Antirust film

Abstract

According to the present invention, a recycled rust-proof film is effectively utilized, and a regenerated resin composition for a rust-proof film, which is used as a regenerated resin, is obtained by treatment under milder conditions. A new rust-proof film can be manufactured using this regenerated resin composition for rust-proof films without foaming, and a combination of rust-proof agents that cannot be originally contained in one layer can be contained in one layer. Furthermore, the present invention addresses the problem of obtaining an anti-rust film using a regenerated resin composition for an anti-rust film, said anti-rust film having more sufficient anti-rust performance, thereby promoting the reuse of the used anti-rust film. As a solution, provided is a regenerated resin composition for an anti-rust film, which is characterized by containing a polyolefin resin, 0.02-0.20 wt% of an amine and / or ammonia-based vaporizable anti-rust agent, a deliquescent anti-rust agent, and 0.30 wt% or less of water.

Description

Technical Field

[0001] The invention relates to an anti-rust film. Background Art

[0002] As described in Patent Document 1, a rust-proof film is known, which comprises: a resin molded body having a resin layer containing an ammonium carboxylate salt having an average particle size of 20 μm or more; and a substrate layer containing one or more of a metal nitrite, a carboxylic acid, a benzotriazole compound, a toluenetriazole compound, and a metal carboxylate salt.

[0003] However, it is unknown to recover and reuse the known rust-proof film using two or more rust-proof agents. Furthermore, when such a rust-proof film is recovered and reused as a resin for a rust-proof film and an arbitrary rust-proof agent is added and used, there is a combination of two or more rust-proof agents that react when they coexist, and it is necessary to completely remove the rust-proof agents. However, this requires a huge amount of work.

[0004] That is, for example, in a rust-proof film composed of two or more layers, each layer generally contains different rust-proof agents. In addition, it is known that a combination of rust-proof agents reacts to generate gas when mixed, and in the case of such a combination, the rust-proof film must be specially made into two or more layers.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2018 / 079458 Summary of the invention

[0008] Problems to be solved by the invention

[0009] The present invention can effectively utilize the antirust film including the two layers of the resin layer containing the amine and / or ammonia gasifying antirust agent and the resin layer containing the deliquescent antirust agent after recovery, and obtain a recycled resin composition for the antirust film as a recycled resin by treating under milder conditions. A new antirust film can be manufactured using the recycled resin composition for the antirust film without foaming, and a combination of rust inhibitors that could not be contained in one layer can be contained in one layer. In addition, the problem is to obtain an antirust film having more sufficient antirust performance and using the recycled resin composition for the antirust film, thereby promoting the reuse of the used antirust film.

[0010] Solutions for solving problems

[0011] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the problems can be solved by the following means, thereby completing the present invention.

[0012] 1. A recycled resin composition for an anti-rust film, characterized in that it contains a polyolefin resin, 0.02 to 0.20 wt% of an amine and / or ammonia-based vaporizing rust inhibitor, a deliquescent rust inhibitor, and 0.30 wt% or less of water.

[0013] 2. A method for producing a recycled resin composition for a rust-proof film, characterized in that a rust-proof film formed by laminating a polyolefin resin layer containing an amine and / or ammonia-based vaporizing rust inhibitor and a polyolefin resin layer containing a deliquescent rust inhibitor is melted, kneaded, and dried as needed, wherein the recycled resin composition for a rust-proof film contains a polyolefin resin, 0.02 to 0.20% by weight of an amine and / or ammonia-based vaporizing rust inhibitor, a deliquescent rust inhibitor, and 0.30% by weight or less of water.

[0014] 3. A rust-proof film, characterized in that, in a rust-proof film formed by laminating a polyolefin resin layer 1 containing an amine and / or ammonia-based vaporizing rust inhibitor and a polyolefin resin layer 2 containing a deliquescent rust inhibitor, the polyolefin resin layer 2 contains a polyolefin resin derived from a recycled resin composition for a rust-proof film, 20 to 220 ppm of an amine and / or ammonia-based vaporizing rust inhibitor, and 400 ppm or less of water.

[0015] 4. The rust-proof film according to 3., wherein a YI value measured by stacking 12 sheets of the rust-proof film is 35.0 or less.

[0016] 5. A method for producing an anti-rust film, characterized in that the anti-rust film is formed by laminating a polyolefin resin layer 1 containing an amine and / or ammonia-based vaporizing rust inhibitor and a polyolefin resin layer 2 containing a deliquescent rust inhibitor, wherein a recycled resin composition for the anti-rust film, a polyolefin resin and a deliquescent rust inhibitor are mixed so that the content of the amine and / or ammonia-based vaporizing rust inhibitor in the polyolefin resin layer 2 derived from the recycled resin composition is 20 to 220 ppm, and the content of water is 400 ppm or less.

[0017] Effects of the Invention

[0018] According to the present invention, a used antirust film, antirust bag, etc., which includes two layers, a resin layer containing an amine and / or ammonia-based vaporizing rust inhibitor and a resin layer containing a deliquescent rust inhibitor, is collected, and the collected material is treated for regeneration, thereby allowing the recycled material to be reused as a recycled resin composition for producing an antirust film in a state containing a certain amount of an amine and / or ammonia-based vaporizing rust inhibitor and a deliquescent rust inhibitor. Hereinafter, it is referred to as a "recycled resin composition for an antirust film".

[0019] The regenerated resin composition for the rust-proof film after regenerating the used rust-proof film, rust-proof bag, etc. contains 0.02 to 0.20 wt % of amine and / or ammonia-based vaporizing rust inhibitor that has not been completely removed, further contains a deliquescent rust inhibitor, and contains 0.30 wt % or less of water.

[0020] In this way, the recycled resin composition for the rust-proof film does not completely remove the rust inhibitor, so the recycled rust-proof bags can be treated under more stringent conditions such as temperature and time (treatment under strict conditions for completely removing the rust inhibitor), and can be treated for regeneration under milder conditions such as temperature and time. Therefore, the energy required to obtain the rust-proof film composition from the recycled material and the amount of energy required to obtain a new rust-proof film can be reduced. Compared with treating the recycled material to completely remove the rust inhibitor to obtain the recycled resin, it is preferable in terms of reducing the required energy.

[0021] As for the new antirust film or the antirust bag obtained by using the recycled resin composition for the antirust film, the content of the gasifying rust inhibitor coexisting in the resin layer is a small amount, so it will not react with the deliquescent rust inhibitor, and as a result, foaming or coloring such as yellowing will not occur during film making. If foaming occurs during film making, the film making property is reduced or the mechanical properties of the film made are reduced. In addition, if coloring such as yellowing occurs, the visual confirmation is reduced. The reason for the coloring such as yellowing is the oxidation of the resin and the deliquescent rust inhibitor in the manufacturing process of the recycled resin composition for the antirust film.

[0022] Furthermore, a new resin layer produced using the above-mentioned recycled resin composition for rust-proof film can be laminated with a resin layer containing an amine and / or ammonia-based vaporizable rust inhibitor to produce a laminated new rust-proof film having sufficient rust-proofing properties.

[0023] That is, even by such a regeneration method under milder conditions, the rust-proof film of the present invention can be used as a rust-proof film having the same rust-proof performance as a rust-proof film using a material not derived from recycling. Thus, the cost, time, and environmental load of regeneration and recycling can be reduced, and the reuse of used rust-proof films can be promoted. DETAILED DESCRIPTION

[0024] <Recycled resin composition for rust-proof film>

[0025] The recycled resin composition for a rust-proof film of the present invention is mainly used to obtain the rust-proof film of the present invention, especially the polyolefin resin layer 2. In addition, it can also be used to obtain other rust-proof films.

[0026] The recycled resin composition for rust-proof film is a resin composition obtained by recovering and recycling one or more of the rust-proof films that have been manufactured and used, the rust-proof bags obtained therefrom, the scraps of the manufactured rust-proof film, the remaining rust-proof films, and the products.

[0027] The rust-proof film before recovery is a rust-proof film formed by laminating a resin layer containing an amine and / or ammonia-based vaporizable rust-proof agent and a resin layer containing a deliquescent rust-proof agent.

[0028] The regeneration method is described below.

[0029] The regenerated resin composition for the anti-rust film of the present invention contains a polyolefin resin, and the content of amine and / or ammonia-based gasifying rust inhibitor can contain at least 0.02% by weight. Making the content less than 0.02% by weight requires more extensive processing, and depending on the situation, it is possible to reduce the physical properties of the resin itself. The more the content of amine and / or ammonia-based gasifying rust inhibitor in the composition obtained by regenerating the anti-rust film after recovery, the more the regeneration process can be processed under mild conditions. However, when more regenerated resin compositions for anti-rust films are to be used to obtain new anti-rust films, it is impossible to use more regenerated resin compositions for anti-rust films in order to manufacture new anti-rust films with more amine and / or ammonia-based gasifying rust inhibitors. Assuming that the amount of regenerated resin compositions for anti-rust films used is too much, the amine and / or ammonia-based gasifying rust inhibitors react with deliquescent rust inhibitors such as nitrites in the process of manufacturing new anti-rust films, and the polyolefin resin layer 2 may foam. In addition, yellowing and coloration were observed in the obtained rust-proof film, and there was a possibility that visual recognition was reduced.

[0030] Therefore, the content of the amine and / or ammonia-based vaporizing rust inhibitor in the recycled resin composition for rust-proof film used as a raw material for a newly produced rust-proof film is preferably 0.20 wt % or less, more preferably 0.15 wt % or less, and even more preferably 0.10 wt % or less.

[0031] The content of the deliquescent rust inhibitor in the recycled resin composition is not particularly limited, but is preferably 0.28% by weight or less, more preferably 0.25% by weight or less, and further preferably 0.22% by weight or less. In addition, it is preferably 0.05% by weight or more, more preferably 0.07% by weight or more, and further preferably 0.10% by weight or more. If the content of the deliquescent rust inhibitor is too much, the water content increases due to moisture absorption, and when a new antirust film is obtained using the recycled resin composition for the antirust film, the possibility of water vaporization and foaming increases. To make the content of the deliquescent rust inhibitor less than 0.05% by weight, it is necessary to treat it under strict temperature, time and other conditions corresponding thereto.

[0032] In addition, it is preferred that the water content of the recycled resin composition for the antirust film is low. The water originates from the moisture absorption of the deliquescent rust inhibitor contained in the recycled resin composition. As the water content, it is preferably 0.30 wt % or less, more preferably 0.20 wt % or less, further preferably 0.10 wt % or less, and most preferably 0.05 wt % or less. If there is too much water, when a new antirust film is obtained using the recycled resin composition for the antirust film, the water vaporizes and foams, or the deliquescent rust inhibitor such as nitrite contained in the new antirust film is deliquesced, or the amount of the recycled resin composition for the antirust film that can be used to manufacture the new antirust film has to be reduced.

[0033] <Method for producing recycled resin composition for rust-proof film>

[0034] The recycled resin composition for the rust-proof film of the present invention is a composition obtained by recycling a rust-proof film including two layers, a resin layer containing an amine and / or ammonia-based gasifying rust-proof agent and a resin layer containing a deliquescent rust-proof agent, and thereby recycling the rust-proof film. It should be noted that the recycled rust-proof film mentioned here includes not only the rust-proof film used in packaging as the rust-proof film, but also the rust-proof film and its materials that have not been used due to manufacturing loss, etc.

[0035] It should be noted that the rust-proof film to be recovered is preferably a film included in the rust-proof film of the present invention.

[0036] In addition, the film to be recovered may be a film containing the same amine and / or ammonia-based vaporizing rust inhibitor as described above. A certain amount of recovered rust-proof film recovered for further regeneration may be mixed with a rust-proof film that does not contain an amine and / or ammonia-based vaporizing rust inhibitor, but it is preferred that a rust-proof film having a resin layer containing an amine and / or ammonia-based vaporizing rust inhibitor and a resin layer containing a deliquescent rust inhibitor, such as the rust-proof film of the present invention, be mixed in the entire recovered rust-proof film to be regenerated.

[0037] It should be noted that the recycled resin composition for the rust-proof film of the present invention is obtained from the recycled rust-proof film, and the rust-proof film of the present invention is newly obtained using the recycled resin composition for the rust-proof film. The used rust-proof film of the newly obtained rust-proof film can be recycled again and recycled into the recycled resin composition for the rust-proof film of the present invention, and the obtained recycled resin composition for the rust-proof film of the present invention can be used again for the production of the rust-proof film of the present invention, or this process can be repeated.

[0038] As a method for producing such a recycled resin composition for an anti-rust film, the following method can be adopted: the recovered anti-rust film is crushed by any method, heated and melted at a high temperature of 140°C or higher to promote gasification and disappearance, and after solidification / granulation by any method, it is dried at about 80 to 95°C for about 60 to 150 minutes as needed. It should be noted that the conditions such as temperature and time can be changed according to conditions related to the device, the recovered anti-rust film, etc.

[0039] By adopting such a heating melting / drying method, not only the water content but also the content of the amine and / or ammonia-based vaporizing rust inhibitor can be reduced, thereby obtaining the recycled resin composition for the rust-proof film of the present invention.

[0040] According to such a method for producing a recycled resin composition for a rust-proof film, it is possible to actively recover and reuse a used rust-proof film or the like which has been difficult to reuse as a resin composition for a rust-proof film.

[0041] The recycled resin composition for rust-proof film of the present invention, which contains a polyolefin resin, 0.02 to 0.20 wt% of an amine and / or ammonia-based vaporizing rust inhibitor, a deliquescent rust inhibitor, and 0.30 wt% or less of water, and the method for producing the same are mainly used to obtain the composition for rust-proof film of the present invention and the method for producing the same. The recycled resin composition for rust-proof film can also be used to produce a rust-proof film including three or more layers.

[0042] <Anti-rust film>

[0043] The rust-proof film of the present invention is characterized in that it is basically composed of a laminated structure of a polyolefin resin layer 1 containing an amine and / or ammonia-based vaporizing rust inhibitor and a polyolefin resin layer 2 containing a deliquescent rust inhibitor, wherein the polyolefin resin layer 2 contains 20 to 220 ppm of an amine and / or ammonia-based vaporizing rust inhibitor derived from a recycled resin composition for a rust-proof film, a deliquescent rust inhibitor, and 400 ppm or less of water.

[0044] It should be noted that the polyolefin resin layer 1 and the polyolefin resin layer 2 are preferably directly laminated, but an adhesive layer, an intermediate layer, etc. may be formed between the polyolefin resin layer 1 and the polyolefin resin layer 2. In addition, an arbitrary layer may be provided on the surface of the polyolefin resin layer 1 opposite to the surface of the polyolefin resin layer 2 side, and / or on the surface of the polyolefin resin layer 2 opposite to the surface of the polyolefin resin layer 1 side, or may not be provided.

[0045] Hereinafter, the polyolefin resin layer 1 may be simply referred to as “resin layer 1 ”, and the polyolefin resin layer 2 may be simply referred to as “resin layer 2 ”.

[0046] The rust-proof film of the present invention can be processed into a bag shape in such a way that the resin layer 1 is on the inner side, i.e., the side facing the packaged object, and the resin layer 2 is on the outer side. In addition, when it includes three or more layers, the resin layer 2 can be provided as the innermost layer. And they can be used to package metal electrical products, electrical parts, electronic parts, mechanical parts, automobile parts, etc.

[0047] For the rust-proof film of the present invention, the YI value measured by stacking 12 rust-proof films is preferably 35.0 or less, more preferably 30.0 or less, further preferably 25.0 or less, and most preferably 20.0 or less. If the YI value is 35.0 or less, the rust-proof film produced using the recycled resin composition for rust-proof film will not be particularly colored (yellowing), and when used as a rust-proof film or a rust-proof bag for packaging, the contents can be visually confirmed without opening the package.

[0048] In addition, within the scope of not impairing the effects of the present invention, the following well-known additives may be added independently to the resin layer 1 and the resin layer 2: anti-blocking agent (AB agent), lubricant, antioxidant, antistatic agent, ultraviolet absorber, light stabilizer, oxygen absorber, acid absorber, flame retardant, nucleating agent, impact strength enhancer, plasticizer, mold release agent, colorant, fluorescent agent, compatibilizer, antifogging agent, filler, coloring agent, dispersant, stabilizer, modifier and antibacterial / antifungal agent. However, it is necessary that the additives do not react with other components contained in the resin layer 1 and the resin layer 2, and do not ooze out and contaminate, for example, the packaged object.

[0049] It should be noted that, for the purpose of retaining the rust inhibitor in the resin layer, the ionomer resin and the functional group-containing polyolefin resin may or may not be blended into the resin layer 1 and the resin layer 2. According to the present invention, the rust inhibitor can fully exert its long-term rust resistance.

[0050] In addition, the thickness of the resin layer 1 and the resin layer 2 is preferably 10 μm or more, more preferably 15 μm or more, and further preferably 20 μm or more independently. In addition, it is preferably 300 μm or less, more preferably 200 μm or less, and further preferably 100 μm or less. In addition, the total thickness of the resin layer 1 and the resin layer 2 is preferably 20 μm or more, more preferably 30 μm or more, and further preferably 40 μm or more. In addition, it is preferably 600 μm or less, more preferably 400 μm or less, and further preferably 200 μm or less.

[0051] Regarding the rust-proof film of the present invention, the following describes resins that can be used in common in the resin layer 1 and the resin layer 2. For the resin layer 1 and the resin layer 2, one or more arbitrary resins can be selected independently from the following resins and used.

[0052] (Polyolefin resin)

[0053] The compositions of the polyolefin resins contained in the resin layer 1 and the resin layer 2 may be different or the same. In the case of being the same, it is preferred that when the rust-proof film recovered after use is regenerated, a rust-proof film composed of the same resin composition as before regeneration can be used.

[0054] As such a polyolefin resin, one or more selected from polyolefin-based polymers, that is, homopolymers of olefins and / or copolymers using olefins as monomers can be selected and used.

[0055] As olefins (olefin monomers) constituting polyolefin polymers, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc. can be listed. Therefore, as polyolefin polymers, ethylene polymers, propylene polymers, 1-butene polymers, 1-hexene polymers, 4-methyl-1-pentene polymers, etc. can be listed. These polymers can be used alone or in combination of two or more. That is, the polyolefin polymer can be a mixture of various polymers.

[0056] Among the above, as ethylene polymers, ethylene homopolymers (polyethylene) and copolymers (ethylene copolymers) of ethylene and other monomers can be listed. As ethylene homopolymers and ethylene copolymers, for example, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE) can be listed.

[0057] Examples of the ethylene copolymer include ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / 1-pentene copolymers, ethylene / 1-hexene copolymers, ethylene / 1-octene copolymers, and ethylene / 4-methyl-1-pentene copolymers.

[0058] It should be noted that the ethylene units (structural units derived from ethylene) contained in the ethylene copolymer only need to be greater than 50% of the total number of structural units (usually less than 99.999%), for example, it can be set to 80.0% to 99.999% of the total number of structural units, and can also be set to 90.0% to 99.995%, and can further be set to 99.0% to 99.990%.

[0059] In addition, examples of propylene-based polymers include propylene homopolymers (polypropylene) and copolymers of propylene and 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.

[0060] It should be noted that the propylene unit (structural unit derived from propylene) contained in the propylene copolymer only needs to account for 50% or more of the total number of structural units (usually 99.999% or less), and can be, for example, 80.0% to 99.999% of the total number of structural units, 90.0% to 99.995%, and further 99.0% to 99.990%.

[0061] In addition, within the scope of not damaging the purpose of the present invention, the structural unit derived from the monomer other than olefin can be included in the polyolefin polymer. As monomers other than olefin, unsaturated carboxylic acids (acrylic acid, methacrylic acid, maleic acid, fumaric acid, etc.), unsaturated carboxylic acid esters (methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dimethyl maleate, diethyl maleate, etc.), vinyl esters (vinyl acetate, vinyl propionate, maleic acid monoester, etc.), etc. can be listed. They can be used only one, or two or more can be used in combination.

[0062] It should be noted that, even if the structural units derived from monomers other than olefins contained in the polyolefin polymer are included, it is preferably 40% or less (usually 0.001% or more) of the total number of structural units. For example, it can be 0.001% to 25% of the total number of structural units, and can also be 0.005% to 15%, and can further be 0.01% to 10%.

[0063] The density of the polyolefin resin is preferably 0.880 to 0.950 g / cm from the viewpoint of processability. 3 In addition, from the viewpoint of mechanical strength and processability, the melt flow rate value (MFR) is preferably in the range of 1.0 to 10.0 g / 10 min. By having a moderate viscosity during melt processing, the carboxylic acid ammonium salt in a particle form can be contained and coated in the resin, and the rust inhibitor can be prevented from falling off the resin molded body.

[0064] (Resin layer 1)

[0065] The resin layer 1 contains an amine and / or an ammonia-based vaporizable rust inhibitor as a rust inhibitor.

[0066] The amine and / or ammonia-based vaporizing rust inhibitor may be any of aliphatic carboxylic acid ammonium salts, aliphatic carboxylic acid amine salts, aromatic carboxylic acid ammonium salts, and aromatic carboxylic acid amine salts.

[0067] For example, one or more of the following substances may be used: butyric acid, isobutyric acid, methacrylic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, sorbic acid, oleic acid, oleic acid, ammonium salts of aliphatic carboxylic acids such as 1,2-dicarboxylic acid, 2-hydroxy- ...

[0068] In addition, as the amine-based vaporizing rust inhibitor, one or more organic amine salts selected from phosphates, nitrites, carbonates, and carboxylates of monoethanolamine, diethanolamine, triethanolamine, n-butylamine, dibutylamine, tert-butylamine, hexamethylenediamine, hexamethylenetetramine, monocyclohexylamine, dicyclohexylamine, isopropylamine, oleylamine, naphthylamine, and diphenylamine can be used. It should be noted that the resin layer 1 does not contain a deliquescent rust inhibitor in an amount that would hinder the effect of the present invention.

[0069] The content of the amine and / or ammonia-based vaporizing rust inhibitor in the resin layer 1 is preferably 0.01% by weight or more, more preferably 0.10% by weight or more, and even more preferably 0.20% by weight or more in the resin layer. It is also preferably 10.00% by weight or less, more preferably 8.00% by weight or less, and even more preferably 6.00% by weight or less. If it is less than 0.01% by weight, it is difficult to exert sufficient rust resistance, and if it exceeds 10.00% by weight, it is difficult to perform molding.

[0070] The amine and / or ammonia-based vaporizing rust inhibitor is contained in the resin layer 1 in the form of particles or in a state compatible with the resin layer. It may be in the form of particles or may be compatible. In the case of particles, the average particle size (d50) is preferably 3 μm or more, more preferably 3 to 400 μm, further preferably 3 to 200 μm, and most preferably 3 to 100 μm.

[0071] Furthermore, the maximum particle size of the amine and / or ammonia-based vaporizing rust inhibitor contained in the resin layer 1 is preferably 5000 μm or less, more preferably 3000 μm or less, and even more preferably 500 μm or less. If the particle size of the amine and / or ammonia-based vaporizing rust inhibitor exceeds 5000 μm, the strength of the resin molded body may be reduced, particles may fall off, and contamination of metal products may occur. The maximum particle size is the largest particle size among the measured values ​​of the particle sizes of 1000 particles.

[0072] If the average particle size and / or maximum particle size are within this range, a convex portion in which the particles of the amine and / or ammonia-based gasifying rust inhibitor are covered by the resin is formed on the surface of the resin layer 1. The presence of such a convex portion can generate more gas for rust prevention, which can help improve the rust resistance. In addition, such a convex portion on the film surface has the effect of preventing the film from adhering to the object of rust prevention, and can prevent the particles of the amine and / or ammonia-based gasifying rust inhibitor from directly contacting the object of rust prevention and contaminating the surface of the object of rust prevention.

[0073] In addition, when the amine and / or ammonia-based vaporizing rust inhibitor is contained in the resin layer in a compatible state, and when the amine and / or ammonia-based vaporizing rust inhibitor is contained in the resin layer in a particle form as described above, the vaporizing property can be adjusted according to the characteristics such as volatility of each vaporizing rust inhibitor.

[0074] By mixing particles of an amine and / or ammonia-based vaporizing rust inhibitor with the resin constituting the resin layer, melting / kneading the resin, and molding the resin into a sheet, for example, the powder of the amine and / or ammonia-based vaporizing rust inhibitor before mixing may be crushed and the average particle size may be reduced. Therefore, the above average particle size in the present invention is a value related to the amine and / or ammonia-based vaporizing rust inhibitor contained in the resin layer 1 after the resin layer 1 is formed.

[0075] By containing an amine and / or an ammonia-based vaporizing rust inhibitor having such a specific particle size or being compatible with the resin, the amount of generated rust-inhibiting gas can be controlled, thereby making it possible to stably maintain the rust-inhibiting effect for a long period of time.

[0076] Although the detailed mechanism is not yet clear, it is considered that by setting the particle size of the amine and / or ammonia-based vaporizable rust inhibitor to a specific range, convex portions are formed on the film surface, thereby exhibiting a long-term rust prevention effect.

[0077] (Resin layer 2)

[0078] The resin layer 2 contains a deliquescent rust inhibitor as a rust inhibitor.

[0079] (Deliquescent rust inhibitor)

[0080] As the deliquescent rust inhibitor in the present invention, various metal nitrites and metal salts of carbonates can be listed, and one or more of them can be used. As the metal nitrite, one or more selected from sodium salts, potassium salts, calcium salts, magnesium salts, etc. of nitrite can be used, and as the metal salt of carbonate, potassium salts and hydrates thereof can be listed.

[0081] The content of these deliquescent rust inhibitors is preferably 0.01% by weight or more, more preferably 0.10% by weight or more, and further preferably 0.20% by weight or more in the resin layer 2. It is also preferably 6.00% by weight or less, more preferably 4.00% by weight or less, and further preferably 2.00% by weight or less. If it is less than 0.01% by weight, it may be difficult to exhibit sufficient rust prevention, and if it exceeds 6.00% by weight, it may be difficult to perform molding or to exhibit long-term rust prevention.

[0082] It should be noted that the resin layer 2 of the rust-proof film of the present invention is obtained by containing the recycled resin composition for rust-proof film of the present invention, and the total amount of the deliquescent rust inhibitor contained in the recycled resin composition for rust-proof film as one of its raw materials and the deliquescent rust inhibitor additionally added as needed is the total amount of the deliquescent rust inhibitor contained in the resin layer 2 of the rust-proof film.

[0083] When the resin layer 2 is used as an outer layer to form a packaging bag, etc., moisture from the outside air is introduced into the package, and the deliquescent rust inhibitor in the outer layer reacts with the amine and / or ammonia-based vaporizing rust inhibitor in the inner layer, promoting the vaporization of the amine and / or ammonia-based vaporizing rust inhibitor in the package, thereby exerting a rust-proofing effect. Furthermore, by generating nitrous acid in the package, the rust-proofing effect can be enhanced.

[0084] (Amine and / or ammonia-based vaporizing rust inhibitor)

[0085] In addition, the resin layer 2 contains 20 to 220 ppm by weight of an amine and / or ammonia-based vaporizing rust inhibitor derived from a recycled resin composition for an anti-rust film. The content of the amine and / or ammonia-based vaporizing rust inhibitor in the resin layer 2 is preferably 60 ppm or more, more preferably 80 ppm or more, and even more preferably 120 ppm or more. It is also preferably 200 ppm or less, more preferably 180 ppm or less, and even more preferably 160 ppm or less.

[0086] When the content exceeds 220 ppm, the resin layer 2 may react with the deliquescent rust inhibitor, resulting in foaming.

[0087] The amine and / or ammonia-based vaporizing rust inhibitor derived from the regenerated resin composition for the rust-proof film mentioned here may be the same compound as the amine and / or ammonia-based vaporizing rust inhibitor contained in the resin layer 1 described above.

[0088] However, in the past, it was not usually practiced to contain both an amine and / or ammonia-based vaporizing rust inhibitor and a deliquescent rust inhibitor in one resin layer because of concerns about the reaction between the two. However, as long as the amine and / or ammonia-based vaporizing rust inhibitor contained in the resin layer 2 is 20 to 220 ppm, the reaction between the two can be suppressed. Therefore, the antirust film of the present invention can be formed using the regenerated resin composition for the antirust film of the present invention (based on a composition obtained by regenerating a used antirust film, its raw material, etc.). Such a regenerated resin composition for the antirust film of the present invention does not completely remove the rust inhibitor, but suppresses the degree of treatment to the extent that the amine and / or ammonia-based vaporizing rust inhibitor remains to a certain extent, thereby reducing the temperature and time of the treatment, so that the amine and / or ammonia-based vaporizing rust inhibitor remains.

[0089] Furthermore, the average particle size of the amine and / or ammonia-based vaporizing rust inhibitor derived from the recycled resin composition for the rust-proof film contained in the resin layer 2 may be smaller than the average particle size of the amine and / or ammonia-based vaporizing rust inhibitor contained in the recovered rust-proof film.

[0090] (water)

[0091] Furthermore, the resin layer 2 contains water derived from the recycled resin composition for the rust-proof film in an amount of 400 ppm or less by weight. The water content of the resin layer 2 is preferably 380 ppm or less, more preferably 300 ppm or less, and further preferably 200 ppm or less. If the water content exceeds 400 ppm, the possibility of film foaming increases.

[0092] (Carboxylic acid metal salt)

[0093] In the present invention, the resin layer 1 and the resin layer 2 may contain a carboxylic acid metal salt independently or not. The carboxylic acid metal salt may be any of an aliphatic carboxylic acid metal salt and an aromatic carboxylic acid metal salt.

[0094] As these carboxylic acid metal salts, one or more of the following carboxylic acid metal salts can be used: isobutyric acid, methacrylic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, sorbic acid, oleic acid, oleic acid, aliphatic carboxylic acids such as isohexanoic acid, 2-methylvaleric acid, 2-ethylbutyric acid, isoheptanoic acid, isooctanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, 2-propylheptanoic acid, isoundecanoic acid, isododecanoic acid, 2-butyloctanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid; and metal salts such as sodium salts, potassium salts, calcium salts, magnesium salts of aromatic carboxylic acids such as benzoic acid, aminobenzoic acid, salicylic acid, p-tert-butylbenzoic acid, o-sulfobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, etc.

[0095] The content of the carboxylic acid metal salt in the resin layer is preferably 0.001 to 10.0% by weight, more preferably 0.01 to 5.0% by weight. If it is less than 0.001% by weight, it is difficult to fully exert rust resistance, and if it exceeds 10.0% by weight, it is difficult to perform molding and long-term rust resistance.

[0096] (carboxylic acid)

[0097] In the present invention, the resin layer 1 and the resin layer 2 may contain a carboxylic acid independently or not. The carboxylic acid may be any of an aliphatic carboxylic acid and an aromatic carboxylic acid.

[0098] As these carboxylic acids, one or more of the following carboxylic acids can be used: aliphatic carboxylic acids such as isobutyric acid, methacrylic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, sorbic acid, oleic acid, oleyl acid, isohexanoic acid, 2-methylvaleric acid, 2-ethylbutyric acid, isoheptanoic acid, isooctanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, 2-propylheptanoic acid, isoundecanoic acid, isododecanoic acid, 2-butyloctanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid; and aromatic carboxylic acids such as benzoic acid, aminobenzoic acid, salicylic acid, p-tert-butylbenzoic acid, o-sulfobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, and cinnamic acid.

[0099] The content of these carboxylic acids in the resin layer is preferably 0.001 to 10.0% by weight, more preferably 0.01 to 5.0% by weight. If it is less than 0.001% by weight, it is difficult to further improve the rust resistance, and if it exceeds 10.0% by weight, it is difficult to perform molding and to exert long-term rust resistance.

[0100] (Benzotriazole compounds and toluenetriazole compounds)

[0101] The resin layer 1 and the resin layer 2 in the present invention may contain a benzotriazole compound and a toluenetriazole compound independently, or may not contain a benzotriazole compound and a toluenetriazole compound. Among them, one or more selected from benzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole, etc. may be used.

[0102] The content of these benzotriazole compounds and toluenetriazole compounds in the resin layer is preferably 0.001 to 10.0% by weight, more preferably 0.01 to 5.0% by weight. If it is less than 0.001% by weight, it is difficult to further improve the long-term rust resistance, and if it exceeds 10.0% by weight, it is not only difficult to perform molding, but also difficult to exert long-term rust resistance.

[0103] (Inorganic acid metal salt)

[0104] In the resin layer 1 and the resin layer 2 of the present invention, the inorganic acid metal salt may be contained independently or not. Among them, one or more selected from borosilicate metal salts, molybdate metal salts, etc. may be used. As the content of these inorganic acid metal salts, preferably 0.001 to 10.0% by weight, more preferably 0.01 to 5.0% by weight, is contained in the resin layer. If it is less than 0.001% by weight, it is difficult to further improve the long-term rust resistance. If it exceeds 10.0% by weight, it is not only difficult to perform molding processing, but also difficult to exert long-term rust resistance.

[0105] <Method for producing anti-rust film>

[0106] In order to obtain the resin layer 2 containing a deliquescent rust inhibitor of the present invention, a regenerated resin composition obtained by regenerating a rust-proof film including two layers, a resin layer containing an amine and / or ammonia-based vaporizing rust inhibitor and a resin layer containing a deliquescent rust inhibitor, is used. The amount of the regenerated resin composition for the rust-proof film used in the resin layer 2 of the present invention is preferably 10.0% by weight or more, more preferably 15.0% by weight or more, further preferably 20.0% by weight or more, and most preferably 25.0% by weight or more in the resin layer 2. The larger the blending amount, the more actively and effectively the regenerated resin composition for the rust-proof film obtained by regenerating the recovered rust-proof film can be used.

[0107] Then, the recycled resin composition for the rust-proof film is mixed with the polyolefin resin as a raw material required for the resin layer 2, a rust inhibitor, and various additives as needed, and the rust-proof film is manufactured by a known film molding method such as extrusion molding, inflation molding, vacuum molding, and press molding.

[0108] Thus, it can have any shape such as a film, a sheet, a bag, and a stacked sheet, a tube, or a box. In this case, the resin layer 1 and the resin layer 2 can be formed into a total of two or more layers by coextrusion. In addition, the resin layer 1 and the resin layer 2 obtained separately can also be stacked by a known method such as bonding / fusion.

[0109] <Use of anti-rust film>

[0110] The surface on the resin layer 1 side can be molded or processed into a bag shape in a manner so as to be located on the inner side of a container or a packaging sheet, that is, on the side of an article to be stored or packaged and to be rust-proofed. Conversely, the surface on the resin layer 2 side can also be used in a manner so as to be located on the inner side of a container or a packaging sheet, that is, on the side of an article to be stored or packaged and to be rust-proofed.

[0111] However, amines and / or ammonia-based vaporizing rust inhibitors may be crushed and have a reduced average particle size during addition and kneading of resins and during molding processes. Therefore, when controlling these particle sizes, attention must be paid to the average particle size after molding.

[0112] Furthermore, by adopting at least two resin layers, moisture gradually penetrates from the surface of the resin layer 2 to the inside, and thus rust-proof gas is gradually generated. Therefore, even without adding rust-proof sustained-release agents such as carboxylic acid-modified polyolefin polymers, waxes, nonionic surfactants, inorganic porous bodies, etc., a good rust-proof effect can be maintained more stably for a long time.

[0113] In addition, articles to be rust-proofed include a wide range of articles such as cast iron, steel plates, and galvanized steel plates, which are known to be packaged for rust-proofing using rust-proof films or bags obtained therefrom.

[0114] (Examples and Comparative Examples)

[0115] The recovered antirust films 1 and 2 (antirust films having two layers, namely, a resin layer containing an amine and / or ammonia-based vaporizing rust inhibitor and a resin layer containing a deliquescent rust inhibitor) shown in Table 1 were prepared. Then, 50 kg of each of these antirust films 1 and 2 were crushed, melted at 140°C or 240°C, granulated into particles with a diameter of about 5 mm, and dried at 90°C for 120 minutes as needed to reduce the amine and / or ammonia-based vaporizing rust inhibitor and water. The melting, kneading, and drying conditions of the thus obtained regenerated resins A to g, as well as the contents of the amine and / or ammonia-based vaporizing rust inhibitor, deliquescent rust inhibitor, and water in the regenerated resins and the recovered antirust films are shown in Table 2.

[0116] Recycled resins e to g are examples in which drying is not performed after melting and granulation at 140°C. In this case, even if the amounts of ammonium benzoate, cyclohexylamine carbamate (CHC), sodium nitrite, and water in each recovered rust-proof film are the same, the contents of the rust-proof agent and water in each recycled resin are not constant. The reason for this is not clear, but it is believed to be related to the low melting temperature and the presence or absence of drying.

[0117] Furthermore, polyethylene (PE), various rust preventive agents, and the recycled resins described in Table 2 were blended so that the compositions of the obtained resin layers 1 and 2 would become the compositions shown in Table 3 below.

[0118] In order to form the resin layer 1 and the resin layer 2 described in the following Table 3, each component was blown at 140°C to obtain a rust-proof film having the layer structure described in Table 3. The presence or absence of foaming, YI / ΔYI, and rust-proof performance of these rust-proof films were determined as follows. The results are shown in Table 4. In Table 3, for the layer containing recycled resin, the total of each component contained in each layer is the total of each component derived from the recycled resin. As the inner number in the total of each component, the content is shown as a component derived from the recycled resin. In addition, the resin layer 3 in Table 3 corresponds to the outermost layer that does not contain a rust inhibitor.

[0119] (Whether there is foaming)

[0120] Method: Check visually to see if there is any foaming.

[0121] (YI / ΔYI)

[0122] Sample: A film formed by overlapping 12 anti-rust films.

[0123] Measured value: average value of measured values ​​at 5 points in one sample.

[0124] Device: Spectrophotometer SD-7000 manufactured by Nippon Denshoku Industries.

[0125] Light source: Specular reflection (SCI).

[0126] Measurement method: According to ASTM D1925, five points in one sample formed by overlapping 12 antirust films were measured, and the average value was defined as YI.

[0127] ΔYI represents the difference between YI0 of the antirust film 1 or the antirust film 2 after recovery and YIx of the antirust film 1 or the antirust film 2 using the recycled resin composition for the antirust film (Formula 1).

[0128] ΔYI=(YIx of the antirust film 1 or the antirust film 2 using the recycled resin composition for the antirust film)-(YI0 of the antirust film 1 or the antirust film 2 after recovery) (Formula 1)

[0129] Note that, by measuring by stacking 12 sheets, there is no variation in the measured value compared to measuring each sheet, and a larger YI can be measured, so that the color change can be measured with high accuracy.

[0130] (Rust-proof performance)

[0131] The test piece [A] described below was suspended by a nylon fishing line in a frame of 100 mm in length x 100 mm in width x 150 mm in height, and the frame was gusseted and sealed with the prepared film.

[0132] This test method is left for a specified period of time under the test environment of the following [B], and then the rust state of the surface is evaluated based on the evaluation method of the following [C].

[0133] 〔A〕Test piece

[0134] Cast iron (JISG5501) size: φ30mm×8mm.

[0135] 〔B〕Test environment

[0136] Cycle test conditions (12 hours / 1 cycle)

[0137]

[0138] 〔C〕Evaluation Method

[0139] Duration: 3 days (6 cycles)

[0140] Benchmark:

[0141] None: No rust or discoloration.

[0142] Yes: rust spots and discoloration occur.

[0143] In addition, the content of each rust preventive agent in the rust-proof film and the recycled resin composition in Table 1, Table 2, and Table 3 was determined as follows.

[0144] (Common measurement conditions)

[0145] Determination method: HPLC method.

[0146] Detector: Shodex CD-5 conductivity detector for ion chromatography.

[0147] Concentration: Calculated based on peak area using a pre-made calibration curve.

[0148] (Measurement conditions of sodium nitrite content)

[0149] Add 10 g of the rust-proof particles / rust-proof film to a mixed solution of 100 g of water and 100 mL of xylene, stir and dissolve at 80°C, separate the resin from the rust-proof agent component, and cool to room temperature to obtain an aqueous solution consisting only of the rust-proof agent component and water. The measurement was performed under the following measurement conditions.

[0150] Measurement conditions

[0151] Column used: ShodexIC I-524 (guard column IC IA-G).

[0152] Eluent: aqueous phthalic acid solution (2.5 mM).

[0153] Flow rate: 1.5mL / min.

[0154] (Measurement conditions of ammonium benzoate content)

[0155] Add 10 g of the rust-proof particles / rust-proof film to a mixed solution of 100 g of water and 100 mL of xylene, stir and dissolve at 80°C, separate the resin from the rust-proof agent component, and cool to room temperature to obtain an aqueous solution consisting only of the rust-proof agent component and water. The measurement was performed under the following measurement conditions.

[0156] Measurement conditions

[0157] Column used: ShodexIC YK-421 (guard column IC YK-G).

[0158] Eluent: aqueous tartaric acid (5 mM).

[0159] Flow rate: 1.0mL / min.

[0160] (Measurement conditions for the content of cyclohexylamine carbamate (CHC))

[0161] Add 10 g of rust-proof particles / rust-proof film to a mixed solution of 150 g of 10 mM nitric acid aqueous solution and 30 mL of xylene, stir and dissolve at 80°C, separate the resin from the rust-proof agent component, and cool it to room temperature to obtain an aqueous solution consisting only of the rust-proof agent component and water. The measurement was performed under the following measurement conditions.

[0162] Measurement conditions

[0163] Column used: ShodexIC YK-421 (guard column IC YK-G)

[0164] Eluent: a mixed solution of 1 mM nitric acid aqueous solution and acetonitrile in a mixing ratio of 3:7.

[0165] Flow rate: 1.0mL / min.

[0166] In addition, the amount of water in the rust-proof film and the regenerated resin composition in Table 1, Table 2, and Table 3 was measured using a Karl Fischer water content meter (manufactured by Hiranuma Sangyo Co., Ltd.: AQV-2200S).

[0167] [Table 1]

[0168]

[0169] [Table 2]

[0170]

[0171] [Table 3]

[0172]

[0173] [Table 4]

[0174]

[0175] Each example is an example in which a recycled resin composition for rust-proof film is used as a material for obtaining resin layer 2, and the recycled source component ammonium benzoate or CHC is 20 to 220 ppm, and contains less than 400 ppm of water. According to each example of the present invention, foaming of the rust-proof film was not confirmed, and the rust-proof agent can be contained in a predetermined amount. In addition, the rust-proof performance is the same as that of films 1 and 2, and no rust is generated.

[0176] Comparative Examples 1 and 2 are examples in which a recycled resin composition for rust-proof film is used as a material for obtaining the resin layer 1. Comparative Examples 3 to 6 are examples in which a recycled resin composition for rust-proof film is used as a material for obtaining the resin layer 2, and the amount of ammonium benzoate is more than 220 ppm and / or water is more than 400 ppm.

[0177] When the resin layer 1 contained the recycled resin composition for the rust-proof film as in Comparative Examples 1 and 2, foaming of the resin layer 1 was confirmed. Also, when the resin layer 2 contained the recycled resin composition for the rust-proof film in an amount exceeding the prescribed amount as in Comparative Examples 3 to 6, foaming was confirmed. In addition, it is known that when the recycled resin compositions e to g used in Comparative Examples 4 to 6 are used as rust-proof films in the same manner as in the examples, the content of the recycled resin compositions e to g must be reduced, and as a result, the amount of the recycled resin composition used in the rust-proof film must be reduced.

[0178] In addition, the films 1 and 2 in Table 1 are all rust-proof films obtained by using materials that are not recycled, without using the recycled resin composition for rust-proof films in the present invention. In addition, the YI0 of the films 1 and 2 are 5 and 8, respectively. These are the films used as the reference when calculating ΔYI indicating the degree of yellowing.

[0179] In addition, the value of YIx in Table 4 is 30 or less according to each Example, and at least 37 according to each Comparative Example. In addition, the value of ΔYI is 25 or less according to each Example, and at least 32 according to each Comparative Example. According to these results, the degree of yellowing of the rust-proof film of the present invention is smaller. In addition, the degree of yellowing of each Comparative Example is large.

[0180] The rust-proof films of each example showed the same rust-proof properties as the rust-proof films 1 and 2 of the same composition without using the recycled resin. It should be noted that the rust-proof films of each comparative example showed no foaming and a large degree of yellowing, so the evaluation of rust-proof properties was not performed.

Claims

1. A recycled resin composition for an anti-rust film, characterized in that: The invention contains a polyolefin resin, 0.02 to 0.20 wt % of an amine and / or an ammonia-based vaporizing rust inhibitor, a deliquescent rust inhibitor, and 0.30 wt % or less of water.

2. A method for producing a recycled resin composition for an anti-rust film, characterized in that: A rust-proof film formed by laminating a polyolefin resin layer containing an amine and / or ammonia-based vaporizing rust inhibitor and a polyolefin resin layer containing a deliquescent rust inhibitor is melted, kneaded, and dried as needed. The recycled resin composition for the rust-proof film contains a polyolefin resin, 0.02 to 0.20 wt % of an amine and / or ammonia-based vaporizing rust inhibitor, a deliquescent rust inhibitor, and 0.30 wt % or less of water.

3. A rust-proof film, characterized in that: In a rust-proof film formed by laminating a polyolefin resin layer (1) containing an amine and / or ammonia-based vaporizing rust inhibitor and a polyolefin resin layer (2) containing a deliquescent rust inhibitor, the polyolefin resin layer (2) contains a polyolefin resin derived from a recycled resin composition for a rust-proof film, 20 to 220 ppm of an amine and / or ammonia-based vaporizing rust inhibitor, and 400 ppm or less of water.

4. The anti-rust film according to claim 3, characterized in that: The YI value measured by stacking 12 rust-proof films was 35.0 or less.

5. A method for producing an anti-rust film, characterized in that: The rust-proof film is formed by laminating a polyolefin resin layer (1) containing an amine and / or ammonia-based vaporizing rust inhibitor and a polyolefin resin layer (2) containing a deliquescent rust inhibitor. In the method for producing the rust-proof film, a recycled resin composition for the rust-proof film, a polyolefin resin and a deliquescent rust inhibitor are mixed so that the content of the amine and / or ammonia-based vaporizing rust inhibitor derived from the recycled resin composition in the polyolefin resin layer (2) is 20 to 220 ppm, and the content of water is less than 400 ppm.

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