Method for recycling collected used plastic package

Abstract

To provide a film excellent in interlayer bondability and heat sealability by blending an adsorbent with a collected used plastic package to adsorb oil and fat, and surfactant remaining in the collected package.SOLUTION: A film comprising a resin composition comprising 100 pts.wt. of a collected used plastic package (A) and 0.05 pt.wt. or more and 10 pts.wt. or less of at least one adsorbent (B) selected from zeolite and hydrotalcite.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to the collection of used plastic packaging containers and zeolite or hygroscopic materials. A resin composition containing at least one adsorbent selected from dorotalcite and a resin composition containing the composition The present invention relates to a film having at least one layer comprising: [Background technology]

[0002] In recent years, environmental pollution caused by plastics has become a problem, and the material recycling of plastic products has become an issue. In addition, with the implementation of the Packaging and Container Recycling Law, There is a demand for recycling plastic packaging containers.

[0003] Generally, the process of recycling waste plastics and obtaining film involves These include washing, dehydrating, crushing, re-pelletizing, and film molding of waste plastic. If the product is a collection of used plastic packaging, the contents of the packaging may be It contains impurities such as oils, fats, and surfactants that are present in the product, but these remain even after the cleaning process. For this reason, films made from recycled plastic materials are being developed. Residual oils and surfactants can reduce the interlayer adhesion and heat sealability of the film. There is a problem that...

[0004] In addition, multi-layer molded products are often used for plastic packaging containers, but Because it is difficult to separate them, when recycling them, they become a mixture of various materials and are difficult to bend. The strength, impact strength, and heat seal strength of the product are all reduced. It has become difficult to do so.

[0005] Against this background, the removal of impurities contained in recycled packaging has been studied to date. It is being done.

[0006] For example, waste plastic containers and packaging and other general plastic product waste. Waste plastics containing vinyl chloride resin are treated with magnesium oxide and hydrotalcite. A method has been proposed in which an acid acceptor is added to suppress the generation of hydrochloric acid (Patent Document 1).

[0007] In addition, zeola is used in multi-layer plastic containers containing recycled resin layers from polyolefin-based packaging containers. Adding absorbents such as cellulose acetate to absorb hydrocarbon volatiles generated by thermal degradation, A recycled resin container with less waste has been proposed (Patent Document 2).

[0008] However, Patent Document 1 is about a method for suppressing hydrochloric acid, and Patent Document 2 is about a method for suppressing hydrocarbon volatilization. This study examines methods for reducing odors caused by adsorption of substances, including oils, fats, and surfactants. The heat seal strength and interlayer adhesive strength of the film have not been investigated. In addition, recycled products containing multiple plastics tend to have inferior physical properties. Therefore, it is difficult to reproduce the product, but these prior patents contain information on methods for improving the physical properties. There is no description. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Patent No. 4828836 [Patent Document 2] Japanese Patent Application Laid-Open No. 1995-33172 Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention is a method for recycling used plastic packaging containers by blending an adsorbent with the collected containers. The oils and surfactants remaining in the collected materials are adsorbed, and the layer remains even after the collected materials are recycled. The purpose of the present invention is to provide a film that has excellent adhesion and heat sealing properties. [Means for solving the problem]

[0011] As a result of intensive research into solving the above problems, the inventors of the present invention have found that the use of used plastic packaging The film is made of a resin composition to which a specific adsorbent is added for the recovered material from the packaging container. The present invention has been completed based on the discovery that the above problems can be solved.

[0012] That is, the present invention uses 100 parts by weight of recycled plastic packaging containers (A). , at least one adsorbent (B) selected from zeolite and hydrotalcite At least one layer is made of a resin composition containing 0.05 parts by weight or more and 10 parts by weight or less. It's a film. [Effects of the Invention]

[0013] The film of the present invention allows reuse of used packaging containers, reduces the environmental impact, and It is useful as a packaging film because it has excellent interfacial adhesion and heat sealing properties. DETAILED DESCRIPTION OF THE INVENTION

[0014] The resin composition according to one embodiment of the present invention will be described in detail below.

[0015] The resin composition of the present invention is prepared by mixing 100 layers of recycled plastic packaging containers (A). At least one adsorbent (B) selected from zeolites and hydrotalcites The resin composition contains 0.05 parts by weight or more and 10 parts by weight or less of the above.

[0016] The collected used plastic packaging containers (A) are plastic packaging containers (a1 ) (hereinafter simply referred to as "a1").

[0017] Plastic packaging containers (a1) are those whose main component is plastic such as thermoplastic resin. The thermoplastic resin is a packaging container. -vinyl alcohol copolymer, polyester, polystyrene, etc. It may be a single-component system containing one type of fat, or a composite system containing two or more types of fat. The packaging container is a composite system containing two or more types of thermoplastic resin.

[0018] The plastic packaging container (a1) preferably contains at least a polyolefin. .

[0019] The plastic packaging container (a1) is preferably made of polyolefin, polyester, polyolefin, or the like. at least one selected from the group consisting of ethylene-vinyl alcohol copolymers and ethylene-vinyl alcohol copolymers; More preferably, it is made of one of polyolefin and polyester or polyamide. In this case, the polyolefin and the polyethylene are at least one selected from the group consisting of Components made of composites of steril and other resins, polyolefin and other resins alone Composite materials made of separate materials, polyolefin and other resins as single materials, Examples of the form of the film include a laminate in which the film is laminated.

[0020] Polyolefins include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and Polyethylene, Polypropylene, Ethylene-Propylene Copolymer, Ethylene-Acrylate Copolymer Examples of the copolymer include ester copolymers and ethylene-methacrylate copolymers.

[0021] Polyamides include nylon 6, nylon 6,6, nylon 11, and nylon 12. Examples include:

[0022] Polyesters include polyethylene terephthalate and glycol-modified polyethylene terephthalate. Examples include polybutylene terephthalate (PETG resin), polybutylene terephthalate, and polylactic acid. do.

[0023] Among these, the resin contained in the plastic packaging container (a1) is a film molding resin. It is preferable that the resin contains at least polyolefin because it has excellent mechanical properties. Other resins include polyethylene terephthalate, polyamide, At least one member from the group consisting of ethylene-vinyl alcohol copolymers is preferred.

[0024] The plastic packaging container (a1) is made of the above-mentioned thermoplastic resin. It may also contain adhesive resins, adhesives, and inks, but these may be removed during the kneading process or during recycling. In order to prevent metal corrosion of the kneader and molding machine caused by outgassing during the molding process, It is preferred that the composition does not contain any compounds, particularly vinyl chloride resins.

[0025] The adhesive resin is not particularly limited, but may be polyether, polyester, silicone, or the like. Polyurethane resin, epoxy resin, vinyl resin, phenolic resin, polyolefin Examples of suitable polyolefins include polyolefins and acid-modified polyolefins.

[0026] The adhesive is not particularly limited, but may be one-component curing type, two-component curing type, non-curing type, or In addition, solvent-free adhesives and solvent-based adhesives are also available. Examples of solvent-free adhesives include polyethersulfones. adhesives, polyester adhesives, silicone adhesives, epoxy adhesives and urethane adhesives Examples of solvent-based adhesives include rubber adhesives, vinyl adhesives, and silicone adhesives. Examples include cone adhesives, epoxy adhesives, phenolic adhesives and olefin adhesives. can be.

[0027] Examples of halogen compounds include halogen-based flame retardants and halogen-based resins. Halogen-based flame retardants include halogenated diphenyl ether compounds, halogenated diphenyl alkyl compounds, and halogenated diphenyl alkyl compounds. compounds, halogenated phthalimide compounds, tris(polyhalogenphenoxy)triazine compounds, halogenated bisphenol A polymers, halogenated styrene-butadiene bromides Styrene-butadiene copolymer, halogenated styrene-butadiene random copolymer, halogenated styrene-butadiene butadiene graft copolymers, etc. Examples of halogen-based resins include vinyl chloride-based resins. Fat, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorosulfon Examples include polyethylene nitrate and chloroprene rubber.

[0028] The shape of the plastic packaging container (a1) is not particularly limited, but may be a film, a pouch, a container, or the like. Examples include container lids, bottles, cups, trays, and tubes.

[0029] The contents of the plastic packaging container (a1) include food, beverages, hygiene products, daily necessities, medicines, etc. Specific examples of the above foods include oily foods, seafood, fresh foods, dried foods, etc. These include dried foods, rice grains, beverages, processed foods, seasonings, spices, livestock products, and snacks. Examples of hygiene products and daily necessities include detergents, soaps, air fresheners, deodorants, shampoos, These include rinses, hair treatments, toothpaste, bath additives, and cosmetics. The plastic packaging container (a1) is a food packaging container, a sanitary packaging container or a daily necessities packaging container. It is preferable that the packaging container is at least one type selected from the group consisting of food packaging containers. and at least one selected from the group consisting of packaging containers and daily necessities packaging containers. Preferably, at least one selected from the group consisting of oily food, beverage detergent, and shampoo. It is even more preferable that the packaging container is a packaging container of the above formula.

[0030] In this application, the collected used plastic packaging containers (A) are the plastic packaging containers. This refers to waste plastic packaging containers (a1) that have been collected for reuse. Since the product has been discarded, the contents (packaged items) remaining in the packaging container and the disposal-recovery process The composition may also include other waste-derived materials that are mixed in during the recycling process.

[0031] The collected used plastic packaging containers (A) may contain residual packaged materials. The packaged item is selected from oils and fats or surfactants (a2) (hereinafter simply referred to as "a2"). In the case of at least one of these, the effect of adding the adsorbent (B) constituting the present invention is high, so this is preferred. Here, the at least one selected from oils and fats and surfactants (a2) is the above-mentioned hygiene It is the main component of detergents and other household items. When expressing the amount, it is expressed as the amount of solids excluding secondary components such as water and alcohol from (a2). .

[0032] The proportion of (a2) contained in the collected used plastic packaging containers (A) is 0.01 weight part or more out of 100 weight parts of recycled plastic packaging containers (A), Preferably, the total of (a1) and (a2) is 100 parts by weight or less. is.

[0033] When (a2) is an oil or fat, it is not particularly limited, but may be vegetable oil or animal oil or fat. Furthermore, the fatty acids constituting the above-mentioned oils and fats are not limited, and may be saturated fatty acids or unsaturated fatty acids. The saturated fatty acids may be any of the fatty acids. Examples of the saturated fatty acids include capric acid, lauric acid, and the like. Acid, Myristic Acid, Palmitic Acid, Stearic Acid, Arachidic Acid, Behenic Acid, Lignose Examples of the unsaturated fatty acids include phosphoric acid, cerotic acid, montanic acid, and melissic acid. For example, palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, gadolinium Examples include leic acid and arachidonic acid.

[0034] In addition, when (a2) is a surfactant, it is not limited to an anionic surfactant. Examples of surfactants include surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.

[0035] The anionic surfactant is not particularly limited, but examples thereof include fatty acid salts, aliphatic acid salts, and the like. Ethynate, hydroxyalkanesulfonate, alkane sulfonate, dialkylsulfonate Succinate salts, linear alkylbenzene sulfonates, branched alkylbenzene sulfonates Sulfonates, alkylnaphthalenesulfonates, alkylphenoxypolyoxyethylenepropanols Polyoxyethylene alkyl sulfophenyl ether salts, poly ... Diethylene lauryl ether sulfate, N-methyl-N-oleyl taurate sodium salt, N-Alkyl sulfosuccinic acid monoamide disodium salt, petroleum sulfonate, sulfated beef tallow Oil, fatty acid alkyl ester sulfate, alkyl sulfate, polyoxyethylene Styrene alkyl ether sulfate, fatty acid monoglyceride sulfate, polio Polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene styryl Phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl Polyoxyethylene alkylphenyl ether phosphate ester salt, polyoxyethylene alkylphenyl ether phosphate ester Terephthalate, partially saponified styrene-maleic anhydride copolymer, olefin-maleic anhydride Partially saponified acid copolymer, naphthalenesulfonate formalin condensate, alkyl polyol Salts of alkenyl polyoxyalkylene sulfoalkyl ethers, alkenyl polyoxyalkylene sulfo Examples include alkyl ether salts.

[0036] The cationic surfactant is not particularly limited, but examples thereof include alkylamines. Salts, quaternary ammonium salts (e.g., hexadecyltrimethylammonium chloride) , polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.

[0037] The amphoteric surfactant is not particularly limited, but examples thereof include carboxybetaine, Examples include aminocarboxylic acids, sulfobetaines, aminosulfuric acid esters, and imitazolines.

[0038] The nonionic surfactant is not particularly limited, but examples thereof include polyoxyethylene Polyoxyethylene alkyl phenyl ether compounds, polyoxyethylene alkyl phenyl ether compounds , polyoxyethylene polystyrylphenyl ether compounds, polyoxyethylene polyethylene Oxypropylene alkyl ether compounds, glycerin fatty acid partial ester compounds, Sorbitan fatty acid partial ester compounds, pentaerythritol fatty acid partial ester compounds compounds, propylene glycol mono-fatty acid ester compounds, sucrose fatty acid partial ester compounds compounds, polyoxyethylene sorbitan fatty acid partial ester compounds, polyoxyethylene isosorbitol fatty acid partial ester compounds, polyethylene glycol fatty acid ester compounds compounds, polyglycerin fatty acid partial ester compounds, polyoxyethylene castor oil compounds compounds, polyoxyethylene glycerin fatty acid partial ester compounds, fatty acid diethanol amide compounds, N,N-bis-2-hydroxyalkylamine compounds, polyoxy Ethylene alkylamine, triethanolamine fatty acid ester, trialkylamine oxide, polyethylene glycol, polyethylene glycol and polypropylene glycol Examples of copolymers include:

[0039] The adsorbent (B) contained in the resin composition of the present invention is zeolite or hydrotalcite. At least one selected from the group consisting of The oils and surfactants in the resin composition are well adsorbed, and the resulting resin composition is pressed. Excellent moldability.

[0040] There are no particular restrictions on the particle size of the zeolite or hydrotalcite among the adsorbents (B). However, from the viewpoint of film formability, the average particle size is 50 μm or less, preferably 20 μm or less. When zeolite is used as the adsorbent (B), the particle size is preferably 5 μm or less, and most preferably 5 μm or less. In terms of adsorption performance, its BET specific surface area is 100m 2 / g or more 800m 2 / g or less, Preferably 500m 2 / g or more 800m 2 / g or less. When talcite is used, its BET specific surface area is 5m 2 / g or more 100m 2 / g or less, good Preferably 5m 2 / g or more 50m 2 / g or less, more preferably 5m 2 / g or more 20m 2 / g or less.

[0041] When the plastic packaging container (a1) is made of two or more resin components, the resin of the present invention It is desirable to blend a compatibilizer (C) in the oil composition.

[0042] The compatibilizer (C) may be an ethylene-vinyl acetate copolymer, an acid-modified polyolefin, ... Styrene-glycidyl methacrylate copolymer, ionomer resin, oxazoline group-containing resin and the like, and preferably ethylene-vinyl acetate copolymer, maleic anhydride modified a small amount selected from the group consisting of polyethylene, ethylene-glycidyl methacrylate copolymer, At least one species can be mentioned.

[0043] When ethylene vinyl acetate copolymer is used as the compatibilizer (C), from the viewpoint of compatibility, Preferably, the vinyl acetate content of the ethylene-vinyl acetate copolymer is 10 parts by weight or more and 80 parts by weight or less. It is preferably 15 parts by weight or more and 50 parts by weight or less.

[0044] Specific examples of acid-modified polyolefins include maleic anhydride-modified polyethylene, Maleic acid modified polypropylene, maleic anhydride modified ethylene-propylene (block or (random) copolymer, maleic anhydride modified ethylene-ethyl acrylate copolymer, Water-maleic acid-modified ethylene-vinyl acetate copolymer, etc. Vinyl acetate copolymer, maleic anhydride modified polyethylene, ethylene-glycol methacrylate A copolymer of silyl is particularly preferred because it has excellent film formability and film physical properties.

[0045] In the resin composition of the present invention, the adsorbent (B) is a material for adsorbing used plastic packaging containers. 0.05 parts by weight or more and 10 parts by weight or less, preferably 0.05 parts by weight or more and 10 parts by weight or less, per 100 parts by weight of recovered material (A). The blending ratio is preferably 0.05 parts by weight or more and 5 parts by weight or less, more preferably 0.05 parts by weight or more and 2 parts by weight or less. If the amount of the adsorbent (B) is less than 0.05 parts by weight, the heat seal strength and interlayer adhesive strength may not be improved. If the amount exceeds 10 parts by weight, the film forming property deteriorates, and therefore it is not preferable. do not have.

[0046] Furthermore, the mixing ratio (X) of the adsorbent (B) and the used plastic constituting the present invention The residual rate (Y) of (a2) in the collected packaging containers (A) satisfies the relationship of the following formula (1). This is preferable because the resulting film has good odor and adhesive properties. 0.1Y≦X≦2Y (1)

[0047] The mixing ratio (X) and residual rate (Y) can be calculated using the following formula. Mixing ratio (X) = Amount of adsorbent (B) / Amount of recovered material (A) Residual rate (Y) = Amount of (a2) / Amount of recovered material (A)

[0048] When the compatibilizer (C) is blended into the resin composition of the present invention, the used plastic packaging container The compatibilizer (C) is preferably added in an amount of 1 part by weight or more to 30 parts by weight of the recovered material (A) from the vessel per 100 parts by weight. parts by weight or less, more preferably 1 part by weight or more and 10 parts by weight or less, and most preferably 1 part by weight or more and 5 parts by weight or less The resin composition of the present invention can be blended in an amount of 0.1 to 1.0 parts by weight or less. The strength can be further improved.

[0049] The resin composition of the present invention may further contain an antistatic agent, a light stabilizer, or the like, within the range not impairing the effects of the present invention. agents, UV absorbers, nucleating agents, lubricants, antioxidants, anti-blocking agents, flow improvers, Mold, colorant, inorganic neutralizer, hydrochloric acid absorbent, filler conductive agent, chain extender, hydrolysis inhibitor etc. may also be used.

[0050] The resin composition of the present invention can be suitably used as a raw material for a molded article.

[0051] The molded article obtained by molding the resin composition of the present invention can be suitably used as a packaging container. Cut.

[0052] Next, a method for producing the resin composition of the present invention will be described.

[0053] The method for producing the resin composition of the present invention is not particularly limited as long as it can disperse each component. For example, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, Screw extruder, Banbury mixer, pressure kneader, rotating roll, internal mixer, etc. Examples of kneading equipment include:

[0054] When the resin composition of the present invention is blended with the compatibilizer (C), the recovered packaging container (A) and the absorbent A method of mixing and kneading the adsorbent (B) and the compatibilizer (C) at once. The method of mixing (C) in advance with (A) and kneading the resulting mixture with the recycled packaging containers is given below. It is possible.

[0055] Next, the film, which is one embodiment of the present invention, will be described.

[0056] The film of the present invention is made of recycled plastic packaging containers (A), an adsorbent (B), and a and (I) a resin composition comprising at least one layer of the resin composition. The laminated structure of the multilayer film is not particularly limited. Although not limited thereto, for example, layers consisting of not only the (I) layer but also other components, such as It may contain an adhesive layer (II) and a barrier layer (III). Specifically, (I) / (II I), (I) / (II) / (III), (I) / (II) / (III) / (II) / (I ), (III) / (II) / (I) / (II) / (III), etc. Packaging containers When the resin composition of the present invention is used as a It is preferable that the multilayer film has three adjacent layers in the order of A layer (III). The symbol / between layers indicates that they are adjacent layers.

[0057] The components constituting the adhesive layer (II) include adhesive resins, and modified olefins. Polyurethane adhesives, isocyanate adhesives, polyethyleneimine adhesives Examples of modified olefin polymers include adhesives and polybutadiene adhesives. Maleic anhydride modified polyethylene, maleic anhydride modified polypropylene, maleic anhydride modified polyethylene, Maleic anhydride modified ethylene-propylene (block or random) copolymer Ethylene-ethyl acrylate copolymer, maleic anhydride modified ethylene-vinyl acetate copolymer Polymers and the like are examples.

[0058] The components constituting the barrier layer (III) may include synthetic polymers. For example, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, low density polyethylene Polyolefin resins such as polyethylene and high-density polyethylene, nylon 6, nylon 6 ,6 and other polyamide resins, polyethylene terephthalate, glycol-modified polyethylene Polyesters such as ethylene terephthalate resin (PETG resin) and polybutylene terephthalate Furthermore, these polymer films and sheets may further include aluminum-based resins. The material may be vapor-deposited, alumina-deposited, silicon dioxide-deposited, or acrylic-treated.

[0059] The film of the present invention can be formed by various film forming methods.

[0060] The method for forming the film of the present invention is not particularly limited, and examples thereof include inflation molding, Co-extrusion inflation molding method, T-die molding method, Co-extrusion T-die molding method, Calendar molding method Among these, inflation molding is preferred because of its superior productivity. The preferred methods are the blown film molding method, the coextrusion inflation molding method, the T-die molding method, and the coextrusion T-die molding method. The film of the present invention may be laminated with other films, and the lamination method is the same. There is no particular limitation to the method, but dry lamination, extrusion lamination, sandwich lamination, etc. Examples include the tot method.

[0061] The film of the present invention is suitable for packaging food, daily necessities, industrial parts, medicines, office supplies, chemical products, etc. Agricultural films such as coating films, surface protection films, silage wraps, shrink films It is useful as a film, transport bag, etc. [Example]

[0062] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these. It's not that.

[0063] (1) Ratio of adsorbent (B) and oil or surfactant (a2) According to the formula above, the mixing ratio of adsorbent (B) is (X), and the amount of used plastic packaging is (X). The remaining rate of (a2) in the collected material (A) of the container was defined as (Y). (2) Melt mass flow rate (MFR) The MFR of maleic anhydride modified polyethylene and ethylene-vinyl acetate copolymer is The temperature was measured using a PT indexer (manufactured by Takara Kogyo Co., Ltd.) at 190°C and a load of 2.16 kg. It was determined. (3) Vinyl acetate content The vinyl acetate content of ethylene-vinyl acetate copolymer conforms to JIS K6924-1 and measured.

[0064] (4) Odor measurement To measure odor, 20 g of melt-mixed pellets were placed in a zippered aluminum bag and left at room temperature for 2 hours. After leaving the sample to stand for a while, a sensory evaluation was carried out by three panelists. The sample was rated as ◯ if it had almost no odor, and rated as 1 if it had a strong odor. In some cases, it was marked as ×. (5) Color The color of the pellets after melt-kneading was checked visually. If there was no coloring, it was marked as ◯. If there was coloring, it was marked as ◯. In this case, it was marked as ×. (6) Fisheye The fisheyes were cut into pieces 250 mm wide and 30 mm long from the multilayer film and visually counted. I got it.

[0065] (7) Heat seal strength Heat seal strength is measured by placing two sheets of laminated film 100mm wide and 100mm long. Cut out the film, overlap the outer surfaces of the film, and test it with a heat seal tester TP-701 (Tester Manufacturing) Using a machine manufactured by KOGYO CO., LTD., set temperature 170℃, single-sided heating, air pressure 0.2MPa, sealing The test piece was heat-sealed with a seal bar 10 mm wide and 300 mm long for 1 second. The specimen was cut into 15 mm width and tested using a tensile tester, Tensilon RTE-1210 (Oriente Co., Ltd.). A peel test was carried out using a tensile tester (manufactured by Epson) at a pulling speed of 300 mm / min and under the condition of T-type peeling. was measured.

[0066] (8) Interlayer adhesion When resins containing oils and surfactants are used in multilayer films, the oils and surfactants It migrates between the adhesive layer and the barrier layer of the film, reducing the adhesive strength between the layers. Peeling may occur between the layers of a multi-layer film, rather than at the surface of the adhesive. When the heat seal strength was measured, the layers were not peeled off, and when the layers were peeled off, the was marked as ×.

[0067] Example 1 Thickness 100μm, density 0.92g / cm 3 , one-sided corona treated linear low density polyethylene Lenfilm (a1-1) (manufactured by Toyobo Co., Ltd., product name RIX L4102) (hereinafter referred to as "L The edge of the LDPE film is sealed with a heat seal tester TP-701 (Tester (manufactured by Sangyo Co., Ltd.) set temperature 170℃, one side heating, air pressure 0.2MPa, sealing Heat seal is performed with a 10mm wide, 300mm long seal bar in 1 second, and the width is 20cm. A film bag measuring 30 cm x 30 cm in length was prepared and used as a plastic packaging container (a1). 99.5 parts by weight of the plastic packaging container (a1) Shampoo containing sodium tert-butyl sulfate (product name: Essential Shampoo, manufactured by Kao Corporation) Put 1.5 parts by weight of Poo sR into the container, place it in an oven, and dry it at 80°C for 3 hours. The dried plastic packaging container (a1) was then used as a plastic container. The collected plastic packaging containers were designated as (A). When the recovered material (A) was weighed, it was 100 parts by weight, so (a2) was 0.5 parts by weight. It was a club.

[0068] 100 parts by weight of the above-mentioned used plastic packaging containers (A) were put into a rotary car. The particles were crushed in a pulverizer to produce adsorbent (B) with a particle size of 2 to 3 μm and a specific surface area of ​​600 m 2 / g Zeola Zeolite (B1) (manufactured by Tosoh Corporation, trade name: High Silica Zeolite HSZ-385HUA) 0.5 parts by weight of the mixture was added, and the mixture was pre-blended in a tumbler mixer. After that, the mixture was extruded at 230°C using a twin-screw extruder. The mixture was melt-kneaded at 200°C to obtain resin composition pellets. The ratio of the remaining rate (Y) of (a2) in the collected waste plastic packaging containers (A) is There (X) / (Y) was 1.0.

[0069] The above resin composition pellets were extruded into a 3-type 5-layer co-extrusion cast molding machine (Plastic Engineering Research Institute Co., Ltd.). A laminated structure of resin composition layer / adhesive layer / barrier layer / adhesive layer / resin composition layer was used. At this time, the cylinder temperature of the barrier layer was 230°C, the cylinder temperature of the adhesive layer was 230°C, and the cylinder temperature of the adhesive layer was 230°C. Cylinder temperature: 240°C, resin composition layer cylinder temperature: 230°C, cooling roll temperature: 30°C The take-up speed was 6.5 m / min, the film width was 250 mm, and the total film thickness was 50 μm. The inner surface of the roll is subjected to corona discharge treatment, and the thickness of each layer is resin composition layer / adhesive layer / barrier layer. / adhesive layer / resin composition layer=18 μm / 4 μm / 6 μm / 4 μm / 18 μm. The barrier layer is made of ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., product name EVAL F171B), the above resin composition for both outer layers, and a melt mass flow rate of 3 g / 10 Maleic anhydride modified polyethylene (manufactured by Mitsui Chemicals, Inc., trade name: Admer NF5) 28) was used.

[0070] The corona-treated inner surface of the film and the 12 μm thick ester film (PET The corona treated side of the film (manufactured by Toyobo Co., Ltd., trade name Ester E5200) was Teflon-based adhesive (manufactured by Mitsui Chemicals, Inc., product name: Takelac A-3210 / manufactured by Mitsui Chemicals, Inc.) , and dry laminated with Takenate A-3072 (mixing ratio 3 / 1) After aging at 0.degree. C. for 1 day, a laminated film was obtained.

[0071] The pellets, multilayer film, and laminated film obtained were evaluated by the above-mentioned evaluation method. The evaluation results are shown in Table 1.

[0072] Example 2 L-LDPE film (a1-1) with a thickness of 15 μm and a density of 1.12 g / cm 3 , double-sided Corona-treated nylon film (a1-2) (manufactured by Toyobo Co., Ltd., product name Harden N1) 200) (hereinafter referred to as "PA6 film"), create a film bag using the following procedure. Successful.

[0073] The corona-treated surface of the L-LDPE film (a1-1) and the PA6 film (a1- 2) was applied to the urethane adhesive (Mitsui Chemicals, Inc., trade name Takelac A-3210 / Mitsui Chemicals) Dry lamination using Takenate A-3072 (mixing ratio 3 / 1) manufactured by Gakushu Co., Ltd. The laminate film was prepared by heating the film and aging it at 40°C for 1 day. Except that the edges of the L-LDPE (a1-1) surfaces of the laminate film were heat sealed. A film bag was prepared in the same manner as in Example 1, and used as a plastic packaging container (a1). did.

[0074] Next, shampoo was poured into the obtained plastic packaging container (a1) in the same manner as in Example 1. The collected used plastic packaging containers (A) were prepared. When this happens, the amount of L-LDPE contained in the collected used plastic packaging containers (A) is 84 0.1 parts by weight, PA6 was 15.4 parts by weight, and (a2) was 0.50 parts by weight.

[0075] Furthermore, as the adsorbent B, 0.5 parts by weight of zeolite (B1) was replaced with an adsorbent having an average particle size of 0.4 μ m, specific surface area 15m 2 / g of hydrotalcite (B2) (Kyowa Kogyo Kagaku Co., Ltd., product The recovered material ( A) was used to prepare pellets, multilayer films, and laminated films. The results are shown in Table 1.

[0076] Example 3 As the adsorbent B, 0.5 parts by weight of hydrotalcite (B2) was replaced with zeolite (B1 ) was used in an amount of 0.5 parts by weight, and a melt mass flow rate of 3 g / 10 Maleic anhydride modified polyethylene (C1) (manufactured by Arkema, trade name OREVAC) The pellets and multilayers were prepared in the same manner as in Example 2, except that 2.0 parts by weight of OE825 was added. The film and the laminated film were obtained. These were measured by the above-mentioned evaluation methods. The results are shown in Table 1.

[0077] Example 4 As the adsorbent (B), 0.5 parts by weight of zeolite (B1) was replaced with hydrotalcite (B Pellets, multilayer films and the like were prepared in the same manner as in Example 3, except that 0.5 parts by weight of 2) was used. The laminated films were measured using the above-mentioned evaluation methods. The evaluation results are shown in Table 1. Shown below.

[0078] Example 5 As the compatibilizer (C), 2.0 parts by weight of maleic anhydride-modified polyethylene (C1) was replaced. , melt mass flow rate 3g / 10min, ethylene vinyl acetate with vinyl acetate content of 25% 2.0 parts by weight of acrylic copolymer (C2) (manufactured by Tosoh Corporation, trade name Ultrathene 640) The pellets, multilayer film, and laminate film were prepared in the same manner as in Example 4, except that These were measured using the evaluation methods described above. The evaluation results are shown in Table 1.

[0079] Example 6 The amount of ethylene-vinyl acetate copolymer (C2) used as the compatibilizer (C) was 5.0 parts by weight. Pellets, multilayer films and laminates were prepared in the same manner as in Example 5, except that the The laminated films were measured using the above-mentioned evaluation methods. The evaluation results are shown in Table 1.

[0080] Comparative Example 1 Pellets and multilayer filters were prepared in the same manner as in Example 2, except that the adsorbent (B) was not added. The film and laminated film were obtained. These were measured using the above evaluation methods. Evaluation results is shown in Table 1.

[0081] Comparative Example 2 Pellets and multilayer filters were prepared in the same manner as in Example 5, except that the adsorbent (B) was not added. The film and laminated film were obtained. These were measured using the above evaluation methods. Evaluation results is shown in Table 1.

[0082] [Table 1]

[0083] Example 7 As the adsorbent (B), the following composition was used in place of 0.5 parts by weight of hydrotalcite (B2). The pellets, multilayer film, and laminate film were prepared in the same manner as in Example 5, except that I got Lum. ·Particle size 2~3μm, specific surface area 600m 2 / g of zeolite (B1) (manufactured by Tosoh Corporation, High Silica Zeolite HSZ-385HUA (product name) 0.25 parts by weight ·Average particle size 0.4μm, specific surface area 15m 2 / g of hydrotalcite (B2) (Kyowa Kogyo) Manufactured by Gyo Kagaku Co., Ltd., product name DHT-4C) 0.25 parts by weight These were measured using the evaluation methods described above. The evaluation results are shown in Table 2.

[0084] Example 8 The amount of hydrotalcite (B2) used as the adsorbent (B) was changed to 0.1 parts by weight. The mixing ratio (X) of the adhesive (B) and the collected used plastic packaging containers (A) The same procedure as in Example 5 was repeated except that the ratio of the residual rate (Y) of (a2) to the residual rate (X) / (Y) was set to 0.2. Pellets, multilayer films, and laminated films were obtained in the same manner as above. The evaluation results are shown in Table 2.

[0085] Example 9 The amount of hydrotalcite (B2) used as the adsorbent (B) was changed to 1.0 part by weight. The mixing ratio (X) of the adhesive (B) and the collected used plastic packaging containers (A) The same procedure as in Example 5 was repeated except that the ratio of the residual rate (Y) of (a2) to the residual rate (X) / (Y) was set to 2.0. Pellets, multilayer films, and laminated films were obtained in the same manner as above. The evaluation results are shown in Table 2.

[0086] Example 10 Instead of PA6 film, thickness 15 μm, density 1.4 g / cm 3 , corona treated on both sides Ester film (a1-3) (manufactured by Toyobo Co., Ltd., product name Ester E5200) (hereinafter (hereinafter referred to as "PET film") was used to make a film bag (PET film) in the same manner as in Example 5. Plastic packaging containers (a1)) and used plastic packaging containers (A) are collected. At this time, L-LDP contained in the collected used plastic packaging containers (A) was E was 84.1 parts by weight, PET was 15.4 parts by weight, and (a2) was 0.50 parts by weight. Furthermore, pellets, multilayer films and the like were obtained from the recovered material (A) by the same method as in Example 5. The laminated films were measured using the above-mentioned evaluation methods. The evaluation results are shown in Table 2. Shown below.

[0087] Example 11 Instead of PA6 film, thickness 12 μm, density 1.2 g / cm 3 , both sides corona untreated Ethylene-vinyl alcohol copolymer film (a1-4) (manufactured by Kuraray Co., Ltd., product name E F-XL) (hereinafter referred to as "EVOH film") in the same manner as in Example 5. Film bags (plastic packaging containers (a1)), collection of used plastic packaging containers At this time, the collected material (A) of used plastic packaging containers was The content of L-LDPE was 86.0 parts by weight, EVOH was 13.5 parts by weight, and (a2) was 0.5 The content was 0 parts by weight. Furthermore, pellets, multilayer films and the like were obtained from the recovered material (A) by the same method as in Example 5. The laminated films were measured using the above-mentioned evaluation methods. The evaluation results are shown in Table 2. Shown below.

[0088] Comparative Example 3 The amount of hydrotalcite (B2) used as the adsorbent (B) was changed to 0.01 parts by weight. The adsorbent (B) mixing ratio (X) and the collected used plastic packaging containers (A) The remaining rate (Y) of (a2) was set to 0.02 (X) / (Y). Pellets, a multilayer film, and a laminated film were obtained in the same manner as in Example 5. These were measured using the evaluation methods described above. The evaluation results are shown in Table 2.

[0089] Comparative Example 4 The amount of hydrotalcite (B2) used as the adsorbent (B) was changed to 11.0 parts by weight. The adsorbent (B) mixing ratio (X) and the collected used plastic packaging containers (A) The remaining ratio (X) / (Y) of (a2) was set to 22.0. Pellets were obtained in the same manner as in Example 5, but film formation from the pellets was not possible. It was not possible to obtain a film or a laminated film. The evaluation results are shown in Table 2.

[0090] [Table 2] [Industrial Applicability]

[0091] The film of the present invention allows reuse of used packaging containers, reduces the environmental impact, and It has excellent adhesiveness and heat sealing properties, making it suitable for food, daily necessities, industrial parts, pharmaceuticals, office supplies, etc. Packaging films for food and chemical products, surface protection films, agricultural films such as silage wrap It is useful for films, shrink films, shipping bags, etc.

Claims

1. A method for recycling recovered used plastic packaging containers (A), comprising blending 0.05 parts by weight or more and 10 parts by weight or less of at least one adsorbent (B) selected from zeolite and hydrotalcite with 100 parts by weight of recovered used plastic packaging containers (A), melt-kneading the resulting resin composition in an extruder, and forming the resulting resin composition into a film.

2. The collected used plastic packaging containers (A) contain polyolefins. The recycling method according to claim 1, wherein the packaging container (a1) is made of plastic.

3. The plastic packaging container (a1) is made of a material selected from polyolefin, polyester, polyamide, At least one selected from the group consisting of ethylene-vinyl alcohol copolymers The recycling method according to claim 2, wherein the recycled material contains

4. The plastic packaging container (a1) is a mixture of polyolefin and polyester or polyester.

4. The recycling method according to claim 2, wherein the organic solvent contains at least one selected from the group consisting of amides.

5. 5. The plastic packaging container (a1) according to any one of claims 2 to 4, wherein the plastic packaging container (a1) does not contain any halogen compound. The recycling method according to any one of claims 1 to 4.

6. The recycling method according to any one of claims 1 to 5, wherein the compatibilizer (C) is blended in an amount of 1 part by weight to 30 parts by weight per 100 parts by weight of the recovered used plastic packaging containers (A).

7. The compatibilizer (C) is an ethylene-vinyl acetate copolymer, a maleic anhydride-modified polyethylene or at least one selected from the group consisting of ethylene-glycidyl methacrylate copolymers The recycling method according to claim 6, wherein the seeds are used.

8. The plastic packaging container (a1) is a food packaging container or a daily necessities packaging container. The recycling method according to any one of claims 2 to 5, wherein the material is at least one selected from the group consisting of:

9. The collected used plastic packaging containers (A) are oily foods, beverages, detergents or and (a2) at least one oil or surfactant selected from the group consisting of shampoos and The recycling method according to any one of claims 1 to 8, comprising:

10. The recycled material (A) of the used plastic packaging containers is 100 parts by weight of the recycled material. The oil or surfactant (a2) is contained in an amount of 0.01 to 5 parts by weight, and the absorbent The mixture ratio (X) of the adhesive (B) and the collected used plastic packaging containers (A) 10. The method according to claim 1, wherein the residual rate (Y) of (a2) satisfies the following formula (1): The recycling method according to claim 1. 0.1Y≦X≦2Y (1)

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