Laminate and its manufacturing method, molded body and its manufacturing method, and sheet

Abstract

The present invention provides a laminate that allows for easy modification of the uneven surface shape, enables the stable application of the uneven surface shape to the molded body surface even after thermoforming, and can be manufactured with a small number of steps. [Solution] A laminate comprising a first resin layer and a second resin layer, wherein the first resin layer comprises a first thermoplastic resin, and the first thermoplastic resin has a structure comprising molecular chains that are compatible with the resin constituting the second resin layer and molecular chains that are incompatible with the resin constituting the second resin layer.

Description

[[Technical Field]]

[0001] The present invention relates to a laminate and a method for producing the same, a molded article and a method for producing the same, and a sheet. [[Background Art]]

[0002] Methods are known in which fine shapes are imparted to the surfaces of resin films or resin sheets to provide functions such as releasability and optical properties. Examples of methods for imparting such shapes include a transfer method, a coating method, and a release method. Examples of the transfer method include a thermal transfer method in which a film is hot-pressed using a mold provided with fine shapes (e.g., Patent Document 1), a melt extrusion transfer method in which molten resin is pressurized and cooled using a cooling roll that has been subjected to fine shape processing (e.g., Patent Document 2), and an embossing roll transfer method using a fine shape roll. As the coating method, there is a method in which fine protrusions are provided on a coating film by dispersing fine particles in a coating liquid (e.g., Patent Document 3). As the release method, there is a method in which a base material and a shape-imparting layer are provided by coextrusion or lamination, and then the latter layer is released to impart a fine shape to the surface of the base material (e.g., Patent Document 4). [[Prior Art Documents]] [[Patent Documents]]

[0003] [[Patent Document 1]] Japanese Unexamined Patent Application Publication No. 2022-124135 [[Patent Document 2]] Japanese Unexamined Patent Application Publication No. 2015-25053 [[Patent Document 3]] International Publication No. WO 2018 / 003978 [[Patent Document 4]] Japanese Unexamined Patent Application Publication No. 2014-218008 [[Summary of the Invention]] [[Problems to be Solved by the Invention]]

[0004] However, the transfer method is a batch process and therefore has low productivity, and it is necessary to change the mold when changing the uneven shape. Furthermore, when the sheet obtained by transfer is thermoformed into a container or the like, the sheet surface softens due to the heat and the uneven structure disappears. The coating method has the risk of particles falling off the obtained sheet and, like the transfer method, the uneven shape changes during thermoforming. In addition, the peeling technology disclosed in Patent Document 4 utilizes fluffing due to cohesive peeling, so there is a concern that the shape will change significantly depending on the peeling method.

[0005] The object of the present invention is to provide a laminate that allows for easy modification of the uneven shape, can stably impart an uneven shape to the surface of the molded body even after thermoforming, and can be manufactured with a small number of steps. [Means for solving the problem]

[0006] According to the present invention, the following laminates and the like are provided. 1. comprising a first resin layer and a second resin layer, The first resin layer comprises a first thermoplastic resin. The first thermoplastic resin has a structure comprising molecular chains that are compatible with the resin constituting the second resin layer and molecular chains that are incompatible with the resin constituting the second resin layer. Laminated structure. 2. The laminate according to claim 1, wherein the first thermoplastic resin is a thermoplastic elastomer. 3. The laminate according to claim 1 or 2, wherein the first thermoplastic resin is one or more selected from the group consisting of an elastomer containing structural units derived from styrene, an elastomer containing structural units derived from urethane, an elastomer containing structural units derived from polyamide, and an elastomer containing structural units derived from polyester. 4. The laminate according to any one of 1 to 3, wherein the second resin layer contains a thermoplastic resin. 5. The laminate according to any one of 1 to 4, wherein the second resin layer contains a polyolefin. 6. The laminate according to any one of 1 to 5, wherein the first resin layer comprises a second thermoplastic resin. 7. The laminate according to 6, wherein the second thermoplastic resin of the first resin layer is incompatible with the resin constituting the second resin layer, and is compatible with molecular chains of the first thermoplastic resin that are incompatible with the resin constituting the second resin layer. 8. The laminate according to 6 or 7, wherein the second thermoplastic resin is one or more selected from the group consisting of polystyrene, acrylic resin, and polycarbonate. 9. A laminate according to any one of 6 to 8, wherein the content of the first thermoplastic resin in the first resin layer is 5 to 95% by mass, and the content of the second thermoplastic resin is 5 to 95% by mass. 10. The laminate according to any one of 1 to 9, wherein the interface between the first resin layer and the second resin layer is sterile. 11. The laminate according to any one of 1 to 10, wherein the first resin layer can be peeled off at the interface between the first resin layer and the second resin layer, and when the first resin layer is peeled off from the second resin layer, irregularities are formed on the surface of the second resin layer on the side where the first resin layer was laminated. 12. comprising a first resin layer and a second resin layer, The first resin layer comprises at least a first thermoplastic resin and a second thermoplastic resin. The second thermoplastic resin is incompatible with the resin constituting the second resin layer. The first thermoplastic resin has a structure comprising molecular chains compatible with the resin constituting the second resin layer and molecular chains compatible with the second thermoplastic resin. Laminated structure. A sheet obtained by peeling the first resin layer from the laminate described in any of sections 13.1 to 12. 14. The sheet described in 13, which is for use in food and beverage packaging, medical product packaging, medical containers, cell culture vessels, cell culture bags, building protection, solar panel protection, transport equipment exteriors, or cosmetic packaging. 15. A method for manufacturing a laminate according to any one of 1 to 12, comprising the step of co-extruding the resin constituting the first resin layer and the resin constituting the second resin layer. A step of molding the laminate according to any one of 16.1 to 12, and comprising a step of peeling off the first resin layer from the molded laminate, a method for producing a molded article. 17. A step of peeling a first resin layer from the laminate according to any one of 1 to 12 to obtain a sheet, and comprising a step of molding the sheet, a method for producing a molded article. 18. The molded article is a container or a bag body, wherein concave-convex shapes are formed on the inner surface, the outer surface, or both the inner surface and the outer surface of the container or the bag body, the method for producing a molded article according to 16 or 17. 19. A molded article obtained by the method for producing a molded article according to any one of 16 to 18. 20. The molded article according to 19, which is for food and drink packaging, medical supply packaging, medical containers, cell culture containers, cell culture bags, building protection, solar panel protection, transportation equipment exterior, or cosmetic packaging. Effects of the Invention

[0007] According to the present invention, a laminate can be provided in which the concave-convex shape can be easily changed, the concave-convex shape can be stably imparted to the surface of the molded article even when thermoforming is performed, and the laminate can be produced by a simple method. Brief Description of Drawings

[0008] [Figure 1] FIG. 1 is a schematic cross-sectional view of a laminate according to one embodiment of the present invention. [Figure 2] FIG. 2 is a schematic cross-sectional view of a laminate according to one embodiment of the present invention. [Figure 3] FIG. 3 is a schematic cross-sectional view showing a state where a first resin layer is peeled off from a laminate according to one embodiment of the present invention. [Figure 4] FIG. 4 is a schematic configuration diagram of a production apparatus used for producing laminates of Examples and Comparative Examples. [Figure 5] FIG. 5 is an enlarged photograph taken by a scanning electron microscope (SEM) of the surface obtained by peeling the first resin layer from the laminate obtained in Example 2. MODE FOR CARRYING OUT THE INVENTION

[0009] Hereinafter, the laminate and the manufacturing method thereof, the molded article and the manufacturing method thereof, and the sheet according to the present invention will be described. In the present specification, "x to y" represents a numerical range of "not less than x and not more than y". With respect to one technical matter, when there are a plurality of lower limit values such as "not less than x", or when there are a plurality of upper limit values such as "not more than y", it shall be possible to arbitrarily select and combine from the upper limit values and the lower limit values.

[0010] [First Laminate] A laminate according to one aspect of the present invention (hereinafter also referred to as "first laminate") comprises a first resin layer and a second resin layer adjacent to each other. The first resin layer contains a first thermoplastic resin, and the first thermoplastic resin comprises a molecular chain compatible with the resin constituting the second resin layer, and a molecular chain incompatible with the resin constituting the second resin layer.

[0011] The laminate is intended to be used for manufacturing a molded article formed of the second resin layer, and by peeling the first resin layer from the laminate at any stage of the manufacturing process of the molded article, a molded article in which the surface of the second resin layer on which the first resin layer was laminated is exposed on the inner surface or outer surface can be obtained.

[0012] The first thermoplastic resin constituting the first resin layer contains at least two types of molecular chains: one is a molecular chain compatible with the resin of the second resin layer (hereinafter also referred to as "molecular chain A"), and the other is a molecular chain incompatible with the resin of the second resin layer (hereinafter also referred to as "molecular chain B"). In other words, the first thermoplastic resin can be described as a polymer with a so-called microphase separation structure (microdomain structure), having molecular chains that are incompatible with each other within a single molecule. By employing such a resin for the first resin layer, the interface between the first resin layer and the second resin layer becomes a state in which countless fine compatible regions originating from molecular chain A are dispersed. When this laminate is manufactured, for example, by co-extrusion, molecular chain A in the first resin layer becomes entangled with the molecular chains of the resin of the second resin layer and welds together, while molecular chain B does not become entangled in such a way and therefore does not weld to the second resin layer. When the first resin layer is peeled off from such a laminate, the welded portion is stretched by the tensile load and eventually breaks. This broken portion becomes countless sharp protrusions (uneven shape) of nano to micro size, reducing the contact area with water and other substances, so the resulting resin sheet (second resin layer) exhibits excellent water repellency and release properties.

[0013] Figure 1 shows a schematic cross-sectional view of the first laminate. Laminate 1 includes a first resin layer 10 and a second resin layer 20 provided adjacent to it. Note that Figure 1 is merely for illustrating the layer structure, and the aspect ratio and film thickness ratio are not necessarily accurate. The same applies to the following drawings. The first resin layer 10 has substantially uniformly dispersed compatible portions 11 with the second resin layer, corresponding to molecular chain A of the first thermoplastic resin (Figure 2). Furthermore, since the laminate 1 is usually manufactured by heating using a method such as co-extrusion, some or all of the compatible portions 11 are welded to the resin constituting the second resin layer 20. When the first resin layer 10 is peeled off the laminate 1, the welded portion is stretched and then ruptured due to tensile stress, and countless fine protrusions 21 are formed on the surface of the second resin layer 20. Since these protrusions 21 (uneven shape) exhibit excellent water-repellent and release effects, the peeled second resin layer 20 can be used as a water-repellent sheet or release sheet in various molded articles and the like where these properties are required.

[0014] As described above, the first laminate forms a textured surface on the sheet by utilizing the microphase separation structure of the first thermoplastic resin, making it possible to achieve extremely fine textures ranging from tens of nanometers to submicrons, which are difficult to achieve by physical means such as transfer methods. Furthermore, since the pitch and size of the texture can be adjusted by appropriately adjusting the first thermoplastic resin, the texture of the sheet can be easily changed according to the required water-repellent performance. In addition, the laminate itself can be manufactured by a normal co-extrusion method, and another advantage is that the texture can be formed by a simple method of peeling off the first resin layer (shape-imparting layer) without using special equipment such as transfer rolls. Moreover, if the first resin layer is thermoformed while still laminated and then peeled off, the texture can be reliably imparted to the surface of the final molded product. In other words, the first resin layer can function as a protective layer for the resin sheet (second resin layer), and there is no concern that the texture will disappear due to thermoforming, as is the case with transfer methods and coating methods. The following describes the various components of the laminate of the present invention.

[0015] (First resin layer) As described above, the first resin layer is a layer containing a specific resin, and the action of this resin imparts fine protrusions (uneven shapes) to the surface of the second resin layer. For this reason, the first resin layer is also called the "shape-imparting layer."

[0016] (First thermoplastic resin) The first resin layer includes at least the first thermoplastic resin. The first thermoplastic resin is a resin containing molecular chain A which is compatible with the resin of the second resin layer, and molecular chain B which is incompatible with the resin of the second resin layer.

[0017] The statement that molecular chain A and the resin of the second resin layer are compatible means that when the resin consisting only of molecular chain A and the resin constituting the second resin layer are melted and mixed, a single phase is formed. The statement that molecular chain B and the resin of the second resin layer are incompatible means that when the resin consisting only of molecular chain B is melted and mixed with the resin constituting the second resin layer, a single phase is not formed.

[0018] The first thermoplastic resin is not particularly limited as long as it has the above characteristics, but examples include thermoplastic elastomers, and examples of thermoplastic elastomers include block copolymers containing a soft segment that exhibits rubber elasticity and a hard segment that serves as a crosslinking point. In this case, there are two patterns: one in which the soft segment becomes molecular chain A which is compatible with the resin of the second resin layer and the hard segment becomes molecular chain B which is incompatible with the resin of the second resin layer, and another in which the soft segment becomes molecular chain B which is incompatible with the resin of the second resin layer and the hard segment becomes molecular chain A which is compatible with the resin of the second resin layer.

[0019] Examples of such thermoplastic elastomers include elastomers containing styrene-derived structural units (hard segments) (styrene-based thermoplastic elastomers, also called "TPS"), elastomers containing urethane-derived structural units (hard segments) (urethane-based thermoplastic elastomers, also called "TPU"), elastomers containing polyamide-derived structural units (hard segments) (polyamide-based thermoplastic elastomers, also called "PAE"), and elastomers containing polyester-derived structural units (hard segments) (polyester-based thermoplastic elastomers, also called "TPEE"). These can be used individually or in combination of two or more types.

[0020] Examples of styrene-based thermoplastic elastomers include styrene-diene block copolymers and hydrogenated styrene-diene block copolymers, specifically styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), and styrene-(styrene-ethylene-butylene copolymer)-styrene copolymer (random SEBS).

[0021] Urethane-based thermoplastic elastomers are copolymers of a hard segment consisting of isocyanate and a chain extender, and a soft segment consisting of a polyol. These can be combined to impart desired properties and are used accordingly. Specifically, examples of isocyanates include 4,4-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), naphthalene diisocyanate (NDI), and 4,4-dicyclohexylmethane diisocyanate (H12MDI). Examples of chain extenders include 1,4-butanediol (BDO), 1,6-hexanediol (HDO), ethylene glycol (EG), diethylene glycol (DEG), 1,4-cyclohexanedimethanol (CHDM), 1,4-bis(hydroxyethyl)hydrazine (BHEH), ethylenediamine (EDA), and 1,2-diaminoethane. Examples of polyols include polyester polyols, polyether polyols, polycaprolactone polyols, and polycarbonate polyols.

[0022] Examples of polyamide-based thermoplastic elastomers include block copolymers of polyester and polyamide, and block copolymers of polyether and polyamide. Specifically, examples of polyamides that form the hard segment include polyamide 6 (PA6), polyamide 66 (PA66), polyamide 12 (PA12), polyamide 11 (PA11), polyamide 610 (PA610), polyamide 612 (PA612), polyamide 6T (PA6T), polyamide 9T (PA9T), and polyamide 46 (PA46). These are copolymerized with soft segment polyester, polyamide, etc., for use.

[0023] Examples of polyester-based thermoplastic elastomers include block copolymers of polyester and polyether, and block copolymers of polyester and polyester.

[0024] By changing the resin type and various components of the first thermoplastic resin (for example, the ratio of soft segments to hard segments, the degree of segment polymerization, etc.), the shape and dispersion state of the protrusions (irregularities) obtained by peeling off the first resin layer can be adjusted in various ways.

[0025] The melt flow rate (MFR) of the first thermoplastic resin is preferably 0.05 g / 10 min or more, and preferably 100 g / 10 min or less. Within this range, the suitability for co-extrusion with the second resin layer is excellent. The MFR measurement of the first thermoplastic resin is performed under conditions of a temperature of 230°C and a load of 2.16 kg.

[0026] (Second thermoplastic resin) The first resin layer may also include a second thermoplastic resin. As the second thermoplastic resin, a resin that is incompatible with the resin constituting the second resin layer is preferred. Furthermore, a resin that is compatible with molecular chain B (the molecular chain incompatible with the second resin layer) of the first thermoplastic resin is preferred. By using such a resin as the second thermoplastic resin, it becomes possible to appropriately adjust the density of the compatible portion caused by molecular chain A, making it easier to obtain the desired uneven shape. In addition, it becomes easier to peel the first resin layer from the second resin layer.

[0027] The second thermoplastic resin can be appropriately selected in accordance with the resin types constituting the first thermoplastic resin and the second resin layer, but examples include polystyrene, acrylic resin, and polycarbonate. These can be used individually or in combination of two or more.

[0028] When a second thermoplastic resin is included, the content of the first thermoplastic resin in the first resin layer is, for example, 1 to 95% by mass, 5 to 70% by mass, or 10 to 50% by mass, and the content of the second thermoplastic resin is, for example, 5 to 99% by mass, 30 to 95% by mass, or 50 to 95% by mass.

[0029] The first resin layer has a composition of 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 98% or more by mass, 99% or more by mass, 99.5% or more by mass, 99.9% or more by mass, or 100% by mass. First thermoplastic resin, or First thermoplastic resin and second thermoplastic resin That's fine. The first resin layer may consist substantially of only the first thermoplastic resin, or substantially of only the first thermoplastic resin and the second thermoplastic resin. In this case, it may contain unavoidable impurities. The first resin layer may consist of only the first thermoplastic resin, or only the first thermoplastic resin and the second thermoplastic resin.

[0030] The thickness of the first resin layer is, for example, 5 to 500 μm, preferably 10 to 200 μm.

[0031] (Second resin layer) The second resin layer is a layer intended to be used as a component material of the molded body after the first resin layer has been removed. For this reason, the second resin layer is also called the "base layer."

[0032] The resin constituting the second resin layer is preferably a thermoplastic resin, such as polyolefin (e.g., polypropylene or polyethylene), polyamide, polycarbonate, acrylic resin, or ABS resin (acrylonitrile-butadiene-styrene copolymer resin).

[0033] The resin constituting the second resin layer should be appropriately selected considering its compatibility with the first thermoplastic resin of the first resin layer (compatibility with molecular chain A and incompatibility with molecular chain B). The combination of the first thermoplastic resin of the first resin layer and the resin constituting the second resin layer (first thermoplastic resin of the first resin layer; resin constituting the second resin layer) is not particularly limited as long as the above compatibility conditions are met, but examples include the following combinations. (Styrene-based thermoplastic elastomer; polypropylene) (Styrene-based thermoplastic elastomer; polyethylene) (Styrene-based thermoplastic elastomer; polycarbonate) (Styrene-based thermoplastic elastomer; acrylic resin) (Styrene-based thermoplastic elastomer; ABS resin) (Urethane-based thermoplastic elastomer; polycarbonate) (Urethane-based thermoplastic elastomer; acrylic resin) (Urethane-based thermoplastic elastomer; ABS resin) (Polyamide-based thermoplastic elastomer; polyamide) (Polyester-based thermoplastic elastomer; polycarbonate) (Polyester-based thermoplastic elastomer; acrylic resin) (Polyester-based thermoplastic elastomer; ABS resin)

[0034] The second resin layer may contain, as needed, additives such as pigments, antioxidants, stabilizers, and UV absorbers in addition to the thermoplastic resin described above.

[0035] The second resin layer may consist of 70% or more by mass of the above-mentioned thermoplastic resin, 80% or more by mass, 90% or more by mass, 95% or more by mass, 98% or more by mass, 99% or more by mass, 99.5% or more by mass, 99.9% or more by mass, or 100% by mass. The second resin layer may consist substantially of the thermoplastic resin described above. In this case, it may contain unavoidable impurities. The second resin layer may consist solely of the thermoplastic resin described above.

[0036] The thickness of the second resin layer is, for example, 1 to 3000 μm, preferably 5 to 2000 μm, and more preferably 15 to 1000 μm.

[0037] (Laminated structure) As described above, the first laminate includes a first resin layer and a second resin layer adjacent to each other. By peeling off the first resin layer, a fine uneven surface is created on the surface of the second resin layer where the first resin layer was laminated, thereby exhibiting water-repellent and release properties. The interface between the first resin layer and the second resin layer is usually sterile.

[0038] The first laminate may have a layer having the same function as the first resin layer on the side of the second resin layer opposite to the first resin layer. The configuration of this layer can be directly applied to the first resin layer. By peeling off each layer from the front and back of such a three-layer laminate, a sheet (second resin layer) with water-repellent properties on both sides can be obtained.

[0039] The first laminate may have additional layers in addition to the layers described above. Examples of these additional layers include an inorganic filler-containing layer, a highly transparent layer (a layer that enhances the transparency of the laminate), an oxygen barrier layer, an anti-fogging layer, and an adhesive layer (a layer that enhances the adhesion between the layers). Known layers can be used for these additional layers.

[0040] The thickness of the first laminate is, for example, 5 to 5500 μm, preferably 20 to 2100 μm.

[0041] [Second layer] A laminate according to another aspect of the present invention (hereinafter also referred to as the "second laminate") comprises a first resin layer and a second resin layer adjacent to each other, wherein the first resin layer comprises at least a first thermoplastic resin and a second thermoplastic resin. The first thermoplastic resin includes molecular chains that are compatible with the resin constituting the second resin layer, and molecular chains that are compatible with the second thermoplastic resin. The second thermoplastic resin is incompatible with the resin constituting the second resin layer.

[0042] The second laminate is the same as the first laminate described above, except that the first resin layer includes a second thermoplastic resin, and the first thermoplastic resin and the second thermoplastic resin each have a specific structure. The matters described for the first laminate can be applied to the second laminate.

[0043] [Resin sheet] By peeling off the first resin layer (shape-imparting layer) from the laminate according to one aspect of the present invention described above (including the first laminate and the second laminate; the same applies hereinafter), a resin sheet consisting of a second resin layer (base layer) is obtained. Since the sheet has a fine uneven surface, it has excellent water-repellent and release properties.

[0044] As described above, the uneven shape is thought to be formed when the compatible portion between molecular chain A in the first thermoplastic resin of the first resin layer and the resin of the second resin layer is stretched and fractured. Therefore, the above resin sheet can also be described as a resin sheet in which protrusions are dispersed on the surface of the second resin layer, and at least a portion of the protrusions contains a compatible portion, at least at their apex, that includes molecular chain A of the first thermoplastic resin and the resin constituting the second resin layer.

[0045] The sheet can be used in any application requiring water repellency and release properties, and has a wide range of applicable technologies. Examples of such applications include food and beverage packaging, medical product packaging, medical containers, cell culture vessels, cell culture bags, building protection, solar panel protection, transport equipment exteriors, and cosmetic packaging.

[0046] When the above-mentioned sheet is used, for example, as a bag-shaped packaging for food and beverages, the release properties of the contents are improved, making it easier to remove the contents and allowing for complete removal without any residue. In the case of container-shaped packaging, removing the food from the container without damaging its shape allows for a more visually enjoyable dining experience. In addition to food and beverage packaging, the sheet's excellent water-repellent and release properties make it suitable for use in fields where preventing the adhesion of dirt and other contaminants is required. Furthermore, since the surface after peeling off the first resin layer becomes sterile, sterile sheets can be provided for applications such as packaging for medical supplies and cell culture vessels for regenerative medicine.

[0047] The uneven shape (fine protrusions) of the resin sheet according to one aspect of the present invention is obtained by the action of specific molecular chains in the microphase separation structure of the first thermoplastic resin in the laminate described above, and is therefore an extremely fine structure of nano to micro size, and difficult to specify in terms of shape. The resin sheet exhibits excellent water-repellent performance due to having this uneven shape, but the microscopic difference from conventional water-repellent sheets cannot be distinguished by ordinary indicators. Furthermore, conducting an unrealistic number of experiments using all kinds of equipment to identify this difference would involve an excessively large economic expenditure, and it would also be difficult to comprehensively express the results in the claims. Therefore, in the present invention, it is practically impractical to directly specify the object by its structure or properties at the time of filing the application.

[0048] [Method for manufacturing laminates] The laminate according to one aspect of the present invention described above can be manufactured by a manufacturing method that includes a step of co-extruding a resin constituting a first resin layer and a resin constituting a second resin layer. Furthermore, by subsequently peeling off the first resin layer, a resin sheet with an uneven surface shape can be manufactured. According to the above manufacturing method, a laminate can be manufactured through a simple process, and an uneven shape can be formed simply by peeling off the first resin layer without using special equipment such as transfer rolls.

[0049] The co-extrusion temperature can be set appropriately according to the type of resin for each layer, but for example, it can be performed in the temperature range of 150 to 450°C. The resin constituting the first resin layer and the resin constituting the second resin layer can be melted separately and co-extruded from a general coat hanger die. Alternatively, it can be co-extruded in a cylindrical shape from a circular die. As for the conditions for peeling the first resin layer, from the viewpoint of uniformity of the uneven surface shape of the second resin layer after peeling, it is preferable to peel the first resin layer from the second resin layer while maintaining a constant peeling speed. Peeling may be done manually or mechanically. Note that the peeling speed and peeling tension do not significantly affect the uniformity of the uneven surface shape.

[0050] [Molded articles and their manufacturing methods] A molded article can be manufactured using a laminate or resin sheet according to one aspect of the present invention. A method for manufacturing a molded article according to one aspect of the present invention (hereinafter also referred to as the "first method for manufacturing a molded article") includes the steps of molding the above-mentioned laminate and peeling off the first resin layer from the molded laminate. According to this manufacturing method, thermoforming is performed with the first resin layer and the second resin layer in a laminated state, and then the first resin layer is peeled off, thereby reliably imparting a desired uneven shape to the surface of the molded body.

[0051] Examples of molding methods include vacuum forming, vacuum pressure forming, hot plate forming, hot plate pressure forming, high-pressure forming, and press forming. Known methods can be used for these.

[0052] The shape of the molded body is not particularly limited, but examples include container shape, bag shape, sheet shape, or film shape.

[0053] A method for manufacturing a molded article according to another aspect of the present invention (hereinafter also referred to as the "second method for manufacturing a molded article") includes the steps of peeling off the first resin layer from the laminate to obtain a resin sheet, and molding the resin sheet. The method for manufacturing the second molded article is the same as the method for manufacturing the first molded article, except that the first resin layer is peeled off before thermoforming. In this method as well, by adjusting the molding conditions, the relaxation of the uneven shape of the sheet surface can be kept to a minimum.

[0054] Applications for the resulting molded articles include, for example, food and beverage packaging, medical product packaging, medical containers, cell culture vessels, cell culture bags, building protection, solar panel protection, and exteriors for transport equipment. [Examples]

[0055] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0056] The materials used in the examples and comparative examples are as follows: • TPS-1: Polystyrene-polyethylene-polybutylene block copolymer, manufactured by Kuraray Co., Ltd. as "Septon 8104", styrene content 60% by mass • TPS-2: Polystyrene-polyethylene-polybutylene block copolymer, manufactured by Asahi Kasei Corporation as "ToughTec H1043", styrene content 67% by mass • TPS-3: Polystyrene-(styrene-ethylene-butylene copolymer) block copolymer, manufactured by Asahi Kasei Corporation, "SOES1614", styrene content 64% by mass • TPS-4: Polystyrene-polyethylene-polybutylene block copolymer, manufactured by Asahi Kasei Corporation as "ToughTec H1517", styrene content 43% by mass • TPS-5: Polystyrene-polyethylene-polybutylene block copolymer, manufactured by Asahi Kasei Corporation as "ToughTec H1272", styrene content 35% by mass • TPS-6: Polystyrene-polyethylene-polybutylene block copolymer, manufactured by Asahi Kasei Corporation as "ToughTec H1221", styrene content 12% by mass • PS-1: Polystyrene (general-purpose polystyrene), manufactured by PS Japan Co., Ltd., "685", MFR = 2.2g / 10 min • PS-2: Impact-resistant polystyrene, manufactured by PS Japan Co., Ltd., "HT478", MFR = 3.0g / 10 min • PP-1: Homopolypropylene, manufactured by Prime Polymer Co., Ltd., "Prime Polypro E-103WA", MFR = 3.0g / 10 min • PP-2: Homopolypropylene, manufactured by Prime Polymer Co., Ltd. "Prime PolyPro F-300SP", MFR = 3.0g / 10 min • PMMA-1: Acrylic resin, manufactured by Kuraray Co., Ltd. as "Parapet GR-F", MFR = 1.3g / 10 min

[0057] Example 1 (1) Manufacturing of laminates A resin composition was prepared by melt-kneading TPS-1 (first thermoplastic resin, 30% by mass) and PS-1 (second thermoplastic resin, 70% by mass) as the resin for the first resin layer (shape-imparting layer). PP-1 was prepared as the resin for the second resin layer (base layer). Note that the polystyrene molecular chains in TPS-1 are molecular chain B, which is incompatible with the resin PP-1 constituting the second resin layer, while the polyethylene molecular chains and polybutylene molecular chains are molecular chain A, which are compatible with the resin PP-1 constituting the second resin layer. Using the manufacturing apparatus shown in Figure 4, a laminate consisting of the two layers described above was manufactured by the following method. Specifically, the resins of each layer were co-extruded, the molten resin co-extruded from the T-die 72 was brought into close contact with the cooling roll 76 by an air knife 74, and cooled by the cooling rolls 76 and 78 to manufacture the laminate 71. The manufacturing conditions are as follows: • Extrusion temperature: 230℃ • Laminate retrieval speed: 2.8 m / min • Thickness of the first resin layer: 20 μm • Thickness of the second resin layer: 220 μm The thickness of each layer and the overall thickness of the laminate were measured using a film thickness gauge (Mitutoyo Corporation "ID-H0530"). The thickness of each layer was measured after separating the first and second resin layers, while the overall thickness of the laminate was measured with the first and second resin layers still laminated together.

[0058] (2) Evaluation The following evaluations were performed on the obtained laminate. The results are shown in Table 1.

[0059] ·Water contact angle The water contact angle was measured using a contact angle meter (CA-XP, manufactured by Kyowa Interface Science Co., Ltd.). Specifically, under conditions of 23°C and 50% RH, approximately 0.9 μm of deionized water was dropped onto the surface of the second resin layer, where the first resin layer had been peeled off, using a syringe. The droplet was then photographed with the contact angle meter's CCD camera, and the contact angle was measured from the shape of the droplet.

[0060] ·Water repellency A water contact angle of 107° or higher was judged to be water-repellent, and was marked with a "○" for water repellency. If the water contact angle was less than 107°, it was not considered to be sufficiently water-repellent, and was marked with a "×" for water repellency.

[0061] Examples 2-7 A laminate was manufactured and evaluated in the same manner as in Example 1, except that the components and composition of the resins constituting each layer were as listed in Table 1. The results are shown in Table 1. Figure 5 shows magnified scanning electron microscope (SEM) images (10,000x and 50,000x) of the surface after peeling off the first resin layer from the laminate obtained in Example 2. In TPS-1 to TPS-6, the polystyrene molecular chains are molecular chain B, which is incompatible with the resin PP-2 that constitutes the second resin layer, and molecular chain A, which is compatible with the resin PP-2 that constitutes the second resin layer.

[0062] Comparative Example 1 The same procedure as in Example 1 was followed and evaluated, except that the first resin layer (shape-imparting layer) was not laminated, and the second resin layer (base layer) was formed as a single layer with the components and composition listed in Table 2. The results are shown in Table 2.

[0063] Comparative Example 2 A laminate was manufactured and evaluated in the same manner as in Example 1, except that the first thermoplastic resin was not used in the first resin layer (shape-imparting layer), and the components and composition listed in Table 2 were adopted. The results are shown in Table 2.

[0064] Comparative Example 3 The laminate was manufactured and evaluated in the same manner as in Comparative Example 2, except that the second thermoplastic resin of the first resin layer was changed to the components and composition shown in Table 2. The results are shown in Table 2.

[0065] [Table 1]

[0066] [Table 2] [Explanation of symbols]

[0067] 1. Laminate 10 First resin layer 11 Compatibility with the second resin layer 20 Second resin layer 21 Protrusion 71 Laminate 72 T-die 74 Air Knife 76,78 Cooling Rolls

Claims

1. It comprises a first resin layer and a second resin layer, The first resin layer comprises a first thermoplastic resin. The first thermoplastic resin has a structure comprising molecular chains that are compatible with the resin constituting the second resin layer and molecular chains that are incompatible with the resin constituting the second resin layer. Laminated structure.

2. The laminate according to claim 1, wherein the first thermoplastic resin is a thermoplastic elastomer.

3. The laminate according to claim 1 or 2, wherein the first thermoplastic resin is one or more selected from the group consisting of an elastomer containing structural units derived from styrene, an elastomer containing structural units derived from urethane, an elastomer containing structural units derived from polyamide, and an elastomer containing structural units derived from polyester.

4. The laminate according to any one of claims 1 to 3, wherein the second resin layer comprises a thermoplastic resin.

5. The laminate according to any one of claims 1 to 4, wherein the second resin layer contains a polyolefin.

6. The laminate according to any one of claims 1 to 5, wherein the first resin layer comprises a second thermoplastic resin.

7. The laminate according to claim 6, wherein the second thermoplastic resin of the first resin layer is incompatible with the resin constituting the second resin layer, and is compatible with molecular chains of the first thermoplastic resin that are incompatible with the resin constituting the second resin layer.

8. The laminate according to claim 6 or 7, wherein the second thermoplastic resin is one or more selected from the group consisting of polystyrene, acrylic resin, and polycarbonate.

9. The laminate according to any one of claims 6 to 8, wherein the content of the first thermoplastic resin in the first resin layer is 5 to 95% by mass, and the content of the second thermoplastic resin is 5 to 95% by mass.

10. The laminate according to any one of claims 1 to 9, wherein the interface between the first resin layer and the second resin layer is sterile.

11. The laminate according to any one of claims 1 to 10, wherein the first resin layer can be peeled off at the interface between the first resin layer and the second resin layer, and when the first resin layer is peeled off from the second resin layer, irregularities are formed on the surface of the second resin layer on the side where the first resin layer was laminated.

12. It comprises a first resin layer and a second resin layer, The first resin layer comprises at least a first thermoplastic resin and a second thermoplastic resin. The second thermoplastic resin is incompatible with the resin constituting the second resin layer. The first thermoplastic resin has a structure comprising molecular chains that are compatible with the resin constituting the second resin layer and molecular chains that are compatible with the second thermoplastic resin. Laminated structure.

13. A sheet obtained by peeling off the first resin layer from the laminate according to any one of claims 1 to 12.

14. The sheet according to claim 13, which is for use in food and beverage packaging, medical product packaging, medical containers, cell culture containers, cell culture bags, building protection, solar panel protection, transport equipment exteriors, or cosmetic packaging.

15. A method for manufacturing a laminate according to any one of claims 1 to 12, comprising the step of co-extruding the resin constituting the first resin layer and the resin constituting the second resin layer.

16. A step of forming a laminate according to any one of claims 1 to 12, and The process includes peeling the first resin layer from the molded laminate, A method for manufacturing a molded product.

17. A step of obtaining a sheet by peeling off a first resin layer from a laminate according to any one of claims 1 to 12, and The process includes molding the aforementioned sheet, A method for manufacturing a molded product.

18. The molded body is a container or a bag, The container or bag has an uneven surface, an uneven surface, or both the inner and outer surfaces. A method for manufacturing a molded article according to claim 16 or 17.

19. A molded article obtained by the method for manufacturing a molded article according to any one of claims 16 to 18.

20. The molded body according to claim 19, which is for use in food and beverage packaging, medical product packaging, medical containers, cell culture containers, cell culture bags, building protection, solar panel protection, transport equipment exteriors, or cosmetic packaging.

Images