Resin film material, laminated structure provided with resin film material, method for manufacturing resin composition, method for manufacturing resin film material, and method for manufacturing laminated structure

Abstract

A resin film material, which is made of a resin material containing a laminate, the laminate being a laminate provided with a resin layer having a metal vapor deposition layer, and the resin film material containing the metal in the form of particles. In the film material, the metal particles are dispersed, and the number of the metal particles present per 1 cm 2 The number of the metal particles present in the resin film material, the area equivalent diameter of which is 200 μm or more, is 1 or less. It is suitable that the resin material contains a laminate group, the laminate group containing the above-mentioned laminate provided with a resin layer having a metal vapor deposition layer, and a laminate provided with a resin layer not having a metal layer.

Description

TECHNICAL FIELD

[0001] The present application relates to a resin film material and a laminate structure provided with the resin film material. In addition, the present application relates to a method for manufacturing a resin composition using resin waste as a raw material. In addition, the present application relates to a method for manufacturing a resin film material and a laminate structure. BACKGROUND

[0002] In recent years, in the operation and growth of a business, a way of thinking about product development based on the three perspectives of environment-society-management, that is, based on the ESG viewpoint, is flourishing. For example, if a resin container is mentioned, it is desired to make the container thinner and lighter to reduce the environmental burden. In addition, by using a material of plant origin that is lower in carbon and can be regenerated instead of a resin of petroleum origin, it is possible to ensure a sustainable raw material. Further, it is desired to actively introduce recycled resin into resin containers to recycle, and to use a material that is easy to recycle for the resin itself.

[0003] For the purpose of improving the stability and preservability of the contents, a layer of various metals represented by aluminum is sometimes provided in a resin container. As a related art concerning recycling of a resin container having a layer of metal, for example, there are the technologies described in Patent Documents 1 to 5.

[0004] In particular, Patent Document 2 describes that a multilayer film in which an aluminum foil is layered on a plastic layer is put into a twin-screw extruder and then melt-kneaded, whereby a resin containing a crushed aluminum foil is recycled.

[0005] In addition, Patent Document 3 describes a method in which packaging material waste is classified into an aluminum foil layered packaging material in which an aluminum foil is layered and an aluminum vapor deposition packaging material in which aluminum is vapor deposited, and the aluminum foil layered packaging material and the aluminum vapor deposition packaging material are subjected to dry distillation treatment at different temperatures, respectively, whereby each packaging material is thermally decomposed to recover aluminum.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2002-309005

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 2006-192748

[0010] Patent Document 3: Japanese Patent Application Laid-Open No. 2012-21200

[0011] Patent Document 4: Japanese Patent Application Laid-Open No. 2013-35272

[0012] Patent Document 5: U.S. Patent Application Publication No. 2019 / 062921 SUMMARY

[0013] The present application relates to a resin film material, which is produced from a resin material containing a laminate, the laminate being a laminate having a resin layer having a metal vapor deposition layer, and the resin film material containing the metal in the form of particles.

[0014] Preferably, the above-mentioned metal particles are dispersed in the above-mentioned film material, and there are 1 or less of the above-mentioned metal particles having an area equivalent diameter of 200 μm or more per 1 cm 2 The above-mentioned metal particles having an area equivalent diameter of 200 μm or more in the above-mentioned resin film material are 1 or less.

[0015] Further, the present application relates to a laminate structure having the above-mentioned resin film material, and a resin layer or a metal foil.

[0016] Further, the present application relates to a method for producing a resin composition.

[0017] In the above-mentioned method for producing, preferably, from a mixture of resin waste materials including a resin waste material having a resin layer having a metal foil layer and a resin waste material having a resin layer having a metal vapor deposition layer, the resin waste material having a resin layer having a metal foil layer is removed.

[0018] In the above-mentioned method for producing, preferably, the resin waste material mixture after the removal is subjected to melt molding to obtain a resin composition in which the above-mentioned metal particles are dispersed.

[0019] Further, the present application relates to a method for producing a resin film material. In this method for producing, preferably, the above-mentioned resin composition is produced by the above-mentioned method, and the above-mentioned resin composition is subjected to extrusion molding.

[0020] Further, the present application relates to a method for producing a laminate structure. In this method for producing, preferably, the above-mentioned resin composition is produced by the above-mentioned method, and the above-mentioned resin composition is subjected to co-extrusion molding or extrusion lamination molding. DETAILED DESCRIPTION

[0021] The recycled resin obtained from the resin container having a layer with metal contains the metal contained in the resin container before recycling. That is, the recycled resin contains the metal. When a film is formed using the recycled resin containing the metal as a raw material, depending on the state of existence of the metal, the metal can cause an obstacle to the formation, and become a factor to decrease the quality of the manufactured film. The technologies described in the above-mentioned Patent Documents 1 to 5 mainly focus on the recycling of the resin container having a layer with metal itself, and the quality of the resin formed body, particularly the film material, using the recycled resin obtained by the recycling as a raw material is not sufficiently studied.

[0022] In particular, the resin regenerated by the method of Patent Document 2 contains a large amount of broken bodies of aluminum foil. At the time of melt molding of the regenerated resin, the broken bodies become a cause of hindrance to molding, and become a factor of lowering the quality of the molded body manufactured.

[0023] In addition, the technology described in Patent Document 3 relates to recovery of aluminum from packaging materials containing aluminum, and does not have any consideration for the recovery of resin.

[0024] In addition, in Patent Documents 4 and 5, there is no study on the technology itself of manufacturing a film from a regenerated resin.

[0025] Therefore, the present application relates to improvement of a resin film material using a regenerated resin as a raw material, the regenerated resin being obtained from a laminate having a resin layer having a metal layer.

[0026] In addition, the present application relates to the provision of a method of manufacturing a useful regenerated resin composition from resin waste material having a resin layer having a metal layer.

[0027] Hereinafter, the present application will be described based on preferred embodiments thereof. The present application relates to a resin film material. The resin film material of the present application contains resin and metal. The kind of metal, and its state of existence will be described below. The resin in the present specification broadly includes a thermoplastic resin, and a thermoplastic resin having a film-forming ability is particularly preferred. A thermoplastic resin having a film-forming ability is broadly included. The resin film material of the present application is in the form of a film. The resin film material of the present application is generally formed from a single layer of film.

[0028] One of the features of the resin film material of the present application is the raw material used to manufacture the film material. The raw material contains a resin material containing a laminate having a resin layer having a metal vapor deposition layer. Hereinafter, the resin material as the raw material of the resin film material of the present application will be described.

[0029] The resin material used in the present application contains a laminate having a resin layer having a metal vapor deposition layer. The laminate is a laminate having at least a two-layer structure of a metal vapor deposition layer and a resin layer. Therefore, in the following description, the laminate will also be referred to as "laminate having a metal vapor deposition layer". The metal vapor deposition layer is a layer obtained by forming various metals in a thin film shape using a dry film formation method. As the dry film formation method, a vacuum evaporation method can be cited as a representative example, but is not limited to this method. For example, in the present application, a metal can be heated and evaporated in a vacuum container reduced to a pressure of about 0.0001 Pa, and the metal can be condensed on a substrate, i.e., the surface of a resin film, which is provided in advance in the container, to form a thin film of the metal, i.e., a metal vapor deposition layer.

[0030] As for the metal deposition layer, it is known that the thickness thereof is extremely thin, and is generally, for example, about 10 nm or more, and further, about 1000 nm or less. As a material similar to the metal deposition layer, a metal foil is also known, but the thickness of the metal deposition layer is about two orders of magnitude smaller than that of the metal foil, and thus, the metal deposition layer and the metal foil can be clearly distinguished in terms of the thickness thereof. As for the metal foil, the thickness thereof is about 5 μm or more at the minimum.

[0031] The kind of metal constituting the metal deposition layer is not particularly limited, and an appropriate metal can be selected depending on the specific use of the target resin film material, the easiness of deposition, and the like. Typically, the use of aluminum is preferred, but metals other than aluminum, such as chromium, zinc, gold, silver, platinum, nickel, and the like, can also be used. Further, two or more kinds of metals can also be used in combination.

[0032] The metal deposition layer is adjacent to the resin layer, and a layered body with a metal deposition layer is constituted by these two layers. The shape of the layered body with a metal deposition layer is not particularly limited, and various kinds of three-dimensional molded bodies, and two-dimensional molded bodies such as films and broken bodies, and the like can be cited. Specifically, a resin container as a three-dimensional molded body, a resin film as a two-dimensional molded body, and the like can be cited. The layered body with a metal deposition layer can have at least one metal deposition layer and at least one resin layer, and can also have two or more metal deposition layers, and two or more resin layers. When the layered body with a metal deposition layer has two or more metal deposition layers, the kind of metal constituting the metal deposition layers can be the same or different. The same also applies to the resin layer, and when the layered body with a metal deposition layer has two or more resin layers, the kind of resin constituting the resin layers can be the same or different.

[0033] When the layered body with a metal deposition layer has two or more resin layers, the layered body with a metal deposition layer preferably has at least one layer of a polyolefin. Further, the layered body with a metal deposition layer preferably has at least one layer of a resin containing one or two or more kinds selected from the group consisting of a polyester, a polyamide, and a polyimide. By using a resin material containing a layered body with a metal deposition layer having such a resin layer as a raw material to produce the resin film material of the present application, the heat sealability, the elastic force, and the dimensional stability when a layered structure is produced using the resin film material are improved, and thus, it is preferred.

[0034] As the above polyolefin, for example, polyethylene, polypropylene, and an ethylene-α-olefin copolymer, and the like can be cited. These polyolefins can be used alone as one kind, or two or more kinds can be used in combination.

[0035] As the polyethylene, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, and the like can be cited.

[0036] As the polypropylene, for example, isotactic polypropylene, syndiotactic polypropylene, and atactic polypropylene, and the like can be mentioned.

[0037] As the α-olefin constituting the ethylene-α-olefin copolymer, for example, propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene, and the like can be mentioned.

[0038] As the polyester, for example, polyethylene terephthalate and polybutylene terephthalate, and the like can be mentioned.

[0039] As the polyamide, for example, nylon 6, nylon 6,6, and nylon 4,6, and the like can be mentioned.

[0040] As the polyimide, for example, poly(4,4'-oxydiphenylene pyromellitimide), and the like can be mentioned.

[0041] In addition, as the polyolefin, a biomass-derived polymer material such as bio-polyethylene and bio-polypropylene can also be used.

[0042] As the laminate with a metal vapor deposition layer, a raw laminate manufactured for the purpose of obtaining a raw material of the resin film material of the present application can be used.

[0043] Alternatively, as the laminate with a metal vapor deposition layer, a used laminate provided with a resin layer having a metal vapor deposition layer can also be used. For example, a used two-dimensional molded body or a three-dimensional molded body provided with a resin layer having a metal vapor deposition layer can be directly used as a laminate with a metal vapor deposition layer for obtaining a raw material of the resin film material of the present application, or a crushed body of the used molded body can be used as a laminate with a metal vapor deposition layer for obtaining a raw material of the resin film material of the present application.

[0044] Alternatively, as the laminate with a metal vapor deposition layer, an end material generated in the process of manufacturing a two-dimensional molded body or a three-dimensional molded body, and which does not have a value as a product by itself can also be used.

[0045] In the following description, a used article and an end material are collectively referred to as "waste". That is, in the present specification, "waste" is a concept including both a used article and an end material generated in the process of manufacturing a product, and which does not have a value as a product by itself.

[0046] Among these laminates with a metal vapor deposition layer, from the viewpoint of reducing environmental burden, it is preferable to directly use a used two-dimensional molded body or a three-dimensional molded body as a laminate compared to the use of a raw laminate, or it is preferable to use a crushed body of the used molded body as a laminate.

[0047] From the same viewpoint, it is also preferable to use the end material produced when manufacturing the two-dimensional shaped body or the three-dimensional shaped body as the laminate with a metal vapor deposition layer.

[0048] As described above, the resin film material of the present application is preferably a regenerated resin film material using a resin material as a waste material as a raw material.

[0049] The resin material used as a raw material in the production of the resin film material of the present application can be composed only of the above-described laminate with a metal vapor deposition layer, or can contain other materials in addition to the laminate with a metal vapor deposition layer. As the other materials, a resin layer not having a metal layer can be cited. The resin layer is preferably formed of a single material, and as the material, for example, a polyolefin can be cited. In addition, as the other materials, a laminate provided with a resin layer not having a metal layer can also be cited. The laminate does not include both a metal vapor deposition layer and a metal foil layer. Therefore, in the following description, the laminate will also be referred to as a "laminate not having a metal layer". The laminate not having a metal layer is preferably formed of two or more resin layers. The two or more resin layers are formed of mutually different resins. Therefore, with respect to the laminate not having a metal layer, at least two or more kinds of resins are contained when viewed from the entirety thereof.

[0050] With respect to the laminate not having a metal layer, it is sufficient to not include a metal layer, and it is permissible to include a metal in a form other than a metal layer. For example, in the laminate not having a metal layer, it is permissible to finely disperse a metal in a resin layer, provided that a metal layer is not included.

[0051] As the laminate not having a metal layer, a raw laminate produced for the purpose of obtaining a raw material of the resin film material of the present application can be used.

[0052] Alternatively, as the laminate not having a metal layer, a used laminate provided with a resin layer not having a metal layer can also be used. For example, a used two-dimensional shaped body or a three-dimensional shaped body provided with a resin layer not having a metal vapor deposition layer can be directly used as a laminate not having a metal layer for obtaining a raw material of the resin film material of the present application, or a crushed body of the used shaped body can be used as a laminate not having a metal layer for obtaining a raw material of the resin film material of the present application.

[0053] Alternatively, as the laminate not having a metal layer, an end material produced in the process of manufacturing a two-dimensional shaped body or a three-dimensional shaped body, and not having a value as a product itself can also be used.

[0054] Among these laminates not having a metal layer, from the viewpoint of reducing environmental burdens, it is preferable to directly use a used two-dimensional shaped body or a three-dimensional shaped body as a laminate, or to use a crushed body of the used shaped body as a laminate, as compared with using a raw laminate.

[0055] From the same viewpoint, it is also preferable to use the end material produced when manufacturing the two-dimensional shaped body or the three-dimensional shaped body as the non-metal layer laminate.

[0056] Regarding the non-metal layer laminate, from the viewpoint of improving heat sealability when manufacturing the laminate structure using the target resin film material, it is preferable to have at least one layer of a polyolefin.

[0057] From the viewpoint of making the advantage even more remarkable, the non-metal layer laminate preferably has two or more layers of a polyolefin. At this time, each layer of the polyolefin can be formed of the same polyolefin, or can be formed of different polyolefins. Specific examples of the polyolefin are as described above.

[0058] As described above, as the raw material resin material used in the manufacturing of the resin film material of the present application, (a) can be composed of only the laminate with a metal vapor deposition layer, or (b) can be composed of a group of laminates including the laminate with a metal vapor deposition layer and the non-metal layer laminate. Whether to use the resin material of (a) or the resin material of (b) can be appropriately selected depending on the proportion of the metal contained in the target resin film material, the proportion of the resin contained, and the like.

[0059] For example, the proportion of the laminate with a metal vapor deposition layer in the resin material can be preferably set to 10 mass% or more and 100 mass% or less, can be further preferably set to 15 mass% or more and 90 mass% or less, and can be still further preferably set to 20 mass% or more and 80 mass% or less.

[0060] In either case of (a) and (b) described above, as the raw material resin material used in the manufacturing of the resin film material of the present application, only one kind of resin is contained, or two or more kinds of resins are contained. In the latter case, the two or more kinds of resins in the resin material are in a blended state. At this time, no adverse effects are caused on the case of manufacturing the resin film material of the present application using the resin material as a raw material.

[0061] By using the resin material described above as a raw material and performing melt molding, the resin film material of the present application can be obtained. For example, by performing extrusion molding on the resin material, the resin film material of the present application can be manufactured. As specific examples of the extrusion molding, T-die molding, blow molding, and injection molding can be given.

[0062] According to the present application, a manufacturing method of a resin film material is also provided, which uses, as a raw material, a resin material containing a laminate having a resin layer with a metal vapor deposition layer, and contains the metal in the form of particles. The manufacturing method has a process of melt molding the resin material described above so that the metal particles are dispersed in the film material, and so that the number of the metal particles per 1 cm 2The number of the above metal particles having an area equivalent diameter of 200 μm or more present in the above resin film material is 1 or less.

[0063] A compatibilizing agent can be added at the time of melt molding. As the compatibilizing agent, for example, a compound having a polar group and a polyolefin is preferably used. With the compound having a polar group and a polyolefin, it is expected that the polyolefin portion has an affinity with the resin contained in the target resin film material, for example, a polyolefin, and on the other hand, the polar group portion reacts or interacts with a foreign substance such as a polyamide, thereby exhibiting an affinity. Thereby, it is expected that a structure having a high affinity is formed in the matrix in the target resin film material.

[0064] The resin film material of the present application is produced using the above resin material as a raw material, and therefore, it is preferable to contain any of a polyolefin resin, a polyester resin, and a polyamide resin, and it is more preferable to contain a polyolefin resin as a main component. From the viewpoint of promoting the regeneration of the resin that is a resin material for a packaging container, it is further more preferable for the resin film material of the present application to contain polyethylene as a main component.

[0065] The resin film material of the present application contains metal in the form of particles, because it is produced using a resin material composed of only a laminate having a metal vapor deposition layer as a raw material, or using a resin material containing a laminate having a metal vapor deposition layer and a laminate having no metal layer as a raw material. The metal particles come from the metal vapor deposition layer in the laminate having a metal vapor deposition layer, and are melt-kneaded during the production process, and therefore, are dispersed in the resin film material. The resin film material in which the metal particles are dispersed is able to lower the thermal expansion rate, which is clarified as a result of the research by the present inventors. In detail, it has been clarified that the thermal expansion rate of a resin is generally known to be higher than that of a metal, and if metal particles are dispersed in a resin, the property of the metal having a relatively low thermal expansion rate is reflected in the resin, and thereby the thermal expansion rate of the resin film material is lowered.

[0066] The resin film material of the present application has a low thermal expansion rate, which means that the dimensional stability to heating is high. Therefore, when a laminate structure is produced using the resin film material of the present application, the resin film material is less likely to be affected by heat, and therefore, exhibits the advantageous effect of improved processability.

[0067] In addition, the resin film material of the present application has a low thermal expansion rate, which also contributes to the improvement of the storage stability of the resin film material.

[0068] From the viewpoint of further lowering the thermal expansion rate of the resin film material, the content of the metal contained in the resin film material is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and further more preferably 0.1 mass% or more.

[0069] From the same point of view, the metal content contained in the resin film material is preferably 0.3% by mass or less, more preferably 0.25% by mass or less, and even more preferably 0.2% by mass or less.

[0070] In summary, the metal content in the resin film material is preferably 0.01% by mass or more and 0.3% by mass or less, more preferably 0.05% by mass or more and 0.25% by mass or less, and even more preferably 0.1% by mass or more and 0.2% by mass or less.

[0071] In this invention, it is particularly preferred that the metal is aluminum, and that the aluminum content in the resin film material is within the range described above.

[0072] When the resin film material of the present invention contains metal as described above, it is preferable that the metal is present in a finely dispersed state rather than in the form of coarse particles. If coarse metal particles are present in the resin film material, the resin film material is easily damaged starting from these coarse particles, which leads to a higher coefficient of thermal expansion of the resin film material, thus reducing the advantages arising from the dispersion of metal in the resin film material.

[0073] Based on the viewpoint of suppressing the increase in thermal expansion rate when coarse metal particles are present in the resin film material, the inventors conducted in-depth research and clarified that: if the thermal expansion rate increases per 1 cm 2 The presence of one or fewer metal particles with an area equivalent diameter of 200 μm or more in the resin film material is preferred, as this effectively suppresses the increase in the coefficient of thermal expansion. From the viewpoint of further enhancing this advantage, the presence of metal particles with an area equivalent diameter of 200 μm or more per 1 cm² is considered optimal. 2 More preferably, the number of metal particles with an area equivalent diameter of 200 μm or more present in the resin film material is 0.7 or less, and even more preferably 0.3 or less. The reason for setting the area equivalent diameter of the metal particles to 200 μm is that the inventors discovered the following phenomenon: when the area equivalent diameter reaches 200 μm or more, the cracking generated in the resin film material becomes dramatically significant.

[0074] From the perspective of further suppressing the increase in thermal expansion rate when coarse metal particles are present in the resin film material, at every 1cm 2 The number of metal particles with an area equivalent diameter of 100 μm or more present in the resin film material is preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less. The reason for setting the area equivalent diameter of the metal particles to 100 μm is that the inventors discovered the following phenomenon: when the area equivalent diameter is 100 μm or more, the thickness unevenness generated in the resin film material becomes drastically significant.

[0075] The inventors' research has clarified that, from the viewpoint of further suppressing the increase in the coefficient of thermal expansion, when the average particle size of the metal particles contained in the resin film material is set as Dp and the average inter-surface distance of the metal particles is set as h, the value of h / Dp is preferably greater than 15. From the viewpoint of making this advantage even more significant, the value of h / Dp is preferably 20 or more, and more preferably 25 or more. The larger the value of h / Dp, the more effective it is in suppressing the increase in the coefficient of thermal expansion, but the upper limit is around 200.

[0076] The average intersurface distance h of the aforementioned metal particles was calculated using Bansal Ardell's approximation. Bansal Ardell's approximation is shown below.

[0077] h=Dp{0.11F -3 / 4}

[0078] In the formula, h represents the average inter-surface distance of metal particles (unit: μm), Dp represents the average particle size of metal particles (unit: μm), and F represents the particle volume concentration (unit: dimensionless number).

[0079] That is, h / Dp = 0.11F -3 / 4 .

[0080] The method for determining F in this formula is described in the examples described below.

[0081] To prevent the resin film material from containing coarse metal particles, one could, for example, fully melt and mix the resin material comprising a laminate with a metal vapor-deposited layer; or, as the resin material, not use a laminate with a resin layer having a metal foil layer. Since the thickness of the metal foil is from several μm to tens of μm, when a resin film material is formed using a resin material comprising a laminate with a resin layer having a metal foil layer as raw material, there is a possibility that coarse particles originating from the metal foil may be generated in the resin film material.

[0082] The presence of coarse metal particles is problematic in this invention because it relates to film materials, i.e., thin-film articles. In contrast, in thick three-dimensional molded articles, the presence of coarse metal particles is less likely to be a major factor contributing to an increase in the coefficient of thermal expansion. This is because cracking is less likely to occur in thick three-dimensional molded articles. Therefore, from the viewpoint of effectively suppressing the increase in the coefficient of thermal expansion of the resin film material of this invention, the average thickness of the resin film material is preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less.

[0083] From the same point of view, for resin film materials, the average thickness is preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more.

[0084] In summary, for resin film materials, the average thickness is preferably 10 μm or more and 500 μm or less, more preferably 15 μm or more and 300 μm or less, and even more preferably 20 μm or more and 100 μm or less.

[0085] The resin film material of the present invention contains very few coarse metal particles, thus exhibiting high surface smoothness even with a thin thickness. Therefore, by laminating resin layers and / or metal foils onto the surface of the resin film material of the present invention, a laminated structure can be easily manufactured. In the laminated structure thus obtained, the interlayer peel strength between the resin film material and the resin layers and / or metal foils can be sufficiently improved. That is, according to the present invention, a resin film material with high surface smoothness and suitable as a raw material for laminates with high interlayer peel strength can be provided.

[0086] When resin layers are stacked on the surface of a resin film material, extrusion lamination can be used, for example. Because of the high smoothness of the surface of resin film materials, extrusion lamination can successfully produce laminated structures with high interlayer peel strength.

[0087] Furthermore, the surface smoothness becomes a problem in this invention because it relates to film materials, i.e., thin-film articles. In contrast, in thick three-dimensional molded bodies, the presence of coarse metal particles is less likely to be a major factor deteriorating surface smoothness. This is because in thick three-dimensional molded bodies, the thickness of the body is much larger than the size of the coarse particles. In other words, the challenge of suppressing the presence of coarse particles to achieve a smooth surface is unique to resin film materials.

[0088] As a laminated structure using the resin film material of the present invention as a raw material, there are two types: two-dimensional molded bodies and three-dimensional molded bodies. For example, the resin film material of the present invention can be used as a raw material to manufacture two-dimensional molded bodies such as films. Alternatively, three-dimensional molded bodies such as stand-up pouches can be manufactured by processing the two-dimensional molded body.

[0089] In the laminated structure using the resin film material of the present invention as raw material, examples of resin layers laminated in the resin film material include polyolefins, polyesters, polyamides, and polyimides. Specific examples of these resins are described above. For example, by laminating and stretching polyethylene terephthalate on the outer side of the laminated structure, a laminated structure with high strength and excellent heat resistance can be obtained. From the viewpoint of promoting the recycling of resins to facilitate the widespread use of resin materials as packaging containers, it is more preferable to include polyethylene as the main component as the resin layer material. Examples of other resins include ethylene-vinyl alcohol copolymers. Ethylene-vinyl alcohol copolymers are resins with excellent barrier properties against various gases, including oxygen. Therefore, the laminated structure obtained by laminating a resin layer containing an ethylene-vinyl alcohol copolymer in the resin film material of the present invention is a laminated structure with high gas barrier properties. Therefore, this laminated structure is suitable as a packaging container for containing contents formed from various liquids or powders.

[0090] Furthermore, to improve barrier properties, materials other than resin layers, such as metal vapor-deposited layers, can also be layered.

[0091] Next, a suitable method for manufacturing the resin material, which is the raw material for the resin film material of the present invention, will be described. This resin material is a composition comprising resin and components other than resin; therefore, in the following description, this resin material will also be referred to as a "resin composition". Furthermore, the resin composition obtained by the method for manufacturing the resin composition of the present invention is suitable as a raw material for the resin film material of the present invention, but it goes without saying that this resin composition can also be used as a raw material for other resin molded articles.

[0092] In this invention, it is suitable to manufacture resin compositions from resin waste.

[0093] In the method for manufacturing the resin composition of the present invention, a resin waste mixture is first prepared. The resin waste mixture includes resin waste having a resin layer with a metal foil layer and resin waste having a resin layer with a metal vapor-deposited layer. Resin waste mixtures are typically generated in households, commercial facilities, factories, etc., and are treated in incineration facilities or industrial waste treatment facilities. In the present invention, the generated resin waste mixture is not incinerated or disposed of, but rather its environmental burden is reduced through reuse. That is, the resin composition manufactured in the present invention is a recycled resin composition.

[0094] As an example of resin waste containing a resin layer with a metal vapor-deposited layer, the above-mentioned laminate containing a resin layer with a metal vapor-deposited layer, i.e., a laminate with a metal vapor-deposited layer, can be cited as an example.

[0095] On the other hand, the resin waste containing a resin layer with a metal foil layer included in the resin waste mixture will be described below.

[0096] Resin waste having a resin layer with a metal foil layer comprises a laminate with at least two layers, having a metal foil layer and a resin layer. Therefore, in the following description, this laminate will also be referred to as a "laminate with a metal foil layer". The metal foil layer is a layer in which various metals are formed into foil by rolling. It is known that the thickness of the metal foil layer is greater than the thickness of the metal vapor-deposited layer described above, generally, for example, about 5 μm or more, and also about 100 μm or less.

[0097] There are no particular restrictions on the types of metals that make up the foil layers. Aluminum is a typical example, but other metals such as chromium, zinc, gold, silver, platinum, and nickel can also be used. Metal foils sometimes contain combinations of two or more metals.

[0098] The metal foil layer and the resin layer are adjacent to each other, and these two layers constitute a laminate with the metal foil layer. The shape of the laminate with the metal foil layer is not particularly limited; for example, various three-dimensional shapes, as well as two-dimensional shapes such as films and fragments, can be included. Specifically, examples include resin containers as three-dimensional shapes and resin films as two-dimensional shapes. The laminate with the metal foil layer may have at least one metal foil layer and at least one resin layer, or it may have two or more metal foil layers and two or more resin layers. When the laminate with the metal foil layer has two or more metal foil layers, the types of metals constituting the metal foil layers may be the same or different. Similarly, when the laminate with the metal foil layer has two or more resin layers, the types of resins constituting the resin layers may be the same or different.

[0099] The laminate with the metal foil layer is removed from the resin waste mixture in the removal process described below, and therefore is hardly included in the raw materials of the resin composition, which is the object of manufacture of the present invention. Therefore, the type of resin constituting the resin layer of the laminate with the metal foil layer has almost no impact on the manufacturing method of the present invention.

[0100] The metal constituting the laminate with the metal foil layer and the metal constituting the laminate with the metal vapor-deposited layer can be the same type of metal or different types of metal. Similarly, the resin constituting the laminate with the metal foil layer and the resin constituting the laminate with the metal vapor-deposited layer can be the same type of resin or different types of resin.

[0101] The resin waste mixture may consist solely of a laminate with a metal foil layer and a laminate with a metal vapor-deposited layer. Alternatively, the resin waste mixture may contain other materials in addition to the laminate with a metal foil layer and the laminate with a metal vapor-deposited layer. Examples of other materials include the aforementioned laminate without a metal layer. Details regarding the laminate without a metal layer are as described above.

[0102] In this invention, resin waste comprising a laminate with a metal foil layer is separated and removed from the resin waste mixture. The separated resin waste mixture may, for example, (a) contain resin waste comprising one or more laminates with metal vapor-deposited layers; or (b) contain resin waste comprising one or more laminates with metal vapor-deposited layers and resin waste comprising one or more laminates without metal layers. Whether to use resin waste (a) or resin waste (b) can be appropriately selected based on the proportion of metal and resin in the target resin composition.

[0103] For example, the proportion of the laminate with the metal vapor-deposited layer in the separated resin waste mixture can be preferably set to 10% by mass or more and 100% by mass or less, more preferably 15% by mass or more and 90% by mass or less, and even more preferably 20% by mass or more and 80% by mass or less.

[0104] Furthermore, the separated resin waste mixture preferably does not contain resin waste formed by the laminate with the metal foil layer, but it is limited to the point that the resin composition manufactured from the separated resin waste mixture does not contain coarse particles as described below, that is, it may contain resin waste formed by the laminate with the metal foil layer to a extent that it does not affect the quality of the manufactured resin composition. For example, the proportion of the laminate with the metal foil layer in the separated resin waste mixture is preferably at most 2% by mass or less, more preferably 1.5% by mass or less, and even more preferably 0% by mass.

[0105] In either case (a) or (b) above, the resin waste mixture after removing the resin waste from the laminate containing the metal foil layer contains only one type of resin, or contains two or more types of resin. In the latter case, the resin composition manufactured from the resin waste mixture is a blend of two or more types of resin. This will not adversely affect the manufacture of molded articles using this resin composition as a raw material.

[0106] The reason for removing the resin waste containing the laminate with the metal foil layer from the resin waste mixture containing both resin waste containing a laminate with a metal foil layer and resin waste containing a laminate with a metal vapor-deposited layer is to improve the grade of the resin composition, which is the object of the manufacturing method of the present invention. The thickness of the metal foil is from several μm to tens of μm. Therefore, if the resin waste mixture contains resin waste containing a laminate with a metal foil layer, it is possible that coarse metal particles from the metal foil will be mixed into the resin composition manufactured from the resin waste mixture. If coarse metal particles are present in the resin composition, they may be mixed into the molded body formed from the resin composition as a raw material, i.e., the resin film material of the present invention described above, thereby potentially reducing the performance of the resin film material of the present invention due to the presence of these coarse particles. The reduction in the performance of the resin film material of the present invention due to the presence of coarse particles is more significant as the thickness of the film decreases. Specifically, the surface smoothness of the resin film material of the present invention is reduced. As a result, when this resin film material is laminated with another material to manufacture a laminate, there is a possibility that the interlayer peel strength cannot be sufficiently improved. Therefore, in the present invention, in order to prevent the introduction of coarse metal particles into the resin composition manufactured from the resin waste mixture, the resin waste containing the laminate with the metal foil layer is removed from the resin waste mixture.

[0107] When removing resin waste containing laminates with metal foil layers from a resin waste mixture, it is preferable to use various separation methods, such as electromagnetic sensors, X-ray sensors, near-infrared sensors, and color sensors, to detect the laminates with metal foil layers, thereby separating them from the laminates with metal vapor-deposited layers. It is particularly preferable to detect laminates with metal foil layers of 1 μm or more thickness, thereby separating them from the laminates with metal vapor-deposited layers. From the viewpoint of high separation accuracy, electromagnetic sensors are preferred as the separation method.

[0108] When using an electromagnetic sensor, the difference in detected voltage values, based on the strength of the magnetic force induced by the current, allows for the separation of laminates with metal foil layers from laminates with metal vapor-deposited layers. Specifically, the difference in magnetic force caused by the difference in thickness between the metal vapor-deposited layer and the metal foil allows for the separation of laminates with metal foil layers from laminates with metal vapor-deposited layers. In particular, when the thickness of the metal foil layer in the laminate with metal foil layers is 1 μm or more, the laminates with metal foil layers and laminates with metal vapor-deposited layers can be separated with even higher precision. Using an electromagnetic sensor offers the advantage of accurate separation even when resin waste is not clean. In contrast, when using color sensors or near-infrared sensors, accurate separation can sometimes be difficult to achieve if resin waste is not clean.

[0109] From the perspective of efficient separation, it is preferable to separate the laminate with the metal foil layer and the laminate with the metal vapor-deposited layer directly in their post-use state. For example, if both the laminate with the metal foil layer and the laminate with the metal vapor-deposited layer are used containers, it is preferable not to break the containers, but to separate them directly while maintaining their shape.

[0110] After separating and removing the resin waste containing the laminated body with the metal foil layer from the resin waste mixture, the separated resin waste mixture is melt-formed. Melt-forming can be performed using a conventional extruder. For efficient melt-forming using an extruder, it is preferable to crush the separated resin waste mixture to a size suitable for supplying the extruder before melt-forming, and then melt-form the resulting crushed material. Crushing can be performed using a plastic crusher, shredder, etc.

[0111] The crushed resin waste mixture is fed to an extruder and melt-formed to obtain a resin composition. The melt-forming temperature is selected appropriately based on the type of resin contained in the resin waste mixture. From the viewpoint of achieving thorough melt mixing, it is preferable to use a temperature between Mp-30 and Mp+30, where the melting point of the resin with the highest melting point among the resins contained in the resin waste mixture is set as Mp (°C).

[0112] The resin composition thus obtained uses the aforementioned resin waste as raw material; therefore, it is preferable to contain any one of polyolefin resin, polyester resin, and polyamide resin, and more preferably, polyolefin resin as the main component. From the viewpoint of promoting the widespread use of resin materials as packaging containers through resin recycling, the resin composition is even more preferably to contain polyethylene as the main component.

[0113] Resin compositions obtained by melt-blending and molding a resin waste mixture generally have a particulate form. In this resin composition, the metals contained in the resin waste mixture are dispersed in the form of particles.

[0114] Using the resin composition thus obtained as a raw material, various molded articles, such as the resin film material of the present invention, can be manufactured. For example, the resin film material of the present invention can be manufactured by extrusion molding of the resin composition. In addition, a three-dimensional resin molded body can be manufactured by injection molding of the resin composition.

[0115] The resin composition obtained from a mixture of separated resin waste materials can be molded to obtain the resin film material of the present invention. Layering other materials onto this resin film material can yield a laminated structure. Alternatively, in the present invention, a laminated structure can also be manufactured by co-extruding the resin composition obtained from the mixture of separated resin waste materials with other resin compositions. Co-extrusion molding consistently yields laminated structures with high interlayer peel strength between resin layers.

[0116] Of course, the manufacturing method of laminated structures is not limited to this. Laminated structures can also be manufactured by heat-sealing between membrane materials, dry lamination, etc.

[0117] The present invention has been described above based on its preferred embodiments, but the present invention is not limited to the above embodiments.

[0118] Regarding the above-described embodiments, the present invention further discloses the following methods for manufacturing resin film materials, laminated structures, resin compositions, resin film materials, and laminated structures.

[0119] <1> A resin film material is made from a resin material comprising a laminate, wherein the laminate is a resin layer having a metal vapor-deposited layer, and the resin film material contains the metal in the form of particles.

[0120] The aforementioned metal particles are dispersed in the above-mentioned membrane material, and per 1 cm 2 The number of metal particles with an area equivalent diameter of 200 μm or more present in the above resin film material is less than one.

[0121] <2> The above <1> The resin film material described herein, wherein, per 1cm 2 The number of metal particles with an area equivalent diameter of 200 μm or more present in the above-mentioned resin film material is preferably 0.7 or less, and more preferably 0.3 or less.

[0122] <3> The above <1> or <2> The resin film material described herein, wherein, per 1cm 2 The number of metal particles with an area equivalent diameter of 100 μm or more present in the above-mentioned resin film material is less than 15.

[0123] <4> The above <3> The resin film material described herein, wherein, per 1cm 2 The number of metal particles with an area equivalent diameter of 100 μm or more present in the above-mentioned resin film material is preferably 10 or less, and more preferably 5 or less.

[0124] <5> The above <1> to <4> The resin film material described in any one of the above-mentioned methods, wherein the laminate having a resin layer with a metal vapor-deposited layer has at least one layer of polyolefin.

[0125] <6> The above <5> The resin film material described herein, wherein the aforementioned polyolefin is polyethylene.

[0126] <7> The above <1> to <6> In any one of the resin film materials described herein, the proportion of the laminate having the resin layer with the metal vapor-deposited layer in the resin material is preferably 10% by mass or more and 100% by mass or less, more preferably 15% by mass or more and 90% by mass or less, and even more preferably 20% by mass or more and 80% by mass or less.

[0127] <8> The above <1> to <7> The resin film material described in any one of the above-mentioned methods, wherein the content of the metal contained in the resin film material is preferably 0.01% by mass or more and 0.3% by mass or less, more preferably 0.05% by mass or more and 0.25% by mass or less, and even more preferably 0.1% by mass or more and 0.2% by mass or less.

[0128] <9> The above <1> to <8> The resin film material described in any one of the following is made from a resin material comprising a laminate assembly, wherein the laminate assembly comprises: the laminate having a resin layer having a metal vapor-deposited layer, and a laminate having a resin layer without a metal layer.

[0129] <10> The above <9> The resin film material described herein includes a layer of polyolefin in the laminate containing a resin layer that does not have a metal layer.

[0130] <11> The above <1> to <10> The resin film material described in any one of the above-mentioned methods, wherein the laminate having a resin layer with a metal vapor deposition layer comprises: a polyolefin layer and a layer comprising one or more resins selected from polyester, polyamide and polyimide.

[0131] <12> The above <1> to <11> In any one of the resin film materials described herein, the proportion of the laminate having the resin layer with the metal vapor-deposited layer in the resin material is preferably 10% by mass or more and 100% by mass or less, more preferably 15% by mass or more and 90% by mass or less, and even more preferably 20% by mass or more and 80% by mass or less.

[0132] <13> The above <1> to <12> The resin film material described in any one of the above-mentioned materials, wherein the metal is aluminum, and the aluminum content is 0.01% by mass or more and 0.3% by mass or less.

[0133] <14> The above <1> to <13> The resin film material described in any one of the above is a waste material, wherein the laminate containing the resin layer having a metal vapor-deposited layer is a waste material.

[0134] <15> The above <1> to <14> The resin film material described in any one of the articles contains polyethylene as the main component.

[0135] <16> The above <1> to <15> The resin film material described in any one of the above has an average thickness of 10 μm or more and 500 μm or less.

[0136] <17> The above <16> The resin film material described herein preferably has an average thickness of 15 μm or more and 300 μm or less, and more preferably 20 μm or more and 100 μm or less.

[0137] <18> The above <1> to <17> The resin film material described in any one of the present inventions, wherein the ratio of the average inter-surface distance of the metal particles to the average particle size of the metal particles is greater than 15.

[0138] <19> A layered structure having the above-mentioned <1> to <18> The resin film material and the resin layer or metal foil described in any of the above.

[0139] <20> The above <19> The laminated structure described herein, wherein the resin layer comprises an ethylene-vinyl alcohol copolymer.

[0140] <21> The above <19> or <20> The layered structure described in the text is the form of a packaging container.

[0141] <22> A method for manufacturing a resin film material, wherein the resin film material is made from a resin material comprising a laminate having a resin layer having a metal vapor-deposited layer, and the metal is contained in the form of particles.

[0142] The manufacturing method includes the following steps: melting and molding the above-mentioned resin material to disperse the above-mentioned metal particles in the above-mentioned film material, and dispersing the metal particles in every 1 cm. 2The number of metal particles with an area equivalent diameter of 200 μm or more present in the above resin film material is less than one.

[0143] <23> The above <22> The method for manufacturing resin film material described herein, wherein, in every 1 cm 2 The number of metal particles with an area equivalent diameter of 200 μm or more present in the above-mentioned resin film material is preferably 0.7 or less, and more preferably 0.3 or less.

[0144] <24> The above <22> or <23> The method for manufacturing resin film material described herein, wherein, in every 1 cm 2 The number of metal particles with an area equivalent diameter of 100 μm or more present in the above-mentioned resin film material is less than 15.

[0145] <25> The above <24> The method for manufacturing resin film material described herein, wherein, in every 1 cm 2 The number of metal particles with an area equivalent diameter of 100 μm or more present in the above-mentioned resin film material is preferably 10 or less, and more preferably 5 or less.

[0146] <26> The above <22> to <25> The method for manufacturing a resin film material as described in any one of the present inventions, wherein the laminate having a resin layer having a metal vapor-deposited layer has at least one layer of polyolefin.

[0147] <27> The above <26> The method for manufacturing resin film material described herein, wherein the polyolefin is polyethylene.

[0148] <28> The above <22> to <27> In any one of the methods for manufacturing a resin film material, the proportion of the laminate having a resin layer with a metal vapor-deposited layer in the resin material is preferably 10% by mass or more and 100% by mass or less, more preferably 15% by mass or more and 90% by mass or less, and even more preferably 20% by mass or more and 80% by mass or less.

[0149] <29> The above <22> to <28> The method for manufacturing a resin film material as described in any one of the claims, wherein the content of the metal contained in the resin film material is preferably 0.01% by mass or more and 0.3% by mass or less, more preferably 0.05% by mass or more and 0.25% by mass or less, and even more preferably 0.1% by mass or more and 0.2% by mass or less.

[0150] <30> The above <22> to <29> The method for manufacturing a resin film material as described in any one of the claims, wherein a resin material comprising a laminate assembly is used as raw material, the laminate assembly comprising: the laminate having a resin layer having a metal vapor-deposited layer, and a laminate having a resin layer without a metal layer.

[0151] <31> The above <30> The method for manufacturing a resin film material described herein includes a layer of polyolefin comprising a resin layer having a resin layer without a metal layer.

[0152] <32> The above <22> to <31> The method for manufacturing a resin film material as described in any one of the following, wherein the laminate having a resin layer with a metal vapor deposition layer comprises: a polyolefin layer and a layer comprising one or more resins selected from polyester, polyamide and polyimide.

[0153] <33> The above <22> to <32> In any one of the methods for manufacturing a resin film material, the proportion of the laminate having a resin layer with a metal vapor-deposited layer in the resin material is preferably 10% by mass or more and 100% by mass or less, more preferably 15% by mass or more and 90% by mass or less, and even more preferably 20% by mass or more and 80% by mass or less.

[0154] <34> The above <22> to <33> The method for manufacturing a resin film material as described in any one of the claims, wherein the metal is aluminum and the aluminum content is 0.01% by mass or more and 0.3% by mass or less.

[0155] <35> The above <22> to <34> The method for manufacturing a resin film material as described in any one of the methods is wherein the laminate containing the resin layer having a metal vapor-deposited layer is waste.

[0156] <36> The above <22> to <35> The method for manufacturing a resin film material as described in any one of the claims, wherein the average thickness is 10 μm or more and 500 μm or less.

[0157] <37> The above <36> The method for manufacturing resin film material described herein preferably has an average thickness of 15 μm or more and 300 μm or less, and more preferably 20 μm or more and 100 μm or less.

[0158] <38> A method for manufacturing a resin composition, comprising removing the resin waste having the metal foil layer from a mixture of resin waste comprising resin waste having a resin layer having a resin layer having a resin foil layer and resin waste having a resin layer having a metal vapor-deposited layer.

[0159] The resin waste mixture after removal is melt-formed to obtain a resin composition in which the above-mentioned metal particles are dispersed.

[0160] <39> The above <38> In the method for manufacturing the resin composition described herein, the proportion of the resin waste having the resin layer having the metal vapor-deposited layer in the resin waste mixture after removing the resin waste having the resin layer having the metal foil layer is preferably 10% by mass or more and 100% by mass or less, more preferably 15% by mass or more and 90% by mass or less, and even more preferably 20% by mass or more and 80% by mass or less.

[0161] <40> The above <38> or <39> The method for manufacturing the resin composition described herein, wherein the proportion of the resin waste having the metal foil layer in the resin waste mixture after removing the resin waste having the metal foil layer is preferably 2% by mass or less, more preferably 1.5% by mass or less, and even more preferably 0% by mass.

[0162] <41> The above <38> to <40> A method for manufacturing a resin composition as described in any one of the claims, wherein, when the melting point of the resin with the highest melting point among the resins contained in the resin waste mixture is set to Mp (°C), the resin waste mixture after removal is melt-formed at a temperature of Mp-30 or higher and Mp+30 or lower.

[0163] <42> The above <38> to <41> A method for manufacturing a resin composition as described in any one of the claims, wherein the metal is aluminum.

[0164] <43> The above <38> to <42> The method for manufacturing a resin composition as described in any one of the claims, wherein the resin waste having a resin layer having a metal foil layer is a resin film or a resin container.

[0165] <44> The above <38> to <43> The method for manufacturing a resin composition as described in any one of the claims, wherein the resin waste having a resin layer with a metal vapor-deposited layer is a resin film or a resin container.

[0166] <45> The above <38> to <44> A method for manufacturing a resin composition as described in any one of the claims, wherein the aforementioned resin waste mixture after removal is crushed, and the resulting crushed material is melt-formed.

[0167] <46> The above <38> to <45> The method for manufacturing the resin composition described in any one of the claims, wherein the resin waste having a resin layer having a metal foil layer with a thickness of 1 μm or more is detected and removed using an electromagnetic sensor, an X-ray sensor, a near-infrared sensor or a color sensor.

[0168] <47> The above <46> The method for manufacturing a resin composition described herein involves using an electromagnetic sensor to detect and remove resin waste having a resin layer having a metal foil layer with a thickness of 1 μm or more, based on the degree of magnetic force induced by an electric current.

[0169] <48> A method for manufacturing a resin film material, wherein the above-mentioned... <38> to <47> The resin composition described herein is manufactured by any one of the methods described herein, and the resin composition is extruded.

[0170] <49> The above <48> The method for manufacturing a resin film material described herein, wherein the content of the aforementioned metal contained in the resin film material is preferably 0.01% by mass or more and 0.3% by mass or less, more preferably 0.05% by mass or more and 0.25% by mass or less, and even more preferably 0.1% by mass or more and 0.2% by mass or less.

[0171] <50> The above <48> or <49> The method for manufacturing resin film material described herein, wherein, in every 1 cm 2 The number of metal particles with an area equivalent diameter of 200 μm or more present in the above-mentioned resin film material is preferably 0.7 or less, and more preferably 0.3 or less.

[0172] <51> The above <48> to <50> The method for manufacturing a resin film material as described in any one of the claims, wherein, in every 1 cm 2 The number of metal particles with an area equivalent diameter of 100 μm or more present in the above-mentioned resin film material is preferably 10 or less, and more preferably 5 or less.

[0173] <52> The above <48> to <51> The method for manufacturing a resin film material as described in any one of the claims, wherein the average thickness is preferably 10 μm or more and 500 μm or less, more preferably 15 μm or more and 300 μm or less, and even more preferably 20 μm or more and 100 μm or less.

[0174] <53> A method for manufacturing a stacked structure, wherein the above-mentioned <38> to <47> The resin composition described herein is manufactured by any of the methods described herein, and the resin composition is co-extruded or extruded and laminated.

[0175] <54> A method for manufacturing a stacked structure, wherein the above-mentioned <48> to <52> The resin film material manufactured by any of the methods described herein is laminated with a resin layer.

[0176] <55> The above <54> The method for manufacturing a laminated structure described herein, wherein the resin layer comprises a polyolefin.

[0177] <56> The above <55> The method for manufacturing a laminated structure described herein, wherein the resin layer contains polyethylene as the main component.

[0178] Example

[0179] The present invention will be further described in detail below through embodiments. However, the scope of the present invention is not limited to these embodiments. Unless otherwise specified, "%" means "mass %".

[0180] [Example 1-1]

[0181] (1) Preparation of resin materials

[0182] The waste from used packaging containers is cleaned and crushed to prepare resin material. The container is formed by laminating a 12μm thick polyethylene terephthalate layer, a 50nm thick aluminum vapor-deposited layer, a 15μm thick nylon layer, and a 120μm thick linear low-density polyethylene layer with an aluminum vapor-deposited layer.

[0183] (2) Manufacturing of resin film materials

[0184] The resin material (100 parts) obtained in (1) and compatibilizer (2.5 parts, UMEX 1001: manufactured by Sanyo Chemical Industries, maleic anhydride modified polypropylene, melt viscosity 15000 mPa·s (160℃, BL type viscometer)) were fed into a twin-screw extruder (TEX-28V screw diameter 28mm, L / D=42, manufactured by Nippon Steel Corporation) and melt-blended at 230℃ to produce granules. Using these granules, a resin film material containing aluminum was produced by continuously forming at 230℃ for 30 minutes using a T-die extruder (manufactured by the Plastics Engineering Research Institute, 300mm T-die) (forming speed 6.9m / min, granule usage approximately 3kg).

[0185] [Examples 1-2]

[0186] (1) Preparation of resin materials

[0187] The waste from used packaging containers is cleaned and crushed to prepare resin material. The container is formed by laminating a 12μm thick polyethylene terephthalate layer, a 50nm thick aluminum vapor-deposited layer, a 15μm thick nylon layer, and a 120μm thick linear low-density polyethylene layer with an aluminum vapor-deposited layer.

[0188] In addition to the aforementioned container, waste from the used packaging containers is washed and crushed. The container is formed of a metal-free laminate consisting of a 15μm thick nylon layer and a 120μm thick linear low-density polyethylene layer.

[0189] Then, in addition to the above-mentioned containers, the waste from the used packaging containers is washed and crushed. The container is formed by laminating a 7μm thick aluminum foil layer, a 15μm thick nylon layer, and a 120μm thick linear low-density polyethylene layer on a 12μm thick polyethylene terephthalate layer.

[0190] A resin material comprising a laminate containing an aluminum vapor-deposited layer, a laminate without a metal layer, and a laminate with an aluminum foil layer are mixed. The proportion of the laminate containing the aluminum vapor-deposited layer in the resin material is 26%, the proportion of the laminate without a metal layer is 73%, and the proportion of the laminate with an aluminum foil layer is 1%.

[0191] (2) Manufacturing of resin film materials

[0192] In addition to using the resin material obtained in (1), a resin film material containing aluminum was manufactured using the same method as in Example 1-1.

[0193] [Examples 1-3]

[0194] (1) Preparation of resin materials

[0195] The waste from used packaging containers is cleaned and crushed to prepare resin material. The container is formed by laminating a 12μm thick polyethylene terephthalate layer, a 50nm thick aluminum vapor-deposited layer, a 15μm thick nylon layer, and a 120μm thick linear low-density polyethylene layer with an aluminum vapor-deposited layer.

[0196] In addition to the aforementioned container, waste from the used packaging containers is washed and crushed. The container is formed of a metal-free laminate consisting of a 15μm thick nylon layer and a 120μm thick linear low-density polyethylene layer.

[0197] A resin material comprising a laminate containing an aluminum vapor-deposited layer and a laminate without a metal layer is obtained by mixing the laminates. The proportion of the laminate containing the aluminum vapor-deposited layer in the resin material is 26%, and the proportion of the laminate without a metal layer is 74%.

[0198] (2) Manufacturing of resin film materials

[0199] In addition to using the resin material obtained in (1), a resin film material containing aluminum was manufactured using the same method as in Example 1-1.

[0200] [Comparative Example 1-1]

[0201] (1) Preparation of resin materials

[0202] The waste material from the end material of the packaging container is cleaned and crushed to prepare the resin material. The container is formed by a metal-free laminate consisting of a 12 μm thick polyethylene terephthalate layer, a 15 μm thick nylon layer, and a 100 μm thick linear low-density polyethylene layer.

[0203] (2) Manufacturing of resin film materials

[0204] The resin material obtained in (1) is fed into a twin-screw extruder (TEX-28V screw diameter 28mm, L / D=42, manufactured by Nippon Steel Corporation) and melt-blended at 230°C to produce granules.

[0205] Using these granules, a metal-free resin film material was produced by continuously extruding them at 230°C using a T-die extruder (manufactured by the Plastics Engineering Research Institute, 300mm T-die) for 30 minutes (forming speed 6.9m / min, granule usage approximately 9kg).

[0206] [Comparative Examples 1-2]

[0207] (1) Preparation of resin materials

[0208] The waste from the used packaging containers is cleaned and then crushed. The container is formed by a laminate with an aluminum vapor-deposited layer, consisting of a 50 nm thick aluminum vapor-deposited layer, a 15 μm thick nylon layer, and a 120 μm thick linear low-density polyethylene layer, stacked on a 12 μm thick polyethylene terephthalate layer.

[0209] In addition to the aforementioned container, waste from the used packaging containers is washed and crushed. The container is formed of a metal-free laminate consisting of a 15μm thick nylon layer and a 120μm thick linear low-density polyethylene layer.

[0210] Furthermore, in addition to the aforementioned containers, the waste from the used packaging containers is washed and crushed. The container is formed by laminating a 7μm thick aluminum foil layer, a 15μm thick nylon layer, and a 120μm thick linear low-density polyethylene layer on a 12μm thick polyethylene terephthalate layer, thus forming a laminate with an aluminum foil layer.

[0211] A resin material comprising a laminate with an aluminum vapor-deposited layer, a laminate without a metal layer, and a laminate with an aluminum foil layer are mixed to obtain a composite material. The composite material contains 25% aluminum vapor-deposited layer, 72% metal-free layer, and 3% aluminum foil layer.

[0212] (2) Manufacturing of resin film materials

[0213] In addition to using the resin material obtained in (1), a resin film material containing aluminum was manufactured using the same method as in Example 1-1.

[0214] 〔evaluate〕

[0215] For the resin film materials obtained in the examples and comparative examples, the following parameters were considered: average thickness, number of aluminum particles with an area equivalent diameter of 200 μm or more, number of aluminum particles with an area equivalent diameter of 100 μm or more, aluminum content, h / Dp, coefficient of thermal expansion, and root mean square height R. Q The interlayer peel strength was determined using the following methods. The results are shown in Table 1 below.

[0216] [Average Thickness]

[0217] The thickness of the resin film material obtained in the examples and comparative examples was measured at 5 points using a micrometer (Mitutoyo Corporation, MDC25-MX), and the average value was taken as the average thickness of the film.

[0218] [The number of aluminum particles with an area equivalent diameter of 200 μm or more, and the number of aluminum particles with an area equivalent diameter of 100 μm or more]

[0219] The resin film materials obtained in the examples and comparative examples were observed using an optical microscope (Keyence Co., Ltd., VHX-5000) at 20x magnification, with the transmitted light intensity set to maximum, focusing only on the non-transmittent aluminum particles. The total field of view was 9.8 cm². 2 The number of aluminum particles with an area equivalent diameter of 200 μm or more and aluminum particles with an area equivalent diameter of 100 μm or more were counted separately, and the number of particles per unit area was calculated.

[0220] [Aluminum content]

[0221] 0.1 g of the resin film material obtained in the examples and comparative examples was accurately weighed into a platinum crucible, heated until no more white smoke was produced, and then a few drops of sulfuric acid were added for ashing. After thorough ashing in an electric furnace at 550°C, 1 g of alkaline flux (sodium carbonate:boric acid = 1:0.4 (mass ratio)) was added, and the mixture was melted in an electric furnace at 950°C. A bell glass was then placed over the mixture, and 5 mL of ultrapure water and 6N hydrochloric acid were added. The mixture was heated to dissolve using a hot plate at 80°C, and after cooling, the volume was adjusted to 50 mL with ultrapure water. The resulting solution was used as the sample determination solution. The aluminum content of the prepared sample determination solution was determined using an ICP-based spectrophotometer (Thermo Fisher Scientific, iCAP 6500Duo) under the following conditions.

[0222] Wavelength: Al 396.152nm

[0223] RF power: 1150W

[0224] Cooling air flow rate: 12L / min

[0225] Sprayer flow rate: 0.70 L / min

[0226] Assist gas: 0.5 L / min

[0227] Pump flow rate: 50 rpm

[0228] [h / Dp]

[0229] Based on the aluminum content and the density of aluminum (2.7 g / cm³) 3 ) and the density of the resin (1.0 g / cm³) 3 ), calculate the particle volume concentration F of aluminum, and use the calculated F to calculate h / Dp according to Bansal Ardell's approximation.

[0230] [Coefficient of thermal expansion]

[0231] Using a thermal stress-strain measuring device (manufactured by Seiko Electronics Co., Ltd., trade name "EXSTAR TMA / SS6100"), a strip sample with a width of 3 mm and a length of 40 mm was heated from room temperature (25°C) to 150°C under a nitrogen atmosphere. The heating rate was set to 5°C / min. The measurement was set to tensile mode, and the load was set to 50 g. The coefficient of thermal expansion at 40°C was calculated.

[0232] Root mean square height R Q ]

[0233] The measurements were performed using a laser microscope (Keyence, trade name: VK-9710) under the following conditions.

[0234] Objective lens: 10x, light intensity: 3%, brightness: 1548, Z-interval: 0.2μm

[0235] Regarding the root mean square (RMS) height of the membrane, five points were measured using the built-in image processing software, and their average value was used. The smaller the RMS height, the higher the smoothness of the membrane.

[0236] [Interlayer peel strength]

[0237] Two pieces of resin film material obtained in the examples and comparative examples were overlapped, heat-sealed using a heat sealer under the following conditions, and then cut out test pieces (15mm × 60mm).

[0238] Sealing temperature: 170℃, sealing time: 2 seconds, sealing pressure: 0.2MPa

[0239] Next, for this test piece, the interlaminar peel strength based on T-shaped peel was determined using an Autograph precision universal testing machine (Shimadzu Corporation, AG-500E) under the following conditions.

[0240] Force sensor: 1kN, tensile speed: 100mm / min, chuck spacing: 50mm

[0241] [Table 1]

[0242]

[0243] As clearly shown in Table 1, the resin film materials obtained in each embodiment have a small coefficient of thermal expansion, and the root mean square height R0 is also small. Q Low. Furthermore, it can be seen that due to the root mean square height R... Q The interlayer peel strength of the resin film materials obtained in each embodiment is low, while the interlayer peel strength shows high values.

[0244] In contrast, the resin film material of Comparative Example 1-1, which does not contain aluminum, exhibits a high coefficient of thermal expansion.

[0245] The resin film materials of Comparative Examples 1-2 have a lower coefficient of thermal expansion compared to the resin film material of Comparative Example 1-1, which does not contain aluminum, because they contain aluminum. However, due to the presence of coarse aluminum particles, they exhibit a higher coefficient of thermal expansion compared to the resin film materials of the Examples.

[0246] [Example 2-1]

[0247] (1) Preparation of resin waste mixture

[0248] The mixture of used packaging container A, used packaging container B, and used packaging container C is used as a resin waste mixture.

[0249] Packaging container A is formed by stacking an aluminum vapor-deposited layer with a thickness of 50 nm, a nylon layer with a thickness of 15 μm, and a linear low-density polyethylene layer with a thickness of 12 μm on a polyethylene terephthalate layer.

[0250] Packaging container B is formed of a metal-free laminate consisting of a nylon layer with a thickness of 15 μm and a linear low-density polyethylene layer with a thickness of 120 μm.

[0251] Packaging container C is formed by laminating an aluminum foil layer, consisting of a 7μm thick aluminum foil layer, a 15μm thick nylon layer, and a 120μm thick linear low-density polyethylene layer on a 12μm thick polyethylene terephthalate layer.

[0252] (2) Separation

[0253] Using a handheld metal detector (manufactured by Japan Metal Detector Co., Ltd., JM-9V2) with an electromagnetic sensor set to sensitivity 1, used packaging container C was detected from the resin waste mixture and selectively separated and removed. The proportion of used packaging container A in the separated resin waste mixture was 26%, the proportion of used packaging container B was 73%, and the proportion of used packaging container C was 1%.

[0254] (3) Melt forming

[0255] After the separated resin waste mixture is crushed into small pieces, it is fed together with compatibilizer (UMEX 1001: manufactured by Sanyo Chemical Industries, maleic anhydride modified polypropylene, melt viscosity 15000 mPa·s (160℃, BL type viscometer)) into a twin-screw extruder (TEX-28V screw diameter 28mm, L / D=42, manufactured by Nippon Steel Corporation) and melt-blended at 230℃ to produce a resin composition containing particles.

[0256] (4) Manufacturing of resin film materials

[0257] Using the manufactured granules, a resin film material containing aluminum is produced by T-die forming at 230°C.

[0258] [Example 2-2]

[0259] (1) Preparation of resin waste mixture

[0260] The procedure is the same as in Example 2-1.

[0261] (2) Separation

[0262] Using a metal detector (manufactured by Nisshin Electronics Industry Co., Ltd., ND-840) with an analog sensitivity set to 5 and a digital sensitivity set to 10, used packaging containers C were detected from the resin waste mixture and selectively separated and removed. The proportion of used packaging containers A in the separated resin waste mixture was 26%, and the proportion of used packaging containers B was 74%.

[0263] (3) Melt forming

[0264] The procedure is the same as in Example 2-1.

[0265] (4) Manufacturing of resin film materials

[0266] The procedure is the same as in Example 2-1.

[0267] [Comparative Example 2-1]

[0268] (1) Preparation of resin waste mixture

[0269] The procedure is the same as in Example 2-1.

[0270] (2) Separation

[0271] No separation was performed in this comparative example. Therefore, the resin waste mixture was formed from used packaging container A, used packaging container B, and used packaging container C. The proportion of used packaging container A in the resin waste mixture was 25%, the proportion of used packaging container B was 72%, and the proportion of used packaging container C was 3%.

[0272] (3) Melt forming

[0273] The procedure is the same as in Example 2-1.

[0274] (4) Manufacturing of resin film materials

[0275] The procedure is the same as in Example 2-1.

[0276] 〔evaluate〕

[0277] For the resin film materials obtained in the examples and comparative examples, the following parameters were considered: average thickness, number of aluminum particles with an area equivalent diameter of 200 μm or more, number of aluminum particles with an area equivalent diameter of 100 μm or more, aluminum content, coefficient of thermal expansion, and root mean square height R. Q The interlayer peel strength was determined using the methods described above. The results are shown in Table 2 below.

[0278] [Table 2]

[0279]

[0280] As clearly shown in Table 2, the resin film materials obtained in Examples 2-1 and 2-2 have a small coefficient of thermal expansion, and the root mean square height R0 is also small. Q Low. Furthermore, it can be seen that due to the root mean square height R... Q The interlaminar peel strength of the resin film materials obtained in Examples 2-1 and 2-2 is low, while the interlaminar peel strength of the resin film materials obtained in Examples 2-1 and 2-2 shows high values.

[0281] In contrast, the resin film material of Comparative Example 2-1, due to the presence of coarse aluminum particles, exhibits a larger coefficient of thermal expansion and a higher root-mean-square height R compared to the resin film materials of Examples 2-1 and 2-2. Q .

[0282] Industrial applicability

[0283] As described in detail above, according to the present invention, a resin film material with high surface smoothness and suitable as a raw material for laminates with high interlayer peel strength can be provided.

[0284] In addition, according to the method of the present invention, a recycled resin suitable for forming resin film materials can be produced, which is suitable as a raw material for laminates with high surface smoothness and high interlayer peel strength.

Claims

1. A resin film material, comprising a resin material including a laminate as raw material, said laminate being a resin layer having a metal vapor-deposited layer, and said resin film material containing the metal in the form of particles. The average thickness of the resin film material is greater than 10 μm and less than 500 μm. The metal particles are dispersed in the resin film material, and per 1 cm 2 The resin film material contains fewer than one metal particle with an area equivalent diameter of 200 μm or larger, and the number of such particles is less than one per 1 cm. 2 The number of metal particles with an area equivalent diameter of 100 μm or more present in the resin film material is less than 15.

2. The resin film material according to claim 1, wherein the resin material comprising a laminate assembly is used as raw material, the laminate assembly comprising: the laminate having a resin layer having a metal vapor-deposited layer, and the laminate having a resin layer without a metal layer.

3. The resin film material according to claim 2, wherein, The laminate containing a resin layer without a metal layer comprises a polyolefin layer.

4. The resin film material according to claim 1 or 2, wherein, The laminate having a resin layer with a metal vapor-deposited layer comprises: a polyolefin layer and a layer containing one or more resins selected from polyester, polyamide and polyimide.

5. The resin film material according to claim 1 or 2, wherein, The laminate containing the resin layer with the metal vapor-deposited layer accounts for 10% by mass or more and 100% by mass or less of the resin material.

6. The resin film material according to claim 1 or 2, wherein, The metal is aluminum, and the aluminum content is more than 0.01% by mass and less than 0.3% by mass.

7. The resin film material according to claim 1 or 2, wherein, The laminate containing the resin layer with the metal vapor-deposited layer is waste material.

8. The resin film material according to claim 1 or 2, wherein, The ratio of the average inter-surface distance of the metal particles to the average particle size of the metal particles is greater than 15.

9. A layered structure having: The resin film material according to any one of claims 1 to 8, and Resin layer or metal foil.

10. The stacked structure according to claim 9, wherein, The resin layer comprises an ethylene-vinyl alcohol copolymer.

11. The laminated structure according to claim 9 or 10, wherein it is in the form of a packaging container.

12. A method for manufacturing a resin film material, comprising removing the resin waste having the metal foil layer from a resin waste mixture comprising resin waste having a resin layer having a resin layer having a metal foil layer and resin waste having a resin layer having a metal vapor-deposited layer. The resin waste mixture after removal is melt-formed to obtain a resin composition containing dispersed metal particles, and the resin composition is then extruded. The average thickness of the resin film material is greater than 10 μm and less than 500 μm. In every 1cm 2 The resin film material contains fewer than one metal particle with an area equivalent diameter of 200 μm or larger, and the number of such particles is less than one per 1 cm. 2 The number of metal particles with an area equivalent diameter of 100 μm or more present in the resin film material is less than 15.

13. The method for manufacturing the resin film material according to claim 12, wherein, The resin waste having a resin layer with a metal foil layer is a resin film or a resin container.

14. The method for manufacturing the resin film material according to claim 12 or 13, wherein, The resin waste having a resin layer with a metal vapor-deposited layer is a resin film or a resin container.

15. The method for manufacturing the resin film material according to claim 12 or 13, wherein, The resin waste mixture after removal is crushed, and the resulting crushed material is melt-formed.

16. The method for manufacturing the resin film material according to claim 12 or 13, wherein, The resin waste having a resin layer with a metal foil layer of more than 1 μm thickness is detected and removed using an electromagnetic sensor, X-ray sensor, near-infrared sensor or color sensor.

17. The method for manufacturing the resin film material according to claim 16, wherein, Using an electromagnetic sensor, the resin waste having a resin layer with a metal foil layer of more than 1 μm thickness is detected and removed based on the degree of magnetic force induced by the current.

18. The method for manufacturing the resin film material according to claim 12 or 13, wherein, In every 1cm 2 The number of metal particles with an area equivalent diameter of 200 μm or more present in the resin film material is less than 0.

7.

19. The method for manufacturing the resin film material according to claim 12 or 13, wherein, In every 1cm 2 The number of metal particles with an area equivalent diameter of 100 μm or more present in the resin film material is less than 10.

20. A method for manufacturing a laminated structure, comprising removing the resin waste having the metal foil layer from a resin waste mixture comprising resin waste having a resin layer having a resin foil layer and resin waste having a resin layer having a metal vapor-deposited layer. The resin waste mixture after removal is melt-formed to obtain a resin composition in which the metal particles are dispersed, and the resin composition is then co-extruded or extruded and laminated. The laminated structure comprises a resin film material. The average thickness of the resin film material is greater than 10 μm and less than 500 μm. In every 1cm 2 The resin film material contains fewer than one metal particle with an area equivalent diameter of 200 μm or larger, and the number of such particles is less than one per 1 cm. 2 The number of metal particles with an area equivalent diameter of 100 μm or more present in the resin film material is less than 15.

21. A method for manufacturing a layered structure, wherein, The resin film material manufactured using the manufacturing method according to any one of claims 12 to 19 is laminated with a resin layer.

22. The method for manufacturing a laminated structure according to claim 21, wherein, The resin layer contains polyolefin.

23. The method for manufacturing a laminated structure according to claim 22, wherein, The resin layer contains polyethylene as its main component.

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