WO2024247643A1 - Solution de séparation pour stratifiés de feuille d'aluminium et procédé de séparation et de récupération de stratifiés de feuille d'aluminium l'utilisant - Google Patents

Solution de séparation pour stratifiés de feuille d'aluminium et procédé de séparation et de récupération de stratifiés de feuille d'aluminium l'utilisant Download PDF

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WO2024247643A1
WO2024247643A1 PCT/JP2024/017260 JP2024017260W WO2024247643A1 WO 2024247643 A1 WO2024247643 A1 WO 2024247643A1 JP 2024017260 W JP2024017260 W JP 2024017260W WO 2024247643 A1 WO2024247643 A1 WO 2024247643A1
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aluminum foil
separation solution
formic acid
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separation
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Japanese (ja)
Inventor
直樹 東
翔 合志
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Toyo Aluminum KK
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Toyo Aluminum KK
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a separation solution for aluminum foil laminates, which is used to separate an aluminum foil laminate having a resin laminated on at least one side of the aluminum foil into aluminum foil and resin, and a method for separating and recovering an aluminum foil laminate using the same.
  • aluminum foil with resin laminated on at least one side has been widely used as a packaging material for food and medicine, in applications that require barrier properties to protect the contents from external environments such as oxygen, water vapor, and ultraviolet rays.
  • aluminum foil is used in electronic materials, etc., due to its electrical properties and ease of processing.
  • JP2020-515655A discloses a method for separating a metal layer from a resin layer by using a separation fluid that contains a mixture of water and a short-chain carboxylic acid, as well as phosphoric acid and an alkali metal hydroxide that reduce dissolution of the metal layer.
  • the separation technology described in Patent Document 1 is not applicable to all kinds of resins, but rather is a technology that selects the type of resin that is laminated, and therefore is not applicable to PVC, which is in particular in demand for recycling as described above, and also requires a processing time of one hour or more for resins other than PVC. Therefore, there is a problem in that the separation technology described in Patent Document 1 is not sufficiently satisfactory for actually implementing (putting into practical use) recycling of aluminum foil laminates on a commercial scale.
  • the present invention aims to provide a separation technology that can separate PVC from aluminum foil PVC laminates, and can also separate the aluminum foil from other aluminum foil laminates in a shorter time than conventional technologies.
  • the inventors conducted extensive research into methods for separating the resin layer and aluminum foil of an aluminum foil laminate (hereinafter also simply referred to as "laminate"), and discovered that by using a solution containing formic acid, a carboxylic acid ester, and water as main components in a specific ratio, the aluminum foil laminate can be easily separated into the aluminum foil and the resin, thus completing the present invention.
  • a separation solution for aluminum foil laminates which contains formic acid at 1 wt% or more and 98 wt% or less, a carboxylate ester consisting of a formate ester having 9 or less carbon atoms and/or an acetate ester having 9 or less carbon atoms at 1 wt% or more and 98 wt% or less, and contains water at 1 wt% or more and 90 wt% or less, and the sum of the contents of the formic acid and the carboxylate ester is 10 wt% or more and 99 wt% or less, and the sum of the contents of the formic acid, the carboxylate ester, and the water is 100 wt% or less.
  • a method for separating a resin layer and aluminum foil using the above-mentioned aluminum foil laminate separation solution comprises the steps of crushing a laminate containing aluminum foil and resin into pieces of 1 mm or more and 70 mm or less in size using a crusher, immersing the crushed pieces in the above-mentioned aluminum foil laminate separation solution, and leaving or stirring the pieces at a temperature of 20°C to 99°C for 1 minute to 72 hours to peel off and separate the aluminum foil and the resin.
  • the separation solution of the present invention allows the carboxylic acid ester to penetrate the resin layer in the laminate, helping to separate the resin layer with formic acid, making it easy to separate even difficult-to-separate resin layers such as PVC.
  • the separation solution of the present invention further contains one or more additives selected from the group consisting of ketones, ethers, alkylbenzenes, dioxolanes and cycloalkanes in an amount of 1 wt % to 89 wt %, and the sum of the contents of the additives, formic acid, carboxylic acid ester and water is preferably 100 wt % or less.
  • the separation solution of the present invention may further contain phosphoric acid and an alkali metal hydroxide for the purpose of adjusting the pH of the solution and adjusting the passivation of the aluminum foil in the laminate.
  • the carboxylic acid ester plays a role in penetrating the resin layer in the laminate, and by helping the formic acid separate the resin layer, even difficult-to-separate resin layers such as PVC can be easily separated.
  • the separating solution for aluminum foil laminates of the present invention contains formic acid at 1 wt% to 98 wt%, a carboxylate ester consisting of a formic acid ester having 9 or less carbon atoms and/or an acetate ester having 9 or less carbon atoms at 1 wt% to 98 wt%, water at 1 wt% to 90 wt%, and the sum of the contents of the formic acid and the carboxylate ester is 10 wt% to 99 wt%, and the sum of the contents of the formic acid, the carboxylate ester, and water is 100 wt% or less.
  • a carboxylate ester consisting of a formic acid ester having 9 or less carbon atoms and/or an acetate ester having 9 or less carbon atoms at 1 wt% to 98 wt%
  • water at 1 wt% to 90 wt%
  • the sum of the contents of the formic acid and the carboxylate ester is
  • Formic acid is a type of carboxylic acid, which is an organic acid. Unlike strong acids such as hydrochloric acid and nitric acid, carboxylic acids react violently with aluminum foil and do not disappear during separation from the resin layer. On the other hand, formic acid exhibits the strongest acidity among monovalent aliphatic carboxylic acids, and has a large acidity constant K a of 1.8 ⁇ 10 -4 .
  • the acidity constant K a of acetic acid is 1.8 ⁇ 10 -5
  • the K of formic acid is 10 times larger, so that the adhesion at the aluminum interface and the resin layer interface is cut, and the separation between the aluminum foil and the resin layer is further promoted.
  • formic acid does not ionize most monovalent aliphatic carboxylic acids. Therefore, in order to promote the separation of aluminum laminates by formic acid, based on Le Chatelier's principle, it is important to (a) increase the concentration of formic acid so that the reaction equilibrium shifts toward the side that exerts the separating action, (b) increase the amount of carboxylic acid that ionizes in the reaction field, and, as a physical effect, (c) make it easier for formic acid to penetrate the resin and penetrate into the interface where the laminates are bonded.
  • formic acid In the separation solution of the present invention, formic acid must be contained at 1 wt% to 98 wt%, and the sum of the content with the carboxylic acid ester described below must be 10 wt% to 99 wt%. If the formic acid content is less than 1 wt%, the separation action will not work sufficiently due to Le Chatelier's principle. On the other hand, if there is only formic acid, that is, if the formic acid content is 100 wt% and does not contain any carboxylic acid ester, the physical penetration into the resin layer will be insufficient as described above, and the resin layer will not be able to be sufficiently separated.
  • the content of formic acid in the separation solution is not particularly limited as long as the sum of the contents of formic acid and carboxylic acid ester is 10 wt% or more and 99 wt% or less, but is preferably 9 wt% or more and 98 wt% or less, more preferably 15 wt% or more and 80 wt% or less, and even more preferably 35 wt% or more and 55 wt% or less.
  • the sum of the contents of formic acid and carboxylic acid ester in the separation solution is preferably 10 wt% or more and 99 wt% or less, more preferably 30 wt% or more and 99 wt% or less, and even more preferably 40 wt% or more and 85 wt% or less. If the sum of the contents of formic acid and carboxylic acid ester exceeds 99 wt%, the remaining water will be less than 1 wt%, making it difficult to obtain the effect of hydrolysis described below. On the other hand, if the sum of the contents of formic acid and carboxylic acid ester is less than 10 wt%, the effect of separating the laminate by formic acid and carboxylic acid ester cannot be obtained.
  • the separation solution of the present invention may further contain acids other than formic acid to the extent that they do not affect the aluminum foil, as long as the separation solution contains formic acid at 1 wt% to 98 wt% and the sum of the contents of formic acid and carboxylic acid ester is 10 wt% to 99 wt%.
  • the separation solution contains formic acid at 1 wt% to 98 wt% and the sum of the contents of formic acid and carboxylic acid ester is 10 wt% to 99 wt%.
  • acids other than formic acid include carboxylic acids such as acetic acid, propionic acid, citric acid, and oxalic acid, and dilute sulfuric acid at 10 wt% or less.
  • the separation solution contains formic acid at 1 wt% to 98 wt% and the sum of the contents of formic acid and carboxylic acid ester is 10 wt% to 99 wt%
  • the content of carboxylic acids other than formic acid in the separation solution is not particularly limited, but is preferably 69 wt% or less, and more preferably 22.5 wt% or less.
  • the carboxylate ester is not limited as long as it is a formate ester having 9 or less carbon atoms and/or an acetate ester having 9 or less carbon atoms, and may be, for example, one or more selected from the group consisting of methyl formate, ethyl formate, propyl formate, butyl formate, pentyl formate, hexyl formate, heptyl formate, octyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, and heptyl acetate.
  • the carboxylate ester penetrates the resin layer of PVC, OPP, or the like, swelling the resin layer and promoting separation from the aluminum foil.
  • the separation solution preferably contains 1 wt% to 98 wt% carboxylate, and the sum of the content with formic acid is preferably 10 wt% to 99 wt%. If the solution does not contain carboxylate, the formic acid will not penetrate the resin layer sufficiently, and the resin layer of PVC, OPP, etc. will not be sufficiently separated. On the other hand, in the separation solution of the present invention that contains at least 1 wt% formic acid, if the content of carboxylate is greater than 98 wt%, the content of the remaining water excluding formic acid will be less than 1 wt% at most, making it difficult to obtain the effect of water (due to hydrolysis) described below.
  • the content of the carboxylate ester in the separation solution is more preferably 5 wt% to 65 wt%, and even more preferably 20 wt% to 65 wt%.
  • carboxylic acids such as formic acid and acetic acid
  • esters that are normally immiscible with water can be miscible with esters up to a maximum of 9 carbon atoms.
  • the carbon number exceeds 9, the aqueous solution becomes less miscible, and if the water and the carboxylate ester separate, it becomes difficult for them to function as a separation solution for the laminate.
  • the separation solution contains 1 wt % to 90 wt % water.
  • the sum of the contents of formic acid, carboxylate, and water is 100 wt % or less.
  • a very small portion of the carboxylate is hydrolyzed in the separation solution under the acidic condition of formic acid to form formic acid or acetic acid, which allows the separation action of the laminate to be sustained for a long period of time.
  • the hydrolysis of normal carboxylate requires an acid catalyst such as a strong acid such as nitric acid or hydrochloric acid, so that the hydrolysis does not proceed sufficiently with water alone.
  • the separation solution of the present invention even though the equilibrium shifts in the direction of ionization of formic acid due to hydrolysis of the carboxylic acid ester in the presence of water, promoting the separation action of the laminate, the carboxylic acid ester is hardly lost in the reaction. Therefore, in the present invention, a separation solution in which formic acid, carboxylic acid ester, and water are present in moderate amounts is preferred, and more specifically, in addition to the above-mentioned range, the water content is more preferably 5 wt% to 50 wt%, and even more preferably 5 wt% to 35 wt%.
  • the separation solution of the present invention may contain one or more additives (solvents) selected from the group consisting of ketones, ethers, alkylbenzenes, dioxolanes, and cycloalkanes as the remainder other than the above-mentioned components.
  • solvents selected from the group consisting of ketones, ethers, alkylbenzenes, dioxolanes, and cycloalkanes as the remainder other than the above-mentioned components.
  • the separation solution of the present invention contains water, the separation solution may be separated into two layers depending on the ratio of carboxylic acid esters and formic acid, so that the above-mentioned solvents may be added appropriately to favorably mix the separation solution.
  • ketones, ethers, aromatic hydrocarbons, and heterocyclic compounds do not have the same effect as carboxylic acid esters, they have the effect of penetrating into the resin layer, so it is more preferable to add the above-mentioned solvents to the remainder.
  • Ketones that can be used in the present invention include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone, acetophenone, benzophenone, etc., and among these, methyl ethyl ketone is often used as a true solvent for resin coating agents and is preferred from the standpoint of solubility.
  • Ethers include dimethyl ether, ethyl methyl ether, diethyl ether, diphenyl ether, ethylene oxide, tetrahydrofuran (THF), furan, 1,4-dioxane, anisole, benzofuran, dibenzofuran, crown ether, etc., and taking into account miscibility with water, tetrahydrofuran (THF), furan, and 1,4-dioxane are preferred.
  • alkylbenzenes xylene or toluene can be added as appropriate.
  • Dioxolane is preferred because it has good miscibility with water and penetrates well into the resin layer.
  • cycloalkanes cyclohexane, cycloheptane, cyclooctane, etc. can be used.
  • the separation solution of the present invention contains additives such as ketones, ethers, alkylbenzenes, dioxolanes, and cycloalkanes as described above
  • the content of the additives is preferably 1 wt% or more and 89 wt% or less, and more preferably 16.7 wt% or more and 50 wt% or less.
  • the separation solution of the present invention may contain additives such as buffer solutions to the extent that the effect of separating the laminate is not impaired.
  • additives such as buffer solutions to the extent that the effect of separating the laminate is not impaired.
  • a buffer solution consisting of phosphoric acid and an alkali metal hydroxide has the effect of stabilizing the pH of the separation solution, but on the other hand, the addition of an excessive amount of additives may slow down the reaction that promotes the separation of the laminate. Therefore, in the present invention, the amount of additive added is preferably 3 wt % or less.
  • Example 1 Preparation of separation solutions for examples and comparative examples [Example 1] To a 100 mL glass bottle were added 45 g of formic acid (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 20 g of butyl acetate (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 25 g of purified water (ASSWS-20, AS ONE Corporation), and 10 g of methyl ethyl ketone (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), and the mixture was stirred at room temperature for 10 minutes to prepare the separation solution of Example 1.
  • formic acid Fluji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • 20 g of butyl acetate Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • 25 g of purified water ASSWS-20, AS ONE Corporation
  • Example 2 To a 100 mL glass bottle were added 22.5 g of formic acid (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 22.5 g of acetic acid (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 20 g of butyl acetate (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), and 35 g of purified water (ASSWS-20, AS ONE Corporation), and the mixture was stirred at room temperature for 10 minutes to prepare a separation solution of Example 2.
  • formic acid Fluji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • acetic acid Fluji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • 20 g of butyl acetate Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • ASSWS-20 purified water
  • Example 3 To a 100 mL glass bottle were added 80 g of formic acid (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 5 g of butyl acetate (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 5 g of purified water (AS ONE Corporation, ASSWS-20), and 10 g of methyl ethyl ketone (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), and the mixture was stirred at room temperature for 10 minutes to prepare a separation solution of Example 3.
  • formic acid Fluji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • 5 g of butyl acetate Fluji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • 5 g of purified water AS ONE Corporation, ASSWS-20
  • 10 g of methyl ethyl ketone Fruji Film Wako Pure Chemical Industries, Ltd.,
  • Example 4 To a 100 mL glass bottle were added 65 g of formic acid (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 20 g of butyl acetate (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 5 g of purified water (ASSWS-20, AS ONE Corporation), and 10 g of methyl ethyl ketone (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), and the mixture was stirred at room temperature for 10 minutes to prepare a separation solution of Example 4.
  • Example 5 To a 100 mL glass bottle were added 45 g of formic acid (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 40 g of butyl acetate (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 5 g of purified water (ASSWS-20, AS ONE Corporation), and 10 g of methyl ethyl ketone (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), and the mixture was stirred at room temperature for 10 minutes to prepare a separation solution of Example 5.
  • formic acid Fluji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • butyl acetate Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • 5 g of purified water ASSWS-20, AS ONE Corporation
  • 10 g of methyl ethyl ketone Fruji Film Wako Pure Chemical Industries, Ltd., special rea
  • Example 6 To a 100 mL glass bottle were added 20 g of formic acid (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 65 g of butyl acetate (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 5 g of purified water (ASSWS-20, AS ONE Corporation), and 10 g of methyl ethyl ketone (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), and the mixture was stirred at room temperature for 10 minutes to prepare a separation solution of Example 6.
  • Example 7 To a 100 mL glass bottle were added 20 g of formic acid (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 20 g of butyl acetate (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 10 g of purified water (AS ONE Corporation, ASSWS-20), and 50 g of methyl ethyl ketone (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), and the mixture was stirred at room temperature for 10 minutes to prepare a separation solution of Example 7.
  • Example 8 To a 100 mL glass bottle, 45 g of formic acid (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 5 g of butyl acetate (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), and 50 g of purified water (AS ONE Corporation, ASSWS-20) were added and stirred at room temperature for 10 minutes to prepare a separation solution of Example 8.
  • formic acid Fluji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • butyl acetate Fruji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • purified water AS ONE Corporation, ASSWS-20
  • Example 9 To a 100 mL glass bottle were added 15 g of formic acid (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 15 g of butyl acetate (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 1 g of purified water (AS ONE Corporation, ASSWS-20), and 69 g of methyl ethyl ketone (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), and the mixture was stirred at room temperature for 10 minutes to prepare a separation solution of Example 9.
  • formic acid Fluji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • butyl acetate Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • 1 g of purified water AS ONE Corporation, ASSWS-20
  • 69 g of methyl ethyl ketone Fruji Film Wako Pure Chemical Industries, Ltd., special
  • Example 10 To a 100 mL glass bottle were added 29 g of formic acid (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 1 g of hexyl acetate (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 1 g of purified water (AS ONE Corporation, ASSWS-20), and 69 g of methyl ethyl ketone (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), and the mixture was stirred at room temperature for 10 minutes to prepare a separation solution of Example 10.
  • formic acid Fluji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • 1 hexyl acetate Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • 1 g of purified water AS ONE Corporation, ASSWS-20
  • 69 g of methyl ethyl ketone Fruji Film Wako Pure Chemical Industries
  • Example 11 To a 100 mL glass bottle, 98 g of formic acid (Fujifilm Wako Pure Chemical Industries, Ltd., special reagent grade), 1 g of hexyl acetate (Fujifilm Wako Pure Chemical Industries, Ltd., special reagent grade), and 1 g of purified water (AS ONE Corporation, ASSWS-20) were added and stirred at room temperature for 10 minutes to prepare a separation solution of Example 11.
  • formic acid Flujifilm Wako Pure Chemical Industries, Ltd., special reagent grade
  • 1 hexyl acetate Frujifilm Wako Pure Chemical Industries, Ltd., special reagent grade
  • purified water AS ONE Corporation, ASSWS-20
  • Example 12 To a 100 mL glass bottle, 15 g of formic acid (Fujifilm Wako Pure Chemical Industries, Ltd., special reagent grade), 84 g of butyl acetate (Fujifilm Wako Pure Chemical Industries, Ltd., special reagent grade), and 1 g of purified water (AS ONE Corporation, ASSWS-20) were added and stirred at room temperature for 10 minutes to prepare a separation solution of Example 12.
  • formic acid Flujifilm Wako Pure Chemical Industries, Ltd., special reagent grade
  • butyl acetate Frujifilm Wako Pure Chemical Industries, Ltd., special reagent grade
  • purified water AS ONE Corporation, ASSWS-20
  • Example 13 To a 100 mL glass bottle, 15 g of formic acid (Fuji Film Wako Pure Chemical Industries, Ltd., special grade reagent), 15 g of ethyl acetate (Fuji Film Wako Pure Chemical Industries, Ltd., special grade reagent), and 70 g of purified water (AS ONE Corporation, ASSWS-20) were added and stirred at room temperature for 10 minutes to prepare a separation solution of Example 13.
  • formic acid Fluji Film Wako Pure Chemical Industries, Ltd., special grade reagent
  • ethyl acetate Fruji Film Wako Pure Chemical Industries, Ltd., special grade reagent
  • purified water AS ONE Corporation, ASSWS-20
  • Example 14 To a 100 mL glass bottle were added 45 g of formic acid (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 20 g of methyl acetate (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), 25 g of purified water (ASSWS-20, AS ONE Corporation), and 10 g of methyl ethyl ketone (Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade), and the mixture was stirred at room temperature for 10 minutes to prepare a separation solution of Example 14.
  • formic acid Fluji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • 20 g of methyl acetate Fuji Film Wako Pure Chemical Industries, Ltd., special reagent grade
  • 25 g of purified water ASSWS-20, AS ONE Corporation
  • 10 g of methyl ethyl ketone Fruji Film Wako Pure Chemical Industries, Ltd., special
  • Example 15 33 g of sodium hydroxide (Fujifilm Wako Pure Chemical Industries, Ltd., granular, special grade reagent) and 77 g of purified water (AS ONE Corporation, ASSWS-20) were placed in a 100 mL PE container and stirred at room temperature for 30 minutes to prepare a 33 wt% aqueous solution of sodium hydroxide. Then, 30 g of phosphoric acid (Fujifilm Wako Pure Chemical Industries, Ltd., Wako Grade 1) and 70 g of purified water (AS ONE Corporation, ASSWS-20) were placed in another 100 mL PE container and stirred at room temperature for 30 minutes to prepare a 30 wt% aqueous solution of phosphoric acid.
  • sodium hydroxide Flujifilm Wako Pure Chemical Industries, Ltd., granular, special grade reagent
  • purified water AS ONE Corporation, ASSWS-20
  • Example 16 To a 100 mL glass bottle were added 9 g of formic acid (Fujifilm Wako Pure Chemical Industries, Ltd., special reagent grade), 1 g of octyl formate (Inoue Fragrance Manufacturing Co., Ltd., octyl formate), 1 g of purified water (AS ONE Corporation, ASSWS-20), and 89 g of methyl ethyl ketone (Fujifilm Wako Pure Chemical Industries, Ltd., special reagent grade), and the mixture was stirred at room temperature for 10 minutes to prepare a separation solution of Example 16.
  • formic acid Flujifilm Wako Pure Chemical Industries, Ltd., special reagent grade
  • 1 octyl formate Inoue Fragrance Manufacturing Co., Ltd., octyl formate
  • purified water AS ONE Corporation, ASSWS-20
  • 89 g of methyl ethyl ketone Frujifilm Wako Pure Chemical Industries, Ltd
  • Example 17 To a 100 mL glass bottle were added 1 g of formic acid (Fujifilm Wako Pure Chemical Industries, Ltd., special reagent grade), 9 g of isoamyl formate (Tokyo Chemical Industry Co., Ltd., purity 95% or higher), 1 g of purified water (AS ONE Corporation, ASSWS-20), and 89 g of methyl ethyl ketone (Fujifilm Wako Pure Chemical Industries, Ltd., special reagent grade), and the mixture was stirred at room temperature for 10 minutes to prepare a separation solution of Example 17.
  • formic acid Flujifilm Wako Pure Chemical Industries, Ltd., special reagent grade
  • 9 g of isoamyl formate Tokyo Chemical Industry Co., Ltd., purity 95% or higher
  • 1 g of purified water AS ONE Corporation, ASSWS-20
  • 89 g of methyl ethyl ketone Frujifilm Wako Pure Chemical Industries, Ltd., special rea
  • Example 18 To a 100 mL glass bottle, 98 g of formic acid (Fujifilm Wako Pure Chemical Industries, Ltd., special reagent grade), 1 g of methyl formate (Tokyo Chemical Industry Co., Ltd., purity 95% or higher), and 1 g of purified water (AS ONE Corporation, ASSWS-20) were added and stirred at room temperature for 10 minutes to prepare a separation solution of Example 18.
  • formic acid Flujifilm Wako Pure Chemical Industries, Ltd., special reagent grade
  • 1 methyl formate Tokyo Chemical Industry Co., Ltd., purity 95% or higher
  • purified water AS ONE Corporation, ASSWS-20
  • Example 19 To a 100 mL glass bottle, 1 g of formic acid (special grade reagent, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), 98 g of isoamyl formate (purity 95% or more, manufactured by Tokyo Chemical Industry Co., Ltd.), and 1 g of purified water (AS ONE Corporation, ASSWS-20) were added and stirred at room temperature for 10 minutes to prepare a separation solution of Example 19.
  • formic acid special grade reagent, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • 98 g of isoamyl formate purity 95% or more, manufactured by Tokyo Chemical Industry Co., Ltd.
  • purified water AS ONE Corporation, ASSWS-20
  • Example 20 To a 100 mL glass bottle, 5 g of formic acid (special grade reagent, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), 5 g of isoamyl formate (purity 95% or higher, manufactured by Tokyo Chemical Industry Co., Ltd.), and 90 g of purified water (AS ONE Corporation, ASSWS-20) were added and stirred at room temperature for 10 minutes to prepare a separation solution of Example 19.
  • formic acid special grade reagent, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • isoamyl formate purity 95% or higher, manufactured by Tokyo Chemical Industry Co., Ltd.
  • purified water AS ONE Corporation, ASSWS-20
  • Test Piece 1 PVC Configuration
  • 45 ⁇ m 8021 material manufactured by Toyo Aluminum Co., Ltd.
  • a urethane-based adhesive was used as the adhesive, and a base agent (manufactured by Toyo Ink Co., Ltd.: base agent TMK-55, solid content 30% by mass) and a hardener (CAT56-3K, solid content 70% by mass) were prepared, and 100 parts by weight, 10 parts by weight, and 40 parts by weight of the base agent, hardener, and ethyl acetate were mixed until the color was uniform, and a 25% by weight urethane resin solution was prepared.
  • the coating liquid was mixed just before coating, and the mixed liquid was applied to the glossy side of aluminum foil using a bar coater #16 so that the weight after drying would be 5.0 g/ m2 , and then dried at 100°C for 40 seconds.
  • a 60 ⁇ m thick hard polyvinyl chloride film (Sumitomo Bakelite Co., Ltd.: VSS-6702) was laminated using a small laminator at a nip temperature of 90° C. and a speed of 5 m/min. Furthermore, a urethane-based adhesive was applied to the matte surface of the aluminum foil in the same manner as the glossy surface side, and then dried.
  • a 60 ⁇ m-thick hard polyvinyl chloride film (VSS-6702, manufactured by Sumitomo Bakelite Co., Ltd.) was laminated thereon, and cured at 40° C. for 4 days to prepare test specimen 1 (laminate) for evaluating the separation solution in the examples and comparative examples.
  • test specimen 1 was cut into 2 mm x 10 mm, the lid was removed, and test specimen 1 was submerged in each separation solution and the lid was replaced.
  • the samples were rated as follows: those in which the PVC peeled off in the separation solution within 1 hour were given an "A”, those in which the PVC peeled off in the separation solution within 5 hours were given a "B”, those in which the PVC peeled off in the separation solution within 24 hours were given a "C”, and those in which the PVC did not peel off in the separation solution even after 24 hours were given an "F".
  • Test Specimen 2 (OPP Configuration)
  • 20 ⁇ m 1N30 material manufactured by Toyo Aluminum Co., Ltd.
  • a urethane-based adhesive was used as the adhesive
  • a base agent manufactured by Rock Paint Co., Ltd.: base agent RU-77, solid content 60% by mass
  • a hardener H-5, solid content 75% by mass
  • 150 parts by weight, 15 parts by weight, and 80 parts by weight of the base agent, hardener, and ethyl acetate were mixed until the color became uniform, and a 41% by weight urethane resin solution was prepared.
  • the coating liquid was mixed just before coating, and the mixed liquid was applied to the glossy side of aluminum foil using a bar coater #12 so that the weight after drying would be 3.0 g/ m2 , and then dried at 100°C for 40 seconds.
  • a 20 ⁇ m thick OPP (P2102 manufactured by Toyobo Co., Ltd.) was laminated using a small laminator at a nip temperature of 60° C. and a speed of 5 m/min. Thereafter, the laminate was cured at 40° C. for 2 days to prepare a test specimen 2 (laminate) for evaluating the separation solution of the examples and comparative examples.
  • test piece 2 was cut into 10 mm x 10 mm, the lid was removed, and test piece 2 was submerged in each separation solution and the lid was replaced.
  • the OPP that peeled off in the separation solution within 30 minutes was given an "A”
  • the OPP that peeled off in the separation solution within 45 minutes was given a "B”
  • the OPP that peeled off in the separation solution within 60 minutes was given a "C”
  • the OPP that did not peel off in the separation solution even after 60 minutes was given an "F”.
  • ⁇ Evaluation Test 3> ⁇ Evaluation test of separation solution> As test specimen 3, a commercially available PVC PTP sheet (Mevalotin Tablet 5, manufactured by Daiichi Sankyo Co., Ltd.) was used. 100 g of the separation solution prepared in each Example and Comparative Example was placed in a 100 mL glass bottle (mouth inner diameter x body diameter x height: ⁇ 31.9 x ⁇ 48.5 x 87 mm). Next, one rotor (As One Corporation, shape tapered, length 25 mm, diameter 8 mm, material PTFE) was placed in the bottle, and the bottle was covered with aluminum foil to prevent the separation solution from volatilizing.
  • a commercially available PVC PTP sheet (Mevalotin Tablet 5, manufactured by Daiichi Sankyo Co., Ltd.) was used. 100 g of the separation solution prepared in each Example and Comparative Example was placed in a 100 mL glass bottle (mouth inner diameter x body diameter x height: ⁇ 31.9 x ⁇ 48.5
  • the glass bottle containing the separation solution was set in a 6-way heating and stirring dry bath (As One Corporation: HDBS-6) and heated while stirring at 200 rpm until it reached 95 ° C. After confirming with a thermometer that the separation solution had reached 95 ° C., test piece 3 was cut into 10 mm x 10 mm, the lid was removed, and test piece 3 was submerged in each separation solution and the lid was replaced.
  • a 6-way heating and stirring dry bath As One Corporation: HDBS-6
  • test piece 3 was cut into 10 mm x 10 mm, the lid was removed, and test piece 3 was submerged in each separation solution and the lid was replaced.
  • the samples were rated as follows: those in which the PVC peeled off in the separation solution within 15 minutes were given an "A”, those in which the PVC peeled off in the separation solution within 30 minutes were given a "B”, those in which the PVC peeled off in the separation solution within 60 minutes were given a "C”, and those in which the PVC did not peel off in the separation solution even after 60 minutes were given an "F”.
  • ⁇ Evaluation Test 4> ⁇ Evaluation test of separation solution>
  • a commercially available NYCPP component manufactured by Dai Nippon Printing Co., Ltd., Al laminate film D-EL40H(3) 200 mm x 100 m, 25 ⁇ m nylon film/adhesive/40 ⁇ m corrosion-resistant aluminum/60 ⁇ m polypropylene coat
  • 100 g of the separation solution prepared in each Example and Comparative Example was placed in a 100 mL glass bottle (mouth inner diameter x body diameter x height: ⁇ 31.9 x ⁇ 48.5 x 87 mm).
  • one rotor (As One Corporation, shape tapered, length 25 mm, diameter 8 mm, material PTFE) was placed in the bottle, and the bottle was covered with aluminum foil to prevent the separation solution from volatilizing. Furthermore, the glass bottle containing the separation solution was set in a 6-way heating and stirring dry bath (As One Corporation: HDBS-6) and heated while stirring at 200 rpm until it reached 95 ° C. After confirming with a thermometer that the separation solution had reached 95 ° C., test piece 4 was cut into 10 mm x 10 mm, the lid was removed, and test piece 4 was submerged in each separation solution and the lid was replaced.
  • a 6-way heating and stirring dry bath As One Corporation: HDBS-6
  • test piece 4 was cut into 10 mm x 10 mm, the lid was removed, and test piece 4 was submerged in each separation solution and the lid was replaced.
  • the samples were rated as follows: those in which the CPP peeled off in the separation solution within 15 minutes were rated as "A”, those in which the CPP peeled off in the separation solution within 30 minutes were rated as “B”, those in which the CPP peeled off in the separation solution within 60 minutes were rated as "C”, and those in which the CPP did not peel off in the separation solution even after 60 minutes were rated as "F”.
  • Table 1 shows the compositions of the separating solutions of Examples 1 to 20 and Comparative Examples 1 to 6, and the evaluation results of Evaluation Tests 1 to 4 using the separating solutions of each of the Examples and Comparative Examples.
  • the separation solutions of Examples 1 to 20 shown in Table 1 contain formic acid at 1 wt% or more and 98 wt% or less, carboxylic acid esters having 9 or less carbon atoms at 1 wt% or more and 98 wt% or less, and water at 1 wt% or more and 90 wt% or less.
  • the sum of the contents of the formic acid and the carboxylic acid ester is 10 wt% or more and 99 wt% or less, and the sum of the contents of the formic acid, the carboxylic acid ester, and the water is 100 wt% or less.
  • evaluation tests 1 to 4 it was found that the separation effect of the aluminum foil laminate was excellent.
  • the aluminum foil laminate separation solution of the present invention can separate PVC and aluminum foil as shown in Table 1, and can also separate aluminum foil from other aluminum foil laminates in a shorter time than the conventional technology. It was found that the separation solution can be used.

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Abstract

La présente invention concerne une technique de séparation par laquelle le PVC peut être séparé d'un stratifié de PVC à feuille d'aluminium et une feuille d'aluminium peut être séparée d'autres stratifiés de feuille d'aluminium en moins de temps que par l'intermédiaire de techniques précédentes. La présente invention concerne une solution de séparation pour stratifiés de feuille d'aluminium, la solution étant caractérisée en ce qu'elle contient : de 1 à 8% en poids d'acide formique inférieur ; de 1 à 98% en poids d'un ester d'acide carboxylique comprenant un ester d'acide formique ayant 9 atomes de carbone ou moins et/ou un ester d'acide acétique ayant 9 atomes de carbone ou moins ; de 1 à 90% en poids d'eau. La somme de la teneur en acide formique et en ester d'acide carboxylique est de 10 à 99% en poids, et la somme de la teneur de l'acide formique, de l'ester d'acide carboxylique et de l'eau est de 100% en poids ou moins. L'invention concerne également un procédé de séparation et de récupération de stratifiés de feuille d'aluminium à l'aide de ladite solution de séparation.
PCT/JP2024/017260 2023-05-31 2024-05-09 Solution de séparation pour stratifiés de feuille d'aluminium et procédé de séparation et de récupération de stratifiés de feuille d'aluminium l'utilisant Ceased WO2024247643A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1157651A (ja) * 1997-08-08 1999-03-02 Ishikawajima Harima Heavy Ind Co Ltd シュレッダーダストの処理方法及び装置
JP2020040302A (ja) * 2018-09-11 2020-03-19 日立化成株式会社 両性金属の回収方法及び再生両性金属の製造方法
JP2020515655A (ja) * 2016-12-15 2020-05-28 ザペラテック ゲゼルシャフト ミット ベシュレンクテル ハフツング 包装材料をリサイクルするための方法及び装置
JP2021526091A (ja) * 2018-06-01 2021-09-30 ザペラテック ゲゼルシャフト ミット ベシュレンクテル ハフツング 不動態化剤を用いて多層材料をリサイクルするための分離流体、方法及び装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1157651A (ja) * 1997-08-08 1999-03-02 Ishikawajima Harima Heavy Ind Co Ltd シュレッダーダストの処理方法及び装置
JP2020515655A (ja) * 2016-12-15 2020-05-28 ザペラテック ゲゼルシャフト ミット ベシュレンクテル ハフツング 包装材料をリサイクルするための方法及び装置
JP2021526091A (ja) * 2018-06-01 2021-09-30 ザペラテック ゲゼルシャフト ミット ベシュレンクテル ハフツング 不動態化剤を用いて多層材料をリサイクルするための分離流体、方法及び装置
JP2020040302A (ja) * 2018-09-11 2020-03-19 日立化成株式会社 両性金属の回収方法及び再生両性金属の製造方法

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