Laminate, molded article, and method for producing molded article

Abstract

To suppress surface deformation of a molded article while preventing a decrease in adhesive strength between a fiber-reinforced resin substrate and a first member.SOLUTION: A laminate 10 includes a substrate 11 and a first member 20. The first member 20 is superposed on the substrate 11. The first member 20 has a resin layer 25. The resin layer 25 contains inorganic nanoparticles having an average primary particle diameter of 1 nm or more and 50 nm or less. The resin layer 25 has an indentation hardness of 20 MPa or more.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] The present disclosure relates to a laminate, a molded article manufactured using the laminate, and a method for manufacturing a molded article using the laminate.

Background Art

[0002] Members used in sports equipment, automobiles, ships, aircraft, etc. can be subjected to large impacts and deformation stresses. As such members, it has been proposed to use molded articles having a substrate made of a fiber-reinforced resin such as carbon fiber-reinforced resin (CFRP) or glass fiber-reinforced resin (GFRP). The fiber-reinforced resin substrate is formed by weaving fibers and impregnating them with resin. The fiber-reinforced resin is a lightweight and tough material. The fiber-reinforced resin substrate is used by being stacked on a first member including a resin layer.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] On the surface of the fiber-reinforced resin substrate, there are formed uneven shapes due to a woven pattern formed by weaving the fibers contained in the fiber-reinforced resin, and uneven shapes formed by arranging the fibers. When a molded article having a fiber-reinforced resin substrate is exposed to a high temperature for a long time, the surface of the molded article may be unintentionally deformed into an uneven shape, or the adhesion between the fiber-reinforced resin substrate and the first member may decrease. It was considered that the surface of the molded article was deformed due to the uneven shape formed on the surface of the fiber-reinforced resin substrate, and the adhesion between the fiber-reinforced resin substrate and the first member decreased during the deformation process. The present disclosure aims to suppress deformation of the surface of the molded article and a decrease in the adhesion between the fiber-reinforced resin substrate and the first member.

Means for Solving the Problems

[0005] The laminate of the present disclosure is a base material, and a first member laminated on the base material. The first member has a resin layer, the resin layer contains inorganic nanoparticles having an average primary particle diameter of 1 nm or more and 50 nm or less, and the indentation hardness of the resin layer is 20 MPa or more.

Advantages of the Invention

[0006] According to the present disclosure, it is possible to suppress deformation of the surface of the molded product and a decrease in the adhesion between the fiber-reinforced resin substrate and the first member.

Brief Description of the Drawings

[0007]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Modes for Carrying Out the Invention

[0008] Hereinafter, an embodiment of the present disclosure will be described with reference to the drawings. The scale, aspect ratio, etc. in the drawings attached to this specification are changed and exaggerated from those of the actual objects for the sake of illustration and easy understanding.

[0009] In this specification, terms specifying shapes, geometric conditions, and their degrees, such as "parallel", "orthogonal", "identical", etc., and values of lengths, angles, etc. are not limited to strict meanings, but are interpreted to include ranges to the extent that similar functions can be expected.

[0010] In this specification, the terms "layer" and "film" are not distinguished from each other based only on the difference in names. For example, the "resin layer" is a concept that also includes a member that can be called a film. Therefore, the "resin layer" cannot be distinguished from a member called a "resin film" based only on the difference in names.

[0011] In this specification, when a plurality of upper limit value candidates and a plurality of lower limit value candidates are listed for a parameter, the parameter may be a numerical range obtained by combining any one upper limit value candidate and any one lower limit value candidate.

[0012] An embodiment of the present disclosure relates to the following [1] to

[15] . [1] A base material, A first member laminated on the base material, and The first member has a resin layer, The resin layer contains inorganic nanoparticles having an average primary particle diameter of 1 nm or more and 50 nm or less, The indentation hardness of the resin layer is 20 MPa or more, a laminate. [2] The content of the inorganic nanoparticles in the resin layer is 5% by mass or more and 60% by mass or less, the laminate according to [1]. [3] The indentation hardness of the resin layer is 500 MPa or less, the laminate according to [1] or [2]. [4] The laminate according to any one of [1] to [3], wherein the resin layer contains a three-dimensionally crosslinked resin. [5] The laminate according to any one of [1] to [4], wherein the thickness of the resin layer is 0.5 μm or more. [6] The laminate according to any one of [1] to [5], wherein the thickness of the resin layer is 0.5 μm or more and 250 μm or less. [7] The laminate according to any one of [1] to [6], wherein the first member further has a hard coat layer disposed between the base material and the resin and / or a functional layer laminated on the resin. [8] A first member having a resin, and a fiber reinforced resin substrate laminated on the first member. The resin layer contains inorganic nanoparticles having an average primary particle diameter of 1 nm or more and 50 nm or less. The molded article, wherein the indentation hardness of the resin layer is 20 MPa or more. [9] The molded article according to [8], wherein in the resin layer, the inorganic nanoparticles are 5% by mass or more and 60% by mass or less.

[10] The molded article according to [8] or [9], wherein the first member further has a hard coat layer and / or a functional layer laminated on the resin layer.

[11] The molded article according to any one of [8] to

[10] , wherein the thickness of the resin layer is 0.1 μm or more.

[12] The molded article according to any one of [8] to

[11] , wherein the thickness of the resin layer is 0.1 μm or more and 250 μm or less.

[13] A step of producing a first member having a resin layer containing inorganic nanoparticles, a step of laminating the first member on a base material to form a laminate, and a lamination step of laminating the laminate on a resin impregnated fiber sheet so that the first member is closer to the resin impregnated fiber sheet than the base material. The average primary particle diameter of the inorganic nanoparticles is 1 nm or more and 50 nm or less, A method for manufacturing a molded article, wherein the indentation hardness of the resin layer after the lamination step is 20 MPa or more.

[14] In the lamination step, the laminate and the resin-impregnated fiber sheet are heated and pressurized. The method for manufacturing a molded article according to

[13] .

[15] The method for manufacturing a molded article according to

[13] or

[14] , further comprising a peeling step of peeling the substrate.

[0013] [Molded article] FIG. 1 is a cross-sectional view of an example of a molded article 1 according to an embodiment of the present disclosure. FIG. 2 is a cross-sectional view of another example of the molded article 1 according to an embodiment of the present disclosure. The molded article 1 shown in FIGS. 1 and 2 has a fiber-reinforced resin substrate 5 and a first member 20. The fiber-reinforced resin substrate 5 is overlaid on the first member 20. In the examples shown in FIGS. 1 and 2, the first member 20 overlaps the entire fiber-reinforced resin substrate 5. The first member 20 may overlap only a part of the fiber-reinforced resin substrate 5. The first member 20 is provided by being overlaid on the fiber-reinforced resin substrate 5. The first member 20 forms the surface of the molded article 1. The thickness of the molded article 1 is, for example, 0.1 mm or more and 50 mm or less.

[0014] In the examples shown in FIGS. 1 and 2, the molded article 1 is flat. Without being limited to the illustrated examples, the molded article 1 may be curved or bent.

[0015] [Fiber-reinforced resin substrate] The fiber-reinforced resin substrate 5 is overlaid on the first member 20. The fiber-reinforced resin substrate 5 is a lightweight and tough substrate. The fiber-reinforced resin substrate 5 includes fibers and a matrix resin. The fiber-reinforced resin substrate 5 is manufactured by weaving fibers such as carbon fibers and glass fibers, impregnating the fibers with a matrix resin such as a thermoplastic resin or a thermosetting resin to form a resin-impregnated fiber sheet, and curing the resin-impregnated fiber sheet. In the present embodiment, carbon fibers are used as the fibers. The resin-impregnated fiber sheet obtained by impregnating carbon fibers with a matrix resin and the fiber-reinforced resin substrate 5 obtained by curing the resin-impregnated fiber sheet are also referred to as prepregs. The fiber-reinforced resin substrate 5 may be manufactured by stacking and curing a plurality of resin-impregnated fiber sheets. An uneven shape is formed on the surface of the fiber-reinforced resin substrate 5. The uneven shape is formed by a three-dimensional and fine twill or plain weave pattern formed by weaving fibers, or by arranging fibers in one direction. The thickness of the fiber-reinforced resin substrate 5 is, for example, 0.1 mm or more and 50 mm or less.

[0016] The fibers included in the fiber-reinforced resin substrate 5 may be various fiber fabrics such as long fibers (UD) aligned in one direction, two-way fabrics, multi-axis fabrics, non-woven fabrics, mats, knits, and braids, for example. The long fibers mean, for example, continuous single fibers or fiber bundles of 10 mm or more.

[0017] The carbon fibers are, for example, polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, etc., or a mixture thereof.

[0018] The matrix resin is, for example, a thermosetting resin, a thermoplastic resin, or a thermoplastic elastomer. The thermosetting resin is, for example, an epoxy resin, an unsaturated polyester resin, a phenol resin, a silicone resin, a urethane resin, a urethane acrylate resin, or a polyimide resin. The thermoplastic resin is, for example, polysulfone, polyethersulfone, polyetherimide, or polyimide.

[0019] <First member> The first member 20 is provided by being overlapped on the fiber-reinforced resin substrate 5. The first member 20 may exhibit various functions. The first member 20 may have a plurality of layers for exhibiting functions. In the examples shown in FIGS. 1 and 2, the first member 20 has a hard coat layer 21, a functional layer 23, a resin layer 25, and a bonding layer 27. As shown in FIGS. 1 and 2, the hard coat layer 21 and the functional layer 23 are overlapped directly or indirectly on the resin layer 25. The surfaces of the molded article 1 and the first member 20 are formed by the hard coat layer 21. The surfaces of the molded article 1 and the first member 20 are maintained in a desired shape by the resin layer 25. The first member 20 protects the surface of the fiber-reinforced resin substrate 5 by the hard coat layer 21, and imparts various functions exhibited by the functional layer 23 to the molded article 1. The first member 20 is joined to the fiber-reinforced resin substrate 5 by the bonding layer 27. The first member 20 may have other members (not shown).

[0020] Not limited to the example shown in FIG. 1, the bonding layer 27 may be omitted. The first member 20 may be directly joined to the fiber-reinforced resin substrate 5 by the resin layer 25. The resin layer 25 and the bonding layer 27 may be the same member. The hard coat layer 21 and the functional layer 23 of the first member 20 may be omitted. When the hard coat layer 21 is omitted, the resin layer 25 may function as a hard coat layer. As shown in FIG. 2, the functional layer 23 may be disposed between the resin layer 25 and the bonding layer 27. The first member 20 may have a plurality of functional layers 23. The molded article 1 may have a base material 11 described later.

[0021] The resin layer 25 has sufficient hardness so as to maintain the surfaces of the molded article 1 and the first member 20 in a desired shape. The indentation hardness of the resin layer 25 is 20 MPa or more, preferably 80 MPa or more, more preferably 140 MPa or more. The indentation hardness of the resin layer 25 is preferably 500 MPa or less.

[0022] In the present disclosure, the indentation hardness is measured by the following method. The member to be measured is cut with a microtome to expose the cut surface. Using a nanoindentation device (manufactured by HYSITRON, Inc., USA, trade name: TriboIndenter TI950), with a load control method (maximum load: 50 μN), a indenter (Berkovich indenter TI-0039) consisting of a diamond tip with a triangular pyramid tip shape is vertically pushed into a position 1 μm to 10 μm away from the side edge of the cut surface. When the member to be measured is thin and the position 1 μm to 10 μm away from the side edge of the cut surface cannot be specified, the position where the indenter is pushed in is the center in the thickness direction on the side of the cut surface. By measuring the displacement of the indenter with respect to the load, the indentation hardness is obtained. The measurement conditions are as follows. · Measurement temperature: 23 °C · Relative humidity: 70% · Pressing load: 50 μN · Pressing depth reaching time: 10 seconds · Load holding time: 5 seconds · Pressing depth unloading time: 10 seconds

[0023] In the molded product 1, it is preferable that the resin layer 25 has a sufficient thickness so as to maintain the surfaces of the molded product 1 and the first member 20 in a desired shape. Specifically, in the molded product 1, the thickness of the resin layer 25 is preferably 0.1 μm or more, and more preferably 0.1 μm or more and 250 μm or less.

[0024] [Laminated body] The first member 20 is stacked on the fiber-reinforced resin substrate 5 as the laminate 10. FIG. 3 shows a cross-sectional view of an example of the laminate 10. FIG. 4 shows a cross-sectional view of another example of the laminate 10. As shown in FIGS. 3 and 4, the laminate 10 has a base material 11 and a first member 20. As described above, the first member 20 has a hard coat layer 21, a functional layer 23, a resin layer 25, and a bonding layer 27. The hard coat layer 21 is disposed on the surface of the first member 20. In the example shown in FIG. 3, the hard coat layer 21 and the functional layer 23 are disposed between the base material 11 and the resin layer 25. The hard coat layer 21 is disposed between the base material 11 and the functional layer 23. A resin layer 25 is disposed between the functional layer 23 and the bonding layer 27. The base material 11, the hard coat layer 21, the functional layer 23, the resin layer 25, and the bonding layer 27 are stacked in this order. The laminate 10 and the first member 20 may have other members. Not limited to the illustrated example, the functional layer 23 may not be between the base material 11 and the resin layer 25 as long as it is directly or indirectly stacked on the resin layer 25. For example, as shown in FIG. 4, the base material 11, the hard coat layer 21, the resin layer 25, the functional layer 23, and the bonding layer 27 may be stacked in this order.

[0025] Each component of the laminate 10 and the first member 20 will be described.

[0026] <Base material> The base material 11 supports the first member 20. The base material 11 is provided so as to overlap the surface of the first member 20. In the example shown in FIG. 3, the base material 11 is provided so as to be in contact with the hard coat layer 21. The base material 11 is provided so as to be peelable from the first member 20. In order to easily peel the base material 11 from the first member 20, a release layer (not shown) may be provided between the base material 11 and the first member 20. The release layer is made of, for example, a silicone resin. The base material 11 may not be peeled from the first member 20.

[0027] When the base material 11 peels off from the first member 20, the base material 11 has appropriate flexibility and rigidity for properly supporting the first member 20 and easily peeling off from the first member 20. The thickness of the base material 11 is, for example, 5 μm or more and 200 μm or less.

[0028] Examples of the material of the base material 11 include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyolefins, polystyrene, vinyl resins, (meth)acrylic resins, amide resins, imide resins, and polycarbonates. In the present disclosure, “(meth)acrylic” includes both “acrylic” and “methacrylic”, and “(meth)acrylate” includes both “acrylate” and “methacrylate”. Considering the heat shrinkage during the production of the laminate 10, the difficulty of shrinkage due to irradiation with ionizing radiation, and the high peelability of the first member 20, the material of the base material 11 is preferably polyethylene terephthalate or polybutylene terephthalate. Considering the heat shrinkage during the production of the laminate 10 and the difficulty of shrinkage due to irradiation with ionizing radiation, the material of the base material 11 is preferably a stretched film, particularly a biaxially stretched film.

[0029] (Hard coat layer) The hard coat layer 21 protects the surface of the molded article 1. The hard coat layer 21 forms the surfaces of the molded article 1 and the first member 20. The hard coat layer 21 has, for example, scratch resistance, weather resistance, abrasion resistance, and chemical resistance. The thickness of the hard coat layer 21 is, for example, 0.5 μm or more and 50 μm or less.

[0030] The hard coat layer 21 is made of a resin composition containing a curable resin. The curable resin is, for example, an ionizing radiation curable resin or an ultraviolet curable resin. From the viewpoints of scratch resistance, weather resistance, abrasion resistance, and chemical resistance, the curable resin is preferably an ionizing radiation curable resin.

[0031] The radiation-curable resin is, for example, a polymerizable monomer, a polymerizable oligomer or a prepolymer. The polymerizable monomer, the polymerizable oligomer or the prepolymer is, for example, an acrylic monomer-based, epoxy (meth) acrylate-based, urethane (meth) acrylate-based, polyether-based urethane (meth) acrylate, caprolactone-based urethane (meth) acrylate, polycarbonate-based urethane (meth) acrylate, polyester (meth) acrylate-based, polyether (meth) acrylate-based oligomer or prepolymer.

[0032] The ionizing radiation irradiated to the radiation-curable resin is, for example, ultraviolet rays (UV), electron beams (EB), electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams.

[0033] The ultraviolet-curable resin is, for example, a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule. The polyfunctional (meth) acrylate is not particularly limited as long as it is a bifunctional or higher (meth) acrylate, and may be either an oligomer or a monomer. Examples of the polyfunctional (meth) acrylate monomer include urethane (meth) acrylate monomers; aliphatic monomers such as trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; monomers having an isocyanurate skeleton such as tris(2-(meth)acryloxyethyl) isocyanurate; and modified products thereof.

[0034] The above-mentioned modified product is, for example, an ethylene oxide (EO) modified product, a propylene oxide (PO) modified product, and a caprolactone (CL) modified product. From the viewpoint that the influence of hydrolysis is small in a high-humidity environment and the weather resistance of the hard coat layer can be further improved, the CL modified product is preferred. Specifically, the above-mentioned modified product is preferably EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO-modified dipentaerythritol hexa(meth)acrylate, PO-modified dipentaerythritol hexa(meth)acrylate, CL-modified dipentaerythritol hexa(meth)acrylate, and CL-modified tris(2-(meth)acryloxyethyl) isocyanurate.

[0035] The urethane (meth)acrylate monomer is obtained by reacting a polyisocyanate with a (meth)acrylate having a hydroxyl group, and is a monomer having a urethane bond and a (meth)acryloyl group in the molecule.

[0036] The polyisocyanate is, for example, an aliphatic polyisocyanate such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; an alicyclic polyisocyanate such as isophorone diisocyanate, norbornane diisocyanate, methylene bis(4-cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, and 2-methyl-1,5-diisocyanatocyclohexane. The polyisocyanate may be a multimer of an aliphatic polyisocyanate or an alicyclic polyisocyanate, such as a trimer such as an isocyanurate form. The number of isocyanate groups in the polyisocyanate is preferably 2 or more, preferably 12 or less, and more preferably 8 or less.

[0037] (Meth)acrylates having a salicylic acid group include, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid, trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, bis((meth)acryloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate; and their EO, PO, or CL modified products. Among these, from the viewpoint of improving the abrasion resistance and weather resistance of the hard coat layer, pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate; and their EO, PO, or CL modified products are preferred.

[0038] The polyfunctional (meth)acrylate oligomer is, for example, a urethane (meth)acrylate-based oligomer, an epoxy (meth)acrylate-based oligomer, a polyester (meth)acrylate-based oligomer, a polyether (meth)acrylate-based oligomer, etc. The urethane (meth)acrylate oligomer is obtained by reacting an isocyanate compound obtained by reacting a polyol and a diisocyanate with a (meth)acrylate having a hydroxyl group, and is an oligomer having a urethane bond and a (meth)acryloyl group in the molecule.

[0039] The polyol is, for example, a polyether polyol, a polycarbonate polyol, and a polyester polyol. The diisocyanate and the (meth)acrylate having a hydroxyl group are the compounds described above.

[0040] Epoxy (meth) acrylate oligomers can be obtained, for example, by reacting (meth) acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolac type epoxy resin for esterification. A carboxyl modified epoxy (meth) acrylate oligomer obtained by partially modifying the epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. As the polyester (meth) acrylate oligomer, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or by esterifying the terminal hydroxyl groups of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth) acrylic acid. Polyether (meth) acrylate oligomers can be obtained by esterifying the hydroxyl groups of polyether polyols with (meth) acrylic acid.

[0041] Various additives may be contained in the resin composition containing the curable resin. The additives are, for example, scratch resistant fillers, ultraviolet absorbers, light stabilizers, polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, defoaming agents, fillers, solvents.

[0042] (Functional layer) The functional layer 23 exhibits various functions imparted to the molded article 1. The functional layer 23 exhibits, for example, a decorative function, an ultraviolet absorption function, an infrared absorption function, a gas barrier function, a humidity barrier function, an electromagnetic wave shielding function, an insulating function, a heat dissipation function, a conductive function, a scratch restoration function, a scratch prevention function, a chemical resistance function, an atomic oxygen resistance function, a galvanic corrosion prevention function. The functional layer 23 may exhibit a plurality of functions. The functional layer 23 is formed of a shape and material suitable for the functions to be exhibited.

[0043] As an example, the functional layer 23 that exhibits a decorative function will be described. The functional layer 23 that exhibits a decorative function is hereinafter referred to as a decorative layer. The decorative layer forms a design. Due to the formed design, the decorative layer exhibits a decorative function of imparting a design to the molded article 1. The decorative layer can form patterns such as figures, patterns, designs, colors, pictures, photos, characters, marks, pictograms, letters, and numbers as designs. The decorative layer may be disposed on the entire surface of the first member 20 or only on a part thereof. The thickness of the decorative layer is, for example, 1 μm or more and 40 μm or less. The decorative layer can be provided by known printing methods such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, and inkjet printing.

[0044] The decorative layer contains a resin material and a colorant. The resin material is, for example, a (meth)acrylic resin, a polyolefin, a chlorinated polyolefin, a vinyl chloride-vinyl acetate copolymer, a polystyrene, a polyester, and a cellulose resin. The colorant is, for example, an inorganic pigment such as carbon black, iron black, titanium white, antimony white, lead yellow, titanium yellow, bengala, cadmium red, ultramarine, and cobalt blue; an organic pigment or dye of the azo type, phthalocyanine type, anthraquinone type, perylene type, perinone type, quinacridone type, thioindigo type, dioxazine type, isoindolinone type, quinophthalone type, azomethine azo type, diketopyrrolopyrrole type, or isoindoline type.

[0045] In the molded article 1 shown in FIG. 2 produced by laminating the laminate 10 as shown in FIG. 4 on the fiber-reinforced resin substrate 5, the functional layer 23 functioning as a decorative layer is located between the resin layer 25 and the fiber-reinforced resin substrate 5. When observing such a molded article 1 from near the resin layer 25 rather than the fiber-reinforced resin substrate 5, the design by the decorative layer and the design of the fiber-reinforced resin substrate 5 are combined and observed. Since the functional layer 23 functioning as a decorative layer is located between the resin layer 25 and the fiber-reinforced resin substrate 5, the molded article 1 can display a more excellent design.

[0046] (Resin layer) The resin layer 25 maintains and adjusts the surfaces of the molded article 1 and the first member 20 to a desired shape. When the hard coat layer 21 is omitted in the first member 20, the resin layer 25 protects the fiber-reinforced resin substrate 5 in the molded article 1. Even when the molded article 1 is exposed to a high temperature for a long time, the resin layer 25 suppresses deformation of the surface of the molded article 1 and suppresses a decrease in the adhesion between the fiber-reinforced resin substrate 5 and the first member 20. The resin layer 25 is made of a resin composition.

[0047] The resin layer 25 has a sufficiently high hardness. Specifically, the indentation hardness of the resin layer 25 is 20 MPa or more, preferably 80 MPa or more, more preferably 140 MPa or more. The indentation hardness of the resin layer 25 is preferably 500 MPa or less.

[0048] The indentation hardness of the resin layer 25 may be 20 MPa or more, preferably 80 MPa or more, more preferably 140 MPa or more before being laminated on the fiber-reinforced resin substrate 5, that is, in the first member 20 of the laminate 10.

[0049] The resin composition constituting the resin layer 25 having a sufficiently high indentation hardness before being laminated on the fiber-reinforced resin substrate 5 contains a three-dimensionally crosslinked resin. The three-dimensionally crosslinked resin may be a cured product of a thermosetting resin, a cured product of an ultraviolet curable resin, or a cured product of an ionizing radiation curable resin. The thermosetting resin is, for example, an acrylic resin, an epoxy resin, or a urethane resin. The ultraviolet curable resin is, for example, a radical polymerization type acrylic resin or a cationic polymerization type epoxy resin. The ionizing radiation curable resin is, for example, a (meth)acrylic-modified unsaturated polyester resin, a (meth)acrylic-modified epoxy resin, or a (meth)acrylic-modified polyurethane resin.

[0050] When the resin composition constituting the resin layer 25 is a thermosetting resin, the resin layer 25 having a sufficiently high indentation hardness before being laminated on the fiber-reinforced resin substrate 5 may contain a curing agent. The curing agent is preferably an isocyanate such as hexamethylene diisocyanurate (HDI nurate) or blocked isocyanate. By containing the curing agent, the indentation hardness of the resin layer 25 can be increased.

[0051] The indentation hardness of the resin layer 25 is less than 20 MPa before being laminated on the fiber-reinforced resin substrate 5, but may be 20 MPa or more, preferably 80 MPa or more, more preferably 140 MPa or more after being laminated on the fiber-reinforced resin substrate 5, that is, in the molded product 1.

[0052] The resin layer 25 has a sufficient thickness so as to have a sufficient indentation hardness. The resin layer 25 has a sufficient thinness for weight reduction of the molded product 1. Specifically, in the laminate 10, the thickness of the resin layer 25 is 0.5 μm or more, preferably 0.5 μm or more and 250 μm or less, more preferably 10 μm or more and 50 μm or less. In the molded product 1 after being laminated on the fiber-reinforced resin substrate 5, the thickness of the resin layer 25 can be 0.1 μm or more, preferably 0.1 μm or more and 250 μm or less.

[0053] The resin layer 25 contains inorganic nanoparticles 25a. The inorganic nanoparticles 25a are encapsulated in the resin layer 25. The inorganic nanoparticles 25a improve the adhesion between the resin layer 25 and the fiber-reinforced resin substrate 5. The average primary particle diameter of the inorganic nanoparticles 25a may be 1 nm or more and 50 nm or less, or may be 10 nm or more and 30 nm or less. The shape of the inorganic nanoparticles 25a may be powdery such as spherical, ellipsoidal, cubic or rectangular such as a cuboid; polygonal plate-like such as cylindrical, disk-like, elliptical disk-like, scaly; needle-like, etc. When the inorganic nanoparticles 25a are not spherical, the average primary particle diameter of the inorganic nanoparticles 25a is the particle diameter of the circumscribed sphere of the inorganic nanoparticles 25a.

[0054] In the present disclosure, the average primary particle diameter of the inorganic nanoparticles 25a is calculated by statistical processing from an image obtained by a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM). Specifically, an image of a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM) is obtained from the front direction of the molded article 1 or the laminate 10 described later. The magnification of the image is 25,000 times or more and 35,000 times or less. The obtained image is subjected to binarization processing. For example, the density of the image is divided into gradations of 0 to 255, and a threshold value of the gradation is set for binarization processing so that the inorganic nanoparticles 25a can be distinguished from other members. FIGS. 5 to 7 show examples of photographs obtained by binarizing an image of the front of the molded article 1 obtained by a scanning electron microscope. In the example shown in FIG. 5, the content of the inorganic nanoparticles 25a in the resin layer 25 is 15% by mass. In the example shown in FIG. 6, the content of the inorganic nanoparticles 25a in the resin layer 25 is 20% by mass. In the example shown in FIG. 7, the content of the inorganic nanoparticles 25a in the resin layer 25 is 30% by mass. In the examples shown in FIGS. 5 to 7, the front of the molded article 1 is observed at 30,000 times magnification. In the binarized image, the inorganic nanoparticles 25a can be confirmed as being distinguished from other members. In FIGS. 5 to 7, the inorganic nanoparticles 25a are shown in black. In the binarized image, N inorganic nanoparticles 25a are randomly selected, and the primary particle diameter is measured. N is, for example, 1000. A histogram in 3 nm intervals is created from the measured particle diameters. Let the primary particle diameter of the i-th inorganic nanoparticle 25a in the histogram be d i , and the frequency be n i . Then, the average primary particle diameter D np of the inorganic nanoparticles 25a is calculated as follows.

Equation

[0055] The processing of the obtained image and the measurement of the particle diameter in the binarized image are carried out using the image processing software "ImageJ".

[0056] The content of the inorganic nanoparticles 25a in the resin layer 25 may be 5% by mass or more, may be 10% by mass or more, may be 60% by mass or less, or may be 50% by mass or less.

[0057] The material of the inorganic nanoparticles 25a may be a metal or a metal compound. The metal may be gold, silver, copper, platinum, palladium, nickel, cobalt, iron, manganese, silicon, titanium, zirconium, tungsten, molybdenum, chromium, zinc, aluminum, or a composite metal composed of two or more of these. The metal compound may be a metal oxide such as iron oxide, silicon oxide, zirconium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, cobalt oxide, nickel oxide, cerium oxide, cupric oxide, zinc oxide, tin oxide, antimony oxide, titanium dioxide, aluminum oxide, and mixtures thereof; metal nitrides such as aluminum nitride, gallium nitride, titanium nitride, silicon nitride, titanium nitride and mixtures of its children; metal sulfides such as cadmium sulfide, zinc sulfide, copper sulfide, molybdenum sulfide and mixtures thereof; metal carbides; metal borides; metal carbonates; zeolites; clays; or composites thereof. In particular, the material of the inorganic nanoparticles 25a is preferably a metal oxide, more preferably silicon oxide, zirconium oxide, or aluminum oxide.

[0058] The thickness of the molded article 1, the thickness of the laminate 10, and the thicknesses of the respective members included in the molded article 1 and the laminate 10, particularly the thickness of the resin layer 25, can be specified by observing a cross-section of the molded article 1 or the laminate 10 with a scanning electron microscope (SEM). The cross-section can be observed by cutting the molded article 1 or the laminate 10 with a microtome. The thickness of the molded article 1, the thickness of the laminate 10, and the thicknesses of the respective members included in the molded article 1 and the laminate 10 are specified as the average of the thicknesses of five locations of the target respective members in an image of the cross-section observed by the scanning electron microscope. The five locations for measuring the thickness are positions arranged at 25-μm intervals in a direction orthogonal to the thickness direction in the image of the cross-section.

[0059] (Bonding layer) The bonding layer 27 bonds the laminate 10 and the first member 20 to the fiber-reinforced resin substrate 5. The bonding layer 27 fills in following the uneven shape on the surface of the fiber-reinforced resin substrate 5. The bonding layer 27 is firmly bonded to the surface of the fiber-reinforced resin substrate 5. The bonding layer 27 forms a surface opposite to the surface of the first member 20 formed by the hard coat layer 21. The thickness of the bonding layer 27 is, for example, 1 μm or more and 10 μm or less.

[0060] The bonding layer 27 is made of a material having various adhesiveness or tackiness. The bonding layer 27 is preferably made of a material having heat sealability. The material of the bonding layer 27 is, for example, a thermoplastic resin such as (meth)acrylic resin, polyolefin, chlorinated polyolefin, vinyl chloride-vinyl acetate copolymer, polystyrene, polyester, amide resin, and urethane resin.

[0061] (Others) The first member 20 may have a primer layer (not shown) between the hard coat layer 21 or the functional layer 23 and the resin layer 25. The primer layer improves the adhesion between the hard coat layer 21 or the functional layer 23 and the resin layer 25. The primer layer is made of, for example, urethane resin. The thickness of the primer layer is, for example, 0.1 μm or more and 10 μm or less.

[0062] The laminate 10 may have a cover film (not shown). The cover film is disposed so as to contact the bonding layer 27 of the first member 20. The cover film protects the bonding layer 27. When the first member 20 is stacked on the fiber-reinforced resin substrate 5 from the laminate 10, the cover film is peeled off from the bonding layer 27. By peeling off the cover film, the bonding layer 27 is exposed. The cover film is made of, for example, a resin material such as polyolefin.

[0063] [Manufacturing method of the first example] A first example of a method for manufacturing a molded article 1 using a laminate 10 will be described with reference to FIG. 8. FIG. 8 shows an example of a laminating apparatus 50 that stacks the laminate 10 on a resin-impregnated fiber sheet that becomes the fiber-reinforced resin substrate 5. The laminating apparatus 50 includes a first belt 51, a second belt 52, a heater 53, a cooler 54, and a film roller 58. The first belt 51 and the second belt 52 face each other. The distance between the first belt 51 and the second belt 52 is substantially the same as the thickness of the molded article 1 to be manufactured.

[0064] The method for manufacturing the molded article 1 includes a step of producing a first member 20, a step of stacking the first member 20 on a base material 11 to form a laminate 10, and a laminating step of stacking the laminate 10 on a resin-impregnated fiber sheet. The method for manufacturing the molded article 1 may further include a peeling step of peeling the base material 11.

[0065] Inorganic nanoparticles 25a are dispersed and arranged in the resin composition that becomes the resin layer 25. The average primary particle diameter of the inorganic nanoparticles 25a is 1 nm or more and 50 nm or less. The amount of the inorganic nanoparticles 25a is an amount such that the content of the inorganic nanoparticles 25a in the resin layer 25 to be produced is 5% by mass or more and 60% by mass or less. The resin composition is irradiated with heat, ultraviolet rays, ionizing radiation, etc. to cure the resin composition and form the resin layer 25. If necessary, a hard coat layer 21, a functional layer 23, and a bonding layer 27 are stacked on the resin layer 25. The first member 20 is produced.

[0066] The produced first member 20 is stacked on the base material 11 to form a laminate 10.

[0067] A resin-impregnated fiber sheet including fibers and a matrix resin impregnated in the fibers is disposed in the laminating apparatus 50 along the first belt 51. As shown in FIG. 8, a plurality of elements constituting the resin-impregnated fiber sheet may be disposed separately. The resin-impregnated fiber sheet is conveyed by the first belt 51.

[0068] The laminate 10 is stretched between a plurality of film rollers 58. When the laminate 10 overlaps the resin-impregnated fiber sheet, the first member 20 is arranged closer to the resin-impregnated fiber sheet than the base material 11. When the laminate 10 has a cover film for protecting the bonding layer 27, the cover film is peeled off from the laminate 10. The laminate 10 is conveyed by the second belt 52.

[0069] <Laminating process> By sandwiching between the first belt 51 and the second belt 52, the laminate 10 is overlapped on the resin-impregnated fiber sheet so that the first member 20 is closer to the resin-impregnated fiber sheet than the base material 11. By being sandwiched between the first belt 51 and the second belt 52, the laminate 10 and the resin-impregnated fiber sheet are pressurized. By pressurizing the resin-impregnated fiber sheet, a plurality of elements constituting the resin-impregnated fiber sheet are integrated. The pressure applied to the laminate 10 and the resin-impregnated fiber sheet is, for example, 1 MPa or more and 10 MPa or less. The laminate 10 and the resin-impregnated fiber sheet are heated by the heater 53 while being pressurized. By heating and pressurizing the laminate 10 and the resin-impregnated fiber sheet, the resin-impregnated fiber sheet becomes the fiber-reinforced resin substrate 5, and the laminate 10 and the fiber-reinforced resin substrate 5 are integrated. The temperature for heating the laminate 10 and the resin-impregnated fiber sheet is, for example, 100°C or more and 230°C or less. The time for heating the laminate 10 and the resin-impregnated fiber sheet is, for example, 10 seconds or more and 180 seconds or less. After being heated, the laminate 10 and the fiber-reinforced resin substrate 5 are preferably cooled by the cooler 54. The temperature for cooling the laminate 10 and the fiber-reinforced resin substrate 5 is, for example, normal temperature or more and 60°C or less. The time for cooling the laminate 10 and the fiber-reinforced resin substrate 5 is, for example, 5 seconds or more and 150 seconds or less. By cooling the laminate 10 and the fiber-reinforced resin substrate 5, it is suppressed that the heated laminate 10 and the fiber-reinforced resin substrate 5 expand and the strength decreases.

[0070] After the laminate 10 is stacked on the fiber-reinforced resin substrate 5, the indentation hardness of the resin layer 25 is 20 MPa or more, preferably 80 MPa or more, more preferably 140 MPa or more. The indentation hardness of the resin layer 25 may be 20 MPa or more, preferably 80 MPa or more, more preferably 140 MPa or more even before the laminate 10 is stacked on the fiber-reinforced resin substrate 5, or may become 20 MPa or more, preferably 80 MPa or more, more preferably 140 MPa or more after the laminate 10 is stacked on the fiber-reinforced resin substrate 5.

[0071] <Peeling process> The base material 11 may be peeled off from the laminate 10. The peeled base material 11 is wound around the film roller 58.

[0072] Through the above steps, the molded product 1 in which the first member 20 overlaps the fiber-reinforced resin substrate 5 is manufactured. By using the laminating apparatus 50, the molded product 1 can be continuously manufactured.

[0073] [Manufacturing method of the second example] A second example of the manufacturing method of the molded product 1 using the laminate 10 will be described with reference to FIG. 9. FIG. 9 shows another example of the laminating apparatus 50 that stacks the laminate 10 on a resin-impregnated fiber sheet that becomes the fiber-reinforced resin substrate 5. The laminating apparatus 50 includes a first belt 51, a second belt 52, a heater 53, a cooler 54, a second heater 55, a heat roll 56, a peeling roll 57, and a film roller 58. The first belt 51 and the second belt 52 face each other. The distance between the first belt 51 and the second belt 52 is substantially the same as the thickness of the molded product 1 to be manufactured.

[0074] The second manufacturing method of the molded product also includes a step of manufacturing the first member 20, a step of stacking the first member 20 on the base material 11 to form the laminate 10, and a laminating step of stacking the laminate 10 on the resin-impregnated fiber sheet. The second manufacturing method of the molded product may further include a peeling step of peeling the base material 11. In the second manufacturing method, the step of manufacturing the first member 20 and the step of stacking the first member 20 on the base material 11 to form the laminate 10 are the same as those of the first manufacturing method described above.

[0075] A resin-impregnated fiber sheet containing fibers and a matrix resin impregnated in the fibers is arranged in the laminating apparatus 50 along the first belt 51. As shown in FIG. 9, a plurality of elements constituting the resin-impregnated fiber sheet may be separately arranged. The resin-impregnated fiber sheet is conveyed by the first belt 51.

[0076] The laminate 10 is stretched between a plurality of film rollers 58 while passing through the heat roll 56 and the peeling roll 57. The laminate 10 overlaps the resin-impregnated fiber sheet at a position away from the first belt 51 and the second belt 52. When the laminate 10 overlaps the resin-impregnated fiber sheet, the first member 20 is arranged closer to the resin-impregnated fiber sheet than the base material 11. When the laminate 10 has a cover film for protecting the bonding layer 27, the cover film is peeled off from the laminate 10. The laminate 10 is conveyed by the rotation of the film rollers 58.

[0077] By being sandwiched between the first belt 51 and the second belt 52, the resin-impregnated fiber sheet is pressurized. When the resin-impregnated fiber sheet is pressurized, a plurality of elements constituting the resin-impregnated fiber sheet are integrated. The pressure applied to the resin-impregnated fiber sheet is, for example, 1 MPa or more and 10 MPa or less. The resin-impregnated fiber sheet is heated by the heater 53 while being pressurized. The temperature for heating the resin-impregnated fiber sheet is, for example, 100°C or more and 230°C or less. The time for heating the resin-impregnated fiber sheet is, for example, 10 seconds or more and 180 seconds or less. By heating and pressurizing the resin-impregnated fiber sheet, the resin-impregnated fiber sheet becomes the fiber-reinforced resin substrate 5. After being heated, the fiber-reinforced resin substrate 5 is preferably cooled by the cooler 54. The temperature for cooling the fiber-reinforced resin substrate 5 is, for example, room temperature or more and 60°C or less. The time for cooling the fiber-reinforced resin substrate 5 is, for example, 5 seconds or more and 150 seconds or less. By cooling the fiber-reinforced resin substrate 5, it is possible to suppress the expansion and strength reduction of the heated fiber-reinforced resin substrate 5.

[0078] <Laminating Process> The fiber-reinforced resin substrate 5 is reheated by the second heater 55. While being heated by the heat roll 56, the first member 20 is overlapped with the fiber-reinforced resin substrate 5 so as to be closer to the fiber-reinforced resin substrate 5 than the base material 11. Between the heat roll 56 and the peeling roll 57, the laminate 10 is pressurized toward the fiber-reinforced resin substrate 5. By heating and pressurizing the laminate 10 and the fiber-reinforced resin substrate 5, the laminate 10 and the fiber-reinforced resin substrate 5 are integrated.

[0079] After the laminate 10 is overlapped with the fiber-reinforced resin substrate 5, the indentation hardness of the resin layer 25 is 20 MPa or more, preferably 80 MPa or more, more preferably 140 MPa or more. The indentation hardness of the resin layer 25 may be 20 MPa or more, preferably 80 MPa or more, more preferably 140 MPa or more even before the laminate 10 is overlapped with the fiber-reinforced resin substrate 5, or may become 20 MPa or more, preferably 80 MPa or more, more preferably 140 MPa or more after the laminate 10 is overlapped with the fiber-reinforced resin substrate 5.

[0080] <Peeling process> When the laminate 10 separates from the peeling roll 57, the base material 11 may be peeled off from the laminate 10. The peeled base material 11 is wound around the film roller 58.

[0081] Through the above steps, the molded product 1 in which the first member 20 overlaps the fiber-reinforced resin substrate 5 is manufactured. By using the laminating device 50, the molded product 1 can be continuously manufactured.

[0082] The manufacturing method of the molded product 1 in which the first member 20 is overlapped on the fiber-reinforced resin substrate 5 using the above-described laminating device 50 is only an example. The molded product 1 may be manufactured, for example, by bonding the first member 20 to the fiber-reinforced resin substrate 5 by dry lamination.

[0083] When a conventional molded product is exposed to a high temperature for a long time, the surface may be deformed into an unintended uneven shape, or the adhesion between the fiber-reinforced resin substrate and the first member may decrease. As a result of the temperature of the molded product rising, the components of the molded product soften and are deformed by the uneven shape formed on the surface of the fiber-reinforced resin substrate, and it was considered that a gap was formed between the fiber-reinforced resin substrate and the first member during the deformation process, resulting in a decrease in adhesion. The appearance of the molded product whose surface is deformed into an uneven shape deteriorates. In the molded product with reduced adhesion, there is a risk that the fiber-reinforced resin substrate and the first member may peel off.

[0084] The molded product 1 of the present embodiment includes a fiber-reinforced resin substrate 5 and a first member 20. The first member 20 has a resin layer 25. The resin layer 25 contains inorganic nanoparticles 25a having an average primary particle diameter of 1 nm or more and 50 nm or less. By the inorganic nanoparticles 25a finely deforming the bonding layer 27, or by the inorganic nanoparticles 25a forming fine irregularities on the surface of the resin layer 25, a so-called anchor effect is generated between the fiber-reinforced resin substrate 5 and the first member 20, improving the adhesion between the fiber-reinforced resin substrate 5 and the first member 20. Since the inorganic nanoparticles 25a are sufficiently large, the adhesion between the fiber-reinforced resin substrate 5 and the first member 20 is sufficiently improved. Since the inorganic nanoparticles 25a are not too large, it is suppressed that the haze of the molded product 1 is significantly observed due to the inorganic nanoparticles 25a. The indentation hardness of the resin layer 25 is 20 MPa or more. The resin layer 25 with a high indentation hardness is less likely to deform even when exposed to high temperatures for a long time. Deformation of the first member 20 forming the surface of the molded product 1 due to the uneven shape formed on the surface of the fiber-reinforced resin substrate 5 is suppressed. Even when the molded product 1 is exposed to high temperatures for a long time, the resin layer 25 suppresses deformation of the surface of the molded product 1 and can maintain a desired shape. For example, the surface of the molded product 1 is maintained flat. Deformation of the surface of the molded product 1 and a decrease in the adhesion between the fiber-reinforced resin substrate 5 and the first member 20 can be suppressed.

[0085] The content of the inorganic nanoparticles 25a in the resin layer 25 is 5% by mass or more and 60% by mass or less. By containing a sufficient amount of the inorganic nanoparticles 25a in the resin layer 25, the effect of improving the adhesion between the fiber-reinforced resin substrate 5 and the first member 20 described above can be sufficiently achieved. Since the amount of the inorganic nanoparticles 25a contained in the resin layer 25 is not too large, it is suppressed that cracks or the like occur in the resin layer 25 due to the inorganic nanoparticles 25a and that the haze of the molded product 1 is significantly observed due to the inorganic nanoparticles 25a.

[0086] The laminate 10 of the present embodiment includes a base material 11 and a first member 20. The first member 20 has a resin layer 25. The resin layer 25 contains inorganic nanoparticles 25a having an average primary particle diameter of 1 nm or more and 50 nm or less. By the inorganic nanoparticles 25a finely deforming the bonding layer 27 or by the inorganic nanoparticles 25a forming fine irregularities on the surface of the resin layer 25, a so-called anchor effect is generated between the fiber-reinforced resin substrate 5 and the first member 20, and the adhesion between the fiber-reinforced resin substrate 5 and the first member 20 is improved. Since the inorganic nanoparticles 25a are sufficiently large, the adhesion between the fiber-reinforced resin substrate 5 and the first member 20 is sufficiently improved. Since the inorganic nanoparticles 25a are not too large, it is suppressed that the molded product 1 is significantly observed to have haze due to the inorganic nanoparticles 25a. The indentation hardness of the resin layer 25 is 20 MPa or more. In the molded product 1 manufactured using the laminate 10, the indentation hardness of the resin layer 25 is 20 MPa or more. Even when the molded product 1 is exposed to a high temperature for a long time, the resin layer 25 suppresses the deformation of the surface of the molded product 1 and can maintain a desired shape. The deformation of the surface of the molded product 1 and the decrease in the adhesion between the fiber-reinforced resin substrate 5 and the first member 20 can be suppressed.

[0087] The indentation hardness of the resin layer 25 is 500 MPa or less. Since the indentation hardness of the resin layer 25 is not too high, when pressure is applied to the resin layer 25 such as when the first member 20 is stacked on the fiber-reinforced resin substrate 5 from the laminate 10, the resin layer 25 is suppressed from being damaged.

[0088] The resin layer 25 contains a three-dimensionally crosslinked resin. The cured resin can increase the indentation hardness of the resin layer 25. The resin layer 25 can suppress the deformation of the surface of the molded product 1 and maintain a desired shape.

[0089] In the laminate 10, the thickness of the resin layer 25 is 0.5 μm or more. Since the resin layer 25 has a sufficient thickness, the indentation hardness of the resin layer 25 can be made sufficiently high. The thickness of the resin layer 25 is 250 μm or less. Since the resin layer 25 is not too thick, the molded product 1 manufactured using the laminate 10 can be lightened.

[0090] In the molded article 1, the thickness of the resin layer 25 is 0.1 μm or more. Since the resin layer 25 has a sufficient thickness, the indentation hardness of the resin layer 25 in the molded article 1 is sufficiently high. The thickness of the resin layer 25 is 250 μm or less. Since the resin layer 25 is not too thick, the molded article 1 is lightweight.

[0091] The first member 20 further has a hard coat layer 21 and / or a functional layer 23. The first member 20 can protect the surface of the fiber-reinforced resin substrate 5 with the hard coat layer 21 or impart various functions exhibited by the functional layer 23 to the molded article 1. The hard coat layer 21 is disposed between the base material 11 and the resin layer 25. The resin layer 25 suppresses the deformation of the hard coat layer 21 that can become the surface of the molded article 1. The deformation of the surface of the molded article 1 can be suppressed to maintain a desired shape. The functional layer 23 is laminated on the resin layer 25. When the functional layer 23 is disposed between the base material 11 and the resin layer 25, the resin layer 25 suppresses the deformation of the functional layer 23. The deformation of the surface of the molded article 1 can be suppressed to maintain a desired shape.

[0092] The laminate 10 of the present embodiment has a base material 11 and a first member 20 laminated on the base material 11. The first member 20 has a resin layer 25. The resin layer 25 contains inorganic nanoparticles having an average primary particle diameter of 1 nm or more and 50 nm or less. The indentation hardness of the resin layer 25 is 20 MPa or more. Even if the molded article 1 manufactured using the laminate 10 is exposed to a high temperature for a long time, the resin layer 25 can suppress the deformation of the surface of the molded article 1.

[0093] Various modifications can be made to the present embodiment.

[0094] In the examples shown in FIGS. 1 and 2, the molded article 1 has one first member 20, and the first member 20 is overlaid on one surface of the fiber reinforced resin substrate 5. When the base material 11 is peeled off, the first member 20 forms one surface of the molded article 1. Not limited to the illustrated example, the molded article 1 may have two first members 20. The first members 20 may be overlaid on both surfaces of the fiber reinforced resin substrate 5. One first member 20 forms one surface of the molded article 1, and the other first member 20 forms the other surface of the molded article 1. By using two laminates 10, the first members 20 can be overlaid on both surfaces of the fiber reinforced resin substrate 5.

[0095] The molded article 1 is used, for example, as an exterior material or an interior material of a moving body such as a vehicle, a ship, or an aircraft, an exterior material or an interior material of a building, or a member of furniture or a household appliance.

[0096] Aspects of the present disclosure are not limited to the above-described embodiments and their modifications, but also include various modifications that can be conceived by those skilled in the art, and the effects of the present disclosure are not limited to the contents related to the above-described embodiments and their modifications. Various additions, changes, and partial deletions are possible without departing from the conceptual ideas and spirit of each disclosure derived from the contents defined in the claims and their equivalents.

Example

[0097] The present disclosure will be described in more detail with reference to examples. The present disclosure is not limited to the following examples.

[0098] As examples and comparative examples, a plurality of molded articles having a fiber-reinforced resin substrate and a first member were produced using a laminate having a base material and a first member. The first member has at least a resin layer. In each example and each comparative example, the base material is polyethylene terephthalate with a thickness of 50 μm. The fiber-reinforced resin substrate is a prepreg with a thickness of 200 μm obtained by curing a resin-impregnated fiber sheet in which carbon fibers aligned in one direction are impregnated with a urethane acrylate resin and a curing agent. In each example and each comparative example, the presence or absence of a hard coat layer and the configuration of the resin layer are different. In each example and each comparative example, the first member does not have a bonding layer. In each example and each comparative example, the thickness of the resin layer is 10 μm.

[0099] (Example 1) In the laminate according to Example 1, the first member has a hard coat layer. The hard coat layer is produced by irradiating an electron beam after applying urethane acrylate on the base material. The thickness of the hard coat layer is 3 μm. Then, a resin layer is provided on the hard coat layer. The resin layer contains an epoxy resin as a resin composition, hexamethylene diisocyanurate (HDI nurate) (TPA-100 manufactured by Asahi Kasei) as a curing agent, and further inorganic nanoparticles with an average primary particle diameter of 15 nm. The inorganic nanoparticles are made of alumina. The content of the inorganic nanoparticles in the resin layer is 20% by mass. After coating the resin layer, it is heated at 130 °C for 10 minutes to cure. The resin layer side of the laminate according to Example 1 prepared in this way is overlapped with the fiber-reinforced resin substrate and passed through the laminating device shown in FIG. 8 under the conditions of a speed of 0.3 m / min, a temperature of 130 °C, and a pressure of 3 MPa to be molded, and a molded article according to Example 1 is produced.

[0100] (Example 2) The laminate and molded article of Example 1 were produced in the same manner except for the inorganic nanoparticles. In the laminate according to Example 2, the resin layer contains inorganic nanoparticles with an average primary particle diameter of 10 nm. The inorganic nanoparticles are made of silica. The content of the inorganic nanoparticles in the resin layer is 30% by mass.

[0101] (Example 3) It was produced in the same manner as the laminate and molded article of Example 1, except that the first member did not have a hard coat layer.

[0102] (Example 4) It was produced in the same manner as the laminate and molded article of Example 2, except that the first member did not have a hard coat layer.

[0103] (Example 5) It was produced in the same manner as the laminate and molded article of Example 3, except for the resin composition of the resin layer. In the laminate according to Example 5, the resin composition of the resin layer is an ultraviolet curable resin. The resin layer does not contain a curing agent.

[0104] (Example 6) It was produced in the same manner as the laminate and molded article of Example 4, except for the resin composition of the resin layer. In the laminate according to Example 6, the resin composition of the resin layer is an ultraviolet curable resin. The resin layer does not contain a curing agent.

[0105] (Example 7) It was produced in the same manner as the laminate and molded article of Example 3, except for the resin composition of the resin layer. In the laminate according to Example 7, the resin composition of the resin layer is a radiation curable resin. The resin layer does not contain a curing agent.

[0106] (Example 8) It was produced in the same manner as the laminate and molded article of Example 4, except for the resin composition of the resin layer. In the laminate according to Example 8, the resin composition of the resin layer is a radiation curable resin. The resin layer does not contain a curing agent.

[0107] (Comparative Example 1) It was produced in the same manner as the laminate and molded article of Example 1, except that the resin layer did not contain inorganic nanoparticles.

[0108] (Comparative Example 2) It was produced in the same manner as the laminate and molded article of Example 3, except that the resin layer did not contain inorganic nanoparticles.

[0109] (Comparative Example 3) It was produced in the same manner as the laminate and molded article of Example 5, except that the resin layer did not contain inorganic nanoparticles.

[0110] (Comparative Example 4) It was produced in the same manner as the laminate and molded article of Example 7, except that the resin layer did not contain inorganic nanoparticles.

[0111] (Evaluation) The indentation hardness of the resin layer in the laminate and molded article according to each example and each comparative example was measured. After exposing the molded article according to each example and each comparative example to a temperature of 80°C for 720 hours, the smoothness of the surface of the molded article was visually confirmed. Those in which no uneven shape was confirmed on the surface were evaluated as A, and those in which no uneven shape that impaired the appearance of the molded article was confirmed on the surface were evaluated as B. Further, after exposing the molded article according to each example and each comparative example to a temperature of 80°C for 720 hours, the adhesion between the fiber-reinforced resin substrate and the first member was visually confirmed. Those in which it was not confirmed that the fiber-reinforced resin substrate and the first member were peeled off were evaluated as A, those in which it was confirmed that the fiber-reinforced resin substrate and the first member were slightly peeled off were evaluated as B, and those in which it was confirmed that the fiber-reinforced resin substrate and the first member were clearly peeled off were evaluated as C.

[0112] The differences in the configurations and the evaluation results of each example and each comparative example are shown in Table 1. In Table 1, the HC layer represents the hard coat layer, and the nanoparticles represent inorganic nanoparticles, respectively.

[0113]

Table 1

[0114] As understood from the examples described in Table 1, when the indentation hardness of the shape-maintaining layer in the molded product is 20 MPa or more, even if the molded product is exposed to high temperatures for a long time, deformation of the surface of the molded product is suppressed. As understood from the comparison between the examples and comparative examples shown in Table 1, when the resin layer contains inorganic nanoparticles having an average primary particle diameter of 1 nm or more and 50 nm or less, even if the molded product is exposed to high temperatures for a long time, peeling of the fiber-reinforced resin substrate and the first member is suppressed.

Explanation of Signs

[0115] 1 Molded product 5 Fiber-reinforced resin substrate 10 Laminate 11 Base material 20 First member 21 Hard coat layer 23 Functional layer 25 Resin layer 25a Inorganic nanoparticles 27 Bonding layer 50 Laminating apparatus

Claims

1. A base material, and a first member laminated on the base material, wherein the first member has a resin layer, the resin layer contains inorganic nanoparticles having an average primary particle diameter of 1 nm or more and 50 nm or less, and the indentation hardness of the resin layer is 20 MPa or more. A laminate.

2. The laminate according to claim 1, wherein the content of the inorganic nanoparticles in the resin layer is 5% by mass or more and 60% by mass or less.

3. The laminate according to claim 1, wherein the indentation hardness of the resin layer is 500 MPa or less.

4. The laminate according to claim 1, wherein the resin layer contains a three-dimensionally crosslinked resin.

5. The laminate according to claim 1, wherein the thickness of the resin layer is 0.5 μm or more.

6. The laminate according to claim 1, wherein the thickness of the resin layer is 0.5 μm or more and 250 μm or less.

7. The laminate according to claim 1, wherein the first member further has a hard coat layer disposed between the base material and the resin layer and / or a functional layer laminated on the resin layer.

8. A first member having a resin layer, and a fiber-reinforced resin substrate laminated on the first member, wherein the resin layer contains inorganic nanoparticles having an average primary particle diameter of 1 nm or more and 50 nm or less, and the indentation hardness of the resin layer is 20 MPa or more. A molded article.

9. The molded article according to claim 8, wherein in the resin layer, the inorganic nanoparticles are 5% by mass or more and 60% by mass or less.

10. The molded article according to claim 8, wherein the first member further has a hard coat layer and / or a functional layer laminated on the resin layer.

11. The molded article according to claim 8, wherein the thickness of the resin layer is 0.1 μm or more.

12. The molded article according to claim 8, wherein the thickness of the resin layer is 0.1 μm or more and 250 μm or less.

13. A step of producing a first member having a resin layer containing inorganic nanoparticles, a step of laminating the first member on a base material to form a laminate, and a laminating step of laminating the laminate on a resin-impregnated fiber sheet so that the first member is closer to the resin-impregnated fiber sheet than the base material, wherein the average primary particle diameter of the inorganic nanoparticles is 1 nm or more and 50 nm or less, and the indentation hardness of the resin layer after the laminating step is 20 MPa or more. A method for manufacturing a molded article.

14. The manufacturing method of the molded article according to claim 13, wherein in the laminating step, the laminate and the resin-impregnated fiber sheet are heated and pressurized.

15. The manufacturing method of the molded article according to claim 13, further comprising a peeling step of peeling the base material.

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