Fiber-reinforced resin sheet, and curtain, roll blind, and tonneau cover using the same

Abstract

To provide a fiber-reinforced resin sheet which has flexibility, is resistant to light transmission through gaps in the weave or the like, and can retain the aesthetic quality and stereoscopic effect of the weave or the like.SOLUTION: A fiber-reinforced resin sheet includes a fiber assembly containing reinforcing fibers, and a thermoplastic polyurethane resin composition impregnated into at least one surface of the fiber assembly. The thermoplastic polyurethane resin composition includes a thermoplastic polyurethane resin and at least one colorant selected from the group consisting of gray colorants and black colorants.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a fiber-reinforced resin sheet and a curtain, roller blind, and tonneau cover using the same.

Background Art

[0002] Conventionally, as a fiber-reinforced plastic, a fiber-reinforced resin sheet including a fabric made of reinforcing fibers and a resin composition (matrix resin) impregnated in the fabric is known.

[0003] As such a fiber-reinforced resin sheet, for example, Patent Document 1 discloses a carbon fiber-reinforced resin processing sheet including a carbon fiber cloth and a polyurethane-based thermoplastic elastomer film or a rubber film laminated on both sides thereof.

[0004] Further, Patent Document 2 discloses a fiber-reinforced resin sheet including a fiber aggregate containing reinforcing fibers and a thermoplastic polyurethane resin composition impregnated on at least one surface thereof.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] The fiber-reinforced resin sheet as described above not only has high strength but also has appropriate flexibility. Further, it is expected that the fiber-reinforced resin sheet can exhibit high designability due to the aesthetics and three-dimensional effect of the fabric texture. Therefore, it is expected that the fiber-reinforced resin sheet can be applied to curtains, roller blinds, tonneau covers, and the like.

[0007] However, in conventional fiber-reinforced resin sheets, light easily passes through the gaps between the weaves, and the aesthetic appearance and three-dimensional effect of the weaves are easily impaired. Therefore, there has been a problem that it is difficult to obtain high design quality.

[0008] The present invention has been made in view of the above circumstances, and provides a fiber-reinforced resin sheet that has flexibility, is difficult for light to pass through gaps such as weaves, and can satisfactorily maintain the aesthetic appearance and three-dimensional effect of the weaves, as well as a curtain, a roller blind, and a tonneau cover using the same.

Means for Solving the Problems

[0009] The above problems can be solved by the following configuration.

[0010] [1] A fiber-reinforced resin sheet including a fiber aggregate containing reinforcing fibers and a thermoplastic polyurethane resin composition impregnated on at least one surface of the fiber aggregate, wherein the thermoplastic polyurethane resin composition contains a thermoplastic polyurethane resin and at least one colorant selected from the group consisting of a gray colorant and a black colorant. [2] The fiber-reinforced resin sheet according to [1], wherein the content of the colorant in the thermoplastic polyurethane resin composition is 0.1% by mass or more and 20% by mass or less based on the total mass of the thermoplastic polyurethane resin and the colorant. [3] The fiber-reinforced resin sheet according to [1] or [2], including the thermoplastic polyurethane resin composition impregnated on one surface of the fiber aggregate and a second thermoplastic polyurethane resin composition impregnated on the other surface of the fiber aggregate and substantially free of the colorant. [4] A curtain including the fiber-reinforced resin sheet according to any one of [1] to [3]. [5] A roller blind including the fiber-reinforced resin sheet according to any one of [1] to [3]. [6] A tonneau cover including the fiber-reinforced resin sheet according to any one of [1] to [3].

Effects of the Invention

[0011] According to the present invention, it is possible to provide a fiber-reinforced resin sheet that has flexibility, is difficult for light to pass through gaps such as weave patterns, and can maintain a good aesthetic appearance and three-dimensional effect of the weave patterns and the like.

Brief Description of the Drawings

[0012]

Figure 1

Embodiments for Carrying Out the Invention

[0013] Hereinafter, a fiber-reinforced resin sheet according to an embodiment of the present invention will be described in detail.

[0014] The present inventors have found that by impregnating at least one surface of a fiber aggregate with a thermoplastic polyurethane resin composition containing a gray or black colorant, while maintaining the flexibility of the fiber aggregate, it is possible to make it difficult for light to pass through the gaps in the weave pattern and to maintain a good aesthetic appearance and three-dimensional effect of the weave pattern and the like. Such a fiber-reinforced resin sheet has good flexibility and high design quality, and is therefore suitable for, for example, curtains, roller blinds, tone covers, and the like. Hereinafter, the configuration of the fiber-reinforced resin sheet will be specifically described.

[0015] 1. Fiber-reinforced resin sheet The fiber-reinforced resin sheet includes a fiber aggregate containing reinforcing fibers and a thermoplastic polyurethane resin composition (first thermoplastic polyurethane resin composition) colored in gray or black and impregnated on at least one surface of the fiber aggregate.

[0016] The above-described thermoplastic polyurethane resin composition may be impregnated only on one surface of the fiber aggregate of the reinforcing fibers, or may be impregnated on both surfaces. When the above-mentioned thermoplastic polyurethane resin composition is impregnated on both surfaces of the fiber aggregate of the reinforcing fiber, the composition and physical properties of the thermoplastic polyurethane resin composition impregnated on one surface and the composition and physical properties of the thermoplastic polyurethane resin composition impregnated on the other surface may be the same or different. When the above-mentioned thermoplastic polyurethane resin composition is impregnated only on one surface of the fiber aggregate of the reinforcing fiber, the other surface of the fiber aggregate may be impregnated with, for example, a transparent thermoplastic polyurethane resin composition (second thermoplastic polyurethane resin composition).

[0017] Figure 1 is a schematic cross-sectional view showing a fiber-reinforced resin sheet according to an embodiment of the present invention. As shown in Figure 1, the fiber-reinforced resin sheet 10 includes a fiber aggregate 11 containing reinforcing fibers, a thermoplastic polyurethane resin composition 12 impregnated on one surface thereof, and a second thermoplastic polyurethane resin composition 13 impregnated on the other surface. Hereinafter, each component will be specifically described.

[0018] 1-1. Fiber aggregate 11 The fiber aggregate contains reinforcing fibers. Examples of the reinforcing fibers include carbon fibers, glass fibers, aramid fibers, alumina fibers, silicon carbide fibers, boron fibers, metal fibers, and cellulose nanofibers. One type of reinforcing fiber may be used, or two or more types may be used in combination. Among them, the reinforcing fiber preferably contains carbon fibers, glass fibers or aramid fibers, more preferably contains carbon fibers or aramid resin from the viewpoint of further increasing the strength of the fiber aggregate, and even more preferably contains carbon fibers from the viewpoint of further enhancing the designability in addition to the strength.

[0019] Examples of the carbon fibers include pitch-based carbon fibers, polyacrylonitrile (PAN)-based carbon fibers, and rayon-based carbon fibers. PAN-based carbon fibers are preferred as the carbon fibers. Note that the fiber material may further contain fibers other than the reinforcing fibers.

[0020] The form of the fiber assembly is not particularly limited, and examples include woven fabrics, knitted fabrics, felts, non-woven fabrics, and unidirectional materials. From the viewpoint of enhancing the designability and bending resilience, woven fabrics are preferred.

[0021] The type of woven fabric is also not particularly limited, and examples include plain weave, twill weave, damask weave, gauze twill weave, and checkered weave. Also, as the type of woven fabric, for example, uniaxial weaving and multiaxial weaving are also included. Among them, from the viewpoint of enhancing the designability and the adhesive force with the thermoplastic polyurethane resin composition, plain weave or twill weave is preferred, and from the viewpoint of further enhancing the adhesive force and improving the peel resistance, plain weave is more preferred. In particular, in the fiber-reinforced resin sheet impregnated with the thermoplastic polyurethane resin composition containing the black or gray colorant described later in the plain weave carbon fiber woven fabric, the adhesive force is more excellent.

[0022] The basis weight of the woven fabric is not particularly limited, but for example, 50 g / m 2 or more and 1000 g / m 2 or less, preferably 100 g / m 2 or more and 400 g / m 2 or less. When the basis weight is 1000 g / m 2 or less, the flexibility of the fiber-reinforced resin sheet can be further enhanced. When the basis weight is 50 g / m 2 or more, the strength of the fiber-reinforced resin sheet can be further enhanced, or the light can be made less likely to pass through the gaps such as the weave.

[0023] The thickness of the fiber assembly is, for example, 50 μm or more and 1000 μm or less, preferably 100 μm or more and 500 μm or less.

[0024] The fiber assembly is formed by shaping a fiber material containing reinforcing fibers into a sheet form by a known method.

[0025] 1-2. Thermoplastic polyurethane resin composition 12 The thermoplastic polyurethane resin composition 12 is a thermoplastic polyurethane resin composition colored in gray or black. The above thermoplastic polyurethane resin composition contains a thermoplastic polyurethane resin and one or more colorants selected from the group consisting of a gray colorant and a black colorant.

[0026] 1-2-1. Thermoplastic Polyurethane Resin The thermoplastic polyurethane resin is a reaction product obtained by reacting a composition containing a polyisocyanate component and a polyol component.

[0027] (Polyisocyanate Component) The polyisocyanate component may be any of an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and an araliphatic polyisocyanate.

[0028] Examples of the aliphatic polyisocyanate include aliphatic diisocyanates such as ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), and hexamethylene diisocyanate (HDI).

[0029] Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanates and polycyclic alicyclic polyisocyanates. The monocyclic alicyclic polyisocyanate is a polyisocyanate monomer containing one alicyclic ring in one molecule. Examples of the monocyclic alicyclic polyisocyanate include monocyclic alicyclic diisocyanates such as 1,4-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, and isophorone diisocyanate. The polycyclic alicyclic polyisocyanate is a polyisocyanate monomer containing two or more alicyclics in one molecule. Examples of the polycyclic alicyclic polyisocyanate include polycyclic alicyclic diisocyanates such as norbornene diisocyanate and methylene bis(cyclohexyl isocyanate).

[0030] Examples of the aromatic polyisocyanate include aromatic diisocyanates such as diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), toluidine diisocyanate (TODI), paraphenylene diisocyanate, and naphthalene diisocyanate (NDI).

[0031] Examples of the araliphatic polyisocyanate include araliphatic diisocyanates such as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI).

[0032] Among them, from the viewpoint of obtaining a fiber-reinforced resin sheet having excellent mechanical strength, the polyisocyanate component preferably contains an alicyclic polyisocyanate, and more preferably contains a monocyclic alicyclic polyisocyanate. The monocyclic alicyclic polyisocyanate is preferably 1,4-bis(isocyanatomethyl)cyclohexane and / or 1,3-bis(isocyanatomethyl)cyclohexane, and more preferably 1,4-bis(isocyanatomethyl)cyclohexane.

[0033] 1,4-Bis(isocyanatomethyl)cyclohexane is classified into cis-1,4-bis(isocyanatomethyl)cyclohexane (also referred to as "cis 1,4 form") and trans-1,4-bis(isocyanatomethyl)cyclohexane (also referred to as "trans 1,4 form"). The total amount of the trans 1,4 form and the cis 1,4 form is 100 mol%.

[0034] 1,4-Bis(isocyanatomethyl)cyclohexane preferably contains the trans-1,4 isomer. The content ratio of the trans-1,4 isomer is, for example, 60 mol% or more and 99.5 mol% or less, preferably 70 mol% or more and 99 mol% or less, more preferably 75 mol% or more and 96 mol% or less, still more preferably 80 mol% or more and 90 mol% or less, based on the total moles of 1,4-bis(isocyanatomethyl)cyclohexane. When the content ratio of the trans-1,4 isomer is at least the lower limit, higher heat resistance can be obtained.

[0035] When the polyisocyanate component contains a monocyclic alicyclic polyisocyanate, the content of the monocyclic alicyclic polyisocyanate is, for example, more than 50 mol%, preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, particularly preferably 100 mol%, based on the total amount of the polyisocyanate component.

[0036] (Polyol component) The polyol component is a compound containing two or more hydroxyl groups in the molecule. Examples of the polyol component include low molecular weight polyols and macropolyols.

[0037] The low molecular weight polyol is an organic compound having two or more hydroxyl groups in the molecule and a relatively low molecular weight. The molecular weight of the low molecular weight polyol is, for example, 40 or more and less than 400, preferably 40 or more and less than 300.

[0038] Examples of the low molecular weight polyol include dihydric alcohols, trihydric alcohols, and tetrahydric or higher alcohols. Examples of the dihydric alcohol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and dipropylene glycol. Examples of the trihydric alcohol include glycerin and trimethylolpropane. Examples of the tetrahydric or higher alcohol include pentaerythritol and diglycerin. The low molecular weight polyol also includes a polymer obtained by addition polymerization of an alkylene (C2-3) oxide to a di- to tetravalent alcohol so that the number average molecular weight is less than 400.

[0039] Preferred examples of these low molecular weight polyols include dihydric alcohols and trihydric alcohols, and more preferred examples include dihydric alcohols.

[0040] The macropolyol has two or more hydroxyl groups in the molecule and is a relatively high molecular weight organic compound. The number average molecular weight of the macropolyol is, for example, 400 or more and 5000 or less, preferably 500 or more and 3000 or less, and more preferably 500 or more and 2200 or less. When the number average molecular weight of the macropolyol is below the upper limit value, the transparency and design properties of the fiber-reinforced resin sheet can be further enhanced. The average functional group number (average hydroxyl group number) of the macropolyol is, for example, 2 or more and 6 or less, preferably 2 or more and 4 or less, and more preferably 2 or more and 3 or less.

[0041] Examples of the macro polyol include polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, and vinyl monomer-modified polyol. Preferred examples of the macro polyol include polyether polyol, polyester polyol, and polycarbonate polyol.

[0042] Examples of the polyether polyol include polyoxyalkylene polyol. Examples of the polyoxyalkylene polyol include polyoxyalkylene (C2-3) polyol and polytetramethylene ether polyol.

[0043] Examples of the polyester polyol include condensation polyester polyol and ring-opening polyester polyol. Examples of the condensation polyester polyol include adipate-based polyester polyol and phthalate-based polyester polyol. Examples of the ring-opening polyester polyol include lactone-based polyester polyol.

[0044] Examples of the polycarbonate polyol include ring-opening polymers of ethylene carbonate using the above low molecular weight polyol as an initiator.

[0045] From the viewpoint of heat resistance, polyether polyol is preferred as the macro polyol, and from the viewpoint of weather resistance, polycarbonate polyol is preferred.

[0046] In addition, the macro polyol can also be classified into crystalline macro polyol and amorphous macro polyol. The crystalline macro polyol is a solid macro polyol at 25°C. The amorphous macro polyol is a liquid macro polyol at 25°C.

[0047] The macro polyol preferably contains an amorphous macro polyol. Thereby, the flexibility and the bending restorability of the fiber reinforced resin sheet can be further enhanced.

[0048] One or more polyol components can be used in combination. As the polyol component, preferably, a combination of a low molecular weight polyol and a macro polyol is mentioned.

[0049] When a low molecular weight polyol and a macro polyol are used in combination, their content ratios can be appropriately set according to the purpose and application. For example, it is preferable to use a low molecular weight polyol and a macro polyol in combination so that the hard segment concentration and the urethane group concentration of the thermoplastic polyurethane resin are within the ranges described later.

[0050] Specifically, the content ratio of the macro polyol can be, for example, 10 mol% or more and 80 mol% or less, preferably 20 mol% or more and 65 mol% or less, based on the total amount of the macro polyol and the low molecular weight polyol. If the content ratio of the macro polyol is within the above range, the heat resistance, weather resistance, flexibility, and bending restorability of the fiber reinforced resin sheet can be further enhanced.

[0051] (Physical properties of thermoplastic polyurethane resin) The hard segment concentration of the thermoplastic polyurethane resin is not particularly limited, but is, for example, 5 mass% or more and 60 mass% or less, preferably 8 mass% or more and 55 mass% or less, more preferably 11 mass% or more and 50 mass% or less, and still more preferably 15 mass% or more and 40 mass% or less. If the hard segment concentration of the thermoplastic polyurethane resin is within the above range, the strength of the fiber reinforced resin sheet can be further enhanced.

[0052] The urethane group concentration of the thermoplastic polyurethane resin is not particularly limited. For example, it is 1.0 mmol / g or more and 8.0 mmol / g or less, preferably 1.5 mmol / g or more and 4.5 mmol / g or less, more preferably 1.7 mmol / g or more and 3.4 mmol / g or less, and even more preferably 2.5 mmol / g or more and 3.0 mmol / g or less. If the urethane group concentration of the thermoplastic polyurethane resin is within the above range, the strength of the fiber-reinforced resin sheet can be further increased. The urethane group concentration can be calculated by a known method based on the formulation (charge) of each component.

[0053] The thermoplastic polyurethane resin preferably satisfies the following formula (1). The following formula (1) indicates the crystallinity of the thermoplastic polyurethane resin. The lower the value of the following formula (1), the lower the crystallinity and the easier it is to have relatively high flexibility. Also, it is less likely to generate wrinkles due to bending, and the bending recovery property is also relatively likely to be high. Formula (1): 0 < [Heat generation amount (mJ / mg) of the recrystallization peak of urethane groups / Heat generation section (°C)] < 0.85

[0054] The heat generation amount of the recrystallization peak represented by formula (1) is more than 0 and 0.85 or less, preferably 0.01 or more and 0.45 or less, and more preferably 0.02 or more and 0.20 or less. If the value of formula (1) is within the above range, the flexibility and bending recovery property of the reinforced fiber resin sheet can be further increased.

[0055] In differential scanning calorimetry (DSC measurement), after heating up to 270 °C, among the peaks that appear during cooling, the exothermic peak (recrystallization peak) at 50 °C or more and 180 °C or less is defined as the recrystallization peak of urethane groups, and the peak width is defined as the heat generation section (°C). Also, the heat amount (enthalpy change) (mJ / mg) at the recrystallization peak is defined as the heat generation amount of the recrystallization peak.

[0056] (Synthesis method) As described above, the thermoplastic polyurethane resin can be obtained by reacting a polyisocyanate component and a polyol component. Examples of the reaction method include the one-shot method and the prepolymer method, and the prepolymer method is preferred.

[0057] In the prepolymer method, first, a polyisocyanate component and a macro polyol are polymerized by a known polymerization method to obtain an isocyanate group-terminated prepolymer (prepolymer synthesis step), and then, a thermoplastic polyurethane elastomer can be obtained by reacting the isocyanate group-terminated prepolymer with a chain extender (chain extension step).

[0058] The compounding ratio of the polyisocyanate component and the macro polyol in the prepolymer synthesis step is adjusted so that the isocyanate groups of the polyisocyanate component are in excess with respect to the hydroxyl groups of the macro polyol. Specifically, the equivalent ratio of the isocyanate groups in the polyisocyanate component to the hydroxyl groups in the macro polyol (isocyanate group / hydroxyl group) is, for example, 1.5 or more and 10 or less, preferably 1.8 or more and 7 or less, more preferably 2 or more and 5 or less, and still more preferably 2.5 or more and 4.5 or less.

[0059] In the chain extension step, the chain extender preferably contains a low molecular weight polyol. The compounding ratio of the isocyanate group-terminated prepolymer and the chain extender is set as appropriate. The equivalent ratio of the isocyanate groups in the isocyanate group-terminated prepolymer to the hydroxyl groups of the chain extender (low molecular weight polyol) (isocyanate group / hydroxyl group) is, for example, 0.75 or more and 1.3 or less, preferably 0.9 or more and 1.2 or less.

[0060] 1-2-2. Colorant The thermoplastic polyurethane resin composition contains at least one colorant selected from the group consisting of a gray colorant and a black colorant.

[0061] Examples of the black colorant include inorganic black pigments such as carbon black and iron black, and organic black pigments such as aniline black. Examples of the gray colorant include a mixture of the above-described black pigment and white pigments such as titanium oxide, barium sulfate, and zinc oxide. Note that the gray pigment is a color in which the lightness index increases when the colorant is contained in an amount of 0.1% by mass or more based on the total amount of the thermoplastic polyurethane resin and the colorant. For example, it means a color such that the lightness index L * falls within the range described later.

[0062] The content of the colorant in the thermoplastic polyurethane resin composition is not particularly limited as long as it can impart sufficient light-shielding properties to the fiber-reinforced resin sheet, but it is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, and preferably 0.2% by mass or more and 4.0% by mass or less, based on the total amount of the thermoplastic polyurethane resin and the colorant. Further, when the colorant is a gray colorant, it is preferably 0.5% by mass or more and 3.5% by mass or less. When the colorant is a black colorant, it is preferably 0.25% by mass or more and 2.0% by mass or less. When the content of the colorant is 0.1% by mass or more, for example, it becomes more difficult for light to pass through gaps such as the texture of the fiber-reinforced resin sheet, and the aesthetic appearance and three-dimensional feeling of the fiber aggregate can be further enhanced. When the content of the colorant is 20% by mass or less, the fiber-reinforced resin sheet is less likely to become hard and can maintain flexibility better. Also, the adhesiveness with the thermoplastic polyurethane resin composition can be maintained better.

[0063] 1-2-3. Other Components The thermoplastic polyurethane resin composition can contain other components other than the above as needed. Examples of the other components include antioxidants, heat stabilizers, ultraviolet absorbers, weather stabilizers, light stabilizers, antiblocking agents, release agents, pigments, dyes, lubricants, fillers, hydrolysis inhibitors, rust preventives, and bluing agents. The content of the other components may be, for example, 1% by mass or less based on the thermoplastic polyurethane resin composition.

[0064] 1-2-4. Physical properties As described above, the thermoplastic polyurethane resin composition is a thermoplastic polyurethane resin composition colored gray or black, and when made into a film with a thickness of 150 μm, the color is in an expressed state. For example, as described later, the lightness index (L * ) is preferably such that it is more than 15 and 60 or less in the case of gray and 15 or less in the case of black as defined in JIS Z 8781-4:2013. By impregnating a fiber assembly with a film of such a thermoplastic polyurethane resin composition, it is possible to further improve the light-shielding property while maintaining the flexibility of the obtained fiber-reinforced resin sheet. The hue of the thermoplastic polyurethane resin composition can be adjusted by the type and content of the colorant.

[0065] The impregnation layer thickness of the thermoplastic polyurethane resin composition with respect to the fiber assembly is not particularly limited, but is, for example, 5 μm or more and 75 μm or less, preferably 10 μm or more and 70 μm or less. When the impregnation layer thickness of the thermoplastic polyurethane resin composition is 5 μm or more, the adhesive force between the fabric and the thermoplastic polyurethane resin composition can be further increased. When the impregnation layer thickness of the thermoplastic polyurethane resin composition is 75 μm or less, the fiber-reinforced resin sheet is less likely to become hard and the flexibility can be more easily maintained.

[0066] The impregnation layer thickness of the thermoplastic polyurethane resin composition can be measured by analyzing an image obtained by a scanning electron microscope observation method or an X-ray CT method.

[0067] 1-3. Second thermoplastic polyurethane resin composition 13 The second thermoplastic polyurethane resin composition 13 is a thermoplastic polyurethane resin composition that is not colored gray or black, and is preferably a transparent thermoplastic polyurethane resin composition. A transparent thermoplastic polyurethane resin composition is a thermoplastic polyurethane resin composition that, when formed into a film with a thickness of 150 μm, has a light transmittance of, for example, 80% or more, preferably 90% or more. By impregnating the other surface of the fiber aggregate with the transparent thermoplastic polyurethane resin composition, the aesthetic appearance and three-dimensional effect of a woven fabric or the like can be maintained more favorably.

[0068] Such a second thermoplastic polyurethane resin composition can be configured in the same or similar manner as the above-described thermoplastic polyurethane resin composition, except that it does not substantially contain a gray or black colorant. "Not substantially containing" means that the content of the above colorant is less than 0.1% by mass, preferably 0.01% by mass or less, based on the total amount of the thermoplastic polyurethane resin and the colorant.

[0069] The impregnation layer thickness of the second thermoplastic polyurethane resin composition with respect to the fiber aggregate may also be the same or similar to the impregnation layer thickness of the thermoplastic polyurethane resin composition.

[0070] 1-4. Physical properties of the fiber-reinforced resin sheet (Light-shielding property) The light-shielding rate of the fiber-reinforced resin sheet is not particularly limited, but is preferably, for example, 99.80% or more, and more preferably 99.99% or more. When the light-shielding rate of the fiber-reinforced resin sheet is within the above range, it is suitable for, for example, roller blinds and curtains. The light-shielding rate of the fiber-reinforced resin sheet can be measured in accordance with the JIS L 1055A method "Test method for light-shielding property of curtains". The measurement conditions are the same as those in the examples described later.

[0071] The light-shielding rate of the fiber-reinforced resin sheet can be adjusted by the type and content of the colorant in the thermoplastic polyurethane resin composition. For example, the light-shielding rate can be further adjusted by using a black colorant as the colorant or increasing the content of the colorant in the thermoplastic polyurethane resin composition.

[0072] (Rigidity-flexibility) The rigidity-flexibility measured by the slide method in accordance with JIS L 1096 (2020) of the fiber-reinforced resin sheet preferably has a δ value exceeding 10 mm, more preferably 20 mm or more and 40 mm or less. When the δ value exceeds 10 mm, the flexibility of the fiber-reinforced resin sheet can be made higher, and for example, the winding property when applied to a roller blind, a tonneau cover, etc. can be further improved.

[0073] The rigidity-flexibility can be measured using a testing machine described in "8.21.2 Method B (slide method)" of JIS L 1096 (2020) with respect to a test piece of 150 mm × 20 mm, set so that l = 100.

[0074] The rigidity-flexibility of the fiber-reinforced resin sheet can be adjusted, for example, by the composition of the thermoplastic polyurethane resin composition (content of coloring agent, type of resin, etc.) and the impregnation layer thickness. When the content of the coloring agent in the thermoplastic polyurethane resin composition is reduced or the impregnation layer thickness is reduced, the rigidity-flexibility of the fiber-reinforced resin sheet tends to increase.

[0075] 2. Method for manufacturing fiber-reinforced resin sheet The above-described reinforced fiber resin sheet can be manufactured through a step of impregnating at least one surface of the fiber aggregate of the reinforcing fiber with the above-described thermoplastic polyurethane resin composition. The method for impregnating the thermoplastic polyurethane resin composition is not particularly limited, and for example, a method of thermocompression bonding a film of the thermoplastic polyurethane resin composition and a fiber aggregate of the reinforcing fiber is preferable.

[0076] For example, the fiber-reinforced resin sheet of FIG. 1 can be manufactured through 1) a step of preparing a film of a thermoplastic polyurethane resin composition and a film of a second thermoplastic polyurethane resin composition, and 2) a step of laminating the film of the thermoplastic polyurethane resin composition on one surface of the fiber aggregate of the reinforcing fiber and laminating the film of the second thermoplastic polyurethane resin composition on the other surface, followed by thermocompression bonding.

[0077] 2-1. Step of preparing the film The thermoplastic polyurethane resin composition can be formed into a film by, for example, a known method. Examples of the forming method include a hot compression molding method, an injection molding method, and an extrusion molding method, and preferably an extrusion molding method.

[0078] In the extrusion molding method, for example, pellets containing a thermoplastic polyurethane resin and pellets containing a black or gray colorant (for example, a masterbatch) are prepared. After these pellets are dry-blended as necessary, they are melted by an extrusion molding machine and extruded into a film. Thereby, a film of the thermoplastic polyurethane resin composition can be obtained.

[0079] The pellets of the thermoplastic polyurethane resin as a raw material are preferably heat-treated as necessary. The heat treatment temperature is, for example, 50°C or higher and 200°C or lower, preferably 80°C or higher and 150°C or lower. The heat treatment time is, for example, 30 minutes or longer and 30 hours or shorter, preferably 1 hour or longer and 20 hours or shorter.

[0080] In addition, after preparing pellets of the thermoplastic polyurethane resin composition containing a thermoplastic polyurethane resin and a colorant, these may be extruded to obtain a film.

[0081] Further, the obtained film of the thermoplastic polyurethane resin composition may be cured as necessary. The curing temperature can be, for example, 10°C or higher and 50°C or lower, preferably 20°C or higher and 40°C or lower. The curing time is, for example, 1 hour or longer, preferably 10 hours or longer.

[0082] The thicknesses of the film of the thermoplastic polyurethane resin composition and the film of the second thermoplastic polyurethane resin composition are preferably thinner than the thickness of the fiber aggregate. This is to make it less likely to impair flexibility, the aesthetics such as the texture, and the three-dimensional feeling. Also, the thicknesses of the film of the thermoplastic polyurethane resin composition and the film of the second thermoplastic polyurethane resin composition may be the same or different. The thicknesses of the film of the thermoplastic polyurethane resin composition and the film of the second thermoplastic polyurethane resin composition are each, for example, 50 μm or more and 1000 μm or less, preferably 100 μm or more and 500 μm or less.

[0083] The value of the lightness index (L * ) of the film of the thermoplastic polyurethane resin composition containing a gray colorant is, for example, more than 15 and 60 or less, preferably 41 or more and 56 or less. The value of the lightness index (L * ) of the film of the thermoplastic polyurethane resin composition containing a black colorant is, for example, 15 or less, preferably 13 or less.

[0084] 2-2. Step of thermocompression bonding Next, the film of the thermoplastic polyurethane resin composition and the fiber aggregate of the reinforcing fiber are thermocompression bonded. The thermocompression bonding can be carried out using a known heating and pressure bonding device such as an autoclave device or a hot press device. In particular, autoclave molding is suitable for obtaining a fiber-reinforced resin sheet with uniform impregnation and excellent appearance because isobaric pressing can be performed.

[0085] The thermocompression bonding conditions are appropriately set according to the purpose and use. The pressing pressure is, for example, 0.1 MPa or more and 5.0 MPa or less, preferably 0.5 MPa or more and 2.5 MPa or less. Also, the heating temperature is, for example, 100 °C or more and 300 °C or less, preferably 140 °C or more and 240 °C or less. Also, the pressing time and the heating time are, for example, 0.5 minutes or more and 180 minutes or less, preferably 1 minute or more and 120 minutes or less.

[0086] Also, the thermocompression bonding may be performed in a normal pressure environment or a reduced pressure environment (including a vacuum environment), but it is preferably performed in a reduced pressure environment. This is because, in a reduced pressure environment, the generation of bubbles in the fiber-reinforced resin sheet can be more effectively suppressed. Further, after the thermocompression bonding, heating may be performed without applying pressure as needed. At this time, heating may also be performed under reduced pressure. Thereby, the adhesive force between the fiber aggregate and the film of the thermoplastic polyurethane resin composition can be further increased.

[0087] Thereby, while melting the thermoplastic polyurethane resin composition, it is impregnated into the fiber aggregate of the reinforcing fibers. Thereby, the thermoplastic polyurethane resin composition can penetrate to a predetermined depth from one side to the other side in the thickness direction of the fiber aggregate of the reinforcing fibers. Note that the inside of the fiber aggregate of the reinforcing fibers may or may not be impregnated with the thermoplastic polyurethane resin composition. From the viewpoints of flexibility and bending recovery property, it is preferable that the inside of the fiber aggregate of the reinforcing fibers is not impregnated with the thermoplastic polyurethane resin composition. The impregnation state of the thermoplastic polyurethane resin composition can be confirmed, for example, by observing a cross section of the fiber-reinforced resin sheet by a scanning electron microscope observation method or an X-ray CT method.

[0088] 3. Use The above fiber-reinforced resin sheet can be used for various applications. Examples of the applications of the fiber-reinforced resin sheet include ornaments, vehicle supplies (e.g., various interior materials such as automobile seats, armrests, door trims, instrument panels, steering wheel covers, ceiling materials, seats in aircraft and railway carriages), furniture supplies (e.g., door handles, chairs, beds, storage shelves, lamp shades), sports supplies (e.g., shoes, various grips, golf bags, horse gear, surface materials for balls (e.g., soccer balls, baseballs, basketballs, volleyballs, tennis balls, etc.)), daily necessities (e.g., wallets, business card holders, small item cases, bags, belts, watch bands, brims of hats, spectacle cases, spectacle frames, grips for various pens, floor mats, lunch mats, tablecloths, smartphone covers, notebook PC casings, mouse pads for PCs) or leisure supplies (tents, parasols, awnings, benches), etc. Among these, the fiber-reinforced resin sheet is preferably used for curtains, roll blinds, tone covers, etc. because it maintains flexibility, is difficult to transmit light through gaps such as weave patterns, and has high design quality.

[0089] That is, the curtain according to an embodiment of the present invention includes the above fiber-reinforced resin sheet. Specifically, the curtain includes a fiber aggregate containing reinforcing fibers and a thermoplastic polyurethane resin composition impregnated on at least one surface thereof.

[0090] Also, the roll blind according to an embodiment of the present invention includes the above fiber-reinforced resin sheet. Specifically, the roll blind includes a fiber aggregate containing reinforcing fibers and a thermoplastic polyurethane resin composition impregnated on at least one surface thereof. Such a roll blind not only has good winding property due to having the above-described flexibility but also has sufficient light-shielding property.

[0091] In addition, the toner cover according to an embodiment of the present invention includes the above fiber-reinforced resin sheet. Specifically, the toner cover includes a fiber aggregate containing reinforcing fibers and a thermoplastic polyurethane resin composition impregnated on at least one surface thereof. Such a toner cover not only has excellent handleability due to the flexibility described above, but also has sufficient light-shielding properties and design properties due to the texture of the reinforcing fibers.

Examples

[0092] Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples. The technical scope of the present invention is not limited by these.

[0093] 1. Preparation of thermoplastic polyurethane resin composition 1-1. Materials 1-1-1. Thermoplastic polyurethane resin (Raw materials) · Polyisocyanate (A) 1,4-H6XDI: 1,4-bis(isocyanatomethyl)cyclohexane obtained according to the description of Production Example 3 in International Publication WO2019 / 069802 The purity of 1,4-H6XDI was measured by gas chromatography. The purity was 99.9%. Also, the hue was measured by APHA measurement. The hue was 5. Also, 13 The trans and cis isomer ratios were measured by C-NMR measurement. The trans isomer was 86 mol% and the cis isomer was 14 mol%. · Macropolyol (B) UP-100: Amorphous polycarbonate diol (manufactured by Ube Industries, Ltd., UP-100, number average molecular weight (Mn) 10000, average number of hydroxyl groups 2) · Low molecular weight polyol (C) 1,4-BD: 1,4-butanediol (manufactured by Mitsubishi Chemical Corporation) · Additive Irganox 245 (manufactured by BASF Japan, hindered phenol compound, antioxidant) Tinuvin 571 (manufactured by BASF Japan, benzotriazole compound, ultraviolet absorber) ADEKA STAB LA-72 (manufactured by ADEKA, hindered amine compound, weather stabilizer)

[0094] (Preparation of thermoplastic polyurethane resin) The macro polyol (B) described in Table 1 was mixed with the above additives. With respect to 100 parts by mass of the macro polyol (B), Irganox 245 (antioxidant) was 0.3 parts by mass, Tinuvin 571 (ultraviolet absorber) was 0.3 parts by mass, and ADEKA STAB LA-72 (weather stabilizer) was 0.3 parts by mass, and the total amount of the additives was 0.9% by mass with respect to the final mass of the thermoplastic polyurethane resin. Next, the mixture of the macro polyol (B) and the additives was put into a container filled with nitrogen and heated at 100 °C for 12 hours. On the other hand, a catalyst solution in which dibutyltin dilaurate (catalyst) was diluted to 4% by mass with DINA (diisononyl adipate, catalyst diluent) was prepared. 173 parts by mass of the polyisocyanate (A), 100 parts by mass of the macro polyol (B) and the mixture of the above additives were put into a container equipped with a stirrer, a thermometer, and a nitrogen inlet tube. These were stirred in a hot water bath at 85 °C for 5 minutes with a high-speed stirring disperser under a nitrogen atmosphere to obtain an isocyanate group-terminated prepolymer. Next, 73 parts by mass of the low molecular weight polyol (C) as a chain extender was added to the isocyanate group-terminated prepolymer, and while appropriately adding the catalyst solution, it was stirred with a high-speed stirring disperser until it reached 90 °C. Next, the mixture of the isocyanate group-terminated prepolymer and the chain extender was poured into a Teflon (registered trademark) vat and subjected to a urethanization reaction at 150 °C for 2 hours, and the reaction was continued at 100 °C for 20 hours. Thereby, a thermoplastic polyurethane resin was obtained.

[0095] Next, the thermoplastic polyurethane resin was removed from the vat and cut into a die shape using a veil cutter. Then, the die-shaped resin was ground using a grinder to obtain ground pellets. The ground pellets were heat-treated at 80°C for 5 days and then dried at 80°C for 12 hours under reduced pressure. Thereafter, the ground pellets were fed into a single-screw extruder (model: SZW20-25MG, manufactured by TechnoBel), and strands were extruded under the conditions of a screw rotation speed of 30 rpm and a cylinder temperature of 140°C or higher and 240°C or lower. Then, the strands were cut to obtain pellets of the thermoplastic polyurethane resin.

[0096] The composition and physical properties of the obtained thermoplastic polyurethane resin are shown in Table 1.

Table 1

[0097] 1-1-2. Pellets of Colorant (Masterbatch) · Pellets of Gray Colorant (Gray Colored Masterbatch) A gray masterbatch (TPU / gray pigment = 67 / 33 (mass ratio)) obtained by dry blending a gray pigment with the above-prepared thermoplastic polyurethane resin · Pellets of Black Colorant (Black Colored Masterbatch) Black masterbatch (manufactured by Resin Color Industry Co., Ltd., MBF-T-7395B-PU, TPU / black pigment = 86 / 17 (mass ratio))

[0098] 1-2. Preparation of Thermoplastic Polyurethane Resin Composition [Synthesis Examples 1 to 7] The obtained pellets of the thermoplastic polyurethane resin were dried at 80°C for 12 hours under reduced pressure. Next, the dried pellets of the thermoplastic polyurethane resin and the pellets of the colorant (masterbatch) in Table 2 were dry blended in the amounts shown in Table 2 until uniform. Next, the dry-blended mixture was charged into a single-screw extruder and melt-kneaded under the conditions of a screw rotation speed of 20 rpm and a cylinder temperature of 140°C or higher and 240°C or lower. Then, the molten resin composition was extruded from a T-die and taken up by a take-up machine. Thereby, films of the thermoplastic polyurethane resin compositions of Synthesis Examples 1 to 7 were obtained. This film was cured for 7 days under the constant temperature and humidity conditions of a room temperature of 23°C and a relative humidity of 55%.

[0099] [L * [Measurement of value] The lightness index (L * ) of the films of the thermoplastic polyurethane resin compositions obtained in Synthesis Examples 1 to 7 was measured using a colorimeter CR-20 (manufactured by Konica Minolta). L * The higher the value of L, the closer the lightness is to white, and the lower the value of L, the closer the lightness is to black. *

[0100] The compositions and physical properties of the films of the thermoplastic polyurethane resin compositions obtained in Synthesis Examples 1 to 7 are shown in Table 2.

Table 2

[0101] 2. Preparation and evaluation of fiber-reinforced resin sheet [Example 1] A fiber aggregate containing the reinforcing fiber described in Table 3 was prepared. Specifically, as a fiber aggregate made of carbon fiber, EC3X (manufactured by FORMOSA TAFFETA, a woven fabric made of carbon fiber (twill weave), thickness 280 μm) which is a woven fabric made of carbon fiber was prepared. A film of the thermoplastic polyurethane resin composition of Synthesis Example 1 was laminated on one side of EC3X, and a film of the thermoplastic polyurethane resin composition of Synthesis Example 2 was laminated on the other side. On each surface, a biaxially stretched polypropylene film (release film, manufactured by Futamura Chemical Co., Ltd., FOR-MP; hereinafter referred to as OPP film) and a CFRP plate (manufactured by Tech Lab Co., Ltd.) were further laminated to obtain a laminate having the following configuration. CFRP plate / OPP film (release film) / film of the thermoplastic polyurethane resin composition of Synthesis Example 1 / carbon fiber fabric (fiber aggregate) / film of the thermoplastic polyurethane resin composition of Synthesis Example 2 / OPP film (release film) / CFRP plate

[0102] The above laminate was wrapped with a non-woven fabric made of polyethylene terephthalate (basis weight 135 g / m 2 , average thickness 2 mm, OSE-135 manufactured by Kao Corporation), and further, the outside thereof was wrapped with a nylon film (WL6400 manufactured by Air-Tech Co., Ltd.) to obtain a package. The opening of the package was sealed with an airtight tape (AT200Y manufactured by Air-Tech Co., Ltd.). The inside of the package (inside the nylon film) was depressurized to a predetermined reduced pressure gauge pressure (-0.1 MPa) with a vacuum pump. While maintaining the depressurized state, the package was placed in an autoclave (DL-2010 manufactured by Haneda Iron Works Co., Ltd.). The inside of the autoclave was maintained at a predetermined molding temperature of 145 °C and a pressurized gauge pressure of 0.5 MPa for 80 minutes, and then the laminate taken out from the autoclave was heated in an oven (PH-402 manufactured by ESPEC Co., Ltd.) at 120 °C for 24 hours. Thereafter, the package was taken out from the oven, and the laminate was taken out from the package. The CFRP plate and the OPP film were peeled off from the laminate to obtain a fiber-reinforced resin sheet in which one surface of the carbon fiber fabric was impregnated with the thermoplastic polyurethane resin composition of Synthesis Example 1 (second thermoplastic polyurethane resin composition) and the other surface was impregnated with the thermoplastic polyurethane resin composition of Synthesis Example 2 (first thermoplastic polyurethane resin composition).

[0103] [Examples 2 to 6, Comparative Example 1] A fiber-reinforced resin sheet was obtained in the same manner as in Example 1, except that the layer structure of the fiber-reinforced resin sheet was changed as shown in Table 3.

[0104] [Example 7] A fiber-reinforced resin sheet was obtained in the same manner as in Example 2, except that a fabric made of carbon fiber (EC3C, manufactured by FORMOSA TAFFETA, carbon fiber fabric (plain weave), thickness 280 μm) was used as the fiber aggregate made of carbon fiber.

[0105] [Examples 8 to 11] A fiber-reinforced resin sheet was obtained in the same manner as in Example 7, except that the layer structure of the fiber-reinforced resin sheet was changed as shown in Table 4.

[0106] [Evaluation] (1) Light-shielding rate The light-shielding rate of each fiber-reinforced resin sheet was measured in accordance with the JIS L 1055A method "Test method for light-shielding properties of curtains". The irradiation conditions were as follows. Test box: A box with a matte black paint applied inside Diameter of the hole: 100 mm in diameter Illuminance meter: Directly below the hole Light bulb: Halogen light bulb for general lighting Illuminance of the light source: 100,000 lx Sample size: 200 mm × 200 mm Number of measurements: n = 3 for each sample

[0107] (2) Light-shielding grade The light-shielding grade of the fiber-reinforced resin sheet was evaluated based on the criteria of the Japan Interior Designers Association "Display Standards, Test Methods and Judgment Criteria 1-1 Light Shielding (Curtain)". Grade 1: Light-shielding rate of 99.99% or more (level where the expression of a person's face cannot be distinguished) Grade 2: Light-shielding rate of 99.80% or more and less than 99.99% (level where a person's face or expression can be distinguished) Grade 3: Light-shielding rate of 99.40% or more and less than 99.80% (level where a person's expression can be distinguished, but it is dark for office work) Those of level 2 or above were considered qualified.

[0108] (3) Design quality (visual evaluation) The degree of light transmission through the gaps of the weave pattern of the fiber-reinforced resin sheet was visually observed and evaluated based on the following criteria. ◎: The aesthetics and three-dimensional effect of the weave pattern are well demonstrated, and it has excellent design quality. ○: The aesthetics and three-dimensional effect of the weave pattern are generally well demonstrated, and it has excellent design quality. △: There are thin areas where light transmits, and it is difficult to demonstrate the aesthetics and three-dimensional effect of the weave pattern. ×: Light transmits through, and the aesthetics and three-dimensional effect of the weave pattern are not demonstrated. Those rated △ or above were considered qualified.

[0109] (4) Rigidity and flexibility The rigidity and flexibility of the fiber-reinforced resin sheet were measured by the slide method in accordance with JIS L 1096 (2020). Specifically, a testing machine described in "8.21.2 Method B (slide method)" of JIS L 1096 (2020) was used. Also, for a test piece of 150 mm × 20 mm, δ was measured with l set to 100. The larger the δ value, the higher the flexibility. If the δ value exceeded 10 mm, it was rated ○.

[0110] (5) Peel resistance (peel marks) After piercing the fiber-reinforced resin sheet with a sewing machine needle (Brother, household size 16), the needle was removed. Then, the area around the needle hole was observed to evaluate the state of the fiber-reinforced resin sheet. Specifically, after removing the needle, the fiber-reinforced resin sheet was photographed. Next, the image was binarized to black and white. And then, the area of the white part in the image (area per hole, mm 2 / hole) was calculated. Also, for 50 holes, observations were made as described above. Then, the average value of the area of the white portion was calculated. The white portion indicates the part where the resin has peeled off from the fiber aggregate. Therefore, the smaller the area of the white portion, the better the fiber-reinforced resin sheet has peel resistance. Note that the evaluation of the peel root marks in Examples 5 to 11 was carried out and observed from the side of the TPU film containing a gray or black colorant.

[0111] (6) Impregnation state The fiber-reinforced resin sheet was cut along the thickness direction. Next, the cross-section was observed with a scanning electron microscope (VH-XD510, manufactured by Keyence Corporation) or X-ray CT. Thereby, the impregnation state of the resin with respect to the fiber aggregate was confirmed and evaluated.

[0112] The evaluation results of the twill-woven fiber-reinforced resin sheets of Examples 1 to 6 and Comparative Example 1 are shown in Table 3, and the evaluation results of the plain-woven fiber-reinforced resin sheets of Examples 7 to 11 are shown in Table 4. Note that "-" in the table means unmeasured.

Table 3

Table 4

[0113] As shown in Table 3 and Table 4, regarding the impregnation state of the resin composition, in any of Examples 1 to 11 and Comparative Example 1, it was confirmed that the resin composition was not impregnated inside the fiber aggregate, and the resin composition was impregnated only in the surface layer portion. Also, in each case, the impregnation layer thickness (one side) of the resin composition was about 75 μm.

[0114] And, the fiber-reinforced resin sheet of Comparative Example 1 in which both sides of the fabric were impregnated with a resin composition not containing a gray or black colorant had high stiffness (flexibility), but had low light-shielding properties and low design properties even in visual observation. On the other hand, the fiber-reinforced resin sheets of Examples 1 to 11 in which one side of the fabric was impregnated with a resin composition containing a gray or black colorant all maintained good stiffness (flexibility), had high light-shielding properties, and also had good design properties.

[0115] Also, from the comparison between Examples 2 to 6 (Table 3) and Examples 7 to 11 (Table 4), it was found that the fiber-reinforced resin sheet using a plain-woven fiber aggregate had fewer peeling marks and was superior in peeling resistance than the fiber-reinforced resin sheet using a twill-woven fiber aggregate.

[0116] From these facts, it can be seen that the fiber-reinforced resin sheet in which one side of the fabric is impregnated with a resin composition containing a gray or black colorant can maintain high light-shielding properties while maintaining flexibility and good design properties.

Industrial Applicability

[0117] According to the present invention, it is possible to provide a fiber-reinforced resin sheet that has flexibility, is difficult for light to transmit through gaps such as weave, and can maintain the aesthetics and three-dimensional feeling of the weave and the like well.

Explanation of Symbols

[0118] 10 Fiber-reinforced resin sheet 11 Fiber aggregate 12 Thermoplastic polyurethane resin composition (first thermoplastic polyurethane resin composition) 13 Second thermoplastic polyurethane resin composition

Claims

1. A fiber-reinforced resin sheet comprising: a fiber aggregate containing reinforcing fibers; and a thermoplastic polyurethane resin composition impregnated on at least one surface of the fiber aggregate, wherein the thermoplastic polyurethane resin composition contains a thermoplastic polyurethane resin and at least one colorant selected from the group consisting of a gray colorant and a black colorant. The fiber-reinforced resin sheet.

2. The content of the colorant in the thermoplastic polyurethane resin composition is 0.1% by mass or more and 20% by mass or less based on the total mass of the thermoplastic polyurethane resin and the colorant. The fiber-reinforced resin sheet according to Claim 1.

3. The thermoplastic polyurethane resin composition impregnated on one surface of the fiber aggregate, and a second thermoplastic polyurethane resin composition impregnated on the other surface of the fiber aggregate and substantially free of the colorant. The fiber-reinforced resin sheet according to Claim 1.

4. A curtain comprising the fiber-reinforced resin sheet according to any one of Claims 1 to 3.

5. A roller blind comprising the fiber-reinforced resin sheet according to any one of Claims 1 to 3.

6. A tone cover comprising the fiber-reinforced resin sheet according to any one of Claims 1 to 3. The tone cover. ​ ​ ​

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