Laminated resin sheet including resin sheet body having hair-like bodies and protective sheet, production method therefor, and molded article thereof

Abstract

To provide a laminated resin sheet in which whitening and loss of tactile properties are suppressed even when secondary molding is performed, a production method therefor, and a molded article thereof.SOLUTION: A laminated resin sheet comprises: a resin sheet body having a plurality of hair-like bodies regularly arranged on one surface of a base layer, the base layer and the hair-like bodies forming a continuous phase with no structural boundary between the base layer and the hair-like bodies; and a protective sheet comprising a protective layer that fills gaps between the hair-like bodies and covers a surface of the resin sheet body on the side having the hair-like bodies, a surface layer that constitutes a surface opposite to the surface of the base layer on the side having no hair-like bodies, and an intermediate layer positioned between the protective layer and the surface layer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminated resin sheet including a resin sheet body having hair-like bodies and a protective sheet, a method for producing the same, and a molded product thereof. [Background technology]

[0002] Sheets made of paper or polymeric materials have been used for various purposes, including interior materials for automobiles, housings for accessories, housings for electronic devices and home appliances, building materials such as wallpaper, housings for toys and game consoles, and components for everyday items. Patent Document 1, for example, proposes a resin sheet having regularly arranged hairs on its surface as a method for imparting a good tactile feel to the surface of a sheet. On the other hand, when such a resin sheet is used as an interior part such as a dashboard or seat of an automobile, it is necessary to perform secondary molding and attach it to the surface of the object. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2018 / 016562 Summary of the Invention [Problem to be solved by the invention]

[0004] However, it has been found that such resin sheets may have the risk of causing the hairs to deform or tilt and fall over during the process of secondary molding and attaching the resin sheets to the surface of an object, resulting in whitening of the appearance of the sheet and a loss of its pleasant tactile feel. The problem to be solved by the present invention is to provide a laminated resin sheet that is suppressed from whitening and loss of tactile feel even when subjected to secondary molding, a method for producing the same, and a molded article made from the same. [Means for solving the problem]

[0005] That is, after examining various means, the inventors have found that by forming a laminated resin sheet comprising a resin sheet main body having regularly arranged hairs on one side of a base layer, with no structural boundary between the base layer and the hairs forming a continuous phase, a protective layer filling the gaps between the hairs and covering the surface of the resin sheet main body having the hairs, a surface layer constituting the surface opposite to the surface of the base layer not having the hairs, and an intermediate layer located between the protective layer and the surface layer, a laminated resin sheet can be obtained that is less susceptible to whitening and loss of tactile feel even when subjected to secondary molding, and have completed the present invention.

[0006] The present invention, which solves the above problems, comprises the following: [1] A resin sheet body having regularly arranged hair-like bodies on one side of a base layer, with no structural boundary between the base layer and the hair-like bodies forming a continuous phase; a protective sheet including a protective layer that fills the gaps between the hairs and covers the surface of the resin sheet body that has the hairs; a surface layer that forms the surface opposite to the surface of the base layer that does not have the hairs; and an intermediate layer located between the protective layer and the surface layer; A laminated resin sheet comprising: [2] A method for producing a laminated resin sheet according to [1], comprising laminating a protective sheet on the surface of the resin sheet body on the side having hair-like bodies. [3] A molded product of the laminated resin sheet described in [1]. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a laminated resin sheet that is suppressed from whitening and loss of tactile feel even when subjected to secondary molding, a method for producing the same, and a molded article made from the same. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a schematic vertical cross-sectional side view showing a laminated resin sheet according to a first embodiment of the present invention. [Figure 2] FIG. 2 is a schematic plan view of a resin sheet body. [Figure 3] FIG. 3 is a schematic vertical cross-sectional side view showing a laminated resin sheet according to a second embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] Below, various embodiments of the resin sheet will be described, followed by a description of a method for manufacturing the resin sheet. However, if a specific description given for one embodiment also applies to other embodiments, that description will be omitted in the other embodiments.

[0010] [First embodiment] The laminated resin sheet according to the first embodiment of the present invention comprises a base layer having regularly arranged hairs on one side thereof, with no structural boundary between the base layer and the hairs forming a continuous phase, a protective layer filling the gaps between the hairs and covering the surface of the base layer on the side having the hairs, a surface layer forming the surface opposite to the side not having the hairs of the base layer, and an intermediate layer positioned between the protective layer and the surface layer. That is, the layer structure of the laminated resin sheet according to this embodiment is, from bottom to top, hairs and base layer (1), protective layer (2), intermediate layer (3), and surface layer (4).

[0011] <Underlayer> The base layer (1a) is a layer underlying the hair-like bodies and refers to the portion of the reference numeral 1 in FIG. 1 other than the surface hair-like bodies (1b). The thickness of the base layer refers to the thickness from the base of the hair-like bodies to the surface opposite the base layer. The average thickness of the base layer is preferably 20 μm or more but less than 150 μm, more preferably 30 μm or more but less than 140 μm, and even more preferably 40 μm or more but less than 140 μm. A thickness of 20 μm or more allows for sufficient height of the hair-like bodies. Furthermore, a thickness of less than 150 μm allows for efficient formation of hair-like bodies. The average thickness of the base layer can be determined by measuring the thickness from the base of the hair-like bodies to the interface with the other layer at 10 points on a sample cut into cross-sections at any three points using a microtome, and then calculating the arithmetic mean value of the 30 measurements. There may be no structural boundary between the base layer and the hair-like bodies, forming a continuous phase. "Structurally boundaryless" means that the base layer and hairs are integrally formed, with no clear structural boundary between them. "Forming a continuous phase" means that there is no seam between the base layer and hairs, and that they are not discontinuous (continuous phase). In this respect, it differs from a structure in which hairs are implanted on a base layer. The base layer and hairs may have the same composition, and the bond between the base layer and hairs may include a covalent bond. A covalent bond is a chemical bond formed by the sharing of an electron pair between two atoms. In thermoplastic resins, which are chain molecules formed by linked monomers, individual polymers are bonded by covalent bonds, which are stronger than the van der Waals bonds or hydrogen bonds that act between polymer molecules. The base layer and the hairs may be derived from the same solid thermoplastic resin sheet, which is not separate. Derived from the same solid thermoplastic resin sheet means, for example, that the hairs and the base layer are obtained directly or indirectly from the same resin sheet. The base layer and the hairs may be formed from the same solid thermoplastic resin sheet, which means that the hairs and the base layer are directly formed by processing a single resin sheet. The absence of a structural boundary between the base layer and the hairs forms a continuous phase, preventing the hairs from separating from the base layer due to external stimuli, resulting in a sheet with a good feel to the touch. Furthermore, the sheet can be manufactured with fewer steps than when the hairs are implanted.

[0012] The base layer and the hair-like bodies are made of the same thermoplastic resin composition, with a thermoplastic resin as the main component. Here, "mainly composed" means that the thermoplastic resin is contained in an amount of 50% by mass or more. Preferably, the amount is 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more. In one embodiment of the present invention, a resin containing at least one of urethane-based elastomer (TPU), styrene-based resin, polyolefin-based resin, polyvinyl chloride resin, thermoplastic elastomer, and fluorine-based resin can be used.

[0013] Urethane elastomers are resins made from diisocyanates and polyols as reaction raw materials. The combination of diisocyanates is as follows: diphenylmethane diisocyanate (MDI), H 12 Any combination of MDI-based or hexamethylene diisocyanate (HDI)-based polyol and polyether-based, polyester-based, or polycarbonate-based polyol may be selected, or a combination of two or more thereof may be used. In one embodiment of the present invention, a combination of an MDI-based or HDI-based diisocyanate and a carbonate-based polyol is preferably used.

[0014] Examples of styrene-based resins that can be used include homopolymers or copolymers of styrene-based monomers such as styrene, α-methylstyrene, p-methylstyrene, dimethylstyrene, pt-butylstyrene, and chlorostyrene; copolymers of these styrene-based monomers with other monomers, such as styrene-acrylonitrile copolymers (AS resins); and graft polymers obtained by graft polymerization of the styrene-based monomers with other polymers, such as diene rubber polymers such as polybutadiene, styrene-butadiene copolymers, polyisoprene, and polychloroprene, such as high-impact polystyrene (HIPS resins) and styrene-acrylonitrile graft polymers (ABS resins). Styrene-based thermoplastic elastomers can also be used.

[0015] Polyolefin resins refer to resins made of polymers containing α-olefins as monomers, and include polyethylene resins and polypropylene resins. Examples of polyethylene resins include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and linear medium-density polyethylene. Not only simple polyethylenes but also copolymers, graft compounds, and blends having these structures can be used. Examples of the latter resins include copolymers and blends of resins having polar groups in the polyethylene chain, such as ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, ethylene-methacrylic acid ester copolymers, ethylene-vinyl acetate-vinyl chloride copolymers, and terpolymers with acid anhydrides.

[0016] Furthermore, examples of polypropylene resins that can be used include homopolypropylene, random polypropylene, and block polypropylene. When homopolypropylene is used, the structure of the homopolypropylene may be isotactic, atactic, or syndiotactic. When random polypropylene is used, the α-olefin copolymerized with propylene preferably has 2 to 20 carbon atoms, more preferably 4 to 12 carbon atoms, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene. When block polypropylene is used, a block copolymer (block polypropylene), a block copolymer containing a rubber component, or a graft copolymer can be used. These olefin resins can be used alone or in combination with other olefin-based resins.

[0017] The polyvinyl chloride resin can be a vinyl chloride homopolymer or a copolymer of vinyl chloride and other comonomers. When polyvinyl chloride is a copolymer, it can be a random copolymer or a graft copolymer. Examples of graft copolymers include those in which vinyl chloride is graft-polymerized onto an ethylene-vinyl acetate copolymer or a thermoplastic urethane polymer as a backbone polymer. The polyvinyl chloride of this embodiment is an extrusion-moldable flexible polyvinyl chloride composition containing additives such as a polymeric plasticizer. Known polymeric plasticizers can be used, but preferred examples include ethylene copolymer polymeric plasticizers such as ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-(meth)acrylate-carbon monoxide copolymer, and ethylene-vinyl acetate copolymer with a high vinyl acetate content.

[0018] Thermoplastic elastomers include those having a structure combining a soft polymeric substance and a hard polymeric substance. Specific examples include styrene-based elastomers, olefin-based elastomers, vinyl chloride-based elastomers, polyester-based elastomers, and polyamide-based elastomers. These elastomers can be selected from commercially available products.

[0019] Examples of fluorine-based resins that can be used include vinylidene fluoride homopolymers and vinylidene fluoride copolymers containing vinylidene fluoride as a main component. Polyvinylidene fluoride (PVDF) resins are crystalline resins that exhibit various crystal structures, such as α-type, β-type, γ-type, and αp-type. Examples of vinylidene fluoride copolymers include vinylidene fluoride-hexafluoropropylene copolymers, vinylidene fluoride-tetrafluoroethylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, vinylidene fluoride-trifluoroethylene copolymers, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymers, vinylidene fluoride-chlorotrifluoroethylene-hexafluoropropylene terpolymers, and mixtures of two or more of these.

[0020] The melt mass flow rate of the thermoplastic resin composition at 190°C to 300°C is preferably 4 g / 10 min or more. By making it 4 g / 10 min or more, the transferability of the shape of the capillaries can be improved. The melt mass flow rate is a value measured according to JIS K 7210 at a test temperature range of 190°C to 300°C under a load of 2.16 kg to 10.0 kg.

[0021] The thermoplastic resin composition may be an alloy of the above-mentioned thermoplastic resins in any ratio, provided that the effects of the present invention are not impaired. Furthermore, other additives may be added. Examples of other additives that may be added, provided that the effects of the present invention are not impaired, include water / oil repellents, colorants such as pigments and dyes, lubricants / release agents such as silicone oils and alkyl esters, fibrous reinforcing agents such as glass fiber, fillers such as granular fine particles such as talc, clay, and silica, and scaly fine particles such as mica, low-molecular-weight antistatic agents such as salt compounds of sulfonic acid and alkali metals, high-molecular-weight antistatic agents such as polyether ester amides, and additives such as flame retardants, antibacterial agents, antiviral agents, and heat stabilizers. Scrap resin generated during the resin sheet manufacturing process may also be added.

[0022] Examples of water- and oil-repellents include silicone-based water- and oil-repellents, carnauba wax, and fluorine-based water- and oil-repellents. Examples of silicones include organopolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, with dimethylpolysiloxane being particularly preferred. Commercially available products include silicone-resin alloys such as "Clinbell CB50-PP," "Clinbell CB-30PE," "Clinbell CB-1," and "Clinbell CB-50AB" (manufactured by Fuji Chemical Co., Ltd.). Commercially available carnauba waxes include "Carnauba No. 1" (manufactured by Nikko Rica Corporation). Fluorine-based water- and oil-repellents include surfactants with perfluoroalkyl groups, such as "Surflon KT-PA" (manufactured by AGC Seimi Chemical Co., Ltd.). The amount of water- and oil-repellent added is preferably 0.5% to 25% by mass. If the content is less than 0.5% by mass, there is a risk that sufficient water and oil repellency may not be obtained, and if the content exceeds 25% by mass, there is a risk that moldability may deteriorate.

[0023] Examples of antistatic agents include polyetheresteramide-based polymeric antistatic agents and ionomer-based polymeric antistatic agents. Commercially available polyetheresteramide-based polymeric antistatic agents include "Pelestat 230," "Pelestat 6500," "Pelectron AS," and "Pelectron HS" (manufactured by Sanyo Chemical Industries, Ltd.). Commercially available ionomer-based polymeric antistatic agents include "Entira SD100" and "Entira MK400" (manufactured by DuPont-Mitsui Polychemicals). The amount of antistatic agent added is preferably 5% to 30% by mass. If the amount is less than 5% by mass, sufficient antistatic properties may not be obtained, and if the amount is more than 30% by mass, production costs increase.

[0024] The antibacterial agent may be either inorganic or organic. In terms of dispersibility, inorganic agents are preferred. Specific examples include inorganic antibacterial agents based on metal ions (Ag, Zn, Cu) and calcined shell calcium antibacterial agents. Commercially available inorganic antibacterial agents based on metal ions include "Bactekiller BM102VT" (manufactured by Fuji Chemical Co., Ltd.), "Novalon VZF200," "Novalon (AG300)" (manufactured by Toagosei Co., Ltd.), "KM-10D-G," and "IM-10D-L" (manufactured by Sinanen Zeomic Co., Ltd.). Examples of calcined shell calcium antibacterial agents include "Scallow" (manufactured by FID). The amount of antibacterial agent added is preferably 0.5% to 5% by mass. Less than 0.5% by mass may result in insufficient antibacterial activity, while more than 5% by mass increases production costs.

[0025] Examples of lubricants and release agents that can be used include alkyl-based lubricants and release agents such as aliphatic hydrocarbon compounds, higher fatty acid compounds, higher aliphatic alcohol compounds, and fatty acid amide compounds, as well as silicone-based lubricants and release agents and fluorine-based lubricants and release agents. When using a lubricant or release agent, the amount added is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass, out of a total of 100 parts by mass of the resin composition. Adding an amount of 0.01 parts by mass or more reduces the risk of reduced release effectiveness, while adding an amount of 5 parts by mass or less reduces the risk of bleeding out onto the sheet surface.

[0026] Masterbatches in which lubricants and release agents are pre-alloyed with thermoplastic resins can also be used. For example, "Wax Master V" (manufactured by BASF) is a commercially available masterbatch based on a urethane-based thermoplastic elastomer, and in terms of production efficiency, it is preferable to use a masterbatch. The amount of masterbatch added is preferably 1 to 8 parts by mass, more preferably 2 to 7 parts by mass, and even more preferably 3 to 6 parts by mass, out of a total of 100 parts by mass including the resin composition.

[0027] <hairy body> The hairs (1b) refer to the hair-like portions extending from the surface of the base layer (1a) as shown in FIG. 1. The hairs are regularly arranged on the surface of the base layer. Regularly arranged here means that the hairs are not randomly arranged, i.e., arranged in an orderly manner (e.g., at regular intervals) in one or two directions. The regularity of the arrangement of the hairs is determined by the arrangement of the hair roots. In one embodiment, the hairs are positioned on the base layer at regular intervals, and the positions of the bases of the hairs are regularly arranged in the longitudinal and lateral directions of the base layer. The arrangement of the hairs is not particularly limited, and may be arranged in a checkerboard pattern or a staggered pattern. Regularly arranging the hairs on the surface of the base layer facilitates the development of a uniform, consistent, and pleasant tactile feel. When a load is applied, such as by tracing the hairs with a finger, the hairs may collapse, forming a finger mark that appears to have a different luster and color tone from the surrounding area. The hairy material can also provide a suede-like feel to the touch.

[0028] The average height (h) of the hairs is preferably 60 μm or more and less than 330 μm, more preferably 80 μm or more and less than 250 μm, even more preferably 80 μm or more and less than 200 μm, and particularly preferably 90 μm or more and less than 180 μm. By setting the average height to 60 μm or more, a good tactile feel can be sufficiently ensured, and by setting the average height to less than 330 μm, it is easy to prevent the hairs from falling over. When the hairs are almost upright relative to the base layer, the length from the base to the tip represents the height of the hairs. On the other hand, when the hairs are inclined relative to the base layer or have a wound portion, the height h of the hairs is the distance from the surface of the base layer to the point where the hairs are furthest from the surface of the base layer. In addition, the total value of the intervals subdivided by multi-point measurement from the tip to the center of the base of the hair is the length L of the hairs. The average height and length of the hairs can be determined by measuring the height and length of the hairs at any number of locations on the resin sheet using an electron microscope and image processing software, and then calculating the arithmetic mean value of the measured values.

[0029] The average diameter (d) of the hairs is preferably 1 μm to 50 μm, more preferably 5 μm to 50 μm, and even more preferably 5 μm to 40 μm. By setting the average diameter of the hairs to 1 μm or more, a good tactile feel can be ensured, while by setting the average diameter of the hairs to 50 μm or less, good tactile feel such as a moist, soft, and fluffy feel can be obtained. The average diameter of the hairs is determined by measuring the diameter at the mid-height (h / 2) of the hairs from several locations on the resin sheet body using an electron microscope and image processing software, and then calculating the arithmetic mean value of the measured values. The aspect ratio of the hairs can be expressed as (average height of hairs / average diameter of hairs). The aspect ratio of the hairs is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 5. An aspect ratio of 2 or more ensures a good tactile sensation, while an aspect ratio of 20 or less not only provides good tactile sensations such as a moist, soft, and fluffy feel, but also reduces the risk of the ratio of height to length of the hairs falling below a certain level. On the other hand, the aspect ratio can also be determined based on the average basal diameter of the hairs. The average basal diameter of the hairs is preferably 10 μm to 150 μm, more preferably 20 μm to 120 μm, and even more preferably 30 μm to 100 μm. The average basal diameter of the hairs is determined by measuring the distance between adjacent hairs at several locations on the resin sheet body and calculating the arithmetic mean value of the measured values. When the basal diameter of the hairs is used as the basis, the aspect ratio is preferably 1.0 to 10, more preferably 1.0 to 5, and even more preferably 1.0 to 2.5. By setting the aspect ratio to 1.0 or more, a good tactile feel can be ensured. By setting the aspect ratio to 10 or less, not only can good tactile feel such as moist, soft, and fluffy feel be obtained, but also the risk of the ratio of height to length of the hairs falling below a certain level can be reduced.

[0030] The average spacing (t) of the hairs is preferably 20 μm to 200 μm, more preferably 40 μm to 150 μm, and even more preferably 40 μm to 100 μm. The spacing of the hairs refers to the distance between the center of the base of one hair and the center of the base of an adjacent hair, as shown in FIG. 2, for example. By setting the average spacing to 20 μm or more, a good tactile sensation is ensured, while by setting it to 200 μm or less, good tactile sensations such as a moist, soft, and fluffy feel are obtained. The average spacing of the hairs is determined by measuring the spacing between adjacent hairs at several points on the resin sheet body and calculating the arithmetic mean value of the measured values.

[0031] The shape of the hairs is not particularly limited, but may be such that they extend in a hair-like manner in the direction away from the base layer and gradually become thinner as they approach the tip, or may have a bulge at the tip. In other words, the cross-sectional area may gradually decrease with increasing distance from the base layer, then increase once and terminate. The tip of the hair may be bud-shaped or mushroom-shaped. The hair may have a base-end portion extending away from the base layer, a portion extending from the base-end portion and bending with a constant curvature or a gradually changing curvature, or even a spiral or spiral-shaped portion. In this case, the tip of the hair may be folded inward. Such a shape provides a good tactile sensation. Furthermore, the bud-shaped or mushroom-shaped portion being hollow provides a more favorable tactile sensation. When bud- or mushroom-shaped hair tips are formed, the ratio of the average diameter of the bud- or mushroom-shaped hairs to the average diameter of the width of the bud- or mushroom-shaped hairs is preferably 1.1 or more. The height of the bud- or mushroom-shaped hairs is preferably 7 μm or more. The average diameter of the hairs, the average diameter of the width of the bud- or mushroom-shaped hairs, and the height are measured using electron scanning microscope photographs, and the arithmetic mean values ​​are used. The hairs are made of a thermoplastic resin. The thermoplastic resin may be the same as the resin that can be used in the base layer.

[0032] The thermoplastic resin contained in the base layer and hairs may at least partially form a three-dimensional crosslinked structure (e.g., a three-dimensional network structure). For example, in one embodiment, at least a portion of the hairs may be crosslinked; in another embodiment, the entire surface of the hairs may be crosslinked; and in yet another embodiment, the entire hairs (from the boundary with the base layer to the tip) may be crosslinked. Methods for forming the crosslinked body include, for example, a method in which a resin sheet is molded and then the surface having the hairs is irradiated with an electron beam, and a method in which an organic peroxide is added and then heated and humidified during or after molding of the resin sheet. Commercially available resins containing added organic peroxide include "Linkron" manufactured by Mitsubishi Chemical Corporation. In this embodiment, it is preferable to form a crosslinked body (electron beam crosslinked body) by irradiating with an electron beam.

[0033] In one embodiment, when the angle of the hairs extending perpendicularly to the surface of the base layer is taken as 0°, the average angle that increases upon heat molding is preferably 0 to 10°, more preferably 0 to 9°, and even more preferably 0 to 8°. The angle can be calculated by measuring the angle of the hair-like bodies using, for example, a laser microscope for the resin sheet body before heat molding and the resin sheet body from which the protective layer has been peeled off after heat molding of the laminated resin sheet, and subtracting the angle before heat molding from the angle after heat molding. Here, "heat molding" refers to placing a laminate resin sheet in a mold, injecting an injection resin such as polycarbonate resin into the mold, and obtaining an insert-molded product in which the laminate resin sheet is decorated, followed by peeling off the protective layer. When placing a laminate resin sheet in a mold, the laminate resin sheet may be placed directly, or may be preformed in advance to impart a three-dimensional shape before placing it. Examples of preforming methods include vacuum forming, pressure forming, vacuum pressure forming, and TOM molding. The preforming temperature conditions can be a sheet surface temperature of 100 to 150°C and a heating time of 40 to 300 seconds. In addition to polycarbonate (PC) resin, ABS resin, AES resin, polyester resin, acrylic resin, or an alloy resin combining these can also be used as the injection resin. The injection temperature conditions can be a mold temperature of 40°C, an injection resin temperature of 280°C, and a holding pressure of 30 MPa. Specifically, the heat molding can be carried out under the following conditions. Using a vacuum and compressed air molding machine, preform the laminated resin sheet under the following conditions to give it a three-dimensional shape. The three-dimensional shape is given by using a mold for a cover panel with a convex shape that is gently curved 10 mm from the edge to the center on a surface 200 mm long and 100 mm short, and bringing the surface of the laminated resin sheet opposite the surface layer into contact with the convex surface of the mold. Sheet surface temperature: 100~150℃ Heating time: 40 to 300 seconds Mold shape: length 200mm, width 100mm The laminated resin sheet with the three-dimensional shape is then removed from the mold, the excess portion is trimmed, and polycarbonate resin is injected using an insert molding machine under the following conditions to obtain a secondary molded product (insert molded product).Insert molding is performed by placing the surface layer side of the laminated resin sheet with the three-dimensional shape in contact with the injection mold, and injecting resin into the side opposite the surface layer using the side gate method. Mold temperature: 40℃ Injection resin temperature: 280℃ Holding pressure: 30MPa After cooling, the molded product is removed from the mold and the protective sheet is peeled off to obtain the final secondary molded product. The average value of the angle increased by heat molding can be adjusted by the composition of the resin sheet body, the shape of the hairs, the composition and average thickness of the protective layer, etc.

[0034] <Resin sheet body> The resin sheet body according to this embodiment has a base layer and hair-like bodies regularly arranged on one side of the base layer. Furthermore, there is no structural boundary between the base layer and the hair-like bodies, forming a continuous phase. In this embodiment, "tactile sensation" refers to the texture and feel of the surface of the resin sheet body. The resin sheet surface is judged to be comfortable to the touch, and if so, a good tactile sensation is defined as a specific feel such as moist, soft, or fluffy.

[0035] In this embodiment, the thickness of the resin sheet body refers to the combined thickness of the average height of the hairs and the average thickness of the base layer. The thickness of the resin sheet body is preferably 80 μm or more and less than 350 μm, more preferably 90 μm or more and less than 330 μm, and more preferably 150 μm or more and less than 310 μm. It may also be 80 μm or more and less than 600 μm, or 60 μm or more and less than 250 μm. By setting the thickness at a certain level or more, a good tactile feel can be sufficiently ensured, while by setting it at a certain level or less, it becomes easy to use in insert molding. The thickness of the resin sheet body can be measured according to Method A of JIS L 1913:2010.

[0036] <Protective layer> The protective layer (2) is a layer that fills the gaps between the hairs and covers the surface of the resin sheet body on the side having the hairs. "Filling the gaps" means filling the spaces between adjacent hairs, more preferably filling the spaces between adjacent hairs from the base to the tip.

[0037] The average thickness of the protective layer is preferably 60 μm to 600 μm, more preferably 80 μm to 400 μm, even more preferably 80 μm to 300 μm, and even more preferably 80 μm to 200 μm. By making the thickness 60 μm or more, the hair-like bodies are completely covered with the protective layer in a large area, which makes it easier to prevent the hair-like bodies from tilting during molding. Furthermore, by making the thickness 600 μm or less, manufacturing costs can be reduced. In one embodiment, the average thickness of the protective layer is greater than the average height of the hairs, so that the hairs are completely covered by the protective layer, which can enhance the effect of suppressing the tilt of the hairs due to molding. The average thickness of the protective layer can be determined by measuring the layer thickness at 10 points on each cross-section of a sample cut out at three random points using a microtome, and then calculating the arithmetic mean value of the 30 measurements. The thickness of the protective layer is defined as the distance from the layer interface with the base layer to the layer interface with the intermediate layer.

[0038] The tensile modulus of the protective layer at 20°C is preferably 0.2 MPa or more and less than 2 MPa, more preferably 0.3 MPa or more and less than 1.9 MPa, even more preferably 0.3 MPa or more and less than 1.8 MPa, and particularly preferably 0.4 MPa or more and less than 1.7 MPa. The tensile modulus of the protective layer can be measured, for example, by cutting out a 115 mm x 6 mm, dumbbell-shaped No. 5 (longer side in the CMD direction) test piece from the protective layer, setting the test piece in a small tabletop testing machine ("EZTest / CE", manufactured by Shimadzu Corporation), and conducting a tensile test at room temperature (20°C) (chuck distance 25 mm, tensile speed 500 mm / min), and determining the tensile modulus in the elastic region (slope at strain 0-4%) from the obtained stress-strain (SS) curve.

[0039] In one embodiment, the tensile strength of the protective layer is preferably 1.0 to 30 MPa, more preferably 1.5 to 30 MPa, and even more preferably 1.5 to 30 MPa. The tensile strength of the protective layer can be determined, for example, by cutting out a test piece of the protective layer (115 mm x 6 mm, dumbbell-shaped No. 5, with the long side in the CMD direction), setting the test piece in a small tabletop testing machine ("EZTest / CE", manufactured by Shimadzu Corporation), and conducting a tensile test at room temperature (20°C) (chuck distance 25 mm, tensile speed 500 mm / min), and then determining the maximum value of the obtained stress-strain (SS) curve.

[0040] The protective layer may be made of a resin composition containing a silicone resin as a main component. The protective layer may be formed, for example, by applying the resin composition to the surface of the resin sheet having hairs using a comma coater, a slot die, or the like and then curing the composition. Alternatively, a hot melt film may be laminated on the surface of the resin sheet having hairs and heated to conform to the uneven shape of the hairs. As the silicone-based resin, a peroxide-curable type, a condensation reaction-curable type, an addition reaction-curable type, an ultraviolet-curable type, or the like can be used. A curing agent and a curing retarder can be used in curing the silicone resin. The curing agent can be a radical polymerization initiator, a cationic polymerization initiator, or an anionic polymerization initiator. The amount of the curing agent is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and even more preferably 5 to 150 parts by mass, per 100 parts by mass of the silicone resin. A cure retarder is a compound that suppresses a rapid increase in viscosity due to the curing reaction by temporarily capturing reactive species, thereby extending the usable time. The cure retarder is preferably a cure retarder selected from the group consisting of phosphoric acid-based cure retarders and ether-based cure retarders. One type of cure retarder can be used alone, or two or more types can be used in combination. The amount of cure retarder is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the silicone resin. As the hot melt film, olefin-based, polyamide-based, polyurethane-based, polyester-based, or other hot melt films can be used. In addition, the resin composition that is the raw material for the protective layer, like the thermoplastic resin composition that forms the base layer and the hair-like bodies, may contain other additives within a range that does not impair the effects of the present invention.

[0041] <Middle class> The intermediate layer (3) is a layer located between the protective layer (2) and the surface layer (4). The average thickness of the intermediate layer is preferably 0.01 μm or more but less than 15 μm, more preferably 0.01 μm or more but less than 10 μm, and even more preferably 0.01 μm or more but less than 8 μm. A thickness of 0.02 μm or more facilitates improved adhesion to the protective layer. The average thickness of the intermediate layer can be determined by measuring the layer thickness at 10 points on a sample obtained by cutting cross-sections at three random locations using a microtome, and then calculating the arithmetic mean value of the 30 measurements. The thickness of the intermediate layer is defined as the distance from the interface with the protective layer to the interface with the surface layer.

[0042] The raw material for the intermediate layer is not particularly limited as long as it can be laminated with the protective layer and the surface layer with sufficient peel strength, and a composition containing an adhesive as a main component can be used. Examples of adhesives include silicone-based adhesives, (meth)acrylic resin-based adhesives, natural rubber adhesives, urethane resin-based adhesives, ethylene-vinyl acetate resin emulsion adhesives, ethylene-vinyl acetate resin-based adhesives, epoxy resin-based adhesives, vinyl chloride resin solvent-based adhesives, chloroprene rubber-based adhesives, cyanoacrylate-based adhesives, styrene-butadiene rubber solvent-based adhesives, nitrile rubber-based adhesives, nitrocellulose-based adhesives, phenolic resin-based adhesives, modified silicone-based adhesives, polyester-based adhesives, polyamide-based adhesives, polyimide-based adhesives, olefin resin-based adhesives, vinyl acetate resin emulsion-based adhesives, polystyrene resin solvent-based adhesives, polyvinyl alcohol-based adhesives, polyvinylpyrrolidone resin-based adhesives, polyvinyl butyral-based adhesives, polybenzimidazole adhesives, polymethacrylate resin solvent-based adhesives, melamine resin-based adhesives, urea resin-based adhesives, and resorcinol-based adhesives. The adhesive may be used alone or in combination of two or more kinds, among which silicone adhesives are preferably used. The intermediate layer can be formed by a common method, for example, a method of applying a composition serving as a raw material for the intermediate layer to the protective layer or to the surface layer.

[0043] <Surface layer> The surface layer (4) is a layer that constitutes the surface of the laminated resin sheet opposite to the surface of the base layer that does not have hair-like bodies. The average thickness of the surface layer is preferably 10 μm or more but less than 100 μm, more preferably 10 μm or more but less than 90 μm, and even more preferably 15 μm or more but less than 80 μm. By making the thickness 10 μm or more, a certain level of rigidity can be easily obtained. Furthermore, by making the thickness less than 100 μm, mold followability can be easily obtained during secondary molding. The average thickness of the surface layer can be determined by cutting cross-sections from three randomly selected locations on a sample using a microtome, measuring the layer thickness at 10 locations on each sample, and then calculating the arithmetic mean value of the 30 measurements. The thickness of the surface layer is defined as the distance from the layer interface with the intermediate layer to the surface of the surface layer.

[0044] The melting point of the resin composition that is the raw material for the surface layer is preferably 100 to 350°C, more preferably 100 to 340°C, and even more preferably 110 to 340°C, from the viewpoint of ensuring heat resistance and formability. A melting point of 100°C or higher prevents the resin from melting upon contact with the mold during secondary molding, making it difficult to peel from the mold and preventing the mold from becoming soiled. Furthermore, a melting point of 350°C or lower prevents the rigidity from becoming too high, making it easier to obtain mold followability during secondary molding. In this specification, the melting point refers to the melting peak temperature measured by differential scanning calorimetry (DSC) using a thermal analyzer (for example, "DSC8500" manufactured by PerkinElmer Co., Ltd.) in the temperature range of 30 to 350°C, when heated at a heating rate of 10°C / min.

[0045] The tensile strength of the surface layer is preferably 80 to 500 MPa, more preferably 90 to 500 MPa, and even more preferably 100 to 500 MPa. By making the tensile strength of the surface layer 80 MPa or more, tearing of the protective sheet when peeling it from the main resin sheet body can be suppressed. The tensile strength of the surface layer can be determined, for example, by cutting out a test piece of the surface layer measuring 10 x 150 mm (with the long side in the CMD direction), setting the test piece in a small tabletop testing machine ("EZTest / CE" manufactured by Shimadzu Corporation), and conducting a tensile test at room temperature (20°C) (chuck distance 50 mm, tensile speed 50 mm / min), and then determining the maximum value of the obtained stress-strain (SS) curve.

[0046] The surface layer may be made of a resin composition containing a polypropylene resin, a polyethylene resin, a polyester resin, or the like as a main component. Polypropylene-based resins are resins containing 50% by mass or more of propylene monomer units. Examples of polypropylene-based resins include propylene homopolymers such as isotactic homopolypropylene, syndiotactic homopolypropylene, and atactic homopolypropylene; ethylene-propylene random copolymers; ethylene-propylene block copolymers; and α-olefin-propylene copolymers, such as soft olefins containing elastomer components (either compound or reactor type). These polypropylene-based resins may be used alone or in combination of two or more types. Examples of polyethylene resins that can be used include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear medium-density polyethylene, etc. In addition to simple substances, copolymers, graft compounds, and blends having these structures can also be used. Examples of the latter resins include copolymers and blends of resins having polar groups in the polyethylene chain, such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, and terpolymers with acid anhydrides. Examples of polyester resins that can be used include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, and polymethylene terephthalate. Examples of copolymerizable components include diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, and dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid. Polyethylene terephthalate can be a polyester containing terephthalic acid as the primary acid component and ethylene glycol as the primary glycol component, with 90 mol% or more of repeating units of ethylene terephthalate. Other copolymerizable components capable of forming ester bonds may also be included within the scope of the present invention, provided that the effects of the present invention are not impaired. Examples of copolymerizable compounds include dicarboxylic acids containing substituents such as isophthalic acid, cyclohexanedicarboxylic acid, adipic acid, dimer acid, sebacic acid, and sulfonic acid groups. In addition, the resin composition that is the raw material for the surface layer, like the thermoplastic resin composition that forms the base layer and the hair-like bodies, may contain other additives within a range that does not impair the effects of the present invention.

[0047] The surface layer can be formed by a general method, for example, a method of applying a composition serving as a raw material for the intermediate layer to a surface layer previously formed in a sheet shape, and then applying a composition serving as a raw material for the protective layer, a method of applying a composition serving as a raw material for the intermediate layer to a surface layer previously formed in a sheet shape, and then laminating the surface of the protective layer, a method of applying a composition serving as a raw material for the intermediate layer to the surface of the protective layer, and then applying a resin composition serving as a raw material for the surface layer to the surface of the intermediate layer, and the like.

[0048] <Protective sheet> The protective sheet in this embodiment has a protective layer, an intermediate layer, and a surface layer. By having the intermediate layer and the surface layer in addition to the protective layer, the protective sheet is less likely to tear when peeled off from the resin sheet body, compared to when only the protective layer is included.

[0049] The tensile modulus of the protective sheet at 23°C is preferably 100 MPa or more and less than 500 MPa, more preferably 100 MPa or more and less than 480 MPa, even more preferably 110 MPa or more and less than 480 MPa, and particularly preferably 110 MPa or more and less than 470 MPa. The tensile modulus of the protective sheet can be measured by, for example, cutting out a 115 mm x 6 mm, dumbbell-shaped No. 5 test piece (with the long side in the CMD direction) from the protective sheet, setting the test piece in a small tabletop testing machine ("EZTest / CE", manufactured by Shimadzu Corporation), and conducting a tensile test at room temperature (20°C) (chuck distance 25 mm, tensile speed 500 mm / min), and determining the tensile modulus in the elastic region (slope at strain 0-4%) from the obtained stress-strain (SS) curve.

[0050] The protective sheet preferably has a tensile strength of 10 to 150 MPa, more preferably 15 to 150 MPa, and even more preferably 20 to 150 MPa, from the viewpoints of improving mold conformability during secondary molding and making it less likely to tear when peeled off from the resin sheet body. The tensile strength of the protective sheet can be determined, for example, by cutting out a 115 mm x 6 mm, dumbbell-shaped No. 5 test piece (with the long side in the CMD direction) from the protective sheet, setting the test piece in a small tabletop testing machine ("EZTest / CE", manufactured by Shimadzu Corporation), and conducting a tensile test (25 mm, tensile speed 500 mm / min) at room temperature (20°C), and then determining the maximum value of the obtained stress-strain (SS) curve.

[0051] <Laminated resin sheet> The laminated resin sheet in this embodiment includes a hair-like body and base layer (1), a protective layer (2), an intermediate layer (3), and a surface layer (4). In this embodiment, the average thickness of the laminate resin sheet refers to the combined average thickness of the base layer, the protective layer, the intermediate layer, and the surface layer. The average thickness of the laminate resin sheet is preferably 100 μm or more and less than 700 μm, more preferably 100 μm or more and less than 600 μm, and even more preferably 110 μm or more and less than 550 μm. The thickness of the laminate resin sheet can be measured in accordance with JIS K 7130:1999.

[0052] In one embodiment, the peel strength between the resin sheet main body and the protective sheet is preferably 0.01 to 1.6 N / mm. The peel strength between the resin sheet main body and the protective sheet is more preferably 0.01 to 1.3 N / mm, even more preferably 0.02 to 1.1 N / mm, and particularly preferably 0.02 to 1.0 N / mm. By setting the peel strength to 0.01 N / mm or more, it is possible to prevent the protective sheet from peeling off during molding, causing hair collapse and resulting in poor appearance. Furthermore, by setting the peel strength to 1.6 N / mm or less, it is possible to prevent the shape of the hair-like bodies from deforming after peeling, resulting in poor appearance. The peel strength between the resin sheet body and the protective sheet in a laminated resin sheet can be determined as follows: a laminated resin sheet consisting of a resin sheet body and a protective sheet is cut to a width of 25 mm, and the resin sheet body is placed horizontally below the gripping jig of a universal material testing machine using a 90-degree peeling jig so that the protective sheet faces upward.The protective layer peeled from the resin sheet below is sandwiched above the gripping jig, and the gripping jig with the protective sheet sandwiched above is pulled in the normal direction to the sheet surface at a tensile speed of 100 mm / min to measure.

[0053] [Second embodiment] An example of the laminate resin sheet according to the second embodiment of the present invention is a laminate resin sheet in which a base layer is formed on the surface of the foundation layer opposite to the side having the hair-like bodies, as shown in Fig. 3. That is, the layer structure of the laminate resin sheet according to the second embodiment is, from bottom to top, a base layer (5), hair-like bodies and foundation layer (1), a protective layer (2), an intermediate layer (3), and a surface layer (4), and the base layer (5) and hair-like bodies and foundation layer (1) constitute the resin sheet body. The average thickness of the base layer is preferably 50 μm or more and less than 300 μm, more preferably 50 μm or more and less than 280 μm, and even more preferably 60 μm or more and less than 280 μm. By setting the average thickness of the base layer to 300 μm or less, production costs can be reduced. Here, the hair-like bodies, the base layer, the protective layer, the intermediate layer, and the surface layer are the same as those described in the first embodiment, so their description will be omitted. The average thickness of the laminated resin sheet including the base layer is preferably 150 μm or more and less than 500 μm, more preferably 150 μm or more and less than 450 μm, and even more preferably 200 μm or more and less than 450 μm. The base layer in the resin sheet according to the second embodiment is preferably made of a thermoplastic resin that can adhere to the underlayer. For example, the same thermoplastic resin composition as the underlayer, polycarbonate resin, polyester resin, or a polymer alloy resin thereof can be suitably used. The mass ratio of the polycarbonate resin to the polyester resin in the polymer alloy resin is preferably 50:50 to 90:10, more preferably 60:40 to 80:20, and even more preferably 65:35 to 75:25. Here, the polymer alloy resin refers to a polymer multi-component system, and may be a polymer blend having a certain degree of compatibility due to mixing, a block copolymer or graft copolymer obtained by copolymerization, or a mixture of resins that are not compatible with each other. Examples of polycarbonate resins include those derived from aliphatic dihydroxy compounds and those derived from aromatic dihydroxy compounds. For example, those derived from aromatic dihydroxy compounds can be suitably used, and particularly those derived from aromatic dihydroxy compounds (bisphenols) in which two aromatic dihydroxy compounds are bonded via a certain type of bonding group are preferred. These can be produced by a known method of polycondensation of a dihydroxy compound with phosgene or a carbonate ester, but are not limited to this production method, and commercially available resins can also be used. Examples of polyester-based resins that can be used include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polymethylene terephthalate, and polyester resins copolymerized with copolymer components such as diol components, such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, and dicarboxylic acid components, such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid. The substrate layer may contain other additives as needed. These additives include water repellents, oil repellents, colorants such as pigments and dyes, lubricants and release agents such as silicone oils and alkyl esters, fibrous reinforcing agents such as glass fiber, fillers such as granular particles such as talc, clay, and silica, and scaly particles such as mica, low-molecular-weight antistatic agents such as salt compounds of sulfonic acid and alkali metals, high-molecular-weight antistatic agents such as polyether ester amides, and additives such as flame retardants, antibacterial agents, antiviral agents, and heat stabilizers, provided that the additives do not impair the effects of the present invention. Furthermore, scrap resin generated during the resin sheet manufacturing process may also be mixed and used. Furthermore, the substrate layer may have a partially crosslinked structure, provided that the additives do not impair the effects of the present invention.

[0054] [Manufacturing of resin sheet body] The method for producing the resin sheet body according to the present invention is not limited and may be any method, but typically includes the steps of melt-extruding a raw resin and providing regularly arranged hair-like bodies on at least one surface of the resulting sheet. For example, a feed block or a multi-manifold die can be used for production. The layer structure of each embodiment of the resin sheet body is basically as described above, but other layers, such as scrap raw materials generated during the production process, may also be laminated as an additional layer as long as the physical properties are not deteriorated.

[0055] The method for providing the hairy bodies is not particularly limited, and any method known to those skilled in the art can be used, such as a manufacturing method using an extrusion molding method, a manufacturing method using a roll-to-roll method, a manufacturing method using a photolithography method, a manufacturing method using a heat press method, a manufacturing method using a pattern roll and a UV-curable resin, a manufacturing method using a 3D printer, or a method in which the hairy bodies are embedded in a resin layer and then covalently bonded by a polymerization reaction.

[0056] For example, when using an extrusion molding method, a sheet is extruded by a T-die method, and this sheet is cast between a transfer roll and a touch roll that have been textured, thereby imparting a capillary shape. As the transfer roll having the textured surface, a roll having fine textures of several μm to several hundred μm in size regularly formed on its surface by laser engraving, electroforming, etching, mill engraving, or the like can be used. Here, "regular" means that the textures are not randomly arranged, i.e., arranged in an orderly manner in one or two directions. In some embodiments, the textures can be arranged in a grid pattern or a staggered pattern, with the textures arranged lengthwise and widthwise. Examples of the shape of the textured portion include, for example, a cone (e.g., a cone, a square pyramid, a triangular pyramid, a hexagonal pyramid), a semicircle, or a rectangle (a square prism). The size of the recesses ranges from several μm to several hundred μm, with the opening diameter, depth, and spacing of the recesses. Examples of materials that can be used for the transfer roll include metals and ceramics. The spacing of the hairs can be adjusted by adjusting the spacing of the recesses on the transfer roll, and the height of the hairs can be adjusted by adjusting the depth of the recesses on the transfer roll, thereby adjusting the tactile feel. It is also preferable to process the transfer roll surface into unevenness with a high aspect ratio. For example, when processing recessed shapes on the transfer roll surface, the aspect ratio (recess depth / recess opening diameter) is preferably 1.0 to 9.0 or 1.0 to 2.0. To process the transfer roll surface into unevenness with a high aspect ratio, laser engraving or electroforming is particularly preferred because it is more suitable for precise processing in the depth direction than etching, blasting, mill engraving, etc. The transfer roll may be made of a material such as metal or ceramic. The touch roll may be made of a variety of materials, including silicone rubber, NBR rubber, EPT rubber, butyl rubber, chloroprene rubber, and fluororubber. In one embodiment, a touch roll having a rubber hardness (JIS K 6253) of 40 to 100 may be used. A Teflon (registered trademark) layer may be formed on the surface of the touch roll. The touch roll can be made of various materials, including, for example, silicone rubber, NBR rubber, EPT rubber, butyl rubber, chloroprene rubber, and fluororubber. In one embodiment, a touch roll having a rubber hardness (JIS K 6253) of 40 to 100 can be used. A Teflon (registered trademark) layer may be formed on the surface of the touch roll. By using the roll set of the transfer roll and the touch roll, the resin sheet body of the present embodiment can be manufactured. In one embodiment, the temperature of the transfer roll is adjusted to a temperature near the crystalline melting temperature, glass transition point, or melting point of the thermoplastic resin (for example, 100 to 150°C when random polypropylene is used), and the pinch pressure between the transfer roll and the touch roll is adjusted to 30 to 120 kg / cm. 2 The resin sheet main body of this embodiment can be manufactured by casting the resin sheet as follows: The cast resin sheet is taken up at a line speed of 0.5 to 30 m / min using a pinch roll or the like.

[0057] [Protective sheet formation] The method for forming the protective sheet according to this embodiment is not particularly limited, and any method known to those skilled in the art can be used. For example, the method for forming the protective layer includes a method including a step of applying a raw resin for the protective layer to the surface of the manufactured resin sheet body having hair-like bodies, and a method including a step of melting and laminating a raw resin preformed in a sheet form. The method for forming the surface layer and the intermediate layer includes a method in which a composition for the raw material for the intermediate layer is applied to the surface layer formed in a sheet form, and then a composition for the raw material for the protective layer is applied and then laminated to the resin sheet body. Other examples include a method in which a composition for the raw material for the intermediate layer is applied to a surface layer formed in a sheet form and then laminated to the surface of the protective layer applied to the resin sheet body, and a method in which a composition for the raw material for the intermediate layer is applied to the surface of the formed protective layer and then laminated to the surface layer formed in a sheet form.

[0058] [Manufacturing laminated resin sheets] The method for producing the laminated resin sheet according to the present embodiment is not limited and may be any method, but may include, for example, a method including laminating a protective sheet on the surface of the resin sheet main body on the side having the hair-like bodies. The method for laminating the protective sheet can be performed by the method for forming the protective sheet described above.

[0059] [Molded products] The molded article of this embodiment is a molded article using the laminated resin sheet of this embodiment. The laminated resin sheet of this embodiment can be used in general molding processes. Examples of molding methods include insert molding, in-mold molding, general vacuum molding, pressure molding, and applications of these methods, such as heating and softening a resin sheet under vacuum and releasing it under atmospheric pressure to overlay (molde) it onto the surface of an existing molded article. Known sheet heating methods, such as non-contact radiant heating using an infrared heater, can also be used to heat and soften the sheet before molding. In vacuum pressure molding of one embodiment, for example, a resin sheet is heated to a surface temperature of 60°C to 220°C for 20 to 480 seconds, and then molded onto the surface of an existing molded article. The resin sheet can be stretched 1.05 to 2.50 times depending on the surface shape.

[0060] The laminated resin sheet of this embodiment can be used in applications requiring the above-described good tactile feel. For example, the laminated resin sheet can be used as an automobile interior material, an electronic device exterior material, or a surface material for cosmetic containers.

[0061] Examples of automobile interior materials include steering wheels, dashboards, levers, switches, and other parts that are touched by the hands inside the automobile. For example, an interior material in which the above-mentioned resin sheet is molded and attached to the surface of a known instrument panel or pillar (for example, JP 2009-184421 A) can be mentioned. Attaching a resin sheet can provide an interior material with a good tactile feel. Considering light resistance and chemical resistance, olefin-based resins, vinyl chloride-based resins, and urethane-based elastomers are preferred as the material for the resin sheet to be attached. The method for attaching the resin sheet to the interior material is not particularly limited.

[0062] Examples of exterior materials for electronic devices include transmitter housings for keyless entry systems, smartphone housings, smartphone cases, music player cases, game console housings, digital camera housings, electronic organizer housings, calculator housings, tablet housings, mobile personal computer housings, keyboards, mice, etc. For example, a portable transmitter can be exemplified in which the resin sheet of the present invention is molded and bonded to the surface of a portable transmitter housing for a known keyless entry system (for example, JP 2005-228911 A). Bonding the resin sheet can provide a portable transmitter with a good tactile feel. The resin sheet to be bonded is preferably an olefin-based resin or a urethane-based elastomer. The method for bonding the resin sheet to the housing is not particularly limited.

[0063] Examples of cosmetic containers include containers for face cream, pack cream, foundation, and eye shadow, such as a cosmetic container in which the resin sheet of the present invention is molded and attached to the surface of the lid of a known foundation container (JP 2017-29608 A). By attaching the resin sheet, a cosmetic container with a good tactile feel can be obtained. The resin sheet to be attached is preferably made of an olefin-based resin or a urethane-based elastomer. The method for attaching the resin sheet is not particularly limited.

[0064] Furthermore, a hairy sheet can be produced by printing letters or patterns on the surface of the hairy material using a common printing method (offset printing, gravure printing, flexographic printing, screen printing, foil stamping, etc.) and used for the above-mentioned purposes. The material of the resin sheet to be printed is not particularly limited, but it is preferable to consider the printability with the ink used for printing.

[0065] Furthermore, a laminate can be produced by laminating (dry laminating, extrusion laminating) a printed material (paper, metal thin film, etc.) with characters, pictures, etc., or a nonwoven fabric, and then laminating the laminate onto the printed surface of a business card, for example, to produce a business card with a tactile feel. There are no particular limitations on the material of the resin sheet to be laminated.

[0066] A non-limiting list of exemplary embodiments and combinations of exemplary embodiments of the present disclosure are disclosed below. [1] A resin sheet body having regularly arranged hair-like bodies on one side of a base layer, with no structural boundary between the base layer and the hair-like bodies forming a continuous phase; a protective sheet including a protective layer that fills the gaps between the hairs and covers the surface of the resin sheet body that has the hairs; a surface layer that forms the surface opposite to the surface of the base layer that does not have the hairs; and an intermediate layer located between the protective layer and the surface layer; A laminated resin sheet comprising: [2] The laminated resin sheet according to [1], wherein the resin sheet body has an average thickness of 80 μm or more and less than 350 μm. [3] The laminated resin sheet according to [1] or [2], wherein the protective layer contains a silicone-based resin. [4] The laminated resin sheet according to any one of [1] to [3], wherein the surface layer contains a resin selected from the group consisting of polypropylene-based resins, polyethylene-based resins, and polyester-based resins. [5] The laminated resin sheet according to any one of [1] to [4], wherein the intermediate layer contains a silicone-based adhesive. [6] A laminated resin sheet according to any one of [1] to [5], wherein the average angle of the hairs that increases by heat molding is 0 to 10° when the angle of the hairs is 0° when the hairs extend perpendicularly to the surface of the base layer. [7] A laminated resin sheet according to any one of [1] to [6], wherein the average height of the hairs is 60 μm or more and 330 μm or less, the average diameter of the hairs is 1 μm or more and 50 μm or less, and the average spacing of the hairs is 20 μm or more and 200 μm or less. [8] A method for producing a laminated resin sheet according to any one of [1] to [7], comprising laminating a protective sheet on the surface of the resin sheet body on the side having the hair-like bodies. [9] A molded product of the laminated resin sheet according to any one of [1] to [7].

[10] The molded product according to [9], which is an insert molded product or a vacuum molded product.

[11] The molded article according to [9] or

[10] , which is an automobile interior material, an electronic device exterior material, or a cosmetic container exterior material. The configurations and combinations thereof in each embodiment are merely examples, and additions, omissions, substitutions, and other modifications of the configurations are possible as appropriate within the scope that does not deviate from the gist of this disclosure. [Example]

[0067] EXAMPLES The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the contents of the examples.

[0068] The various raw materials used in the examples and the methods for producing them are as follows. (1) Hairy body and underlayer (A-1) TPU (urethane elastomer) "A3086A17J" (manufactured by BASF Japan Ltd.) (2) Base material layer (B-1) PC / Polyester "PCX-6694" (manufactured by Sumika Polycarbonate Co., Ltd.) (3) Protective layer (C-1) Silicone resin "KE-1316" (Shin-Etsu Chemical Co., Ltd.) + Hardener "CAT-1316" (Shin-Etsu Chemical Co., Ltd.) + Curing retarder "Seigyozai No. 6 10" (Shin-Etsu Chemical Co., Ltd.) (C-2) Silicone resin "KE-1300T" (Shin-Etsu Chemical Co., Ltd.) + Hardener "CAT-1300" (Shin-Etsu Chemical Co., Ltd.) (C-3) Silicone resin "KE-1314-2" (Shin-Etsu Chemical Co., Ltd.) + Hardener "CAT-1314S" (Shin-Etsu Chemical Co., Ltd.) (4) Intermediate layer + surface layer (D-1) "NS-40+A-1180(P)" (manufactured by Nakamoto Pax Co., Ltd. (intermediate layer: silicone adhesive, surface layer: polypropylene resin film (average thickness 40 μm, tensile strength: MD 158 MPa, TD 360 MPa))

[0069] The methods for evaluating various properties of the resin sheet bodies, laminated resin sheets, and molded articles of the laminated resin sheets produced in the examples and comparative examples are as follows.

[0070] (1) Average height of hairs, average diameter of hairs, average spacing between hairs, average thickness of base layer The height (h), diameter (d), spacing (t), and thickness of the base layer of the resin sheet were measured using a laser microscope (VK-X100, Keyence Corporation). The samples were cross-sectional slices cut from three random locations on the resin sheet using a microtome. The average height of the hairs was determined by measuring the height of 10 hairs for each sample, and the arithmetic mean of 30 measurements was used. The average diameter of the hairs was determined by measuring the diameter of 10 hairs at the mid-height (h / 2) of each sample, and the arithmetic mean of 30 measurements was used. The average spacing of the hairs was determined by measuring the distance between the center of the base of a hair and the center of the base of an adjacent hair at 10 locations for each sample, and the arithmetic mean of 30 measurements was used. The average thickness of the base layer was determined by measuring the thickness of each layer at 10 locations for each sample, and the arithmetic mean of 30 measurements was used. The thickness of the base layer was determined by measuring the distance from the base of a hair to the interface with the other layer.

[0071] (2) Evaluation of the physical properties of the protective layer The tensile modulus and tensile strength of the protective layer were determined as follows: 115 mm x 6 mm, dumbbell-shaped No. 5 test pieces (longer side in the CMD direction) were cut out from the protective layer. The test pieces were then placed in a small benchtop testing machine ("EZTest / CE" manufactured by Shimadzu Corporation) and subjected to tensile testing at room temperature (20°C) (chuck distance 25 mm, tensile speed 500 mm / min). The tensile modulus in the elastic region (slope at strains of 0-4%) was determined from the obtained stress-strain (SS) curve. The point at which the maximum stress occurred was recorded as the tensile strength.

[0072] (3) Evaluation of the physical properties of protective sheets The tensile modulus and tensile strength of the protective sheet were determined as follows: A 115 mm x 6 mm, dumbbell-shaped No. 5 test piece (longer side in the CMD direction) was cut out of the protective sheet. The test piece was then placed in a small tabletop testing machine ("EZTest / CE," manufactured by Shimadzu Corporation) and a tensile test was performed at room temperature (20°C) (chuck distance 25 mm, tensile speed 500 mm / min). The tensile modulus in the elastic region (slope at strains of 0-4%) was then determined from the obtained stress-strain (SS) curve. The point at which the maximum stress was reached was recorded as the tensile strength.

[0073] (4) Measurement of the peel strength between the resin sheet body and the protective sheet The peel strength between the resin sheet body and the protective sheet in a laminated resin sheet was determined as follows: a laminated resin sheet consisting of a resin sheet body and a protective sheet was cut to a width of 25 mm, and a 90-degree peeling jig (manufactured by Toyo Seiki Co., Ltd.) was attached to the bottom of a universal material testing machine (manufactured by Toyo Seiki Co., Ltd., "Strograph VE1D"), and the resin sheet body was placed horizontally with the protective sheet facing upward. The protective sheet peeled from the resin sheet below was clamped between the upper gripping jig, and the gripping jig with the protective layer clamped above was pulled in the normal direction to the sheet surface at a tensile speed of 100 mm / min to measure.

[0074] (5) Handling of protective sheets When the protective sheet was removed from the laminated resin sheet, a mark "O" was given if it could be peeled off without any problems, and a mark "X" was given if it could not be peeled off cleanly due to tearing or the like.

[0075] (6) Measurement of the angle of the capillary The angle of the hairs was measured using a laser microscope (VK-X100, manufactured by Keyence Corporation) for the resin sheet body before secondary molding and for the resin sheet body from which the protective sheet was peeled off after secondary molding of the laminated resin sheet. The measured samples were cross-sectional slices cut from three arbitrary locations on the resin sheet body using a microtome. The hair tilt angle was determined by measuring the angles of 10 hairs for each sample and using the arithmetic average of 30 measured values. The hair tilt angle was defined as 0° when the hairs extended perpendicular to the surface of the base layer.

[0076] (7) Confirmation of bleaching The appearance of the resin sheet itself before secondary molding and the secondary molded product of the laminated resin sheet was judged by a total of 10 external panelists, 5 men and 5 women. Regarding the difference in color when comparing the two and the difference in color within the secondary molded product, if no difference was found in either, it was judged as "no whitening," and if a difference was found in at least one of them, it was judged as "whitening present." If 8 or more panelists judged it as "no whitening," the overall rating was "○," if 4 to 7 out of 10 panelists judged it as "no whitening," the overall rating was "△," and if 3 or less out of 10 panelists judged it as "no whitening," the overall rating was "×."

[0077] (8) Sensory evaluation of good tactile sensation For the good tactile feel, a sensory evaluation was conducted in which 10 external panelists (5 men and 5 women) touched the resin sheet body after the protective sheet was peeled off after the laminated resin sheet was post-molded. The specific tactile feel (smooth, moist, dry, rough, etc.) when touching the surface of the resin sheet body was evaluated on a scale of 1 to 10, and the feel with the highest score was designated as the feel of the resin sheet surface. In Table 2, "◯" indicates that the score for smoothness or moistness was high, and a good tactile feel like a suede-like brushed sheet was obtained even after post-molding. "△" indicates that the score for smoothness or moistness was high, but the highest score for the feel was reduced by 3 points or more after post-molding. "X" indicates that the score for dryness or roughness was high, and a good tactile feel was not obtained after post-molding.

[0078] (9) Check for mold contamination When the laminated resin sheet was subjected to secondary molding, the staining of the mold on the side that came into contact with the protective sheet was evaluated according to the following criteria. ○: No resin adhesion △: Resin adhered to some areas ×: Resin adhered to the entire surface

[0079] (Manufacturing of laminated resin sheets) [Example 1] A 40mm single-screw extruder was used to extrude (A-1) a urethane elastomer for the capillaries and underlayer, and a 65mm single-screw extruder was used to extrude (B-1) a PC / polyester resin for the base layer. The resin sheet extruded by the coextrusion multilayer T-die method was then subjected to chromium oxide spraying and laser engraving to create a textured transfer roll adjusted to 60°C to 150°C, and a silicone rubber touch roll adjusted to 10°C to 90°C with a rubber hardness of 70. The resin sheet was then taken up at a line speed of 1m / min to 15m / min using a pinch roll. This resulted in a resin sheet having the composition, thickness, and surface shape shown in Table 1. Next, the silicone resin (C-1) that will become the protective layer was mixed with the curing agent and curing retarder in a ratio of 100:10:1 on the surface of the intermediate layer + surface layer (D-1) on the intermediate layer side, and then applied using a comma coater and semi-cured by the heat of a drying oven. In the semi-cured state, the resin sheet was laminated with a pre-prepared resin sheet body so that the gaps between the hairs were filled.

[0080] [Comparative Examples 1 to 2] A 40mm single-screw extruder was used to extrude (A-1) thermoplastic resin, which would form the capillary body and underlayer, and a 65mm single-screw extruder was used to extrude (B-1) PC / polyester resin, which would form the base layer. The resin sheet extruded by the coextrusion multilayer T-die method was then subjected to chromium oxide spraying and laser engraving to create a textured transfer roll adjusted to 60°C to 150°C, and a silicone rubber touch roll adjusted to 10°C to 90°C with a rubber hardness of 70. The resin sheet was then drawn off at a line speed of 1m / min to 15m / min using a pinch roll. This resulted in a resin sheet body with the composition, thickness, and surface shape shown in Table 1. No protective layer was formed.

[0081] [Comparative Examples 3 to 9] A 40mm single-screw extruder was used to extrude (A-1) a urethane-based elastomer for the capillaries and base layer, and a 65mm single-screw extruder was used to extrude (B-1) a PC / polyester resin for the base layer. The resin sheet extruded using a coextrusion multilayer T-die method was then applied to a transfer roll with a textured surface, which had been textured using chromium oxide thermal spraying and laser engraving and adjusted to 60-150°C, and a silicone-based rubber touch roll with a rubber hardness of 70 adjusted to 10-90°C. The resulting sheet was then drawn up at a line speed of 1-15 m / min using a pinch roll. This yielded a resin sheet body with the composition, thickness, and surface shape shown in Table 1. Next, the silicone-based resin (C-1) for the protective layer was mixed with a curing agent and a cure retarder in a ratio of 100:10:1. The mixture was then spread over the surface of the resin sheet body with a brass rod to form a protective layer with the thickness shown in Table 1, resulting in a laminated resin sheet. The intermediate layer and the surface layer were not formed.

[0082] [Comparative Examples 8 and 9] Laminated resin sheets were obtained in the same manner as in Comparative Examples 3 to 7, except that no curing retarder was used and the silicone resin (C-2) or (C-3) to form the protective layer was mixed with the curing agent in a ratio of 9:1.

[0083] (Secondary molding production) Using a vacuum pressure forming machine (NGF-0406s manufactured by Fuse Vacuum Co., Ltd.), the laminated resin sheet was preformed under the following conditions to give it a three-dimensional shape. The three-dimensional shape was given using a convex cover panel mold that was 200 mm long and 100 mm short and gently curved 10 mm from the edge to the center, and the surface of the laminated resin sheet facing the base layer, i.e., the surface opposite the protective layer, was brought into contact with the convex surface of the mold. Sheet surface temperature: 100~150℃ Heating time: 40 to 300 seconds Mold shape: length 200mm, width 100mm The laminated resin sheet with the three-dimensional shape was then removed from the mold, the excess was trimmed, and a polycarbonate resin (Mitsubishi Engineering Plastics H3700UR) was injected into it using an insert molding machine (Sumitomo Heavy Industries SE315EV-A-HD) under the following conditions to obtain a secondary molded product (insert molded product).The insert molding was performed by placing the laminated resin sheet with the three-dimensional shape so that the protective layer side was in contact with the injection mold, and injecting the resin into the base layer side using the side gate method. Mold temperature: 40℃ ·Injection resin temperature: 260-310℃ ·Holding pressure: 30MPa After cooling, the molded product was removed from the mold and the protective layer was peeled off to obtain the final secondary molded product.

[0084] Using the resin sheets and the like obtained in each of the Examples and Comparative Examples, evaluation tests were carried out on various properties, and the results are shown in Table 2.

[0085] [Table 1]

[0086] [Table 2]

[0087] The results shown in Tables 1 and 2 reveal the following: The laminate resin sheet of Example 1 was shown to be suppressed from whitening and loss of tactile feel even when subjected to secondary molding. Furthermore, there were no problems with handling of the laminate resin sheet during secondary molding, handling of the protective sheet when peeling it from the resin sheet body, or mold contamination. On the other hand, the laminated resin sheets of Comparative Examples 1 and 2 suffered from whitening and loss of tactile sensation when subjected to secondary molding. In the laminated resin sheet of Comparative Example 3-9, when secondary molding was carried out, the resin constituting the protective layer adhered to the entire mold, and mold contamination was observed.

[0088] Although the present invention has been described above using various embodiments, it goes without saying that the technical scope of the present invention is not limited to the scope described in the above embodiments. It will be apparent to those skilled in the art that various modifications and improvements can be made to the above embodiments. Furthermore, it is clear from the claims that such modifications and improvements can also be included within the technical scope of the present invention. [Explanation of symbols]

[0089] 1. Trichome and substratum 1a Base layer 1b Ciliary body d Ciliary body diameter h height of the hair t Trichome Spacing 2 protective layer 3. Middle class 4 Surface layer 5 Base material layer

Claims

1. a resin sheet body having regularly arranged hair-like bodies on one surface of a base layer, with no structural boundary between the base layer and the hair-like bodies forming a continuous phase; a protective sheet including a protective layer that fills the gaps between the hairs and covers the surface of the resin sheet body that has the hairs; a surface layer that forms the surface opposite to the surface of the base layer that does not have the hairs; and an intermediate layer located between the protective layer and the surface layer; A laminated resin sheet comprising:

2. 2. The laminated resin sheet according to claim 1, wherein the resin sheet body has an average thickness of 80 μm or more and less than 350 μm.

3. The laminated resin sheet according to claim 1 or 2, wherein the protective layer comprises a silicone-based resin.

4. 3. The laminated resin sheet according to claim 1, wherein the surface layer comprises a resin selected from the group consisting of polypropylene-based resins, polyethylene-based resins, and polyester-based resins.

5. The laminated resin sheet according to claim 1 or 2, wherein the intermediate layer comprises a silicone-based adhesive.

6. 3. The laminated resin sheet according to claim 1, wherein the average value of the angle increased by heat molding is 0 to 10 degrees when the angle of the hairs when they extend perpendicular to the surface of the base layer is 0 degrees.

7. 3. The laminated resin sheet according to claim 1, wherein the average height of the hairs is 60 μm or more and 330 μm or less, the average diameter of the hairs is 1 μm or more and 50 μm or less, and the average spacing of the hairs is 20 μm or more and 200 μm or less.

8. 3. A method for producing a laminated resin sheet according to claim 1, comprising laminating a protective sheet on the surface of the resin sheet body on the side having the hair-like bodies.

9. A molded article made from the laminated resin sheet according to claim 1 or 2.

10. The molded article according to claim 9, which is an insert molded article or a vacuum molded article.

11. The molded article according to claim 9, which is an automobile interior material, an electronic device exterior material, or a cosmetic container exterior material.

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