Method for recycling recovered material of used plastic packaging container

Abstract

To provide a bottle which adsorbs oils and fats and a surface active agent remaining in a recovered material of a used plastic packaging container, and is excellent in reduction in odor and interlayer adhesiveness, by blending an adsorbent in the recovered material.SOLUTION: A bottle has a layer containing a resin composition containing 100 pts.wt. of a recovered material (A) of a used plastic packaging container, and 0.05 pts.wt. or more and 10 pts.wt. or less of at least one kind of adsorbent (B) selected from zeolite or 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 comprising the composition The present invention relates to a bottle 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 bottles involves These include washing, dehydrating, crushing, re-pelletizing, and blow 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, which often remain even after the cleaning process. For this reason, bottles made from recycled plastic materials are The residual oils and surfactants can cause odors in the bottle and reduce the interlayer adhesion of multi-layer bottles. 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 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 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 through the adsorption of substances, such as oils and fats, surfactants, and bottles. The interlayer adhesive strength of the recycled plastics has not been examined. Recycled materials are difficult to remanufacture due to their inferior physical properties. does not describe any means for improving the physical properties. [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 characterized in that by blending an adsorbent with recovered used plastic packaging containers, A bottle that absorbs oils, fats, and surfactants remaining in collected materials, reducing odors and providing excellent interlayer adhesion. The purpose is to provide. [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 bottle, which is made of a resin composition to which a specific adsorbent is added for the recovered material of the packaging container, solves the above-mentioned problem. The inventors have found that this problem can be solved, and have completed the present invention.

[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 A bottle having at least one layer containing a resin composition containing 0.05 parts by weight or more and 10 parts by weight or less. is. [Effects of the Invention]

[0013] The bottle of the present invention allows reuse of used packaging containers, reduces environmental impact, and eliminates odors. The bottle is useful as a packaging bottle because of its excellent water-reducing properties and interlayer adhesion. 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 composed of a polyolefin and an ethylene-vinyl alcohol copolymer. In this case, the composition of polyolefin and polyester or other resins is and polyolefin and other resin materials as separate components. Composite materials, polyolefin and other resin films laminated together Examples of the form of the compound include a carbohydrate form.

[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 resin having a moldability of a bottle. It is preferable that the resin contains at least polyolefin because it has excellent properties. Other resins may include polyethylene terephthalate, polyamide, ethylene At least one of the group consisting of ethylene-vinyl alcohol copolymers is preferred, Even more preferably, it is a vinyl alcohol copolymer.

[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 polyethers. 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] The recovered used plastic packaging containers (A) in the present invention are the above-mentioned plastics. This refers to waste plastic packaging containers (a1) that have been collected for reuse. Since it is a discarded product, the contents (packaged items) remaining in the packaging container and the disposal-recovery It may also be a composition that includes other waste-derived materials that are mixed in during the 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 a main component of detergents and other household items. When expressing the amount of solids, it is expressed as the amount of solids obtained by excluding the water content, alcohol content, and other secondary components from (a2). vinegar.

[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 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, alkylphenoxypolyoxyethylenepropanol 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 Amido 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 bottle molding, the average particle size is 50 μm or less, preferably 20 μm. The particle size is preferably 5 μm or less, and most preferably 5 μm or less. When zeolite is used as the adsorbent (B), From the viewpoint of adsorption performance, the BET specific surface area is preferably 100 m2 / g or more and 800 m2 / g or less. Preferably, the surface area is 500 m2 / g or more and 800 m2 / g or less. When lucite is used, its BET specific surface area is preferably 5 m2 / g or more and 100 m2 / g or less. Preferably, 5 m2 / g or more and 50 m2 / g or less, and more preferably 5 m2 / g or more and 20 m2 / g or less. The following is the result.

[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, or an ethylene-vinyl acetate copolymer. 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, Here, the compatibilizer (C) may be the same as the adhesive resin. When using the same material, e.g., maleic anhydride modified polyolefin, MFR or maleic anhydride Preferably, the acid content is different.

[0043] When ethylene vinyl acetate copolymer is used as the compatibilizer (C), from the viewpoint of compatibility, The vinyl acetate content of the ethylene-vinyl acetate copolymer is preferably 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 The copolymer is particularly preferred because it has excellent bottle formability and bottle 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 effect of improving the interlayer adhesive strength is insufficient. If the amount exceeds 10 parts by weight, the bottle moldability will be adversely affected, which is undesirable.

[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 bottle 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 with the resin composition of the present invention, the resin composition may be used in a wide range of applications, such as packaging made of used plastic. The compatibilizer (C) is preferably added in an amount of 1 part by weight or more to 30 parts by weight per 100 parts by weight of the recovered material (A) in the container. parts by weight or less, more preferably 1 part by weight to 10 parts by weight, most preferably 1 part by weight or more The amount of the resin composition of the present invention can be 5 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, Forming agent, coloring agent, inorganic neutralizing agent, 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 the same time; 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, a bottle according to one embodiment of the present invention will be described.

[0056] The bottle of the present invention is made of 100 parts by weight of recycled plastic packaging containers (A). At least one adsorbent selected from the group consisting of zeolite and hydrotalcite A bottle having a layer containing a resin composition containing 0.05 parts by weight or more and 10 parts by weight or less of (B). That is, the bottle has a layer containing the resin composition of the present invention.

[0057] The bottle of the present invention is made of recycled plastic packaging containers (A), an adsorbent (B), and The present invention is characterized in that it has at least one layer (I) made of a resin composition containing The multilayer bottle may be either a single-layer bottle or a multilayer bottle. Although not limited to, for example, not only the (I) layer but also layers composed of other components, e.g. For example, it may contain an adhesive layer (II) or a barrier layer (III). III), (I) / (II) / (III), (I) / (II) / (III) / (II) / (I), (III) / (II) / (I) / (II) / (III), etc. When the bottle is used as a packaging container, the layer (I) composed of the resin composition of the present invention, the adhesive Preferably, the bottle is a multi-layer bottle having three adjacent layers in this order: a layer (II) and a barrier layer (III). The symbol / between layers indicates that they are adjacent layers.

[0058] The adhesive layer (II) is made of a modified olefin polymer, which is an adhesive resin. Specific examples of modified olefin polymers include maleic anhydride modified polyolefins. Ethylene, maleic anhydride modified polypropylene, maleic anhydride modified ethylene-propylene (Block or random) copolymer, maleic anhydride modified ethylene-ethyl acrylate copolymer, maleic anhydride-modified ethylene-vinyl acetate copolymer, etc.

[0059] 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 Examples of suitable resins include acrylic resins.

[0060] The bottle of the present invention can be formed by various bottle forming methods.

[0061] The method for molding the bottle of the present invention is not particularly limited, and may be extrusion blow molding, injection stretch molding, or the like. Low molding, multi-layer blow molding, co-extrusion blow molding, co-injection blow molding, suction blow molding, 3 Examples include D blow molding and sequential coextrusion blow molding.

[0062] The bottle of the present invention can be used for food, daily necessities, industrial parts, medicines, office supplies, chemical supplies, etc. It is particularly suitable for use in beverage bottles, shampoo bottles, oil containers, etc. [Example]

[0063] 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.

[0064] (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. (4) Odor measurement To measure the odor, 20 g of melt-mixed pellets were placed in an aluminum bag with a zipper 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 ×.

[0065] (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) Surface smoothness Direct blow molding machine equipped with a mold, extruder, and die head for 500ml square bottles ( The molding temperature was 200°C and the die gap was 1.4 mm. The surface smoothness of the resulting bottles was visually observed. Evaluated. ○:Smooth surface ×: The surface is matte and not smooth.

[0066] (7) Interlayer adhesion If resin containing oils, fats, or surfactants is used in a multi-layer bottle, the oils, fats, or surfactants will It migrates between the adhesive layer and the barrier layer of the multilayer board, reducing the adhesive strength between the layers. Therefore, the interlayer adhesion is important when it comes to the side of the blow-molded bottle. Cut out a 10cm x 20cm piece and test it with a Gelboflex tester (manufactured by Tester Sangyo). The sample was bent 50 times. If the sample did not peel between the layers when bent, it was marked as ◯. If the sample peeled between the layers, it was marked as ◯. The answer was ×.

[0067] Example 1 Direct blow molding with mold, extruder and single-layer die head for 500ml square bottles A high-density polyethylene (manufactured by Tosoh, product name Nipolonha) was extruded using a machine (manufactured by Tahara Co., Ltd.). The mold (8300A) is inserted to form a single-layer 500ml square bottle, which is then wrapped in plastic. The extruder and die head were set at 200°C. The gap was 1.4 mm and the average thickness of the bottle body was 400 μm. 99.5 parts by weight of a packing container (a1-1) made of wood, polyoxyethylene lauryl ether sulfur Shampoo containing sodium hydroxybenzoate (product name: Essential Shampoo S, manufactured by Kao Corporation) R) was added, and the container was placed in an oven and dried at 80°C for 3 hours to remove moisture and The alcohol was removed. The dried plastic packaging container (a1) was then repackaged into a used plastic container. The collected plastic packaging containers were classified as (A). When the substance (A) was weighed, it was 100 parts by weight, so the surfactant (a2-1) was 0 It was 0.5 parts by weight.

[0068] 100 parts by weight of the collected used plastic packaging containers (A) were put into a rotary car. The adsorbent (B) was pulverized in a pulverizer and treated with zeolite having a particle size of 2 to 3 μm and a specific surface area of ​​600 m2 / g. 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 200°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 resin composition was subjected to a 500 ml square bottle mold, an extruder, and a die equipped with a single-layer die head. A 500ml square bottle was molded using a recto-blow molding machine (manufactured by Tahara Co., Ltd.) and a single-layer bottle was created. At this time, the extruder and die head were set at temperatures of 200°C, and the die gap was 1.4 The average wall thickness of the bottle body was 400 μm.

[0070] The pellets and single-layer bottles obtained were evaluated by the above-mentioned evaluation methods. The evaluation results are shown in Table 1. show.

[0071] Example 2 As the adsorbent B, 0.5 parts by weight of zeolite (B1) was replaced with hydrotalcite (B2 Pellets and a single-layer bottle were obtained in the same manner as in Example 1, except that 0.5 parts by weight of These were measured using the evaluation methods described above. The evaluation results are shown in Table 1.

[0072] Example 3 Except for changing the amount of hydrotalcite (B2) used as an adsorbent to 0.1 parts by weight Pellets and single-layer bottles were obtained in the same manner as in Example 2. These were measured using the above-mentioned evaluation method. The evaluation results are shown in Table 1.

[0073] Example 4 Except for changing the amount of hydrotalcite (B2) used as an adsorbent to 1.0 parts by weight Pellets and single-layer bottles were obtained in the same manner as in Example 2. These were measured using the above-mentioned evaluation method. The evaluation results are shown in Table 1.

[0074] Comparative Example 1 Pellets and single-layered bottles were prepared in the same manner as in Example 1, except that the adsorbent (B) was not added. These were measured using the evaluation methods described above. The evaluation results are shown in Table 1.

[0075] Comparative Example 2 The amount of hydrotalcite (B2) used as an adsorbent was changed to 0.01 parts by weight. Other than that, pellets and single-layer bottles were obtained in the same manner as in Example 2. The evaluation results are shown in Table 1.

[0076] Comparative Example 3 The amount of hydrotalcite (B2) used as an adsorbent was changed to 11.0 parts by weight. The pellets were obtained in the same manner as in Example 2, but blow molding was not possible from the pellets. The pellets obtained were evaluated by the above-mentioned method. The evaluation results are shown in Table 1.

[0077] [Table 1]

[0078] Example 5 Direct injection molding machine with a 500ml square bottle mold, first to third extruders, and a multi-layer die head Using a blow molding machine (manufactured by Tahara Co., Ltd.), melt mass flow adhesive resin was injected into the first extruder. Maleic anhydride-modified polyester with a content of 0.1 parts by weight and a polymer chain length of 3 g / 10 min. ethylene (Mitsui Chemicals, Inc., product name, Admer NF528), and a barrier resin in the second extruder. An ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., trade name EVAL F171B ), and the third extruder was high-density polyethylene (manufactured by Tosoh, product name Nipolonhard 8300A). is added to form a 500ml square bottle with a 3-type, 5-layer structure, and then used as a plastic packaging container (a 1-2). At this time, the set temperature of all extruders and multi-layer die heads was 200°C, and the die The bottle was blow molded under the condition of a gap of 1.6 mm. The average wall thickness of the body of this bottle was 40 0 μm, and the layer structure of the multi-layer bottle is high density polyethylene (120 μm) from the inner layer Adhesive layer (20 μm) / Barrier layer (120 μm) / Adhesive layer (20 μm) / High density polyethylene The thickness was 120 μm.

[0079] Next, the obtained plastic packaging container (a1-2) was subjected to the same process as in Example 2. The collected plastic packaging containers (A) are then added and processed. Furthermore, the recovered material (A) was mixed with a compatibilizer (C) having a melt mass flow rate of 3 g / 10 min and anhydrous Maleic anhydride-modified polyethylene (manufactured by Arkema Co., Ltd.) containing 0.8 parts by weight of maleic acid 2.0 parts by weight of OREVAC OE825 (trade name) was added, and the mixture was mixed in the same manner as in Example 2. Created a let.

[0080] In addition, a die for a 500 ml square bottle, the first to third extruders, and a die equipped with a multi-layer die head are installed. Using an e-blow molding machine (manufactured by Tahara Co., Ltd.), melt mass, which is an adhesive resin, is injected into the first extruder. Maleic anhydride modified with a flow rate of 3 g / 10 min and a maleic anhydride content of 0.1 parts by weight Polyethylene (Mitsui Chemicals, Inc., product name: Admer NF528), burr in the second extruder Ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., product name EVAL F) 171B), the resin composition pellets were fed into the third extruder, and a 500 ml square extruder with a 3-type 5-layer structure was produced. Bottles were molded into plastic packaging containers (a1-2). And blow molding under the conditions of multi-layer die head set temperature 200℃, die gap 1.6mm The average thickness of the body of this bottle was 400 μm, and the layer structure of the multi-layer bottle was as follows: From the inner layer: resin composition layer (120 μm) / adhesive layer (20 μm) / barrier layer (120 μm) / The thickness was adhesive layer (20 μm) / resin composition layer (120 μm).

[0081] The pellets and multilayer bottles obtained were evaluated by the above-mentioned evaluation methods. The evaluation results are shown in Table 2. show.

[0082] Example 6 Instead of 2.0 parts by weight of maleic anhydride-modified polyethylene (C1) as a compatibilizer, Ethylene-vinyl acetate copolymer with a mass flow rate of 3 g / 10 min and a vinyl acetate content of 25% The same procedure as in Example 5 was repeated except that 2.0 parts by weight of polymer (C2) was used. The bottles were obtained and measured using the evaluation methods described above. The evaluation results are shown in Table 2.

[0083] Example 7 Plastic packaging container (a1-2) 99.5 layers produced in the same manner as in Example 5 For the quantity, use edible rapeseed oil (manufactured by J-Oil Mills, AJINOMOTO smooth canola 0.5 parts by weight of oil was added, and the mixture was dried in the same manner as in Example 5. The collected plastic packaging containers (A) were used as the collected plastic packaging containers (A). ) was weighed and found to be 100 parts by weight, so the fat (a2-2) was 0.5 parts by weight. there were.

[0084] Thereafter, pellets and multi-layer bottles were obtained in the same manner as in Example 6. The results of the evaluation are shown in Table 2.

[0085] Comparative Example 4 Pellets and multilayer bottles were prepared in the same manner as in Example 5, except that the adsorbent (B) was not added. These were measured using the evaluation methods described above. The evaluation results are shown in Table 2.

[0086] [Table 2] [Industrial Applicability]

[0087] The bottle of the present invention allows reuse of used packaging containers, reduces environmental impact, and has low odor. It is used in food, daily necessities, industrial parts, pharmaceuticals, office supplies, chemicals, etc. due to its excellent adhesion to the layers. It is useful for packaging bottles for products, 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 molding the resulting resin composition into a bottle.

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 made of polyolefin and ethylene-vinyl alcohol.

4. The recycling method according to claim 2 or 3, wherein the recycled material contains a vinyl copolymer.

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 resin composition contains a compatibilizer (C).

7. The compatibilizer (C) is an ethylene-vinyl acetate copolymer, a maleic anhydride-modified polyethylene at least one selected from the group consisting of ethylene and ethylene-glycidyl methacrylate copolymer; The recycling method according to claim 6, wherein the recycled material is one of the above.

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 7, 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)

Images