Laminated resin sheet comprising resin sheet body having hair-like body and protective

Abstract

The purpose of the present invention is to provide: a laminated resin sheet in which whitening and loss of tactile sensation are suppressed even when secondary molding is performed; a method for producing the same; and a molded article thereof. A laminated resin sheet according to the present invention comprises: a resin sheet main body having regularly arranged hairy bodies on at least one surface of a base layer and forming a continuous phase without structural boundaries between the base layer and the hairy bodies; and a protective layer that fills the gaps between the hairy bodies and covers the surface of the resin sheet main body on the side having the hairy bodies, the tensile elastic modulus of the protective layer at 20 DEG C being 0.2 MPa or more and less than 2 MPa, and the average thickness of the protective layer being greater than the average height of the hairy bodies.

Description

Technical Field

[0001] The present invention relates to a laminated resin sheet comprising a resin sheet main body having hair-like bodies and a protective layer, a method for producing the same, and a molded article thereof. Background Art

[0002] Conventionally, sheets made of paper and polymer materials have been used as automotive interior materials, accessory housings, housings for electronic devices and home appliances, building materials such as wallpaper, housings for toys and game consoles, and components for daily necessities. Furthermore, as a method for imparting good tactile properties to the surface of a sheet, for example, Patent Document 1 proposes a resin sheet having regularly arranged hairs on its surface.

[0003] On the other hand, when such a resin sheet is used as an interior product such as an instrument panel or a seat of an automobile, it is necessary to perform secondary molding and adhere it to the surface of the object.

[0004] Existing technology

[0005] Patent Document 1: International Publication No. 2018 / 016562 Summary of the Invention

[0006] However, it is known that such resin sheets may deform the hairs or tilt the hairs to cause hair loss during the process of secondary molding and affixing the sheets to the surface of an object, which may cause the sheet to appear white or lose its good tactile feel.

[0007] The technical problem to be solved by the present invention is to provide a laminated resin sheet in which whitening and loss of tactile properties are suppressed even when secondary molding is performed, a method for producing the same, and a molded product thereof.

[0008] Specifically, the present inventors have studied various technical means and, as a result, discovered that by producing a laminated resin sheet comprising the following resin sheet body and the following protective layer, they have discovered a laminated resin sheet capable of suppressing whitening and loss of tactile properties even during secondary molding, thereby completing the present invention. The resin sheet body has regularly arranged trichomes on at least one surface of a base layer, with the base layer and the trichomes forming a continuous phase with no structural boundary. The protective layer fills the gaps between the trichomes and covers the surface of the resin sheet body on the side having the trichomes. The protective layer has a tensile modulus of elasticity at 20°C of 0.2 MPa or more and less than 2 MPa.

[0009] The present invention for solving the above-mentioned technical problems is constructed as follows.

[0010] [1] A laminated resin sheet comprising: a resin sheet body having regularly arranged trichomes on at least one surface of a base layer, wherein the base layer and the trichomes form a continuous phase with no structural boundary; and a protective layer that fills gaps between the trichomes and covers the surface of the resin sheet body on the side having the trichomes, wherein the protective layer has a tensile modulus of elasticity of 0.2 MPa or more and less than 2 MPa at 20°C, and an average thickness of the protective layer is greater than an average height of the trichomes.

[0011] [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.

[0012] [3] The laminated resin sheet according to [1] or [2], wherein the tensile strength of the protective layer is 1.0 to 10.0 MPa.

[0013] [4] The laminated resin sheet according to any one of [1] to [3], wherein the average thickness of the protective layer is 50 μm to 600 μm.

[0014] [5] The laminated resin sheet according to any one of [1] to [4], wherein, when the angle of the trichomes when the trichomes extend perpendicularly to the surface of the base layer is set to 0°, the average value of the angle increased by heat molding is 0° to 10°.

[0015] [6] The laminated resin sheet according to any one of [1] to [5], wherein the average height of the trichomes is 30 μm to 500 μm, the average diameter of the trichomes is 1 μm to 50 μm, and the average spacing between the trichomes is 20 μm to 200 μm.

[0016] [7] The 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.

[0017] [8] A method for producing a laminated resin sheet according to any one of [1] to [6], comprising forming a protective layer on a surface of a resin sheet body having hair-like bodies.

[0018] [9] A molded product of the laminated resin sheet according to any one of [1] to [6].

[0019]

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

[0020]

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

[0021] 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 when secondary molding is performed, a method for producing the same, and a molded product thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a schematic longitudinal sectional view showing a laminated resin sheet according to a first embodiment of the present invention.

[0023] Figure 2 This is a schematic plan view of the resin sheet main body.

[0024] Figure 3 This is a schematic longitudinal sectional view showing a laminated resin sheet according to a second embodiment of the present invention. DETAILED DESCRIPTION

[0025] Hereinafter, various embodiments of the resin sheet will be described, and then a method for producing the resin sheet will be described. However, if a specific description described in one embodiment is also applicable to other embodiments, the description will be omitted in other embodiments.

[0026] [First embodiment]

[0027] A resin sheet according to a first embodiment of the present invention is a laminated resin sheet comprising: a resin sheet body having regularly arranged trichomes on at least one surface of a base layer, wherein the base layer and the trichomes form a continuous phase with no structural boundary; and a protective layer that fills the gaps between the trichomes and covers the surface of the resin sheet body on the side having the trichomes, 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 trichomes. Specifically, the laminated resin sheet according to this embodiment has a layer structure comprising, from top to bottom, a protective layer (2), trichomes, and a base layer (1).

[0028] <Basal layer>

[0029] The basal layer (1a) is the layer that becomes the base of the trichomes. Figure 1The portion of the surface of the material (1b) in symbol 1 is defined as the thickness of the basal layer, excluding the trichomes (1b). The thickness of the basal layer refers to the thickness from the base of the trichomes to the surface opposite the basal layer. The average thickness of the basal layer 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 greater allows for sufficient expression of the height of the trichomes. A thickness of 300 μm or less allows for efficient trichome formation. The average thickness of the basal layer can be determined by measuring the thickness at 10 points from the base of the trichomes to the interface with the other layer, using a microtome to cut a cross-section of the sample at three arbitrary locations. The arithmetic average of these 30 measured values ​​can be used. The basal layer and the trichomes may have no structural boundary, forming a continuous phase. "Structurally absent" means that the basal layer and the trichomes are integrally formed, with no distinct structural boundary between them. "Forming a continuous phase" also means that the basal layer and the trichomes are discontinuous (continuous) without a seam between them. This differs from a structure in which trichomes are embedded in the base layer. The base layer and trichomes can have the same composition, and the bond between the base layer and trichomes can include covalent bonds. A covalent bond is a chemical bond formed by sharing an electron pair between two atoms. In thermoplastic resins, which are chain-like molecules formed by linked monomers, each polymer is bonded by covalent bonds, which are stronger than van der Waals bonds and hydrogen bonds that operate between polymer molecules.

[0030] Furthermore, the base layer and the trichomes may be derived from a thermoplastic resin sheet that is not a single solid. The term "derived from a thermoplastic resin sheet that is a single solid" means, for example, that the trichomes and the base layer are directly or indirectly obtained from the same resin sheet.

[0031] Alternatively, the base layer and the hair-like bodies may be formed from the same solid thermoplastic resin sheet. Forming them from the same solid thermoplastic resin sheet means that the hair-like bodies and the base layer are directly formed by processing a single resin sheet.

[0032] There is no structural boundary between the basal layer and the trichomes. By forming a continuous phase, the trichomes are prevented from separating from the basal layer due to external stimuli, resulting in a sheet with good tactile feel. In addition, it can be manufactured with fewer steps than when trichomes are implanted.

[0033] The base layer and the hairs are composed of the same thermoplastic resin composition, primarily composed of a thermoplastic resin. Here, "primarily composed" means comprising 50% by mass or more. Preferably, it comprises 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 comprising at least one of polyurethane elastomers (TPU), styrene-based resins, polyolefin-based resins, polyvinyl chloride resins, thermoplastic elastomers, and fluororesins can be used.

[0034] Polyurethane elastomer is a resin with diisocyanate and polyol as reaction raw materials. As its combination, the diisocyanate can be selected from diphenylmethane diisocyanate (MDI) series, H 12 MDI, hexamethylene diisocyanate (HDI), and polyols are any combination of polyether, polyester, and polycarbonate, and multiple combinations thereof are also possible. In one embodiment of the present invention, a combination of an MDI or HDI diisocyanate and a carbonate polyol is preferably used.

[0035] As styrene-based resins, homopolymers or copolymers of styrene-based monomers such as styrene, α-methylstyrene, p-methylstyrene, dimethylstyrene, p-tert-butylstyrene, and chlorostyrene, copolymers of these styrene-based monomers with other monomers, such as styrene-acrylonitrile copolymers (AS resins), or graft polymers obtained by graft polymerization of the above-mentioned styrene-based monomers with other polymers, such as polybutadiene, styrene-butadiene copolymers, polyisoprene, and polychloroprene, such as high-impact polystyrene (HIPS resins) and styrene-acrylonitrile graft polymers (ABS resins), can be used. In addition, styrene-based thermoplastic elastomers can also be used.

[0036] Polyolefin resins refer to resins containing polymers containing α-olefins as monomers, and include polyethylene resins and polypropylene resins. Polyethylene resins include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear medium-density polyethylene, and the like. Furthermore, not only monomers but also copolymers, grafts, and mixtures having these structures can be used. Examples of the latter resins include those obtained by copolymerizing and blending resins having polar groups in the polyethylene chain, such as those blended with ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-acrylate copolymers, ethylene-methacrylate copolymers, ethylene-vinyl acetate-vinyl chloride copolymers, and further with terpolymers of acid anhydrides.

[0037] In addition, as polypropylene resin, homopolypropylene, random polypropylene, block polypropylene, etc. can be used. When using homopolypropylene, the structure of the homopolypropylene can be any one of isotactic, atactic, and syndiotactic. When using random polypropylene, as the α-olefin copolymerized with propylene, preferably an α-olefin having 2 to 20 carbon atoms, more preferably an α-olefin having 4 to 12 carbon atoms, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene can be used. When using block polypropylene, block copolymers (block polypropylene), block copolymers containing rubber components, or graft copolymers can be used. In addition to using these olefin resins alone, other olefin resins can also be used in combination.

[0038] As the polyvinyl chloride resin, a vinyl chloride homopolymer or a copolymer of vinyl chloride and other comonomers can be used. In the case where the polyvinyl chloride is a copolymer, it can be a random copolymer, and it can also be a graft copolymer. As an example of a graft copolymer, for example, an ethylene-vinyl acetate copolymer or a thermoplastic polyurethane polymer is used as a main polymer, and a polymer with vinyl chloride grafted thereon can be cited. The polyvinyl chloride of this embodiment represents a soft polyvinyl chloride that can be extruded and is a composition containing additives such as a polymer plasticizer. As the polymer plasticizer, a well-known polymer plasticizer can be used, for example, ethylene copolymer polymer 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 can be cited as preferred examples.

[0039] Thermoplastic elastomers include those having a structure formed by combining a soft polymer and a hard polymer. 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 commonly available commercially available elastomers.

[0040] As the fluorine-based resin, a homopolymer of vinylidene fluoride and a vinylidene fluoride copolymer with 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, and αp-type. Examples of the vinylidene fluoride copolymer include 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 thereof.

[0041] The thermoplastic resin composition preferably has a melt flow rate of 4 g / 10 minutes or greater at 190°C to 300°C. Setting the melt flow rate to 4 g / 10 minutes or greater for 10 minutes improves the transferability of the trichome shape. The melt flow rate is a value measured in accordance with JIS K7210 within a test temperature range of 190°C to 300°C and under a load of 2.16 kg to 10.0 kg.

[0042] The thermoplastic resin composition can be alloyed with the above-mentioned thermoplastic resins in any proportion within the scope that does not impair the effects of the present invention. Furthermore, it may also contain other additives. As other additives, within the scope that does not hinder the effects of the present invention, waterproof and oil-proof agents, colorants such as pigments and dyes, lubricants and release agents such as silicone oils and alkyl esters, fibrous reinforcing agents such as glass fiber, granular particles such as talc, clay, and silica as fillers, flaky particles such as mica, low-molecular antistatic agents such as salt compounds of sulfonic acid and alkali metals, polymer antistatic agents such as polyether ester amides, flame retardants, antibacterial agents, antiviral agents, additives such as heat stabilizers, etc. can be added. In addition, waste resins generated in the resin sheet manufacturing process can also be mixed and used.

[0043] Examples of water- and oil-repellent agents include silicone-based water-repellents, Carnauba, and fluorine-based water- and oil-repellents. Examples of silicone include organopolysiloxanes, dimethylpolysiloxanes, methylphenylpolysiloxanes, and methylhydrogenpolysiloxanes, among which dimethylpolysiloxanes are preferred. Commercially available products include, for example, "CLINEBELL CB50-PP" (Japanese: クリンベル), "CLINEBELL CB-30PE," "CLINEBELL CB-1," and "CLINEBELL CB-50AB" (manufactured by Fuji Chemical Co., Ltd.), which are alloys of silicone and resin. Commercially available products of Carnauba include "CARNAUBA No. 1" (manufactured by Nikko Rica Co., Ltd.), and fluorine-based water- and oil-repellent agents include surfactants having perfluoroalkyl groups, and commercially available products include "SURFLON KT-PA" (manufactured by AGC Kiyomi Chemical Co., Ltd.). The amount of the water- and oil-repellent agent added is preferably 0.5 to 25% by mass. If it is less than 0.5% by mass, sufficient water- and oil-repellency may not be achieved, while if it exceeds 25% by mass, moldability may deteriorate.

[0044] As antistatic agents, polyetheresteramide-based polymer antistatic agents, ionomer-based polymer antistatic agents, etc. can be cited. As for polyetheresteramide-based polymer antistatic agents, commercially available products include "PELESTAT 230", "PELESTAT 6500", "PELECRON AS", "PELECRON HS" (manufactured by Sanyo Chemical Co., Ltd.), etc. Commercially available products of ionomer-based polymer antistatic agents include "ENTIRA SD100", "ENTIRA MK400" (manufactured by DuPont Mitsui Polychemicals Co., Ltd.), etc. The amount of antistatic agent added is preferably 5% to 30% by mass. When it is less than 5% by mass, sufficient antistatic properties may not be obtained, and when it exceeds 30% by mass, the production cost increases.

[0045] As an antibacterial agent, any of an inorganic system and an organic system can be added. If dispersibility is considered, an inorganic system is preferred. Specifically, inorganic antibacterial agents of metal ions (Ag, Zn, Cu), shell-calcined calcium antibacterial agents, etc. can be cited. Commercially available products of inorganic antibacterial agents of metal ions include "Vabaxylar BM102 VT" (made by Fuji Chemical Co., Ltd.), "NOVARON VZF200", "NOVARON (AG300)" (made by Toagosei Co., Ltd.), "KM-10D-G", "IM-10D-L" (made by SINANEN ZEOMIC Co., Ltd.), etc. As shell-calcined calcium antibacterial agents, "SCALLOW" (made by FID Co., Ltd.) can be cited. The addition amount of the antibacterial agent is preferably 0.5% to 5% by mass. If it is less than 0.5% by mass, it is possible that sufficient antibacterial activity cannot be obtained. If it exceeds 5% by mass, the production cost rises.

[0046] As lubricants and release agents, alkyl lubricants and release agents such as aliphatic hydrocarbon compounds, higher fatty acid compounds, higher aliphatic alcohol compounds, and fatty acid amide compounds, silicone lubricants and release agents, and fluorine lubricants and release agents can be used. When using lubricants and release agents, 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 in a total of 100 parts by mass of the resin composition. By setting the addition amount to 0.01 parts by mass or more, the possibility of a reduction in the release effect can be reduced, and by setting it to 5 parts by mass or less, the possibility of bleeding onto the sheet surface can be reduced.

[0047] Alternatively, a masterbatch prepared by pre-alloying a lubricant, a release agent, and a thermoplastic resin may be used. For example, a commercially available masterbatch based on a polyurethane thermoplastic elastomer includes "Waxmaster V" (manufactured by BASF). Considering production efficiency, the use of a masterbatch is preferred. The amount of the 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, per 100 parts by mass of the total weight of the masterbatch and the resin composition.

[0048] <Trichomes>

[0049] Trichome (1b) refers to Figure 1 The portion shown extends hairily from the surface of the base layer (1a). The trichomes are regularly arranged on the surface of the base layer. Regular arrangement here means that the trichomes are not randomly arranged, but rather are arranged regularly (e.g., at regular intervals) in one or two directions. Whether the trichomes are regularly arranged is determined by the arrangement of the base of the trichomes. In one embodiment, the trichomes are located at regular intervals on the base layer, and the bottom surfaces of the trichomes are regularly arranged in the longitudinal and width directions of the base layer. The arrangement of the trichomes is not particularly limited, and can be arranged in a checkerboard pattern or a staggered pattern, for example. Regularly arranging the trichomes on the surface of the base layer facilitates achieving a uniform, uniform, and good tactile feel. The trichomes can be tucked down by applying a load, such as by tracing with a finger, to form finger marks that appear different in gloss and color from the surrounding areas. Furthermore, the trichomes can create a tactile feel similar to that of a raised sheet with a suede-like color.

[0050] The average height (h) of the trichomes 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. By setting the average height to 30 μm or greater, a sufficiently good feel can be ensured, while by setting the average height to 500 μm or less, a good feel such as moistness, softness, and volume can be achieved.

[0051] When the trichomes are roughly upright relative to the basal layer, the length from the base to the tip of the trichome represents the trichome height. On the other hand, when the trichomes are tilted relative to the basal layer, or when the trichomes have a curled portion, the distance from the basal layer surface to the trichome's surface at the point farthest from the trichome's tip is the trichome height h. Furthermore, the sum of the intervals measured at multiple points from the tip to the center of the base is the trichome length L.

[0052] The average height and average length of trichomes can be determined by measuring the height and length of trichomes at a plurality of arbitrary locations on the resin sheet using an electron microscope and image processing software, and using the arithmetic mean of the measured values.

[0053] The average diameter (d) of the trichomes 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 trichomes to 1 μm or greater, a good feel can be ensured. By setting the average diameter of the trichomes to 50 μm or less, a good feel, such as moistness, softness, and volume, can be achieved. The average diameter of the trichomes is determined by measuring the diameter of the trichomes at their mid-height (h / 2) at multiple locations on the resin sheet using an electron microscope and image processing software, and calculating the arithmetic average of these measured values.

[0054] The aspect ratio of trichomes can be expressed as (average height of trichomes / average diameter of trichomes). The aspect ratio of 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 greater, good tactile feel can be ensured. By setting the aspect ratio to 20 or less, good tactile feel such as moist, soft, and fluffy can be achieved while also reducing the likelihood that the ratio of trichome height to length will fall below a specified value.

[0055] Alternatively, the aspect ratio can be based on the average base diameter of the trichomes. The average base diameter of the trichomes is preferably 10 to 150 μm, more preferably 20 to 120 μm, and even more preferably 30 to 100 μm. The average base diameter of the trichomes is the arithmetic mean of the distances between adjacent trichomes measured at multiple locations on the resin sheet body. The aspect ratio based on the base diameter of the trichomes is preferably 1.0 to 10, more preferably 1.0 to 5, and even more preferably 1.0 to 2.5. An aspect ratio of 1.0 or greater ensures a good tactile feel. An aspect ratio of 10 or less not only achieves good tactile properties such as moistness, softness, and volume, but also reduces the likelihood that the trichome height-to-length ratio will fall below a specified value.

[0056] The average interval (t) between trichomes is preferably 20 μm to 200 μm, more preferably 40 μm to 150 μm, and even more preferably 40 μm to 100 μm. Figure 2The distance between the center of a trichome's base and the center of an adjacent trichome's base is shown in the figure. Setting the average spacing to 20 μm or greater ensures a good feel, while setting it to 200 μm or less provides a good feel, such as moistness, softness, and volume. The average spacing between trichomes is the arithmetic mean of the measured distances between adjacent trichomes at multiple locations on the resin sheet.

[0057] The shape of the trichomes is not particularly limited. They can extend hair-like in a direction away from the basal layer, gradually tapering toward the tip, or have a protrusion at the tip. Specifically, they can have a shape where the cross-sectional area gradually decreases as they move away from the basal layer, then temporarily increases before terminating. Furthermore, the tip of the trichomes can have a bud-like or mushroom-like shape. Furthermore, the trichomes can have a base portion extending away from the basal layer, a portion extending from the base portion and curved with a constant or gradually changing curvature, or a portion coiled in a spiral or whorl shape. In this case, the tips of the trichomes can also be folded inward. Such shapes provide a pleasant feel. Furthermore, making the bud-like or mushroom-shaped portion hollow further enhances the feel. When the tips of the trichomes are bud-like or mushroom-shaped, the ratio of the average width of the bud or mushroom to the average diameter of the trichomes is preferably at least 1.1 times. The height of the bud or mushroom is preferably at least 7 μm. The average diameter of the trichomes, the average width of the buds or mushrooms, and the average height were measured using scanning electron microscope photographs, and the values ​​were calculated using the arithmetic mean. The trichomes are composed of a thermoplastic resin. The thermoplastic resin used can be the same as that used in the base layer described above.

[0058] The thermoplastic resin contained in the base layer and trichomes can 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 trichomes may be crosslinked, in another embodiment, the entire surface of the trichomes may be crosslinked, and in yet another embodiment, the entire trichomes (from the boundary with the base layer to the tip) may be crosslinked. Examples of methods for forming a crosslinked structure include: forming a resin sheet and then irradiating the trichome-bearing surface with electron beams; and adding an organic peroxide and then heating and humidifying the resin sheet during or after molding. Commercially available resins containing organic peroxides include "LINKRON" manufactured by Mitsubishi Chemical Corporation. In this embodiment, the crosslinked structure is preferably formed by irradiation with electron beams (electron beam crosslinked structure).

[0059] In one embodiment, when the angle of the trichomes when the trichomes extend perpendicularly to the base layer surface is set to 0°, the average value of the angle increased by heat molding is preferably 0° to 10°, more preferably 0° to 9°, and even more preferably 0° to 8°.

[0060] The above angle can be calculated by measuring the angle of the trichomes of the resin sheet body before heat molding and the resin sheet body after heat molding the laminated resin sheet and peeling off the protective layer, for example, using a laser microscope, and subtracting the angle before heat molding from the angle after heat molding.

[0061] Here, heat forming means that a laminated resin sheet is set in a mold, polycarbonate resin is injected into the mold, and an insert molded product decorated with a laminated resin sheet is obtained, and finally the protective layer is peeled off. When the laminated resin sheet is set in the mold, the laminated resin sheet can be set directly, or it can be set after pre-forming to give it a three-dimensional shape. As methods for preforming, vacuum forming, pressure forming, vacuum pressure forming, TOM forming, etc. can be listed. As temperature conditions for preforms, the sheet surface temperature can be: 100-150°C, and the heating time can be: 40-300 seconds. As the resin to be injected, in addition to polycarbonate (PC) resin, ABS resin, AES resin, polyester resin, acrylic resin, and alloy resins composed of these can also be used. As temperature conditions for injection, the mold temperature can be: 40°C, the injection resin temperature can be: 280°C, and the holding pressure can be: 30MPa.

[0062] Specific thermoforming can be performed under the following conditions.

[0063] Using a vacuum compression molding machine, preform the laminated resin sheet under the following conditions to impart a three-dimensional shape. This three-dimensional shape can be achieved by using a cover sheet mold with a convex shape gently curved 10 mm from the end to the center on a surface with a long side of 200 mm and a short side of 100 mm. The surface of the laminated resin sheet facing the substrate layer, i.e., the surface opposite the protective layer, is brought into contact with the convex surface of the mold.

[0064] Sheet surface temperature: 100~150℃

[0065] Heating time: 40 seconds to 300 seconds

[0066] Mould shape: long side 200mm, short side 100mm

[0067] The laminated resin sheet having a three-dimensional shape is then removed from the mold, the excess material is trimmed, and a polycarbonate resin is injected into the insert molding machine under the following conditions to obtain a secondary molded product (insert molded product). Insert molding is performed by placing the protective layer side of the laminated resin sheet having a three-dimensional shape in contact with the injection mold, and injecting the resin into the substrate layer side using a side gate method.

[0068] Mold temperature: 40℃

[0069] Injection resin temperature: 280℃

[0070] Holding pressure: 30MPa

[0071] After cooling, the molded product is removed from the mold and the protective layer is peeled off to obtain the final secondary molded product.

[0072] The average value of the angle increased by thermoforming can be adjusted by the composition of the resin sheet body, the shape of the trichomes, the composition and average thickness of the protective layer, and the like.

[0073] <Resin Sheet Body>

[0074] In this embodiment, "tactile properties" refers to the feel of the surface of the resin sheet body and the skin feel. Whether the resin sheet surface feels comfortable when touched is determined. If it feels comfortable, the specific skin feel such as moist, soft, and fluffy is considered good touch.

[0075] In one embodiment of the present invention, the thickness of the resin sheet body refers to the sum of the average height of the trichomes and the average thickness of the base 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 can be 80 μm or greater and less than 350 μm. A thickness of 45 μm or greater ensures a sufficiently good tactile feel, 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 L1913:2010.

[0076] <Protection layer>

[0077] The protective layer (2) is a layer that fills the gaps between the trichomes and covers the surface of the resin sheet body on the side having the trichomes. "Filling the gaps" means filling the spaces between adjacent trichomes, and more preferably, filling the spaces between adjacent trichomes from the base to the tip. The protective layer has a tensile modulus of elasticity of 0.2 MPa or more and less than 2 MPa at 20°C. The protective layer preferably has a tensile modulus of elasticity of 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. By setting the tensile modulus of elasticity of the protective layer at 20°C to 0.2 MPa or more, the generation of cut residues when the protective layer is peeled off after molding can be suppressed. Furthermore, by setting the tensile modulus to 2 MPa or less, a reduction in cushioning properties can be suppressed.

[0078] The tensile modulus of the protective layer can be measured, for example, by cutting a 12 cm × 2.5 cm (long side in the CMD direction) test piece of the protective layer, placing the test piece in a small tabletop testing machine (manufactured by Shimadzu Corporation, "EZTest / CE"), and conducting a tensile test at room temperature (20°C) (chuck distance 50 mm, tensile speed 100 mm / min). The tensile modulus in the elastic region (slope at a strain of 0-4%) is then determined from the obtained stress-strain (SS) curve.

[0079] In one embodiment, the tensile strength of the protective layer is 1.0 to 30 MPa. The tensile strength of the protective layer is preferably 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 generation of cut residues when the protective layer is peeled after molding.

[0080] The tensile strength of the protective layer can be determined, for example, by cutting a 12 cm × 2.5 cm (long side in the CMD direction) test piece of the protective layer, placing the test piece in a small tabletop testing machine (manufactured by Shimadzu Corporation, "EZTest / CE"), and conducting a tensile test at room temperature (20°C) (chuck distance 50 mm, tensile speed 100 mm / min). The tensile strength is then determined from the maximum value of the obtained stress-strain (SS) curve.

[0081] 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 even more preferably 100 μm to 250 μm. A thickness of 50 μm or greater increases the amount of trichomes completely covered by the protective layer, making it easier to suppress trichome tilting during molding. Furthermore, a thickness of 600 μm or less can reduce manufacturing costs. The average thickness of the protective layer can be measured directly using a micrometer by removing the protective layer from the laminated resin sheet.

[0082] In this embodiment, the average thickness of the protective layer is greater than the average height of the trichomes. By making the average thickness of the protective layer greater than the average height of the trichomes, the trichomes are completely covered by the protective layer, which can enhance the effect of suppressing the tilting of the trichomes caused by molding.

[0083] The material and method for forming the protective layer are not particularly limited, as long as the material has a tensile modulus of 0.2 MPa or more and less than 2 MPa at 20°C, 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 the trichomes and cured, or a hot-melt film may be laminated to the surface of the resin sheet having the trichomes and heated so that the film conforms to the uneven shape of the trichomes.

[0084] As the silicone-based resin, a peroxide-curable, condensation-curable, addition-curable, ultraviolet-curable, or other silicone-based resin may be used.

[0085] As the hot-melt film, olefin-based, polyamide-based, polyurethane-based, polyester-based or the like hot-melt films can be used.

[0086] Furthermore, the composition serving as the raw material of the protective layer may contain other additives, similarly to the thermoplastic resin composition forming the base layer and the hair-like bodies, within a range that does not inhibit the effects of the present invention.

[0087] <Laminated Resin Sheet>

[0088] The laminated resin sheet in this embodiment comprises a resin sheet body and a protective layer. The resin sheet body has regularly arranged trichomes on at least one surface of a base layer, with the base layer and the trichomes forming a continuous phase with no structural boundary. The protective layer fills the gaps between the trichomes and covers the surface of the resin sheet body on the side having the trichomes. The protective layer has a tensile modulus of elasticity at 20°C of 0.2 MPa or more and less than 2 MPa.

[0089] In one embodiment, the peel strength between the resin sheet body and the protective layer is 0.01 to 0.10 N / mm. The peel strength between the resin sheet body and the protective layer is preferably 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 greater, it is possible to prevent the protective layer from peeling off during molding, resulting in fuzz and poor appearance. Furthermore, by setting the peel strength to 0.10 N / mm or less, it is possible to prevent the protective layer from being left behind after molding, resulting in unpeelable parts, or from the trichomes being deformed after peeling, resulting in poor appearance. The peel strength can be adjusted by selecting the materials for the resin sheet and the protective layer.

[0090] The peel strength between the resin sheet body and the protective layer in a laminated resin sheet can be determined as follows: the laminated resin sheet consisting of the resin sheet body and the protective layer is cut into 25 mm widths, and the resin sheet body is horizontally set with the protective layer facing upward using a 90-degree peeling jig below the clamp of a universal material testing machine. The protective layer peeled from the resin sheet below is clamped above the jig, and the jig holding the protective layer above is stretched in the normal direction of the sheet surface at a tensile speed of 100 mm / minute to perform the measurement.

[0091] In one embodiment of the present invention, the average thickness of the laminated resin sheet refers to the total 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 K7130:1999.

[0092] [Second embodiment]

[0093] As an example of the laminated resin sheet according to the second embodiment of the present invention, Figure 3 The laminated resin sheet shown in FIG. 1 is a laminated resin sheet having a base layer formed on the surface of the base layer opposite to the side having the hair-like bodies. That is, the laminated resin sheet of the second embodiment has a layer structure of, from top to bottom, a protective layer (2), hair-like bodies and a base layer (1), and a base layer (3).

[0094] 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 setting the average thickness of the substrate layer to 1000 μm or less, production costs can be reduced.

[0095] Here, the trichomes and 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, trichomes, 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.

[0096] The substrate layer in the resin sheet of the second embodiment preferably uses a thermoplastic resin that is adhesive to the base layer. For example, the same thermoplastic resin composition as that used for the base layer, a polycarbonate resin, a polyester resin, or a polymer alloy thereof can be preferably 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.

[0097] Here, the polymer alloy resin refers to a high molecular multi-component system, and may be a polymer blend having a certain degree of compatibility through mixing or the like, a block copolymer or graft copolymer based on copolymerization, or a mixture of incompatible resins.

[0098] Examples of polycarbonate resins include resins derived from aliphatic dihydroxy compounds and resins derived from aromatic dihydroxy compounds. For example, compounds derived from aromatic dihydroxy compounds are preferably used, and compounds derived from aromatic dihydroxy compounds (bisphenols) in which two aromatic dihydroxy compounds are bonded via a certain bonding group are particularly preferred. These can be produced by a known method of polycondensation of a dihydroxy compound with phosgene or carbonate, but are not limited to this method, and commercially available resins can also be used.

[0099] As polyester resins, those obtained by copolymerizing polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polymethylene terephthalate, and 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-naphthalene dicarboxylic acid can be used.

[0100] The substrate layer may contain other additives as needed. As other additives, within the scope that does not hinder the effect of the present invention, waterproofing agents, oil repellents, colorants such as pigments and dyes, lubricating materials and release agents such as silicone oils and alkyl esters, fibrous reinforcing agents such as glass fiber, granular particles such as talc, clay, and silicon dioxide as fillers, flaky particles such as mica, low-molecular antistatic agents such as salt compounds of sulfonic acid and alkali metals, polymer antistatic agents such as polyether ester amides, flame retardants, antibacterial agents, antiviral agents, additives such as heat stabilizers, etc. may be added. In addition, waste resins generated in the resin sheet manufacturing process may also be mixed and used. In addition, within the scope that does not damage the effect of the present invention, the substrate layer may partially have a cross-linked structure.

[0101] [Manufacturing of Resin Sheet Body]

[0102] The method for producing the resin sheet body of the present invention is not limited and any method may be employed. Typically, the method includes melt-extruding a raw resin and imparting regularly arranged hairs to at least one surface of the resulting sheet. During production, for example, a feed block or a multi-manifold die may be used. It should be noted that the layer configuration of each embodiment of the resin sheet body is basically as described above. Furthermore, for example, scrap raw materials generated during the production process may be laminated as additional layers, provided that no degradation of physical properties is observed.

[0103] The method for imparting trichomes is not particularly limited, and any method known to those skilled in the art can be used. Examples include methods using extrusion molding, roll-to-roll molding, photolithography, hot pressing, a patterned roll and UV-curable resin, a 3D printer, and methods in which trichomes are embedded in a resin layer and then covalently bonded via polymerization.

[0104] For example, when extrusion molding is used, the resin sheet body can be manufactured by extruding a sheet by a T-die method and casting it using a transfer roll and a touch roll with convex and concave processing so as to give the surface of the sheet a hair-like shape.

[0105] Transfer rollers with irregularities can be used, where fine irregularities ranging in size from several to several hundred μm are regularly applied to the surface of the roller by laser engraving, electroforming, etching, abrasion, or other methods. Regularity here means that the irregularities are not randomly arranged, but rather are arranged in a regular pattern in one or two directions. In certain embodiments, the arrangement of the irregularities can be a checkerboard pattern, a staggered pattern, or the like. Examples of the shape of the irregularities include, for example, concave shapes (cones, square pyramids, triangular pyramids, hexagonal pyramids, etc.), semicircular shapes, and rectangular shapes (quadrangular prisms). The dimensions of the concave openings, depth, and spacing between concave shapes range from several to several hundred μm. Materials for the transfer roller can be metal, ceramic, or the like. Adjusting the spacing of the transfer roller's concave shapes allows for adjustment of the spacing between the hairs, and adjusting the depth of the transfer roller's concave shapes allows for adjustment of the height of the hairs, thereby adjusting the feel.

[0106] Furthermore, the transfer roller surface is preferably processed with high-aspect-ratio concave and convex shapes. For example, the aspect ratio (concave depth / concave opening diameter) when processing the concave shape on the transfer roller surface is preferably 1.0 to 9.0 or 1.0 to 2.0. Laser engraving or electroforming are particularly preferred for processing the transfer roller surface with high-aspect-ratio concave and convex shapes, as they are more suitable for precise processing in the depth direction than etching, sandblasting, or abrasion.

[0107] The transfer roller may be made of, for example, metal or ceramic. The contact roller may be made of a variety of materials, such as silicone rubber, NBR rubber, EPT rubber, butyl rubber, chloroprene rubber, or fluororubber. In one embodiment, a contact roller having a rubber hardness (JIS K6253) of 40 to 100 may be used. A Teflon (registered trademark) layer may also be formed on the surface of the contact roller.

[0108] The touch roller can be made of various materials, such as silicone rubber, NBR rubber, EPT rubber, butyl rubber, chloroprene rubber, or fluororubber. In one embodiment, a touch roller having a rubber hardness (JIS K6253) of 40 to 100 can be used. Alternatively, a Teflon (registered trademark) layer may be formed on the surface of the touch roller.

[0109] The resin sheet main body of this embodiment can be manufactured by using the roller group of the transfer roller and the touch roller.

[0110] In one embodiment, the temperature of the transfer roller is adjusted to a temperature near the crystalline melting temperature, glass transition temperature, or melting point of the thermoplastic resin (for example, 100 to 150°C when using random polypropylene), and the clamping pressure between the transfer roller and the contact roller is set to 30 to 120 kg / cm 2 The resin sheet body of the present embodiment can be manufactured by casting. The casted resin sheet is pulled at a line speed of 0.5 to 30 m / min using a pinch roll or the like.

[0111] [Formation of protective layer]

[0112] The method for forming the protective layer of this embodiment is not particularly limited, and any method known to those skilled in the art can be used. For example, a method including a step of applying a raw material resin for the protective layer to the surface of the manufactured resin sheet body having the hair-like structures, and a method including a step of melting and laminating a raw material resin previously formed into a sheet, can be used.

[0113] [Molded products]

[0114] The molded product of the present embodiment is a molded product using the laminated resin sheet of the present embodiment. The laminated resin sheet of the present embodiment can cope with general molding. As a molding method, in addition to insert molding and in-mold molding, as general vacuum molding, pressure molding and their applications, there can also be cited a method of heating and softening the resin sheet in a vacuum state and opening it under atmospheric pressure to cover (mold) it on the surface of an existing molded product, etc., but it is not limited to these. In addition, as a method of heating and softening the sheet before molding, a well-known sheet heating method such as radiation heating using an infrared heater or the like as non-contact heating can be applied. In the vacuum pressure molding of a certain embodiment, for example, the resin sheet is heated at a surface temperature of 60°C to 220°C for 20 seconds to 480 seconds and then molded into the surface of an existing molded product. Depending on the shape of the surface, it can be stretched to 1.05 to 2.50 times.

[0115] The laminated resin sheet of this embodiment can be used in applications requiring good tactile properties as described above. For example, the laminated resin sheet can be used as an automotive interior material, an electronic device exterior material, or a surface material for cosmetic containers.

[0116] As the automotive interior material, as the part that contacts with the hand in the interior of the car, a steering wheel, an instrument panel, a rod, a switch etc. can be enumerated. For example, the surface of a known instrument panel, a pillar (for example, Japanese Patent Laid-Open Gazette No. 2009-184421) can be enumerated by molding and laminating the above-mentioned resin sheet to form an interior material. By laminating the resin sheet, an interior material having good tactility can be made. As the material of the resin sheet to be laminated, in consideration of light resistance and chemical resistance, preferably olefin resin, vinyl chloride resin, or polyurethane elastomer is used. The method of laminating the resin sheet to the interior material is not particularly limited.

[0117] As electronic equipment exterior materials, transmitter housings, smart phone housings, smart phone housings, music player housings, game console housings, digital camera housings, electronic notepad housings, calculator housings, tablet housings, mobile personal computer housings, keyboards, mice, etc. of keyless entry systems can be cited. For example, a portable transmitter in which the resin sheet of the present invention is molded and bonded to the surface of a portable transmitter frame of a known keyless entry system (e.g., Japanese Patent Publication No. 2005-228911) can be cited. By bonding the resin sheet, a portable transmitter having a good tactile feel can be made. As the material of the resin sheet to be bonded, preferably an olefin resin or a polyurethane elastomer is used. The method of bonding the resin sheet to the housing is not particularly limited.

[0118] Examples of cosmetic containers include containers for face creams, facial masks, foundations, and eye shadows. For example, a cosmetic container can be obtained by molding and laminating the resin sheet of the present invention onto the surface of a lid member of a known foundation container (Japanese Patent Application Laid-Open No. 2017-29608). By laminating the resin sheet, a cosmetic container with a good tactile feel can be produced. The material of the laminated resin sheet is preferably an olefin resin or a polyurethane elastomer. The method of laminating the resin sheet is not particularly limited.

[0119] Furthermore, characters and patterns can be printed on the surface of the trichomes using common printing methods (offset printing, gravure printing, flexographic printing, screen printing, foil pressing, etc.) to produce a trichome sheet suitable for the above-mentioned applications. The material of the printed resin sheet is not particularly limited, but is preferably selected in consideration of the printability of the ink used for printing.

[0120] Alternatively, a laminated body can be produced by laminating (dry lamination or extrusion lamination) the printed material (paper, metal film, etc.) printed with text or patterns, or a nonwoven fabric. For example, the laminated body can be laminated onto the printed surface of a business card to create a tactile business card. The material of the laminated resin sheet is not particularly limited.

[0121] [Example]

[0122] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited in any way by the contents of Examples, etc. In addition, "parts" in the present examples are based on weight.

[0123] Various raw materials and their production methods used in Examples and the like are as follows.

[0124] (1) Trichomes and basal layer

[0125] (A-1) TPU (polyurethane elastomer) "A3086 A17J" (manufactured by BASF)

[0126] (2) Base material layer

[0127] (B-1) PC / polyester "PCX-6694" (manufactured by Sumika Polycarbonate Co., Ltd.)

[0128] (3) Protective layer

[0129] (C-1) Silicone resin "KE-1316" (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0130] + Curing agent "CAT-1316" (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0131] (C-2) Silicone resin "KE-1300T" (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0132] + Curing agent "CAT-1300" (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0133] (C-3) Silicone resin "KE-1314-2" (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0134] + Curing agent "CAT-1314S" (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0135] The evaluation methods for various properties of the resin sheet main body, the laminated resin sheet, and the laminated resin sheet formed products produced in the Examples and Comparative Examples are as follows.

[0136] (1) Average height of trichomes, average diameter of trichomes, average spacing between trichomes, and average thickness of the basal layer

[0137] The height (h), diameter (d), spacing (t) of the trichomes in the resin sheet body, and the thickness of the basal layer were measured using a laser microscope (VK-X100, manufactured by KEYENCE). For the measurements, cross-sections were cut from three random locations on the resin sheet using a microtome. The average trichome height was determined by measuring the heights of 10 trichomes for each sample, and the arithmetic mean of these 30 measurements was used. The average trichome diameter was determined by measuring the diameter at the mid-height (h / 2) of 10 trichomes for each sample, and the arithmetic mean of these 30 measurements was used. The average spacing between trichomes was determined by measuring the distance between the center of the trichome base and the center of the adjacent trichome base at 10 locations for each sample, and the arithmetic mean of these 30 measurements was used. The average thickness of the basal layer was determined by measuring the thickness of each layer at 10 locations for each sample, and the arithmetic mean of these 30 measurements was used. The basal layer thickness refers to the distance from the base of the trichome to the interface with the other layer.

[0138] (2) Physical property evaluation of protective layer

[0139] The tensile modulus and tensile strength of the protective layer were determined as follows: A 12 cm x 2.5 cm test piece of the protective layer (long side in the CMD direction) was cut. The test piece was then placed in a small tabletop testing machine (Shimadzu Corporation, "EZTest / CE") and subjected to a tensile test at room temperature (20°C) (chuck distance 50 mm, tensile speed 100 mm / min). The tensile modulus in the elastic region (slope at 0-4% strain) was then determined from the resulting stress-strain (SS) curve. The point at which the maximum stress was reached was taken as the tensile strength.

[0140] (3) Measurement of peel strength between the resin sheet body and the protective layer

[0141] The peel strength between the resin sheet main body and the protective layer in a laminated resin sheet is determined as follows: the laminated resin sheet consisting of the resin sheet main body and the protective layer is cut into 25 mm widths, and a 90-degree peeling jig (manufactured by Toyo Seiki Co., Ltd., "Strograph VE1D") is installed below a universal testing machine (manufactured by Toyo Seiki Co., Ltd.). The resin sheet main body is horizontally set with the protective layer facing upward, and the protective layer peeled from the resin sheet below is clamped in the upper clamping jig. The clamping jig holding the protective layer above is stretched in the normal direction of the sheet surface at a tensile speed of 100 mm / minute to perform the measurement.

[0142] (4) Operability of the protective layer

[0143] When the protective layer was removed from the laminated resin sheet, it was evaluated as ◯ if it could be peeled off without any problem, and as × if it was cracked or the like and could not be peeled off cleanly.

[0144] (5) Determination of the tilt angle of trichomes

[0145] The angles of the trichomes were measured using a laser microscope (VK-X100, manufactured by KEYENCE) on the resin sheet body before secondary molding and on the resin sheet body after secondary molding of the laminated resin sheet and the protective layer removed. The samples for measurement were obtained by cutting cross-sections from three arbitrary locations on the resin sheet body using a microtome. For each sample, the angles of trichomes were measured for 10 trichomes, and the arithmetic mean of these 30 measured values ​​was used. The angle of the trichomes when the trichomes extend perpendicularly to the basal layer surface was defined as 0°.

[0146] (6) Confirmation of whitening

[0147] Ten external evaluators, five male and five female, evaluated the appearance of the resin sheet before secondary molding and the secondary molded product formed from the laminated resin sheet. A panel of evaluators, including five male and five female, evaluated the differences in color tone when comparing the two, as well as the differences in color tone within the secondary molded product. A panel of evaluators, with no observed differences in either category, was evaluated as "no whitening." A panel of evaluators, with an overall rating of "○," rated "no whitening" if eight or more of the ten panelists rated it "no whitening," a panel of evaluators, with a rating of "△" if four or more and seven or fewer of the ten panelists rated it "no whitening," and a panel of evaluators, with a rating of "×" if three or fewer of the ten panelists rated it "no whitening."

[0148] (7) Good tactile sensory evaluation

[0149] For good tactile properties, the following sensory evaluation was performed: an external panel of 10 people, 5 males and 5 females, was asked to touch the main body of the resin sheet after the protective layer of the laminated resin sheet was peeled off after secondary molding. The specific tactile sensation (smooth, wet, dry, rough, etc.) when touching the surface of the resin sheet main body was evaluated with a full score of 10 points, and the tactile sensation with the highest score was taken as the tactile sensation of the resin sheet surface. In Table 1, "0" indicates that the score for smoothness or wetness is high, and a good tactile sensation like a suede-like raised sheet was obtained after secondary molding. "△" indicates that the score for smoothness or wetness is high, but the tactile sensation with the highest score is reduced by more than 3 points due to secondary molding. "×" indicates that the score for dryness or roughness is high, and a good tactile sensation after secondary molding cannot be obtained.

[0150] (Manufacturing of Laminated Resin Sheet)

[0151] [Examples 1 to 3, Comparative Examples 2 to 4]

[0152] The polyurethane elastomer (A-1) serving as the hair-like body and base layer was introduced from a 40 mm single-screw extruder, and the PC / polyester resin (B-1) serving as the substrate layer was introduced from a 65 mm single-screw extruder. The resulting resin sheet was extruded using a co-extrusion multi-layer T-die method. This was cast using a transfer roller that had been chromium oxide sprayed and laser-engraved, and embossed at 60°C to 150°C, and a silicone rubber touch roller with a rubber hardness of 70 and 10°C to 90°C. The sheet was then pulled using pinch rolls at a line speed of 1 m / min to 15 m / min. This yielded a resin sheet body having the composition, thickness, and surface shape shown in Table 1. Next, any of the silicone resins (C-1) to (C-3) serving as the protective layer was mixed with a curing agent at a ratio of 9:1. The sheet was then spread on the surface of the resin sheet body using a brass rod to form a protective layer having the thickness shown in Table 1, yielding a laminated resin sheet.

[0153] [Comparative Example 1]

[0154] The thermoplastic resin (A-1) serving as the hair-like body and base layer was introduced from a 40 mm single-screw extruder, and the PC / polyester resin (B-1) serving as the substrate layer was introduced from a 65 mm single-screw extruder. The resulting resin sheet was extruded by a co-extrusion multi-layer T-die method. This was cast using a transfer roll that had been chromium oxide spray-coated and laser-engraved, and was conditioned at 60°C to 150°C. It was also cast using a silicone rubber touch roll with a rubber hardness of 70 and conditioned at 10°C to 90°C. The sheet was then pulled using pinch rolls at a linear speed of 1 to 15 m / min. This yielded a resin sheet having the composition, thickness, and surface shape shown in Table 1. No protective layer was formed.

[0155] (Manufacturing of secondary molded products)

[0156] A vacuum compression molding machine ("NGF-0406s" manufactured by Fushigi Vacuum Co., Ltd.) was used to preform the laminated resin sheet under the following conditions to impart a three-dimensional shape. The three-dimensional shape was imparted as follows: a mold for a cover sheet was used, in which a convex shape with a surface having a long side of 200 mm and a short side of 100 mm was gently curved 10 mm from the end to the center. The surface of the laminated resin sheet on the substrate layer side, i.e., the surface opposite to the protective layer, was brought into contact with the convex surface of the mold.

[0157] ·Sheet surface temperature: 100℃~150℃

[0158] Heating time: 40 seconds to 300 seconds

[0159] Mould shape: long side 200mm, short side 100mm

[0160] The laminated resin sheet, which had been given a three-dimensional shape, was then removed from the mold, and the excess material was trimmed. Using an insert molding machine (Sumitomo Heavy Industries, Ltd., "SE315 EV-A-HD"), polycarbonate resin (Mitsubishi Engineering-Plastics, "H3700 UR") was injected under the following conditions to produce a secondary molded product (insert molded product). Insert molding was performed by placing the protective layer side of the laminated resin sheet, which had been given a three-dimensional shape, in contact with the injection mold, and injecting the resin using a side gate method so that the resin flowed into the substrate layer side.

[0161] Mold temperature: 40℃

[0162] Injection resin temperature: 280℃

[0163] Holding pressure: 30MPa

[0164] After cooling, the molded product is removed from the mold and the protective layer is peeled off to obtain the final secondary molded product.

[0165] Table 1 shows the results of evaluation tests on various properties conducted using the resin sheets obtained in the respective Examples and Comparative Examples.

[0166] Table 1

[0167]

[0168] The following can be seen from the results shown in Table 1.

[0169] All the laminated resin sheets of Examples 1 to 3 were able to suppress whitening and loss of tactile feel even when subjected to secondary molding.

[0170] On the other hand, the molded article of the laminated resin sheet of Comparative Example 1 whitened and lost its tactile feel due to secondary molding.

[0171] The molded article of the laminated resin sheet of Comparative Example 2 was whitened and had a loss of tactile feel due to secondary molding.

[0172] The laminated resin sheet molded article of Comparative Example 3 suppressed whitening and loss of tactile feel even after secondary molding. However, the protective layer adhered strongly to the resin sheet body and broke when peeling, preventing clean peeling.

[0173] In the molded article of the laminated resin sheet of Comparative Example 4, the adhesion of the protective layer to the resin sheet body was weak, and the resin sheet body and the protective layer were misaligned during secondary molding, causing whitening.

[0174] While various embodiments have been used to describe the present invention, the technical scope of the present invention is certainly not limited to the scope described in the above embodiments. It is obvious to those skilled in the art that various changes or improvements can be made to the above embodiments. In addition, as can be seen from the description of the claims, modes in which such changes or improvements are made are also included in the technical scope of the present invention.

[0175] Industrial Application Possibilities

[0176] The resin sheet of the present embodiment can suppress whitening and loss of tactile feel even when subjected to secondary molding, and therefore has industrial applicability as a secondary moldable resin sheet and a molded product thereof.

[0177] Explanation of symbols

[0178] 1Trichomes and basal layer

[0179] 1a basal layer

[0180] 1b Trichome

[0181] Trichome diameter

[0182] Trichome height

[0183] tTrichome spacing

[0184] 2 protective layers

[0185] 3 base material layer

Claims

1. A laminated resin sheet comprising: a resin sheet body having regularly arranged trichomes on at least one surface of a base layer, wherein the base layer and the trichomes form a continuous phase with no structural boundary; and a protective layer that fills gaps between the trichomes and covers the surface of the resin sheet body on the side having the trichomes. in, The tensile modulus of elasticity 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 trichomes.

2. The laminated resin sheet according to claim 1, wherein The peel strength between the resin sheet main body and the protective layer is 0.01 to 0.10 N / mm.

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

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

5. The laminated resin sheet according to claim 1 or 2, wherein When the angle of the trichomes when the trichomes extend perpendicularly to the surface of the basal layer is defined as 0°, the average value of the angle increased by heat molding is 0° to 10°.

6. The laminated resin sheet according to claim 1 or 2, wherein The average height of the trichomes is 30 μm to 500 μm, the average diameter of the trichomes is 1 μm to 50 μm, and the average interval between the trichomes is 20 μm to 200 μm.

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

8. A method for producing a laminated resin sheet, the method for producing a laminated resin sheet according to claim 1 or 2, comprising: A protective layer is formed on the surface of the resin sheet main body on the side having the hairs.

9. A molded article of 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 provided on the surface of an automobile interior material, an electronic device exterior material, or a cosmetic container.

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