WO2024075412A1 - Film anti-rouille - Google Patents

Film anti-rouille Download PDF

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Publication number
WO2024075412A1
WO2024075412A1 PCT/JP2023/029927 JP2023029927W WO2024075412A1 WO 2024075412 A1 WO2024075412 A1 WO 2024075412A1 JP 2023029927 W JP2023029927 W JP 2023029927W WO 2024075412 A1 WO2024075412 A1 WO 2024075412A1
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WO
WIPO (PCT)
Prior art keywords
rust
acid
film
resin layer
resin composition
Prior art date
Application number
PCT/JP2023/029927
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English (en)
Japanese (ja)
Inventor
志郎 澤田
晴司 鳥山
Original Assignee
株式会社アイセロ
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Filing date
Publication date
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Publication of WO2024075412A1 publication Critical patent/WO2024075412A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent

Definitions

  • the present invention relates to an anti-rust film.
  • a rust-preventive film that includes a resin molded body having a resin layer containing an ammonium carboxylate with an average particle size of 20 ⁇ m or more, and a substrate layer containing one or more of a metal nitrite, a carboxylic acid, a benzotriazole-based compound, a tolyltriazole-based compound, and a metal carboxylate.
  • the present invention makes effective use of the two-layered anti-rust film, consisting of a resin layer containing an amine and/or ammonia-based volatile anti-rust agent and a resin layer containing a deliquescent anti-rust agent, after recovery, to obtain a recycled resin composition for anti-rust film, which is a recycled resin, by treatment under milder conditions.
  • a recycled resin composition for anti-rust film a new anti-rust film can be manufactured without foaming, and a combination of anti-rust agents that cannot be contained in one layer can be contained in one layer.
  • the objective of the present invention is to obtain an anti-rust film that has sufficient anti-rust performance and uses a recycled resin composition for anti-rust film, thereby promoting the reuse of used anti-rust film, etc.
  • a recycled resin composition for anti-rust films comprising a polyolefin resin, 0.02 to 0.20% by weight of an amine and/or ammonia-based volatile anti-rust agent, a deliquescent anti-rust agent, and 0.30% by weight or less of water. 2.
  • a method for producing a recycled resin composition for use in a rust-preventive film comprising laminating a polyolefin resin layer containing an amine and/or ammonia-based volatile rust inhibitor and a polyolefin resin layer containing a deliquescent rust inhibitor, melting, kneading, and optionally drying the resulting rust-preventive film, the recycled resin composition containing the polyolefin resin, 0.02 to 0.20% by weight of the amine and/or ammonia-based volatile rust inhibitor, 0.30% by weight or less of the deliquescent rust inhibitor, and water.
  • the rust-preventive film according to 3. characterized in that the YI value measured by stacking 12 sheets of the rust-preventive film is 35.0 or less. 5.
  • a method for producing an anti-rust film comprising laminating a polyolefin resin layer 1 containing an amine and/or ammonia-based volatile rust inhibitor and a polyolefin resin layer 2 containing a deliquescent rust inhibitor, the method being characterized in that the polyolefin resin layer 2 is prepared by mixing a recycled resin composition for anti-rust films, a polyolefin resin, and a deliquescent rust inhibitor, and the recycled resin composition is made to contain 20 to 220 ppm of the amine and/or ammonia-based volatile rust inhibitor and 400 ppm or less of water.
  • used anti-rust films, anti-rust bags, etc. each of which is composed of two layers, an amine and/or ammonia-based volatile anti-rust agent-containing resin layer and a deliquescent anti-rust agent-containing resin layer, are collected, and the collected materials are subjected to a regeneration process, so that the collected materials can be reused as a regenerated resin composition for producing anti-rust films, containing a certain amount of amine and/or ammonia-based volatile anti-rust agent and containing a deliquescent anti-rust agent.
  • the composition will be referred to simply as "regenerated resin composition for anti-rust films”.
  • the recycled resin composition for the anti-rust film after recycling the above-mentioned used anti-rust film, anti-rust bag, etc. contains 0.02 to 0.20% by weight of the amine and/or ammonia-based volatile anti-rust agent not completely removed, further contains a deliquescent anti-rust agent, and contains 0.30% by weight or less of water.
  • the recycled resin composition for anti-rust film does not completely remove the rust inhibitor, so there is no need to treat the recovered anti-rust bags, etc. under harsher conditions such as temperature and time (harsh conditions for completely removing the rust inhibitor), and the treatment for regeneration can be performed under milder conditions such as temperature and time.
  • the amount of energy required to obtain the composition for anti-rust film from the recovered material and the amount of energy required to obtain a new anti-rust film can be reduced.
  • the new anti-rust film and the anti-rust bag produced by using this recycled resin composition for anti-rust film have a small content of the volatile anti-rust agent coexisting in the resin layer, so that they do not react with the deliquescent anti-rust agent, and as a result, they do not foam or discolor, such as yellowing, during film formation. If foaming occurs during film formation, the film formability decreases and the mechanical properties of the completed film decrease.
  • the anti-rust film of the present invention can be used as an anti-rust film having the same anti-rust performance as an anti-rust film using a material not derived from recycling. As a result, the cost, time and environmental load associated with the regeneration and reuse can be reduced, and the reuse of used anti-rust films can be promoted.
  • the recycled resin composition for the rust-preventive film of the present invention is a composition used exclusively for obtaining the rust-preventive film of the present invention, particularly the polyolefin resin layer 2. It can also be used for obtaining other rust-preventive films.
  • the recycled resin composition for anti-rust films is obtained by recovering and recycling one or more of anti-rust films that have been produced and used, anti-rust bags obtained therefrom, scraps of produced anti-rust films, surplus anti-rust films, products, etc.
  • the rust-preventive film before recovery is a rust-preventive film comprising a resin layer containing an amine and/or ammonia-based volatile rust inhibitor and a resin layer containing a deliquescent rust inhibitor laminated together.
  • This regeneration method is described below.
  • the recycled resin composition for the rust-preventive film of the present invention may contain a polyolefin resin and may contain at least 0.02% by weight of an amine and/or ammonia-based volatile rust inhibitor. To reduce the content to less than 0.02% by weight, a further extensive treatment is required, which may cause a deterioration in the physical properties of the resin itself in some cases.
  • a new rust-preventive film is obtained by blending a larger amount of the recycled resin composition for the rust-preventive film, the higher the content of the amine and/or ammonia-based volatile rust inhibitor in the recycled resin composition for the rust-preventive film, the less the recycled resin composition for the rust-preventive film can be used to manufacture the new rust-preventive film.
  • the recycled resin composition for anti-rust films used as a raw material for newly produced anti-rust films preferably has an amine and/or ammonia-based volatile anti-rust agent content of 0.20% by weight or less, more preferably 0.15% by weight or less, and even more preferably 0.10% by weight or less.
  • 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 even more preferably 0.22% by weight or less. Also, 0.05% by weight or more is preferable, more preferably 0.07% by weight or more, and even more preferably 0.10% by weight 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 heightened concern that water will evaporate and foam when a new rust-preventive film is obtained using the recycled resin composition for rust-preventive film. To reduce the content of the deliquescent rust inhibitor to less than 0.05% by weight, treatment under stricter conditions such as temperature and time will be required.
  • the recycled resin composition for the rust-preventive film has a low water content.
  • the water comes from the moisture absorption of the deliquescent rust inhibitor contained in the recycled resin composition.
  • the water content is preferably 0.30% by weight or less, more preferably 0.20% by weight or less, even more preferably 0.10% by weight or less, and most preferably 0.05% by weight or less.
  • the water may evaporate and foam, or the deliquescent rust inhibitors such as nitrite contained in the new rust-preventive film may be deliquesced, and the amount of the recycled resin composition for the rust-preventive film that can be used to manufacture a new rust-preventive film may have to be reduced.
  • the recycled resin composition for anticorrosive films in the present invention is a composition recycled from anticorrosive films, etc., which are composed of two layers, a resin layer containing an amine and/or ammonia-based volatile anticorrosive agent and a resin layer containing a deliquescent anticorrosive agent.
  • the recycled anticorrosive films referred to here include anticorrosive films that have been used for packaging as anticorrosive films, as well as anticorrosive films and materials thereof that have not been used due to production losses, etc.
  • the anti-rust film to be recovered is preferably a film that falls within the scope of the anti-rust film of the present invention.
  • the same amine and/or ammonia-based volatile rust inhibitor as above may be contained in the recovered rust-preventive film.
  • a certain amount of the recovered rust-preventive film recovered for regeneration may contain a rust-preventive film that does not contain an amine and/or ammonia-based volatile rust inhibitor, but it is preferable that the whole of the recovered rust-preventive film to be regenerated contains a rust-preventive film having a resin layer containing an amine and/or ammonia-based volatile rust inhibitor and a resin layer containing a deliquescent rust inhibitor, such as the rust-preventive film of the present invention.
  • the recycled resin composition for the rust-preventive film of the present invention is obtained from the once recovered rust-preventive film, and the recycled resin composition for the rust-preventive film is used to newly obtain the rust-preventive film of the present invention.
  • the newly obtained rust-preventive film after use may be recovered again and recycled into the recycled resin composition for the rust-preventive film of the present invention, and the obtained recycled resin composition for the rust-preventive film of the present invention may be used again to produce the rust-preventive film of the present invention, or this process may be repeated.
  • a method for producing such a recycled resin composition for anticorrosive films a method can be adopted in which the recovered anticorrosive film is pulverized by any means, heated and melted at a high temperature of 140° C. or higher to promote vaporization and disappearance, solidified and pelletized by any means, and then dried for about 60 to 150 minutes at about 80 to 95° C. as necessary.
  • the conditions such as temperature and time can be changed depending on the conditions of the apparatus and the recovered anticorrosive film, etc.
  • By employing such a heating, melting and drying means not only the water content but also the content of the amine and/or ammonia-based volatile rust inhibitor is reduced to obtain a recycled resin composition for use in the rust-preventive film of the present invention.
  • Such a method for producing a recycled resin composition for an anti-rust film makes it possible to actively recover and reuse used anti-rust films and the like, which have previously been difficult to reuse as resin compositions for anti-rust films.
  • the recycled resin composition for anti-rust films of the present invention which contains a polyolefin resin, 0.02 to 0.20% by weight of an amine and/or ammonia-based volatile rust inhibitor, a deliquescent rust inhibitor, and 0.30% by weight or less of water, and the manufacturing method thereof, are exclusively compositions for obtaining the anti-rust films of the present invention, and manufacturing methods thereof.
  • the recycled resin composition for anti-rust films may also be used to manufacture anti-rust films consisting of three or more layers.
  • the rust-preventive film of the present invention is basically constructed by laminating a polyolefin resin layer 1 containing an amine and/or ammonia-based volatile rust inhibitor and a polyolefin resin layer 2 containing a deliquescent rust inhibitor, and is characterized in that the polyolefin resin layer 2 contains 20 to 220 ppm of the amine and/or ammonia-based volatile rust inhibitor derived from a recycled resin composition for rust-preventive films, 400 ppm or less of the deliquescent rust inhibitor, and water.
  • the polyolefin resin layer 1 and the polyolefin resin layer 2 are directly laminated, 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.
  • an arbitrary layer may or may not be provided on the surface of the polyolefin resin layer 1 opposite to the surface on the polyolefin resin layer 2 side and/or the surface of the polyolefin resin layer 2 opposite to the surface on the polyolefin resin layer 1 side.
  • the polyolefin resin layer 1 and the polyolefin resin layer 2 may be simply referred to as the "resin layer 1" and the "resin layer 2", respectively.
  • the rust-preventive film of the present invention may be processed into a bag shape so that resin layer 1 faces the inside, i.e., the side facing the packaged item, and resin layer 2 faces the outside. When the film is made of three or more layers, resin layer 2 may be provided as the innermost layer. These films are used to package metallic electrical products, electrical parts, electronic parts, machine parts, automotive parts, etc.
  • the rust-preventive film of the present invention preferably has a YI value of 35.0 or less, more preferably 30.0 or less, even more preferably 25.0 or less, and most preferably 20.0 or less, measured by stacking 12 sheets of the rust-preventive film.
  • the rust-preventive film produced using the recycled resin composition for the rust-preventive film does not show any particular coloring (yellowing), and when used as a rust-preventive film or a rust-preventive bag for packaging, the contents can be visually confirmed without opening the package.
  • additives such as antiblocking agents (AB agents), lubricants, antioxidants, antistatic agents, ultraviolet absorbers, light stabilizers, oxygen absorbers, acid absorbers, flame retardants, nucleating agents, impact strength enhancers, plasticizers, release agents, colorants, fluorescent agents, compatibilizers, antifogging agents, fillers, auxiliary colorants, dispersants, stabilizers, modifiers, and antibacterial and antifungal agents can be added independently to the resin layers 1 and 2. However, it is necessary that they do not react with other components contained in the resin layers 1 and 2, and that they do not bleed out, etc., thereby contaminating, for example, the packaged item.
  • AB agents antiblocking agents
  • an ionomer resin or a functional group-containing polyolefin resin may or may not be blended in the resin layer 1 or the resin layer 2. According to the present invention, the rust inhibitor can be exhibited sufficiently for a long period of time.
  • the thickness of resin layers 1 and 2 is preferably independently 10 ⁇ m or more, more preferably 15 ⁇ m or more, and even more preferably 20 ⁇ m or more. Also, it is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, and even more preferably 100 ⁇ m or less. Furthermore, the combined thickness of resin layers 1 and 2 is preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more, and even more preferably 40 ⁇ m or more. And it is preferably 600 ⁇ m or less, more preferably 400 ⁇ m or less, and even more preferably 200 ⁇ m or less.
  • resins that can be commonly used for the resin layer 1 and the resin layer 2.
  • resins that can be commonly used for the resin layer 1 and the resin layer 2.
  • one or more resins can be independently selected from the following resins and used.
  • the compositions of the polyolefin resins contained in the resin layer 1 and the resin layer 2 may be different from each other or may be the same. If they are the same, it is preferable that when the anticorrosive film is recovered after use or the like and regenerated, it can be used as an anticorrosive film having the same resin composition as before the regeneration.
  • a polyolefin resin one or more types selected from polyolefin-based polymers, that is, olefin homopolymers and/or copolymers using olefins as monomers, can be selected and used.
  • Examples of the olefins (olefin monomers) that make up polyolefin-based polymers include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, and 1-octene.
  • 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 may be used alone or in combination of two or more types. In other words, the polyolefin-based polymer may be a mixture of various polymers.
  • the ethylene-based polymer includes ethylene homopolymer (polyethylene) and copolymer of ethylene and other monomer (ethylene copolymer).
  • ethylene homopolymer and ethylene copolymer include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE).
  • ethylene copolymer include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-pentene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, and an ethylene-4-methyl-1-pentene copolymer.
  • the ethylene units (structural units derived from ethylene) contained in the ethylene copolymer may account for more than 50% of the total number of structural units (usually 99.999% or less), but can account for, for example, 80.0 to 99.999% of the total number of structural units, or 90.0 to 99.995%, or even 99.0 to 99.990%.
  • propylene polymer examples include propylene homopolymers (polypropylene) and copolymers of propylene and other monomers (propylene copolymers).
  • propylene copolymers examples include propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-pentene copolymers, and propylene-1-octene copolymers.
  • the propylene units (structural units derived from propylene) contained in the propylene copolymer may account for 50% or more (usually 99.999% or less) of the total number of structural units, but can be, for example, 80.0 to 99.999% of the total number of structural units, or 90.0 to 99.995%, or even 99.0 to 99.990%.
  • the polyolefin polymer may contain a structural unit derived from a monomer other than olefin, as long as it does not impair the object of the present invention.
  • monomers other than olefin include 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.), and vinyl esters (vinyl acetate, vinyl propionate, maleic acid monoester, etc.).
  • the proportion of structural units derived from monomers other than olefins contained in the polyolefin polymer is preferably 40% or less (usually 0.001% or more) of the total number of structural units, for example, 0.001 to 25%, 0.005 to 15%, or even 0.01 to 10% of the total number of structural units.
  • the density of the polyolefin resin is preferably 0.880 to 0.950 g/cm 3.
  • melt flow rate is preferably in the range of 1.0 to 10.0 g/10 min, and by having an appropriate viscosity during melt processing, it becomes possible to include and coat the particulate ammonium carboxylate in the resin, and it becomes possible to prevent the rust inhibitor from falling off from the resin molded body.
  • the resin layer 1 contains an amine and/or ammonia-based volatile rust inhibitor as a rust inhibitor.
  • the amine and/or ammonia-based volatile rust inhibitor may be any of an aliphatic carboxylic acid ammonium salt, an aliphatic carboxylic acid amine salt, an aromatic carboxylic acid ammonium salt, and an aromatic carboxylic acid amine salt.
  • ammonium salts of aliphatic carboxylic acids such as ruthric acid
  • one or more organic amine salts selected from phosphoric acid, nitrous acid, carbonic acid, and carboxylate salts of mono-, di-, and tri-ethanolamine, n-, di-, and tert-butylamine, hexamethylenediamine, hexamethylenetetramine, mono- and di-cyclohexylamine, isopropylamine, oleylamine, naphthylamine, and diphenylamine can be used.
  • the resin layer 1 does not contain a deliquescent rust inhibitor in an amount that inhibits the effects of the present invention.
  • the content of the amine and/or ammonia-based volatile 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 contained therein. 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 achieve sufficient rust prevention, and if it exceeds 10.00% by weight, molding processing becomes difficult.
  • the amine and/or ammonia-based volatile rust inhibitor is contained in the resin layer 1 in a particulate form or in a state of being compatible with the resin layer. It may be in a particulate form or may be compatible with the resin layer. When it is in a particulate form, its average particle size (d50) is preferably 3 ⁇ m or more, more preferably 3 to 400 ⁇ m, even more preferably 3 to 200 ⁇ m, and most preferably 3 to 100 ⁇ m. Furthermore, the maximum particle size of the amine and/or ammonia-based volatile rust inhibitor contained in the resin layer 1 is preferably 5000 ⁇ m or less, more preferably 3000 ⁇ m or less, and even more preferably 500 ⁇ m or less.
  • the maximum particle size is the maximum particle size among the measured particle sizes of 1000 particles.
  • the particles of the amine and/or ammonia-based volatile rust inhibitor are covered with resin to form convex portions on the surface of the resin layer 1. The presence of such convex portions allows more gas for rust prevention to be generated, which contributes to improving rust prevention.
  • such convex portions on the film surface have the effect of preventing adhesion to the article to be rust-inhibited, and can prevent the particles of the amine and/or ammonia-based volatile rust inhibitor from directly contacting the article to be rust-inhibited and contaminating the surface of the article to be rust-inhibited.
  • the amine and/or ammonia-based volatile rust inhibitor when the amine and/or ammonia-based volatile rust inhibitor is contained in the resin layer in a compatible state, or when it is contained in the resin layer in particulate form as described above, the vaporization property can be adjusted depending on the characteristics such as volatility of each type of volatile rust inhibitor.
  • the powder of the amine and/or ammonia-based volatile rust inhibitor before blending may be pulverized to reduce the average particle size. Therefore, the above-mentioned average particle size in the present invention is a value related to the amine and/or ammonia-based volatile rust inhibitor contained in the resin layer 1 after the resin layer 1 is formed.
  • the amount of rust-preventing gas generated can be controlled, and the rust-preventing effect can be stably maintained for a long period of time.
  • the detailed mechanism is unclear, it is believed that by setting the particle size of the amine and/or ammonia-based volatile rust inhibitor within a specific range, convex portions are formed on the film surface, thereby providing a long-term rust prevention effect.
  • the resin layer 2 contains a deliquescent rust inhibitor as a rust inhibitor.
  • the deliquescent rust inhibitor in the present invention may be any of various metal nitrites and metal carbonates, and one or more of these may be used.
  • the metal nitrite one or more selected from sodium, potassium, calcium, magnesium, etc. of nitrite may be used, and as the metal carbonate, potassium salt or its hydrate may be used.
  • the content of these deliquescent rust inhibitors 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 2.
  • it is preferably 6.00% by weight or less, more preferably 4.00% by weight or less, and even more preferably 2.00% by weight or less. If it is less than 0.01% by weight, it may be difficult to achieve sufficient rust prevention, and if it exceeds 6.00% by weight, it may be difficult to perform molding or to achieve long-term rust prevention.
  • the resin layer 2 of the rust-preventive film of the present invention is obtained by containing the recycled resin composition for rust-preventive films of the present invention, and the total amount of the deliquescent rust inhibitor contained in the recycled resin composition for rust-preventive films, which is one of the raw materials, and the deliquescent rust inhibitor added as necessary, is the total amount of the deliquescent rust inhibitor contained in the resin layer 2 of the rust-preventive film.
  • the resin layer 2 When the resin layer 2 is used as the outer layer to form a packaging bag or the like in this way, moisture from the outside air is taken into the packaging, causing the deliquescent rust inhibitor in the outer layer to react with the amine and/or ammonia-based volatile rust inhibitor in the inner layer, promoting the evaporation of the amine and/or ammonia-based volatile rust inhibitor within the packaging, thereby achieving a rust-preventing effect. Furthermore, the rust-preventing effect can be improved by generating nitrous acid within the packaging.
  • the resin layer 2 contains 20 to 220 ppm by weight of an amine and/or ammonia-based volatile rust inhibitor derived from a recycled resin composition for anticorrosive films.
  • the content of the amine and/or ammonia-based volatile 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.
  • the content is preferably 200 ppm or less, more preferably 180 ppm or less, and even more preferably 160 ppm or less. If it exceeds 220 ppm, it may react with the deliquescent rust inhibitor in the resin layer 2, which may result in foaming.
  • the amine and/or ammonia-based volatile rust inhibitor derived from the recycled resin composition for the rust-preventive film referred to here may be the same compound as the amine and/or ammonia-based volatile rust inhibitor contained in the above-mentioned resin layer 1.
  • the resin layer 2 contains 20 to 220 ppm of the amine and/or ammonia-based volatile rust inhibitor, the reaction between the two can be suppressed.
  • the rust-preventive film of the present invention can be formed using the recycled resin composition for rust-preventive film of the present invention (which is basically a composition made by regenerating used rust-preventive film or its raw materials, etc.).
  • a recycled resin composition for rust-preventive 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 volatile rust inhibitor remains to a certain extent, so that the amine and/or ammonia-based volatile rust inhibitor remains by reducing the temperature, time, etc. of the treatment.
  • the amine and/or ammonia-based volatile rust inhibitor contained in the resin layer 2 and derived from the recycled resin composition for anti-rust films may have an average particle size smaller than that of the amine and/or ammonia-based volatile rust inhibitor contained in the recovered anti-rust film.
  • the resin layer 2 contains 400 ppm or less of water derived from the recycled resin composition for the anticorrosive film on a weight basis.
  • the water content of 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 water content exceeds 400 ppm, there is a high concern that the film will foam.
  • a metal carboxylate may or may not be contained independently in the resin layers 1 and 2.
  • the metal carboxylate may be either an aliphatic metal carboxylate or an aromatic metal carboxylate.
  • the metal salts of these carboxylates include 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, oleic acid, isohexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, isoheptanoic acid, isooctanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, 2-propylheptanoic acid, isoundecanoic acid, isododecanoic acid,
  • aliphatic 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, and the like; and metal salts such as sodium salts, potassium salts, calcium salts, and 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, and cinnamic acid.
  • aromatic carboxylic acids such as benzoic acid, aminobenzoic acid, salicylic acid, p-tert-buty
  • the content of the metal carboxylate 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 obtain sufficient rust prevention, and if it exceeds 10.0% by weight, not only is molding difficult, but it is also difficult to obtain long-term rust prevention.
  • a carboxylic acid may or may not be contained independently in each of the resin layers 1 and 2.
  • the carboxylic acid may be either an aliphatic carboxylic acid or an aromatic carboxylic acid.
  • These carboxylic acids include 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, oleic acid, isohexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, isoheptanoic acid, isooctanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, 2-propylheptanoic acid, isoundecanoic acid, isododecanoic acid, One or more of the following can
  • 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 prevention properties, and if it exceeds 10.0% by weight, not only will molding processing become difficult, but it will also be difficult to achieve long-term rust prevention properties.
  • 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 compounds selected from benzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole, etc. may be used.
  • the content of these benzotriazole-based compounds and tolyltriazole-based 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 prevention properties, and if it exceeds 10.0% by weight, not only will molding processing become difficult, but it will also be difficult to exert long-term rust prevention properties.
  • the resin layers 1 and 2 may or may not independently contain an inorganic acid metal salt. Among them, one or more selected from metal borosilicates, metal molybdates, etc. may be used.
  • the content of these inorganic acid metal salts in the resin layer is preferably 0.001 to 10.0% by weight, more preferably 0.01 to 5.0% by weight. If the content is less than 0.001% by weight, it is difficult to further improve the long-term rust prevention, and if the content exceeds 10.0% by weight, not only is molding difficult, but it is also difficult to exert long-term rust prevention.
  • a recycled resin composition is used that is recycled from a rust-preventive film consisting of two layers, a resin layer containing an amine and/or ammonia-based volatile rust inhibitor and a resin layer containing a deliquescent rust inhibitor.
  • the amount of the recycled resin composition for rust-preventive 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, even more preferably 20.0% by weight or more, and most preferably 25.0% by weight or more in the resin layer 2.
  • the raw material polyolefin resin, rust inhibitor, and various additives required for the resin layer 2 are mixed into the recycled resin composition for the anti-rust film as necessary, and the anti-rust film is produced by a well-known film molding method such as extrusion molding, inflation molding, vacuum molding, or pressure molding.
  • a film molding method such as extrusion molding, inflation molding, vacuum molding, or pressure molding.
  • any shape such as a film, a sheet, a bag, a laminated sheet, a cylinder, or a box can be obtained.
  • the resin layers 1 and 2 may be molded into a total of two or more layers by coextrusion. Also, the resin layers 1 and 2 obtained separately may be laminated by a known means such as adhesion or welding.
  • the surface on the resin layer 1 side may be molded or processed into a bag shape so that it is positioned inside a container or packaging sheet, i.e., on the side of the item to be stored or packaged and protected from rust, or conversely, the surface on the resin layer 2 side may be used so that it is positioned inside a container or packaging sheet, i.e., on the side of the item to be stored or packaged and protected from rust.
  • the amine and/or ammonia-based volatile rust inhibitors have the property of being crushed to a small average particle size while being added to and kneaded with the resin, and during the molding process, if the particle size of these particles is to be controlled, attention must be paid to the average particle size after molding. Furthermore, by employing at least two resin layers, moisture gradually penetrates from the surface of the resin layer 2 toward the inside, and the anti-rust gas generated is also gradually generated, so that a high anti-rust effect can be more stably maintained for a long period of time without adding anti-rust release agents such as carboxylic acid-modified polyolefin polymers, waxes, nonionic surfactants, inorganic porous bodies, etc. Furthermore, the target articles to be rust-proofed may include a wide range of articles, such as cast iron, steel plates, and galvanized steel plates, which are known to be packaged for rust prevention using rust-proofing films or bags made therefrom.
  • the recovered rust-preventive films 1 and 2 shown in Table 1 (having two layers, a resin layer containing an amine and/or ammonia-based volatile rust inhibitor and a resin layer containing a deliquescent rust inhibitor) were prepared. Next, 50 kg of each of these rust-preventive films 1 and 2 was crushed separately, melted at 140°C or 240°C, granulated into pellets of about 5 mm diameter, and then dried at 90°C for 120 minutes as necessary to reduce the amount of amine and/or ammonia-based volatile rust inhibitor and water.
  • each component was inflation-molded at 140°C to form resin layer 1 and resin layer 2 as shown in Table 3 below, to obtain anti-rust films with the layer configurations shown in Table 3.
  • the presence or absence of foaming, YI, ⁇ YI, and anti-rust performance were determined as follows. The results are shown in Table 4.
  • Table 3 the total of each component contained in each layer is the total including each component derived from the recycled resin for layers containing recycled resin. The content of each component derived from the recycled resin is shown as an internal number within the total of each component.
  • Resin layer 3 in Table 3 corresponds to the outermost layer that does not contain a rust inhibitor.
  • ⁇ YI (YIx of anti-rust film 1 or 2 using recycled resin composition for anti-rust film) ⁇ (YI 0 of recovered anti-rust film 1 or 2) (Equation 1)
  • Test piece Cast iron (JIS G 5501) Size: ⁇ 30mm x 8mm
  • the amount of water in the anti-rust films and recycled resin compositions in Tables 1, 2, and 3 was measured using a Karl Fischer moisture meter (Hiranuma Sangyo Co., Ltd.: AQV-2200S).
  • the recycled resin composition for anti-rust film was used as a material for obtaining the resin layer 2, and the recycled component ammonium benzoate or CHC was contained at 20 to 220 ppm, and water was contained at 400 ppm or less. According to each of the examples of the present invention, no foaming was observed in the anti-rust film, and a predetermined amount of each anti-rust agent was contained. In addition, the anti-rust performance was similar to that of films 1 and 2, and no rust was generated. Comparative Examples 1 and 2 are examples in which a recycled resin composition for an anticorrosive film was used as a material for obtaining a resin layer 1.
  • Comparative Examples 3 to 6 are examples in which a recycled resin composition for an anticorrosive film was used as a material for obtaining a resin layer 2, and in which the ammonium benzoate content was more than 220 ppm and/or the water content was more than 400 ppm.
  • the recycled resin composition for the rust-preventive film when the recycled resin composition for the rust-preventive film was contained in the resin layer 1, foaming was observed in the resin layer 1.
  • Comparative Examples 3 to 6 when the recycled resin composition for the rust-preventive film was contained in the resin layer 2 in an amount exceeding a predetermined amount, foaming was observed.
  • neither film 1 nor film 2 in Table 1 was made using the recycled resin composition for the rust-preventive film of the present invention, but was made using materials that were not derived from recycling.
  • the YI0 of films 1 and 2 was 5 and 8, respectively. These films are the standard for determining ⁇ YI, which indicates the degree of yellowing.
  • the YIx value in Table 4 was 30 or less in each Example, but at least 37 in each Comparative Example.
  • the ⁇ YI value was 25 or less in each Example, but at least 32 in each Comparative Example.
  • the anti-rust films of each Example exhibited the same anti-rust properties as the anti-rust films 1 and 2, which had the same composition but did not use recycled resin. However, the anti-rust films of each Comparative Example were not evaluated for anti-rust properties because foaming was confirmed and the degree of yellowing was large.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention permet d'utiliser efficacement un film anti-rouille après récupération et d'obtenir, par traitement dans des conditions modérées, une composition de résine recyclée, qui est une résine recyclée, pour un film anti-rouille. La présente invention permet de produire, à l'aide de la composition de résine recyclée pour un film anti-rouille, un nouveau film anti-rouille sans générer de mousse et de telle sorte qu'une couche unique contienne une combinaison d'agents anti-rouille qui ne peut normalement pas être contenue dans une couche unique. Le problème à résoudre par la présente invention est d'obtenir un film anti-rouille ayant une performance anti-rouille plus satisfaisante et qui est obtenu à l'aide d'une composition de résine recyclée pour un film anti-rouille, de sorte à favoriser la réutilisation d'un film anti-rouille tel qu'un film anti-rouille usagé. La solution selon l'invention porte sur une composition de résine recyclée pour un film anti-rouille, la composition de résine recyclée étant caractérisée en ce qu'elle contient une résine de polyoléfine, 0,02 % à 0,20 % en poids d'un inhibiteur de rouille volatile à base d'amine et/ou d'ammoniac, un inhibiteur de rouille déliquescent et 0,30 % ou moins, en poids, d'eau.
PCT/JP2023/029927 2022-10-06 2023-08-21 Film anti-rouille WO2024075412A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01210340A (ja) * 1988-02-19 1989-08-23 Aisero Kagaku Kk 多層フイルム
JPH07186289A (ja) * 1993-11-09 1995-07-25 Cortec Corp 回収樹脂を含む防食性プラスチックフィルム
JP2006521471A (ja) * 2003-03-25 2006-09-21 ノーザン テクノロジーズ インターナショナル コーポレーション 腐食防止剤及び不活性充填材粒子を含む生分解性成形品

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01210340A (ja) * 1988-02-19 1989-08-23 Aisero Kagaku Kk 多層フイルム
JPH07186289A (ja) * 1993-11-09 1995-07-25 Cortec Corp 回収樹脂を含む防食性プラスチックフィルム
JP2006521471A (ja) * 2003-03-25 2006-09-21 ノーザン テクノロジーズ インターナショナル コーポレーション 腐食防止剤及び不活性充填材粒子を含む生分解性成形品

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