RUST PROTECTION FILM

Abstract

The present invention effectively recycles a rust-preventive film after its collection, and a recycled resin composition for rust-preventive film, which is a recycled resin, is obtained by treating it under milder conditions. With the present invention, a new rust-preventive film can be produced using the recycled resin composition for rust-preventive film without foaming, and a single layer can contain a combination of rust-preventive agents that cannot normally be contained in a single layer. The present invention addresses the problem of obtaining a rust-preventive film having a sufficient rust-preventive effect, which is obtained by using a recycled resin composition for rust-preventive film, and thus promotes the reuse of a rust-preventive film such as a used rust-preventive film.As a solution, a recycled resin composition for a rust-inhibiting film is provided, the recycled resin composition being characterized in that it contains a polyolefin resin, 0.02-0.20 wt% of an evaporable amine- and / or ammonia-based rust inhibitor, a deliquescent rust inhibitor, and 0.30 wt% or less of water.

Description

TECHNICAL FIELD

[0001] The present invention relates to a rust protection film. STATE OF THE ART

[0002] As described in Patent Literature 1, there is known a rust-preventive film comprising a resin molded product having a resin layer containing an ammonium carboxylate having an average particle diameter of 20 μm or more, and a substrate layer containing one or more kinds of a metal nitrite, a carboxylic acid, a benzotriazole-based compound, a tolyltriazole-based compound, and a metal carboxylate.

[0003] However, it is not known how to recover and reuse such a known anti-rust film containing two or more types of rust inhibitors after use. To recover such an anti-rust film and reuse it as a resin for an anti-rust film and add any rust inhibitor to it, it was necessary to completely remove the existing rust inhibitor, because among the combinations of two or more types of rust inhibitors, there is a combination in which the rust inhibitors react with each other during their coexistence. However, this requires a tremendous amount of labor.

[0004] This means that in a rust-proof film with, for example, two or more layers, the rust inhibitors contained in the layers are generally different rust inhibitors. In particular, a combination of rust inhibitors is known that react with each other to generate a gas when mixed together. In the case of such a combination, it was particularly necessary to form the rust-proof film in two or more layers. CITATION LISTPATENT LITERATURE

[0005] Patent literature 1: WO2018 / 079458 SUMMARY OF THE INVENTION TECHNICAL PROBLEM

[0006] According to the present invention, a reclaimed rust-inhibiting film having two layers, namely a resin layer containing a vaporizable amine- and / or ammonia-based rust inhibitor and a resin layer containing a deliquescent rust inhibitor, can be effectively utilized to obtain a recycled resin composition for a rust-inhibiting film in the form of a recycled resin by using a treatment under milder conditions. By using the recycled resin composition for a rust-inhibiting film, a new rust-inhibiting film can be produced without foaming, and a single layer can contain a combination of rust inhibitors that cannot normally be contained in a single layer.Another objective is to obtain a rust protection film that has a sufficient rust protection effect and that is obtained by using a recycled resin composition for a rust protection film, thus promoting the reuse of the used rust protection film. SOLUTION TO THE PROBLEM

[0007] As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that the problems can be solved by the following methods and thus have completed the present invention. 1. A recycled resin composition for a rust-inhibiting film, comprising: a polyolefin resin; 0.02 wt% to 0.20 wt% of an evaporable amine- and / or ammonia-based rust inhibitor; a deliquescent rust inhibitor; and 0.30 wt% or less of water. 2. A method for producing a recycled resin composition for a rust-inhibiting film, which comprises: melting, kneading, and optionally drying a rust-inhibiting film having a layered structure which comprises a polyolefin resin layer containing a vaporizable amine- and / or ammonia-based rust inhibitor and a polyolefin resin layer containing a deliquescent rust inhibitor, the recycled resin composition for a rust-inhibiting film containing a polyolefin resin, 0.02% to 0.20% by weight of the vaporizable amine- and / or ammonia-based rust inhibitor, the deliquescent rust inhibitor, and 0.30% by weight or less of water. 3. A layered rust-preventive film comprising a polyolefin resin layer 1 containing a vaporizable amine- and / or ammonia-based rust-preventive agent, and a polyolefin resin layer 2 containing a deliquescent rust-preventive agent, wherein the polyolefin resin layer 2 contains a polyolefin resin, 20 ppm to 220 ppm of a vaporizable amine- and / or ammonia-based rust-preventive agent, and 400 ppm or less of water, which are derived from a recycled resin composition for a rust-preventive film. 4. The rust-proof film according to 3, wherein a YI value measured by stacking 12 rust-proof films is 35.0 or less. 5. A method for producing a rust-inhibiting film, the rust-inhibiting film having a layered structure comprising a polyolefin resin layer 1 containing a vaporizable amine- and / or ammonia-based rust inhibitor, and a polyolefin resin layer 2 containing a deliquescent rust inhibitor, comprising: the polyolefin resin layer 2 is obtained by mixing a recycled resin composition for a rust-inhibiting film with a polyolefin resin and the deliquescent rust inhibitor to have a content of 20 ppm to 220 ppm of the vaporizable amine- and / or ammonia-based rust inhibitor and 400 ppm or less of water derived from the recycled resin composition. ADVANTAGEOUS EFFECTS OF THE INVENTION

[0008] According to the present invention, a used rust-inhibiting film, a used rust-inhibiting bag, or the like having two layers, namely a resin layer containing a vaporizable amine- and / or ammonia-based rust inhibitor and a resin layer containing a deliquescent rust inhibitor, is recovered, and the recovered material is subjected to recycling treatment. The recovered material can be reused as a recycled resin composition for producing a rust-inhibiting film in a state containing a certain amount of the vaporizable amine- and / or ammonia-based rust inhibitor and in a state containing the deliquescent rust inhibitor. Hereinafter, it is simply referred to as a "recycled resin composition for a rust-inhibiting film."

[0009] The recycled resin composition for a rust-preventive film contains 0.02 wt% to 0.20 wt% of the not completely removed evaporable amine- and / or ammonia-based rust inhibitor after recycling the used rust-preventive film, the used rust-preventive bag, or the like, and further contains a deliquescent rust inhibitor and 0.30 wt% or less of water.

[0010] Since the rust inhibitor is not completely removed from the recycled resin composition for rust prevention film, the rust prevention bag or the like does not need to be subjected to treatment under harsher temperature and time conditions (treatment under harsh conditions to completely remove the rust inhibitor), and can be subjected to recycling treatment under milder temperature and time conditions. Therefore, it is possible to reduce the amount of energy required to obtain a rust prevention film composition from the reclaimed material and the amount of energy required to obtain a new rust prevention film.This is advantageous in that the amount of energy required can be reduced compared to the case where the recovered material is subjected to a treatment to completely remove the rust inhibitor to obtain a recycled resin.

[0011] A new rust-proof film produced using this recycled resin composition for rust-proof film or a rust-proof bag made therefrom contains only a low content of evaporable rust inhibitors that coexist in the resin layer and therefore do not react with a deliquescent rust inhibitor. As a result, foaming or discoloration such as yellowing does not occur during film formation. If foaming occurs during film formation, the film-forming properties and mechanical properties of the resulting film deteriorate. In addition, if discoloration such as yellowing occurs, the appearance deteriorates. The cause of discoloration such as yellowing lies in the oxidation of the resin or the deliquescent rust inhibitor during the process for producing the recycled resin composition for rust-proof film.

[0012] Furthermore, a new resin layer prepared by using this recycled resin composition for a rust-preventive film and a resin layer containing an amine- and / or ammonia-based vaporizable rust-preventive agent can be laminated to form a new rust-preventive film having a layered structure with sufficient rust-preventive property.

[0013] That is, even with such recycling treatment under milder conditions, the rust-preventing film according to the present invention can be used as a rust-preventing film with a rust-preventing effect equivalent to that of a rust-preventing film containing non-reclaimed materials. Therefore, the cost, time, and environmental impact associated with recycling and reuse can be reduced, and the reuse of the used rust-preventing film can be promoted. DESCRIPTION OF THE EMBODIMENTS<Recyclierte Harzzusammensetzung für eine Rostschutz-Folie>

[0014] A recycled resin composition for a rust-proof film according to the present invention is a composition mainly used for producing a polyolefin resin layer 2 in a rust-proof film according to the present invention. It can also be used for producing other rust-proof films.

[0015] The recycled resin composition for a rust-proof film is obtained by recovering and recycling one or more types of manufactured and used rust-proof films, rust-proof bags obtained therefrom, residues of the manufactured rust-proof film, and excess rust-proof films or products.

[0016] The rust protection film before recovery is a layered rust protection film comprising a resin layer containing an evaporable amine- and / or ammonia-based rust protection agent and a resin layer containing a deliquescent rust protection agent.

[0017] The recycling treatment will be described later.

[0018] The recycled resin composition for an anti-rust film according to the present invention contains a polyolefin resin and may contain the evaporable amine- and / or ammonia-based rust inhibitor in a proportion of at least 0.02 wt%. A content of less than 0.02 wt% requires extensive treatment and may, in some cases, lead to deterioration of the physical properties of the resin itself. The higher the content of the evaporable amine- and / or ammonia-based rust inhibitor in the composition obtained by recycling the reclaimed anti-rust film, the milder the recycling treatment conditions can be.However, when attempting to obtain a new rust-preventive film by blending a larger amount of the recycled resin composition for rust-preventive film, the larger the content of the evaporable amine- and / or ammonia-based rust-preventive agent in the recycled resin composition for rust-preventive film, the smaller the amount of the recycled resin composition for rust-preventive film that can be used to produce a new rust-preventive film. If the amount of the recycled resin composition for rust-preventive film used is too large, the evaporable amine- and / or ammonia-based rust-preventive agent may react with the deliquescent rust-preventive agent, such as a nitrite, during production of a new rust-preventive film, resulting in foaming of the polyolefin resin layer 2. In addition, the obtained rust-preventive film may yellow or discolor, and the appearance may deteriorate.

[0019] Therefore, in the recycled resin composition for an anti-rust film to be used as a raw material for the new production of an anti-rust film, the content of the evaporable amine- and / or ammonia-based rust inhibitor is preferably 0.20 wt% or less, more preferably 0.15 wt% or less, and even more preferably 0.10 wt% or less.

[0020] The content of the deliquescent rust inhibitor in the recycled resin composition is not particularly limited and is preferably 0.28 wt% or less, more preferably 0.25 wt% or less, and even more preferably 0.22 wt% or less. Furthermore, it is preferably 0.05 wt% or more, more preferably 0.07 wt% or more, and even more preferably 0.10 wt% or more. If the content of the deliquescent rust inhibitor is too high, the water content increases due to moisture absorption, and there is a greater risk of water evaporation and foaming when a new rust-inhibiting film is produced using the recycled resin composition for a rust-inhibiting film. To reduce the content of the deliquescent rust inhibitor to less than 0.05 wt%, treatment under correspondingly harsher conditions of temperature and time is required.

[0021] Furthermore, the recycled resin composition for rust-proofing film preferably has a low water content. The water comes from moisture absorption by the deliquescent rust inhibitor contained in the recycled resin composition. The water content is preferably 0.30 wt% or less, more preferably 0.20 wt% or less, even more preferably 0.10 wt% or less, and most preferably 0.05 wt% or less. If the water content is too high, the water may evaporate during the production of a new rust-proofing film using the recycled resin composition for rust-proofing film, causing foaming or deliquescing of the deliquescent rust inhibitor, such as nitrite, contained in the new rust-proofing film.As a result, the amount of recycled resin composition for an anti-rust film that can be used to produce the new anti-rust film may inevitably be reduced. <Verfahren zur Herstellung einer Recyclierten Harzzusammensetzung für eine Rostschutz-Folie>

[0022] The recycled resin composition for an anti-rust film according to the present invention is a composition recycled from a reclaimed anti-rust film having two layers, namely a resin layer containing an amine- and / or ammonia-based vaporizable rust inhibitor and a resin layer containing a deliquescent rust inhibitor or the like. Note that the reclaimed anti-rust film mentioned here includes not only a film used as an anti-rust film for packaging, but also a rust-proof film that was not used due to production loss or the like, and materials thereof.

[0023] It should be noted that the rust-proof film to be recovered is preferably a film falling within the scope of the rust-proof film according to the present invention.

[0024] Furthermore, the same vaporizable amine- and / or ammonia-based rust inhibitor as above may be contained in the rust-inhibiting film to be recycled. Furthermore, a certain portion of the rust-inhibiting film recovered for recycling may contain a rust-inhibiting film that does not contain a vaporizable amine- and / or ammonia-based rust inhibitor. However, it is preferable that the entire recovered rust-inhibiting film to be recycled comprises a rust-inhibiting film having a resin layer containing a vaporizable amine- and / or ammonia-based rust inhibitor and a resin layer containing a deliquescent rust inhibitor, such as the rust-inhibiting film according to the present invention.

[0025] Note that the recycled resin composition for a rust-preventive film according to the present invention is obtained from the once-recovered rust-preventive film, and the rust-preventive film according to the present invention is newly obtained by using this recycled resin composition for a rust-preventive film. This newly obtained rust-preventive film can be reclaimed after use and recycled into a recycled resin composition for a rust-preventive film according to the present invention, and the obtained recycled resin composition for a rust-preventive film according to the present invention can be used again to produce the rust-preventive film according to the present invention, and this process can be repeated.

[0026] As a method for producing such a recycled resin composition for an anti-rust film, a method can be used in which the reclaimed anti-rust film is subjected to grinding by any method, heating at a high temperature of 140°C or higher, and melting to promote evaporation and removal, followed by solidification and pelletization by any method, and then drying at about 80°C to 95°C for about 60 minutes to 150 minutes, if necessary. Note that the conditions, such as temperature and time, may be changed depending on the specific equipment and the reclaimed anti-rust film.

[0027] By using such heating, melting and drying methods, not only the water content but also the content of the evaporable amine and / or ammonia-based rust inhibitor is reduced to obtain the recycled resin composition for a rust-proof film according to the present invention.

[0028] With such a method for producing a recycled resin composition for a rust-proof film, it is possible to actively recover and reuse the used rust-proof film or the like, which was previously difficult to reuse as a resin composition for a rust-proof film.

[0029] The recycled resin composition for a rust-proof film according to the present invention, containing a polyolefin resin, 0.02 wt.% to 0.20 wt.% of an amine- and / or ammonia-based vaporizable rust inhibitor, a deliquescent rust inhibitor, and 0.30 wt.% or less of water, and a manufacturing method thereof are primarily intended to provide a composition for manufacturing the rust-proof film according to the present invention and a manufacturing method thereof. The recycled resin composition for a rust-proof film can be used to manufacture a rust-proof film having three or more layers. <rostschutz-folie>

[0030] The rust-preventive film according to the present invention has a basic layered structure construction comprising a polyolefin resin layer 1 containing a vaporizable amine- and / or ammonia-based rust inhibitor and a polyolefin resin layer 2 containing a deliquescent rust inhibitor, wherein the polyolefin resin layer 2 contains 20 ppm to 220 ppm of a vaporizable amine- and / or ammonia-based rust inhibitor, a deliquescent rust inhibitor, and 400 ppm or less of water, which are derived from a recycled resin composition for a rust-preventive film.

[0031] Note that the polyolefin resin layer 1 and the polyolefin resin layer 2 are preferably directly laminated together, but an adhesive layer, an intermediate layer, or the like may be formed between the polyolefin resin layer 1 and the polyolefin resin layer 2. Furthermore, an optional layer may or may not be present on a surface of the polyolefin resin layer 1 opposite to a surface on one side of a polyolefin resin layer 2, and / or on a surface of the polyolefin resin layer 2 opposite to a surface on one side of a polyolefin resin layer 1.

[0032] Hereinafter, the polyolefin resin layer 1 and the polyolefin resin layer 2 may be simply referred to as “resin layer 1” and “resin layer 2,” respectively.

[0033] The rust-preventive film according to the present invention can be processed into a bag shape such that the resin layer 1 is on the inside, that is, the side facing the packaged article, and the resin layer 2 is on the outside. In the case of three or more layers, the resin layer 2 can be provided as the innermost layer. They are used for packaging metal electrical products, electrical parts, electronic parts, mechanical parts, automotive parts, and the like.

[0034] In the rust-preventive film according to the present invention, a YI value measured by stacking 12 rust-preventive films is preferably 35.0 or less, more preferably 30.0 or less, even more preferably 25.0 or less, and most preferably 20.0 or less. When the YI value is 35.0 or less, the rust-preventive film produced by using the recycled resin composition for a rust-preventive film does not exhibit particular discoloration (yellowing), and when used as a rust-preventive film or as a rust-preventive bag for packaging, the contents can be visually observed without opening the package.

[0035] In addition, known additives such as antiblocking agents (AB agents), lubricants, antioxidants, antistatic agents, UV absorbers, light stabilizers, oxygen absorbers, acid absorbers, flame retardants, nucleating agents, impact modifiers, plasticizers, release agents, dyes, fluorescent agents, compatibilizers, antifogging agents, fillers, auxiliary dyes, dispersants, stabilizers, modifiers, and antibacterial and antifungal agents can be added to the resin layers 1 and 2 independently within a range that does not impair the effects of the present invention. However, it is necessary that the additive does not react with other components contained in the resin layer 1 and the resin layer 2, and that the additive does not contaminate a packaged article, for example, by bleeding.

[0036] Note that, for the purpose of retaining the rust preventive in the resin layer, an ionomer resin or a functional group-containing polyolefin resin may or may not be blended into the resin layer 1 or the resin layer 2. Then, according to the present invention, the rust preventive property can be sufficiently maintained over a long period of time.

[0037] The thickness of each of the resin layers 1 and 2 is preferably 10 µm or more, more preferably 15 µm or more, and even more preferably 20 µm or more. Furthermore, the thickness is preferably 300 µm or less, more preferably 200 µm or less, and even more preferably 100 µm or less. Further, the total thickness of the resin layers 1 and 2 is preferably 20 µm or more, more preferably 30 µm or more, and even more preferably 40 µm or more. Furthermore, the total thickness is preferably 600 µm or less, more preferably 400 µm or less, and even more preferably 200 µm or less.

[0038] Regarding the rust-preventive film according to the present invention, a resin is described that can be commonly used for both the resin layer 1 and the resin layer 2. For the resin layer 1 and the resin layer 2, one or more types of resins can be independently selected and used from the following resins. (polyolefin resin)

[0039] The compositions of the polyolefin resins contained in resin layer 1 and resin layer 2 may be different or the same. The compositions are preferably the same because, when the rust-preventive film is recovered and recycled after use or the like, it can be used as a rust-preventive film with the same resin composition as the rust-preventive film before recycling.

[0040] As such a polyolefin resin, one or more types selected from polyolefin-based polymers, ie, olefin homopolymers and / or copolymers using an olefin as a monomer can be selected and used.

[0041] Examples of the olefin constituting the polyolefin-based polymer (olefin monomer) 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-based polymers include ethylene-based polymers, propylene-based polymers, 1-butene-based polymers, 1-hexene-based polymers, and 4-methyl-1-pentene-based polymers. These polymers can be used alone or in combination of two or more types. That is, the polyolefin-based polymer can be a mixture of various polymers.

[0042] The above examples of ethylene-based polymers include an ethylene homopolymer (polyethylene) and a copolymer of ethylene with another monomer (ethylene copolymer). Examples of the ethylene homopolymer and the ethylene copolymer include a low-density polyethylene (LDPE), a linear low-density polyethylene (LLDPE), a medium-density polyethylene (MDPE), and a high-density polyethylene (HDPE).

[0043] Other 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.

[0044] It should be noted that the ethylene unit (structural unit derived from ethylene) contained in the ethylene copolymer is considered sufficient if it accounts for more than 50% of the total number of structural units (generally 99.999% or less), and may be, for example, 80.0% to 99.999%, 90.0% to 99.995% or 99.0% to 99.990% of the total number of structural units.

[0045] Other examples of propylene-based polymers include propylene homopolymers (polypropylene) and a copolymer of propylene with another monomer (propylene copolymer). Examples of the propylene copolymer include a propylene-ethylene copolymer, a propylene-1-butene copolymer, a propylene-1-pentene copolymer, and a propylene-1-octene copolymer.

[0046] It should be noted that the propylene unit (structural unit derived from propylene) contained in the propylene copolymer is considered sufficient if it accounts for 50% or more of the total number of structural units (generally 99.999% or less), and may be, for example, 80.0% to 99.999%, 90.0% to 99.995%, or 99.0% to 99.990% of the total number of structural units.

[0047] Furthermore, the polyolefin-based polymer may contain structural units derived from monomers other than olefins, as long as the purpose of the present invention is not compromised. Examples of monomers other than olefins include unsaturated carboxylic acids (acrylic acid, methacrylic acid, maleic acid, and fumaric acid, etc.), unsaturated carboxylates (methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dimethyl maleate, and diethyl maleate, etc.), vinyl esters (vinyl acetate, vinyl propionate, and maleic acid monoester, etc.). These can be used alone or in combination of two or more types.

[0048] It should be noted that the structural unit derived from monomers other than olefins, if present, preferably accounts for 40% or less (generally 0.001% or more) of the total number of structural units contained in the polyolefin-based polymer. For example, it may be 0.001% to 25%, 0.005% to 15%, or 0.01% to 10% of the total number of structural units.

[0049] The polyolefin-based resin preferably has a density of 0.880 g / cm 3 up to 0.950 g / cm 3 from the perspective of processability. Furthermore, it preferably has a melt flow rate (MFR) in the range of 1.0 g / 10 min to 10.0 g / 10 min from the perspective of mechanical strength and processability. With appropriate viscosity during melt processing, it is possible to retain and recover a particulate ammonium carboxylate in the resin, and it is possible to prevent the rust inhibitor from falling off a resin-molded product. (Resin layer 1)

[0050] The resin layer 1 contains a vaporizable amine and / or ammonia-based rust inhibitor as a rust inhibitor.

[0051] The vaporizable amine and / or ammonia-based rust inhibitor may be selected from an aliphatic ammonium carboxylate, an aliphatic amine carboxylate, an aromatic ammonium carboxylate and an aromatic amine carboxylate.

[0052] One or more kinds of, for example, ammonium salts of aliphatic carboxylic acids such as butyric acid, isobutyric acid, methacrylic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, sorbic acid, oleic acid, oleanolic acid, isohexanoic acid, 2-methylpentanoic acid, 2-ethylbutyric acid, isoheptic acid, isooctanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, 2-propylheptanoic acid, issoundecanoic acid, isododecanoic acid, 2-butyloctanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid and dodecanedioic acid can be used;Ammonium 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 and cinnamic acid, as well as cyclohexylamine salts and dicyclohexylamine salts of the above-mentioned acids.;

[0053] As the vaporizable amine-based rust inhibitor, one or more types of organic amine salts selected from phosphates, nitrites, carbonates, and carboxylates of mono-, di-, and tri-ethanolamine, n-, di-, and tert-butylamine, hexamethylenediamine, hexamethylenetetramine, mono- and di-cyclohexylamine, isopropylamine, oleylamine, naphthylamine, and diphenylamine can also be used. Note that the resin layer 1 does not contain a deliquescent rust inhibitor in an amount that inhibits the effects of the present invention.

[0054] The content of the evaporable amine- and / or ammonia-based rust inhibitor in the resin layer 1 is preferably 0.01 wt% or more, more preferably 0.10 wt% or more, and even more preferably 0.20 wt% or more, based on the resin layer contained. Furthermore, it is preferably 10.00 wt% or less, more preferably 8.00 wt% or less, and even more preferably 6.00 wt% or less. If the content is less than 0.01 wt%, it is difficult to obtain a sufficient rust-preventive property, and if the content is more than 10.00 wt%, molding is difficult.

[0055] The vaporizable amine- and / or ammonia-based rust inhibitor is contained in the resin layer 1 in particulate form or in a state where it is dissolved in the resin layer. It may be in particulate form or in dissolved form. When the rust inhibitor is in particulate form, its average particle diameter (d50) is preferably 3 µm or more, more preferably 3 µm to 400 µm, even more preferably 3 µm to 200 µm, and most preferably 3 µm to 100 µm.

[0056] Furthermore, a maximum particle diameter of the amine- and / or ammonia-based vaporizable 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 diameter of the amine- and / or ammonia-based vaporizable rust inhibitor is more than 5000 μm, there is a risk of deterioration of the strength of a resin molded product or contamination of metal products due to particle falling off. The maximum particle diameter is the largest particle diameter among the measured particle diameters of 1000 particles.

[0057] When the average particle diameter and / or the maximum particle diameter are within these ranges, the particles of the amine- and / or ammonia-based vaporizable rust inhibitor are covered with resin to form convex portions on the surface of the resin layer 1. The presence of such a convex portion can generate more rust-inhibiting gas, which in turn contributes to improving the rust-inhibiting property. Furthermore, the convex portion on the surface of the film has the effect of preventing adhesion to an object to be protected from rust and can prevent the particles of the amine- and / or ammonia-based vaporizable rust inhibitor from coming into direct contact with the object to be protected from rust, thereby preventing the surface of the object to be protected from rust from being contaminated.

[0058] In addition, in the case where the amine- and / or ammonia-based vaporizable rust inhibitor is contained in the resin layer in a dissolved state and in the case where it is contained in the resin layer in a particulate form as described above, the evaporability can be adjusted depending on the volatility and other properties of each type of vaporizable rust inhibitor.

[0059] By a series of steps of mixing the particles of the amine- and / or ammonia-based evaporable rust preventive into the resin forming the resin layer, melting and kneading the resin, and shaping it, e.g., into a plate form, the powder of the amine- and / or ammonia-based evaporable rust preventive can be ground before mixing to reduce the average particle diameter. Therefore, the average particle diameter described above according to the present invention is a value that relates to the amine- and / or ammonia-based evaporable rust preventive contained in the resin layer 1 after the resin layer 1 is formed.

[0060] By incorporating the vaporizable amine- and / or ammonia-based rust inhibitor with a specific particle diameter or in a dissolved state in the resin, the amount of rust inhibitor gas generated can be controlled, thereby maintaining the rust inhibitor effect stably over a long period of time.

[0061] In addition, although the exact mechanism is unclear, it is believed that by adjusting the particle diameter of the evaporable amine- and / or ammonia-based rust inhibitor within a certain range, convex portions are formed on the surface of the film, which ensures the rust protection effect for a long period of time. (Resin layer 2)

[0062] Resin layer 2 contains a deliquescent rust inhibitor as a rust inhibitor. (Deliquescent rust inhibitor)

[0063] The deliquescent rust inhibitor according to the present invention includes various metal nitrites and metal carbonates, one or more of which may be used. As the metal nitrite, one or more of which may be selected from a sodium salt, a potassium salt, a calcium salt, and a magnesium salt of nitrite may be used, and as the metal carbonate, a potassium salt and a hydrate thereof may be used.

[0064] The content of the deliquescent rust inhibitor in the resin layer 2 is preferably 0.01 wt% or more, more preferably 0.10 wt% or more, and even more preferably 0.20 wt% or more. Furthermore, it is preferably 6.00 wt% or less, more preferably 4.00 wt% or less, and even more preferably 2.00 wt% or less. If the content is less than 0.01 wt%, it may be difficult to obtain sufficient rust prevention property, and if the content is more than 6.00 wt%, molding may be difficult or it may be difficult to obtain the rust prevention property for a long time.

[0065] It should be noted that the resin layer 2 in the rust-preventive film according to the present invention is obtained by containing the recycled resin composition for a rust-preventive film according to the present invention, and the total amount of the deliquescent rust-preventive agent contained in the recycled resin composition for a rust-preventive film, which is one of the raw materials, and a deliquescent rust-preventive agent added as needed is the total amount of the deliquescent rust-preventive agent contained in the resin layer 2 in the rust-preventive film.

[0066] When the resin layer 2 is used in this way as an outer layer to form a packaging bag or the like, moisture from the outside air is absorbed into the packaging bag, causing the deliquescent rust inhibitor in the outer layer to react with the evaporable amine- and / or ammonia-based rust inhibitor in the inner layer, promoting the evaporation of the amine- and / or ammonia-based rust inhibitor within the package, thereby exhibiting the rust prevention effect. Furthermore, the rust prevention effect can be further enhanced by generating nitrous acid within the package. (Vaporizable amine and / or ammonia-based rust inhibitor)

[0067] Furthermore, the resin layer 2 contains 20 to 220 ppm by weight of an evaporable amine- and / or ammonia-based rust inhibitor derived from a recycled resin composition for an anti-rust film. The content of the evaporable amine- and / or ammonia-based 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. Furthermore, it is preferably 200 ppm or less, more preferably 180 ppm or less, and even more preferably 160 ppm or less.

[0068] If the content is more than 220 ppm, the evaporable amine and / or ammonia-based rust inhibitor may react with the deliquescent rust inhibitor in the resin layer 2, which may lead to foaming.

[0069] The amine- and / or ammonia-based vaporizable rust preventive agent derived from the recycled resin composition for a rust-preventive film referred to herein may be the same compound as the amine- and / or ammonia-based vaporizable rust preventive agent contained in the resin layer 1 described above.

[0070] However, until now, it has not been common to contain both the evaporable amine- and / or ammonia-based rust inhibitor and the deliquescent rust inhibitor in one resin layer for fear of reaction between the two. However, as long as the content of the evaporable amine- and / or ammonia-based rust inhibitor in the resin layer 2 is 20 ppm to 220 ppm, the reaction between the two can be effectively prevented. Therefore, the rust-inhibiting film according to the present invention can be formed using the recycled resin composition for a rust-inhibiting film according to the present invention (which is basically a composition obtained by recycling the used rust-inhibiting film, its raw materials, or the like).Such a recycled resin composition for a rust-preventive film according to the present invention is not one in which the rust inhibitor is completely removed, but one in which the evaporable amine- and / or ammonia-based rust inhibitor remains by reducing the treatment temperature, treatment time, or the like, because the degree of treatment is reduced to such an extent that the evaporable amine- and / or ammonia-based rust inhibitor remains to some extent.

[0071] In addition, the amine- and / or ammonia-based vaporizable rust inhibitor derived from the recycled resin composition for a rust-inhibiting film and contained in the resin layer 2 may have an average particle diameter smaller than that of the amine- and / or ammonia-based vaporizable rust inhibitor contained in the reclaimed rust-inhibiting film. (Water)

[0072] Furthermore, the resin layer 2 contains 400 ppm or less by weight of water derived from the recycled resin composition for an anti-rust film. The water content in the resin layer 2 is preferably 380 ppm or less, more preferably 300 ppm or less, and even more preferably 200 ppm or less. If the content exceeds 400 ppm, there is a greater risk of foaming in the film. (metal carboxylate)

[0073] According to the present invention, resin layers 1 and 2 may or may not independently contain a metal carboxylate. The metal carboxylate may be either an aliphatic metal carboxylate or an aromatic metal carboxylate.

[0074] As the metal carboxylate, one or more kinds of metal salts such as sodium salts, potassium salts, calcium salts and magnesium salts of aliphatic carboxylic acids such as isobutyric acid, methacrylic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, sorbic acid, oleic acid, oleanolic acid, isohexanoic acid, 2-methylpentanoic acid, 2-ethylbutyric acid, isoheptic acid, isooctanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, 2-propylheptanoic acid, issoundecanoic acid, isododecanoic acid, 2-butyloctanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic 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.

[0075] The content of the metal carboxylate in the contained resin layer is preferably 0.001 wt% to 10.0 wt%, and more preferably 0.01 wt% to 5.0 wt%. If the content is less than 0.001 wt%, it is difficult to achieve sufficient anti-rust performance, and if the content is more than 10.0 wt%, molding is difficult, and it is difficult to achieve the anti-rust performance for a long time. (carboxylic acid)

[0076] According to the present invention, resin layers 1 and 2 may or may not independently contain a carboxylic acid. The carboxylic acid may be either an aliphatic carboxylic acid or an aromatic carboxylic acid.

[0077] One or more kinds of aliphatic carboxylic acids such as isobutyric acid, methacrylic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, sorbic acid, oleic acid, oleanolic acid, isohexanoic acid, 2-methylpentanoic acid, 2-ethylbutyric acid, isoheptic acid, isooctanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, 2-propylheptanoic acid, issoundecanoic acid, isododecanoic acid, 2-butyloctanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic 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.

[0078] The content of the carboxylic acid in the contained resin layer is preferably 0.001 wt% to 10.0 wt%, and more preferably 0.01 wt% to 5.0 wt%. If the content is less than 0.001 wt%, it is difficult to further improve the anti-rust property, and if the content is more than 10.0 wt%, molding is difficult, and it is difficult to achieve the anti-rust property for a long time. (Benzotriazole-based compound and tolyltriazole-based compound)

[0079] According to the present invention, the resin layers 1 and 2 may or may not independently contain a benzotriazole-based compound and a tolyltriazole-based compound. Among them, one or more types selected from benzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole, and the like may be used.

[0080] The content of the benzotriazole-based compound and the tolyltriazole-based compound in the contained resin layer is preferably 0.001 wt% to 10.0 wt%, and more preferably 0.01 wt% to 5.0 wt%. If the content is less than 0.001 wt%, it is difficult to further improve the rust prevention property over a long period of time, and if the content is more than 10.0 wt%, molding is difficult, and it is difficult to achieve the rust prevention property over a long period of time. (metal salt of an inorganic acid)

[0081] According to the present invention, the resin layers 1 and 2 may or may not independently contain a metal salt of an inorganic acid. Among them, one or more types selected from a metal borosilicate, a metal molybdate, and the like may be used. The content of the metal salt of an inorganic acid in the contained resin layer is preferably 0.001 wt% to 10.0 wt%, and more preferably 0.01 wt% to 5.0 wt%. If the content is less than 0.001 wt%, it is difficult to further improve the rust prevention property over a long period of time, and if the content is more than 10.0 wt%, molding is difficult and it is difficult to achieve the rust prevention property over a long period of time. <Verfahren zur Herstellung einer Rostschutz-Folie>

[0082] To obtain the resin layer 2 containing the deliquescent rust inhibitor according to the present invention, a recycled resin composition recycled from a rust-inhibiting film having two layers, namely a resin layer containing an amine- and / or ammonia-based vaporizable rust inhibitor and a resin layer containing a deliquescent rust inhibitor, is used. The amount of the recycled resin composition for a rust-inhibiting film used in the resin layer 2 according to the present invention is preferably 10.0 wt% or more, more preferably 15.0 wt% or more, even more preferably 20.0 wt% or more, and most preferably 25.0 wt% or more in the resin layer 2. The larger the blended amount, the more actively the resin composition for a rust-inhibiting film recycled from the reclaimed rust-inhibiting film is used, which is preferable.

[0083] The rust-proof film is manufactured by mixing the raw materials polyolefin resin, rust inhibitor, and various additives required for the resin layer 2 with the recycled resin composition for a rust-proof film as required, and forming it by a known film forming method such as extrusion forming, blow forming, vacuum forming, or compression forming.

[0084] Accordingly, the rust-proof film can have any shape, such as a film, a sheet, a bag, a layered sheet, a cylinder, or a box. At this time, the resin layers 1 and 2 can be formed by co-extrusion to form a total of two or more layers. Alternatively, the separately obtained resin layers 1 and 2 can be laminated together using known methods such as bonding or welding. <Verwendung der Rostschutz-Folie>

[0085] The surface on the resin layer 1 side can be molded or processed into a bag shape so that it lies on the inside of a container or packaging film, that is, on the side facing the article to be stored or packaged and protected from rust. Conversely, the surface on the resin layer 2 side can be molded or processed into a bag shape so that it lies on the inside of a container or packaging film, that is, on the side facing the article to be stored or packaged and protected from rust.

[0086] However, the vaporizable amine- and / or ammonia-based rust inhibitor may have the property of being ground to a small average particle diameter during addition to the resin and kneading, as well as during molding. Therefore, if particle diameter control is required, attention must be paid to the average particle diameter after molding.

[0087] In addition, when at least two resin layers are used, moisture gradually penetrates from the surface of the resin layer 2 into the interior and the rust-inhibiting gas is also gradually generated, so that a high rust-inhibiting effect can be stably maintained for a long period of time without the need to add a slow-release rust-inhibiting agent such as a carboxylic acid-modified polyolefin-based polymer, a wax, a nonionic surfactant, and an inorganic porous material.

[0088] In addition, the object to be protected from rust can include a variety of objects such as cast iron, steel plates and galvanized steel plates, which are known to be packaged with the help of the rust protection film or a bag made of it for rust protection. (Examples and comparison examples)

[0089] The recovered rust-inhibiting films 1 and 2 shown in Table 1 (consisting of two layers, namely a resin layer containing a vaporizable amine- and / or ammonia-based rust inhibitor and a resin layer containing a deliquescent rust inhibitor) were prepared. Subsequently, 50 kg of each of these rust-inhibiting films 1 and 2 were separately ground, melted at 140 °C or 240 °C, and granulated into pellets with a diameter of approximately 5 mm. Then, if necessary, dried at 90 °C for 120 minutes to reduce the contents of the vaporizable amine- and / or ammonia-based rust inhibitor and water. Table 2 shows the conditions for melting, kneading and drying of the thus obtained recycled resins A to g, as well as the contents of the evaporable amine- and / or ammonia-based rust inhibitor, the deliquescent rust inhibitor and the water in the recycled resin and the recovered rust inhibitor film.

[0090] Recycled resins e to g are examples where no drying was performed after melting and granulation at 140 °C. In this case, the rust inhibitor and water contents in the recycled resins are not constant, even when the amounts of ammonium benzoate or cyclohexylamine carbamate (CHC), sodium nitrite, and water in the recovered rust-protection films are the same. The reason for this is unclear, but it is suspected to be related to a low melting temperature and whether drying was performed.

[0091] Further, polyethylene (PE), the respective rust inhibitor, and the recycled resin listed in Table 2 were mixed so that the compositions of the obtained resin layers 1 and 2 were as shown in Table 3 below.

[0092] Each component was blow-molded at 140°C to form resin layer 1 and resin layer 2 shown in Table 3, thereby obtaining rust-inhibiting films with the layer configurations shown in Table 3. The presence or absence of foaming, YI, ΔYI, and the rust-inhibiting effect of these rust-inhibiting films were determined as described below. The results are shown in Table 4. In Table 3, the total amount of each component contained in each layer corresponds to the total amount including the component derived from the recycled resin in the layer containing the recycled resin. The proportion of the component derived from the recycled resin is shown as a fraction of the total amount of each component. In addition, resin layer 3 in Table 3 corresponds to the outermost layer that does not contain any rust inhibitor. (Presence or absence of foam formation) Method: Visual inspection for the presence or absence of foam formation (YI and ΔYI) Sample: obtained by stacking 12 rust protection films Measured value: Average value of five measured values ​​per sample Instrument: Spectrophotometer SD-7000 from NIPPON DENSHOKU INDUSTRIES Co, Ltd. Light source: specularly reflected light (SCI) Measurement method: According to ASTM D1925 standard, 12 rust protection films were stacked, five points of a sample were measured, and the average value was taken as YI. ΔYI stands for the difference between YI 0 of the recovered rust-proof film 1 or 2 and YIx of the rust-proof film 1 or 2 using the recycled resin composition for a rust-proof film (Equation 1). ΔYI=(YIx of the rust-proof film 1 or 2 using the recycled resin composition for the rust-proof film)−(YI0 of the recovered rust-proof film 1 or 2)

[0093] It should be noted that when measuring 12 sheets stacked on top of each other, a smaller scatter of measured values ​​and a larger YI can be measured than when measuring each sheet individually, which allows color change to be measured with high accuracy. (rust protection effect)

[0094] A test piece [A] described below was hung in a frame measuring 100 mm length × 100 mm width × 150 mm height with a nylon fishing line, and the frame was gusseted and closed with the prepared film.

[0095] This test form was placed in the test environment [B] described below for a certain period of time and then the condition of the surface rust was evaluated using the evaluation method [C] described below. [A] Test piece

[0096] Cast iron (JIS G 5501), size: 30 mm in diameter × 8 mm [B] Test environment

[0097] Cycle test conditions (12 hours / 1 cycle)

[0098] Hold at 25 °C and 70% RH (4 hours) → Transition to 50 °C and 95% RH (2 hours) → Hold at 50 °C and 95% RH (4 hours) → Transition to 25 °C and 70% RH (2 hours) [C] Valuation method

[0099] Duration: 3 days (6 cycles)

[0100] Criteria: No: no rust or discoloration Yes: rust spots and color changes

[0101] The content of each rust inhibitor in the rust-proof film and the recycled resin composition in Tables 1, 2 and 3 was determined as follows. (General measuring conditions)

[0102] Measurement method: HPLC method

[0103] Detector: Shodex CD-5 electrical conductivity detector for ion chromatography

[0104] Concentration: calculated from the peak area using a previously created calibration curve (Measurement conditions for sodium nitrite content)

[0105] The rust-inhibiting pellet / film (10 g) was added to a stirred solution of 100 g of water and 100 mL of xylene. After stirring and dissolving at 80 °C, the resin and rust inhibitor were separated, and the solution was cooled to room temperature to obtain an aqueous solution consisting only of the rust inhibitor and water. The aqueous solution was measured under the following conditions. Measurement conditions Column used: Shodex IC I-524 (protective column IC IA-G) Eluent: aqueous phthalic acid solution (2.5 mM) Flow rate: 1.5 mL / min. (Measurement conditions for the content of ammonium benzoate)

[0106] The rust-inhibiting pellet / film (10 g) was added to a stirred solution of 100 g of water and 100 mL of xylene. After stirring and dissolving at 80 °C, the resin and rust inhibitor were separated, and the solution was cooled to room temperature to obtain an aqueous solution consisting only of the rust inhibitor and water. The aqueous solution was measured under the following conditions. Measurement conditions Column used: Shodex IC YK-421 (protective column IC YK-G) Eluent: aqueous tartaric acid solution (5 mM) Flow rate: 1.0 mL / min. (Measurement conditions for the content of cyclohexylamine carbamate (CHC))

[0107] The rust-inhibiting pellet / film (10 g) was added to a stirred solution of 150 g of a 10 mM nitric acid aqueous solution and 30 mL of xylene. After stirring and dissolving at 80 °C, the resin and rust inhibitor were separated, and the solution was cooled to room temperature to obtain an aqueous solution consisting only of the rust inhibitor and water. The aqueous solution was measured under the following conditions. Measurement conditions Column used: Shodex IC YK-421 (protective column IC YK-G) Eluent: stirred solution of an aqueous 1 mM nitric acid solution and acetonitrile in a mixing ratio of 3:7 Flow rate: 1.0 mL / min.

[0108] The water content in the rust-proof film and the recycled resin composition in Tables 1, 2, and 3 was measured using a Karl Fischer moisture meter (AQV-2200S from HIRANUMA Co., Ltd.).

[0048] [Table 1] Content (wt%) of each component in the entire rust protection film Rust protection film Ammonium benzoate CHC Sodium nitrite Water Slide 1 0,87 0,48 0,65 Slide 2 0,40 0,30 0,43 [Table 1 (continued)] Property and components (wt%) of each layer in rust protection film Rust protection film resin layer Thickness (µm) PE Ammonium benzoate CHC Sodium nitrite Slide 1 Inner layer Resin layer 1 32 97,8 2,2 Outer layer Resin layer 2 48 99,2 0,8 Slide 2 Inner layer Resin layer 2 30 99,0 1,0 Intermediate layer Resin layer 1 40 99,0 1,0 Outer layer Resin layer 3 30 100,0 [Table 1 (continued)] Properties of the rust protection film Rust protection film Presence or absence of foam formation DO 0 Presence or absence of rust Slide 1 No 5 No Slide 2 No 8 No

[0049] [Table 2] Recycled resin Recovered rust protection film Recycling treatment conditions Conditions for melting and kneading Conditions for drying Temperature (°C) Ventilation Temperature (°C) Time (min) A 1 240 Yes 90 120 B 2 240 Yes 90 120 C 1 240 Yes No No D 1 140 No 90 120 e 1 140 No No No f 1 140 No No No g 1 140 No No No [Table 2 (continued)] Recycled resin Component contained in the recycled resin (excluding PE) (wt.%) Ammonium benzoate CHC Sodium nitrite Water A 0,04 0,10 0,04 B 0,04 0,05 0,03 C 0,06 0,10 0,23 D 0,11 0,21 0,03 e 0,15 0,21 0,31 f 0,24 0,12 0,22 g 0,23 0,13 0,32

[0050] [Table 3] Rust protection film resin layer Thickness (µm) Recycled resin and content (wt%) Amount (wt%) of newly blended PE Example 1 Inner layer Resin layer 1 32 97,8 Outer layer Resin layer 2 48 A (16,5) 82,7 Example 2 Inner layer Resin layer 1 32 97,8 Outer layer Resin layer 2 48 A (33,0) 66,2 Example 3 Inner layer Resin layer 1 32 97,8 Outer layer Resin layer 2 48 A (50,0) 49,2 Example 4 Inner layer Resin layer 1 32 97,8 Outer layer Resin layer 2 48 C (16,5) 82,7 Example 5 Inner layer Resin layer 1 32 97,8 Outer layer Resin layer 2 48 D (16,5) 82,7 Example 6 Inner layer Resin layer 2 30 B (50,0) 49,0 Intermediate layer Resin layer 1 40 99,0 Outer layer Resin layer 3 30 100,0 See Example 1 Inner layer Resin layer 1 32 C (33,0) 64,8 Outer layer Resin layer 2 48 99,2 See Example 2 Inner layer Resin layer 1 32 D (33,0) 64,8 Outer layer Resin layer 2 48 99,2 See Example 3 Inner layer Resin layer 1 32 97,8 Outer layer Resin layer 2 48 A (66,7) 32,5 See Example 4 Inner layer Resin layer 1 32 97,8 Outer layer Resin layer 2 48 e (16,5) 82,7 See Example 5 Inner layer Resin layer 1 32 97,8 Outer layer Resin layer 2 48 f (16,5) 82,7 See Example 6 Inner layer Resin layer 1 32 97,8 Outer layer Resin layer 2 48 g (16,5) 82,7 [Table 3 (continued)] Rust protection film Total amount of each component contained in each layer Component derived from recycled resin Total ammonium benzoate (wt%) Total CHC (wt%) Total sodium nitrite (wt%) Ammonium benzoate (ppm) CHC (ppm) Sodium nitrite (ppm) Water (ppm) Example 1 Inner layer 2,2 Outer layer 0,8 66 165 66 Example 2 Inner layer 2,2 Outer layer 0,8 132 330 132 Example 3 Inner layer 2,2 Outer layer 0,8 200 500 200 Example 4 Inner layer 2,2 Outer layer 0,8 99 165 380 Example 5 Inner layer 2,2 Outer layer 0,8 182 347 50 Example 6 Inner layer 1,0 200 150 Intermediate layer 1,0 250 Outer layer See Example 1 Inner layer 2,2 198 330 759 Outer layer 0,8 See Example 2 Inner layer 2,2 363 693 99 Outer layer 0,8 See Example 3 Inner layer 2,2 Outer layer 0,8 266 667 267 See Example 4 Inner layer 2,2 Outer layer 0,8 248 347 512 See Example 5 Inner layer 2,2 Outer layer 0,8 396 198 363 See Example 6 Inner layer 2,2 Outer layer 0,8 380 215 528 [Table 4] Presence or absence of foam formation YIx ΔYI Presence or absence of rust Example 1 No 18 13 No Example 2 No 25 20 No Example 3 No 30 25 No Example 4 No 18 13 No Example 5 No 18 13 No Example 6 No 29 21 No See Example 1 Yes 40 35 Not carried out See Example 2 Yes 42 37 Not carried out See Example 3 Yes 38 33 Not carried out See Example 4 Yes 37 32 Not carried out See Example 5 Yes 42 37 Not carried out See Example 6 Yes 47 42 Not carried out

[0109] Each example is an example in which the recycled resin composition for an anti-rust sheet was used as the material for preparing the resin layer 2, and which was formulated to contain 20 ppm to 220 ppm of ammonium benzoate or CHC and 400 ppm or less of water, the components of which are derived from the recycled material. According to each of the examples of the present invention, no foaming is observed in the anti-rust sheet, and a predetermined amount of each rust inhibitor can be contained. In addition, the anti-rust effect was similar to that of Sheets 1 and 2, and no rust was observed.

[0110] Comparative Examples 1 and 2 are examples in which the recycled resin composition for a rust-preventive film was used as a material for preparing the resin layer 1. Furthermore, Comparative Examples 3 to 6 are examples in which the recycled resin composition for a rust-preventive film was used as a material for preparing the resin layer 2 and were formulated to contain more than 220 ppm of ammonium benzoate and / or more than 400 ppm of water.

[0111] As in Comparative Examples 1 and 2, when the resin layer 1 contained the recycled resin composition for an anti-rust film, foaming was observed in the resin layer 1. Furthermore, as in Comparative Examples 3 to 6, when the recycled resin composition for an anti-rust film was contained in the resin layer 2 in an amount greater than a predetermined amount, foaming was observed. Furthermore, it was found that in order to use the recycled resin compositions e to g used in Comparative Examples 4 to 6 as an anti-rust film in the same manner as in the examples, the content of the recycled resin compositions e to g must be reduced, and consequently, the amount of the recycled resin composition that can be incorporated into the anti-rust film must be reduced.

[0112] Furthermore, both Film 1 and Film 2 in Table 1 do not contain the recycled resin composition for a rust-preventive film according to the present invention, but are rust-preventive films made using materials that are not recycled. The YI 0 of slides 1 and 2 is 5 and 8 respectively. These are slides used as criteria for determining the ΔYI, which indicates the degree of yellowing.

[0113] The YIx value in Table 4 is 30 or less in each example, but at least 37 in each comparative example. Furthermore, the ΔYI value is 25 or less in each example, but at least 32 in each comparative example. These results show that the rust-preventive film of the present invention exhibits a lower degree of yellowing. In each comparative example, the degree of yellowing was high.

[0114] Furthermore, the rust-proof film in each example exhibited rust-proof performance similar to that of rust-proof films 1 and 2 with the same composition but without recycled resin. Note that the rust-proof performance was not evaluated because foaming was observed in the rust-proof film in each comparative example and the degree of yellowing was high. QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] WO 2018 / 079458

[0005]

Claims

A recycled resin composition for an anti-rust film, comprising: a polyolefin resin; 0.02 wt% to 0.20 wt% of an evaporable amine- and / or ammonia-based rust inhibitor; a deliquescent rust inhibitor; and 0.30 wt% or less of water. A method for producing a recycled resin composition for a rust-inhibiting film, which comprises:melting, kneading, and optionally drying a rust-inhibiting film having a layered structure comprising a polyolefin resin layer containing a vaporizable amine- and / or ammonia-based rust inhibitor and a polyolefin resin layer containing a deliquescent rust inhibitor, the recycled resin composition for a rust-inhibiting film containing a polyolefin resin, 0.02% to 0.20% by weight of the vaporizable amine- and / or ammonia-based rust inhibitor, the deliquescent rust inhibitor, and 0.30% by weight or less of water. A layered rust-preventive film comprising a polyolefin resin layer 1 containing a vaporizable amine- and / or ammonia-based rust-preventive agent, and a polyolefin resin layer 2 containing a deliquescent rust-preventive agent, wherein the polyolefin resin layer 2 contains a polyolefin resin, 20 ppm to 220 ppm of a vaporizable amine- and / or ammonia-based rust-preventive agent, and 400 ppm or less of water, which are derived from a recycled resin composition for a rust-preventive film. The rust-proof film according to claim 3, wherein a YI value measured by stacking 12 rust-proof films is 35.0 or less. A method for producing a rust-inhibiting film, the rust-inhibiting film having a layered structure comprising a polyolefin resin layer 1 containing a vaporizable amine- and / or ammonia-based rust-inhibiting agent, and a polyolefin resin layer 2 containing a deliquescent rust-inhibiting agent, comprising: the polyolefin resin layer 2 is obtained by mixing a recycled resin composition for a rust-inhibiting film with a polyolefin resin and a deliquescent rust-inhibiting agent to have a content of 20 ppm to 220 ppm of the vaporizable amine- and / or ammonia-based rust-inhibiting agent and 400 ppm or less of water derived from the recycled resin composition.