raw fish from rising when stored chilled, and can maintain freshness suitable for raw consumption for 7 days. This disclosure was completed after further consideration based on the aforementioned findings.

[0012] This disclosure is resolved by the following embodiments: <1> A packaging material comprising a first substrate layer, a barrier layer, and a sealant layer in this order, wherein the first substrate layer comprises a polyester resin, the barrier layer is a metal oxide vapor-deposited film, and the sealant layer comprises a heat-sealable resin, and the L in the CIE 1976 color space is calculated from the reflection spectral spectrum measured in accordance with JIS Z 8722:2009 under the conditions of a D65 light source and a 2° viewing angle. ＊ 99.159, and a ＊ The value is -0.038, and b ＊ The color difference ΔE between the color tone of the film, which has a value of 0.349, and the color tone of the packaging material. ＊ab(1) is 0.40 or more and 0.80 or less, and the oxygen permeability measured in accordance with JIS K 7126-2:2006 under the environment of a temperature of 23°C and a relative humidity of 90% RH is 1.5 mL / m ２ ・day・MPa or less, a packaging material. <2> A packaging material including a first base material layer, a barrier layer, and a sealant layer in this order, wherein the first base material layer contains a polyester resin, the barrier layer is a vapor deposition film of a metal oxide, the sealant layer contains a heat-sealable resin, and L in the CIE1976 color space calculated from the reflection spectroscopic spectrum measured in accordance with JIS Z 8722:2009 under the conditions of a D65 light source and a 2° viewing angle ＊ is 98.869, a ＊ is -0.079, b ＊ is 0.298, the color difference ΔE between the color tone of the film and the color tone of the packaging material ＊ ab(2) is 0.25 or more and 0.50 or less, and the oxygen permeability measured in accordance with JIS K 7126-2:2006 under the environment of a temperature of 23°C and a relative humidity of 90% RH is 1.5 mL / m ２ ・day・MPa or less, a packaging material. <3> A packaging material including a first base material layer, a barrier layer, and a sealant layer in this order, wherein the first base material layer contains a polyester resin, the barrier layer is a vapor deposition film of a metal oxide, the sealant layer contains a heat-sealable resin, and the color difference ΔE between the color tone of the packaging material and the color tone of the D65 light source in the CIE1976 color space calculated from the reflection spectroscopic spectrum measured in accordance with JIS Z 8722:2009 under the conditions of a D65 light source and a 2° viewing angle ＊ ab(3) is 1.20 or more and 1.80 or less, and the oxygen permeability measured in accordance with JIS K 7126-2:2006 under the environment of a temperature of 23°C and a relative humidity of 90% RH is 1.5 mL / m ２- Packaging material having a pressure of 1 day MPa or less. <4> The packaging material according to any one of <1> to <3>, further comprising a second base layer between the barrier layer and the sealant layer, wherein the second base layer contains a polyamide resin. <5> The packaging material according to any one of <1> to <4>, wherein the first base layer constitutes one side of the packaging material. <6> The packaging material according to any one of <1> to <3>, comprising a second base layer, the first base layer, the barrier layer, and the sealant layer in this order, wherein the second base layer contains a polyamide resin or a polyester resin. <7> The packaging material according to <6>, wherein the second base layer constitutes one side of the packaging material. <8> The packaging material according to <5> or <7>, wherein the puncture strength from the one side is 3 N / 1 mmΦ or more. <9> The packaging material according to any one of <1> to <8>, wherein the sealant layer constitutes the other side of the packaging material. <10> The packaging material according to <9>, wherein the puncture strength from the other surface is 3 N / 1 mmΦ or more. <11> The packaging material according to any one of <1> to <10>, wherein the total thickness is 70 μm or more and 100 μm or less. <12> The packaging material according to any one of <1> to <11>, wherein the first base layer contains polyethylene terephthalate. <13> The packaging material according to any one of <1> to <12>, wherein the metal oxide is aluminum oxide. <14> The packaging material according to any one of <1> to <13>, wherein the heat-sealable resin is linear low-density polyethylene. <15> The water vapor transmission rate measured in accordance with JIS K 7129:2008 under conditions of 40°C and 90% RH is 0.5 g / m ２- A packaging material according to any one of <1> to <14>, which is less than or equal to day. <16> A packaging material according to any one of <1> to <15>, which has a tensile strength in the MD direction of 20 N / 15 mm or more. <17> A packaging material according to any one of <1> to <16>, which has a tensile strength in the TD direction of 20 N / 15 mm or more. <18> A packaging material according to any one of <1> to <17>, which has a tear strength in the MD direction of 0.1 N or more. <19> A packaging material according to any one of <1> to <18>, which has a tear strength in the TD direction of 0.1 N or more. <20> A packaging bag comprising the packaging material according to any one of <1> to <19>. <21> A vacuum pack containing raw fish in the packaging bag according to <20>. <22> The vacuum pack according to <21>, wherein the raw fish is sea bream. <23> A method for preserving raw fish, comprising the step of preserving the vacuum pack described in <21> or <22> at 0°C or higher and 2°C or lower. <24> A step of measuring the reflectance spectral spectrum of the vacuum pack described in <21> or <22> in accordance with JIS Z 8722:2009 under the condition of a 2° viewing angle, and from the reflectance spectral spectrum, L in the CIE1976 color space ＊ a ＊ or b ＊ A process for calculating the L of the vacuum pack ＊ , the above a ＊ or the above b ＊ A method for inspecting raw fish, comprising the step of determining the color tone of the raw fish by comparing it with a reference value.

[0013] This disclosure provides a packaging material that can maintain the freshness of raw fish for a long period of time and is expected not to affect the measurement of the color of raw fish through the packaging bag. Furthermore, this disclosure provides a packaging bag using the packaging material, a vacuum pack, a method for preserving raw fish, and a method for inspecting raw fish.

[0014] This is a schematic cross-sectional view showing one embodiment of the packaging material of the present disclosure. This is a schematic cross-sectional view showing one embodiment of the packaging material of the present disclosure. This is a schematic cross-sectional view showing one embodiment of the packaging material of the present disclosure. This is a diagram showing an example of a film deposition apparatus used to manufacture the packaging material of the present disclosure. This is a cross-sectional view showing an example of the plasma pretreatment mechanism of the film deposition apparatus. This is a plan view showing an example of the electrode section and magnetic field forming section of the plasma pretreatment mechanism of the film deposition apparatus. This is a cross-sectional view showing an example of the electrode section and magnetic field forming section of the plasma pretreatment mechanism of the film deposition apparatus. This is a cross-sectional view showing an example of the film deposition mechanism of the film deposition apparatus. This is a front view showing one embodiment of the packaging bag of the present disclosure. This is a perspective view showing one embodiment of the packaging bag of the present disclosure. This is a perspective view showing one embodiment of the packaging bag of the present disclosure. This is a front view showing one embodiment of the vacuum pack of the present disclosure.

[0015] In this specification, when multiple candidate upper limits and multiple candidate lower limits are given for a certain parameter, the numerical range of that parameter may be constructed by combining any one candidate upper limit and any one candidate lower limit. As an example, let's consider the statement, "Parameter B is preferably A1 or greater, more preferably A2 or greater, even more preferably A3 or greater, and also preferably A4 or less, more preferably A5 or less, and even more preferably A6 or less." In this example, the numerical range of parameter B may be A1 or greater and A4 or less, A1 or greater and A5 or less, A1 or greater and A6 or less, A2 or greater and A4 or less, A2 or greater and A5 or less, A2 or greater and A6 or less, A3 or greater and A4 or less, A3 or greater and A5 or less, and A3 or greater and A6 or less.

[0016] The embodiments of this disclosure will be described in detail below. This disclosure can be implemented in many different forms and is not construed as being limited to the embodiments described below. The drawings may schematically represent the width, thickness, and shape of each layer, etc., compared to the embodiments, in order to clarify the explanation, but these are merely examples and do not limit the interpretation of this disclosure. In this specification and in each figure, elements similar to those already described in the previously shown figures are denoted by the same reference numerals, and detailed explanations may be omitted as appropriate.

[0017] Each component mentioned in the following description (for example, polyester resin, metal, metal oxide, heat-sealable resin, polyamide resin, and adhesive) may be used individually or in combination of two or more types.

[0018] [Packaging Material] The packaging material of this disclosure comprises a first base layer, a barrier layer, and a sealant layer in this order. The packaging material of this disclosure may further comprise a second base layer between the barrier layer and the sealant layer. The packaging material of this disclosure may also comprise a second base layer, a first base layer, a barrier layer, and a sealant layer in this order. The packaging material of this disclosure may further comprise a gas barrier coating film.

[0019] The packaging material 2 shown in Figure 1 comprises a first base layer 3, a barrier layer 4, and a sealant layer 5 in that order. The first base layer 3 constitutes one side of the packaging material 2. The sealant layer 5 constitutes the other side of the packaging material 2. The barrier layer 4 and the sealant layer 5 are joined by a first adhesive layer 6. As a result, the barrier layer 4 and the first adhesive layer 6 are in contact, and the first adhesive layer 6 and the sealant layer 5 are in contact.

[0020] The packaging material 2 shown in Figure 2 comprises a first base layer 3, a barrier layer 4, a second base layer 7, and a sealant layer 5 in this order. The first base layer 3 constitutes one side of the packaging material 2. The sealant layer 5 constitutes the other side of the packaging material 2. The barrier layer 4 and the second base layer 7 are joined by a first adhesive layer 6. As a result, the barrier layer 4 and the first adhesive layer 6 are in contact, and the first adhesive layer 6 and the second base layer 7 are in contact. The second base layer 7 and the sealant layer 5 are joined by a second adhesive layer 8. As a result, the second base layer 7 and the second adhesive layer 8 are in contact, and the second adhesive layer 8 and the sealant layer 5 are in contact.

[0021] The packaging material 2 shown in Figure 3 comprises a second base layer 7, a first base layer 3, a barrier layer 4, and a sealant layer 5 in this order. The second base layer 7 constitutes one side of the packaging material 2. The sealant layer 5 constitutes the other side of the packaging material 2. The barrier layer 4 and the sealant layer 5 are joined by a first adhesive layer 6. As a result, the barrier layer 4 and the first adhesive layer 6 are in contact, and the first adhesive layer 6 is in contact with the sealant layer 5. The second base layer 7 and the first base layer 3 are joined by a second adhesive layer 8. As a result, the second base layer 7 and the second adhesive layer 8 are in contact, and the second adhesive layer 8 is in contact with the first base layer 3.

[0022] As described later, the first base layer contains a polyester resin, preferably polyethylene terephthalate or polybutylene terephthalate. Embodiments in which the first base layer containing polyethylene terephthalate constitutes one side of the packaging material are preferred from the viewpoint of hygroscopicity. Embodiments in which the first base layer containing polybutylene terephthalate constitutes one side of the packaging material are preferred from the viewpoint of puncture strength.

[0023] As described later, the second base layer contains a polyamide resin. In the embodiment in which the second base layer containing the polyamide resin constitutes one surface of the packaging material, the second base layer is less likely to crack or wear down due to friction between packaging bags, thus preventing poor appearance of the packaging bag and deterioration of its gas barrier properties. Furthermore, the embodiment in which the second base layer containing the polyamide resin constitutes one surface of the packaging material is preferable from the viewpoint of transparency.

[0024] The oxygen permeability of the packaging material disclosed herein, under conditions of 23°C and 90% relative humidity, is 1.5 mL / m³. ２ - The pressure is less than or equal to day·MPa, preferably 1.2 mL / m² ２ - day·MPa or less, more preferably 1.0 mL / m² ２ The oxygen permeability is less than or equal to day·MPa. Such packaging materials have excellent oxygen barrier properties and can suppress the deterioration of the contents of the packaging bag. The oxygen permeability of the packaging material disclosed herein at a temperature of 23°C and a relative humidity of 90% is preferably 0.05 mL / m³. ２ - day·MPa or higher, more preferably 0.1 mL / m² ２- The pressure is 1 / day MPa or higher, and more preferably 0.2 mL / m². ２ - The pressure must be 1 / day MPa or higher. Oxygen permeability measurement shall be performed in accordance with JIS K 7126-2:2006 (isobaric method).

[0025] The water vapor transmission rate of the packaging material disclosed herein, under conditions of 40°C and 90% relative humidity, is preferably 0.8 g / m³. ２ - Less than or equal to 0.5 g / m² ２ - less than or equal to 0.45 g / m² ２ - less than or equal to 1 day. Such packaging materials have excellent water vapor barrier properties and can suppress deterioration of the contents of the packaging bag. The water vapor transmission rate of the packaging material disclosed herein at a temperature of 40°C and a relative humidity of 90% is preferably 0.01 g / m³. ２ - day or more, more preferably 0.1 g / m ２ - day or more, more preferably 0.3 g / m ２ - The value is 2 days or more. Water vapor transmission rate will be measured in accordance with JIS K 7129:2008 (Method B).

[0026] The puncture strength from one side of the packaging material is preferably 3 N / 1 mmΦ or higher, more preferably 4 N / 1 mmΦ or higher, and even more preferably 5 N / 1 mmΦ or higher. Such packaging material exhibits excellent resistance to external punctures. The puncture strength from the other side of the packaging material is preferably 3 N / 1 mmΦ or higher, more preferably 4 N / 1 mmΦ or higher, and even more preferably 5 N / 1 mmΦ or higher. Packaging bags made from such packaging material exhibit excellent resistance to internal punctures, even when containing sharp contents. Puncture strength is measured in accordance with JIS Z 1707:2019 7.4.

[0027] The tear strength in the MD direction of the packaging material of this disclosure is preferably 0.1 N or higher, more preferably 0.2 N or higher, and even more preferably 0.3 N or higher. Such packaging material exhibits excellent resistance to bag breakage. The tear strength in the TD direction of the packaging material of this disclosure is preferably 0.1 N or higher, more preferably 0.2 N or higher, and even more preferably 0.3 N or higher. Such packaging material exhibits excellent resistance to bag breakage. The tear strength is measured in accordance with JIS K 7128-2:1998.

[0028] The tensile strength in the MD direction of the packaging material of this disclosure is preferably 20 N / 15 mm or more, more preferably 30 N / 15 mm or more, and even more preferably 40 N / 15 mm or more. Such packaging material has excellent tear resistance. The tensile strength in the TD direction of the packaging material of this disclosure is preferably 20 N / 15 mm or more, more preferably 30 N / 15 mm or more, and even more preferably 40 N / 15 mm or more. Such packaging material has excellent tear resistance. The tensile strength is measured in accordance with JIS K 7127:1999.

[0029] In this disclosure, the mechanical flow direction of the first base material layer, the second base material layer, or the packaging material is referred to as the MD direction, and the direction perpendicular to the MD direction is referred to as the TD direction.

[0030] In one embodiment, the color difference ΔE between the color tone of SigmaTube (registered trademark, product number GT-1525, thickness 60 μm, manufactured by Chlorin Chemicals Co., Ltd.; hereinafter also simply referred to as "SigmaTube") and the packaging material of this disclosure. ＊ ab(1) is between 0.40 and 0.80. The commonly used color difference ΔE ＊ The criterion for determining ab is the color difference ΔE. ＊ The range in which ab is between 0.4 and 0.8 is called the AAA tolerance, and it represents the limit for setting strict tolerance color difference standards in terms of the reproducibility of visual judgment. In other words, the packaging material of this disclosure has a slightly different color tone compared to Sigma Tube.

[0031] Under the conditions of a D65 light source and a 2° field of view, and in accordance with JIS Z 8722:2009, the reflectance spectral spectrum of the sigma tube was measured in 1 nm increments in the wavelength range of 380 to 780 nm using a UV-Vis-Infrared spectrophotometer (product name: V-670, manufactured by JASCO Corporation), and the color tone of the sigma tube was defined according to CIE1976L. ＊ a ＊ b ＊ When displayed in the color space, L ＊ 99.159, and a ＊ The value is -0.038, and b ＊ This is 0.349. That is, the color difference ΔE between the color tone of the Sigma Tube and the packaging material of this disclosure. ＊ If ab(1) is between 0.40 and 0.80, it means that the L in the CIE 1976 color space is calculated from the reflection spectral spectrum measured in accordance with JIS Z 8722:2009 under the conditions of a D65 light source and a 2° viewing angle. ＊ 99.159, and a ＊ The value is -0.038, and b ＊ The color difference ΔE between the color tone of the film, which has a value of 0.349, and the color tone of the packaging material of this disclosure. ＊ This means that ab(1) is between 0.40 and 0.80.

[0032] In one embodiment, the color difference ΔE ＊ ab(1) measures the color tone of the packaging material of the present disclosure in the same manner as SigmaTube, and the color tone of the packaging material of the present disclosure is CIE1976L ＊ a ＊ b ＊ L when displayed in the color space ＊ a ＊ and b ＊ The values ​​are calculated by determining each of the following equations (1): ΔE ＊ ab(1)={(99.159-L ＊ ) ２ +(-0.038-a ＊ ) ２ + (0.349 - b) ＊ ) ２} １／２ ...Formula (1)

[0033] In one embodiment, the color of nylon poly TL type 10-15 (product name, thickness 70 μm, size 100 mm x 150 mm, manufactured by Fukusuke Kogyo Co., Ltd., hereinafter also simply referred to as "nylon poly") and the color difference ΔE between it and the packaging material of this disclosure. ＊ ab(2) is between 0.25 and 0.50. Such packaging materials have a slightly different color tone compared to nylon poly.

[0034] Under the conditions of a D65 light source and a 2° field of view, and in accordance with JIS Z 8722:2009, the reflectance spectral spectrum of nylon poly was measured in the wavelength range of 380 to 780 nm in 1 nm increments using a UV-Vis-Infrared spectrophotometer (product name: V-670, manufactured by JASCO Corporation), and the color tone of the nylon poly was determined according to CIE1976L. ＊ a ＊ b ＊ When displayed in the color space, L ＊ 98.869, a ＊ The value is -0.079, and b ＊ This is 0.298. That is, the color difference ΔE between the color tone of nylon poly and the packaging material of this disclosure. ＊ If ab(2) is between 0.25 and 0.50, it means that the L in the CIE 1976 color space is calculated from the reflectance spectral spectrum measured in accordance with JIS Z 8722:2009 under the conditions of a D65 light source and a 2° viewing angle. ＊ 98.869, a ＊ The value is -0.079, and b ＊ The color difference ΔE between the color tone of the film, where ΔE is 0.298, and the color tone of the packaging material of this disclosure. ＊ This means that ab(2) is between 0.25 and 0.50.

[0035] In one embodiment, the color difference ΔE ＊ ab(2) measures the color tone of the packaging material of the present disclosure in the same manner as nylon poly, and the color tone of the packaging material of the present disclosure is CIE1976L ＊ a ＊ b ＊ L when displayed in the color space ＊ a ＊ and b ＊ The values ​​are calculated by determining each of the following equations (2): ΔE ＊ab(2) = {(98.869 - L ＊ ) ２ + (-0.079 - a ＊ ) ２ + (0.298 - b ＊ ) ２} １／２ ・・・Equation (2)

[0036] In one embodiment, the color difference ΔE ＊ ab(3) between the packaging material of the present disclosure and the color tone of the D65 light source is 1.20 or more and 1.80 or less. Such a packaging material has a somewhat different color tone compared to the D65 light source.

[0037] When the color tone of the D65 light source is displayed in the CIE1976L ＊ a ＊ b ＊ color space, L ＊ is 100.000, a ＊ is -0.070, and b ＊ is 0.129. Also, the color tone of the packaging material of the present disclosure is calculated from the reflection spectrum measured in accordance with JIS Z 8722:2009 under the conditions of the D65 light source and a 2° viewing angle. That is, the fact that the color difference ΔE ＊ ab(3) between the packaging material of the present disclosure and the color tone of the D65 light source is 1.20 or more and 1.80 or less means that the color difference ΔE ＊ ab(3) between the color tone of the packaging material of the present disclosure, calculated from the reflection spectrum measured in accordance with JIS Z 8722:2009 under the conditions of the D65 light source and a 2° viewing angle, and the color tone of the D65 light source is 1.20 or more and 1.80 or less.

[0038] In one embodiment, the color difference ΔE ＊ ab(3) is a value calculated by the following equation (3) by measuring the packaging material of the present disclosure in accordance with JIS Z 8722:2009 under the conditions of the D65 light source and a 2° viewing angle, and obtaining L ＊ a ＊ b ＊ when the color tone of the packaging material of the present disclosure is displayed in the CIE1976L ＊ a ＊ and b ＊ respectively. ΔE ＊ab(3)={(100.000-L ＊ ) ２ +(-0.070-a ＊ ) ２ + (0.129 - b) ＊ ) ２} １／２ ...Formula (3)

[0039] Details of the color tone measurement method are as described in the examples below.

[0040] The total thickness of the packaging material of this disclosure is preferably 70 μm or more, more preferably 76 μm or more, and also preferably 100 μm or less, and more preferably 93 μm or less. Such packaging material has the above color difference ΔE ＊ It becomes easier to adjust ab(1) to a range of 0.40 or more and 0.80 or less, and the above color difference ΔE ＊ This makes it easier to adjust ab(2) to a range of 0.25 or more and 0.50 or less, and the above color difference ΔE ＊ This makes it easier to adjust ab(3) to a range of 1.20 to 1.80.

[0041] Next, each layer constituting the packaging material of this disclosure will be described.

[0042] [First Substrate Layer] The first substrate layer is a layer that has excellent chemical and physical strength, can withstand the conditions for forming a vapor-deposited film, and can maintain the film properties of the vapor-deposited film well without impairing them. The first substrate layer contains a polyester resin and may further contain a resin other than a polyester resin. Examples of resins other than polyester resins include polyolefin resins such as polyethylene resins or polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), poly(meth)acrylic resins, polycarbonate resins, polyvinyl alcohol resins, ethylene-vinyl ester copolymer saponifies, polyamide resins, polyurethane resins, acetal resins, and cellulose resins. In one embodiment, the first substrate layer is a film containing a polyester resin.

[0043] Examples of polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polypropylene terephthalate (PPT), 1,4-polycyclohexylenedimethylene terephthalate, and terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer. Among these, polyethylene terephthalate or polybutylene terephthalate is preferred from the viewpoint of strength, and polyethylene terephthalate is more preferred. Furthermore, polybutylene terephthalate is preferred from the viewpoint of puncture strength.

[0044] The first substrate layer may contain various additives to the extent that the properties of the present disclosure are not impaired. Examples of additives include plasticizers, ultraviolet stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducers, mold release agents, antioxidants, ion exchange agents, and coloring pigments. The content of these additives is, for example, 5% by mass or more and 50% by mass or less.

[0045] To obtain a first base material layer by processing a resin such as polyester resin into a film, a general method for forming a film from resin can be employed. Specifically, resin pellets are dried and then supplied to a melt extruder heated to a temperature above the melting point (Tm) of the pellets and below Tm + 70°C to melt the pellets. The pellets are then extruded into a sheet shape through a die, such as a T-die, and the extruded sheet is rapidly cooled and solidified in a rotating cooling drum or the like to form the first base material layer. The first base material layer obtained in this way consists of a single layer. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vented extruder, a tandem extruder, etc., can be used depending on the purpose.

[0046] The first substrate layer is preferably biaxially stretched. Biaxial stretching can be carried out by conventionally known methods, and may be sequential or simultaneous biaxial stretching. Sequential and simultaneous biaxial stretching will be described below.

[0047] <Sequential Biaxial Stretching> In sequential biaxial stretching, the film extruded onto the cooling drum as described above is stretched longitudinally, and then the film is stretched transversely. Longitudinal stretching is usually performed by the difference in peripheral speed of the rolls and may be done in one stage or in multiple stages using multiple pairs of rolls. The longitudinal stretching ratio is preferably 2.0 times or more, more preferably 2.5 times or more, also preferably 15.0 times or less, more preferably 7.0 times or less, even more preferably 5.0 times or less, and even more preferably 4.2 times or less. This suppresses variations in optical properties such as in-plane phase difference. The stretching temperature is preferably 50°C or higher, more preferably 80°C or higher, even more preferably 95°C or higher, also preferably 120°C or lower, more preferably 115°C or lower, and even more preferably 110°C or lower. This suppresses variations in optical properties such as in-plane phase difference.

[0048] Transverse stretching is usually performed using the tenter method, where the film is transported while being held at both ends with clips and stretched transversely. The transverse stretching ratio is preferably 2 times or more, more preferably 2.5 times or more, and preferably 15 times or less, and more preferably 5 times or less. This suppresses variations in optical properties such as in-plane phase difference. The stretching temperature is preferably 50°C or higher, more preferably 90°C or higher, even more preferably 95°C or higher, and also preferably 120°C or lower, more preferably 110°C or lower, and even more preferably 105°C or lower. This suppresses variations in optical properties such as in-plane phase difference.

[0049] As described above, the sequentially biaxially stretched film is preferably subjected to a heat treatment in a tenter, above the stretching temperature but below the melting point, in order to impart flatness and dimensional stability. Specifically, heat setting is preferably performed at 120°C or higher, more preferably 190°C or higher, and more preferably 235°C or lower, and more preferably 225°C or lower. Furthermore, from the viewpoint of suppressing variations in optical properties such as in-plane phase difference, it is preferable to perform a heat treatment follow-up stretch of 1% to 10% in the first half of the heat treatment. This suppresses variations in optical properties such as in-plane phase difference. After the heat treatment, the film is slowly cooled to room temperature and then wound up. In addition, if necessary, a relaxation treatment may be used in combination with the heat treatment and slow cooling. The relaxation rate during heat treatment is preferably 0.5% or higher, more preferably 0.8% or higher, even more preferably 1% or higher, also preferably 5% or lower, more preferably 3% or lower, even more preferably 2.5% or lower, and even more preferably 2% or lower. This suppresses variations in optical properties such as in-plane phase difference. The relaxation rate during slow cooling is preferably 0.5% or more, more preferably 3% or less, more preferably 2% or less, even more preferably 1.5% or less, and even more preferably 1.0% or less. This suppresses variations in optical properties such as in-plane phase difference. From the viewpoint of flatness, the temperature during slow cooling is preferably 80°C or more, more preferably 90°C or more, even more preferably 100°C or more, more preferably 150°C or less, more preferably 130°C or less, and even more preferably 120°C or less.

[0050] <Simultaneous Biaxial Stretching> In simultaneous biaxial stretching, the film extruded onto the cooling drum as described above is guided to a simultaneous biaxial tenter, and while gripping both ends of the film with clips, it is transported and stretched simultaneously and / or in stages in the longitudinal and transverse directions. Simultaneous biaxial stretching machines include pantograph type, screw type, drive motor type, and linear motor type, but the drive motor type or linear motor type is preferred because the stretching ratio can be changed arbitrarily and relaxation processing can be performed at any point.

[0051] The magnification ratio for simultaneous biaxial stretching is preferably 2 times or more, more preferably 3 times or more, even more preferably 6 times or more, even more preferably 10 times or more, and also preferably 50 times or less, more preferably 30 times or less, even more preferably 25 times or less, even more preferably 20 times or less, and particularly preferably 15 times or less. This suppresses variations in optical properties such as in-plane phase difference. Furthermore, in the case of simultaneous biaxial stretching, in order to suppress in-plane orientation differences, it is preferable to make the stretching magnification ratio in the longitudinal and transverse directions the same, and to make the stretching speeds approximately equal.

[0052] The stretching temperature for simultaneous biaxial stretching is preferably 50°C or higher, more preferably 90°C or higher, even more preferably 100°C or higher, and also preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 140°C or lower. This suppresses variations in optical properties such as in-plane phase difference.

[0053] It is preferable to subsequently heat-treat the simultaneously biaxially stretched film in a heat-setting chamber within a tenter, above the stretching temperature and below the melting point, in order to impart flatness and dimensional stability. The conditions for this heat treatment are the same as those for the heat treatment after sequential biaxial stretching.

[0054] The thickness of the first substrate layer is preferably 5 μm or more, more preferably 6 μm or more, even more preferably 9 μm or more, and also preferably 2000 μm or less, more preferably 500 μm or less, and even more preferably 100 μm or less. The breaking strength of such a first substrate layer is 1 kg / mm ​​in the MD direction. ２ 40 kg / mm² or more ２ Below, 1 kg / mm² in the TD direction. ２ 35kg / mm ​​or more ２ The following conditions apply, and the elongation at break is 10% to 350% in the MD direction and 3% to 300% in the TD direction.

[0055] Although the first base layer 3 shown in Figures 1 and 2 is composed of a single layer, the first base layer of the packaging material of this disclosure is not limited to a single layer configuration and may be a multilayer configuration. If the first base layer is a multilayer configuration, at least one layer may contain a polyester resin, and the other layers may not contain a polyester resin.

[0056] The first substrate layer may be subjected to secondary processing for the purpose of imparting chemical, electrical, magnetic, mechanical, friction / wear / lubrication, optical, thermal, biocompatibility, and other surface functions. Examples of secondary processing include embossing, painting, bonding, printing, and machining. Furthermore, metallizing (such as plating) may be applied as a secondary processing to the surface on which the vapor-deposited film is not formed (the side opposite to the surface on which the vapor-deposited film is formed), as long as the properties of this disclosure are not impaired.

[0057] Furthermore, as a secondary process, the first substrate layer may be subjected to surface treatment. By performing surface treatment on one side of the first substrate layer before forming the vapor-deposited film, the adhesion between the substrate and the vapor-deposited film can be improved. 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. Alternatively, a primer coat agent, undercoat agent, vapor deposition anchor coat agent, etc., can be applied to the surface of the first substrate layer beforehand as a surface treatment. As a coating agent, for example, a resin composition in which polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenolic resin, (meth)acrylic resin, polyvinyl acetate resin, polyolefin resin such as polyethylene or polypropylene, or copolymers or modified resins thereof, cellulose resin, etc., can be used as the main component of the vehicle.

[0058] Among surface treatments, corona treatment or plasma treatment is preferred, and plasma treatment is more preferred. Plasma treatment includes surface modification using plasma gas generated by ionizing a gas with an arc discharge. Inorganic gases such as oxygen, nitrogen, argon, and helium can be used as plasma gases. For example, by performing plasma treatment in-line immediately before forming a deposited film by chemical vapor deposition, moisture, dust, etc. on the surface of the first substrate layer can be removed, and the surface can be smoothed, activated, and other surface treatments can be performed. Plasma treatment can also be performed after deposition to improve the adhesion between the deposited film and other layers. Plasma discharge treatment is preferably performed considering the plasma output, type of plasma gas, amount of plasma gas supplied, treatment time, and other conditions. Methods for generating plasma include DC glow discharge, high-frequency discharge, and microwave discharge. Plasma treatment can also be performed using atmospheric pressure plasma treatment.

[0059] [Barrier Layer] The barrier layer provided by the packaging material according to this disclosure is a vapor-deposited metal oxide film. The vapor-deposited film can be formed using a conventionally known metal oxide and by a conventionally known method, and its composition and formation method are not particularly limited. By providing the packaging material with a vapor-deposited metal oxide film, gas barrier properties that prevent the transmission of oxygen gas and water vapor, and light-shielding properties that prevent the transmission of visible light and ultraviolet light can be provided or improved. The packaging material may have two or more vapor-deposited films. If there are two or more vapor-deposited films, each may have the same composition or different compositions.

[0060] As the metal oxide vapor-deposited film, for example, vapor-deposited films of metal oxides such as silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), and yttrium (Y) can be used. In particular, suitable metal oxides for the packaging material of this disclosure include aluminum oxide or silicon oxide, with aluminum oxide being preferred.

[0061] Metal oxides are written as, for example, SiO Ｘ AlO Ｘ MO Ｘ (However, in the formula, M represents a metallic element, and the range of X varies depending on the metallic element.) The range of X values ​​is as follows: silicon (Si) is greater than 0 and less than or equal to 2, aluminum (Al) is greater than 0 and less than or equal to 1.5, magnesium (Mg) is greater than 0 and less than or equal to 1, calcium (Ca) is greater than 0 and less than or equal to 1, potassium (K) is greater than 0 and less than or equal to 0.5, tin (Sn) is greater than 0 and less than or equal to 2, sodium (Na) is greater than 0 and less than or equal to 0.5, boron (B) is greater than 0 and less than or equal to 1.5, titanium (Ti) is greater than 0 and less than or equal to 2, lead (Pb) is greater than 0 and less than or equal to 1, zirconium (Zr) is greater than 0 and less than or equal to 2, and yttrium (Y) is greater than 0 and less than or equal to 1.5. When X = 0, it is a perfect elemental metal (pure substance), which is not transparent, and the upper limit of the range of X is the value when it is completely oxidized. Suitable packaging materials include silicon (Si) and aluminum (Al). For silicon (Si), the X range can be 1.0 to 2.0, and for aluminum (Al), the X range can be 0.5 to 1.5.

[0062] In this disclosure, the thickness of the metal oxide vapor-deposited film as described above varies depending on the type of metal oxide used, but is preferably 50 Å or more, more preferably 100 Å or more, and also preferably 2000 Å or less, and more preferably 1000 Å or less. By adjusting the thickness of the vapor-deposited film, the above color difference ΔE ＊ ab can be adjusted to a range of 0.40 to 0.80. When the vapor-deposited film is an aluminum oxide or silicon oxide vapor-deposited film, the film thickness is preferably 50 Å or more, more preferably 100 Å or more, and also preferably 500 Å or less, and more preferably 300 Å or less.

[0063] Examples of methods for forming deposited films include physical vapor deposition (PVD) methods such as vacuum deposition, sputtering, or ion plating, or chemical vapor deposition (CVD) methods such as plasma chemical vapor deposition, thermochemical vapor deposition, or photochemical vapor deposition.

[0064] As one aspect of this disclosure, a metal oxide deposition film by physical vapor deposition will be described in more detail below.

[0065] As a metal oxide deposition film by physical vapor deposition (PVD), for example, metal oxide deposition films can be formed using physical vapor deposition methods such as vacuum deposition, sputtering, ion plating, and ion cluster beam deposition.

[0066] Specifically in this disclosure, a deposited film can be formed using a vacuum deposition method in which a metal oxide is used as a raw material, heated to vaporize it, and deposited onto the surface of a first substrate layer or a second substrate layer described later; an oxidation reaction deposition method in which a metal or metal oxide is used as a raw material, oxygen is introduced to oxidize it, and it is deposited onto the surface of a first substrate layer or a second substrate layer; or a plasma-assisted oxidation reaction deposition method in which the oxidation reaction is assisted by plasma. In the above, the heating method for the deposition material can be, for example, a resistance heating method, a high-frequency induction heating method, an electron beam heating method (EB), etc.

[0067] As the metal oxide deposition film by the above physical vapor deposition method, for example, specifically, it is preferable to use an amorphous thin film of aluminum oxide, and more specifically, the formula AlO Ｘ An amorphous thin film of aluminum oxide represented by the formula AlO(A) (wherein X represents a number in the range of 0.5 to 1.5) can be used, wherein the amorphous thin film of aluminum oxide consists of an amorphous thin film of aluminum oxide in which the value of X decreases in the depth direction from the surface of the thin film toward the interior. Alternatively, in this disclosure, the amorphous thin film of aluminum oxide may be the amorphous thin film of aluminum oxide represented by the formula AlO(A)Ｘ An amorphous thin film of aluminum oxide represented by the formula (wherein X represents a number in the range of 0.5 to 1.5) can be used, wherein the amorphous thin film of aluminum oxide has an increasing value of X in the depth direction from the surface of the thin film toward the interior. In this disclosure, as for the value of X in the above formula, basically, a value of X of 0.5 or more can be used, but in this disclosure, if X is less than 1.0, the discoloration is severe and the transparency is poor, so it is preferable to use a value of X of 1.0 or more, and since a value of X of 1.5 represents a state in which aluminum and oxygen are completely oxidized, as an upper limit, a value of X of 1.5 or less can be used.

[0068] Next, in this disclosure, the thickness of the amorphous thin film of aluminum oxide is preferably 10 Å or more, more preferably 60 Å or more, and preferably 3000 Å or less, and more preferably 1000 Å or less.

[0069] Furthermore, in this disclosure, an amorphous thin film of aluminum oxide can be formed using a roll-up type vacuum deposition apparatus. In the above deposition, the vacuum level of the vacuum chamber is preferably 10 －５ mbar or higher, more preferably 10 －４ It is 10 mbar or higher, and preferably 10 ０ It is less than or equal to mbar, more preferably 10 －１ It is less than or equal to mbar. Furthermore, the vacuum level of the deposition chamber is preferably 10 before oxygen is introduced. －８ mbar or higher, more preferably 10 －７ It is 10 mbar or higher, and preferably 10 －２ It is less than or equal to mbar, more preferably 10 －３ It is less than or equal to mbar, and after oxygen introduction, preferably 10 －６ mbar or higher, more preferably 10 －５ It is 10 mbar or higher, and preferably 10 －１ It is less than or equal to mbar, more preferably 10 －２The pressure is less than or equal to mbar. The transport speed of the first or second substrate layer is preferably 10 m / min or more, more preferably 50 m / min or more, and preferably 800 m / min or less, and more preferably 600 m / min or less. The amount of oxygen introduced will vary depending on the size of the vapor deposition machine, etc.

[0070] In this disclosure, in the thin film layer made of a metal oxide by the above-described physical vapor deposition method, the ultraviolet (wavelength 366 nm) transmittance of the aluminum oxide vapor deposition film during and immediately after deposition is preferably 85% or more, more preferably 87% or more, and also preferably 96% or less, and more preferably 94% or less. If the ultraviolet transmittance is too low, the transparency decreases. Also, if the ultraviolet transmittance of the aluminum oxide vapor deposition film is too high, the degree of oxidation of the aluminum oxide is high, and the resulting film becomes hard, making it prone to cracking. The thickness of the aluminum oxide vapor deposition film is preferably 150 Å or more and 600 Å or less, taking into consideration suitability for post-processing. Furthermore, as the silicon oxide vapor deposition film, a silicon oxide vapor deposition film made by physical vapor deposition using a mixture of silicon monoxide and silicon as raw materials, with a thickness in the range of 50 Å or more and 300 Å or less, taking into consideration suitability for post-processing, is preferred.

[0071] In this disclosure, when forming a metal oxide vapor-deposited film on a first substrate layer, it is preferable to pre-treat the surface of the first substrate layer with an inert gas plasma treatment to provide a plasma-treated surface, etc., from the viewpoint of improving the adhesion between the surface of the first substrate layer and the surface of the metal oxide vapor-deposited film, and ultimately firmly bonding the two together to prevent the occurrence of delamination (derami). In this disclosure, when forming a metal oxide vapor-deposited film on a second substrate layer, it is preferable to pre-treat the surface of the second substrate layer with an inert gas plasma treatment to provide a plasma-treated surface, etc., from the viewpoint of improving the adhesion between the surface of the second substrate layer and the surface of the metal oxide vapor-deposited film, and ultimately firmly bonding the two together to prevent the occurrence of delamination (derami).

[0072] In this disclosure, a plasma-treated surface using an inert gas will be described. Such a plasma-treated surface can be formed on one surface of either the first or second substrate layer by using a plasma surface treatment method that modifies the surface using plasma gas generated by ionizing a gas by arc discharge. Specifically, in this disclosure, a plasma-treated surface can be formed by performing plasma treatment using a plasma surface treatment method that uses an inert gas such as nitrogen gas, argon gas, or helium gas as the plasma gas. In this disclosure, a mixed gas obtained by adding oxygen gas to the above-mentioned inert gas can also be used as the plasma gas.

[0073] Furthermore, in this disclosure, when forming a plasma-treated surface with an inert gas, it is desirable to perform plasma treatment in-line immediately before forming a deposited metal oxide film by, for example, physical vapor deposition or chemical vapor deposition, as this removes moisture, dust, etc. from the surface of the first or second substrate layer, and enables surface treatment such as smoothing and activation of the surface.

[0074] Furthermore, in this disclosure, it is preferable to perform plasma discharge processing as the plasma processing, taking into consideration conditions such as plasma output, type of plasma gas, amount of plasma gas supplied, and processing time. In addition, in this disclosure, plasma can be generated using, for example, devices such as DC glow discharge, high-frequency discharge, and microwave discharge. In addition, in this disclosure, a plasma-treated surface can also be formed using atmospheric pressure plasma processing or the like.

[0075] (Film Deposition Apparatus) Next, an example of a film deposition apparatus 10 used for forming a vapor-deposited film will be described. As shown in Figure 4, the film deposition apparatus 10 includes a substrate transport mechanism 11A for transporting a substrate 1 that will become the first substrate layer or the second substrate layer, a plasma pretreatment mechanism 11B for applying plasma pretreatment to the surface of the substrate 1, and a film deposition mechanism 11C for depositing a vapor-deposited film. In the example shown in Figure 4, the film deposition apparatus 10 further includes a vacuum chamber 12. The vacuum chamber 12 has a vacuum mechanism, such as a vacuum pump described later, that adjusts the atmosphere of at least a part of the space inside the vacuum chamber 12 to below atmospheric pressure.

[0076] In the example shown in Figure 4, the depressurization chamber 12 includes a substrate transport chamber 12A where the substrate transport mechanism 11A is located, a plasma pretreatment chamber 12B where the plasma pretreatment mechanism 11B is located, and a film deposition chamber 12C where the film deposition mechanism 11C is located. Preferably, the depressurization chamber 12 is configured to suppress the mixing of the atmospheres inside each chamber. For example, as shown in Figure 4, the depressurization chamber 12 may have partition walls 35a to 35c located between the substrate transport chamber 12A and the plasma pretreatment chamber 12B, between the plasma pretreatment chamber 12B and the film deposition chamber 12C, and between the substrate transport chamber 12A and the film deposition chamber 12C, separating each chamber.

[0077] The substrate transport chamber 12A, the plasma pretreatment chamber 12B, and the film deposition chamber 12C will now be described. The plasma pretreatment chamber 12B and the film deposition chamber 12C are each provided in contact with the substrate transport chamber 12A and each has a portion that connects to the substrate transport chamber 12A. This allows the substrate 1 to be transported between the substrate transport chamber 12A and the plasma pretreatment chamber 12B, and between the substrate transport chamber 12A and the film deposition chamber 12C, without being exposed to the atmosphere. For example, between the substrate transport chamber 12A and the plasma pretreatment chamber 12B, the substrate 1 can be transported through an opening provided in the partition wall 35a. The structure between the substrate transport chamber 12A and the film deposition chamber 12C is similar, and the substrate 1 can be transported between the substrate transport chamber 12A and the film deposition chamber 12C.

[0078] The function of the depressurization mechanism of the depressurization chamber 12 will now be described. The depressurization mechanism of the depressurization chamber 12 is configured to reduce the atmosphere in the space where at least the plasma pretreatment mechanism 11B or the film deposition mechanism 11C of the film deposition apparatus 10 is located to below atmospheric pressure. The depressurization mechanism may be configured to reduce the pressure in each of the substrate transport chamber 12A, the plasma pretreatment chamber 12B, and the film deposition chamber 12C, which are partitioned by partition walls 35a to 35c, to below atmospheric pressure.

[0079] The configuration of the depressurization mechanism of the depressurization chamber 12 will now be described. The depressurization chamber 12 may have, for example, a vacuum pump connected to the plasma pretreatment chamber 12B. By adjusting the vacuum pump, the pressure inside the plasma pretreatment chamber 12B can be appropriately controlled when performing the plasma pretreatment described later. Furthermore, the diffusion of the plasma supplied to the plasma pretreatment chamber 12B into other chambers can be suppressed by the method described later. The depressurization mechanism of the depressurization chamber 12 may have a vacuum pump connected to the film deposition chamber 12C, similar to the vacuum pump connected to the plasma pretreatment chamber 12B. As the vacuum pump, a dry pump, turbomolecular pump, cryopump, rotary pump, diffusion pump, etc. can be used.

[0080] The substrate transport mechanism 11A of the film deposition apparatus 10 according to this embodiment will be described along with the transport path of the substrate 1. The substrate transport mechanism 11A is a mechanism for transporting the substrate 1 located in the substrate transport chamber 12A. In the example shown in Figure 4, the substrate transport mechanism 11A has an unwinding roller 13 to which a roll of the substrate 1 is attached, a winding roller 15 for winding the substrate 1, and guide rolls 14a to 14d. The substrate 1 sent out from the substrate transport mechanism 11A is then transported by a pre-treatment roller 20 located in the plasma pre-treatment chamber 12B, which will be described later, and a film deposition roller 25 located in the film deposition chamber 12C, which will be described later.

[0081] Although not shown in the figures, the substrate transport mechanism 11A may further include a tension pickup roller. By having a tension pickup roller in the substrate transport mechanism 11A, the substrate 1 can be transported while adjusting the tension applied to the substrate 1.

[0082] (Plasma Pretreatment Mechanism) The plasma pretreatment mechanism 11B will now be described. The plasma pretreatment mechanism 11B is a mechanism for applying plasma pretreatment to the surface of the substrate 1. The plasma pretreatment mechanism 11B shown in Figure 4 generates plasma P and uses the generated plasma P to apply plasma pretreatment to the surface of the substrate 1. Plasma pretreatment activates the surface of the substrate 1, making it easier for nitrogen contained inside the substrate 1 to accumulate on the surface of the substrate 1, or for nitrogen contained in the environment surrounding the substrate 1 to be incorporated into the surface of the substrate 1. As a result, when a vapor-deposited film is formed on the surface of the plasma pretreatment-treated substrate 1, a peak of element-bonded CN can be formed at the interface between the substrate 1 and the vapor-deposited film. The plasma pretreatment mechanism 11B shown in Figure 4 includes a pretreatment roller 20 located in the plasma pretreatment chamber 12B, an electrode section 21 facing the pretreatment roller 20, and a magnetic field forming section 23 that forms a magnetic field between the pretreatment roller 20 and the electrode section 21.

[0083] The pre-treatment roller 20 will now be described. Figure 5 is an enlarged view of the area enclosed by the dashed line labeled VI in Figure 4. Note that in Figure 5, the power supply wiring 31 connecting the power supply 32 shown in Figure 4 and the electrode section 21, which will be described later, and the plasma P generated by the plasma pre-treatment mechanism 11B are omitted. The pre-treatment roller 20 has a rotation axis X. The pre-treatment roller 20 is installed such that at least the rotation axis X is located within the plasma pre-treatment chamber 12B partitioned by partition walls 35a and 35b. A substrate 1 having dimensions in the direction of the rotation axis X is wound around the pre-treatment roller 20. In the following description, the dimensions of the substrate 1 in the direction of the rotation axis X will also be referred to as the width of the substrate 1. The direction of the rotation axis X will also be referred to as the width direction of the substrate 1.

[0084] As shown in Figure 4, the pre-treatment roller 20 may be provided such that a portion of it is exposed to the substrate transport chamber 12A. In the example shown in Figure 4, the plasma pre-treatment chamber 12B and the substrate transport chamber 12A are connected via an opening in the partition wall 35a, and a portion of the pre-treatment roller 20 is exposed to the substrate transport chamber 12A through this opening. There is a gap between the partition wall 35a between the substrate transport chamber 12A and the plasma pre-treatment chamber 12B and the pre-treatment roller 20, and the substrate 1 can be transported from the substrate transport chamber 12A to the plasma pre-treatment chamber 12B through this gap. Although not shown, the pre-treatment roller 20 may be provided such that its entirety is located inside the plasma pre-treatment chamber 12B.

[0085] Although not shown in the figures, the pre-treatment roller 20 may have a temperature control mechanism for adjusting the surface temperature of the pre-treatment roller 20. For example, the pre-treatment roller 20 may have a temperature control mechanism inside the pre-treatment roller 20 that includes piping for circulating a temperature control medium such as a refrigerant or a heat transfer medium. The temperature control mechanism adjusts the surface temperature of the pre-treatment roller 20 to a target temperature within a range of, for example, -20°C to 100°C.

[0086] The pre-treatment roller 20 has a temperature control mechanism, which helps to suppress shrinkage and damage of the substrate 1 due to heat during plasma pre-treatment.

[0087] The pre-treatment roller 20 is made of a material containing at least one of stainless steel, iron, copper, and chromium. The surface of the pre-treatment roller 20 may be treated with a hard chromium hard coat or the like to prevent scratching. These materials are easy to process. Furthermore, by using the above materials as the material for the pre-treatment roller 20, the thermal conductivity of the pre-treatment roller 20 itself is increased, making it easier to control the temperature of the pre-treatment roller 20.

[0088] The electrode portion 21 will now be described. In the example shown in Figures 4 and 5, the electrode portion 21 has a first surface 21c facing the pre-treatment roller 20 and a second surface 21d located on the opposite side of the first surface 21c. In the example shown in Figures 4 and 5, the electrode portion 21 is a plate-shaped member, and both the first surface 21c and the second surface 21d are planar. The electrode portion 21 generates plasma between itself and the pre-treatment roller 20 by applying an AC voltage to it. Preferably, the electrode portion 21 forms an electric field between itself and the pre-treatment roller 20 such that the generated plasma moves perpendicular to the surface of the substrate 1 so that it is directed toward the surface of the substrate 1. This allows the substrate 1 to be pre-treated efficiently. As a result, when a vapor-deposited film is formed on the surface of the plasma-pre-treated substrate 1, the peak intensity of the element-bonded CN peak formed at the interface between the substrate 1 and the vapor-deposited film can be increased.

[0089] The number of electrode sections 21 is preferably two or more. Preferably, the two or more electrode sections 21 are arranged along the transport direction of the substrate 1. In the examples shown in Figures 4 and 5, an example is shown in which the film deposition apparatus 10 has two electrode sections 21. Also, the number of electrode sections 21 is, for example, 12 or less.

[0090] The effect of having two or more electrode portions 21 arranged along the transport direction of the substrate 1 will be explained. As described above, plasma is generated between the electrode portion 21 and the pre-processing roller 20. The area where plasma is generated expands as the dimensions of the electrode portion 21 in the transport direction increase. On the other hand, if the electrode portion 21 is a flat plate-shaped member, as the dimensions of the electrode portion 21 in the transport direction increase, the distance from the edge of the first surface 21c of the electrode portion 21, which is the surface facing the pre-processing roller 20, to the pre-processing roller 20 increases, and the processing capacity by plasma decreases.

[0091] In the film deposition apparatus 10, two or more electrode sections 21 are arranged along the transport direction of the substrate 1. Therefore, even if the dimensions of the electrode sections 21 in the transport direction of the substrate 1 are small, plasma can be generated over a wide area in the transport direction. Furthermore, by reducing the dimensions of the electrode sections 21, the distance from the edge of the first surface 21c of the electrode section 21 in the transport direction to the pre-treatment roller 20 can be reduced, and plasma can be generated uniformly in the transport direction.

[0092] As shown in Figures 4 and 5, the electrode portion 21 has a first end 21e and a second end 21f located on the first surface 21c of the electrode portion 21. The first end 21e is the upstream end in the conveying direction of the substrate 1, and the second end 21f is the downstream end in the conveying direction of the substrate 1. As described above, by reducing the dimensions of the electrode portion 21 in the conveying direction of the substrate 1, the distance from the first end 21e and the second end 21f of the electrode portion 21 to the pre-processing roller 20 in the conveying direction can be reduced. The dimensions of the electrode portion 21 in the conveying direction of the substrate 1 correspond to the angle θ shown in Figure 5. The angle θ is the angle formed by the line passing through the first end 21e and the rotation axis X and the line passing through the second end 21f and the rotation axis X. The angle θ is preferably 20° or more and 90° or less, more preferably 60° or less, and even more preferably 45° or less. When the angle θ falls within the above range, and the first surface 21c of the electrode portion 21 is flat, plasma can be generated uniformly in the transport direction between the electrode portion 21 and the pre-processing roller 20.

[0093] The material of the electrode portion 21 is not particularly limited as long as it is electrically conductive. Specifically, aluminum, copper, and stainless steel are preferably used as the material for the electrode portion 21.

[0094] The thickness L3 of the electrode portion 21, when viewed in a direction perpendicular to the first surface 21c of the electrode portion 21, is not particularly limited, but is, for example, 15 mm or less. The thickness of the electrode portion 21 being this value allows the magnetic field forming unit 23 to effectively form a magnetic field between the pre-processing roller 20 and the electrode portion 21. Alternatively, the thickness L3 of the electrode portion 21 may be, for example, 3 mm or more.

[0095] The magnetic field forming section 23 will now be described. As shown in Figures 4 and 5, the magnetic field forming section 23 is provided on the side of the electrode section 21 opposite to the side facing the pre-treatment roller 20. The magnetic field forming section 23 is a component that forms a magnetic field between the pre-treatment roller 20 and the electrode section 21. The magnetic field between the pre-treatment roller 20 and the electrode section 21 contributes to the generation of a higher density plasma, for example, when generating plasma using the plasma pre-treatment mechanism 11B. The magnetic field forming section 23 shown in Figures 4 and 5 has a first magnet 231 and a second magnet 232 provided on the second surface 21d of the electrode section 21.

[0096] The number of magnetic field forming units 23 is preferably two or more. When the plasma pretreatment mechanism 11B has two or more electrode units 21 and two or more magnetic field forming units 23, it is preferable that each of the two or more magnetic field forming units 23 is provided on the side of each of the two or more electrode units 21 that is opposite to the side facing the pretreatment roller 20. In the example shown in Figures 4 and 5, each of the two magnetic field forming units 23 is provided on the second surface 21d of each of the two electrode units 21.

[0097] The structure of the first magnet 231 and the second magnet 232 in the direction normal to the second surface 21d of the electrode portion 21 will now be described. As shown in Figures 4 and 5, the first magnet 231 and the second magnet 232 each have an N pole and an S pole. The symbol N in Figures 4 and 5 indicates the N pole of the first magnet 231 or the second magnet 232. The symbol S in Figures 4 and 5 indicates the S pole of the first magnet 231 or the second magnet 232. One of the N poles or S poles of the first magnet 231 is located closer to the base material 1 than the other. The other of the N poles or S poles of the second magnet 232 is located closer to the base material 1 than the other. In the example shown in Figures 4 and 5, the N pole of the first magnet 231 is located closer to the base material 1 than the S pole of the first magnet 231, and the S pole of the second magnet 232 is located closer to the base material 1 than the N pole of the second magnet. Although not shown in the diagram, the south pole of the first magnet 231 may be located closer to the substrate 1 than the north pole of the first magnet 231, and the north pole of the second magnet 232 may be located closer to the substrate 1 than the south pole of the second magnet 232.

[0098] Next, the structure of the first magnet 231 and the second magnet 232 in the planar direction of the second surface 21d of the electrode portion 21 will be described. Figure 6 is a plan view of the electrode portion 21 and magnetic field forming portion 23 shown in Figure 4, as seen from the magnetic field forming portion 23 side. Figure 7 is a cross-sectional view showing a cross section along the line VIII-VIII in Figure 6. Also, in Figure 6, direction D1 is the direction in which the rotation axis X of the pre-processing roller 20 extends.

[0099] As shown in Figures 6 and 7, the first magnet 231 has a first axial portion 231c. As shown in Figure 6, the first axial portion 231c extends along direction D1, that is, along the rotation axis X of the pre-processing roller 20. A first magnet 231 provided on one electrode portion 21 may have one first axial portion 231c, or it may have two or more first axial portions 231c. In the example shown in Figure 6, a first magnet 231 provided on one electrode portion 21 has one first axial portion 231c.

[0100] Furthermore, as shown in Figures 6 and 7, the second magnet 232 has a second axial portion 232c. As shown in Figure 6, the second axial portion 232c, like the first axial portion 231c, extends along direction D1, that is, along the axis of rotation X.

[0101] Since both the first magnet 231 and the second magnet 232 include portions that extend along the rotation axis X, the uniformity of the magnetic field strength formed around the substrate 1 in the width direction of the substrate 1 can be increased. This makes it possible to increase the uniformity of the plasma distribution density formed around the substrate 1 in the width direction of the substrate 1.

[0102] A second magnet 232 provided on one electrode portion 21 may have one second axial portion 232c, or it may have two or more second axial portions 232c. In the example shown in Figures 6 and 7, a second magnet 232 provided on one electrode portion 21 has two second axial portions 232c. The two second axial portions 232c may be positioned so as to sandwich the first axial portion 231c in the direction D2 perpendicular to the rotation axis X in the planar direction of the second surface 21d of the electrode portion 21.

[0103] As shown in Figure 7, the dimensions L4 of the first axial portion 231c and L5 of the second axial portion 232c of the base material 1 in the transport direction are not particularly limited. Furthermore, the ratio of the dimensions L4 of the first axial portion 231c and L5 of the second axial portion 232c in the transport direction of the base material 1 is not particularly limited. The dimensions L4 of the first axial portion 231c and L5 of the second axial portion 232c may be equal, or the dimensions L4 of the first axial portion 231c may be larger than the dimensions L5 of the second axial portion 232c.

[0104] The distance L6 between the first axial portion 231c and the second axial portion 232c in direction D2 is set so that the magnetic field generated by the first axial portion 231c and the second axial portion 232c is formed between the pre-processing roller 20 and the electrode portion 21.

[0105] The second magnet 232 may surround the first magnet 231 when the magnetic field forming portion 23 is viewed along the direction normal to the second surface 21d of the electrode portion 21. For example, as shown in Figure 6, the second magnet 232 may have two second axial portions 232c and two connecting portions 232d provided to connect the two second axial portions 232c.

[0106] Examples of magnets used as the magnetic field forming section 23, such as the first magnet 231 and the second magnet 232, include permanent magnets such as ferrite magnets, neodymium magnets, and rare earth magnets such as samarium cobalt (samarium-cobalt). Electromagnets can also be used as the magnetic field forming section 23.

[0107] The magnetic flux density of the magnets in the magnetic field generating section 23, such as the first magnet 231 and the second magnet 232, is, for example, between 100 gauss and 10,000 gauss. If the magnetic flux density is 100 gauss or more, a sufficiently strong magnetic field can be formed between the pre-treatment roller 20 and the electrode section 21, thereby generating a sufficiently high-density plasma and enabling the formation of a good pre-treatment surface at high speed. On the other hand, to increase the magnetic flux density on the surface of the substrate 1 to more than 10,000 gauss requires expensive magnets or a magnetic field generating mechanism.

[0108] Although not shown in the figures, the plasma pretreatment mechanism 11B may have a plasma raw material gas supply unit. The plasma raw material gas supply unit supplies the gas that will be used as the raw material for the plasma into the plasma pretreatment chamber 12B. The configuration of the plasma raw material gas supply unit is not particularly limited. For example, the plasma raw material gas supply unit may be provided on the wall surface of the plasma pretreatment chamber 12B and may include holes for ejecting the gas that will be used as the raw material for the plasma. The plasma raw material gas supply unit may also have a nozzle that discharges the plasma raw material gas at a position closer to the substrate 1 than the wall surface of the plasma pretreatment chamber 12B. The plasma raw material gas supplied by the plasma raw material gas supply unit may be, for example, an inert gas such as argon, an active gas such as oxygen, nitrogen, carbon dioxide, or ethylene, or a mixture of these gases. As the plasma raw material gas, one type of inert gas may be used alone, one type of active gas may be used alone, or a mixture of two or more gases contained in the inert gas or active gas may be used. It is preferable to use a mixture of an inert gas such as argon and an active gas as the plasma raw material gas. For example, the plasma raw material gas supply unit supplies a mixed gas of argon (Ar) and oxygen (O2).

[0109] The plasma pretreatment mechanism 11B has a plasma density of, for example, 100 W·sec / m³. 2 More than 8000W・sec / m 2 The following plasma is supplied between the pre-treatment roller 20 and the electrode unit 21.

[0110] In the example shown in Figure 4, the plasma pretreatment mechanism 11B is located in a plasma pretreatment chamber 12B, which is separated from the substrate transport chamber 12A and the film deposition chamber 12C by a partition wall. By separating the plasma pretreatment chamber 12B from other areas such as the substrate transport chamber 12A and the film deposition chamber 12C, it becomes easier to independently adjust the atmosphere of the plasma pretreatment chamber 12B. This makes it easier to control the plasma raw material gas concentration in the space where the pretreatment roller 20 and the electrode section 21 face each other, thereby improving the productivity of laminated films.

[0111] In this embodiment, the voltage applied between the pre-treatment roller 20 and the electrode section 21 of the plasma pre-treatment mechanism 11B is an AC voltage. Plasma is generated between the pre-treatment roller 20 and the electrode section 21 by applying the AC voltage. Preferably, the electric field is formed by applying the AC voltage so that the generated plasma moves perpendicular to the surface of the substrate 1 so that it moves toward the surface of the substrate 1.

[0112] The value of the AC voltage applied between the pre-treatment roller 20 and the electrode section 21 is preferably 250V or more and 1000V or less. When the AC voltage has the above value, a plasma with sufficient plasma density can be generated between the pre-treatment roller 20 and the electrode section 21. Here, the value of the AC voltage is the effective value V ｅ This means the effective value V of AC voltage. ｅ V is the maximum value of the AC voltage. ｍ In that case, it can be calculated using the following formula (4).

[0113]

[0114] The AC voltage applied between the pre-treatment roller 20 and the electrode section 21 has a frequency of, for example, 20 kHz or more and 500 kHz or less.

[0115] (Film Formation Mechanism) Next, the film formation mechanism 11C will be described. In the example shown in Figure 4, the film formation mechanism 11C has a film formation roller 25 located in the film formation chamber 12C and an evaporation mechanism 24.

[0116] The film deposition roller 25 will now be described. The film deposition roller 25 is a roller that wraps around and transports the substrate 1, which has been pre-treated in the plasma pre-treatment mechanism 11B, with the treated surface facing outwards.

[0117] The material of the film-forming roller 25 will now be described. Preferably, the film-forming roller 25 is made from a material containing at least one of stainless steel, iron, copper, and chromium. The surface of the film-forming roller 25 may be treated with a hard chromium hard coat or the like to prevent scratches. These materials are easy to process. Furthermore, by using the above materials as the material for the film-forming roller 25, the thermal conductivity of the film-forming roller 25 itself is increased, resulting in excellent temperature control when temperature control is performed. The average surface roughness Ra of the surface of the film-forming roller 25 is, for example, 0.1 μm or more and 10 μm or less.

[0118] Although not shown in the figures, the film-forming roller 25 may also have a temperature control mechanism for adjusting the surface temperature of the film-forming roller 25. The temperature control mechanism may have, for example, a circulation path inside the film-forming roller 25 for circulating a cooling medium or a heat source medium. The cooling medium (refrigerant) may be, for example, an aqueous solution of ethylene glycol, and the heat source medium (heat transfer medium) may be, for example, silicone oil. The temperature control mechanism may also have a heater installed at a position opposite to the film-forming roller 25. When the film-forming mechanism 11C forms a film by vapor deposition, due to constraints on the heat resistance of the related mechanical parts and in terms of versatility, the temperature control mechanism preferably adjusts the surface temperature of the film-forming roller 25 to a target temperature within the range of -20°C to 200°C. By having a temperature control mechanism in the film-forming roller 25, fluctuations in the temperature of the substrate 1 caused by the heat generated during film formation can be suppressed.

[0119] The evaporation mechanism 24 will now be described. Figure 8 is an enlarged view of the area enclosed by the dashed line labeled IX in Figure 4, showing the specific form of the evaporation mechanism 24 which was omitted in Figure 4, and also showing the deposition material supply unit 61 which supplies the deposition material, which was omitted in Figure 4. Note that the vacuum chamber 12 and partitions 35b and 35c are omitted in Figure 8. The evaporation mechanism 24 is a mechanism for evaporating the deposition material containing aluminum, and for convenience, the evaporated aluminum vapor 63 is shown in Figure 8. The evaporated deposition material adheres to the substrate 1, forming a deposition film containing aluminum on the surface of the substrate 1. The evaporation mechanism 24 in this embodiment employs a resistance heating type. In the example shown in Figure 8, the evaporation mechanism 24 has a boat 24b. In this embodiment, the boat 24b has a power supply (not shown) and a resistor (not shown) electrically connected to the power supply. Multiple boats 24b may be arranged in the width direction of the substrate 1.

[0120] As shown in Figure 8, the film formation mechanism 11C may have a deposition material supply unit 61 that supplies deposition material to the evaporation mechanism 24. In Figure 8, an example is shown in which the deposition material supply unit 61 continuously feeds out aluminum metal wire.

[0121] Although not shown in the diagram, the film formation mechanism 11C includes a gas supply mechanism. The gas supply mechanism supplies gas between the evaporation mechanism 24 and the film formation roller 25. The gas supply mechanism supplies at least oxygen gas. The oxygen gas reacts with or combines with the evaporation material, such as aluminum, that evaporates from the evaporation mechanism 24 and is directed toward the substrate 1 on the film formation roller 25. This allows a vapor-deposited film containing aluminum oxide to be formed on the surface of the substrate 1.

[0122] Furthermore, the film deposition mechanism 11C includes a plasma supply mechanism 50 that supplies plasma between the surface of the substrate 1 and the evaporation mechanism 24. In the examples shown in Figures 4 and 8, the plasma supply mechanism 50 has a hollow cathode 51. In this embodiment, the hollow cathode 51 is a cathode having a cavity that is partially open. The hollow cathode 51 can generate plasma within its cavity. In the example shown in Figure 8, the hollow cathode 51 is provided such that the opening of the cavity of the hollow cathode 51 is located diagonally above the boat 24b. Although not shown, the plasma supply mechanism 50 according to this embodiment also has an anode facing the opening that draws plasma out from the opening of the cavity of the hollow cathode 51. The plasma supply mechanism 50 according to this embodiment generates plasma within the cavity of the hollow cathode 51 and draws that plasma out between the surface of the substrate 1 and the evaporation mechanism 24 by the opposing anode, thereby generating a powerful plasma between the surface of the substrate 1 and the evaporation mechanism 24. The positions of the opposing anodes are not particularly limited, as long as the opposing anodes can draw plasma from the opening of the cavity of the hollow cathode 51 and supply plasma between the surface of the substrate 1 and the evaporation mechanism 24. In this embodiment, the case in which the opposing anodes are arranged on both sides of the boat 24b in the width direction of the substrate 1 will be described. In this case, the film deposition mechanism 11C has a plurality of boats 24b and a plurality of opposing anodes, and the plurality of boats 24b and the plurality of opposing anodes may be arranged alternately in the width direction of the substrate 1. Although not shown, the plasma supply mechanism 50 may have a raw material supply device that supplies plasma raw material gas into at least the cavity of the hollow cathode 51. As the plasma raw material gas supplied by the raw material supply device, for example, a gas similar to the gas that can be used as the plasma raw material gas supplied by the plasma raw material gas supply unit of the plasma pretreatment mechanism 11B can be used.

[0123] The plasma supply mechanism 50 supplies plasma between the surface of the substrate 1 and the evaporation mechanism 24, thereby activating the aluminum and oxygen gas evaporated in the evaporation mechanism 24 and promoting the reaction or bonding between aluminum and oxygen gas. This increases the proportion of aluminum present as aluminum oxide in the vapor-deposited film formed on the surface of the substrate 1, thereby stabilizing the properties of the vapor-deposited film.

[0124] Although not shown in the figures, the film deposition apparatus 10 may include a substrate charge removal unit in the portion of the substrate transport chamber 12A located downstream of the film deposition chamber 12C in the transport direction of the substrate 1, for post-processing to remove static charge generated on the substrate 1 due to film deposition by the film deposition mechanism 11C. The substrate charge removal unit may be provided to remove static charge from one side of the substrate 1, or it may be provided to remove static charge from both sides of the substrate 1.

[0125] The apparatus used as a substrate charge removal unit for post-treatment of the substrate 1 is not particularly limited, but for example, a plasma discharge apparatus, an electron beam irradiation apparatus, an ultraviolet irradiation apparatus, a static elimination bar, a glow discharge apparatus, a corona treatment apparatus, etc., can be used.

[0126] When post-processing is performed by forming a discharge using a plasma processing apparatus or glow discharge apparatus, it is possible to supply a discharge gas such as argon, oxygen, nitrogen, or helium, or a mixture thereof, to the vicinity of the substrate 1 and perform post-processing using any discharge method such as alternating current (AC) plasma, direct current (DC) plasma, arc discharge, microwave, or surface wave plasma. In a reduced pressure environment, it is most preferable to perform post-processing using a plasma discharge apparatus.

[0127] The substrate charge removal unit is installed in the substrate transport chamber 12A, in the downstream direction of substrate 1 transport from the film formation chamber 12C. By removing the charge from the substrate 1, the substrate 1 can be quickly separated from the film formation roller 25 at a predetermined position and transported. This enables stable substrate transport, prevents damage to the substrate 1 and deterioration of quality caused by static charge, and improves the suitability for post-processing by improving the wettability of the front and back surfaces of the substrate.

[0128] (Power supply) In the example shown in Figure 4, the film deposition apparatus 10 further includes a power supply 32 electrically connected to the pre-treatment roller 20 and the electrode section 21. In the example shown in Figure 4, the power supply 32 is electrically connected to the pre-treatment roller 20 and the electrode section 21 via a power supply wiring 31. The power supply 32 is, for example, an AC power supply. When the power supply 32 is an AC power supply, the power supply 32 can apply an AC voltage having a frequency of, for example, 20 kHz or more and 500 kHz or less between the pre-treatment roller 20 and the electrode section 21. The input power that can be applied by the power supply 32 (power that can be applied per 1 m width of the electrode section 21 in the width direction of the substrate 1) is not particularly limited, but for example, it is 0.5 kW / m or more and 20 kW / m or less. The pre-treatment roller 20 may be electrically installed at the ground level or electrically installed at the floating level.

[0129] [Gas Barrier Coating Film] The gas barrier coating film is intended to mechanically and chemically protect the vapor-deposited film and improve the barrier properties of barrier film B, and is laminated in contact with the vapor-deposited film. The gas barrier coating film is a cured film formed by a coating agent for gas barrier coating films, which consists of a resin composition containing a metal alkoxide, a hydroxyl group-containing water-soluble resin, and a silane coupling agent added as needed.

[0130] The thickness of the gas barrier coating film is preferably between 100 nm and 800 nm. If it is thinner than the above range, the barrier effect of the gas barrier coating film tends to be insufficient, and if it is thicker than the above range, the rigidity and brittleness tend to increase. Furthermore, by adjusting the thickness of the gas barrier coating film, the above color difference ΔE can be controlled. ＊ ab can be adjusted to a range of 0.40 to 0.80.

[0131] Metal alkoxides have the general formula: R １ｎ M (OR ２ ) ｍ ... (I) (However, in the formula, R １ , R ２R represents a hydrogen atom or an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n+m represents the valence of M. Multiple R in one molecule １ , R ２ Each of these may be the same or different.

[0132] Examples of specific metal atoms represented by M in metal alkoxides include silicon, zirconium, titanium, aluminum, tin, lead, borane, and others. For example, it is preferable to use an alkoxysilane in which M is Si (silicon).

[0133] In the above general formula (I), OR ２ Specific examples include hydroxyl groups, methoxy groups, ethoxy groups, n-propoxy groups, n-butoxy groups, i-propoxy groups, butoxy groups, 3-methacryloxy groups, 3-acryloxy groups, phenoxy groups, and other alkoxy groups or phenoxy groups.

[0134] In the above, R １ Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, phenyl group, p-styryl group, 3-chloropropyl group, trifluoromethyl group, vinyl group, γ-glycidoxypropyl group, methacrylic group, γ-aminopropyl group, etc.

[0135] Specific examples of alkoxysilanes include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriphenoxysilane, phenylphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, dimethyldiethoxysilane, and diphenyldimethoxysilane. Examples of alkoxysilanes and phenoxysilanes include diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, trifluoromethyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and others. In this embodiment, condensed polymers of these alkoxysilanes can also be used, specifically, for example, polytetramethoxysilane and polytetraethoxysilane can be used.

[0136] Silane coupling agents are used to adjust the crosslinking density of a cured film formed by a metal alkoxide and a hydroxyl group-containing water-soluble resin, thereby creating a film with barrier properties and resistance to hot water treatment.

[0137] Silane coupling agents have the general formula: R ３ｎ Si ( OR ４ ) ４－ｎ ... (II) (wherein R ３ and R ４ Each of these independently represents an organic functional group, and n is between 1 and 3. )

[0138] In the above general formula (II), R ３ Examples include hydrocarbon groups such as alkyl groups and alkylene groups, epoxy groups, (meth)acryloxy groups, ureido groups, vinyl groups, amino groups, isocyanurate groups, or functional groups having isocyanate groups. ３ These may be the same or different.

[0139] In the above general formula (II), R ４ Examples include organic functional groups having 1 to 8 carbon atoms, preferably branched alkyl groups having 1 to 8 carbon atoms or alkoxyalkyl groups having 3 to 7 carbon atoms. Examples of alkyl groups having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, etc. Examples of alkoxyalkyl groups having 3 to 7 carbon atoms include groups obtained by removing one hydrogen atom from linear or branched ethers such as methyl ethyl ether, diethyl ether, methyl propyl ether, methyl isopropyl ether, ethyl propyl ether, ethyl isopropyl ether, methyl butyl ether, ethyl butyl ether, methyl sec-butyl ether, ethyl sec-butyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, etc. Note that (OR ４ These may be the same or different.

[0140] Examples of silane coupling agents represented by the above general formula (II) include, when n=1, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane; when n=2, 3-glycidoxypropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane; and when n=3, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2-(3,4-epoxycyclohexyl)dimethylmethoxysilane, and 2-(3,4-epoxycyclohexyl)dimethylethoxysilane.

[0141] In particular, the crosslinking density of the cured barrier coating film using 3-glycidoxypropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane is lower than that of the system using trialkoxysilane. Therefore, while it is an excellent film in terms of gas barrier properties and resistance to hot water treatment, it is a flexible cured film with excellent bending resistance, and packaging materials using this barrier film are less likely to experience deterioration in gas barrier properties even after Gelboflex testing.

[0142] The silane coupling agent can also be used by mixing n=1, 2, and 3, and the ratio of these mixtures and the amount of silane coupling agent used are determined by the design of the cured film of the barrier coating layer.

[0143] The hydroxyl group-containing water-soluble resin can undergo dehydration cocondensation with metal alkoxides, and the degree of saponification is preferably 90% or more and 100% or less, more preferably 95% or more and 100% or less, and even more preferably 99% or more and 100% or less. If the degree of saponification is lower than the above range, the hardness of the barrier coating layer tends to decrease.

[0144] Specific examples of hydroxyl group-containing water-soluble resins include, for example, polyvinyl alcohol-based resins, ethylene-vinyl alcohol copolymers, polymers of difunctional phenol compounds and difunctional epoxy compounds, and these may be used individually, mixed in combination of two or more, or copolymerized. Among these, polyvinyl alcohol is particularly preferred due to its excellent flexibility and affinity, and polyvinyl alcohol-based resins are preferred.

[0145] Specifically, for example, polyvinyl alcohol resins obtained by saponifying polyvinyl acetate, or ethylene-vinyl alcohol copolymers obtained by saponifying a copolymer of ethylene and vinyl acetate can be used. Examples of such polyvinyl alcohol resins include PVA-124 (saponification degree = 99%, polymerization degree = 2,400) manufactured by Kuraray Co., Ltd., and Gosenol NM-14 (saponification degree = 99%, polymerization degree = 1,400) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.

[0146] Next, an example of a method for forming a gas barrier coating film will be described. First, a coating agent for a gas barrier coating film consisting of a resin composition is prepared by mixing the above-mentioned metal alkoxide, silane coupling agent, hydroxyl group-containing water-soluble resin, reaction accelerator (sol-gel catalyst, acid, etc.), and an organic solvent such as water, methyl alcohol, ethyl alcohol, or isopropanol.

[0147] Next, the above-mentioned gas barrier coating agent is applied to the vapor-deposited film by a conventional method and dried. This drying process further promotes condensation or co-condensation reactions, forming a coating film. The above application operation may be repeated on the first coating film to form multiple coating films consisting of two or more layers.

[0148] Furthermore, the material is heat-treated for 3 seconds to 10 minutes at a temperature in the range of 20 to 200°C, preferably 50 to 180°C, which is below the softening point of the polyester resin constituting the first or second base layer. This allows a gas barrier coating film made of the above-mentioned gas barrier coating agent to be formed on the vapor-deposited film.

[0149] [Sealant Layer] The sealant layer is a layer formed from a film containing a heat-sealable resin that can fuse with itself upon heat. The heat-sealable resin is not particularly limited as long as it can fuse with itself upon heat, and examples include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), ethylene-α-olefin copolymer polymerized using a metallocene catalyst, random or block copolymer of ethylene-polypropylene, polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), and ethylene-methacrylate. Examples of resins include polyolefin resins such as acrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ionomer resins, heat-sealable ethylene-vinyl alcohol resins, ethylene-propylene copolymers, methylpentene polymers, polybutene polymers, or cyclic olefin copolymers; acid-modified polyolefin resins obtained by modifying polyolefin resins with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid; polyvinyl acetate resins; poly(meth)acrylic resins; and polyvinyl chloride resins. Among these, low-density polyethylene or linear low-density polyethylene is preferred from the viewpoint of water resistance, and linear low-density polyethylene is more preferred.

[0150] Low-density polyethylene is, for example, polyethylene obtained by polymerizing ethylene by high-pressure polymerization (high-pressure low-density polyethylene). Linear low-density polyethylene is, for example, polyethylene obtained by polymerizing ethylene and a small amount of α-olefin by polymerization using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst.

[0151] Examples of linear low-density polyethylene include ethylene-1-butene copolymer (C4-LLDPE) in which the comonomer is at least 1-butene, ethylene-1-hexene copolymer (C6-LLDPE) in which the comonomer is at least 1-hexene, and ethylene-1-octene copolymer (C8-LLDPE) in which the comonomer is at least 1-octene. From the viewpoint of improving the tearability of the packaging material, the resin contained in the sealant layer is preferably C4-LLDPE. From the viewpoint of improving the impact resistance of the packaging material, the resin contained in the sealant layer is preferably C6-LLDPE. In these copolymers, the comonomers are not limited to those listed above, and further comonomers may be used.

[0152] The heat-sealable resin may be used alone or as a mixture of two or more types. The sealant layer can be used as a film or sheet of the above-mentioned resin, or as a coating film thereof.

[0153] The content of the heat-sealable resin in the sealant layer is preferably more than 50% by mass, more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more. Such a sealant layer is preferred, for example, from the viewpoint of heat-sealability.

[0154] The sealant layers shown in Figures 1 to 3 are single-layered, but the sealant layer of the packaging material of this disclosure is not limited to a single-layered configuration and may be multi-layered. In particular, the sealant layer is preferably a three-layered configuration comprising an outer layer, an intermediate layer, and an inner layer in that order. When the sealant layer is a multi-layered configuration, the intermediate layer only needs to contain linear low-density polyethylene, and the outer and inner layers do not need to contain linear low-density polyethylene. By having a three-layered sealant layer in which the intermediate layer contains linear low-density polyethylene, the ease of opening can be improved.

[0155] When the sealant layer has a multilayer structure, it is preferable that the density of the intermediate layer is greater than the density of the outer layer. When the sealant layer has a multilayer structure, it is preferable that the density of the intermediate layer is greater than the density of the inner layer. A sealant layer with a high density in the intermediate layer can improve tear resistance.

[0156] In the packaging material 2 shown in Figures 1 and 2, there is one sealant layer, but there may be two or more sealant layers. If there are two or more sealant layers, each may have the same composition or different compositions.

[0157] The thickness of the sealant layer is preferably 20 μm or more, more preferably 30 μm or more, even more preferably 40 μm or more, and also preferably 200 μm or less, more preferably 130 μm or less, and even more preferably 60 μm or less. Such a sealant layer has excellent transparency and sealing properties, can adequately protect the contents, and is reasonable from the viewpoint of economic rationality.

[0158] Methods for laminating a sealant layer to the other side of the packaging material (the inner surface when it becomes a packaging bag) include, for example, dry lamination and melt extrusion lamination. Furthermore, when performing the above lamination, pretreatments such as corona treatment, ozone treatment, and flame treatment can be applied to the film as needed. Among these, dry lamination is preferred due to its superior adhesive strength.

[0159] Furthermore, the packaging material according to this disclosure is not limited to a configuration comprising only a first base layer, a barrier layer, and a sealant layer. As long as these layers are present, it may have at least one other layer, provided that it does not impair the properties of the packaging material. For example, as shown in Figure 2, a second base layer 7 may be provided between the barrier layer 4 and the sealant layer 5.

[0160] [Second base layer] The second base layer is a layer with excellent chemical or physical strength. Packaging material equipped with the second base layer has excellent mechanical strength, for example. In one embodiment, the second base layer contains a polyamide resin and may further contain a resin other than a polyamide resin. Examples of resins other than polyamide resins include polyolefin resins such as polyethylene resins or polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), poly(meth)acrylic resins, polycarbonate resins, polyvinyl alcohol resins, ethylene-vinyl ester copolymer saponified products, polyester resins, polyurethane resins, acetal resins, and cellulose resins. In one embodiment, the second base layer is a film containing a polyamide resin.

[0161] Examples of polyamide resins include aliphatic polyamides and semi-aromatic polyamides.

[0162] Examples of aliphatic polyamides include aliphatic homopolyamides and aliphatic copolymer polyamides. Aliphatic homopolyamides may be polyamide resins composed of one lactam or one aminocarboxylic acid, or polyamide resins composed of a combination of one aliphatic diamine and one aliphatic dicarboxylic acid. In this specification, the latter case is also classified as a homopolyamide. Aliphatic copolymer polyamides may be polyamide resins composed of two or more monomers selected from lactam and aminocarboxylic acid, or polyamide resins composed of a combination of lactam and / or aminocarboxylic acid, an aliphatic diamine and an aliphatic dicarboxylic acid, or polyamide resins composed of a combination of one or more aliphatic diamines and one or more aliphatic dicarboxylic acids (excluding the combination of one aliphatic diamine and one aliphatic dicarboxylic acid).

[0163] In the following examples, polyamide resins will also be referred to as "PA". Aliphatic homopolyamides specifically include polycaprolactam (PA6), polyenanthractam (PA7), polyundecanelactam (PA11), polylauryllactam (PA12), polyhexamethyleneadipamide (PA66), polytetramethylenedodecadamide (PA412), polypentamethyleneazeramide (PA59), polypentamethylenesebamide (PA510), polypentamethylenedodecadamide (PA512), polyhexamethyleneazeramide (PA69), polyhexamethylenesebamide (PA610), polyhexamethylenedodecadamide (PA612), poly Examples include nonamethylene adipamide (PA96), polynonameethylene azeramide (PA99), polynonameethylene sebaamide (PA910), polynonameethylene dodecamide (PA912), polydecamethylene adipamide (PA106), polydecamethylene azeramide (PA109), polydecamethylene decamamide (PA1010), polydecamethylene dodecamide (PA1012), polidodecamethylene adipamide (PA126), polidodecamethylene azeramide (PA129), polidodecamethylene sebaamide (PA1210), and polidodecamethylene dodecamide (PA1212).

[0164] Specifically, aliphatic copolymer polyamides include caprolactam / hexamethylenediaminoadipic acid copolymer (PA6 / 66), caprolactam / hexamethylenediaminoazelaic acid copolymer (PA6 / 69), caprolactam / hexamethylenediaminosebacic acid copolymer (PA6 / 610), caprolactam / hexamethylenediaminoundecanoic acid copolymer (PA6 / 611), caprolactam / hexamethylenediaminododecanoic acid copolymer (PA6 / 612), and caprolactam / amino Examples include undecanoic acid copolymer (PA6 / 11), caprolactam / lauryl lactam copolymer (PA6 / 12), caprolactam / hexamethylenediaminoadipic acid / lauryl lactam copolymer (PA6 / 66 / 12), caprolactam / hexamethylenediaminoadipic acid / hexamethylenediaminosebacic acid copolymer (PA6 / 66 / 610), and caprolactam / hexamethylenediaminoadipic acid / hexamethylenediaminododecanedicarboxylic acid copolymer (PA6 / 66 / 612).

[0165] Semi-aromatic polyamides are polyamide resins having structural units derived from aromatic diamines and structural units derived from aliphatic dicarboxylic acids, or polyamide resins having structural units derived from aliphatic diamines and structural units derived from aromatic dicarboxylic acids. Examples include polyamide resins composed of aromatic diamines and aliphatic dicarboxylic acids, and polyamide resins composed of aliphatic diamines and aromatic dicarboxylic acids.

[0166] Polyamide resins composed of aromatic diamines and aliphatic dicarboxylic acids do not necessarily require all diamines to be aromatic diamines, and may further contain structural units derived from aliphatic diamines. Polyamide resins composed of aliphatic diamines and aromatic dicarboxylic acids do not necessarily require all dicarboxylic acids to be aromatic dicarboxylic acids, and may further contain structural units derived from aliphatic dicarboxylic acids. These polyamide resins may further contain structural units derived from lactams and / or aminocarboxylic acids.

[0167] Specifically, the semi-aromatic polyamides include polyhexamethylene terephthalamide (PA6T), polyhexamethylene isophthalamide (PA6I), polynonamethylene terephthalamide (PA9T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (PA66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (PA66 / 6I), polyhexamethylene terephthalamide / polycaproamide copolymer (PA6T / 6), polyhexamethylene isophthalamide / polycaproamide copolymer (PA6I / 6), and polyhexamethylene terephthalamide / poly Examples include lidodecamido copolymer (PA6T / 12), polyhexamethylene isophthalamide / polyhexamethylene terephthalamide copolymer (PA6I / 6T), polyhexamethylene terephthalamide / poly(2-methylpentamethylene terephthalamide) copolymer (PA6T / M5T), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (PA66 / 6T / 6I), polyhexamethylene adipamide / polycaproamide / polyhexamethylene isophthalamide copolymer (PA66 / 6 / 6I), and polymetaxylylene adipamide (PAMXD6). Among these, PA6I / 6T and PAMXD6 are preferred, and PA6I / 6T is more preferred.

[0168] In one embodiment, the second base layer contains a polyester resin and may further contain a resin other than a polyester resin. Examples of resins other than polyester resins include polyolefin resins such as polyethylene resins or polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), acrylonitrile-butadiene-styrene copolymers (ABS resins), poly(meth)acrylic resins, polycarbonate resins, polyvinyl alcohol resins, ethylene-vinyl ester copolymer saponifies, polyamide resins, polyurethane resins, acetal resins, and cellulose resins. In one embodiment, the second base layer is a film containing a polyester resin.

[0169] Examples of polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polypropylene terephthalate (PPT), 1,4-polycyclohexylenedimethylene terephthalate, and terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer. Among these, polyethylene terephthalate or polybutylene terephthalate is preferred from the viewpoint of strength, and polyethylene terephthalate is more preferred. Furthermore, polybutylene terephthalate is preferred from the viewpoint of puncture strength.

[0170] The second substrate layer may contain various additives to the extent that the properties of the present disclosure are not impaired. Examples of additives include plasticizers, ultraviolet stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducers, mold release agents, antioxidants, ion exchange agents, and coloring pigments. The content of these additives is, for example, 5% by mass or more and 50% by mass or less.

[0171] To obtain a second base layer by processing a resin such as polyester resin into a film, a general method of forming a film from resin can be employed. Specifically, after drying resin pellets, they are supplied to a melt extruder heated to a temperature above the melting point (Tm) of the pellets and below Tm + 70°C to melt the pellets. The pellets are then extruded into a sheet shape through a die such as a T-die, and the extruded sheet is rapidly cooled and solidified in a rotating cooling drum or the like to form the second base layer. The second base layer obtained in this way consists of a single layer. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vented extruder, a tandem extruder, etc., can be used depending on the purpose.

[0172] The second base material layer is preferably biaxially stretched. Biaxial stretching can be carried out by conventionally known methods, and may be sequential or simultaneous biaxial stretching. The characteristics of sequential and simultaneous biaxial stretching in the second base material layer are the same as those of sequential and simultaneous biaxial stretching in the first base material layer, so they are not described here.

[0173] The thickness of the second substrate layer is preferably 5 μm, more preferably 6 μm or more, even more preferably 9 μm or more, and also preferably 2000 μm or less, more preferably 500 μm or less, and even more preferably 100 μm or less. By adjusting the thickness of the second substrate layer, the above color difference ΔE ＊ ab can be adjusted to a range of 0.40 to 0.80. The tensile strength of such a second base material layer is 1 kg / mm² in the MD direction. ２ 40 kg / mm² or more ２ Below, 1 kg / mm² in the TD direction. ２ 35kg / mm ​​or more ２ The following conditions apply, and the elongation at break is 10% to 350% in the MD direction and 3% to 300% in the TD direction.

[0174] Although the second base layer 7 shown in Figure 2 is composed of a single layer, the second base layer of the packaging material of this disclosure is not limited to a single layer configuration and may be a multilayer configuration. If the second base layer is a multilayer configuration, at least one layer may contain a polyamide resin, and the other layers may not contain a polyamide resin.

[0175] The second substrate layer can also be subjected to secondary processing for the purpose of imparting chemical, electrical, magnetic, mechanical, friction / wear / lubrication, optical, thermal, biocompatibility, and other surface functions. 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.).

[0176] [Adhesive Layer] The packaging material of this disclosure may have adhesive layers between any layers, such as between the barrier layer 4 and the sealant layer 5, between the barrier layer 4 and the second base layer 7, between the second base layer 7 and the sealant layer 5, and between the second base layer 7 and the first base layer 3. A packaging material having adhesive layers has excellent interlayer adhesion, for example. For example, as shown in Figure 1, a first adhesive layer 6 may be provided between the barrier layer 4 and the sealant layer 5. Alternatively, as shown in Figure 2, a first adhesive layer 6 may be provided between the barrier layer 4 and the second base layer 7, and a second adhesive layer 8 may be provided between the second base layer 7 and the sealant layer 5. Alternatively, as shown in Figure 3, a first adhesive layer 6 may be provided between the barrier layer 4 and the sealant layer 5, and a second adhesive layer 8 may be provided between the second base layer 7 and the first base layer 3. In this specification, the first adhesive layer and the second adhesive layer are collectively referred to as the "adhesive layer". Therefore, the characteristics of the adhesive layer described herein apply to both the first and second adhesive layers.

[0177] The adhesive layer is composed of, for example, an adhesive, which may be a one-component curing adhesive, a two-component curing adhesive, or a non-curing adhesive. The adhesive may be solvent-free or solvent-based. Examples of adhesives include polyether-based adhesives, polyester-based adhesives, polyurethane-based adhesives, silicone-based adhesives, epoxy-based adhesives, rubber-based adhesives, vinyl-based adhesives, olefin-based adhesives, and phenol-based adhesives. Among these, polyurethane-based adhesives are preferred, and two-component curing polyurethane-based adhesives are more preferred.

[0178] The thickness of the adhesive layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, even more preferably 0.5 μm or more, even more preferably 0.8 μm or more, and also preferably 10 μm or less, more preferably 8 μm or less, even more preferably 6 μm or less, and even more preferably 5 μm or less.

[0179] The adhesive layer can be formed by applying an adhesive to an object using conventionally known methods such as the direct gravure roll coating method, gravure roll coating method, kiss coating method, reverse roll coating method, fontein method, and transfer roll coating method, and drying as desired. The packaging material of this disclosure may be manufactured by laminating a substrate and a sealant film, or a polypropylene resin substrate and a polypropylene resin substrate and a sealant film, using a non-solvent lamination method with a solvent-free adhesive, or by laminating them using a dry lamination method with a solvent-type adhesive.

[0180] [Layer structure of packaging material] The following are specific examples of the layer structure of the packaging material disclosed herein.

[0181] In one embodiment, the packaging material of the present disclosure comprises, in this order, a first base layer, a barrier layer, a gas barrier coating film, a first adhesive layer, and a sealant layer, wherein the first base layer is a film containing polyethylene terephthalate, and the sealant layer is a film containing linear low-density polyethylene.

[0182] In one embodiment, the packaging material of the present disclosure comprises a first base layer, a barrier layer, a first adhesive layer, and a sealant layer in this order, wherein the first base layer is a film containing polybutylene terephthalate, and the sealant layer is a film containing linear low-density polyethylene.

[0183] In one embodiment, the packaging material of the present disclosure comprises a first base layer, a barrier layer, a first adhesive layer, a second base layer, a second adhesive layer, and a sealant layer in this order, wherein the first base layer is a film containing polybutylene terephthalate, the second base layer is a film containing polyethylene terephthalate, and the sealant layer is a film containing linear low-density polyethylene.

[0184] In one embodiment, the packaging material of the present disclosure comprises a first base layer, a first adhesive layer, a barrier layer, a second base layer, a second adhesive layer, and a sealant layer in this order, wherein the first base layer is a film containing polybutylene terephthalate, the second base layer is a film containing polyethylene terephthalate, and the sealant layer is a film containing linear low-density polyethylene.

[0185] In one embodiment, the packaging material of the present disclosure comprises a first base layer, a barrier layer, a first adhesive layer, a second base layer, a second adhesive layer, and a sealant layer in this order, wherein the first base layer is a film containing polyethylene terephthalate, the second base layer is a film containing polyamide, and the sealant layer is a film containing linear low-density polyethylene.

[0186] In one embodiment, the packaging material of the present disclosure comprises a first base layer, a first adhesive layer, a barrier layer, a second base layer, a second adhesive layer, and a sealant layer in this order, wherein the first base layer is a film containing polyethylene terephthalate, the second base layer is a film containing polyamide, and the sealant layer is a film containing linear low-density polyethylene.

[0187] In one embodiment, the packaging material of the present disclosure comprises a first base layer, a barrier layer, a first adhesive layer, a second base layer, a second adhesive layer, and a sealant layer in this order, wherein the first base layer is a film containing polyethylene terephthalate, the second base layer is a film containing polybutylene terephthalate, and the sealant layer is a film containing linear low-density polyethylene.

[0188] In one embodiment, the packaging material of the present disclosure comprises, in this order, a first base layer, a first adhesive layer, a barrier layer, a second base layer, a second adhesive layer, and a sealant layer, wherein the first base layer is a film containing polyethylene terephthalate, the second base layer is a film containing polybutylene terephthalate, and the sealant layer is a film containing linear low-density polyethylene.

[0189] In one embodiment, the packaging material of the present disclosure comprises a second base layer, a second adhesive layer, a first base layer, a barrier layer, a first adhesive layer, and a sealant layer in this order, wherein the first base layer is a film containing polyethylene terephthalate, the second base layer is a film containing polyamide, and the sealant layer is a film containing linear low-density polyethylene.

[0190] [Packaging Bags] The packaging materials of this disclosure are used to make packaging bags. Accordingly, the packaging bags of this disclosure comprise the packaging materials of this disclosure. Packaging bags can be made by using at least the packaging materials of this disclosure.

[0191] Examples of packaging bags include various types such as standing pouches, side-sealed bags, two-sided sealed bags, three-sided sealed bags, four-sided sealed bags, envelope-type sealed bags, gusset-type sealed bags (pillow seals), pleated sealed bags, flat-bottom sealed bags, square-bottom sealed bags, and gusseted bags. Specific examples of packaging bags include small bags and standing pouches. Packaging bags may be equipped with an easy-open section. Examples of an easy-open section include a notch that serves as the starting point for tearing the packaging bag, and a half-cut line formed by laser processing or a cutter as a tearing path.

[0192] In one embodiment, a packaging bag can be made by folding the packaging material of the present disclosure in half so that one side, composed of the first base layer, etc., is on the outside and the other side, composed of the sealant layer, is on the inside, overlapping the two halves, and then heat-sealing the edges. The packaging bag made in this way is a three-sided sealed packaging bag. Figure 9 shows an example of a three-sided sealed packaging bag. In Figure 9, the halftone areas represent the heat-sealed areas. In another embodiment, a packaging bag can be made by overlapping multiple packaging materials of the present disclosure so that the sealant layers face each other, and then heat-sealing the edges. The entire packaging bag may be composed of the packaging material of the present disclosure, or only a part of the packaging bag may be composed of the packaging material of the present disclosure. The packaging bag made in this way is a four-sided sealed packaging bag. Figure 10 shows an example of a four-sided sealed packaging bag. In Figure 10, the shaded areas represent the heat-sealed areas.

[0193] In one embodiment, a standing pouch comprises a body (side sheet) and a bottom (bottom sheet). The side sheet and the bottom sheet may be made of the same material or of different materials. The bottom sheet maintains the shape of the side sheet, thereby giving the pouch self-supporting properties and enabling it to be a standing pouch. A storage space for containing contents is formed within the area enclosed by the side sheet and the bottom sheet. In a standing pouch, only the body may be made of the packaging material of the disclosure, only the bottom may be made of the packaging material of the disclosure, or both the body and the bottom may be made of the packaging material of the disclosure.

[0194] In one embodiment, the side sheet can be formed by making a bag such that the sealant layer in the packaging material of the present disclosure is the innermost layer. In one embodiment, the side sheet can be formed by preparing two sheets of the packaging material of the present disclosure, overlapping them so that the sealant layers face each other, and heat-sealing the side edges on both sides to form a bag.

[0195] In another embodiment, the side sheet can be formed by preparing two sheets of the packaging material of this disclosure, overlapping them so that the sealant layers face each other, and inserting two V-shaped folded packaging materials between the packaging materials at the side edges on both sides of the overlapped packaging material, with the sealant layers facing outwards, and then heat sealing. According to this manufacturing method, a standing pouch having a body with side gussets can be obtained. An example of a standing pouch is shown in Figure 11. In Figure 11, the shaded area represents the heat-sealed portion.

[0196] In one embodiment, the bottom sheet can be formed by inserting the packaging material of the present disclosure between the lower parts of the manufactured side sheets and heat sealing. More specifically, the bottom sheet can be formed by inserting a laminate folded in a V-shape with the sealant layer facing outwards between the lower parts of the manufactured side sheets and heat sealing.

[0197] In one embodiment, two sheets of the packaging material of the present disclosure are prepared and placed on top of each other with their sealant layers facing each other. Then, the other sheet of packaging material of the present disclosure is folded into a V-shape with the sealant layer facing outwards, and this is sandwiched between the bottoms of the facing packaging materials and heat-sealed to form the bottom. Next, the two sides adjacent to the bottom are heat-sealed to form the body. In this way, a standing pouch of one embodiment can be formed.

[0198] After placing the contents into the packaging bag, the opening of the packaging bag can be sealed by heat sealing. The contents to be placed in the packaging bag of this disclosure are not particularly limited and include frozen meat, frozen fish, frozen shellfish, raw meat, raw fish, fresh shellfish, etc. Among these, raw fish is preferred. By placing raw fish in the packaging bag of this disclosure, which is resistant to deterioration of contents, the deterioration of the raw fish can be suppressed without freezing.

[0199] The types of meat used are not limited to frozen or fresh meat. Examples of frozen or fresh meat include chicken, beef, pork, lamb, venison, wild boar, rabbit, etc.

[0200] The frozen or fresh fish may be red-fleshed or white-fleshed, and is not particularly limited. Examples of frozen or fresh fish include sea bream, yellowtail, amberjack, tuna, and skipjack tuna, with sea bream being preferred. The frozen or fresh fish may be whole and unprocessed, or it may have been cut or otherwise processed. Examples of processed fish include semi-dressed fish with the internal organs removed, dressed fish with the internal organs and head removed, and fillets with the dressed fish filleted and the backbone removed, with fillets being preferred.

[0201] Frozen or fresh shellfish are not particularly limited. Examples of frozen or fresh shellfish include ark clams, pearl oysters, Manila clams, sea hares, abalone, cone shells, surf clams, sea slugs, Buccinidae, limpets, oysters, snails (a general term for land-dwelling gastropods), turban shells, freshwater mussels, cherry blossom shells, turban shells, white clams, ornate clams, clams, clams, clams, giant clams, conch, pen shells, cowrie shells, pond snails, whelks, moon snails, abalone, cockles, slugs, whelks, ark clams, paua clams, surf clams, hard clams, razor clams, water clams, mussels, turban shells, and other shellfish, with scallops being the most preferred.

[0202] [Vacuum Packaging] The vacuum packaging of this disclosure involves placing contents in the packaging bag of this disclosure and sealing the inside of the packaging bag in a vacuum state. To seal in a vacuum state, the contents are inserted through the opening of the packaging bag, gas is replaced and degassed from the inside of the packaging bag, and the opening is heat-sealed. In this specification, "vacuum state" does not mean only an absolute vacuum state with a pressure of 0, but may also mean a negative pressure state with a pressure lower than standard atmospheric pressure. Therefore, "vacuum state" can mean, for example, a low vacuum state (100 Pa or more), a medium vacuum state (0.1 Pa or more and 100 Pa or less), and a high vacuum state (10 Pa) as defined in the Japanese Industrial Standards (JIS). －５ Pa or higher and 0.1 Pa or lower) state and ultra-high vacuum (10 －５ This includes all conditions (below Pa). By using vacuum packaging, the oxygen concentration inside the packaging bag can be reduced, which suppresses deterioration of the contents.

[0203] [Storage Method] The storage method of this disclosure comprises the step of storing the vacuum-packed product of this disclosure, which contains raw fish, at a temperature of 0°C to 2°C. The temperature range of 0°C to 2°C is generally referred to as the chilled temperature range. By storing the raw fish at a temperature of 0°C to 2°C, the rise in the K value of the raw fish can be suppressed without freezing the fish, and the freshness suitable for raw consumption can be maintained for a long period of time.

[0204] [Inspection Method] The inspection method of this disclosure comprises the steps of measuring the reflectance spectral spectrum of the vacuum-packed product of this disclosure, in accordance with JIS Z 8722:2009, under the condition of a 2° viewing angle, and determining the L color in the CIE 1976 color space from the reflectance spectral spectrum. ＊ a ＊ or b ＊ The process of calculating the L size of the vacuum pack ＊ a ＊ or b ＊ The process includes a step of determining the color tone of raw fish by comparing it with a standard value.

[0205] In the process of measuring the reflectance spectral spectrum, the color tone of the vacuum-packed product is measured in 10 nm increments within the wavelength range of 400 to 700 nm using a spectrophotometer (product name: CM-17d, manufactured by Konica Minolta, Inc.) in accordance with JIS Z 8722:2009. At that time, a pulsed xenon lamp with a UV cut filter is used as the light source, and the light emitted from the light source is irradiated onto the raw fish through the packaging bag.

[0206] From the reflectance spectral spectrum, the tristimulus values ​​XYZ in the CIE 1931 color space can be obtained. From the reflectance spectral spectrum, the L values ​​in the CIE 1976 color space can be obtained. ＊ a ＊ or b ＊ In the process of calculating the tristimulus values ​​XYZ, CIE1976L ＊ a ＊ b ＊ L in color space ＊ a ＊ or b ＊ The calculation is performed using the following formulas (5) to (7).

[0207]

[0208]

[0209]

[0210] In the process of determining the color tone of raw fish, L in the CIE 1976 color space ＊ a ＊ or b ＊ The L of the vacuum pack obtained in the process of calculating ＊ a ＊ or b ＊ This is compared to a standard value. The standard value is, for example, the L value of the vacuum-packed raw fish immediately after it is placed in the packaging bag. ＊ a ＊ or b ＊ This includes the L size of the vacuum-sealed package to be inspected. ＊ a ＊ or b ＊ This is the L size of the vacuum-packed raw fish immediately after it has been placed in the packaging bag. ＊ a ＊ or b ＊ By comparing it to the L of the vacuum-packed raw fish being tested, it can be determined that the color of the raw fish contained in the vacuum-packed product being tested has not changed significantly from the color immediately after being placed in the packaging bag. One method of comparison is to compare the L of the vacuum-packed product being tested. ＊ a ＊ or b ＊ A method to check whether the difference between the value and the standard value is within a certain range, and the L size of the vacuum-sealed package to be inspected. ＊ a ＊ or b ＊ Methods for determining whether the value obtained by dividing by a reference value falls within a certain range include the following:

[0211] Furthermore, as shown in Figure 12, a reference patch 41 is provided on a part of the surface of the vacuum pack 40, and L is measured from the reference patch 41. ＊ a ＊ or b ＊ This can be used as a reference value. By using such a vacuum-sealed pack 40 as the subject of inspection, the color tone of the raw fish seen through the packaging bag and the color tone of the reference patch 41 can be efficiently obtained in a single measurement.

[0212] According to the inspection method disclosed herein, the color of raw fish can be determined through the packaging bag without opening the vacuum pack and removing the raw fish. Since the color of raw fish influences consumers' purchasing decisions, determining the color of the raw fish in advance allows for easy selection of vacuum packs that are more likely to attract consumers' purchasing decisions, without having to open the packs.

[0213] The packaging materials of this disclosure will be described in detail below based on examples, but the sealant films of this disclosure are not limited to the examples.

[0214] [Example 1] A biaxially oriented polyethylene terephthalate film (product name: CB981, thickness 12 μm, manufactured by KOLON) was prepared as the first substrate layer, and a plasma pretreatment process and a film deposition process were performed using the film deposition apparatus 10 shown in Figure 4. In the pretreatment process, a plasma pretreatment was applied to the surface of the first substrate layer using the plasma pretreatment mechanism 11B shown in Figures 4 and 5. Specifically, first, a mixed gas of argon (Ar) and oxygen (O2) was supplied to the plasma pretreatment chamber 12B using the plasma raw material gas supply unit, and the air pressure inside the plasma pretreatment chamber 12B was adjusted using the depressurization chamber 12. Next, a voltage was applied between the pretreatment roller 20 and the electrode unit 21 to generate plasma, and a plasma pretreatment was applied to the surface of the first substrate layer. In the film deposition process, a vapor deposition film containing aluminum oxide was deposited by vacuum deposition using the evaporation mechanism 24 shown in Figure 8. Specifically, after adjusting the atmospheric pressure in the deposition chamber 12C to 1 Pa, an aluminum metal wire was supplied into the boat 24b as the deposition material. Using a resistance heating evaporation mechanism 24, the deposition material in the boat 24b was heated, and the aluminum was evaporated so that it reached the surface of the first substrate layer, thereby forming a vapor-deposited film on the surface of the first substrate layer and producing a vapor-deposited film. Hereinafter, this vapor-deposited film will be referred to as "vapor-deposited film A". The thickness of the deposited vapor-deposited film was 8 nm.

[0215] The specific conditions are as follows: [Conditions for Plasma Pretreatment Mechanism 11B] Configuration of Plasma Pretreatment Mechanism 11B: The configuration shown in Figures 4 and 5. Plasma raw material gas supplied to Plasma Pretreatment Chamber 12B: Argon (Ar) and oxygen (O ２) is a mixed gas. Atmospheric pressure in plasma pretreatment chamber 12B: 3 Pa. Magnetic field forming section 23: A permanent magnet with a magnetic field of 1000 gauss. [Conditions for film formation mechanism 11C] Configuration of plasma supply mechanism 50: It has a hollow cathode 51 as shown in Figure 8, and anodes (not shown) arranged on both sides in the width direction of the first substrate layer as viewed from the boat 24b, facing the opening of the cavity of the hollow cathode 51. Method of using plasma supply mechanism 50: Plasma raw material gas is supplied to the cavity of the hollow cathode 51 and a discharge is made to excite the plasma. This plasma is drawn out between the surface of the first substrate layer and the evaporation mechanism 24 by the opposing anodes.

[0216] A gas barrier coating film was prepared on a vapor-deposited film A, containing a barrier composition that includes a silicon alkoxide and a polyvinyl alcohol-based resin, and further obtained by polycondensation using a sol-gel method. The above gas barrier coating film was prepared by the following method. First, a solution (hereinafter also referred to as "Solution A") was prepared by mixing 677 g of water, 117 g of isopropyl alcohol, and 16 g of 0.5 N hydrochloric acid (hydrochloric acid with a concentration of 0.5 mol / L) and then mixing in 285 g of tetraethoxysilane. Next, separately from Solution A, a solution (hereinafter also referred to as "Solution B") was prepared by mixing 70 g of polyvinyl alcohol, 1540 g of water, and 80 g of isopropyl alcohol. Solution A and Solution B were mixed in a weight ratio of 13:7 to obtain a solution which was used as the barrier coating agent. The obtained barrier coating agent was applied to the surface of the vapor-deposited film and dried at 110°C for 30 seconds to prepare a gas barrier coating film with a thickness of 250 nm.

[0217] An ester-based adhesive (product name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.) was applied to a gas barrier coating film and laminated with a linear low-density polyethylene film (product name: MTNST, thickness 60 μm, manufactured by Futamura Chemical Co., Ltd.). The linear low-density polyethylene film was a single layer, and the linear low-density polyethylene contained in the linear low-density polyethylene film was ethylene-1-hexene copolymer (C6-LLDPE). In this way, the packaging material of Example 1 was obtained, in which the first base layer, barrier layer, gas barrier coating film, first adhesive layer, and sealant layer were laminated in this order. In the packaging material of Example 1, the thickness of the adhesive layer was 4 μm, and the total thickness of the packaging material was 76.258 μm.

[0218] [Example 2] An ester-based adhesive (product name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.) was applied to the vapor-deposited film A prepared in Example 1, and it was laminated with a biaxially oriented polyamide film (product name: Bonil W, thickness 15 μm, manufactured by Kojin Film & Chemicals Co., Ltd.). Next, an ester-based adhesive (product name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.) was applied to the biaxially oriented polyamide film, and it was laminated with a linear low-density polyethylene film (product name: MTNST, thickness 60 μm, manufactured by Futamura Chemical Co., Ltd.). The linear low-density polyethylene film was a single layer, and the linear low-density polyethylene contained in the linear low-density polyethylene film was ethylene-1-hexene copolymer (C6-LLDPE). In this way, the packaging material of Example 2 was obtained, in which the first base layer, barrier layer, first adhesive layer, second base layer, second adhesive layer and sealant layer were laminated in this order. The thickness of the adhesive layer was 3.5 μm in all cases, and the total thickness of the packaging material was 94.008 μm.

[0219] [Example 3] An ester-based adhesive (product name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.) was applied to a biaxially oriented polyamide film (product name: Bonil W, thickness 15 μm, manufactured by Kojin Film & Chemicals Co., Ltd.), and it was laminated with the biaxially oriented polyethylene terephthalate film of vapor-deposited film A prepared in Example 1. Next, an ester-based adhesive (product name: RU-77T / H-7, manufactured by Rock Paint Co., Ltd.) was applied to the vapor-deposited film of vapor-deposited film A, and it was laminated with a linear low-density polyethylene film (product name: MTNST, thickness 60 μm, manufactured by Futamura Chemical Co., Ltd.). The linear low-density polyethylene film had a single-layer structure, and the linear low-density polyethylene contained in the linear low-density polyethylene film was ethylene-1-hexene copolymer (C6-LLDPE). In this way, the packaging material of Example 3 was obtained, in which the second base layer, the second adhesive layer, the first base layer, the barrier layer, the first adhesive layer, and the sealant layer were laminated in this order. The thickness of each adhesive layer was 3.5 μm, and the total thickness of the packaging material was 94.008 μm.

[0220] [Comparative Example 1] Techbarrier® LS (manufactured by Mitsubishi Chemical Corporation) was prepared as the packaging material for Comparative Example 1. The packaging material for Comparative Example 1 consisted of a 12 μm thick biaxially oriented polyethylene terephthalate film, a silicon oxide vapor-deposited film, a 3 μm thick adhesive layer, a 15 μm thick biaxially oriented polyamide film, a 3 μm thick adhesive layer, and an 80 μm thick linear low-density polyethylene film, all laminated in this order. The total thickness of the packaging material for Comparative Example 1 was 113 μm.

[0221] [Comparative Example 2] As the packaging material for Comparative Example 2, a material having a layer structure similar to the oxygen-impermeable film described in paragraph

[0043] of Patent Document 1 was prepared. Specifically, a 12 μm thick biaxially oriented polyethylene terephthalate film, a 15 nm thick aluminum oxide vapor-deposited film, a 15 nm thick gas barrier coating film, a 3 μm thick adhesive layer, a 12 μm thick biaxially oriented polyethylene terephthalate film, a 3 μm thick adhesive layer, and a 40 μm thick linear low-density polyethylene film were laminated in this order. The total thickness of the packaging material for Comparative Example 2 was 70.265 μm.

[0222] [Comparative Example 3] For Comparative Example 3, Sigma Tube (registered trademark, product number GT-1525, thickness 60 μm, manufactured by Chlorin Chemicals Co., Ltd.) was prepared as the packaging material. The packaging material for Comparative Example 3 consisted of two layers: a 22 μm thick biaxially oriented polyamide film, a 5 μm thick adhesive layer, a 15 μm thick polyethylene film, and an 18 μm thick polyethylene film, all laminated in this order.

[0223] [Comparative Example 4] For Comparative Example 4, Kyobijin (product name, product number XS-1527, thickness 70 μm, size 150 mm x 270 mm, manufactured by Chlorin Chemicals Co., Ltd.) was prepared as the packaging material. The packaging material for Comparative Example 4 consisted of two layers: a 27 μm thick biaxially oriented polyamide film, a 5 μm thick adhesive layer, a 17 μm thick polyethylene film, and a 21 μm thick polyethylene film, all laminated in this order.

[0224] [Comparative Example 5] For Comparative Example 5, Nylon Poly TL Type 10-15 (product name, thickness 70 μm, size 100 mm x 150 mm, manufactured by Fukusuke Kogyo Co., Ltd.) was prepared as the packaging material. The packaging material for Comparative Example 5 consisted of a 15 μm thick polyamide film, a 25 μm thick linear low-density polyethylene film, and a 30 μm thick linear low-density polyethylene film, laminated in this order.

[0225] [Measurement of Oxygen Permeability] Test specimens were obtained by cutting out the packaging materials of Examples 1-3 and Comparative Examples 1-5. The test specimens were set in an oxygen permeability measuring device (product name: OX-TRAN2 / 20, manufactured by MOCON Corporation) so that the first base material layer side (the side composed of biaxially oriented polyethylene terephthalate film or polyamide film) was the oxygen supply side. The oxygen permeability (unit: cc / m³) was measured in accordance with JIS K 7126-2:2006 (isobaric method) under conditions of 23°C and 90% relative humidity RH. ２ The daily pressure (MPa) was measured. The results are shown in Tables 1 and 2.

[0226] [Measurement of Water Vapor Permeability] Test specimens were obtained by cutting out the packaging materials of Examples 1-3 and Comparative Examples 1-5. The test specimens were set in a water vapor permeability measuring device (product name: PERMATRAN-w 3 / 33, manufactured by MOCON) so that the first base material layer side (the side composed of biaxially oriented polyethylene terephthalate film or polyamide film) was the water vapor supply side. The water vapor permeability (unit: g / m³) was measured in accordance with JIS K 7129:2008 (Method B) under conditions of 40°C and 90% relative humidity RH. ２ The daily values ​​were measured. The results are shown in Tables 1 and 2.

[0227] [Measurement of Puncture Strength] In the packaging material of Example 1, the side composed of the sealant layer was defined as the other side, and the side opposite to the other side (the side composed of the first base material layer) was defined as the first side. The packaging material of Example 1 was fixed to a measuring instrument (A&D Tensilon Universal Material Tester RTC-1310). In a measurement environment of 23°C and 50% relative humidity, in accordance with JIS Z 1707:2019 7.4, a semicircular needle with a diameter of 1.0 mm and a tip radius of 0.5 mm was pierced from one side of the packaging material at a speed of 50 mm / min (50 mm per minute), and the maximum stress until the needle penetrated the packaging material was measured. The same measurement was performed three times, and the average value of the three measured values ​​was calculated and taken as the puncture strength from one side of the packaging material of Example 1. The puncture strength from the other side of the packaging material in Example 1 was determined in the same manner as described above, except that the puncture was performed from the other side of the packaging material instead of from one side. For the packaging materials in Examples 2 and 3 and Comparative Examples 1 and 2, the puncture strength from one side and the puncture strength from the other side were determined using the same procedure as for the packaging material in Example 1. The results are shown in Tables 1 and 2.

[0228] [Measurement of Tear Strength] For the packaging material of Example 1, the mechanical flow direction of the packaging material was defined as the MD direction, and the direction perpendicular to the MD direction was defined as the TD direction. The packaging material of Example 1 was cut into a rectangular shape measuring 63 mm in the MD direction and 75 mm in the TD direction. A straight cut (I-notch) with a length of 20 mm was made in the center of the long side in the TD direction (37.5 mm away from both ends in the TD direction) to form a notched portion, which was used as a test specimen. Sixteen such test specimens were prepared. The sixteen test specimens were stacked so that the notched portions of the test specimens coincided in a plan view. Sixteen stacked test pieces were mounted on a measuring instrument (a load-type Elmendorf tear tester IM-702 manufactured by Tester Industries Co., Ltd.), and in a measurement environment of 23°C and 50% relative humidity, a fan-shaped pendulum was swung down toward the notch portion in accordance with JIS K 7128-2:1998, and the force required to tear the sixteen test pieces in the MD direction with the notch portion as the pivot point (the force required to tear 47 mm) was measured. The same measurement was performed three times, and the average value of the three measurements was calculated and used as the tear strength in the MD direction of the packaging material of Example 1. The packaging material of Example 1 was cut into a rectangle measuring 63 mm in the TD direction and 75 mm in the MD direction, and a 20 mm long straight cut (I-notch) was made in the center of the long side in the MD direction (37.5 mm away from both ends in the MD direction) to form a notch portion, and this was used as a test piece. Sixteen of these test pieces were prepared. Sixteen test specimens were stacked so that their notches coincided in a plan view. The stack of 16 test specimens was mounted on a measuring instrument (a load-type Elmendorf tear tester IM-702 manufactured by Tester Industries Co., Ltd.), and in a measurement environment of 23°C and 50% relative humidity, a fan-shaped pendulum was swung down toward the notches in accordance with JIS K 7128-2:1998, and the force required to tear the 16 test specimens in the TD direction with the notches as the pivot point (the force required to tear 47 mm) was measured. The same measurement was performed three times, and the average value of the three measurements was calculated and used as the tear strength in the TD direction for the packaging material of Example 1. For the packaging materials of Examples 2 and 3 and Comparative Examples 1 and 2, the tear strength in the MD direction and the tear strength in the TD direction were determined using the same procedure as for the packaging material of Example 1. The results are shown in Tables 1 and 2.

[0229] [Measurement of Tensile Strength] For the packaging material of Example 1, the mechanical flow direction of the packaging material was defined as the MD direction, and the direction perpendicular to the MD direction was defined as the TD direction. The packaging material of Example 1 was cut into a rectangular shape measuring 150 mm in the MD direction and 15 mm in the TD direction to obtain a test specimen. The test specimen was set in a measuring instrument (a tensile testing machine RTC-1310A manufactured by Orientec Co., Ltd.). The initial distance between the pair of chucks holding the test specimen was set to 50 mm, and the tensile speed was set to 300 mm / min. The tensile strength in the MD direction was measured in a measurement environment of 23°C and 50% relative humidity in accordance with JIS K 7127:1999. The same measurement was performed three times, and the average value of the three measurements was calculated and taken as the tensile strength in the MD direction of the packaging material of Example 1. The packaging material of Example 1 was cut into a rectangular shape measuring 150 mm in the TD direction and 15 mm in the MD direction to obtain a test specimen. The test specimen was set in a measuring instrument (Orientec Co., Ltd. RTC-1310A tensile testing machine). The initial distance between the pair of chucks holding the test specimen was set to 50 mm, and the tensile speed was set to 300 mm / min. The tensile strength in the TD direction was measured in accordance with JIS K 7127:1999 at a temperature of 23°C and a relative humidity of 50%. The same measurement was performed three times, and the average value of the three measurements was calculated and used as the tensile strength in the TD direction for the packaging material of Example 1. For the packaging materials of Examples 2 and 3 and Comparative Examples 1 and 2, the tensile strength in the MD direction and the tensile strength in the TD direction were determined using the same procedure as for the packaging material of Example 1. The results are shown in Tables 1 and 2.

[0230] [Color Tone Measurement] Samples were prepared by cutting the packaging materials of Examples 1-3 and Comparative Examples 1-5 to a size of 3 cm x 3 cm. The samples were mounted in an ultraviolet-visible-infrared spectrophotometer (product name: V-670, manufactured by JASCO Corporation), and the tristimulus values ​​XYZ in the CIE 1931 color space were measured on the first substrate layer side of the sample (the side composed of biaxially oriented polyethylene terephthalate film or polyamide film) under the following measurement conditions. (Measurement conditions) ・Measurement wavelength: 380-780 nm (1 nm increments) ・Light source: Deuterium lamp ・Measurement environment: Room temperature, humidity controlled environment Reflectance spectral measurements were performed three times each using a standard white plate attached to the ultraviolet-visible-infrared spectrophotometer as 100% reflectance, and the average values ​​of X, Y, and Z were calculated using a standard light source (D65 light source) and a 2° field of view. Other conditions conformed to JIS Z 8722:2009. From the average values ​​of X, Y, and Z, CIE1976L ＊ a ＊ b ＊ L in color space ＊ a ＊ and b ＊ The following was calculated. L measured using the packaging material of Example 1. ＊ a ＊ and b ＊ L １ ＊ a １ ＊ and b １ ＊ L measured using the packaging material of Comparative Example 3 ＊ a ＊ and b ＊ L ２ ＊ a ２ ＊ and b ２ ＊ The color difference ΔE of the packaging material of Example 1 is compared to the packaging material of Comparative Example 3. ＊ ab(1) was calculated using the following formula: ΔE ＊ ab = {(L ２ ＊ -L １ ＊ ) ２ + (a ２ ＊ -a １ ＊) ２ + (b ２ ＊ -b １ ＊ ) ２} １／２ Color difference ΔE of the packaging materials in Examples 2 and 3 and Comparative Examples 1, 2, 4 and 5 ＊ ab(1) were calculated in the same manner. L measured using the packaging material of Example 1. ＊ a ＊ and b ＊ L １ ＊ a １ ＊ and b １ ＊ L measured using the packaging material of Comparative Example 5 ＊ a ＊ and b ＊ L ３ ＊ a ３ ＊ and b ３ ＊ The color difference ΔE of the packaging material of Example 1 is compared to the packaging material of Comparative Example 5. ＊ ab(2) was calculated using the following formula: ΔE ＊ ab = {(L ３ ＊ -L １ ＊ ) ２ + (a ３ ＊ -a １ ＊ ) ２ + (b ３ ＊ -b １ ＊ ) ２} １／２ Color difference ΔE of packaging materials in Examples 2 and 3 and Comparative Examples 1 to 4 ＊ ab(2) were calculated in the same manner. L measured using the packaging material of Example 1. ＊ a ＊ and b ＊ L １ ＊ a １ ＊ and b １ ＊, Color difference ΔE of the packaging material in Example 1 when the D65 light source is used as the reference. ＊ ab(3) was calculated using the following formula: ΔE ＊ ab(3)={(100.000-L １ ＊ ) ２ +(-0.070-a １ ＊ ) ２ + (0.129 - b) １ ＊ ) ２} １／２ Color difference ΔE of the packaging materials in Examples 2 and 3 and Comparative Examples 1 to 5 ＊ ab(3) were calculated in the same manner. The results are shown in Tables 1 and 2.

[0231] [Storage Test] Two sheets each of the packaging materials from Examples 1 and 2 and Comparative Examples 1 to 3 were prepared. The sealant layer sides (sides made of linear low-density polyethylene film or polyethylene film) were placed facing each other and overlapped. Three sides were heat-sealed at 180°C, 0.1 MPa, and 1 second to produce a flat packaging bag of B5 size (182 mm x 257 mm). One fillet of raw sea bream was inserted through the opening of the obtained packaging bag, and the opening was heat-sealed under the above conditions while vacuuming was performed to produce a vacuum pack. The obtained vacuum pack was placed in a refrigerator set to 1°C and stored for 7 days. After 7 days of storage, the sea bream fillet was removed from the vacuum pack, and the amount of ATP and its degradation products, ADP (adenosine diphosphate), AMP (adenosine monophosphate), IMP (inosinic acid), HxR (inosine), and Hx (hypoxanthine), was measured by high-performance liquid chromatography, and the K value was calculated using the following formula. High-performance liquid chromatography analysis was outsourced to Bureau Veritas FEAC, Inc. The results are shown in Tables 1 and 2. K value [%] = (HxR + Hx) / (ATP + ADP + AMP + IMP + HxR + Hx) × 100

[0232]

[0233]

[0234] As is clear from Tables 1 and 2, the vacuum packs made from the packaging materials of Examples 1 and 2 were able to suppress the K value of the sea bream fillet contents to 14% even after a 7-day storage test, demonstrating that the freshness of raw fish can be maintained for a long period of time. Furthermore, although the packaging materials of Comparative Examples 1 and 2 can maintain the freshness of raw fish for a long period of time, the color difference ΔE compared to the Sigma tube is... ＊ The large values ​​of a and b raised concerns about their impact on measuring the color of raw fish through the packaging bag.

[0235] D1, D2: Direction P: Plasma X: Rotation axis θ: Angle 1: Substrate 2: Packaging material 3: First substrate layer 4: Barrier layer 5: Sealant layer 6: First adhesive layer 7: Second substrate layer 8: Second adhesive layer 10: Film deposition apparatus 11A: Substrate transport mechanism 11B: Plasma pretreatment mechanism 11C: Film deposition mechanism 12: Reduced pressure chamber 12A: Substrate transport chamber 12B: Plasma pretreatment chamber 12C: Film deposition chamber 13: Unwinding roller 14a-d: Guide rolls 15: Take-up roller 20: Pretreatment roller 21: Electrode section 21c: First surface 21d: Second surface 21e: First end 21f: Second end 23: Magnetic field forming section 23a: First surface 23b: Second surface 231: First magnet 231c: First axial section 232: Second magnet 232c: Second axial section 232d: Connection section 24: Evaporation mechanism 24b: Boat 25: Film deposition roller 31: Power supply wiring 32: Power supply 35a-35c: Partition 40: Vacuum pack 41: Reference patch 50: Plasma supply mechanism 51: Hollow cathode 61: Evaporation material supply section 63: Aluminum vapor

Claims

A packaging material comprising a first base layer, a barrier layer, and a sealant layer in this order, The first substrate layer contains a polyester resin, The barrier layer is a deposited film of a metal oxide, The sealant layer contains a heat-sealable resin, The L in the CIE 1976 color space is calculated from the reflection spectral spectrum measured in accordance with JIS Z 8722:2009 under the conditions of a D65 light source and a 2° viewing angle. ＊ 99.159, and a ＊ The value is -0.038, and b ＊ The color difference ΔE between the color tone of the film, which has a value of 0.349, and the color tone of the packaging material. ＊ ab(1) is 0.40 or more and 0.80 or less, The oxygen permeability measured in accordance with JIS K 7126-2:2006 under conditions of 23°C and 90% relative humidity was 1.5 mL / m³. ２ Packaging materials with a pressure of 1 / day MPa or less. 　 A packaging material comprising a first base layer, a barrier layer, and a sealant layer in this order, The first substrate layer contains a polyester resin, The barrier layer is a deposited film of a metal oxide, The sealant layer contains a heat-sealable resin, L in the CIE 1976 color space, calculated from the reflectance spectrum measured in accordance with JIS Z 8722:2009 under the conditions of a D65 light source and a 2° viewing angle ＊ is 98.869, a ＊ is -0.079, and b ＊ is 0.298, and the color difference ΔE ＊ ab(2) is 0.25 or more and 0.50 or less, The oxygen permeability measured in accordance with JIS K 7126-2:2006 under conditions of 23°C and 90% relative humidity was 1.5 mL / m³. ２ Packaging materials with a pressure of 1 / day MPa or less. 　 A packaging material comprising a first base layer, a barrier layer, and a sealant layer in this order, The first substrate layer contains a polyester resin, The barrier layer is a deposited film of a metal oxide, The sealant layer contains a heat-sealable resin, The color difference ΔE between the color tone of the packaging material in the CIE 1976 color space and the color tone of the D65 light source, calculated from the reflectance spectral spectrum measured in accordance with JIS Z 8722:2009 under the conditions of a D65 light source and a 2° viewing angle. ＊ ab(3) is 1.20 or more and 1.80 or less, The oxygen permeability measured in accordance with JIS K 7126-2:2006 under conditions of 23°C and 90% relative humidity was 1.5 mL / m³. ２ Packaging materials with a pressure of 1 / day MPa or less. 　 A second substrate layer is further provided between the barrier layer and the sealant layer. The packaging material according to any one of claims 1 to 3, wherein the second base material layer comprises a polyamide resin or a polyester resin. 　 The packaging material according to any one of claims 1 to 4, wherein the first base material layer constitutes one surface of the packaging material. 　 The second substrate layer, the aforementioned first substrate layer, the barrier layer, and the sealant layer are provided in this order. The packaging material according to any one of claims 1 to 3, wherein the second base material layer comprises a polyamide resin or a polyester resin. 　 The packaging material according to claim 6, wherein the second base material layer constitutes one surface of the packaging material. 　 The packaging material according to claim 5 or 7, wherein the puncture strength from one of the aforementioned surfaces is 3 N / 1 mmΦ or more. 　 The packaging material according to any one of claims 1 to 8, wherein the sealant layer constitutes the other surface of the packaging material. 　 The packaging material according to claim 9, wherein the puncture strength from the other surface is 3 N / 1 mmΦ or more. 　 A packaging material according to any one of claims 1 to 10, wherein the total thickness is 70 μm or more and 100 μm or less. 　 The packaging material according to any one of claims 1 to 11, wherein the first base layer comprises polyethylene terephthalate. 　 The packaging material according to any one of claims 1 to 12, wherein the metal oxide is aluminum oxide. 　 The packaging material according to any one of claims 1 to 13, wherein the heat-sealable resin is linear low-density polyethylene. 　 The water vapor transmission rate measured in accordance with JIS K 7129:2008 under conditions of 40°C and 90% RH relative humidity was 0.5 g / m³. ２ - A packaging material according to any one of claims 1 to 14, wherein the number of days is less than or equal to [number] days. 　 The packaging material according to any one of claims 1 to 15, wherein the tensile strength in the MD direction is 20 N / 15 mm or more. 　 The packaging material according to any one of claims 1 to 16, wherein the tensile strength in the TD direction is 20 N / 15 mm or more. 　 A packaging material according to any one of claims 1 to 17, wherein the tear strength in the MD direction is 0.1 N or more. 　 A packaging material according to any one of claims 1 to 18, wherein the tear strength in the TD direction is 0.1 N or more. 　 A packaging bag comprising the packaging material described in any one of claims 1 to 19. 　 A vacuum-packed bag containing raw fish, as described in claim 20. 　 The vacuum pack according to claim 21, wherein the raw fish is sea bream. 　 A method for preserving raw fish, comprising the step of storing the vacuum-packed product described in claim 21 or 22 at a temperature of 0°C or higher and 2°C or lower. 　 A step of measuring the reflectance spectral spectrum of the vacuum pack described in claim 21 or 22 in accordance with JIS Z 8722:2009 under the condition of a 2° field of view, From the aforementioned reflection spectral spectrum, L in the CIE 1976 color space ＊ a ＊ or b ＊ The process of calculating, The L of the vacuum pack ＊ , the above a ＊ or the above b ＊ A method for inspecting raw fish, comprising the step of determining the color tone of the raw fish by comparing it with a reference value.

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