Transparent anti-corrosion barrier laminate, its manufacturing method, and anti-corrosion packaging material

Abstract

To provide a transparent antirust barrier laminate that is easy to handle and has long-lasting antirust performance.SOLUTION: A transparent antirust barrier laminate (10) comprises at least a barrier layer (1) having gas or water vapor barrier properties and an antirust sealant film (2) containing an organic acid.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a transparent anticorrosive barrier laminate and a method for producing the same, as well as anticorrosive packaging materials produced using the transparent anticorrosive barrier laminate. [Background technology]

[0002] Parts or products (hereinafter simply referred to as "parts") made of iron or iron alloys are prone to rust due to oxidation. Parts made of non-ferrous metals such as copper and aluminum can also corrode due to oxidation. Such rust and corrosion (hereinafter, the term "rust" is used to refer to both rust and corrosion) can render the parts unusable. Therefore, there is a need for rust prevention, and one method for achieving this is to use anti-rust films containing volatile anti-rust agents. For example, such anti-rust films can be applied to parts or processed into bags and parts placed inside the bags. The volatile anti-rust agent gradually vaporizes and adheres to the parts, forming a uniform, thin protective film on the surface of the parts. This protective film prevents the parts from reacting with oxygen and water vapor, thereby preventing rust from forming on the parts.

[0003] Patent Document 1 discloses a rust-preventive packaging material in which a polyolefin resin sheet, an adhesive layer, an ethylene-vinyl alcohol copolymer layer, another adhesive layer, and a polyolefin resin layer containing a rust inhibitor are laminated in this order. It also discloses that an amine-based rust inhibitor can be used as the rust inhibitor.

[0004] Because amine-based rust inhibitors may generate carcinogenic substances such as nitrosamines, rust-preventive packaging materials containing amine-based rust inhibitors must be handled appropriately. Specifically, manufacturers of rust-preventive packaging materials are required to control the rust inhibitor content to ensure an appropriate level, and users of rust-preventive packaging materials are required to take protective measures, such as wearing gloves, to prevent the rust inhibitor from coming into contact with their bodies, in consideration of the possibility of the rust inhibitor bleeding out. As such, conventional rust-preventive films using amine-based rust inhibitors or rust-preventive packaging materials using such films require workers to take protective measures, so the development of products that reduce the burden on workers has been desired.

[0005] Against this background, Patent Document 2 teaches a rust-preventive film that uses caproic acid, a type of saturated fatty acid, as a non-amine rust inhibitor mixed with an amine rust inhibitor. Caproic acid is a component extracted from coconut oil and is harmless to the human body, making this rust-preventive film easy to handle. However, the rust-preventive effect of this rust-preventive film only lasts about four months, making it unsuitable for long-term storage of parts.

[0006] Furthermore, since it is convenient to be able to see the components through the anti-rust film, there is a need for the anti-rust film to have transparency as a property. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Microfilm of Utility Model Application No. 61-97317 (Utility Model Application No. 63-3432) [Patent Document 2] European Patent Application Publication No. 1916276 Summary of the Invention [Problem to be solved by the invention]

[0008] One aspect of an embodiment of the present disclosure has been made to overcome the above-mentioned problems of the conventional art and to meet the above-mentioned needs, and aims to provide a transparent anticorrosion barrier laminate that is easy to handle and has anticorrosion performance for a long period of time. [Means for solving the problem]

[0009] According to one aspect of the transparent anticorrosive barrier laminate according to an embodiment of the present disclosure, the laminate includes at least a barrier layer having gas barrier properties or water vapor barrier properties, and an anticorrosive sealant film containing an organic acid. [Effects of the Invention]

[0010] According to one aspect of the transparent anticorrosive barrier laminate of the embodiment of the present disclosure, the transparent anticorrosive barrier laminate is configured to include at least a barrier layer having gas barrier properties or water vapor barrier properties and an anticorrosive sealant film containing an organic acid, as described above, and therefore can prevent oxygen or water vapor from passing from one surface of the transparent anticorrosive barrier laminate to the other surface, thereby suppressing the organic acid used as the anticorrosive agent from reacting with oxygen or water vapor in the environment to which the one surface is exposed, and suppressing a decrease in the concentration of the organic acid contained in the anticorrosive sealant film.

[0011] Furthermore, the gas barrier properties of the barrier layer prevent the vaporized organic acid from passing through the barrier layer, allowing the organic acid to be effectively utilized on the other surface side. Therefore, the transparent anticorrosive barrier laminate of the present disclosure exhibits the effect of maintaining anticorrosive performance for a long period of time.

[0012] Furthermore, according to one aspect of the transparent anticorrosive barrier laminate according to the embodiment of the present disclosure, an organic acid is used as the anticorrosive agent, which provides the effect of ease of handling. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is a schematic cross-sectional view of a transparent anticorrosive barrier laminate 10a of the present disclosure. [Figure 2] FIG. 1 is a schematic cross-sectional view of a transparent anticorrosive barrier laminate 10b of the present disclosure. [Figure 3] FIG. 1 is a schematic cross-sectional view of a transparent anticorrosive barrier laminate 10c of the present disclosure. [Figure 4] FIG. 1 is a schematic cross-sectional view of a transparent anticorrosive barrier laminate 10d of the present disclosure. [Figure 5] FIG. 1 is a schematic cross-sectional view of a transparent anticorrosive barrier laminate 10e of the present disclosure. [Figure 6] FIG. 1 is a schematic cross-sectional view of a transparent anticorrosive barrier laminate 10f of the present disclosure. [Figure 7] 1 is a schematic cross-sectional view of a transparent anticorrosive barrier laminate 10g of the present disclosure. [Figure 8] 1 is a schematic cross-sectional view of a transparent anticorrosive barrier laminate 10h of the present disclosure. [Figure 9] 1 is a schematic cross-sectional view of a transparent anticorrosive barrier laminate 10i of the present disclosure. [Figure 10] FIG. 1 is a schematic cross-sectional view of a transparent anticorrosive barrier laminate 10j of the present disclosure. [Figure 11] 1 is a schematic cross-sectional view of a transparent anticorrosive barrier laminate 10k of the present disclosure. [Figure 12] FIG. 1 is a schematic cross-sectional view of a transparent anticorrosive barrier laminate 101 of the present disclosure. [Figure 13] 1 is a perspective view of a rust-proof bag 20 according to one embodiment of the rust-proof packaging material of the present disclosure. FIG. DETAILED DESCRIPTION OF THE INVENTION

[0014] In order to explain the present invention in more detail, the following describes an embodiment of the present invention with reference to the accompanying drawings. The resin names used in this disclosure are those commonly used in the industry. Furthermore, in this disclosure, density is a value measured in accordance with JIS K7112. Furthermore, MFR is a value measured in accordance with JIS K7210-1.

[0015] Furthermore, in this disclosure, the terms "film" and "laminate" are synonymous in that they refer to an object in which multiple layers are stacked, and when used in this sense, the two terms are interchangeable. However, the two terms differ in that a "film" includes a single layer, while a "laminate" does not include a single layer.

[0016] Furthermore, in this disclosure, the term "transparent" refers to a haze of 0.1% to 50% for light of any wavelength within the visible light range, in accordance with JIS K7136. The possible range of haze values ​​may be narrower, in the range of 0.3% to 45%, or even narrower, in the range of 0.5% to 40%. Note that the visible light range here refers to a light wavelength range of 380 nm to 780 nm, in accordance with JIS B7079.

[0017] In the following description of the embodiments, first, various layer configurations of the transparent anticorrosive barrier laminate will be described. Next, each component of the transparent anticorrosive barrier laminate will be described. Next, a method for manufacturing the transparent anticorrosive barrier laminate will be described. Next, a packaging material using the transparent anticorrosive barrier laminate will be described.

[0018] 1.Layer structure of transparent anti-corrosion barrier laminate <Basic layer configuration> 1 to 12 are schematic cross-sectional views showing the layer structure of a transparent anticorrosive barrier laminate 10 (10a to 10l) of the present disclosure. FIG. 1 is a schematic cross-sectional view showing the layer structure of a transparent anticorrosive barrier laminate 10a. As shown in FIG. 1, the transparent anticorrosive barrier laminate 10a comprises a barrier layer 1 having gas barrier properties or water vapor barrier properties and an anticorrosive sealant film 2 containing an organic acid. The barrier layer 1 comprises a transparent resin film 1a made of a transparent resin and an inorganic oxide film 1b made of an inorganic oxide. As shown in FIG. 1, the transparent anticorrosive barrier laminate 10a has a structure in which a transparent resin film 1a, an inorganic oxide film 1b, and an anticorrosive sealant film 2 are laminated in this order. The inorganic oxide film 1b can be formed on the transparent resin film 1a by vapor-depositing an inorganic oxide on the transparent resin film 1a. Furthermore, by using a heat-sealable resin as the anticorrosive sealant film 2, the barrier layer 1 and the anticorrosive sealant film 2 can be laminated by heat sealing.

[0019] <Layer structure with adhesive layer> Fig. 2 is a schematic cross-sectional view showing the layer structure of a transparent anticorrosive barrier laminate 10b. Similar to the transparent anticorrosive barrier laminate 10a of Fig. 1, the transparent anticorrosive barrier laminate 10b comprises a barrier layer 1 and an anticorrosive sealant film 2. The transparent anticorrosive barrier laminate 10b further comprises an adhesive layer 3 made of an adhesive or adhesive resin provided between the barrier layer 1 (inorganic oxide film 1b) and the anticorrosive sealant film 2, and has a structure in which the barrier layer 1 (inorganic oxide film 1b) and the anticorrosive sealant film 2 are bonded via the adhesive layer 3. This allows the barrier layer 1 and the anticorrosive sealant film 2 to be more firmly bonded together.

[0020] <Layer structure with gas barrier film> Fig. 3 is a schematic cross-sectional view showing the layer structure of a transparent anticorrosive barrier laminate 10c. Similar to the transparent anticorrosive barrier laminate 10a in Fig. 1, the transparent anticorrosive barrier laminate 10c comprises a barrier layer 1 and an anticorrosive sealant film 2. The transparent anticorrosive barrier laminate 10c further comprises a gas barrier film 4 between the barrier layer 1 (inorganic oxide film 1b) and the anticorrosive sealant film 2.

[0021] Fig. 4 is a schematic cross-sectional view showing the layer structure of a transparent anticorrosive barrier laminate 10d. Similar to the transparent anticorrosive barrier laminate 10b in Fig. 2, the transparent anticorrosive barrier laminate 10d comprises a barrier layer 1, an adhesive layer 3, and an anticorrosive sealant film 2. The transparent anticorrosive barrier laminate 10d further comprises a gas barrier film 4 between the barrier layer 1 (inorganic oxide film 1b) and the adhesive layer 3.

[0022] By providing the gas barrier film 4 as in the transparent anticorrosive barrier laminate 10c or the transparent anticorrosive barrier laminate 10d, it is possible to improve the gas barrier properties and weather resistance.

[0023] <Layer structure with co-extruded multilayer film> Fig. 5 is a schematic cross-sectional view showing the layer structure of a transparent anticorrosive barrier laminate 10e. Similar to the transparent anticorrosive barrier laminate 10a in Fig. 1, the transparent anticorrosive barrier laminate 10e comprises a barrier layer 1 and an anticorrosive sealant film 2. Unlike the transparent anticorrosive barrier laminate 10a, the transparent anticorrosive barrier laminate 10e has the anticorrosive sealant film 2 formed as a co-extruded multilayer film of two layers 2a and 2b.

[0024] Fig. 6 is a schematic cross-sectional view showing the layer structure of a transparent anticorrosive barrier laminate 10f. Similar to the transparent anticorrosive barrier laminate 10b in Fig. 2, the transparent anticorrosive barrier laminate 10f comprises a barrier layer 1, an adhesive layer 3, and an anticorrosive sealant film 2. Unlike the transparent anticorrosive barrier laminate 10b, the transparent anticorrosive barrier laminate 10f has the anticorrosive sealant film 2 formed as a co-extruded multilayer film of two layers 2a and 2b.

[0025] Fig. 7 is a schematic cross-sectional view showing the layer structure of a transparent anticorrosive barrier laminate 10g. Similar to the transparent anticorrosive barrier laminate 10c of Fig. 3, the transparent anticorrosive barrier laminate 10g comprises a barrier layer 1, a gas barrier film 4, and an anticorrosive sealant film 2. Unlike the transparent anticorrosive barrier laminate 10c, the transparent anticorrosive barrier laminate 10g has the anticorrosive sealant film 2 formed as a co-extruded multilayer film of two layers 2a and 2b.

[0026] Fig. 8 is a schematic cross-sectional view showing the layer structure of a transparent anticorrosive barrier laminate 10h. Similar to the transparent anticorrosive barrier laminate 10d of Fig. 4, the transparent anticorrosive barrier laminate 10h comprises a barrier layer 1, a gas barrier film 4, an adhesive layer 3, and an anticorrosive sealant film 2. Unlike the transparent anticorrosive barrier laminate 10d, the transparent anticorrosive barrier laminate 10h has the anticorrosive sealant film 2 formed as a co-extruded multilayer film of two layers 2a and 2b.

[0027] By forming the anticorrosive sealant film 2 as a co-extruded multilayer film, as in the transparent anticorrosive barrier laminates 10e to 10h, it is possible to add an anticorrosive agent to only one of the two layers to form the anticorrosive layer 2b, and to add no anticorrosive agent to the other to form the non-anticorrosive layer 2a, thereby improving the laminate strength of the non-anticorrosive layer 2a and reducing the amount of expensive anticorrosive agent used.

[0028] Although not shown, the anticorrosive sealant film 2 can also be a co-extruded multilayer film of three or more layers. For example, by making at least one layer, such as the middle layer, a layer made of polypropylene and the remaining layers layers made of an olefin-based resin that exhibits the desired seal strength, it is possible to improve the oxygen gas barrier property and water vapor barrier property while maintaining the desired seal strength and lamination strength, and further impart oil resistance to the laminate of the present disclosure.

[0029] <Layer structure with protective film> Fig. 9 is a schematic cross-sectional view showing the layer structure of a transparent anticorrosive barrier laminate 10i. Similar to the transparent anticorrosive barrier laminate 10b in Fig. 2, the transparent anticorrosive barrier laminate 10i comprises a barrier layer 1, an adhesive layer 3, and an anticorrosive sealant film 2. The transparent anticorrosive barrier laminate 10i further comprises a protective film 5 made of a primer coating resin between the barrier layer 1 (inorganic oxide film 1b) and the adhesive layer 3.

[0030] Fig. 10 is a schematic cross-sectional view showing the layer structure of a transparent anticorrosive barrier laminate 10j. Similar to the transparent anticorrosive barrier laminate 10d in Fig. 4, the transparent anticorrosive barrier laminate 10j comprises a barrier layer 1, a gas barrier film 4, an adhesive layer 3, and an anticorrosive sealant film 2. The transparent anticorrosive barrier laminate 10j further comprises a protective film 5 made of a primer coating resin between the gas barrier film 4 and the adhesive layer 3.

[0031] Fig. 11 is a schematic cross-sectional view showing the layer structure of a transparent anticorrosive barrier laminate 10k. Similar to the transparent anticorrosive barrier laminate 10f in Fig. 6, the transparent anticorrosive barrier laminate 10k comprises a barrier layer 1, an adhesive layer 3, and an anticorrosive sealant film 2. The transparent anticorrosive barrier laminate 10k further comprises a protective film 5 made of a primer coating resin between the barrier layer 1 (inorganic oxide film 1b) and the adhesive layer 3.

[0032] Fig. 12 is a schematic cross-sectional view showing the layer structure of a transparent anticorrosive barrier laminate 10l. Similar to the transparent anticorrosive barrier laminate 10h of Fig. 8, the transparent anticorrosive barrier laminate 10l comprises a barrier layer 1, a gas barrier film 4, an adhesive layer 3, and an anticorrosive sealant film 2. The transparent anticorrosive barrier laminate 10l further comprises a protective film 5 made of a primer coating resin between the gas barrier film 4 and the adhesive layer 3.

[0033] When printing letters, pictures, etc. on the transparent anticorrosive barrier laminate 10, this can be done on any surface of the transparent resin film 1a, but for example, by printing in advance by reverse printing on the surface of the barrier layer 1 facing the adhesive layer 3 or on the gas barrier film 4, it is possible to form a printed image that will not be damaged by surface friction, etc. In this case, before reverse printing, a protective film 5 made of a primer coat resin may be provided on the surface of the barrier layer 1 or the gas barrier film 4 to be printed, as in the transparent anticorrosive barrier laminates 10i to 10l.

[0034] The transparent anticorrosive barrier laminate 10 may have any thickness depending on its intended use, desired seal strength, tear resistance, gas barrier properties, and the like.

[0035] 2. Components of transparent anti-corrosion barrier laminate <Transparent resin film> In the transparent anticorrosive barrier laminate 10 of the present disclosure, any resin film that maintains the desired strength, heat resistance, transparency, etc., depending on the packaging application can be used as the transparent resin film 1a. Specifically, resin films such as polyester-based resins, polyamide-based resins, polyaramid-based resins, polyolefin-based resins, polycarbonate-based resins, polystyrene-based resins, polyacetal-based resins, and fluorine-based resins can be used. In particular, polyethylene terephthalate (PET) film is preferably used in the present disclosure for reasons such as its printability, vapor deposition suitability, and antistatic properties after vapor deposition.

[0036] The resin film may be an unstretched film or a stretched film stretched uniaxially or biaxially. The thickness of the film can be determined by those skilled in the art depending on the packaging application, but is 50 to 120 μm or 70 to 120 μm to provide rust prevention. A thickness of 50 μm or less would result in insufficient rust prevention performance, while a thickness of 200 μm or more would result in high costs and excessive rust prevention performance. Furthermore, if desired, an additional layer, such as a printed pattern layer or a surface protective layer to protect the printed pattern layer, may be provided on the surface of the transparent resin film opposite the surface on which the inorganic oxide vapor deposition film is provided.

[0037] <Inorganic oxide film> By providing an inorganic oxide film 1b on one surface of the transparent resin film, the barrier layer 1 constituting the laminate of the present disclosure is obtained. The material for forming the inorganic oxide film 1b may be any material that is transparent and has gas barrier properties against oxygen, water vapor, etc., such as oxides such as silicon oxide, aluminum oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, and barium oxide. In particular, aluminum oxide, silicon oxide, and magnesium oxide are preferred from the standpoints of gas barrier properties and production efficiency.

[0038] To prevent the organic acid used as a rust inhibitor from evaporating and dissipating far away from the component to be rust-prevented, it is preferable to select a material for inorganic oxide film 1b that has a high barrier effect against the evaporated rust inhibitor depending on the organic acid used. By selecting the material for inorganic oxide film 1b depending on the organic acid, the rust inhibitor's anti-rust effect can be maintained for a long period of time. For example, when saturated fatty acid or caproic acid is used as the organic acid, aluminum oxide, which has a high barrier effect against saturated fatty acid, may be selected as the material for inorganic oxide film 1b.

[0039] Furthermore, inorganic oxide film 1b may consist of a single layer formed by a single vapor deposition process, or may have a multilayer structure formed by repeating the vapor deposition process multiple times. In the case of a multilayer structure, each layer may be made of the same material or different materials, and may be formed by the same or different formation methods. The film thickness of inorganic oxide film 1b can be set in the range of 5 to 100 nm as the total film thickness, or more specifically, can be set appropriately in the range of 10 to 90 nm, 10 to 80 nm, 10 to 70 nm, 10 to 60 nm, 10 to 50 nm, 20 to 90 nm, 20 to 80 nm, 20 to 70 nm, 20 to 60 nm, or 20 to 50 nm.

[0040] If the film thickness exceeds 100 nm, flexibility will decrease, and external forces such as bending or pulling after film formation may cause cracks in the deposited film, transparency will decrease, and the stress on the material itself will increase, causing discoloration, which is undesirable. Furthermore, if the thickness exceeds 100 nm, productivity will decrease significantly, and protrusions will tend to form due to abnormal grain growth, which is also undesirable. On the other hand, if the film thickness is less than 5 nm, transparency will be good, but it will be difficult to obtain a uniform layer and it will be difficult to fully fulfill the gas barrier function.

[0041] Examples of methods for forming the vapor deposition layer include physical vapor deposition methods such as vacuum deposition, sputtering, and ion plating, and chemical vapor deposition methods such as plasma-enhanced chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition. In the present disclosure, a vapor deposition method in a vacuum deposition method is preferred, and a resistance heating method, an induction heating method, an electron beam heating method, or the like can be appropriately selected and used as needed.

[0042] In particular, when the laminate of the present disclosure is used as, for example, a rust-preventive package for packaging metal parts, it is preferable to form an inorganic oxide vapor deposition film by a resistance heating vacuum deposition method. The resistance heating vacuum deposition method heats the vapor deposition material with Joule heat using an electric resistor, and compared to other heating methods, it is possible to form a uniform vapor deposition film because it heats the entire surface, and also to set a high line speed.

[0043] The resistance heating method is particularly suitable for the laminate of the present disclosure because it suppresses static electricity buildup on the film. Furthermore, in the present disclosure, it is particularly preferred to provide a vapor-deposited film of aluminum oxide by a vacuum vapor deposition method using the resistance heating method from the viewpoints of antistatic properties, gas barrier properties, transparency, cost, etc.

[0044] <Gas barrier film> In the present disclosure, by providing a gas barrier film 4 (described below) on the inorganic oxide film 1b, not only is even better gas barrier property obtained, but also tighter adhesion with the adhesive layer is improved, resulting in even higher gas barrier property. In the present disclosure, the gas barrier film 4 is a film formed by applying a gas barrier composition obtained by polycondensing an alkoxide and a water-soluble polymer by a sol-gel method.

[0045] The alkoxide used in the gas barrier composition is a compound represented by the general formula R 1 n M(OR 2 ) m (In the formula, R 1 , R 2is an organic group having 1 to 8 carbon atoms, M is a metal atom, n is an integer of 0 or more, m is an integer of 1 or more, and n + m is the valence of M. In addition, as the water-soluble polymer, either a polyvinyl alcohol resin or an ethylene-vinyl alcohol copolymer, or both, can be preferably used.

[0046] In the present disclosure, the general formula R 1 n M(OR 2 ) m In the alkoxide represented by the formula (I), silicon, zirconium, titanium, aluminum, etc. can be used as the metal atom M. In the present disclosure, alkoxides of a single metal atom or two or more different metal atoms can be mixed and used in the same solution.

[0047] In addition, the above general formula R 1 n M(OR 2 ) m In the alkoxide represented by the formula 1 Specific examples of the organic group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an n-hexyl group, an n-octyl group, and other alkyl groups.

[0048] In addition, the above general formula R 1 n M(OR 2 ) m In the alkoxide represented by the formula 2 Specific examples of the organic group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, etc. In the present disclosure, these alkyl groups may be the same or different in the same molecule.

[0049] In the present disclosure, the above general formula R 1 n M(OR 2 )m As the alkoxide represented by the formula (I), for example, an alkoxysilane in which M is Si can be used. Examples of the alkoxysilane include tetramethoxysilane Si(OCH3)4, tetraethoxysilane Si(OC2H5)4, tetrapropoxysilane Si(OC3H7)4, and tetrabutoxysilane Si(OC4H9)4.

[0050] In the present disclosure, the content of polyvinyl alcohol and / or ethylene vinyl alcohol is preferably in the range of 5 to 500 parts by mass per 100 parts by mass of the total amount of the alkoxides. If the content exceeds 500 parts by mass, the resulting gas barrier film 4 will be undesirably brittle.

[0051] In the present disclosure, polyvinyl alcohol that can be used is generally obtained by saponifying polyvinyl acetate. Specific examples of polyvinyl alcohol that can be used include PVA110 (saponification degree = 98 to 99%, polymerization degree = 1,100), PVA117 (saponification degree = 98 to 99%, polymerization degree = 1,700), PVA124 (saponification degree = 98 to 99%, polymerization degree = 2,400), and PVA135H (saponification degree = 99.7% or more, polymerization degree = 3,500), all manufactured by Kuraray Co., Ltd.; RS polymer RS-110 (saponification degree = 99%, polymerization degree = 1,000), all manufactured by Kuraray Co., Ltd.; Kuraray Poval LM-20SO (saponification degree = 40%, polymerization degree = 2,000), all manufactured by the same company; and Gohsenol NM-14 (saponification degree = 99%, polymerization degree = 1,400) and Gohsenol NH-18 (saponification degree = 98 to 99%, polymerization degree = 1,700), all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.

[0052] Furthermore, in the present disclosure, the ethylene-vinyl alcohol may be a saponified copolymer of ethylene and vinyl acetate, i.e., a product obtained by saponifying an ethylene-vinyl acetate random copolymer. Such saponified products range from partially saponified products in which several tens of mole percent of acetate groups remain to fully saponified products in which only a few mole percent of acetate groups remain or no acetate groups remain at all. While not particularly limited, from the perspective of gas barrier properties, it is desirable to use a product with a degree of saponification of 80 mole % or more, more preferably 90 mole % or more, and even more preferably 95 mole % or more.

[0053] The content of repeating units derived from ethylene in the ethylene-vinyl alcohol (hereinafter also referred to as "ethylene content") is usually 0 to 50 mol%, preferably 20 to 45 mol%. Specific examples of the ethylene-vinyl alcohol include EVAL EP-F101 (ethylene content: 32 mol%) manufactured by Kuraray Co., Ltd. and Soarnol D2908 (ethylene content: 29 mol%) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.

[0054] In the present disclosure, a conventional silane coupling agent or the like can be added to prepare the gas barrier composition that forms the gas barrier film 4. The gas barrier composition used in the present disclosure can be prepared by hydrolysis and polycondensation of an alkoxide and a water-soluble polymer by a sol-gel method in the presence of an acid, water, and an organic solvent.

[0055] The gas barrier film 4 can be formed by applying a gas barrier composition onto an inorganic oxide vapor deposition film and then heat treating it for 10 seconds to 10 minutes at a temperature of 20°C to 200°C, preferably 100°C or higher and below the melting point of the transparent resin film.

[0056] The acid used in preparing the gas barrier composition may be, for example, a mineral acid such as sulfuric acid, hydrochloric acid, or nitric acid, or an organic acid such as acetic acid or tartaric acid, etc. Furthermore, the organic solvent may be, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, or n-propyl alcohol.

[0057] Furthermore, with regard to the gas barrier composition, it is preferable that the polyvinyl alcohol and / or ethylene-vinyl alcohol is dissolved in a coating liquid containing the alkoxide, silane coupling agent, etc., and therefore the type of organic solvent is appropriately selected. In the present disclosure, the ethylene-vinyl alcohol solubilized in a solvent may be, for example, a commercially available product such as Soarnol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

[0058] The gas barrier composition is applied onto an inorganic oxide vapor-deposited film and heated to remove the solvent and alcohol produced by the polycondensation reaction, completing the polycondensation reaction and forming a transparent gas barrier film 4.

[0059] Furthermore, hydroxyl groups generated by hydrolysis and silanol groups derived from the silane coupling agent bond with hydroxyl groups on the surface of the vapor-deposited film, improving the adhesiveness between the vapor-deposited film and the gas barrier film 4 .

[0060] <Protective film made of primer coat resin> A protective film 5 made of a primer coat resin may be provided on the surface of the barrier layer 1 facing the adhesive layer 3, i.e., on the inorganic oxide vapor-deposited film 1b, or on the gas barrier film 4. The presence of the protective film 5 can prevent abrasion with the roll during the printing process and deterioration of the barrier properties due to white ink when reverse printing is performed on the barrier layer 1.

[0061] The primer coating resin used in the present disclosure is not particularly limited, and examples thereof include those containing, as the main component of the vehicle, one or more mixtures of resins such as polyurethane resins, polyester resins, polyamide resins, epoxy resins, phenolic resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymers, acid-modified polyolefin resins, (meth)acrylic resins, polybutadiene resins, and rubber compounds, or prepolymers or monomers thereof. The primer coating resin can be applied to the inorganic oxide vapor-deposited film 1b or the gas barrier film 4 and dried to form the protective film 5.

[0062] <Anti-rust sealant film> The resin constituting the anti-rust sealant film 2 can be independently selected from one or more polyolefin polymers, i.e., olefin homopolymers and / or copolymers using olefins as monomers. Examples of the olefin (olefin monomer) constituting the polyolefin polymer include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Therefore, examples of polyolefin polymers include ethylene polymers, propylene polymers, 1-butene polymers, 1-hexene polymers, and 4-methyl-1-pentene polymers. These polymers may be used alone or in combination of two or more. In other words, the polyolefin polymer may be a mixture of various polymers.

[0063] Among the above, ethylene-based polymers include ethylene homopolymers (polyethylenes) and copolymers of ethylene with other monomers (ethylene copolymers). Examples of ethylene homopolymers include low-density polyethylene (LDPE), linear low-density polyethylene (L-LDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE). Examples of ethylene copolymers include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, and ethylene-4-methyl-1-pentene copolymer. The ethylene units (structural units derived from ethylene) contained in the ethylene copolymer need only account for more than 50% of the total number of structural units (usually 99.999% or less). For example, it can account for 80 to 99.999%, 90 to 99.995%, or even 99.0 to 99.990% of the total number of structural units. Examples of propylene-based polymers include propylene homopolymers (polypropylene) and copolymers of propylene with other monomers (propylene copolymers). Examples of propylene copolymers include propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-pentene copolymers, and propylene-1-octene copolymers. The propylene units (structural units derived from propylene) contained in the propylene copolymer may account for 50% or more (usually 99.999% or less) of the total number of structural units, but can be, for example, 80 to 99.999% of the total number of structural units, or 90 to 99.995%, or even 99.0 to 99.990%.

[0064] Furthermore, the polyolefin polymer may contain structural units derived from monomers other than olefins, provided that the objectives of the present disclosure are not impaired. Examples of monomers other than olefins include unsaturated carboxylic acids (acrylic acid, methacrylic acid, etc.), unsaturated carboxylic acid esters (methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dimethyl maleate, diethyl maleate, etc.), and vinyl esters (vinyl acetate, vinyl propionate, fumaric acid, maleic anhydride, maleic acid monoester, etc.). These may be used alone or in combination of two or more. Furthermore, even if a polyolefin polymer contains structural units derived from monomers other than olefins, the proportion of the total number of structural units is preferably 40% or less (usually 0.001% or more), for example, 0.001 to 25%, 0.005 to 15%, or even 0.01 to 10% of the total number of structural units. The density of polyolefin resin is 0.880 to 0.950 g / cm from the viewpoint of processability. 3 From the viewpoint of mechanical strength and processability, the melt flow rate (MFR) is preferably in the range of 1.0 to 10.0 g / 10 min, and by having an appropriate viscosity during melt processing, it becomes possible to include and coat particulate saturated fatty acids in the resin, and it becomes possible to prevent the saturated fatty acids from falling off from the film.

[0065] Furthermore, known additives that are added to resins, such as antiblocking agents (AB agents), lubricants, antioxidants, antistatic agents, UV absorbers, and processability improvers, can be added to the film layer, as long as they do not interfere with the effects of the present disclosure. The thickness of the film layer is preferably 30 to 200 μm, more preferably 50 to 120 μm.

[0066] <Rust inhibitor> Organic acids are used in rust inhibitor compositions. These include fatty acids such as valeric acid, caproic acid, caprylic acid, capric acid, nonanoic acid, and lauric acid, substances in which some of the hydrogen atoms in the hydrocarbon chains of these fatty acids have been substituted with hydroxyl groups or amino groups (lactic acid, aminocaproic acid), and also benzoic acid and its derivatives, succinic acid, L-glutamic acid, L-ascorbic acid, nicotinic acid, sorbic acid, tartaric acid, oxalic acid, citric acid, cinnamic acid, fumaric acid, and gallic acid, used alone or in combination. Among these, caproic acid is preferred because of its low cost and excellent rust inhibitory properties. The amount of the rust inhibitor relative to the total weight of the rust-preventive sealant film 2 is preferably 0.3 wt % or more and 10 wt % or less. If the amount of the rust inhibitor exceeds 10 wt %, the rust-preventive effect is not improved, and the rust inhibitor may become powdery or fall off the film surface, which may contaminate the metal product, which is undesirable. On the other hand, if the amount is less than 0.3 wt %, the rust-preventive performance cannot be fully exhibited.

[0067] The method for kneading the rust inhibitor into the polyolefin resin is not particularly limited, but a general kneader can be used. Suitable kneaders include single-screw extruders, twin-screw extruders, Banbury kneaders, roll kneaders, and intensive mixers. The rust inhibitor is generally prepared as a masterbatch in which the amount of compounded rust inhibitor during kneading is greater than the amount compounded during film molding. The amount of compounded rust inhibitor in the masterbatch is preferably 5% by weight or more and 50% by weight or less. A content exceeding 50% by weight is undesirable because it reduces the fluidity of the resin, while a content less than 5% by weight is undesirable because it reduces productivity.

[0068] In the rust inhibitor composition of the present disclosure, the oxidation promoter is a substance that promotes oxygen absorption by the saturated fatty acid compound or the chain hydrocarbon polymer having an unsaturated group, which is the main component, and examples thereof include a transition metal or a compound thereof, and a radical initiator.

[0069] 3. Manufacturing method of transparent anticorrosion barrier laminate The transparent anticorrosive barrier laminate 10 can be produced by preparing a barrier layer 1 and laminating an anticorrosive sealant film 2 made of a heat-sealable resin containing an organic acid to the barrier layer 1. When the anticorrosive sealant film 2 is produced by an inflation method and has a tubular shape, the anticorrosive sealant film 2 may be prepared first, and the barrier layer 1 may be laminated to the anticorrosive sealant film 2.

[0070] The barrier layer 1 can be prepared by preparing a transparent resin film 1a made of a transparent resin and depositing an inorganic oxide on one surface of the transparent resin film 1a to form an inorganic oxide film 1b. The deposition can be performed by, for example, a resistance heating vacuum deposition method.

[0071] The barrier layer 1 and the anticorrosive sealant film 2 may be bonded together by, other than heat sealing, applying an adhesive or adhesive resin to the inorganic oxide film 1b to form an adhesive layer 3, and then bonding the anticorrosive sealant film 2 to the adhesive layer 3 by dry lamination. In this case, the adhesive forming the adhesive layer can be selected from conventional adhesives depending on the application. Specific examples include, but are not limited to, polyvinyl acetate adhesives, polyacrylic ester adhesives, cyanoacrylate adhesives, ethylene copolymer adhesives, cellulose adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives, phenolic resin adhesives, epoxy adhesives, polyurethane adhesives, reactive (meth)acrylic adhesives, rubber adhesives, and silicone adhesives. The two films (barrier layer 1 and anticorrosive sealant film 2) can also be bonded together by extrusion lamination (so-called sandwich lamination). In this case, the adhesive resin forming the adhesive layer 3 can be a polyolefin-based thermal adhesive resin, such as LDPE, or a simple substance such as an ethylene-methacrylic acid copolymer, an ethylene-acrylic acid copolymer, or an ionomer, or a resin obtained by blending these with an adhesion improver such as a hard resin. In the present disclosure, the layer thickness (coating amount) of the adhesive layer 3 is 0.1 to 10 g / m 2 (Dry state) is preferable.

[0072] Between the inorganic oxide film 1b and the anticorrosive sealant film 2 or adhesive layer 3, a compound of the general formula R 1 n M(OR 2 ) m (In the formula, R 1 , R 2A gas barrier film 4 may be formed containing one or more alkoxides represented by the formula (wherein n is an organic group having 1 to 8 carbon atoms, M is a metal atom, n is an integer of 0 or more, m is an integer of 1 or more, and n+m is the valence of M) and either or both of a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer. The gas barrier film 4 can be formed by applying a gas barrier composition obtained by polycondensing either or both of the polyvinyl alcohol resin and the ethylene-vinyl alcohol copolymer by a sol-gel method.

[0073] A protective film 5 made of a primer coating resin may be provided on the surface of the barrier layer 1 facing the adhesive layer 3, i.e., on the inorganic oxide vapor-deposited film 1b, or on the gas barrier film 4. The protective film 5 can be formed by applying the primer coating resin to the inorganic oxide vapor-deposited film 1b or the gas barrier film 4 and drying it. It is also conceivable to manufacture a packaging material (packaging bag) described below using the transparent anticorrosive barrier laminate 10 of the present disclosure, and use the packaging material (packaging bag) to contain sharp steel materials. Therefore, as a reinforcing material, stretched nylon, PBT (polybutylene terephthalate) film, various polyethylene nonwoven fabrics (with a coarse mesh that allows the contents to be seen through), etc. may be provided on the barrier layer or between the anticorrosive sealant, via an adhesive or the like. The thickness of the reinforcing material is appropriately selected from the range of 12 to 50 μm (not shown).

[0074] 4. Packaging material FIG. 13 is a perspective view of a rust-preventive bag 20 according to one embodiment of the rust-preventive packaging material of the present disclosure, manufactured with three-sided sealing. The transparent rust-preventive barrier laminate 10 of the present disclosure can be used as a packaging material for bags, boxes, and the like. FIG. 13 illustrates the rust-preventive bag 20 in the form of a bag. The rust-preventive bag 20 can be manufactured, for example, by folding the transparent rust-preventive laminate 10 of the present disclosure in half with the surfaces of the rust-preventive sealant films 2 facing each other, or by preparing two transparent rust-preventive laminates 10 and overlapping them with the surfaces of the rust-preventive sealant films 2 facing each other, and then heat-sealing the peripheral edges of the folded or overlapped transparent rust-preventive laminate 10 with two-sided sealing (in the case of two-sided folding) or three-sided sealing (in the case of overlapping). FIG. 13 shows the case where heat-sealed portions 22a, 22b, and 22c are sealed (three-sided sealing). FIG. 13 shows a state in which a metal part 21 is placed in the rust-proof bag 20 manufactured in this manner, the interior of the rust-proof bag 20 is evacuated, and the heat-sealed portion 22d is further heat-sealed.

[0075] The rust-proof packaging bag can have various heat seal configurations in addition to one-sided, two-sided, or three-sided seals, such as an envelope seal, a palm seal (pillow seal), a pleated seal, a flat bottom seal, a square bottom seal, and a gusset seal.

[0076] The rust-preventive packaging material may be in the form of a box. In this case, the transparent rust-preventive barrier laminate 10 may be attached to at least a part of a container body made of transparent or opaque resin that does not lose its shape at least when touched by a person. Box-shaped containers can be stacked, which allows for organized storage of parts.

[0077] In the above, the heat sealing method can be any known method such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing, ultrasonic sealing, etc.

[0078] The transparent anticorrosive barrier laminate 10 of the present disclosure has excellent oxygen gas barrier properties, water vapor barrier properties, and anticorrosive properties, is compact, and can be produced at low cost, making it suitable for use as a packaging material for a variety of applications.

[0079] In particular, it can be suitably used for packaging materials that are easily decomposed or deteriorated by light or oxygen gas.Furthermore, it exhibits high water vapor barrier properties.

[0080] As described above, the rust-preventive packaging material using the transparent rust-preventive barrier laminate 10 of the present disclosure has a laminated structure of a barrier layer having gas or water vapor barrier properties and a sealant layer containing a volatile rust inhibitor. Because the transparent gas barrier film in the outer layer has high barrier properties, it hardly passes oxygen and water vapor, which cause rusting of steel, and has a high level of airtightness and stability. Furthermore, the inorganic oxide film prevents vaporized organic acids from passing through the transparent resin film and escaping to the outside of the rust-preventive packaging. This enhances the rust-preventive effect inside the rust-preventive packaging material. The transparent anticorrosion barrier laminate of the present disclosure has a two-layer structure, is inexpensive to manufacture and transport, and exhibits both excellent gas barrier properties and anticorrosion properties. Furthermore, by providing a gas barrier film made of a gas barrier composition containing an alkoxide and a polyvinyl alcohol resin or an ethylene-vinyl alcohol copolymer on the inorganic oxide vapor-deposited film, the barrier properties against oxygen and water vapor can be further improved. Furthermore, in the laminate of the present disclosure, the heat-sealable resin film may be a co-extruded multilayer film of two or more layers instead of a single-layer film, which can further improve the gas barrier properties or impart additional functions, such as oil resistance, to the laminate. In addition, the rust-preventing component is gradually released into the packaging space, allowing for long-term rust prevention. Furthermore, since the volatile rust inhibitor is not an amine-based compound, it is easy for workers to handle. [Example]

[0081] In the present disclosure, examples in which the layer structure shown in FIG. 4 is used as an example and the components are formed under several film-forming conditions will be specifically described. [Example 1] (1) One side of a 12 μm-thick biaxially stretched PET film (transparent resin film) 1a was plasma-treated with argon gas using a magnetron sputtering device. The resulting film was placed in a resistance heating vacuum deposition device, and a 20 nm-thick aluminum oxide vapor-deposited film (inorganic oxide film) 1b was formed on the plasma-treated surface under the following deposition conditions: (Deposition conditions) Evaporation source: Aluminum Supply gas: oxygen Vacuum level in deposition chamber: 2 x 10 -4 mbar Vacuum level in the winding chamber: 2 x 10 -2 mbar Inline OD value: 0.2 Film transport speed: 600m / min Next, a plasma-treated surface was formed on the aluminum oxide vapor-deposited film in the same manner as above.

[0082] (2) On the other hand, a hydrolyzed liquid consisting of ethyl silicate 40, isopropyl alcohol, aluminum acetylacetone, hydrochloric acid, and ion-exchanged water, which had been previously prepared as composition (b), was added to a mixed liquid consisting of polyvinyl alcohol, acetic acid, isopropyl alcohol, and ion-exchanged water, which had been prepared as composition (a) according to the formula shown below, and the mixture was stirred to obtain a colorless and transparent gas barrier composition.

[0083] <Coating film liquid composition> a. Polyvinyl alcohol 1.24% by mass Isopropyl alcohol 20.1% by mass H2O 43.8% by mass Acetic acid 0.10% by mass b. Ethyl silicate 40 (manufactured by Colcoat Co., Ltd.) 9.26% by mass Isopropyl alcohol 8.88% by mass Aluminum acetylacetone 0.02% by mass Hydrochloric acid 0.10% by mass H2O 16.5% by mass Total 100% by mass

[0084] Next, the gas barrier composition prepared above was coated on the plasma-treated surface formed in (1) above by gravure roll coating, and then heat-treated at 100°C for 30 seconds to form a film with a thickness of 0.4 g / m 2 A gas barrier film 4 (in a dry state) was formed to produce a transparent gas barrier film.

[0085] (3) On the other hand, 100 parts by weight of an ethylene-1-hexene copolymer with a density of 0.920, polymerized using a metallocene catalyst, was thoroughly mixed with 0.5 parts by weight of zeolite with a particle size of 3.5 μm as an antiblocking agent and 3.0 parts by weight of caproic acid, and the mixture was formed into a film using an inflation film extrusion method to produce a low-density polyethylene resin film with a thickness of 100 μm. One side of this film was subjected to a corona treatment to produce anti-rust sealant film 2.

[0086] (4) Next, a desired print pattern is formed on the surface of the gas barrier layer 4 of the transparent gas barrier film produced in (2) above, and then a two-component curing polyurethane-based dry laminating adhesive is applied to the entire surface including the print pattern in a thickness of 4.0 g / m using a gravure roll coating method. 2 (in a dry state) to form an adhesive layer 3, and the anti-corrosion sealant film 2 obtained in (2) above was superimposed on the surface of this adhesive layer 3 with the corona-treated surface facing it and dry-laminated to produce the transparent anti-corrosion barrier laminate 10d of the present disclosure.

[0087] (5) The final layer structure was PET film 1a / aluminum oxide vapor deposition film 1b / gas barrier film 4 / adhesive layer 3 / linear low-density polyethylene resin film 2.

[0088] (6) The laminate obtained above was evaluated for oxygen gas barrier property, water vapor barrier property, and haze by the following methods. (Oxygen gas barrier properties) The oxygen permeability was measured under conditions of a temperature of 23°C and a humidity of 90% RH using OXTRAN manufactured by MOCON, USA. (Water vapor barrier properties) The water vapor permeability was measured under conditions of a temperature of 40°C and a humidity of 90% RH using a PERMATRAN manufactured by MOCON, USA. (Haze) The haze was measured using a haze meter HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd. (Rust prevention test method) The test metal specimens were 5cm square pieces of iron that had been immersed in an acetone solution for 30 minutes to remove any oil. A 10cm square bag was made with a four-sided seal and one of these metal specimens was placed inside for comparative evaluation. After leaving the bags in an environment of 60°C and 90% humidity for 2, 4, and 6 weeks, the bags were opened and the condition of the rust on the metal surface was visually examined.

[0089] [Example 2] A transparent anticorrosive barrier laminate according to the present disclosure was produced in the same manner as in Example 1, except that 0.3 parts by weight of caproic acid was added to the sealant described in Example 1.

[0090] [Example 3] A transparent anticorrosive barrier laminate according to the present disclosure was produced in the same manner as in Example 1, except that 10.0 parts by weight of caproic acid was added to the sealant described in Example 1.

[0091] [Example 4] A transparent anticorrosive barrier laminate according to the present disclosure was produced in the same manner as in Example 1, except that in the transparent gas barrier film described in Example 1, lauric acid was used instead of the anticorrosive agent caproic acid.

[0092] [Example 5] A transparent anticorrosive barrier laminate according to the present disclosure was produced in the same manner as in Example 1, except that the transparent gas barrier film described in Example 1 was not coated with the gas barrier composition.

[0093] [Comparative Example 1] A barrier laminate was produced in the same manner as in Example 1, except that the rust inhibitor (caproic acid) was not added to the formulation of Example 1.

[0094] Comparative Example 2 A transparent anticorrosive barrier laminate was produced in the same manner as in Example 1, except that the amount of anticorrosive agent (caproic acid) added was changed to 0.2%.

[0095] Comparative Example 3 A transparent anticorrosive barrier laminate was produced in the same manner as in Example 1, except that the amount of anticorrosive agent (caproic acid) added in the formulation of Example 1 was changed to 11.0%.

[0096] Comparative Example 4 One surface of the PET film used in Example 1 was subjected to a corona treatment, and a printed pattern was formed on the corona-treated surface in the same manner as in Example 1. In addition, one surface of the linear low-density polyethylene resin film used in Example 1 was subjected to a corona treatment.

[0097] An adhesive layer was formed on the surface of the PET film on which the printed pattern was formed in the same manner as in Example 1, and the linear low-density polyethylene resin film was then superimposed on the surface of this adhesive layer with the corona-treated surface facing the adhesive layer and dry-laminated to produce a transparent anticorrosive barrier laminate.

[0098] The results are summarized in Table 1. It can be seen that each example of the present disclosure has excellent rust prevention ability. Furthermore, because an amine compound is not used as the rust inhibitor, it is possible to provide a rust prevention film that is easy for workers to handle.

[0099] [Table 1]

[0100] 5. Supplementary Notes Below, some of the various embodiments disclosed in this specification will be summarized. <Appendix 1> The transparent anticorrosive barrier laminate (10: 10a, 10b, 10d, 10f, 10h, 10i to 10l) according to Appendix 1 comprises at least a barrier layer (1) having gas barrier properties or water vapor barrier properties, and an anticorrosive sealant film (2) containing an organic acid. <Appendix 2> The transparent anticorrosive barrier laminate according to Appendix 2 is the transparent anticorrosive barrier laminate (10) according to Appendix 1, wherein the barrier layer (1) comprises a transparent resin film (1a) made of a transparent resin and an inorganic oxide film (1b) made of an inorganic oxide vapor-deposited on one surface of the transparent resin film, and the transparent anticorrosive barrier laminate (10) further comprises an adhesive layer (3) provided between the inorganic oxide film (1b) and the anticorrosive sealant film. <Appendix 3> The transparent anticorrosive barrier laminate according to Supplementary Note 3 is the transparent anticorrosive barrier laminate (10) according to Supplementary Note 2, wherein a compound represented by the general formula R is present between the inorganic oxide film (1b) and the anticorrosive sealant film (2) or the adhesive layer (3). 1 n M(OR 2 ) m (In the formula, R 1 , R 2 is an organic group having 1 to 8 carbon atoms, M is a metal atom, n is an integer of 0 or more, m is an integer of 1 or more, and n+m is the atomic valence of M), and a gas barrier film (4) containing either or both of a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer. <Appendix 4> The transparent anticorrosive barrier laminate according to Supplementary Note 4 is the transparent anticorrosive barrier laminate (10) according to Supplementary Note 3, in which the gas barrier film (4) is applied to the inorganic oxide film (1b). <Appendix 5> The transparent anticorrosive barrier laminate according to Appendix 5 is the transparent anticorrosive barrier laminate (10) according to any one of Appendixes 2 to 4, wherein the inorganic oxide is aluminum oxide. <Appendix 6> The transparent anticorrosive barrier laminate according to Supplementary Note 6 is the transparent anticorrosive barrier laminate according to any one of Supplementary Note 2 to Supplementary Note 5, wherein the inorganic oxide film (1b) has a thickness within the range of 5 to 100 nm. <Appendix 7> The transparent anticorrosive barrier laminate according to Supplementary Note 7 is the transparent anticorrosive barrier laminate (10) according to any one of Supplementary Note 2 to Supplementary Note 6, further comprising a protective film (5) made of a primer coating resin between the inorganic oxide film (1b) and the adhesive layer (3) or between the gas barrier film (4) and the adhesive layer (3). <Appendix 8> The transparent anticorrosive barrier laminate according to Appendix 8 is the transparent anticorrosive barrier laminate (10) according to any one of Appendixes 1 to 7, wherein the anticorrosive sealant film (2) comprises at least a non-anticorrosive layer (2a) that does not contain an organic acid and an anticorrosive layer (2b) that contains an organic acid, and the anticorrosive layer (2b) that contains an organic acid is positioned on the opposite side of the non-anticorrosive layer (2a) that does not contain an organic acid from the barrier layer (1). <Appendix 9> The transparent anticorrosive barrier laminate according to Supplementary Note 9 is the transparent anticorrosive barrier laminate (10) according to any one of Supplementary Note 1 to Supplementary Note 8, wherein the anticorrosive sealant film (2) is made of an olefin-based resin layer. <Appendix 10> The transparent anticorrosive barrier laminate according to Supplementary Note 10 is the transparent anticorrosive barrier laminate (10) according to any one of Supplementary Note 1 to Supplementary Note 8, wherein the anticorrosive sealant film (2) is made of a polyethylene resin. <Appendix 11> The transparent anticorrosive barrier laminate according to Appendix 11 is the transparent anticorrosive barrier laminate (10) according to any one of Appendixes 1 to 10, wherein the organic acid is a saturated fatty acid. <Appendix 12> The transparent anticorrosive barrier laminate according to claim 12 is the transparent anticorrosive barrier laminate (10) of claim 11, wherein the saturated fatty acid is caproic acid.

[0101] <Appendix 13> The transparent anticorrosive barrier laminate (10:10c, 10g) according to Appendix 13 is a transparent anticorrosive barrier laminate comprising a barrier layer (1) having gas barrier properties or water vapor barrier properties and an anticorrosive sealant film (2) containing an organic acid, wherein the barrier layer (1) comprises a transparent resin film (1a) made of a transparent resin and an inorganic oxide film (1b) made of an inorganic oxide vapor-deposited on one surface of the transparent resin film, and the transparent anticorrosive barrier laminate comprises a compound of the general formula R 1 n M(OR 2 ) m (In the formula, R 1 , R 2 is an organic group having 1 to 8 carbon atoms, M is a metal atom, n is an integer of 0 or more, m is an integer of 1 or more, and n+m is the atomic valence of M), and a gas barrier film (4) containing either or both of a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer. <Appendix 14> The transparent anticorrosive barrier laminate according to Appendix 14 is the transparent anticorrosive barrier laminate (10) of Appendix 13, wherein the anticorrosive sealant film (2) comprises at least a non-anticorrosive layer (2a) that does not contain an organic acid and an anticorrosive layer (2b) that contains an organic acid, and the anticorrosive layer (2b) that contains an organic acid is provided so as to be located on the opposite side of the non-anticorrosive layer (2a) that does not contain an organic acid from the gas barrier film (4). <Appendix 15> The transparent anticorrosive barrier laminate according to Appendix 15 is the transparent anticorrosive barrier laminate (10) according to Appendix 13 or 14, wherein the inorganic oxide (1b) is aluminum oxide. <Appendix 16> The transparent anticorrosive barrier laminate according to Appendix 16 is the transparent anticorrosive barrier laminate (10) according to any one of Appendixes 13 to 15, wherein the inorganic oxide film (1b) has a thickness within the range of 5 to 100 nm. <Appendix 17> The transparent anticorrosive barrier laminate according to claim 17 is the transparent anticorrosive barrier laminate (10) of any one of claims 13 to 16, wherein the organic acid is a saturated fatty acid. <Appendix 18> The transparent anticorrosive barrier laminate according to Appendix 18 is the transparent anticorrosive barrier laminate (10) according to Appendix 17, wherein the saturated fatty acid is caproic acid.

[0102] <Appendix 19> The transparent anticorrosive barrier laminate (10e) according to Appendix 19 comprises a barrier layer (1) having gas barrier properties or water vapor barrier properties, an anticorrosive sealant film (2) containing an organic acid, and A transparent anticorrosive barrier laminate (10e) comprising: The barrier layer (1) comprises a transparent resin film (1a) made of a transparent resin, and an inorganic oxide film (1b) made of an inorganic oxide vapor-deposited on one surface of the transparent resin film, The anticorrosive sealant film (2) comprises at least a non-anticorrosive layer (2a) that does not contain an organic acid and an anticorrosive layer (2b) that contains an organic acid, The rust-preventive layer (2b) containing the organic acid is provided so as to be located on the opposite side of the non-rust-preventive layer (2a) containing no organic acid from the inorganic oxide film (1b). <Appendix 20> The transparent anticorrosive barrier laminate (10e) according to claim 20 is the transparent anticorrosive barrier laminate (10e) of claim 19, wherein the inorganic oxide is aluminum oxide. <Appendix 21> The transparent anticorrosive barrier laminate (10e) according to Supplementary Note 21 is the transparent anticorrosive barrier laminate (10e) according to Supplementary Note 19 or 20, wherein the inorganic oxide film (1b) has a thickness within the range of 5 to 100 nm. <Appendix 22> The transparent anticorrosive barrier laminate (10e) according to claim 22 is the transparent anticorrosive barrier laminate (10e) of any one of claims 19 to 21, wherein the organic acid is a saturated fatty acid. <Appendix 23> The transparent anticorrosive barrier laminate (10e) according to Appendix 23 is the transparent anticorrosive barrier laminate (10e) according to Appendix 22, wherein the saturated fatty acid is caproic acid.

[0103] <Appendix 24> The anti-corrosion packaging material according to Appendix 24 is manufactured using the transparent anti-corrosion barrier laminate (10) of any one of Appendixes 1 to 23. <Appendix 25> The anti-rust packaging material according to Appendix 25 is the anti-rust packaging material according to Appendix 24, which is bag-shaped, and the anti-rust sealant film (2) is arranged inside the bag-shaped anti-rust packaging material.

[0104] <Appendix 26> A method for producing a transparent anticorrosive barrier laminate according to Appendix 26 includes the steps of: preparing a barrier layer (1) having gas barrier properties or water vapor barrier properties; and laminating an anticorrosive sealant film (2) containing an organic acid to the barrier layer (1); Equipped with. <Appendix 27> The manufacturing method of a transparent anticorrosive barrier laminate according to Appendix 27 is the manufacturing method of a transparent anticorrosive barrier laminate according to Appendix 26, wherein the step of preparing the barrier layer (1) comprises the steps of preparing a transparent resin film (1a) made of a transparent resin and forming an inorganic oxide film (1b) by vapor-depositing an inorganic oxide on one side of the transparent resin film (1a), and the step of laminating the anticorrosive sealant film (2) comprises the steps of applying an adhesive or adhesive resin to the inorganic oxide film (1b) to form an adhesive layer (3), and adhering the anticorrosive sealant film (2) to the adhesive layer (3). <Appendix 28> The method for producing a transparent anticorrosive barrier laminate according to Appendix 28 is the method for producing a transparent anticorrosive barrier laminate according to Appendix 27, further comprising: providing a compound of the general formula R between the inorganic oxide film (1b) and the anticorrosive sealant film (2) or the adhesive layer (3). 1 n M(OR 2 ) m (In the formula, R 1 , R 2is an organic group having 1 to 8 carbon atoms, M is a metal atom, n is an integer of 0 or more, m is an integer of 1 or more, and n+m is the atomic valence of M), and either or both of a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer. <Appendix 29> The method for producing a transparent anticorrosive barrier laminate according to Appendix 29 is the method for producing a transparent anticorrosive barrier laminate according to Appendix 28, wherein the gas barrier film (4) is formed by applying a gas barrier composition obtained by polycondensing the alkoxide and either or both of the polyvinyl alcohol resin and the ethylene-vinyl alcohol copolymer by a sol-gel method. <Appendix 30> The method for manufacturing a transparent anticorrosive barrier laminate according to Appendix 30 is the method for manufacturing a transparent anticorrosive barrier laminate according to any one of Appendixes 27 to 29, wherein the step of forming the inorganic oxide film (1b) is carried out by a resistance heating vacuum deposition method. [Industrial Applicability]

[0105] The transparent anticorrosive barrier laminate 10 according to the embodiment of the present disclosure provides anticorrosive effects over a long period of time, and can therefore be used as an anticorrosive packaging material for enclosing metal parts. [Explanation of symbols]

[0106] 1: Barrier layer 1a: Transparent resin film (PET film) 1b: Inorganic oxide film (evaporated aluminum oxide film) 2: Anti-rust sealant film (linear low-density polyethylene resin film) 2a: Non-corrosive layer 2b: Rust prevention layer 3: Adhesive layer 4: Gas barrier film 5:Protective film 10a-10l: Transparent anti-corrosion barrier laminate 20: Rust prevention bag 21: Metal parts 22a to 22d: Heat seal section

Claims

1. The laminate comprises: a barrier layer having gas barrier properties or water vapor barrier properties, the barrier layer being a transparent resin film; a barrier layer including an inorganic oxide film formed by vapor deposition on one surface of the transparent resin film; an adhesive layer; a rust-preventive sealant film containing a saturated fatty acid selected from caproic acid, caprylic acid, capric acid, and lauric acid in an amount of 0.3% by weight to 10% by weight; A compound having the general formula R 1 n M (OR 2 ) m (In the formula, R 1 , R 2 is an organic group having 1 to 8 carbon atoms, M is a metal atom, n is an integer of 0 or more, m is an integer of 1 or more, and n+m is the atomic valence of M), and a gas barrier film containing either or both of a polyvinyl alcohol resin and an ethylene-vinyl alcohol copolymer; Equipped with The haze value of the laminate according to JIS K7136 is in the range of 0.3% to 45%. Transparent anti-corrosion barrier laminate.

2. The transparent anticorrosive barrier laminate according to claim 1 , wherein the gas barrier film is applied to the inorganic oxide film.

3. 3. The transparent anticorrosive barrier laminate according to claim 1, wherein the inorganic oxide is aluminum oxide.

4. 4. The transparent anticorrosive barrier laminate according to claim 1, wherein the inorganic oxide film has a thickness in the range of 5 to 100 nm.

5. The anticorrosive sealant film includes at least a non-anticorrosive layer that does not contain an organic acid and an anticorrosive layer that contains an organic acid, 5. The transparent anticorrosive barrier laminate according to claim 1, wherein the anticorrosive layer containing the organic acid is provided on the opposite side of the non-anticorrosive layer containing no organic acid from the barrier layer.

6. The transparent anticorrosive barrier laminate according to claim 1 , wherein the anticorrosive sealant film comprises an olefin-based resin layer.

7. The transparent anticorrosive barrier laminate according to claim 1 , wherein the anticorrosive sealant film is made of a polyethylene resin.

8. 8. The transparent anticorrosive barrier laminate according to claim 7, wherein the saturated fatty acid is caproic acid.

9. A rust-preventing packaging material produced using the transparent rust-preventing barrier laminate according to any one of claims 1 to 8.

10. The rust-preventive packaging material is in a bag shape, The rust-preventive packaging material according to claim 9, wherein the rust-preventive sealant film is disposed inside the bag-shaped rust-preventive packaging material.

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