Laminated resin sheet comprising a resin sheet body having fibrous material and a protective layer, method for manufacturing the same, and molded article thereof

Abstract

The purpose of the present invention is to provide: a laminated resin sheet in which whitening and loss of tactile properties are inhibited even when secondary molding is performed thereon; a method for producing the laminated resin sheet; and a molded product of the laminated resin sheet.　This laminated resin sheet comprises: a resin sheet body having hair-like bodies regularly arranged on at least one surface of an underlying layer, and forming a continuous phase in which there are no structural boundaries between the underlying layer and the hair-like bodies; and a protective layer that fills gaps between the hair-like bodies and covers the surface of the resin sheet body on which the hair-like bodies are provided. The tensile elastic modulus of the protective layer at 20°C is not less than 0.2 MPa but less than 2 MPa, and the average thickness of the protective layer is greater than the average height of the hair-like bodies.

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 layer, a method for manufacturing the same, and a molded product thereof.

Background Art

[0002] Conventionally, sheets of paper materials and polymer materials have been used as interior materials for automobiles, housings for accessory parts, housings for electronic devices and home appliances, building materials such as wallpapers, housings for toys and game machines, and members for daily necessities. Further, as a method for imparting good touch sensitivity to the sheet surface, for example, Patent Document 1 proposes a resin sheet having hair-like bodies regularly arranged on the surface. On the other hand, when using such a resin sheet as an interior product such as an automobile dashboard or seat, etc., it is necessary to perform secondary molding and attach it to the surface of the object.

[0003]

Patent Document 1

Summary of the Invention

[0004] However, it has been found that such a resin sheet may cause the appearance of the sheet to turn white or the good touch sensitivity to be lost due to the deformation of the hair-like bodies or the inclination of the hair-like bodies causing hair collapse during the process of secondary molding and attaching to the surface of the object. The problem to be solved by the present invention is to provide a laminated resin sheet in which whitening and loss of touch sensitivity are suppressed even when secondary molding is performed, a method for manufacturing the same, and a molded product thereof.

[0005] In other words, the inventors, after considering various means, have found that by providing a laminated resin sheet comprising a resin sheet body having regularly arranged fibrous bodies on at least one surface of the base layer, with no structural boundary between the base layer and the fibrous bodies forming a continuous phase, and a protective layer filling the gaps between the fibrous bodies and covering the surface of the resin sheet body on the side having the fibrous bodies, and wherein the tensile modulus of elasticity of the protective layer at 20°C is 0.2 MPa or more and less than 2 MPa, a laminated resin sheet can be obtained in which whitening and loss of tactile properties are suppressed even after secondary molding, thus completing the present invention.

[0006] The present invention, which solves the above problems, consists of the following: [1] A laminated resin sheet comprising a resin sheet body having regularly arranged fibrous bodies on at least one surface of a substrate, with no structural boundary between the substrate and the fibrous bodies forming a continuous phase, and a protective layer filling the gaps between the fibrous bodies and covering the surface of the resin sheet body on the side having the fibrous bodies, wherein the tensile modulus of the protective layer at 20°C is 0.2 MPa or more and less than 2 MPa, and the average thickness of the protective layer is greater than the average height of the fibrous bodies. [2] The laminated resin sheet according to [1], wherein the peel strength between the resin sheet body and the protective layer is 0.01 to 0.10 N / mm. [3] A laminated resin sheet according to [1] or [2], wherein the tensile strength of the protective layer is 1.0 to 10.0 MPa. [4] A laminated resin sheet according to any one of [1] to [3], wherein the average thickness of the protective layer is 50 to 600 μm. [5] A laminated resin sheet according to any one of [1] to [4], wherein the angle of the fibrous material when it extends perpendicularly to the surface of the underlying layer is taken as 0°, and the average value of the angle that increases due to heat molding is 0 to 10°. [6] A laminated resin sheet according to any one of [1] to [5], wherein the average height of the pilosa is 30 μm or more and 500 μm or less, the average diameter of the pilosa is 1 μm or more and 50 μm or less, and the average spacing between the pilosa is 20 μm or more and 200 μm or less. [7] A laminated resin sheet according to any one of [1] to [6], wherein the average thickness of the resin sheet body is 80 μm or more and less than 350 μm. A method for manufacturing a laminated resin sheet according to any one of [8], [1] to [6], comprising forming a protective layer on the surface of the side of the resin sheet body that has fibrous material. A molded product of a laminated resin sheet as described in any of [9], [1], or [6].

[10] The molded article described in [9], which is an insert molded article or a vacuum molded article.

[11] A molded article according to [9], provided on the surface of an automotive interior material, an electronic equipment exterior material, or a cosmetic container.

[0007] According to the present invention, it is possible to provide a laminated resin sheet in which whitening and loss of tactile properties are suppressed even after secondary molding, a method for producing the same, and a molded product thereof. [Brief explanation of the drawing]

[0008] [Figure 1] This is a schematic longitudinal cross-sectional view showing a laminated resin sheet according to the first embodiment of the present invention. [Figure 2] This is a schematic plan view of the resin sheet body. [Figure 3] This is a schematic longitudinal cross-sectional view showing a laminated resin sheet according to a second embodiment of the present invention. [Modes for carrying out the invention]

[0009] The following describes various embodiments of the resin sheet, followed by a description of the method for manufacturing the resin sheet. However, if a specific description given for one embodiment also applies to other embodiments, that description is omitted in the other embodiments.

[0010] [First Embodiment] The resin sheet according to the first embodiment of the present invention is a laminated resin sheet comprising a resin sheet body having regularly arranged fibrous bodies on at least one surface of a base layer, with no structural boundary between the base layer and the fibrous bodies forming a continuous phase, and a protective layer that fills the gaps between the fibrous bodies and covers the surface of the resin sheet body on the side having the fibrous bodies, wherein the tensile modulus of the protective layer at 20°C is 0.2 MPa or more and less than 2 MPa, and the average thickness of the protective layer is greater than the average height of the fibrous bodies. That is, the layer configuration of the laminated resin sheet according to this embodiment is, from top to bottom, a protective layer (2), fibrous bodies, and a base layer (1).

[0011] <Underlayer> The underlayer (1a) is the layer that forms the base of the pilosa, and refers to the portion of the surface 1 in Figure 1 other than the pilosa (1b). The thickness of the underlayer refers to the thickness from the base of the pilosa to the surface opposite the underlayer. The average thickness of the underlayer is preferably 15 μm to 300 μm, more preferably 30 μm to 280 μm, and even more preferably 50 μm to 250 μm. A thickness of 15 μm or more allows for sufficient expression of the pilosa height. A thickness of 300 μm or less allows for efficient formation of the pilosa. The average thickness of the underlayer can be determined by measuring the thickness from the base of the pilosa to the interface of the other layer at 10 points on a sample obtained by cutting cross-sections from any three locations using a microtome, and using the arithmetic mean of these 30 measurements. There may be no structural boundary between the underlayer and the pilosa, and a continuous phase may be formed. The absence of a structural boundary means that the base layer and the pilosa are formed as a single unit, with no clear structural boundary between them. Furthermore, the formation of a continuous phase means that there are no seams or discontinuities between the base layer and the pilosa (it is a continuous phase). In this respect, it differs from a structure in which the pilosa are implanted into the base layer. The base layer and the pilosa may have the same composition, and the bond between the base layer and the pilosa may include covalent bonds. A covalent bond is a chemical bond formed when an electron pair is shared between two atoms. In thermoplastic resins, which are chain-like molecules made up of linked monomers, the individual polymers are bonded together by covalent bonds, which are stronger than the van der Waals bonds and hydrogen bonds that act between polymer molecules. Furthermore, the base layer and the fibrous material may be derived from the same solid thermoplastic resin sheet, not separate components. Derived from the same solid thermoplastic resin sheet means, for example, that the fibrous material and the base layer are obtained directly or indirectly based on the same resin sheet. Furthermore, the base layer and the fibrous material may be formed from the same solid thermoplastic resin sheet. Formed from the same solid thermoplastic resin sheet means that the fibrous material and the base layer are directly formed by processing a single resin sheet. Because there is no structural boundary between the base layer and the pilosa, forming a continuous phase, the separation of the pilosa from the base layer due to external stimuli is suppressed, resulting in a sheet with good tactile properties. Furthermore, it can be manufactured with fewer steps than when the pilosa are implanted.

[0012] The base layer and the fibrous material consist of the same thermoplastic resin composition, with a thermoplastic resin as the main component. Here, "main component" means containing 50% by mass or more. Preferably, it contains 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 the following can be used: urethane elastomer (TPU), styrene resin, polyolefin resin, polyvinyl chloride resin, thermoplastic elastomer, and fluororesin.

[0013] Urethane elastomers are resins that use diisocyanate and polyol as reaction raw materials, and in combination, the diisocyanate is diphenylmethane diisocyanate (MDI), H 12 Any combination of MDI-based, hexamethylene diisocyanate (HDI)-based, and polyols (polyether-based, polyester-based, or polycarbonate-based) may be selected, and multiple combinations may also be used. In one embodiment of the present invention, a combination of an MDI-based or HDI-based diisocyanate and a carbonate-based polyol can be suitably used.

[0014] As styrene-based resins, styrene monomers such as styrene, α-methylstyrene, p-methylstyrene, dimethylstyrene, pt-butylstyrene, and chlorostyrene, either alone or in copolymers thereof; copolymers of these styrene monomers with other monomers, such as styrene-acrylonitrile copolymer (AS resin); or graft polymers obtained by graft polymerization of the styrene monomers in the presence of other polymers, such as polybutadiene, styrene-butadiene copolymer, polyisoprene, and polychloroprene diene-based rubber polymers, such as high-impact polystyrene (HIPS resin) and styrene-acrylonitrile graft polymer (ABS resin). 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. Polyethylene resins can include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear medium-density polyethylene, etc. Furthermore, not only individual materials but also copolymers, grafts, 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] In addition, as the polypropylene resin, homopolypropylene, random polypropylene, block polypropylene, etc. can be used. When using homopolypropylene, the structure of the homopolypropylene may be any of isotactic, atactic, and syndiotactic. When using random polypropylene, as the α-olefin copolymerized with propylene, those having preferably 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, 1-decene can be used. When using block polypropylene, block copolymers (block polypropylene), block copolymers containing a rubber component, graft copolymers, etc. can be used. In addition to using these olefin resins alone, other olefin-based resins can also be used in combination.

[0017] As the polyvinyl chloride resin, a vinyl chloride homopolymer or a copolymer of vinyl chloride and other comonomers can be used. When polyvinyl chloride is a copolymer, it may be a random copolymer or a graft copolymer. As an example of the graft copolymer, for example, those obtained by graft-polymerizing vinyl chloride onto a trunk polymer such as an ethylene-vinyl acetate copolymer or a thermoplastic urethane polymer can be mentioned. The polyvinyl chloride of the present embodiment represents a soft polyvinyl chloride capable of extrusion molding and is a composition containing additives such as a high molecular plasticizer. As the high molecular plasticizer, known high molecular plasticizers can be used, and preferably examples include ethylene copolymer high molecular plasticizers such as ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-(meth)acrylate-carbon monoxide copolymer, and ethylene-vinyl acetate copolymer having a high vinyl acetate content.

[0018] Thermoplastic elastomers include those having a structure combining a soft polymer substance and a hard polymer substance. Specifically, styrene-based elastomers, olefin-based elastomers, vinyl chloride-based elastomers, polyester-based elastomers, and polyamide-based elastomers can be mentioned. These elastomers can generally be selected and used from commercially available ones.

[0019] As the fluororesin, a homopolymer of vinylidene fluoride and a vinylidene fluoride copolymer having vinylidene fluoride as the main component can be used. Polyvinylidene fluoride (PVDF) resin is a crystalline resin showing various crystal structures such as α-type, β-type, γ-type, αp-type, etc. As the vinylidene fluoride copolymer, for example, vinylidene fluoride - hexafluoropropylene copolymer, vinylidene fluoride - tetrafluoroethylene copolymer, vinylidene fluoride - chlorotrifluoroethylene copolymer, vinylidene fluoride - trifluoroethylene copolymer, vinylidene fluoride - tetrafluoroethylene - hexafluoropropylene terpolymer, vinylidene fluoride - chlorotrifluoroethylene - hexafluoropropylene terpolymer, and mixtures of two or more of these can be mentioned.

[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 setting it to 4 g / 10 min or more, the transferability of the shape of the hair-like body can be improved. The melt mass flow rate is a value measured under the conditions of a load (2.16 Kg to 10.0 Kg) in the temperature range of the test temperature from 190°C to 300°C in accordance with JIS K 7210.

[0021] The thermoplastic resin composition may be an alloy of the above thermoplastic resins in any proportion, as long as it does not impede the effects of the present invention. Furthermore, it may contain other additives. Other additives that do not impede the effects of the present invention include water and 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 fibers, fillers such as granular fine particles such as talc, clay, and silica, or flake-like 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, flame retardants, antibacterial agents, antiviral agents, and heat stabilizers. Scrap resin generated in the resin sheet manufacturing process can also be mixed and used.

[0022] Examples of water-repellent and oil-repellent agents include silicone-based water repellents, carnauba wax, and fluorine-based water-repellent and oil-repellent agents. Examples of silicones include organopolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, among which dimethylpolysiloxane is preferably used. Examples of commercially available products include "Cleanbell CB50-PP," "Cleanbell CB-30PE," "Cleanbell CB-1," and "Cleanbell CB-50AB" (manufactured by Fuji Chemical Co., Ltd.), which are silicone alloys with resin. Examples of commercially available carnauba wax include "Carnauba No. 1" (manufactured by Nikko Rica Co., Ltd.), and examples of fluorine-based water-repellent and oil-repellent agents include surfactants having perfluoroalkyl groups, with an example of a commercially available product being "Surflon KT-PA" (manufactured by AGC Seimi Chemical Co., Ltd.). The amount of water-repellent and oil-repellent agent added is preferably 0.5% to 25% by mass. If the concentration is less than 0.5% by mass, sufficient water-repellent and oil-repellent effects may not be obtained, and if it exceeds 25% by mass, moldability may deteriorate.

[0023] Examples of antistatic agents include polyether ester amide polymer antistatic agents and ionomer polymer antistatic agents. Commercially available polyether ester amide polymer antistatic agents include "Perestat 230," "Perestat 6500," "Perectron AS," and "Perectron HS" (manufactured by Sanyo Chemical Industries). Commercially available ionomer polymer antistatic agents include "Entira SD100" and "Entira MK400" (manufactured by Mitsui DuPont Polychemicals). The amount of antistatic agent added is preferably between 5% and 30% by mass. Below 5% by mass, sufficient antistatic properties may not be obtained, and above 30% by mass, production costs will increase.

[0024] Either inorganic or organic antibacterial agents may be added. Inorganic agents are preferred considering dispersibility. Specifically, examples include inorganic antibacterial agents containing metal ions (Ag, Zn, Cu) and antibacterial agents derived from calcined seashells. Commercially available inorganic antibacterial agents containing metal ions include "Bactekiller BM102VT" (manufactured by Fuji Chemical Co., Ltd.), "Novaron VZF200", "Novaron (AG300)" (manufactured by Toagosei Co., Ltd.), "KM-10D-G", and "IM-10D-L" (manufactured by Sinanen Zeomic Co., Ltd.). An example of a calcined seashell calcium antibacterial agent is "Scalo" (manufactured by FID Co., Ltd.). The amount of antibacterial agent to be added is preferably between 0.5% by mass and 5% by mass. Below 0.5% by mass, sufficient antibacterial activity may not be obtained, and above 5% by mass, production costs will increase.

[0025] Alkyl 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 lubricants and release agents and fluorine lubricants and release agents can be used as lubricants and release agents. When using a lubricant and 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 100 parts by mass of the total amount with the resin composition. Adding an amount of 0.01 parts by mass or more reduces the risk of a reduced release effect, and adding an amount of 5 parts by mass or less reduces the risk of bleed-out to the sheet surface.

[0026] Furthermore, masterbatches in which lubricants and release agents are pre-alloyed to thermoplastic resins can also be used. For example, "Wax Master V" (manufactured by BASF) is a commercially available masterbatch based on urethane-based thermoplastic elastomers, and it is preferable to use a masterbatch when considering production efficiency. 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 100 parts by mass of the total resin composition.

[0027] <hairy body> The fibrous tissue (1b) refers to the hair-like extensions from the surface of the substrate layer (1a), as shown in Figure 1. The fibrous tissue is arranged regularly on the surface of the substrate layer. Here, "arranged regularly" means that the fibrous tissue is not arranged randomly, that is, it is arranged in an orderly manner (for example, at regular intervals) in one or two directions. Whether the arrangement of the fibrous tissue is regular is determined by the arrangement of the base of the fibrous tissue. In one embodiment, the fibrous tissue is located on the substrate layer at predetermined intervals, and the position of the bottom surface of the fibrous tissue is arranged in an orderly manner in the longitudinal and transverse directions of the substrate layer. Furthermore, the arrangement of the fibrous tissue is not particularly limited, and a grid pattern or a staggered pattern can be selected. The regular arrangement of the fibrous tissue on the surface of the substrate layer makes it easier to achieve a uniform and even surface with good tactile properties. When pressure is applied to the fibrous tissue, such as by tracing with a finger, the hairs may bend, forming fingerprints that appear different in gloss and color from the surrounding areas. Furthermore, the presence of fibrous structures can create a texture similar to a suede-like, napped sheet.

[0028] The average height (h) of the hair-like structures is preferably 30 μm to 500 μm, more preferably 60 μm to 250 μm, even more preferably 80 μm to 200 μm, and even more preferably 90 μm to 180 μm. A good tactile feel can be sufficiently ensured by setting the average height to 30 μm or more, and a good tactile feel such as moistness, softness, and fluffiness can be obtained by setting the average height to 500 μm or less. If the fibrous tissue is almost upright relative to the underlying layer, the length from the base to the tip of the fibrous tissue represents its height. On the other hand, if the fibrous tissue is inclined relative to the underlying layer, or if it has a coiled portion, the height h of the fibrous tissue is defined as the distance from the surface of the underlying layer at the point where the fibrous tissue is furthest from the surface of the underlying layer. Furthermore, the length L of the fibrous tissue is defined as the sum of the intervals obtained by subdividing the distance from the tip of the fibrous tissue to the center of the base using multi-point measurement. The average height and length of the trichomes can be determined by measuring the height and length of the trichomes at any number of locations on the resin sheet using an electron microscope and image processing software, and then using the arithmetic mean of these measurements.

[0029] The average diameter (d) of the pilosa is preferably 1 μm to 50 μm, more preferably 5 μm to 50 μm, and even more preferably 5 μm to 40 μm. A good tactile feel can be ensured by setting the average diameter of the pilosa to 1 μm or more, and a good tactile feel such as moistness, softness, and fluffiness can be obtained by setting the average diameter of the pilosa to 50 μm or less. The average diameter of the pilosa is determined by measuring the diameter at the midpoint height (h / 2) of the pilosa at several points on the resin sheet using an electron microscope and image processing software, and using the arithmetic mean of the measured values. Furthermore, the aspect ratio of the trichomes can be expressed as (average height of trichomes / average diameter of trichomes). The aspect ratio of the trichomes is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 5. By setting the aspect ratio to 2 or higher, good tactile properties can be ensured, and by setting the aspect ratio to 20 or lower, not only can good tactile properties such as moistness, softness, and fluffiness be obtained, but the risk of the ratio of height to length of trichomes falling below a certain level can be reduced. On the other hand, the aspect ratio can also be determined based on the average base diameter of the bristles. The average base diameter of the bristles 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 base diameter of the bristles is determined by measuring the distance between adjacent bristles at several points on the resin sheet body and using the arithmetic mean of the measured values. When the aspect ratio is based on the base diameter of the bristles, it 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 higher, good tactile properties can be ensured, and by setting the aspect ratio to 10 or lower, not only can good tactile properties such as moistness, softness, and fluffiness be obtained, but the risk of the ratio of height to length of the bristles falling below a certain level can be reduced.

[0030] The average spacing (t) of the trichomes 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 trichomes refers to the distance between the center of the base of one trichome and the center of the base of an adjacent trichome, as shown in Figure 2, for example. By setting the average spacing to 20 μm or more, good tactile properties are ensured, and by setting it to 200 μm or less, good tactile properties such as moistness, softness, and fluffiness can be obtained. The average spacing of the trichomes is determined by measuring the spacing between adjacent trichomes at several locations on the resin sheet body and using the arithmetic mean of these measurements.

[0031] The shape of the trichomes is not particularly limited, but they may extend in a hair-like manner away from the underlying layer, gradually becoming thinner as they approach the tip, or they may have a bulge at the tip. In other words, they may have a shape in which the cross-sectional area gradually decreases as they move away from the underlying layer, then temporarily increases before terminating. The shape of the tip of the trichomes may also be bud-shaped or mushroom-shaped. Furthermore, the trichomes may have a base portion that extends away from the underlying layer, a portion that extends from this base portion and is curved with a constant curvature or with a gradually changing curvature, and even a spiral or helical portion. In this case, the tip of the trichomes may be folded inward. Such shapes result in a good tactile sensation. Furthermore, a hollow bud-shaped or mushroom-shaped portion results in an even better tactile sensation. When forming bud-like or mushroom-shaped structures at the tips of the hair-like structures, it is preferable that the ratio of the average diameter of the width of the bud-like or mushroom-shaped structure to the average diameter of the hair-like structures is 1.1 times or more. It is preferable that the height of the bud-like or mushroom-shaped structure is 7 μm or more. The average diameter of the hair-like structures, the average diameter of the width of the bud-like or mushroom-shaped structure, and the height are measured using an electronic scanning microscope image, and the arithmetic mean is used. The hair-like structures are made of a thermoplastic resin. As the thermoplastic resin, the same resin that can be used in the above-mentioned underlayer can be used.

[0032] The thermoplastic resin contained in the base layer and the bristles may form at least partially a three-dimensional crosslinked structure (e.g., a three-dimensional network structure). For example, in one embodiment, at least a part of the bristles may be a crosslinked body, in another embodiment, the entire surface of the bristles may be a crosslinked body, and in yet another embodiment, the entire bristles (from the boundary with the base layer to the tip) may be a crosslinked body. Methods for forming the crosslinked body include, for example, irradiating the surface having the bristles with an electron beam after molding the resin sheet, or adding an organic peroxide and forming it by heating and humidifying during or after molding the resin sheet. A commercially available resin to which an organic peroxide has been added is "Linkron" manufactured by Mitsubishi Chemical Corporation. In this embodiment, it is preferable to form the crosslinked body (electron beam crosslinked body) by electron beam irradiation.

[0033] In one embodiment, when the angle of the fibrous material is set to 0° when it extends perpendicular to the surface of the underlying layer, the average value of the angle increased by heat molding is preferably 0 to 10°. More preferably, it is 0 to 9°, and even more preferably 0 to 8°. The aforementioned angle can be calculated by measuring the angle of the hair-like structures on the resin sheet body before heat molding and on the resin sheet body after heat molding and the protective layer has been removed, for example, using a laser microscope, and subtracting the angle before heat molding from the angle after heat molding. Here, heat molding refers to the process of setting a laminated resin sheet in a mold, injecting polycarbonate resin into the mold to obtain an insert molded product decorated with the laminated resin sheet, and finally peeling off the protective layer. When setting the laminated resin sheet in the mold, the laminated resin sheet may be set as is, or it may be preformed to give it a three-dimensional shape before setting. Methods for preforming include vacuum forming, pressure forming, vacuum pressure forming, and TOM forming. The temperature conditions for preforming 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, and alloy resins combining these can be used as the resin to be injected. The temperature conditions for injection can be a mold temperature of 40°C, an injection resin temperature of 280°C, and a holding pressure of 30 MPa. The specific heat molding process can be carried out under the following conditions. Using a vacuum pressure forming machine, a preform is carried out on a laminated resin sheet under the following conditions to impart a three-dimensional shape. The three-dimensional shape is imparted using a mold for a convex cover panel that is 200 mm long and 100 mm short, with a gently curved shape of 10 mm from the edge to the center, and the surface of the laminated resin sheet on the base layer side, i.e., the side opposite to the protective layer, is brought into contact with the convex surface of the mold. Sheet surface temperature: 100~150℃ Heating time: 40-300 seconds Mold shape: Length 200mm, width 100mm Subsequently, the laminated resin sheet with the three-dimensional shape is 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 positioning the laminated resin sheet with the three-dimensional shape so that the protective layer side contacts the injection mold, and injecting the resin into the base material layer side using a side gate method. Mold temperature: 40℃ Injection resin temperature: 280℃ Holding pressure: 30MPa After cooling, the molded product can be removed from the mold, and the protective layer can be peeled off to obtain the final secondary molded product. The average value of the angle increase due to heat molding can be adjusted by the composition of the resin sheet body, the shape of the fibrous material, the composition and average thickness of the protective layer, etc.

[0034] <Resin sheet body> In this embodiment, "tactile sensation" refers to the texture and feel of the surface of the resin sheet itself. When touching the surface of the resin sheet, it is judged whether a pleasant feeling is perceived, and if so, a good tactile sensation is defined as one that is moist, soft, fluffy, or has a good specific feel.

[0035] In one embodiment of the present invention, the thickness of the resin sheet body refers to the combined thickness of the average height of the fibrous material and the average thickness of the underlying layer. The thickness of the resin sheet body is preferably 45 μm to 800 μm, more preferably 100 μm to 500 μm, and even more preferably 130 μm to 300 μm. The thickness of the resin sheet body may also be 80 μm or more and less than 350 μm. A thickness of 45 μm or more ensures sufficient tactile properties, while a thickness of 800 μm or less reduces manufacturing costs. 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 hair-like structures and covers the surface of the resin sheet body on the side having the hair-like structures. "Filling the gaps" means filling the space between adjacent hair-like structures, and more preferably filling the space from the root to the tip of adjacent hair-like structures. The tensile modulus of the protective layer at 20°C is 0.2 MPa or more and less than 2 MPa. Preferably, the tensile modulus of the protective layer at 20°C is 0.3 MPa or more and less than 1.9 MPa, more preferably 0.3 MPa or more and less than 1.8 MPa, and even more preferably 0.4 MPa or more and less than 1.7 MPa. Setting the tensile modulus of the protective layer at 20°C to 0.2 MPa or more can suppress the occurrence of uncut material when the protective layer is peeled off after molding. Also, setting it to 2 MPa or less can suppress a decrease in cushioning properties. The tensile modulus of the protective layer can be measured, for example, by cutting out a test piece of the protective layer measuring 12 cm × 2.5 cm (with the longer side facing the CMD direction), setting the test piece in a small benchtop testing machine (Shimadzu Corporation, "EZTest / CE"), conducting a tensile test at room temperature (20°C) (chuck distance 50 mm, tensile speed 100 mm / min), and determining the tensile modulus of the elastic region (slope at strain 0-4%) from the obtained stress-strain (SS) curve.

[0037] In one embodiment, the tensile strength of the protective layer is 1.0 to 30 MPa. Preferably, the tensile strength of the protective layer is 1.5 to 30 MPa, and more preferably 1.5 to 30 MPa. By setting the tensile strength of the protective layer to 1.0 MPa or higher, it is possible to suppress the occurrence of uncut pieces when the protective layer is peeled off after molding. The tensile strength of the protective layer can be determined, for example, by cutting out a test piece of the protective layer measuring 12 cm x 2.5 cm (with the longer side facing the CMD direction), setting the test piece in a small benchtop testing machine (Shimadzu Corporation, "EZTest / CE"), conducting a tensile test at room temperature (20°C) (chuck distance 50 mm, tensile speed 100 mm / min), and obtaining the maximum value of the stress-strain (SS) curve.

[0038] The average thickness of the protective layer is preferably 50 μm to 600 μm, more preferably 80 μm to 400 μm, even more preferably 90 μm to 300 μm, and still more preferably 100 μm to 250 μm. A thickness of 50 μm or more increases the area where the fibrous material is completely covered by the protective layer, making it easier to suppress the tilting of the fibrous material due to molding. Furthermore, a thickness of 600 μm or less can reduce manufacturing costs. The average thickness of the protective layer can be directly measured using a micrometer after peeling the protective layer from the laminated resin sheet. In this embodiment, the average thickness of the protective layer is greater than the average height of the bristles. By making the average thickness of the protective layer greater than the average height of the bristles, the bristles are completely covered by the protective layer, thereby strengthening the effect of suppressing the tilting of the bristles due to molding.

[0039] The material and method of forming the protective layer are not particularly limited, as long as the tensile modulus at 20°C is 0.2 MPa or more and less than 2 MPa, and the peel strength between the resin sheet body and the protective layer is 0.01 N / mm or more and less than 0.10 N / mm. For example, a silicone resin may be applied to the surface of the resin sheet having fibrous material and cured, or a hot melt film may be laminated and heated on the surface of the resin sheet having fibrous material to conform to the uneven shape of the fibrous material. As for silicone resins, peroxide-curing type, condensation reaction curing type, addition reaction curing type, and UV-curing type silicone resins can be used. As the hot melt film, olefin-based, polyamide-based, polyurethane-based, polyester-based, and other types of hot melt films can be used.

[0040] Furthermore, the composition used as the raw material for the protective layer may contain other additives, to the extent that they do not hinder the effects of the present invention, similar to the thermoplastic resin composition that forms the base layer and the fibrous material.

[0041] <Laminated resin sheet> The laminated resin sheet in this embodiment is a laminated resin sheet comprising a resin sheet body having regularly arranged fibrous bodies on at least one surface of the base layer, with no structural boundary between the base layer and the fibrous bodies forming a continuous phase, and a protective layer that fills the gaps between the fibrous bodies and covers the surface of the resin sheet body on the side having the fibrous bodies, wherein the tensile modulus of the protective layer at 20°C is 0.2 MPa or more and less than 2 MPa.

[0042] In one embodiment, the peel strength between the resin sheet body and the protective layer is 0.01 to 0.10 N / mm. Preferably, the peel strength between the resin sheet body and the protective layer is 0.01 to 0.08 N / mm, more preferably 0.02 to 0.08 N / mm, and even more preferably 0.02 to 0.05 N / mm. By setting the peel strength to 0.01 N / mm or higher, it is possible to suppress the peeling of the protective layer during molding, which can cause the fibers to collapse and result in an unsightly appearance. Furthermore, by setting the peel strength to 0.10 N / mm or lower, it is possible to suppress the occurrence of unpeeled protective layers after molding, or deformation of the fibrous material after peeling, which can result in an unsightly appearance. The peel strength can be adjusted by selecting the materials for the resin sheet and the protective layer. The peel strength between the resin sheet body and the protective layer in a laminated resin sheet can be determined as follows: A laminated resin sheet consisting of a resin sheet body and a protective layer is cut to a width of 25 mm. 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 layer faces upwards. The protective layer, peeled from the resin sheet below, is placed above the gripping jig, and the gripping jig holding the protective layer above is pulled in the direction normal to the sheet surface at a tensile speed of 100 mm / min to measure the peel strength.

[0043] In one embodiment of the present invention, the average thickness of the laminated resin sheet refers to the combined thickness of the average thickness of the base layer and the average thickness of the protective layer. The average thickness of the laminated resin sheet is preferably 65 μm to 900 μm, more preferably 100 μm to 700 μm, and even more preferably 200 μm to 500 μm. The thickness of the laminated resin sheet can be measured in accordance with JIS K 7130:1999.

[0044] [Second Embodiment] As an example of a laminated resin sheet according to the second embodiment of the present invention, as shown in Figure 3, the base layer is formed on the side opposite to the side of the base layer that has the fibrous material. That is, the layer structure of the laminated resin sheet according to the second embodiment is, from top to bottom, a protective layer (2), a fibrous material and base layer (1), and a base layer (3). The average thickness of the substrate layer is preferably 50 μm to 1000 μm, more preferably 100 μm to 800 μm, and even more preferably 150 μm to 500 μm. By making the average thickness of the substrate layer 1000 μm or less, production costs can be reduced. Here, the fibrous material and the base layer are the same as those described in the first embodiment, so their description is omitted. The total average thickness of the protective layer, fibrous material, base layer, and substrate layer is 80 μm to 1000 μm, more preferably 200 μm to 800 μm, and even more preferably 300 μm to 600 μm. In the resin sheet according to the second embodiment, it is preferable to use a thermoplastic resin that can adhere to the underlayment as the base layer. For example, the same thermoplastic resin composition as the underlayment, polycarbonate resins, polyester resins, and polymer alloy resins thereof can be suitably used. In the polymer alloy resin, the mass ratio of polycarbonate resin to polyester 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, polymer alloy resin refers to a high-molecular-weight multi-component system, and may be a polymer blend having a certain degree of compatibility through mixing, a block copolymer or graft copolymer formed by copolymerization, or a mixture of incompatible resins. 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 those derived from aromatic dihydroxy compounds (bisphenol) in which two aromatic dihydroxy compounds are linked via a certain type of bonding group are particularly preferred. These can be produced by known methods involving the polycondensation of dihydroxy compounds with phosgene or carbonate esters, but are not limited to such methods, and commercially available resins can also be used. Polyester resins that can be used include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polymethylene terephthalate, and polyester resins copolymerized with diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, or dicarboxylic acid components such as adipic acid, sebatic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid. The base layer may contain other additives as needed. Other additives that do not impair the effects of the present invention 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 fibers, fillers such as granular fine particles of talc, clay, and silica, or flake-like 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, flame retardants, antibacterial agents, antiviral agents, and heat stabilizers. Scrap resin generated in the resin sheet manufacturing process can also be mixed and used. Furthermore, the base layer may have a partially cross-linked structure as long as it does not impair the effects of the present invention.

[0045] [Manufacturing of resin sheet body] The method for manufacturing the resin sheet body according to the present invention is not limited and may be any method, but typically it includes the step of melt-extruding the raw resin and applying regularly arranged fibrous bodies to at least one surface of the obtained sheet. For example, a feed block or a multi-manifold die can be used during manufacturing. The layer configuration of each embodiment of the resin sheet body is basically as described above, but for example, scrap raw materials generated in the manufacturing process may be laminated as further layers as long as no deterioration in physical properties is observed.

[0046] There are no particular limitations on the method for imparting the fibrous material, and any method known to those skilled in the art can be used. For example, methods include manufacturing using an extrusion molding method, a roll-to-roll method, a photolithography method, a hot press method, manufacturing using a pattern roll and UV-curing resin, manufacturing using a 3D printer, and a method in which the fibrous material is embedded in a resin layer and then covalently bonded by a polymerization reaction.

[0047] For example, when using an extrusion molding method, a sheet can be extruded using a T-die method, and the resin sheet body can be manufactured by casting it with a transfer roll that has been processed to create a fuzzy texture on the surface of the sheet, and a touch roll. As a transfer roll with a textured surface, a roll can be used in which fine irregularities ranging in size from several micrometers to several hundred micrometers are regularly applied to the surface of the roll by methods such as laser engraving, electroforming, etching, or mill engraving. Here, "regular" means that the irregularities are not arranged randomly, that is, they are arranged in an orderly manner in one or two directions. In one embodiment, the arrangement of the irregularities can be selected to be a grid pattern or a staggered pattern arranged vertically and horizontally. As for the shape of the irregularities, for example, the shape of the recesses can be a cone (cone, square pyramid, triangular pyramid, hexagonal pyramid, etc.), a semicircle, or a rectangle (rectangular prism). In terms of size, the opening diameter of the recesses, the depth of the recesses, and the spacing between the recesses range from several micrometers to several hundred micrometers. As for the material of the transfer roll, for example, metal or ceramic can be used. By adjusting the spacing between the recesses of the transfer roll, the spacing of the bristles can be adjusted, and by adjusting the depth of the recesses of the transfer roll, the height of the bristles can be adjusted, thereby allowing for adjustment of the tactile feel. Furthermore, it is preferable to process the transfer roll surface with high aspect ratio irregularities. 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. Laser engraving or electroforming is particularly preferred for processing high aspect ratio irregularities on the transfer roll surface because it is more suitable for precise processing in the depth direction compared to etching, blasting, mill engraving, etc. The transfer roll can be made of materials such as metal or ceramic. The touch roll can be made of various materials, including silicone rubber, NBR rubber, EPT rubber, butyl rubber, chloroprene rubber, and fluororubber. In one embodiment, a touch roll with a rubber hardness (JIS K 6253) of 40 to 100 can be used. Furthermore, a Teflon® layer may be formed on the surface of the touch roll. Various materials can be used for the touch roll, but for example, rolls made of silicone rubber, NBR rubber, EPT rubber, butyl rubber, chloroprene rubber, or fluororubber can be used. In one embodiment, a touch roll with a rubber hardness (JIS K 6253) of 40 to 100 can be used. In addition, a Teflon® layer may be formed on the surface of the touch roll. By using the above-described transfer roll and touch roll roll set, the resin sheet body of this embodiment can be manufactured. In one embodiment, the temperature of the transfer roll is adjusted to a temperature near the crystal melting temperature, glass transition temperature, or melting point of the thermoplastic resin (for example, 100-150°C when using random polypropylene), and the pinch pressure between the transfer roll and the touch roll is set to 30-120 kg / cm². 2 The resin sheet body of this embodiment can be manufactured by casting. The cast resin sheet is taken up at a line speed of 0.5 to 30 m / min using pinch rolls or the like.

[0048] [Formation of a protective layer] The method for forming the protective layer according to this embodiment is not particularly limited, and any method known to those skilled in the art can be used. For example, this could include a method that includes a step of applying the raw material resin for the protective layer to the surface of the manufactured resin sheet body having fibrous material, or a method that includes a step of melting and bonding raw material resins that have been previously formed into sheets.

[0049] [Molded products] The molded product of this embodiment is a molded product using the laminated resin sheet of this embodiment. The laminated resin sheet of this embodiment can be used for general molding, and in addition to insert molding and in-mold molding, molding methods include general vacuum forming and pressure forming, and as an application thereof, a method in which the resin sheet is heated and softened in a vacuum state and then released under atmospheric pressure to overlay (mold) onto the surface of an existing molded product, but is not limited to these. Furthermore, as a method of heating and softening the sheet before molding, known sheet heating methods such as radiant heating using an infrared heater, which is a non-contact heating method, can be applied. In vacuum pressure forming of one embodiment, for example, the resin sheet is heated to a surface temperature of 60°C to 220°C for 20 seconds to 480 seconds before being molded onto the surface of an existing molded product, and can be stretched to 1.05 to 2.50 times its original size depending on the shape of the surface.

[0050] The laminated resin sheet of this embodiment can be applied to applications requiring the aforementioned good tactile properties. For example, the laminated resin sheet can be used as an interior material for automobiles, an exterior material for electronic equipment, or a surface material for cosmetic containers.

[0051] Examples of automotive interior materials include parts that are frequently touched by hands inside a vehicle, such as the steering wheel, dashboard, levers, and switches. For example, an interior material can be made by molding and laminating the above-mentioned resin sheet onto the surface of a known instrument panel or pillar (e.g., Japanese Patent Publication No. 2009-184421). By laminating the resin sheet, an interior material with a good tactile feel can be created. As for the material of the resin sheet to be laminated, olefin resins, vinyl chloride resins, and urethane elastomers are preferred, taking into consideration light resistance and chemical resistance. The method of laminating the resin sheet and the interior material is not particularly limited.

[0052] Examples of electronic device exterior materials 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 PC housings, keyboards, mice, and the like. For example, a portable transmitter can be made by molding and laminating the resin sheet of the present invention onto the surface of a known portable transmitter housing for a keyless entry system (e.g., Japanese Patent Application Publication No. 2005-228911). By laminating the resin sheet, a portable transmitter with good tactile properties can be made. The material of the resin sheet to be laminated is preferably an olefin resin or a urethane elastomer. The method of laminating the resin sheet and the housing is not particularly limited.

[0053] Examples of cosmetic containers include those for face cream, face pack cream, foundation, and eyeshadow. For example, a cosmetic container can be made by molding and laminating the resin sheet of the present invention onto the surface of the lid member of a known foundation container (Japanese Patent Publication No. 2017-29608). By laminating the resin sheet, a cosmetic container with a good tactile feel can be created. The material of the resin sheet to be laminated is preferably an olefin resin or a urethane elastomer. The method of laminating the resin sheet is not particularly limited.

[0054] Furthermore, a fibrous sheet can be prepared by printing characters and patterns on the surface of the fibrous material using common printing methods (offset printing, gravure printing, flexographic printing, screen printing, foil stamping, etc.) and applying it to the above-mentioned applications. 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.

[0055] Furthermore, laminates can be created by laminating printed materials (paper, thin metal films, etc.) or nonwoven fabrics with printed text, images, etc., using dry lamination or extrusion lamination. For example, a business card can be laminated to the printed surface to create a business card with a tactile feel. The material of the resin sheet to be laminated is not particularly limited. [Examples]

[0056] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited in any way to the contents of the examples, etc. In these examples, "parts" is based on weight.

[0057] The various raw materials used in the examples and their manufacturing methods are as follows. (1) Hairy tissue and underlayer • (A-1) TPU (urethane elastomer) "A3086A17J" (manufactured by BASF) (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" (manufactured by Shin-Etsu Chemical Co., Ltd.) +Hardening agent "CAT-1316" (manufactured by Shin-Etsu Chemical Co., Ltd.) • (C-2) Silicone resin "KE-1300T" (manufactured by Shin-Etsu Chemical Co., Ltd.) +Hardening agent "CAT-1300" (manufactured by Shin-Etsu Chemical Co., Ltd.) • (C-3) Silicone resin "KE-1314-2" (manufactured by Shin-Etsu Chemical Co., Ltd.) +Hardening agent "CAT-1314S" (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0058] The methods for evaluating various properties of the resin sheet body, laminated resin sheet, and laminated resin sheet product manufactured in the examples and comparative examples are as follows.

[0059] (1) Average height of the trichomes, average diameter of the trichomes, average spacing of the trichomes, average thickness of the underlying layer The height (h), diameter (d), spacing (t) of the bristles of the resin sheet, and the thickness of the underlying layer were measured using a laser microscope (VK-X100, Keyence Corporation). For the samples measured, cross-sectional sections were cut from three arbitrary locations on the resin sheet using a microtome. The average height of the bristles was calculated by measuring the height of 10 bristles in each sample and using the arithmetic mean of these 30 measurements. The average diameter of the bristles was calculated by measuring the diameter at the midpoint height (h / 2) of 10 bristles in each sample and using the arithmetic mean of these 30 measurements. The average spacing of the bristles was calculated by measuring the distance between the center of the base of one bristle and the center of the base of an adjacent bristle at 10 locations in each sample and using the arithmetic mean of these 30 measurements. The average thickness of the underlying layer was calculated by measuring the thickness of each layer at 10 locations in each sample and using the arithmetic mean of these 30 measurements. The thickness of the underlying layer is defined as the distance from the base of one bristle to the interface of the other layer.

[0060] (2) Evaluation of the physical properties of the protective layer The tensile modulus and tensile strength of the protective layer were determined as follows: A 12cm × 2.5cm specimen of the protective layer (with the longer side facing the CMD direction) was cut out. The specimen was then placed in a small benchtop testing machine (Shimadzu Corporation, "EZTest / CE"), and a tensile test was performed at room temperature (20°C) (chuck distance 50mm, tensile speed 100mm / min). The tensile modulus in the elastic region (slope at strain 0-4%) was determined from the obtained stress-strain (SS) curve. The point at which the maximum stress occurred was defined as the tensile strength.

[0061] (3) Measurement of peel strength between the resin sheet body and the protective layer The peel strength between the resin sheet body and the protective layer in a laminated resin sheet was determined as follows: A laminated resin sheet consisting of a resin sheet body and a protective layer was cut to a width of 25 mm. A 90-degree peeling jig (manufactured by Toyo Seiki Co., Ltd.) was attached below a universal material testing machine ("Strograph VE1D" manufactured by Toyo Seiki Co., Ltd.), and the resin sheet body was placed horizontally with the protective layer facing upwards. The protective layer, peeled from the resin sheet below, was clamped in the upper gripping jig, and the gripping jig holding the protective layer was pulled in the direction normal to the sheet surface at a tensile speed of 100 mm / min to measure the peel strength.

[0062] (4) Handling of protective layer When removing the protective layer from the laminated resin sheet, a circle (○) was used if it could be peeled off without any problems, and a cross (×) was used if it could not be peeled off cleanly, such as by tearing.

[0063] (5) Measurement of the angle of the pilosa The angle of the bristles was measured using a laser microscope (VK-X100, Keyence Corporation) on the resin sheet body before secondary molding and on the resin sheet body after secondary molding and removal of the protective layer. The samples used for measurement were cross-sectional sections cut from three arbitrary locations on the resin sheet body using a microtome. For each sample, the angle of 10 bristles was measured, and the arithmetic mean of these 30 measurements was used. The angle of the bristles was defined as 0° when the bristles extended perpendicular to the surface of the underlying layer.

[0064] (6) Confirmation of bleaching An external panel of 10 people (5 men and 5 women) evaluated the appearance of the resin sheet body before secondary molding and the secondary molded product of the laminated resin sheet. When comparing the two, if no difference in color was observed, it was judged as "no whitening"; if a difference was observed in at least one of them, it was judged as "whitening present". If 8 or more out of 10 judged it as "no whitening", the overall evaluation was "○"; if 4 to 7 out of 10 judged it as "no whitening", the overall evaluation was "△"; and if 3 or fewer out of 10 judged it as "no whitening", the overall evaluation was "×".

[0065] (7) Sensory evaluation of good tactile sensation To assess tactile quality, a sensory evaluation was conducted by 10 external panelists (5 men and 5 women) who touched the resin sheet body after secondary molding and removal of the protective layer. Each specific tactile sensation (smooth, moist, dry, rough, etc.) of the resin sheet body surface was evaluated on a scale of 1 to 10, and the tactile sensation with the highest score was defined as the tactile sensation of that resin sheet surface. In Table 1, "○" indicates that the score for smooth or moist was high, and that good tactile quality, similar to a suede-like napped sheet, was obtained even after secondary molding. "△" indicates that the score for smooth or moist was high, but the highest-scoring tactile sensation decreased by 3 points or more after secondary molding. "×" indicates that the score for dry or rough was high, and that good tactile quality was not obtained after secondary molding.

[0066] (Manufacturing of laminated resin sheets) [Examples 1-3, Comparative Examples 2-4] From one 40mm single-screw extruder, (A-1) urethane elastomer, which will serve as the fibrous material and base layer, was extruded, and from one 65mm single-screw extruder, (B-1) PC / polyester resin, which will serve as the base layer, was extruded. The resin sheet extruded by co-extrusion multilayer T-die method was then processed with a textured surface using chromium oxide spraying and laser engraving. Using a transfer roll with a textured surface adjusted to 60°C to 150°C and a touch roll made of silicone rubber with a rubber hardness of 70 adjusted to 10°C to 90°C, the sheet was cast and pulled up at a line speed of 1m / min to 15m / min using a pinch roll. This obtained resin sheets with the composition, thickness, and surface shape shown in Table 1. Next, one of the silicone resins (C-1) to (C-3) and a hardener were mixed in a 9:1 ratio to form a protective layer. This mixture was then spread onto the surface of the resin sheet using a brass rod to form a protective layer of the thickness shown in Table 1, thus obtaining a laminated resin sheet.

[0067] [Comparative Example 1] A thermoplastic resin (A-1), which will form the fibrous material and base layer, was extruded from one 40 mm single-screw extruder, and a PC / polyester resin (B-1), which will form the base layer, was extruded from another 65 mm single-screw extruder. The resin sheets extruded by co-extrusion multilayer T-die method were then embossed using chromium oxide spraying and laser engraving. The embossed transfer rolls, adjusted to a temperature of 60°C to 150°C, and touch rolls made of silicone rubber with a rubber hardness of 70, adjusted to a temperature of 10°C to 90°C, were used for casting. The sheets were then taken up using pinch rolls at a line speed of 1 m / min to 15 m / min. This resulted in resin sheets with the composition, thickness, and surface shape shown in Table 1. No protective layer was formed.

[0068] (Manufacturing of secondary molded products) Using a vacuum pressure forming machine (NGF-0406s manufactured by Fuse Vacuum Co., Ltd.), a three-dimensional shape was imparted to a laminated resin sheet by preforming it under the following conditions. The three-dimensional shape was imparted using a mold for a convex cover panel with a long side of 200 mm and a short side of 100 mm, which curved gently by 10 mm from the edge to the center. The surface of the laminated resin sheet on the base layer side, i.e., the side opposite the protective layer, was brought into contact with the convex surface of the mold. • Sheet surface temperature: 100~150℃ • Heating time: 40-300 seconds • Mold shape: Length 200mm, width 100mm Subsequently, the laminated resin sheet with the three-dimensional shape was removed from the mold, the excess portion was trimmed, and polycarbonate resin (Mitsubishi Engineering Plastics "H3700UR") was injected using an insert molding machine (Sumitomo Heavy Industries "SE315EV-A-HD") under the following conditions to obtain a secondary molded product (insert molded product). For insert molding, the laminated resin sheet with the three-dimensional shape was positioned so that the protective layer side was in contact with the injection mold, and the resin was injected into the base material layer side using a side gate method. • Mold temperature: 40°C ·Injection resin temperature: 280℃ ·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.

[0069] Table 1 shows the results of evaluation tests conducted on various properties using the resin sheets obtained in each example and comparative example.

[0070] [Table 1]

[0071] The following became clear from the results shown in Table 1. It was shown that whitening and loss of tactile properties were suppressed in all laminated resin sheets of Examples 1 to 3 even after secondary molding. On the other hand, the molded product of the laminated resin sheet in Comparative Example 1 underwent whitening and loss of tactile properties after secondary molding. In Comparative Example 2, the molded laminated resin sheet underwent whitening and loss of tactile properties after secondary molding. In Comparative Example 3, the molded laminated resin sheet showed suppressed whitening and loss of tactile properties even after secondary molding. However, the protective layer adhered strongly to the resin sheet body, and it tore when peeled off, making clean removal impossible. In Comparative Example 4, the molded laminated resin sheet had weak adhesion of the protective layer to the resin sheet body, causing the resin sheet body and the protective layer to shift during secondary molding, resulting in whitening.

[0072] 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 embodiments described above. It will be obvious to those skilled in the art that various modifications or improvements can be made to the above embodiments. Furthermore, it is clear from the claims that such modified or improved forms may also be included within the technical scope of the present invention. [Industrial applicability]

[0073] Since the resin sheet of this embodiment exhibits suppressed whitening and loss of tactile properties even after secondary molding, it has industrial applicability as a resin sheet and molded product that can be subjected to secondary molding. [Explanation of symbols]

[0074] 1. Hair-like structures and underlying layers 1a Base layer 1b Ciliary body d Hair diameter h Height of the hair-like structure t Spacing of the hair-like structures 2 protective layer 3 Base material layer

Claims

1. The present invention comprises a resin sheet body having regularly arranged fibrous bodies on at least one surface of the substrate, with no structural boundary between the substrate and the fibrous bodies forming a continuous phase, and a protective layer that fills the gaps between the fibrous bodies and covers the surface of the resin sheet body on the side having the fibrous bodies, wherein the tensile modulus of the protective layer at 20°C is 0.2 MPa or more and less than 2 MPa, the average thickness of the protective layer is greater than the average height of the fibrous bodies, and the peel strength between the resin sheet body and the protective layer is 0.01 to 0.10 N / mm. A laminated resin sheet in which the resin sheet body contains a resin that includes at least one of the following: urethane elastomer (TPU), styrene resin, polyolefin resin, polyvinyl chloride resin, thermoplastic elastomer, and fluororesin. The average height of the pilosa is 30 μm or more and 500 μm or less, the average diameter of the pilosa is 1 μm or more and 50 μm or less, the average spacing between the pilosa is 20 μm or more and 200 μm or less, the aspect ratio of the pilosa (average height of the pilosa / average diameter of the pilosa) is 2 to 20, and the resin sheet body contains a resin that includes at least one of the following: urethane elastomer (TPU), styrene resin, polyolefin resin, polyvinyl chloride resin, thermoplastic elastomer, and fluororesin.

2. The laminated resin sheet according to claim 1, wherein the tensile strength of the protective layer is 1.0 to 10.0 MPa.

3. The laminated resin sheet according to claim 1 or 2, wherein the average thickness of the protective layer is 50 to 600 μm.

4. The laminated resin sheet according to claim 1 or 2, wherein when the angle of the fibrous material is defined as 0° when the fibrous material extends perpendicularly to the surface of the underlying layer, the average value of the angle increased by heat molding is 0 to 10°.

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

6. A method for manufacturing a laminated resin sheet according to claim 1 or 2, comprising forming a protective layer on the surface of the resin sheet body having fibrous material.

7. A molded article of a laminated resin sheet according to claim 1 or 2.

8. The molded article according to claim 7, which is an insert molded article or a vacuum molded article.

9. A molded article according to claim 7, provided on the surface of an automotive interior material, an electronic equipment exterior material, or a cosmetic container.

Images