Polymer laminated sheet

Abstract

The present invention provides, as a sheet that can be directly attached to an attachment target and that has excellent resistance to rubbing and sticking, a polymer laminated sheet obtained by laminating at least one polymer thin film layer and at least one nonwoven fabric layer that are bonded together by an intermolecular force, wherein one outermost layer is the polymer thin film layer that has a thickness of 10-1000 nm, and the other outermost layer is the nonwoven fabric layer that is composed of polymer fibers having a diameter of 10 nm to 10 μm.

Description

Polymer laminated sheet

[0001] The present invention relates to a polymer laminate sheet, and more particularly to a polymer laminate sheet that is used by being attached to an object.

[0002] In recent years, flexible electronics has been considered for various applications due to the softness of its materials, and interest in the healthcare field has been growing. For example, flexible electronics can be attached to the surface or inside of a living body to directly obtain biological information from cells and tissues.

[0003] Generally, flexible electronics are fabricated by forming electronic devices on a flexible substrate. The flexible substrate is typically a patch sheet. The patch sheet is a sheet that can be attached to an object. The flexible substrate adheres to the object by using an adhesive or pressure-sensitive adhesive and / or by reducing its thickness to enhance conformability to the object. Using the adhesive or pressure-sensitive adhesive also includes dissolving a portion of the substrate before application. When adhesives or pressure-sensitive adhesives are used for long-term wear, drawbacks include rashes due to reduced breathability, reduced adhesive strength, and / or discomfort. Furthermore, adhesives and pressure-sensitive adhesives contain low-molecular-weight components (e.g., tackifiers, plasticizers, etc.) that easily penetrate the skin, contributing to the occurrence of rashes and other issues.

[0004] As the flexible electronics, for example, the following electronic functional components (A) and (B) have been proposed.

[0005] (A) An electronic functional component that has a fiber network formed by combining materials with different solubilities in water, and is attached to the skin when water is added, causing the first fiber network to dissolve (Patent Document 1).

[0006] (B) An electronic functional component having a fiber network composed of fibers of a polyvinyl alcohol-based resin having a specific side chain structure due to modification with an active methylene-containing group, and in which a device is attached by dissolving the fiber network in a solvent (Patent Document 2).

[0007] As other examples of flexible electronics, the following electronic device (C) and electronic functional polymer (D) have been proposed: (C) An electronic device in which electronic elements are closely attached to a polymer nanosheet (Patent Document 3). (D) An electronic functional polymer including a fiber network formed from fibers as a flexible substrate and a thin film with coating layers on the surfaces of the fibers and in the voids between the fibers (Patent Document 4).

[0008] The electronic functional component described in Patent Document 4 uses urethane nanofiber fibers and a coating layer formed of a silicone resin such as polymethylsiloxane on the nanometer order. The thin film described in Patent Document 4 is a sheet in which the coating layer is reinforced by the fibers present in the coating layer.

[0009] International Publication WO2020 / 179907 A1 JP 2021-41036 A International Publication WO2016 / 181958 A1 JP 2023-37936 A

[0010] However, the electronic functional components described in Patent Documents 1 and 2 are attached to the skin by dissolving part of the fiber net in water, and there is a problem in that if the fiber net gets wet during use, it will easily re-dissolve and peel off.

[0011] Furthermore, in the electronic device described in Patent Document 3 and the electronic functional component described in Patent Document 4, the polymer nanosheet in the electronic device and the sheet serving as the coating layer in the electronic functional component, if their film thickness is thin, may follow the object when they come into contact with an object other than the object to be adhered. This may result in the polymer nanosheet and the sheet serving as the coating layer peeling off or being damaged. Furthermore, thin film sheets are generally manufactured using a roll-to-roll process. However, the electronic device described in Patent Document 3 and the electronic functional component described in Patent Document 4 have the problem that, due to their high conformability, the polymer nanosheet and the sheet serving as the coating layer are easily damaged during the manufacturing process using the roll-to-roll process.

[0012] An object of the present invention is to provide a sheet that has excellent adhesive strength to the body surface and is resistant to peeling and breakage due to contact with an object other than the object to which it is attached.

[0013] As a result of intensive research into solving the above-mentioned problems, the inventors discovered that the above-mentioned problems can be solved by a polymer laminate sheet having one outermost layer which is a polymer thin film having a specific thickness and the other outermost layer which is a nonwoven fabric layer composed of fibers having a specific diameter, and thus completed the present invention.

[0014] One embodiment of the present invention is a polymer laminate sheet formed by laminating at least one polymer thin film layer and at least one nonwoven fabric layer, wherein one outermost layer is the polymer thin film layer and the other outermost layer is the nonwoven fabric layer, the polymer thin film layer and the nonwoven fabric layer are bonded by intermolecular forces, the one outermost polymer thin film layer has a film thickness of 10 nm or more and 1000 nm or less, and the other outermost nonwoven fabric layer is made of polymer fibers having a diameter of 10 nm or more and 10 μm or less.

[0015] The polymer laminate sheet according to one embodiment of the present invention can be directly attached to an object without the need for adhesives and / or gels. Furthermore, the polymer laminate sheet according to one embodiment of the present invention can reduce the likelihood of peeling and / or damage due to contact with other objects after attachment. Even if damage to the polymer laminate sheet does occur, the degree of damage can be reduced.

[0016] 1 is a schematic diagram showing a method for attaching a jig to a sheet used in Examples and Comparative Examples. 2 is a schematic diagram showing a method for testing adhesive strength to a skin model in Examples and Comparative Examples. 3 is a "displacement-load curve" obtained in Examples and Comparative Examples.

[0017] The following describes in detail the embodiments of the present invention. However, the present invention is not limited to these, and various modifications are possible within the scope of the description. The technical scope of the present invention also includes embodiments obtained by appropriately combining the technical means disclosed in different embodiments. Unless otherwise specified in this specification, "A to B" representing a numerical range means "greater than or equal to A and less than or equal to B."

[0018] [Summary of the Invention] "Applied adhesive sheets" are generally manufactured by the roll-to-roll method. When an applied adhesive sheet is manufactured by the roll-to-roll method, the applied adhesive sheet is manufactured by forming a film on a long roll-shaped carrier film. Subsequently, the applied adhesive sheet manufactured on the carrier film is wound up together with the carrier film onto another roll while applying a constant winding pressure by a tension roll.

[0019] In this case, if the adhesive strength between the carrier film and the adhesive sheet is weak, the adhesive sheet may be transferred to the back surface of the carrier film, the protective film surface and / or the roll during processing or transportation, etc. Transferring may cause damage to the adhesive sheet.

[0020] On the other hand, if the adhesive strength between the surface of the carrier film and the adhesive sheet is strong, transfer is unlikely to occur. However, since the adhesive sheet is peeled off from the carrier film and used independently as a flexible substrate, the adhesive strength between the adhesive sheet and the carrier film cannot be increased more than necessary.

[0021] Other means for reducing the possibility of transfer include strengthening the release treatment on the surface that comes into contact with the adhesive sheet and setting a low winding pressure, but in such cases, it becomes difficult to control the edge position of the roll that winds up the adhesive sheet, which makes it difficult to stably produce the adhesive sheet.

[0022] On the other hand, in a polymer laminate sheet according to one embodiment of the present invention, one outermost layer is a polymer thin film layer and the other outermost layer is a nonwoven fabric layer, and the difference in adhesive strength between the two layers and the carrier film is large. Specifically, in a polymer laminate sheet according to one embodiment of the present invention, the adhesive strength of the polymer thin film layer, which is one outermost layer in contact with the carrier film and the object to be attached, is large, and the adhesive strength of the nonwoven fabric layer, which is the other outermost layer, is small, thereby preventing the transfer.

[0023] In view of the above, the present invention relates to a polymer laminate sheet that can be directly attached to an object to be attached and is difficult to peel off.

[0024] [Embodiment 1: Polymer laminate sheet] A polymer laminate sheet according to embodiment 1 of the present invention (hereinafter also referred to as "polymer laminate sheet of the present invention") is a polymer laminate sheet formed by laminating at least one polymer thin film layer and at least one nonwoven fabric layer, wherein one outermost layer is the polymer thin film layer and the other outermost layer is the nonwoven fabric layer, the polymer thin film layer and the nonwoven fabric layer are bonded by intermolecular forces, the one outermost polymer thin film layer having a film thickness of 10 nm or more and 1000 nm or less, and the other outermost nonwoven fabric layer is made of polymer fibers having a diameter of 10 nm or more and 10 μm or less.

[0025] In the polymer laminate sheet of the present invention, the polymer thin film layer contacts the target and functions to bond the polymer laminate sheet to the target. Meanwhile, by laminating the other outermost layer as a nonwoven fabric layer, the polymer thin film layer does not come into contact with anything other than the target. Therefore, for example, when the polymer laminate sheet of the present invention is placed so that the polymer thin film layer contacts the body surface and is pressed against the body surface with the palm, the polymer laminate sheet does not stick to the palm. Therefore, the polymer laminate sheet of the present invention can be easily applied to the body surface and is easy to handle during use. To achieve this effect, it is preferable that there is no portion of the polymer thin film layer that does not overlap with the nonwoven fabric layer.

[0026] In the polymer laminate sheet of the present invention, one (one) of the outermost layers is a polymer thin film layer having a thickness of 10 nm or more and 1000 nm or less. Hereinafter, unless otherwise specified, the term "polymer thin film layer" refers to the polymer thin film layer that is the one outermost layer.

[0027] In the polymer laminate sheet of the present invention, the polymer thin film layer functions as a layer that contacts the target. Because the polymer thin film layer has a thickness of 1000 nm or less, it conforms to the minute irregularities on the target surface, allowing the polymer laminate sheet of the present invention to adhere to the target. Therefore, the polymer laminate sheet of the present invention can be directly attached to the target without the need for adhesives, gels, etc. Furthermore, because the polymer thin film layer has a thickness of 10 nm or more, the strength of the polymer thin film layer and the polymer laminate sheet of the present invention can be ensured to a degree that prevents breakage during the manufacturing process.

[0028] In the polymer laminate sheet of the present invention, the other (other) outermost layer is a nonwoven fabric layer composed of polymer fibers having a diameter of 10 nm or more and 10 μm or less. Hereinafter, unless otherwise specified, the term "nonwoven fabric layer" refers to the other outermost nonwoven fabric layer.

[0029] The polymer thin film layer is bonded to the nonwoven fabric layer by intermolecular forces. Here, "bonded by intermolecular forces" means that the polymer thin film layer and the nonwoven fabric layer are not integrated, but are laminated as independent layers. The polymer thin film layer conforms to and adheres not only to the object to which it is attached but also to the nonwoven fabric. Therefore, when laminating the nonwoven fabric layer to the polymer thin film layer, there is no need to melt the fibers of the nonwoven fabric layer or the polymer thin film layer by heat, and no adhesive or adhesive is required. If the fibers of the nonwoven fabric layer or the polymer thin film layer are melted by heat, the polymer laminate sheet becomes hard, resulting in reduced flexibility and stretchability.

[0030] The nonwoven fabric layer has a structure in which fibers are entangled and is easily deformed. Therefore, even if a nonwoven fabric layer is laminated on a polymer thin film layer that has good conformability to the target, the high conformability of the polymer thin film layer to the target is unlikely to be impaired. Therefore, the polymer laminate sheet of the present invention has excellent conformability to the surface irregularities and deformations of the target, and as a result, it can be directly attached to the target without applying an adhesive, gel, etc. to the outermost layer of the polymer laminate sheet on the target side.

[0031] When the polymer laminate sheet of the present invention is attached to an object to be attached, as described above, the polymer thin film layer, which is one of the outermost layers, comes into contact with the object to be attached, and the nonwoven fabric layer, which is the other outermost layer, is exposed to the outside and may come into contact with objects other than the object to be attached.

[0032] In one embodiment of the present invention, the nonwoven fabric layer is composed of polymer fibers having a diameter of 10 nm or more and 10 μm or less. Therefore, when the polymer thin film layer is attached to a target, the nonwoven fabric layer can come into contact with an object other than the target. In this case, the contact between the nonwoven fabric layer and the object other than the target is a suitable point contact. Hereinafter, the contact surface of the object other than the target that comes into contact with the nonwoven fabric layer is also referred to as the "other surface." Hereinafter, suitable point contact means that the contact area between the fibers in the nonwoven fabric layer and the other surface is smaller than the contact area between conventional fibers having a diameter of more than 10 μm and the other surface. By being composed of polymer fibers having a diameter of 10 nm or more, the nonwoven fabric layer has sufficient strength to prevent breakage. As a result, when the nonwoven fabric layer and the other surface are in suitable point contact, shear stress caused by friction between the other surface and the nonwoven fabric layer is reduced. Therefore, the nonwoven fabric layer and the polymer laminate sheet of the present invention are less likely to tear, reducing the likelihood of breakage.

[0033] This is particularly useful in the manufacturing process. Flexible substrates such as polymer laminate sheets are generally formed on a carrier film using a roll-to-roll method. In this case, the carrier film and the polymer laminate sheet of the present invention are produced while being wound around a roll. During this process, the polymer thin film layer of the present invention and the nonwoven fabric layer come into contact with the carrier film, protective sheet, roll, etc. When the adhesive sheet has the configuration of the present invention, the nonwoven fabric layer and the carrier film, protective sheet, roll, etc. are in good point contact. This reduces the shear stress generated during the film formation, and as a result, the nonwoven fabric layer and the polymer laminate sheet of the present invention are less likely to break. Furthermore, as described above, the polymer laminate sheet of the present invention prevents the transfer of adhesion during film formation. Therefore, the polymer laminate sheet of the present invention can be stably produced on a carrier film using a roll-to-roll method.

[0034] For the above reasons, the polymer laminate sheet of the present invention can be directly attached to an object to be attached without applying an adhesive, gel, etc. to the outermost layer of the polymer laminate sheet on the side of the object to be attached, and has the effect of improving the handleability required for a stable manufacturing process. In addition, the polymer laminate sheet of the present invention has the effect of reducing the possibility of damage due to contact with other objects after attachment, and, even if damage does occur, reducing the severity of the damage.

[0035] Furthermore, during use, the polymer laminate sheet of the present invention may change the shape of the surface of the polymer thin film layer attached to the object to which it is attached. If the shape of the surface of the polymer thin film layer changes, stress is applied to the polymer thin film layer, which may cause a shift between the polymer laminate sheet of the present invention and the object to which it is attached, potentially reducing the adhesive strength between the polymer laminate sheet and the object to which it is attached. However, this stress is alleviated by being dispersed through the structure (network) formed from the fibers in the nonwoven fabric layer, thereby preventing or reducing the decrease in adhesive strength between the polymer laminate sheet and the object to which it is attached.

[0036] The polymer laminate sheet of the present invention has a nonwoven fabric layer laminated on a thin polymer layer, but its thin thickness ensures high moisture permeability and air permeability, and causes little discomfort during use. Furthermore, the polymer laminate sheet of the present invention can be easily fixed to a desired position on a target surface without using adhesives, gels, etc., which would impair moisture permeability and conformability to deformation, and is less likely to cause rashes, etc.

[0037] [Polymer Thin Film Layer] In one embodiment of the present invention, the polymer thin film layer, which is one of the outermost layers, has a thickness of 10 nm or more and 1,000 nm or less. Here, a smaller polymer thin film layer provides better conformability to fine irregularities on the surface of the object to which it is to be attached. Therefore, a smaller polymer thin film layer is preferable because it improves adhesion between the polymer laminate sheet of the present invention and the object to which it is to be attached. From the viewpoint of enabling direct attachment without the use of a pressure-sensitive adhesive or adhesive, the polymer thin film layer of the present invention is preferably 500 nm or less, more preferably 300 nm or less. Furthermore, if the polymer thin film layer has a thickness of a predetermined value or more, the strength of the polymer thin film layer and the polymer laminate sheet of the present invention can be ensured to a degree that prevents damage during the manufacturing process. From this viewpoint, the polymer thin film layer is preferably 30 nm or more, more preferably 50 nm or more.

[0038] In one embodiment of the present invention, the polymer thin film layer may have a multilayer structure as long as the thickness of the polymer thin film layer that is one of the outermost layers in the polymer laminate sheet of the present invention is within the above-mentioned range. That is, the polymer thin film layer may include a polymer thin film layer that is one of the outermost layers and another polymer thin film layer. In this case, the preferred thickness of the polymer thin film layer described above is the thickness of only the polymer thin film layer that is one of the outermost layers.

[0039] The polymer constituting the polymer thin film layer in one embodiment of the present invention is not particularly limited and can be appropriately selected depending on the type of object to which the film is to be applied. For example, when the object to be applied is the surface of body tissue, examples of polymers constituting the polymer thin film layer, from the viewpoint of water resistance and / or elasticity, include styrene-based elastomers such as styrene-butadiene-styrene (SBS) block copolymer, styrene-isoprene-styrene (SIS) block copolymer, and hydrogenated versions thereof such as styrene-ethylene-butylene-styrene (SEBS) block copolymer and styrene-ethylene-propylene-styrene (SEPS) block copolymer; and silicones such as polydimethylsiloxane (PDMS). Here, the water-resistant polymer may also include polymers that are resistant to hydrolysis. Furthermore, examples of polymers constituting the polymer thin film layer, from the viewpoint of affinity with body tissue, include, for example, polystyrene; acrylic resins such as polyacrylates and polymethacrylates; polylactic acid; polylactic-glycolic acid copolymers; polyvinyl acetate; chitosan; alginic acid; cellulose acetate; hyaluronic acid; gelatin; and collagen. It is preferable to select one or more of the above specific examples because they have excellent adhesion and conformability between the polymer thin film layer and the surface of the body tissue to which it is to be applied. When the polymer thin film layer has a multi-layer structure, it is preferable that at least one of the outermost polymer thin film layers and the contact surface with the surface to which it is to be applied be made of the above polymer material.

[0040] In one embodiment of the present invention, the polymer thin film layer may contain a conductive polymer. In this case, conductivity can be suitably imparted to the polymer laminate sheet of the present invention. In one embodiment of the present invention, the conductive polymer refers to a polymer having a conductivity of 0.1 S / cm or more. A specific example of a conductive polymer is poly(3,4-ethylenedioxythiophene) (PEDOT) / poly(4-styrenesulfonic acid) (PSS).

[0041] [Nonwoven Fabric Layer] In one embodiment of the present invention, the nonwoven fabric layer is composed of polymer fibers having a diameter of 10 nm or more and 10 μm or less. Here, the smaller the diameter of the polymer fibers constituting the nonwoven fabric layer, the smaller the contact area between the polymer fibers and other surfaces. As a result, as described above, the possibility of damage to the nonwoven fabric layer and the polymer laminate sheet of the present invention due to transfer and rubbing is suitably reduced. Furthermore, the smaller the diameter of the polymer fibers constituting the nonwoven fabric layer, the easier it is to deform, resulting in high conformability, allowing for a thinner film thickness while maintaining strength. As a result, the nonwoven fabric layer has superior conformability to the polymer thin film layer, allowing the polymer laminate sheet of the present invention to be directly attached to a target without the need to apply an adhesive, gel, or the like to the outermost layer of the polymer laminate sheet on the target side. From the above perspective, the diameter of the polymer fibers constituting the nonwoven fabric layer is preferably 3 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less. Furthermore, from the viewpoint of ensuring that the nonwoven fabric layer has sufficient strength to prevent breakage, the diameter of the polymer fibers constituting the nonwoven fabric layer is preferably 100 nm or more, and more preferably 300 nm or more.

[0042] In one embodiment of the present invention, the cross-sectional shape of the fibers constituting the nonwoven fabric layer may typically be approximately circular or approximately elliptical. This is because the fibers of the nonwoven fabric layer are not subjected to a heat treatment or the like after the nonwoven fabric layer is laminated on the polymer thin film layer, and their shape is not changed by dissolution. Furthermore, the cross-sectional shape of the fibers of the nonwoven fabric layer is approximately circular or approximately elliptical, thereby reducing the contact area between the nonwoven fabric layer and other surfaces. This results in good point contact between the polymer laminate sheet and other surfaces, rather than surface contact with a certain area, and sufficiently reduces the adhesive strength of the polymer laminate sheet of the present invention to other surfaces. The ratio of the major axis to the minor axis of the cross-section of the fibers in the nonwoven fabric layer is preferably 1 to 2, more preferably 1 to 1.5, even more preferably 1 to 1.2, and most preferably 1. The cross-sectional shape of the fibers and the ratio of the major axis to the minor axis of the cross-section of the fibers can be measured using a scanning electron microscope or the like.

[0043] In one embodiment of the present invention, the nonwoven fabric layer may have a multilayer structure. In this case, it is sufficient that the polymer fibers constituting one layer in the multilayer structure have a diameter within the aforementioned range. In this case, it is preferable that the outermost layer in the multilayer structure is composed of polymer fibers having a diameter within the aforementioned range, and it is more preferable that all layers are composed of polymer fibers having a diameter within the aforementioned range. Typically, the thickness of the nonwoven fabric layer is greater than the thickness of the thin polymer layer. The thickness of the nonwoven fabric layer is typically 50 nm to 30 μm.

[0044] The polymer fiber according to one embodiment of the present invention is a fiber made of a polymer. The polymer in the polymer fiber is not particularly limited. Specific examples of polymers in the polymer fiber, from the viewpoint of water resistance and / or stretchability, include styrene-based elastomers such as styrene-butadiene-styrene (SBS) block copolymer, styrene-isoprene-styrene (SIS) block copolymer, and hydrogenated versions thereof such as styrene-ethylene-butylene-styrene (SEBS) block copolymer and styrene-ethylene-propylene-styrene (SEPS) block copolymer; and silicones such as polydimethylsiloxane (PDMS). Here, the water-resistant polymer may also include polymers that are resistant to hydrolysis. Furthermore, from the viewpoint of affinity with body tissue, examples of polymers in the polymer fiber include polystyrene; acrylic resins such as polyacrylates and polymethacrylates; polylactic acid; polylactic-glycolic acid copolymer; polyvinyl acetate; chitosan; alginic acid; cellulose acetate; hyaluronic acid; gelatin; and collagen. It is preferable to use polymer fibers made of one or more polymers selected from the specific examples of polymers listed above for the following reasons (I) and (II): (I) The adhesion between the polymer laminate sheet of the present invention and the surface of the body tissue to which it is to be applied can be suitably improved. (II) The adhesion between the polymer laminate sheet of the present invention and other surfaces can be suitably reduced.

[0045] In one embodiment of the present invention, the polymer fiber may contain a conductive polymer. In this case, conductivity can be suitably imparted to the polymer laminate sheet of the present invention. In one embodiment of the present invention, the conductive polymer may be the same as the conductive polymer defined in the above-mentioned "polymer thin film layer" section. In a form in which the conductive polymer is contained in the polymer fiber, the entire polymer fiber may be composed of a conductive polymer. Furthermore, the polymer fiber may be composed of a core made of a polymer other than the conductive polymer and a coating film made of a conductive polymer that coats the core.

[0046] The polymer fiber has a storage modulus of 1 x 10 at 35°C. ４ Pa or more, 1×10 １０ The storage modulus at 35°C is preferably 1×10 ５ Pa or more, 1×10 ９ It is more preferable that the polymer fiber is made of a polymer having a storage modulus of 1×10 Pa or less. １０ When the storage modulus of the polymer constituting the polymer fiber is 1×10 Pa or less, the ability of the polymer laminate sheet of the present invention to follow the deformation of the object to which it is attached can be further improved. As a result, the adhesion between the polymer laminate sheet of the present invention and the object to which it is attached can be further improved. ４ When the storage modulus is 100 Pa or more, the adhesion between the polymer fiber and another surface can be suitably reduced. As a result, the adhesion between the polymer laminate sheet of the present invention and another surface can be suitably reduced. The method for measuring the storage modulus will be described later as a measuring method in the Examples.

[0047] The polymer fiber has a Young's modulus of 1×10 ３ Pa or more, 1×10 １０ It is preferable that the material is made of a polymer having a Young's modulus of 1×10 Pa or less. ４ Pa or more, 1×10 ９ It is more preferable that the polymer fiber is made of a polymer having a Young's modulus of 1×10 Pa or less. １０On the other hand, when the Young's modulus of the polymer constituting the polymer fiber is 1×10 Pa or less, the nonwoven fabric layer has excellent conformability to the polymer thin film. ３ When the elastic modulus is 1 Pa or more, the nonwoven fabric layer has excellent deformability.

[0048] The Young's modulus of the nonwoven fabric layer made of the polymer fibers is 1×10 ２ Pa or more, 1×10 ９ Pa or less, and 3 Pa or more, 1×10 ８ It is more preferable that the Young's modulus is 0.01 Pa or less. The Young's modulus of the nonwoven fabric layer is measured, for example, as follows. 1. A nonwoven fabric layer composed of polymer fibers is cut into a size of 5 mm wide x 30 mm long, and the upper and lower ends are attached to an adhesive tape frame to prepare a sample. 2. The sample is held in a tensile tester (Shimadzu Corporation, Autograph AGS-X) with a chuck distance of 20 mm, and then the adhesive tape frame is cut, and the chuck side equipped with a load cell is moved at a speed of 2 mm / min at room temperature. The load value when the sample is distorted is detected and recorded. 3. The recorded load-displacement curve is converted into a stress-strain curve (stress = load / sample cross-sectional area, strain = elongation / chuck distance), and the Young's modulus of the nonwoven fabric layer is calculated from the initial slope at this time.

[0049] The weight of the nonwoven fabric layer is 0.02 mg / cm ２ Above, 0.35mg / cm ２ Preferably, it is 0.05 mg / cm or less. ２ Above, 1.75mg / cm ２ It is more preferable that the basis weight of the nonwoven fabric layer is less than or equal to 100%. The basis weight of the nonwoven fabric layer can be adjusted by controlling the weight of the polymer fibers discharged onto the substrate in the manufacturing method of the nonwoven fabric layer described below. When the basis weight of the nonwoven fabric layer is within the above-mentioned range, breakage of the polymer laminate sheet of the present invention can be more suitably prevented, and the adhesion between the polymer laminate sheet of the present invention and the object to which it is attached can be more suitably improved.

[0050] [Configuration of Polymer Laminate Sheet] The polymer laminate sheet of the present invention may have one outermost layer as a polymer thin film layer with a thickness of 10 nm or more and 1000 nm or less, and the other outermost layer as a nonwoven fabric layer composed of polymer fibers with a diameter of 10 nm or more and 10 μm or less. The polymer laminate sheet of the present invention may include a layer other than the one outermost layer and the other outermost layer (hereinafter referred to as "other layer"). The "other layer" may be a polymer thin film layer or a nonwoven fabric layer, or a layer other than the polymer thin film layer and the nonwoven fabric layer. Examples of layers other than the polymer thin film layer and the nonwoven fabric layer include an adhesive layer, a conductive layer, etc. Note that, from the viewpoint of ensuring good properties such as breathability, the polymer laminate sheet of the present invention preferably does not include any layers other than the polymer thin film layer and the nonwoven fabric layer, and instead consists of at least one polymer thin film layer and at least one nonwoven fabric layer. In one embodiment, the polymer laminate sheet of the present invention does not include any other layers and consists of only one polymer thin film layer and one nonwoven fabric layer. In one embodiment, there is no region between the polymeric film layer and the nonwoven fabric layer where they are integrated. In one embodiment, there is no region between the polymeric film layer and the nonwoven fabric layer that contains an adhesive and / or bonding agent.

[0051] The constituent materials and physical properties of the other layers, i.e., the polymer thin film layer and the nonwoven fabric layer, are not particularly limited, and may be, for example, the preferred constituent materials and physical properties of the polymer thin film layer and the nonwoven fabric layer listed above.

[0052] In a polymer laminate sheet, the voids between the fibers of the nonwoven fabric layer at the interface with the polymer thin film layer are typically filled with the polymer thin film layer. Meanwhile, the voids between the fibers of the nonwoven fabric at locations away from the interface between the polymer thin film layer and the nonwoven fabric layer are maintained. The location away from the interface between the polymer thin film layer and the nonwoven fabric layer refers to the center in the thickness direction of the nonwoven fabric layer, for example, a region 40% to 70% of the thickness of the nonwoven fabric layer away from the polymer thin film contact surface of the nonwoven fabric layer in the thickness direction of the nonwoven fabric layer. In this region, the void filling rate of the nonwoven fabric layer with the polymer thin film is typically 0%, or at most 5%.

[0053] Even if the polymer laminate sheet of the present invention does not include layers other than the polymer thin film layer and the nonwoven fabric layer, such as an adhesive layer, the polymer thin film layer itself has high conformability and adhesiveness to the nonwoven fabric layer or other polymer thin film layer in contact with the polymer thin film layer, thereby ensuring sufficient adhesive strength between the polymer thin film layer and the nonwoven fabric layer or other polymer thin film layer in contact with the polymer thin film layer.

[0054] When the polymer laminate sheet of the present invention does not include any layers other than the polymer thin film layer and the nonwoven fabric layer, it is thin and has a high porosity, as compared to conventional laminate sheets that include an adhesive layer, etc., because an increase in film thickness and a decrease in porosity due to an adhesive layer, etc. are prevented. Therefore, when the polymer laminate sheet of the present invention does not include any layers other than the polymer thin film layer and the nonwoven fabric layer, it exhibits the effects of being excellent in permeability to gases such as water vapor and flexibility.

[0055] In the polymer laminate sheet of the present invention, it is preferable that the polymer constituting the polymer thin film layer and the polymer in the polymer fiber constituting the nonwoven fabric layer are the same type of polymer. This configuration improves the affinity between the polymer thin film layer and the nonwoven fabric layer, ensuring sufficient adhesive strength between the polymer thin film layer and the nonwoven fabric layer. Furthermore, from the viewpoint of more suitably ensuring adhesive strength between the polymer laminate sheet of the present invention and the object to be attached, it is preferable that the thickness of all polymer thin film layers in the polymer laminate sheet of the present invention be within the same range as the thickness of one of the outermost polymer thin film layers. From the viewpoint of conformability to the object to be attached and other layers, it is even more preferable that the thickness of all polymer thin film layers in the polymer laminate sheet of the present invention be within the above-mentioned range.

[0056] Furthermore, when the polymer thin film layer and the nonwoven fabric layer are directly laminated, the nonwoven fabric layer functions more effectively as a stress relief layer for the polymer thin film layer. As a result, stress is more effectively dispersed through the structure (network) formed by the fibers in the nonwoven fabric layer, and a decrease in adhesive strength between the polymer laminate sheet of the present invention and the object to which it is attached can be more effectively prevented or the amount of decrease can be more effectively reduced. Therefore, from the viewpoint of improving adhesive strength between the polymer laminate sheet of the present invention and the object to which it is attached, it is preferable that the polymer thin film layer and the nonwoven fabric layer be directly laminated in the polymer laminate sheet of the present invention.

[0057] From the viewpoint of simplifying the manufacturing method and reducing manufacturing costs, the polymer laminate sheet of the present invention preferably has a configuration consisting of only two layers: a polymer thin film layer that is one outermost layer, and a nonwoven fabric layer that is the other outermost layer. In other words, the polymer laminate sheet of the present invention preferably has a structure consisting of only two laminated layers: a polymer thin film layer having a thickness of 10 nm or more and 1000 nm or less, and a nonwoven fabric layer made of polymer fibers having a diameter of 10 nm or more and 10 μm or less.

[0058] In the polymer laminate sheet of the present invention, the polymer thin film layer and / or nonwoven fabric layer may be provided with functionality such as conductivity. For example, when a functionalized nonwoven fabric layer is used in the polymer laminate sheet of the present invention, the functionalized nonwoven fabric layer can be fixed and adhered to the target without the need for a separate adhesive, gel, or the like. Furthermore, when functionality is provided to both the polymer thin film layer and the nonwoven fabric layer in the polymer laminate sheet of the present invention, the functionality can be enhanced. Here, when conductivity is provided as a functionality to both the polymer thin film layer and the nonwoven fabric layer, the conductive paths throughout the polymer laminate sheet of the present invention are thicker than when conductivity is provided to the polymer thin film layer, thereby further reducing the overall resistance.

[0059] [Uses] The use of the polymer laminate sheet of the present invention is not particularly limited as long as it utilizes the ability to be attached to a predetermined target. The polymer laminate sheet of the present invention is particularly suitable for uses requiring high conformability to the target and / or high moisture permeability. Specifically, the polymer laminate sheet of the present invention is used, for example, in uses where the target is the surface of a body tissue. In other words, the polymer laminate sheet of the present invention can be a polymer laminate sheet intended to be attached to the surface of a body tissue.

[0060] Further, the present invention can be used in the manufacture of electronic functional members and electronic devices according to one embodiment of the present invention, which will be described later.

[0061] [Manufacturing Method] The method for manufacturing the polymer laminate sheet of the present invention is not particularly limited, and examples thereof include a method comprising the following steps (1) and (2): (1) a step of applying a solution of a polymer that constitutes the polymer thin film layer onto a substrate to form a coating layer, and removing the solvent from the coating layer to form the polymer thin film layer on the substrate; and (2) a step of preparing polymer fibers that constitute a nonwoven fabric, and then depositing the polymer fibers on a substrate to form the nonwoven fabric on the substrate.

[0062] One specific method for producing the polymer laminate sheet of the present invention includes the following steps (a) to (c): (a) First, using a substrate other than a polymer thin film layer and a nonwoven fabric layer as the substrate, step (1) is carried out to form a polymer thin film layer, which is one of the outermost layers, on the substrate. (b) Subsequently, in step (2), a nonwoven fabric layer, which is the other outermost layer, is formed on the polymer thin film layer obtained in step (a). (c) Finally, the substrate used in step (a) is removed to produce the polymer laminate sheet of the present invention.

[0063] The polymer laminate sheet of the present invention, which comprises one polymer thin film layer and one nonwoven fabric layer, can be produced by a method including the above-mentioned steps (a) to (c).

[0064] One specific example of a method for producing a polymer laminate sheet of the present invention containing two or more polymer thin film layers and / or two or more nonwoven fabric layers is a method comprising the following steps (a') to (d'): (a') First, using a substrate other than a polymer thin film layer and a nonwoven fabric layer as the substrate, step (1) is performed to form one of the outermost polymer thin film layers on the substrate; (b') Steps (1) or (2) are performed continuously to laminate one or more polymer thin film layers and / or one or more nonwoven fabric layers on the polymer thin film layer obtained in step (a'); (c') Step (2) is performed using the polymer thin film layer or nonwoven fabric layer obtained in step (1) or (2) last performed in step (b') as the substrate to form the other outermost nonwoven fabric layer on the polymer thin film layer or nonwoven fabric layer; (d') Finally, the substrate used in step (a') is removed to produce a polymer laminate sheet of the present invention.

[0065] In step (b'), the polymer thin film layer or nonwoven fabric layer obtained in the immediately preceding step is used as the substrate in step (1) and step (2). In step (b'), step (1) or step (2) may be performed multiple times, step (1) and step (2) may be performed alternately once each, one or more times of step (1) and two or more times of step (2) may be performed alternately, or two or more times of step (1) and one or more times of step (2) may be performed alternately.

[0066] Variations of the method for producing a polymer laminate sheet of the present invention include a method comprising the following steps (a") and (b"). (a") Between the two steps shown below, the "other layer" such as an adhesive layer is laminated by a known method on the polymer thin film layer or nonwoven fabric layer obtained in the earlier of the two steps: - Between step (a) and step (b) - Between step (a') and step (b') - Between each of step (1) or step (2) that are performed consecutively in step (b') - Between step (b') and step (c') (b") The "other layer" is used as a substrate in the later of the two steps.

[0067] By the above-mentioned modification, it is possible to produce a polymer laminate sheet of the present invention that includes the above-mentioned "other layer" in addition to one or more polymer thin film layers and one or more nonwoven fabric layers.

[0068] In steps (a) and (a'), a sacrificial layer may be formed on the substrate, and a polymer thin film layer may be formed on the sacrificial layer. The sacrificial layer is not particularly limited as long as it is a layer that dissolves in the stripping solution described below. For example, when water is used as the stripping solution, a water-soluble polymer such as water-soluble polyvinyl alcohol can be used as the material for the sacrificial layer. The method for producing the sacrificial layer is not particularly limited, and known methods can be used.

[0069] The substrate other than the polymer thin film layer and the nonwoven fabric layer is not particularly limited, and examples thereof include polymer films such as polyethylene terephthalate (PET) film, polypropylene (PP) film, polyphenylene ether (PPE) film, cycloolefin (COP) film, polyimide (PI) film, and silicone resin film; metal foils such as aluminum foil; conductive polymer films; paper; polysaccharide films; wafer (gelatin) films; silicon wafers; and glass plates.

[0070] In one embodiment of the present invention, in steps (b), (b'), and (c'), a process for integrating the polymer thin film layer and the nonwoven fabric layer, such as a heat treatment, is not performed when forming a nonwoven fabric layer on the polymer thin film layer or when forming a polymer thin film layer on the nonwoven fabric layer, thereby producing a polymer laminate sheet in which the polymer thin film layer and the nonwoven fabric layer are bonded by intermolecular forces.

[0071] In steps (c) and (d'), the method for removing the substrate used in steps (a) and (a') is not particularly limited as long as it does not damage the resulting polymer laminate sheet. Examples of methods for removing the substrate used in steps (a) and (a') include a method of removing the substrate using adhesive tape. Other methods for removing the substrate include the following methods (1) and (2). (1) In steps (a) and (a'), a sacrificial layer is formed on the substrate, thereby forming a laminate in which the substrate, the sacrificial layer, and the polymer laminate sheet of the present invention are laminated in this order. (2) Thereafter, the laminate is immersed in a stripping solution, the sacrificial layer is dissolved in the stripping solution, and the substrate is removed.

[0072] The remover liquid is not particularly limited as long as it is a solvent that can dissolve the sacrificial layer and does not adversely affect the polymer laminate sheet of the present invention. For example, when the sacrificial layer is formed from a water-soluble polymer, the remover liquid can be water.

[0073] The solvent for the solution in step (1) is not particularly limited as long as it can dissolve the polymer constituting the target polymer thin film layer and does not dissolve the substrate. The solvent can be appropriately selected depending on the type of substrate and the type of polymer constituting the polymer thin film layer. The solvent is, for example, tetrahydrofuran.

[0074] The coating method in step (1) is not particularly limited as long as it can form a coating layer with a uniform thickness and then form a polymer thin film layer with a uniform thickness, and any known coating method can be used. Examples of the coating method that can be used include gravure coating, screen printing, offset coating, bar coating, spin coating, knife coating, roll coating, and slot die coating. Here, gravure coating is preferred when continuous film formation using a roll-to-roll method is used.

[0075] The solvent is generally removed by drying in step (1). Drying conditions such as drying temperature and drying time may be appropriately selected depending on the thickness of the resulting polymer thin film layer, the composition of the coating liquid and the coating layer, and other factors.

[0076] In step (2), the polymer fibers constituting the nonwoven fabric can be prepared by any known spinning method capable of producing polymer fibers of a specified diameter, and are not particularly limited. The polymer fiber can be prepared by a spinning method selected from, for example, electrospinning, meltblowing, carbon dioxide laser supersonic drawing, islands-in-the-sea melt spinning, electrobubble spinning, and flash spinning. Electrospinning is preferred because it produces fibers with a relatively small diameter and provides high fiber diameter uniformity. When a nonwoven fabric layer is laminated on a polymer thin film layer, the small diameter of the polymer fibers in the nonwoven fabric layer allows most of the solvent dissolved in the polymer fibers to evaporate before reaching the polymer thin film layer. Therefore, even if the polymer thin film layer and the polymer fibers are made of the same polymer, the polymer thin film layer is not dissolved or damaged by the solvent in the fiber polymer solution, and a laminated film can be formed consisting of the polymer thin film layer and the nonwoven fabric layer, with high affinity between the polymer thin film layer and the nonwoven fabric layer. The polymer fibers obtained by the above spinning method are generally approximately circular, and the ratio of the major axis to the minor axis of the fiber cross section is about 1 to 1.2.

[0077] In step (2), the method for depositing polymer fibers on the substrate is not particularly limited, and any known method can be used, for example, a method using a drum collector.

[0078] In step (1), the thickness of the resulting polymer thin film layer can be controlled by adjusting the production conditions, such as the concentration of the polymer in the solution and the coating amount of the solution. When producing the polymer laminate sheet of the present invention, for example, in the step of preparing the polymer thin film layer, which is one of the outermost layers, such as step (a) or step (a'), the production conditions are appropriately adjusted to control the thickness of the resulting polymer thin film layer to 10 nm or more and 1000 nm or less. Examples of production conditions for the polymer thin film layer include the following: - Concentration of the polymer in the solution: 0.5 to 10 wt % - Coating amount of the solution: 2 x 10 －４ ~1 x 10 －３ g / cm ２ Drying temperature in step (1): 30 to 100°C Drying time in step (1): 10 seconds to 2 minutes In step (2), the diameter of the polymer fiber can be controlled by adjusting the manufacturing conditions for preparing the polymer fiber. For example, when using an electrospinning method, manufacturing conditions include the concentration of the raw material solution, the amount of raw material solution discharged, the applied voltage, and the distance between the syringe needle tip and the collector in the spinning apparatus used. When manufacturing the polymer laminate sheet of the present invention, for example, in the step of preparing the other outermost nonwoven fabric layer, such as step (b) or step (c'), the manufacturing conditions are appropriately adjusted to control the diameter of the resulting polymer fiber to 10 nm or more and 10 μm or less. When using an electrospinning method, the manufacturing conditions for preparing the polymer fiber constituting the nonwoven fabric layer can include, for example, the following conditions. Concentration of raw material solution: 1 to 20% by weight Discharge rate of raw material solution: 0.1 to 5 mL / hour (h) Distance between the syringe needle tip and the collector: 50 to 200 mm In addition, in step (2), it is preferable to adjust the amount of polymer fibers deposited on the substrate so that the basis weight of the obtained nonwoven fabric layer falls within the suitable range of the basis weight of the nonwoven fabric layer described above.

[0079] Another method for producing the polymer laminate sheet of the present invention includes, for example, the following steps (i) to (iii): (i) Using a substrate other than a polymer thin film layer and a nonwoven fabric layer as the substrate, step (1) is carried out to form a polymer thin film layer on the substrate; (ii) Using a substrate other than a polymer thin film layer and a nonwoven fabric layer as the substrate, step (2) is carried out to form a nonwoven fabric layer on the substrate; (iii) The polymer thin film layer obtained in step (i) and the nonwoven fabric layer obtained in step (ii) are superimposed on each other to obtain a laminate, and the substrate is then removed from the laminate to obtain a laminate sheet.

[0080] In steps (i) and (ii), a sacrificial layer may be formed on the substrate, and a polymer thin film layer or a nonwoven fabric layer may be formed on the sacrificial layer. The sacrificial layer in steps (i) and (ii) may be the same as the sacrificial layer in steps (a) and (a').

[0081] In step (iii), the method for overlapping the polymer thin film layer and the nonwoven fabric layer is not particularly limited, and the polymer thin film layer and the nonwoven fabric layer may be overlapped by directly contacting each other, or may be attached via an "other layer" such as an adhesive layer. However, in step (iii), the polymer thin film layer and the nonwoven fabric layer are overlapped without performing a treatment for integrating the polymer thin film layer and the nonwoven fabric layer, such as a heat treatment such as heat pressing. This makes it possible to produce a polymer laminate sheet in which the polymer thin film layer and the nonwoven fabric layer are bonded by intermolecular forces.

[0082] In step (iii), the method for removing the substrate can be the same as the method for removing the substrate in steps (c) and (d').

[0083] The laminate sheet obtained in step (iii) is a polymer laminate sheet of the present invention that includes one polymer thin film layer and one nonwoven fabric layer, where the polymer thin film layer is one outermost layer and the nonwoven fabric layer is the other outermost layer.

[0084] Another method for producing a polymer laminate sheet of the present invention may include, after step (iii), a step of further overlaying another polymer thin film layer and / or another nonwoven fabric layer on the polymer thin film layer or nonwoven fabric layer of the laminate sheet obtained in step (iii). Here, the other polymer thin film layer and / or another nonwoven fabric layer may be prepared by separately performing step (i) and / or step (ii). In this case, a polymer laminate sheet of the present invention including two or more polymer thin film layers and / or two or more nonwoven fabric layers can be produced. When further overlaying another polymer thin film layer and / or another nonwoven fabric layer, the other polymer thin film layer or another nonwoven fabric layer is overlaid on the polymer thin film layer or nonwoven fabric layer of the laminate sheet without performing the aforementioned treatment to integrate the polymer thin film layer and the nonwoven fabric layer. This allows for the production of a polymer laminate sheet in which the polymer thin film layer and the nonwoven fabric layer are bonded by intermolecular forces.

[0085] In the other method for producing the polymer laminate sheet of the present invention, in step (1) of preparing one of the outermost polymer thin film layers, the production conditions are appropriately adjusted as described above to prepare a polymer thin film layer having a thickness controlled within a range of 10 nm to 1,000 nm, and in step (2) of preparing the other outermost nonwoven fabric layer, the production conditions are appropriately adjusted as described above to prepare a nonwoven fabric layer made of polymer fibers having a diameter controlled within a range of 10 nm to 10 μm.

[0086] [Embodiment 2: Electronic Functional Member, Embodiment 3: Electronic Device] An electronic functional member according to embodiment 2 of the present invention (hereinafter referred to as "electronic functional member of the present invention") includes the polymer laminate sheet of the present invention. Also, an electronic device according to embodiment 3 of the present invention (hereinafter referred to as "electronic device of the present invention") includes the electronic functional member of the present invention. Therefore, the electronic device of the present invention includes the polymer laminate sheet of the present invention.

[0087] Therefore, both the electronic functional member and the electronic device of the present invention can be directly attached to the target object, such as the surface of body tissue, and are unlikely to be damaged by contact with other objects after attachment, and even if damage does occur, the degree of damage is minor.

[0088] An example of the electronic functional component of the present invention is a component consisting solely of the conductive polymer laminate sheet of the present invention. Here, "conductive" means that in the polymer laminate sheet of the present invention, the polymer constituting one or more polymer thin film layers contains a conductive polymer and / or the polymer fibers constituting one or more nonwoven fabric layers contain a conductive polymer.

[0089] Another example of the electronic functional component of the present invention is a configuration in which a conductive member is formed on the polymer laminate sheet of the present invention. The conductive member can be any commonly used conductive member and is not particularly limited. From the viewpoint of high flexibility and moisture permeability, a thin polymer laminate sheet is preferable. Therefore, in order to impart high flexibility and moisture permeability to the polymer laminate sheet of the present invention while maintaining electrical conductivity and reducing the thickness, it is preferable to form the polymer thin film and / or nonwoven fabric from a conductive polymer. Examples of conductive polymers include PEDOT / PSS (manufactured by Merck). Furthermore, when a metal is used as the conductive member, specific examples include conductive patterns made of metals such as copper, gold, aluminum, silver, and zinc. Known methods can be used to form a conductive pattern on the polymer laminate sheet of the present invention, such as vapor deposition, sputtering, chemical vapor deposition, inkjet printing, screen printing, gravure printing, and flexographic printing.

[0090] A specific example of the electronic functional member of the present invention is an electrode, more specifically, a wearable electrode.

[0091] The electronic device of the present invention can be produced by a known method using the electronic functional component of the present invention. Specific examples of the electronic device of the present invention include wearable devices and implantable devices.

[0092] One embodiment of the present invention includes the following aspects [1] to [7]. [1] A polymer laminate sheet comprising at least one polymer thin film layer and at least one nonwoven fabric layer laminated together, wherein one outermost layer is the polymer thin film layer and the other outermost layer is the nonwoven fabric layer, the polymer thin film layer and the other outermost layer are bonded by intermolecular forces, the polymer thin film layer having a thickness of 10 nm or more and 1000 nm or less, and the other outermost nonwoven fabric layer being made of polymer fibers having a diameter of 10 nm or more and 10 μm or less. [2] The polymer laminate sheet according to [1], wherein the one outermost polymer thin film layer and the nonwoven fabric layer are directly laminated. [3] The polymer laminate sheet according to [1] or [2], wherein the polymer constituting the polymer thin film layer and the polymer in the polymer fiber constituting the nonwoven fabric layer are the same type of polymer. [4] The polymer fiber constituting the nonwoven fabric layer has a storage modulus at 35° C. of 1×10 ４ Pa or more, 1×10 １０ [5] The polymer laminate sheet according to any one of [1] to [4], which is intended to be attached to the surface of body tissue. [6] An electronically functional member comprising the polymer laminate sheet according to any one of [1] to [5]. [7] An electronic device comprising the electronically functional member according to [6].

[0093] The scope of the polymer laminate sheet, electronic functional component, and electronic device according to one embodiment of the present invention may include any combination of the items shown in each of the above-mentioned configurations within the scope of the claims.

[0094] EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0095] [Methods for Measuring Various Physical Properties] Various physical properties in Examples 1 and 2 and Comparative Example 1 were measured by the following methods.

[0096] [Film Thickness of Polymer Thin Film] The film thickness of the polymer thin film layer in Example 1 and Comparative Example 1 was measured by observation using an atomic force electron microscope (manufacturer: Shimadzu Corporation, product name: Scanning Probe Microscope SPM-9700).

[0097] [Diameter of Polymer Fibers] The diameter and cross-sectional shape of the polymer fibers constituting the nonwoven fabric layer of Example 1 were measured by observation using a scanning electron microscope (manufacturer: JEOL Ltd., product name: JEOL-7100F).

[0098] [Storage Modulus at 35°C] 0.5 g of the polymer fibers prepared to form the nonwoven fabric layer in Example 1 was melted and formed into a cylindrical shape with a diameter of 8 mm and a film thickness of 1 to 2 mm, to obtain a sample for measuring storage modulus. The storage modulus of the polymer forming the polymer fiber at 35°C was measured for the sample for measuring storage modulus using a dynamic viscoelasticity measuring device (rotational rheometer, DHR-2 manufactured by TA Instruments) with a parallel plate geometry of 8 mm in diameter. The measurement conditions were a measurement frequency of 1 Hz, a strain of 0.05%, and a measurement temperature of 35°C.

[0099] [Adhesion] A test sheet was sandwiched between frames (5 mm wide) with 30 mm square openings, and the frames were attached to each other with adhesive tape. A sample was prepared by attaching a handle to the frame. As shown in FIG. 1 , the outer periphery of the test sheet was fixed by a jig 2. Sample A used the polymer laminate sheet piece 1 produced in Example 1 as the test sheet, and was prepared so that the polymer thin film layer of the polymer laminate sheet piece 1 was exposed through the opening in the frame of the jig 2. Sample B, like Sample A, used the polymer laminate sheet piece 1 produced in Example 1 as the test sheet, and was prepared so that the nonwoven fabric layer of the polymer laminate sheet piece 1 was exposed through the opening in the frame of the jig 2. Sample C used the thin film sheet piece 1 produced in Comparative Example 1 as the test sheet, and was prepared so that the thin film sheet piece 1 was exposed through the opening in the frame of the jig 2.

[0100] As shown in the left diagram of Figure 2, a skin model 3 (manufactured by Viewlux Co., Ltd., product name: Bioskin Plate P001-001) shaped to 10 (mm) x 10 (mm) x 5 (mm) was fixed to a tensile tester. Next, the bottom surface of the sample exposed through the opening of the jig 2 was brought into contact with the skin model 3 for 15 minutes under a load of 0.01 N to adhere it. The bottom surface of the sample was the back surface (lower surface) of the polymer laminate sheet piece 1 or thin film sheet piece 1.

[0101] Next, as shown in the right diagram of Figure 2, a peel test was performed by pulling the jig 2 upward at a speed of 10 mm / min until the polymer laminate sheet piece 1 or thin film sheet piece 1 peeled off from the skin model 3. As a result, a displacement-load curve of the sample during the peel test was obtained. Note that the displacement in the displacement-load curve is the amount of change (unit: mm) in the distance of the tensile tester chucked with the jig 2, and the load in the displacement-load curve is the load applied to the sample when the displacement is a specific value. Based on the displacement-load curve, the value obtained by integrating the load with respect to the displacement was taken as the adhesive strength of the sample.

[0102] A peel test was performed using each of Sample A, Sample B, and Sample C as samples using the method described above. As a result, displacement-load curves were obtained for each of Sample A, Sample B, and Sample C, and the adhesive strength of each of Sample A, Sample B, and Sample C was calculated using the method described above based on the displacement-load curves. Specifically, the adhesive strength of Sample A is the adhesive strength between the polymer thin film layer in the polymer laminate sheet and the skin model. The adhesive strength of Sample B is the adhesive strength between the nonwoven fabric layer in the polymer laminate sheet and the skin model. The adhesive strength of Sample C is the adhesive strength between the thin film sheet consisting of the polymer thin film layer and the skin model.

[0103] The displacement-load curves of Samples A to C are shown in FIG.

[0104] [Example 1] (Creation of Sacrificial Layer) A commercially available polyethylene terephthalate (PET) film (Lumirror (registered trademark) Type T60, manufactured by Toray Industries, Inc., thickness 25 μm, film width 10 cm) was used as the substrate. Using a gravure coater (ML-120, manufactured by Yasui Seiki Co., Ltd.), a 5 wt % aqueous solution of water-soluble polyvinyl alcohol (PVA, PVA500 manufactured by Kanto Chemical Co., Ltd.) was coated onto the substrate while winding it up in a roll-to-roll manner, and then dried to form a film, thereby forming a sacrificial layer on the substrate. The production conditions at that time were a linear speed of 0.8 m / min, and a coating amount of the 5 wt % aqueous solution of PVA of 1 × 10 －３ g / cm ２ The drying temperature was 80° C. and the drying time was 30 seconds.

[0105] (Creation of Polymer Thin Film Layer) A polymer thin film layer was formed on a sacrificial layer. Specifically, a polymer thin film layer substrate was formed by the following method. Polystyrene butadiene styrene (SBS, manufactured by Sigma-Aldrich Japan, styrene 30 wt %, average Mw ∼140,000 by GPC) was dissolved in tetrahydrofuran (THF) to a SBS concentration of 5 wt %, to prepare SBS solution A. Using a gravure coater (ML-120, manufactured by Yasui Seiki Co., Ltd.), SBS solution A was applied to the sacrificial layer, and then dried to form a film, forming a polymer thin film layer on the sacrificial layer. The film formation was carried out by a roll-to-roll method. The production conditions were a linear velocity of 1.3 m / min, and a coating amount of SBS solution A of 2 × 10 －４ g / cm ２ The drying temperature was 40° C. and the drying time was 30 seconds.

[0106] (Formation of Nonwoven Fabric Layer and Fabrication of Polymer Laminate Sheet) The polymer thin film layer was placed on a drum collector (width 200 mm, diameter 200 mm). Polystyrene butadiene styrene (SBS, manufactured by Asahi Kasei Corporation, Asaprene® T432) was dissolved in a mixed solvent of THF and N,N-dimethylformamide in a weight ratio of 75:25 (by weight) to obtain SBS solution B, so that the SBS concentration was 25 wt%. Polymer fibers were obtained by spinning SBS solution B using a nanofiber electrospinning device NANON-01 manufactured by MEC Corporation under the following conditions: solution discharge rate: 1 ml / h, applied voltage: 22.5 kV, and syringe needle tip-to-collector distance: 150 mm. The obtained polymer fibers were deposited on the polymer thin film layer placed on the drum collector for a predetermined time of 1 h while rotating the drum collector at a rotation speed of 100 rpm and a syringe movement speed of 30 mm / sec. As a result, a nonwoven fabric layer formed from polymer fibers was laminated on the polymer thin film layer, and a polymer laminated sheet was obtained. At this time, the amount of deposited polymer fibers was 0.116 mg / cm ２ Thereafter, two polymer laminate sheet pieces (40 mm square) were cut out from the polymer laminate sheet, and one polymer laminate sheet piece was used to prepare sample A, and the other polymer laminate sheet piece was used to prepare sample B.

[0107] Comparative Example 1 A thin film sheet was produced by forming a polymer thin film layer on a sacrificial layer using the same method as in Example 1. The sheet produced in Comparative Example 1 differs from the polymer laminate sheet produced in Example 1 in that a nonwoven fabric layer is not laminated on the polymer thin film layer. Then, thin film sheet pieces having the same shape as the polymer laminate sheet pieces were cut from the thin film sheet using the same method as in Example 1, and used to prepare Sample C.

[0108] [Results] The physical properties of the polymer laminate sheet of Example 1 and the thin film sheet described in Comparative Example 1 were measured by the above-mentioned methods, and the results are shown in Tables 1 and 2 below. The cross-sectional shape of the fibers constituting the nonwoven fabric layer was approximately circular. In Table 2 below, the adhesive strength of Sample C prepared using the thin film sheet of Comparative Example 1 was set to 100, and the adhesive strength values ​​of Samples A and B prepared using the polymer laminate sheet of Example 1 were calculated. The polymer laminate sheet of Example 1 is formed by laminating a polymer thin film layer as one outermost layer and a nonwoven fabric layer as the other outermost layer. As shown in Table 1, in the polymer laminate sheet of Example 1, the polymer thin film layer has a thickness in the range of 10 nm to 1000 nm, and the nonwoven fabric layer is made of polymer fibers having a diameter of 10 nm to 10 μm.

[0109] Samples A and B are identical except for the contact surface with the skin model. Furthermore, the thin film sheet of Comparative Example 1 included in Sample C corresponds to an adhesive sheet conventionally used as a flexible substrate. From the above and the information in Table 2, it can be seen that the adhesive strength of Sample A, which uses the polymer laminate sheet of Example 1, is higher than that of Sample C, which uses the thin film sheet of Comparative Example 1, which simulates a conventional adhesive sheet. Although the polymer thin film layers of Example 1 and Comparative Example 1 are the same, the polymer thin film layer of Example 1 has higher adhesive strength. It is believed that the nonwoven fabric layer relieves stress on the polymer thin film layer, improving adhesive strength. Therefore, it can be seen that the polymer laminate sheet of Example 1 has excellent conformability and self-adhesion to the target, and can be directly attached to the target without coating an adhesive, gel, or the like on the outermost layer of the polymer laminate sheet on the target side.

[0110] As shown in Table 2, the adhesive strength of Sample B was 1 / 50 of that of Sample A. The polymer laminate sheet of Example 1 exhibited extremely low adhesion between the nonwoven fabric side and the skin model. While the adhesive strength between the nonwoven fabric layer and the skin model was evaluated here, similar behavior was observed when the sheet came into contact with objects other than the skin model. To prevent transfer, the difference in adhesive strength between one outermost layer and the other outermost layer must be at least 10 times greater than that of the target object. For example, if the adhesive strength of the nonwoven fabric layer were approximately 1 / 3 of that of the polymer thin film layer, the adhesive strength of the nonwoven fabric layer would still be high and insufficient to prevent transfer. As described above, the adhesive strength of Sample B of the polymer laminate sheet of the present invention was 1 / 50 of that of Sample A, demonstrating sufficient transfer prevention. Therefore, the polymer laminate sheet of Example 1 is prevented from transferring to carrier films, etc., when manufactured using a roll-to-roll process, and from transferring to other surfaces during use. Therefore, it can be seen that the polymer laminate sheet of Example 1 has improved handleability, which is necessary for a stable manufacturing process. It can also be seen that, even when using the polymer laminate sheet of Example 1, the nonwoven fabric layer exposed on the surface does not stick to objects other than the target object even if it comes into contact with them. It can also be seen that, as a result, the polymer laminate sheet of Example 1 has a reduced possibility of breakage due to the aforementioned transfer, and even if breakage does occur, the degree of breakage can be reduced.

[0111] From the above, it has been found that the polymer laminate sheet of the present invention can be directly attached to an object without coating the outermost layer of the polymer laminate sheet on the side of the object with an adhesive, gel, etc., and has the effect of improving the handleability necessary for a stable manufacturing process. It has also been found that the polymer laminate sheet of the present invention has the effect of reducing the possibility of damage due to contact with other objects after attachment, and even if damage does occur, it can reduce the severity of the damage.

[0112] The polymer laminate sheet of the present invention can be used to produce self-adhesive sheets and electrodes when wearable devices / implantable devices, etc. come into contact with the surface of body tissue. The polymer laminate sheet of the present invention can also be used to produce sheets and electrodes that are highly moisture permeable and breathable and are unlikely to cause skin problems even when worn for several days.

[0113] 1 Polymer laminate sheet piece or sheet piece consisting of a polymer thin film layer 2 Jig 3 Skin model

Claims

1. A polymer laminate sheet formed by laminating at least one polymer thin film layer and at least one nonwoven fabric layer, wherein one outermost layer is the polymer thin film layer and the other outermost layer is the nonwoven fabric layer, the polymer thin film layer and the nonwoven fabric layer are bonded by intermolecular forces, the one outermost layer being a polymer thin film layer having a thickness of 10 nm or more and 1000 nm or less, and the other outermost layer being a nonwoven fabric layer, which is made of polymer fibers having a diameter of 10 nm or more and 10 μm or less.

2. The polymer laminate sheet according to claim 1, wherein the one outermost layer, the polymer thin film layer, and the nonwoven fabric layer are directly laminated to each other.

3. The polymer laminate sheet according to claim 1, wherein the polymer constituting said thin polymer layer and the polymer in the polymer fibers constituting said nonwoven fabric layer are of the same type of polymer.

4. The polymer fiber constituting the nonwoven fabric layer has a storage modulus of 1×10 at 35° C. ４ Pa or more, 1×10 １０ The polymer laminate sheet according to claim 1 , which is composed of a polymer having a viscosity of 0.1 Pa or less.

5. The polymer laminate sheet according to claim 1, intended to be attached to the surface of body tissue.

6. An electronic functional component comprising the polymer laminate sheet according to any one of claims 1 to 5.

7. An electronic device comprising the electronic functional component according to claim 6.

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