Transfer sheet, manufacturing method of decorative mold body, and decorative mold body

Abstract

To provide a transfer sheet for transferring a transfer layer to a fiber-reinforced resin substrate, which has good transferability to the fiber-reinforced resin substrate.SOLUTION: A transfer sheet 10 has a release film 1 and a transfer layer X arranged on one side of the release film, and the transfer layer X has, from the side of the release film 1, a protective layer 2 and a decorative layer 3 in this order in a thickness direction, and the indentation hardness of a cross section of the decorative layer 3 is 100 MPa or over.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a transfer sheet, a method for producing a decorated molded article, and a decorated molded article. [Background technology]

[0002] Components used in sports equipment, aircraft, and the like may be subjected to large impacts and deformation stresses. For such components, it has been proposed to use molded bodies having a substrate made of fiber-reinforced resin such as carbon fiber reinforced plastic (CFRP) and glass fiber reinforced plastic (GFRP). Fiber-reinforced resin substrates are generally manufactured by impregnating reinforcing fibers such as carbon fibers and glass fibers with a matrix resin and curing them as necessary. Because the fiber-reinforced resin substrate is reinforced by fibers, it is a relatively lightweight yet strong component.

[0003] In some cases, the fiber-reinforced resin substrate is required to have not only light weight and mechanical properties but also design. For example, Patent Document 1 discloses a fiber-reinforced resin molded product with a hard coat layer that utilizes the design properties unique to carbon fiber-reinforced resins and the like. Patent Document 2 discloses a heat-weldable film for joining a first member made of a decorative film and a second member made of a fiber-reinforced plastic, the surface on one side and the surface on the other side being made of a heat-weldable resin layer containing a predetermined amount of acid-modified polyolefin. In recent years, the fiber-reinforced resin substrate has been considered for use in building materials such as window frames, and higher design properties are required than ever before. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2020-142487 A [Patent Document 2] Patent Publication No. 2021-008568 Summary of the Invention [Problem to be solved by the invention]

[0005] As a method for imparting design to a fiber-reinforced resin substrate, a method of transferring a decorative layer to the fiber-reinforced resin substrate using a transfer sheet is considered. The transfer sheet has, for example, a release film and a transfer layer, and the transfer layer has, in this order, a protective layer and a decorative layer from the release film side. When transferring a decorative layer to a fiber-reinforced resin substrate using a transfer sheet, the transfer layer side surface of the transfer sheet and a prepreg in which reinforcement fibers are impregnated with a matrix resin are opposed to each other, and both are pressed together to harden the matrix resin, thereby obtaining a fiber-reinforced resin substrate from the prepreg, and integrating the transfer sheet and the fiber-reinforced resin substrate. Thereafter, the release film in the transfer sheet is peeled off. However, when the release film is peeled off, the release film may break, and the protective layer may remain on the release film side. Such a decrease in transferability does not occur when the transfer layer is transferred to a resin member such as a polycarbonate substrate or an acrylic substrate using a transfer sheet, and is therefore a problem specific to the transfer sheet for transferring the transfer layer to the fiber-reinforced resin substrate.

[0006] The present disclosure has been made in consideration of the above problems, and has as its main object to provide a transfer sheet for transferring a transfer layer to a fiber-reinforced resin substrate, the transfer sheet having good transferability to the fiber-reinforced resin substrate. [Means for solving the problem]

[0007] The present disclosure provides a transfer sheet for transferring a transfer layer to a fiber-reinforced resin substrate, the transfer sheet having a release film and the transfer layer arranged on one side of the release film, the transfer layer having, from the release film side, a protective layer and a decorative layer in this order in the thickness direction, and the indentation hardness of the cross section of the decorative layer is 100 MPa or more.

[0008] The present disclosure also provides a method for producing a decorated molded body, the method comprising: a preparation step of preparing the above-mentioned transfer sheet; a step of opposing the transfer layer side of the transfer sheet to a prepreg having reinforcing fibers impregnated with a matrix resin, pressing the two together, and curing the matrix resin to obtain the fiber-reinforced resin substrate from the prepreg; an integration step of integrating the transfer sheet with the fiber-reinforced resin substrate; and a peeling step of peeling off the release film on the transfer sheet.

[0009] The present disclosure provides a decorated molded body having a protective layer, a decorative layer, and a fiber-reinforced resin substrate, in that order in the thickness direction, wherein the indentation hardness of the cross section of the decorative layer is 100 MPa or more. Effect of the Invention

[0010] The present disclosure has an effect of providing a transfer sheet that has good transferability to a fiber-reinforced resin substrate. [Brief description of the drawings]

[0011] [Figure 1] 1 is a schematic cross-sectional view illustrating a transfer sheet according to the present disclosure. [Diagram 2] 1A to 1C are schematic cross-sectional views illustrating a method for producing a transfer sheet in the present disclosure. [Diagram 3] 1A to 1C are schematic cross-sectional views illustrating a method for producing a decorated molded body according to the present disclosure. [Figure 4] 1 is a schematic cross-sectional view showing an example of a decorated molded body according to the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The following describes the embodiments with reference to the drawings. However, the present disclosure can be implemented in many different forms and should not be limited to the description of the embodiments exemplified below. In addition, the drawings may show the width, thickness, and shape of each part in a schematic manner compared to the actual form in order to make the description clearer, but this is merely an example and should not be interpreted as being limiting.

[0013] In this specification, when describing a mode in which another component is disposed on a certain component, the term "above" or "below" includes both cases in which another component is disposed directly above or below the certain component so as to be in contact with the component, and cases in which another component is disposed above or below the certain component with another component interposed therebetween, unless otherwise specified. In addition, in this specification, when describing a mode in which another component is disposed on the surface of a certain component, the term "on the surface" includes both cases in which another component is disposed directly above or below the certain component so as to be in contact with the component, and cases in which another component is disposed above or below the certain component with another component interposed therebetween, unless otherwise specified.

[0014] The inventors of the present application have found that the deterioration of transferability to a fiber-reinforced resin substrate that occurs when the above-mentioned transfer sheet is used is caused by the matrix resin contained in the prepreg penetrating to the interface between the protective layer and the release film in the transfer sheet during the integration process in which the transfer sheet and the prepreg are pressure-bonded. They have also found that penetrating of the matrix resin into the protective layer can be suppressed by setting the indentation hardness of the cross section of the decorative layer to a predetermined value or more, and have completed the present invention.

[0015] The transfer sheet, the method for producing the decorated molded article, and the decorated molded article according to the present disclosure will be described in detail below.

[0016] A. Transfer sheet The transfer sheet in the present disclosure is a transfer sheet for transferring a transfer layer to a fiber-reinforced resin substrate. FIG. 1(a) is a schematic cross-sectional view illustrating the transfer sheet in the present disclosure. As shown in FIG. 1(a), the transfer sheet 10 has a release film 1 and a transfer layer X arranged on one surface of the release film 1. The transfer layer X is a layer formed by attaching a protective layer 2 and a decorative layer 3 from the release film 1 side in a thickness direction D. T 1(b), the transfer sheet 10 may have a permeation prevention layer 4 on the surface of the decorative layer 3 opposite to the protective layer 2. As shown in FIG. 1(c), the transfer sheet 10 may have a primer layer 5 between the protective layer 2 and the decorative layer 3. As shown in FIG. 1(d), the transfer sheet 10 may have a permeation prevention layer 4 on the surface of the decorative layer 3 opposite to the protective layer 2, and may have a primer layer 5 between the protective layer 2 and the decorative layer 3.

[0017] In the transfer sheet of the present disclosure, the indentation hardness of the cross section of the decorative layer is equal to or greater than a predetermined value. Therefore, the density of the decorative layer is high, and during the integration process in which the transfer sheet and the prepreg are pressure-bonded, the matrix resin contained in the prepreg is less likely to penetrate into the protective layer. Therefore, it is possible to peel off the release film at the interface between the protective layer and the release film, and it is possible to suppress breakage of the release film and the protective layer remaining on the release film side. In other words, the transferability to the fiber-reinforced resin substrate is good.

[0018] 1.Decorative layer The transfer sheet in the present disclosure has a decorative layer. The decorative layer is disposed on the surface of the protective layer opposite to the release film. The decorative layer imparts design to the fiber-reinforced resin substrate. The decorative layer and the protective layer may be disposed so as to be in direct contact with each other, or may be disposed via another layer.

[0019] (1) Indentation hardness In the present disclosure, the indentation hardness in the cross section of the decorative layer is usually 100 MPa or more, may be 130 MPa or more, or may be 150 MPa or more. When the indentation hardness in the cross section of the decorative layer is in the above range, it is possible to suppress the matrix resin contained in the prepreg from seeping into the protective layer in the integration process with the prepreg when manufacturing the decorative molded body. Therefore, it is possible to suppress the influence of the matrix resin on the interface between the protective layer and the release film, and the transferability is improved. Furthermore, when the indentation hardness in the cross section of the decorative layer is in the above range, it is possible to utilize the hardness specific to the fiber reinforced resin substrate, and scratch resistance is easily obtained.

[0020] On the other hand, the indentation hardness of the decorative layer in a cross section is, for example, 400 MPa or less, may be 350 MPa or less, or may be 300 MPa or less. If the indentation hardness of the decorative layer in a cross section is within the above range, for example, good adhesion can be obtained between the decorative layer and the protective layer.

[0021] The indentation hardness of the cross section of the decorative layer can be adjusted, for example, by the type of binder resin in the ink composition for the decorative layer for producing the decorative layer. For example, the indentation hardness can be adjusted by using a resin having a reactive functional group such as a hydroxyl group as the binder resin. For example, by increasing the number of reactive functional groups of the binder resin, the number of crosslinking points in the decorative layer increases, and the indentation hardness can be increased. Furthermore, the indentation hardness can be increased by blending a curing agent in the ink composition for the decorative layer.

[0022] The indentation hardness of the cross section of the decorative layer is a value obtained by measuring a cross section sample piece prepared by the resin embedding method and a microtome by the following indentation hardness measurement method. When the decorative layer includes a solid layer and a pattern layer, it is preferable to measure the indentation hardness of the cross section of the solid layer.

[0023] (Method of preparing cross-sectional sample pieces for measurement) The transfer sheet is cut to an arbitrary size to prepare a cut sample. The cut sample is embedded in resin (a room temperature curing type epoxy two-part curing resin) and left at room temperature for 24 hours or more to harden, thereby preparing an embedded sample in which the cut sample is embedded in resin (resin embedding method). The embedded sample is cut vertically using a microtome to expose the cross section of the layer to be measured, thereby preparing a cross-sectional sample piece for indentation hardness measurement. Specifically, a cross section is prepared in an environment of -120°C by using an ultramicrotome (Leica EM UC6, manufactured by Leica Microsystems) equipped with a freezing cutting system (Leica EM FC6, manufactured by Leica Microsystems) and a diamond knife, exposing the cross section of the layer to be measured. Compared to a cross section cut in an environment of room temperature, cross-sectional roughness can be suppressed, and a cross section suitable for indentation testing can be obtained. In particular, cross-sectional roughness can be suppressed in the case of soft materials.

[0024] (Method of measuring indentation hardness) In this specification, the "indentation hardness" is measured by the nanoindentation method, which is a method for continuously measuring the load and displacement during the process of pressing an indenter into the surface of a sample and unloading it, and calculating the mechanical quantity from the obtained load-displacement curve.

[0025] Specifically, the indentation hardness of the cross section of the decorative layer is measured by pressing a Berkovich indenter (material: diamond triangular pyramid) vertically into the cut surface of the above-mentioned measurement sample using the following nanoindenter. The measurement device and measurement conditions are as follows. Here, it is preferable that the position where the Berkovich indenter is pressed is approximately the center in the thickness direction of the decorative layer. Approximately the center means that when the thickness of the decorative layer is defined as T [μm], the deviation from the center in the thickness direction of the decorative layer is within ±0.1T. Furthermore, when fine particles such as pigments and fillers are contained in the layer, the Berkovich indenter is pressed into a position that avoids the fine particles.

[0026] Equipment used: Nanoindenter (TI 950 TriboIndenter, manufactured by BRUKER) Indenter used: Berkovich indenter (model number: TI-0039, manufactured by BRUKER) Push-in control method: Displacement control method (no lift operation) Maximum indentation depth: 100nm Push rate: 10nm / sec Loading time: 10 seconds (pushing from 0 to 100 nm) ·Holding time: 5 seconds (100nm constant) Unloading time: 10 seconds (100 nm → return to 0) Number of measurements: 5

[0027] The indentation hardness of the cross section of the decorative layer can be calculated as follows. First, the indentation depth h (nm) corresponding to the indentation load P (N) is continuously measured, and a load-displacement curve is created. The created load-displacement curve is analyzed, and the maximum indentation load P max (N) is the projected area A (mm 2 ) is the indentation hardness H IT can be calculated (formula (1) below). H IT =P max / A …(1) Here, A is the contact projected area obtained by correcting the indenter tip shape using a standard sample of fused quartz in a standard manner.

[0028] In this specification, the indentation hardness of the cross section of the decorative layer is the arithmetic average value of five measurements of the same sample, with the position shifted. Each measurement is measured with a shift of 5 μm or more. During the measurement, in order to confirm that the correction of the indenter shape is correctly performed and that there are no problems with the operation and measurement of the device, it is preferable to confirm that the measurement is performed within ±5% of the reference value using fused quartz, which is the standard sample of the device manufacturer. The indentation hardness is measured in an atmosphere with a temperature of 23°C ±5°C and a humidity of 40% to 65%.

[0029] (2) Composition Examples of the decorative layer include a solid layer and a pattern layer. In the present disclosure, the solid layer means a layer formed so as to cover the entire surface of the transfer area of ​​the fiber-reinforced resin substrate. The transfer area of ​​the fiber-reinforced resin substrate refers to the area where the fiber-reinforced resin substrate and the transfer layer overlap, and the "entire surface of the transfer area" refers to 90% or more of the transfer area. The pattern layer means a layer formed partially (particularly in a pattern) so as to cover a part of the transferred area. In the transfer sheet of the present disclosure, it is preferable that the decorative layer has a solid layer. This is because the effect of suppressing the penetration of the matrix resin by the decorative layer can be obtained more effectively. In particular, it is preferable that the decorative layer includes both a solid layer and a pattern layer.

[0030] The decorative layer preferably has a high concealing property so that it can conceal the color and pattern of the underlying fiber-reinforced resin substrate. In other words, when the decorative layer includes a solid layer and a pattern layer, the decorative layer including the solid layer and the pattern layer preferably has a high concealing property. Specifically, the decorative layer preferably has a concealing rate of the transfer layer within the range described below.

[0031] The decorative layer in the present disclosure preferably has, in order from the release film side, a pattern layer and a solid layer. Examples of the pattern in the pattern layer include wood grain, stone grain, sand grain, tiled pattern, brickwork pattern, cloth grain, leather-squeezed pattern, geometric figures, letters, symbols, abstract patterns, floral patterns, wave patterns, stripes, metallic patterns, and rust-like patterns.

[0032] (3) Thickness The thickness of the decorative layer is, for example, 3 μm or more, may be 5 μm or more, or may be 10 μm or more. When the thickness of the decorative layer is in the above range, the concealment property of the fiber reinforced resin substrate is improved. On the other hand, the thickness of the decorative layer is, for example, 20 μm or less, and may be 15 μm or less. When the thickness of the decorative layer is in the above range, peeling between layers of the decorative layer can be suppressed.

[0033] (4) Material The decorative layer usually contains a colorant and a binder resin. Examples of the colorant include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue, organic pigments (including dyes) such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue, and azomethine azo black, metal pigments such as aluminum and brass, and pearl pigments such as titanium dioxide-coated mica and basic lead carbonate.

[0034] Examples of the binder resin include urethane resin, acrylic polyol resin, (meth)acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane acrylic copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-acrylic copolymer, chlorinated propylene resin, nitrocellulose resin, and cellulose acetate resin. Among them, it is more preferable to use acrylic polyol resin.

[0035] The binder resin may be a resin that is crosslinked and cured by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to the above-mentioned resin. For example, a resin that is crosslinked and cured by adding an isocyanate-based curing agent to a polyol-based resin such as an acrylic polyol resin is preferred.

[0036] The decorative layer may contain additives such as an ultraviolet absorbing agent, a light stabilizer, a curing agent, a plasticizer, and a catalyst, if necessary.

[0037] 2.Protective layer The protective layer contributes to improving the surface properties (for example, scratch resistance, abrasion resistance, etc.) of the decorated molded body. The protective layer and the release film are preferably disposed so as to be in direct contact with each other.

[0038] (1) Indentation hardness The indentation hardness of the cross section of the protective layer is, for example, 100 MPa or more, may be 150 MPa or more, or may be 200 MPa or more. If the indentation hardness of the cross section of the protective layer is the above value or more, good scratch resistance can be obtained. On the other hand, the indentation hardness of the cross section of the protective layer is, for example, 400 MPa or less, may be 300 MPa or less, or may be 250 MPa or less. If the indentation hardness of the cross section of the protective layer is within the above range, for example, the conformability of the protective layer to the decorative layer or primer layer is good, and the weather-resistant adhesion is improved. The method of preparing the cross section sample piece of the transfer sheet and the method of measuring the indentation hardness of the protective layer are the same as those described for the decorative layer above.

[0039] The indentation hardness in the cross section of the protective layer may be larger, the same, or smaller than the indentation hardness in the cross section of the decorative layer. The indentation hardness in the cross section of the protective layer and the indentation hardness in the cross section of the decorative layer being the same means that the absolute value of the difference between the two is 10 MPa or less. In addition, when the indentation hardness in the cross section of the protective layer is larger than the indentation hardness in the cross section of the decorative layer, the difference is usually larger than 10 MPa, may be 30 MPa or more, may be 50 MPa or more. Conversely, when the indentation hardness in the cross section of the protective layer is smaller than the indentation hardness in the cross section of the decorative layer, the difference is usually larger than 10 MPa, may be 30 MPa or more, may be 50 MPa or more, may be 100 MPa or more. It is preferable that the decorative molded body described later also has the above-mentioned indentation hardness relationship.

[0040] The indentation hardness of the cross section of the protective layer can be adjusted, for example, by the number of functional groups of the curable resin in the first curable resin composition for producing the protective layer. For example, by reducing the number of functional groups of the ionizing radiation curable compound, the number of crosslinking points in the cured product of the first curable resin composition can be reduced, resulting in a more flexible structure and a lower indentation hardness.

[0041] (2) Thickness The thickness of the protective layer is, for example, 2 μm or more, may be 3 μm or more, or may be 5 μm or more. By having the thickness of the protective layer in the above range, sufficient scratch resistance can be obtained. On the other hand, for example, it is 20 μm or less, may be 15 μm or less, or may be 10 μm or less. By having the thickness of the protective layer in the above range, it is preferable in terms of cost and can suppress cracks.

[0042] (3) Material (a) Resin component The protective layer contains, for example, a cured product (crosslinked structure) of the first curable resin composition. The cured product of the first curable resin composition preferably contains a (meth)acrylic component and a urethane component. The (meth)acrylic component refers to an acrylic component or a methacrylic component. The urethane component refers to a urethane bond. The proportion of the cured product of the first curable resin composition is, for example, 70% by mass or more, may be 90% by mass or more, may be 95% by mass or more, or may be 100% by mass, based on the total resin components constituting the protective layer.

[0043] Examples of the first curable resin composition include an ionizing radiation curable resin composition and a heat curable resin composition. Examples of the ionizing radiation curable resin composition include an electron beam curable resin composition and an ultraviolet ray curable resin composition. Among these, an electron beam curable resin composition is preferred because it does not require a polymerization initiator, has little odor, and is less likely to cause coloring.

[0044] The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as "ionizing radiation curable compound"). The ionizing radiation curable functional group is a group that crosslinks and cures when irradiated with ionizing radiation. The ionizing radiation curable resin composition preferably contains at least a compound having a (meth)acryloyl group. The (meth)acryloyl group refers to an acryloyl group or a methacryloyl group. The ionizing radiation curable resin composition may also contain a compound having a functional group having an ethylenic double bond, such as a vinyl group or an allyl group, in addition to the compound having a (meth)acryloyl group.

[0045] The number of functional groups of the ionizing radiation curable compound is preferably from 2 to 20, more preferably from 2 to 18, and even more preferably from 2 to 15. This is because the indentation hardness of the protective layer can be easily adjusted to the above range.

[0046] Ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Examples of ionizing radiation include electron beams (EB) and ultraviolet rays (UV). Other examples of ionizing radiation include electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams.

[0047] The ionizing radiation curable resin composition preferably contains at least a urethane (meth)acrylate as an ionizing radiation curable compound. (Meth)acrylate refers to acrylate or methacrylate. The ionizing radiation curable resin composition may further contain at least one of epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polycarbonate (meth)acrylate, and acrylic (meth)acrylate as an ionizing radiation curable compound in addition to the urethane (meth)acrylate.

[0048] The ionizing radiation curable resin composition preferably contains a caprolactone-based urethane (meth)acrylate as the urethane (meth)acrylate. The ionizing radiation curable resin composition may also contain a caprolactone-based urethane (meth)acrylate and a urethane (meth)acrylate that is not modified with caprolactone. In this case, the content of the caprolactone-based urethane (meth)acrylate contained in the protective layer is set to M CLUA The content of urethane (meth)acrylate not modified with caprolactone is M UA Let us assume that UA and M. CLUA M for the sum of CLUA Mass ratio (M CLUA / (M UA +M CLUA )) is, for example, 10% by mass or more and 90% by mass or less, alternatively 20% by mass or more and 80% by mass or less, or alternatively 30% by mass or more and 70% by mass or less.

[0049] When the ionizing radiation curable compound contains a caprolactone-based urethane (meth)acrylate, the number of functional groups of the caprolactone-based urethane (meth)acrylate is preferably from 2 to 9, and more preferably from 2 to 5. This is because, by setting the number of functional groups of the caprolactone-based urethane (meth)acrylate within the above range, it is easy to adjust the indentation hardness of the cross section of the protective layer to the above range.

[0050] Caprolactone-based urethane (meth)acrylate can usually be obtained by reacting caprolactone-based polyol, organic isocyanate, and hydroxy (meth)acrylate. For example, the synthesis method includes reacting polycaprolactone-based polyol with organic polyisocyanate to generate a polyurethane prepolymer containing -NCO groups (isocyanate groups) at both ends, and then reacting it with hydroxy (meth)acrylate.

[0051] As the caprolactone-based polyol, commercially available products can be used, preferably those having two hydroxyl groups and a number average molecular weight of preferably 500 to 3000, more preferably 750 to 2000. In addition, polyols other than caprolactone-based polyols, such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, etc., can be used by mixing one or more polyols at any ratio. As the organic polyisocyanate, diisocyanates having two isocyanate groups are preferred, and from the viewpoint of suppressing yellowing, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate, etc. are preferred. As the hydroxy(meth)acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, caprolactone-modified 2-hydroxyethyl acrylate, etc. are preferred.

[0052] When using a caprolactone-based polyol, the caprolactone-based urethane (meth)acrylate is preferably a caprolactone diol-based urethane (meth)acrylate. The caprolactone diol-based urethane (meth)acrylate refers to a urethane (meth)acrylate having a diethylene glycol terminal among caprolactone-based urethane (meth)acrylates. By using the caprolactone diol-based urethane (meth)acrylate, it is possible to suppress the occurrence of cracks and whitening in the protective layer.

[0053] The number average molecular weight of the ionizing radiation curable compound is, for example, from 1,000 to 10,000, and may be from 2,000 to 10,000. The number average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0054] For example, when the ionizing radiation curable compound is an ultraviolet ray curable compound, the ionizing radiation curable compound preferably contains at least one of a photopolymerization initiator and a photopolymerization accelerator. Examples of the photopolymerization initiator include acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyloxime ester, acylphosphine oxide, and thioxanthones. Examples of the photopolymerization accelerator include p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester.

[0055] The first curable resin composition may be a thermosetting resin composition. Details of the thermosetting resin composition are the same as those of the thermosetting resin composition in the primer layer described below.

[0056] (b) Weatherproofing agent The protective layer contains, for example, a weathering agent. Examples of the weathering agent include an ultraviolet absorbing agent and a light stabilizer. The protective layer preferably contains at least one of an ultraviolet absorbing agent and a light stabilizer. The protective layer may contain one or more ultraviolet absorbing agents. Similarly, the protective layer may contain one or more light stabilizers.

[0057] Examples of the ultraviolet absorber contained in the protective layer include organic ultraviolet absorbers such as triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, oxybenzophenone-based ultraviolet absorbers, salicylic acid ester-based ultraviolet absorbers, and cyano(meth)acrylate-based ultraviolet absorbers, and inorganic ultraviolet absorbers such as titanium dioxide, cerium oxide, and zinc oxide. Among these, triazine-based ultraviolet absorbers are more preferred.

[0058] Examples of triazine-based ultraviolet absorbers include hydroxyphenyl triazine-based ultraviolet absorbers. Examples of hydroxyphenyl triazine-based ultraviolet absorbers include 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, azine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5[2-(2-ethylhexanoyloxy)ethoxy]phenol.

[0059] The ultraviolet absorber may be a reactive ultraviolet absorber having a reactive functional group having an ethylenic double bond in the molecule, such as a (meth)acryloyl group, a vinyl group, an allyl group, etc. If an ultraviolet absorber containing such a reactive group is used, it becomes difficult to bleed out during the integration step with the prepreg, and therefore weather resistance can be further improved.

[0060] The content of the ultraviolet absorber in the protective layer is, for example, 0.5 parts by mass to 10 parts by mass, alternatively 0.8 parts by mass to 8 parts by mass, or alternatively 1 part by mass to 5 parts by mass, relative to 100 parts by mass of the ionizing radiation curable compound. If the content of the ultraviolet absorber is high, bleeding out of the ultraviolet absorber may occur, whereas if the content of the ultraviolet absorber is low, sufficient ultraviolet absorbing performance may not be obtained.

[0061] The light stabilizer contained in the protective layer may be, for example, a hindered amine light stabilizer. Examples of the hindered amine light stabilizer include, for example, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, and 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine).

[0062] The light stabilizer may be a reactive light stabilizer having a reactive functional group having an ethylenic double bond such as a (meth)acryloyl group in the molecule. When a light stabilizer containing such a reactive group is used, it becomes difficult for the stabilizer to bleed out during the integration step with the prepreg, and therefore weather resistance can be further improved.

[0063] The content of the light stabilizer in the protective layer is, for example, 1 part by mass to 10 parts by mass, or may be 1.5 parts by mass to 8 parts by mass, or may be 2 parts by mass to 5 parts by mass, relative to 100 parts by mass of the ionizing radiation curable compound. If the content of the light stabilizer is high, bleeding out of the light stabilizer may occur, and if the content of the light stabilizer is low, sufficient light stability may not be obtained.

[0064] (c) Additives The protective layer may contain additives such as a silicone compound, a polymerization inhibitor, a crosslinking agent, an antistatic agent, an adhesion improver, an antioxidant, a leveling agent, a thixotropy imparting agent, a coupling agent, a plasticizer, an antifouling agent, an antifoaming agent, a filler, an anti-wear agent, an antibacterial agent, an antiviral agent, and an antifungal agent.

[0065] 3. Transfer layer The transfer sheet in the present disclosure has a release film and a transfer layer disposed on one side of the release film. The transfer layer has at least a protective layer and a decorative layer in order from the release film side. The transfer layer may further have other layers. Examples of the other layers include a permeation prevention layer and a primer layer. As shown in FIG. 1(b), the transfer layer X may have, in order from the release film side 1, a protective layer 2, a decorative layer 3, and a permeation prevention layer 4. Also, as shown in FIG. 1(c), the transfer layer X may have, in order from the release film side 1, a protective layer 2, a primer layer 5, and a decorative layer 3. Also, as shown in FIG. 1(d), the transfer layer X may have, in order from the release film side 1, a protective layer 2, a primer layer 5, a decorative layer 3, and a permeation prevention layer 4.

[0066] (1) Other layers (a) Penetration prevention layer The transfer sheet in the present disclosure may or may not have a permeation prevention layer on the surface of the decorative layer opposite to the protective layer. By having the permeation prevention layer, the matrix resin contained in the prepreg can be further suppressed from permeating into the protective layer in the integration process. The permeation prevention layer is not particularly limited as long as it is a layer that can suppress the matrix resin contained in the prepreg from permeating into the protective layer, but it is preferable that the permeation prevention layer is a layer that has good adhesion to the decorative layer and the fiber-reinforced resin substrate. The permeation prevention layer may be the outermost layer of the transfer sheet. It is preferable that the permeation prevention layer and the decorative layer are in direct contact with each other.

[0067] The permeation prevention layer preferably contains a resin component. The permeation prevention layer preferably contains a cured product (crosslinked structure) of the third curable resin composition. The third curable resin composition may be, for example, a thermosetting resin composition. The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a composition that is cured by heating. The third curable resin composition may further contain at least one of a (meth)acrylic resin, an epoxy resin, a urethane resin, and the like, as a thermosetting resin. In addition, the thermosetting resin composition may further contain a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent.

[0068] The indentation hardness of the cross section of the permeation prevention layer is, for example, 400 MPa or less, may be 350 MPa or less, or may be 300 MPa or less. When the indentation hardness of the cross section of the permeation prevention layer is within the above range, the adhesion (initial adhesion) to the decorative layer and the fiber reinforced resin substrate is good, and the followability to the fiber reinforced resin substrate is good, so that the weather resistance adhesion is also improved. On the other hand, the indentation hardness of the cross section of the permeation prevention layer is, for example, 20 MPa or more, may be 80 MPa or more, or may be 140 MPa or more. The method of preparing the cross section sample piece of the transfer sheet and the method of measuring the indentation hardness of the permeation prevention layer are the same as those described for the decorative layer above.

[0069] The thickness of the permeation prevention layer is, for example, 1 μm or more, and may be 3 μm or more. By having the thickness of the permeation prevention layer in the above range, the adhesion to the fiber reinforced resin substrate and the decorative layer is improved. On the other hand, from the viewpoint of cost reduction and light weight, the thickness of the permeation prevention layer is, for example, 50 μm or less, and may be 30 μm or less.

[0070] (b) Primer layer The transfer sheet in the present disclosure may have a primer layer between the protective layer and the decorative layer. The primer layer and the protective layer may be arranged so as to be in direct contact with each other, or may be arranged through another layer. The primer layer and the decorative layer may be arranged so as to be in direct contact with each other, or may be arranged through another layer.

[0071] In the transfer sheet, the adhesion between the protective layer and the primer layer is easily insufficient. In the case of the transfer sheet, the protective layer is usually formed on the release film, then the primer layer is formed on the protective layer, and then the decorative layer is formed on the primer layer. The protective layer is typically produced by curing a composition for forming the protective layer on the release film. Since the primer layer is formed on the cured protective layer, the adhesion between the protective layer and the primer layer is easily insufficient.

[0072] In the present disclosure, the indentation hardness of the cross section of the primer layer is, for example, 50 MPa or less, and may be 40 MPa or less. When the indentation hardness of the cross section of the primer layer is within the above range, the adhesion (particularly the initial adhesion) with the protective layer is good. On the other hand, the indentation hardness of the cross section of the primer layer is, for example, 2 MPa or more, and may be 10 MPa or more. The method of preparing the cross section sample piece of the transfer sheet and the method of measuring the indentation hardness of the cross section of the primer layer are the same as those described for the decorative layer above.

[0073] The primer layer contains a cured product (crosslinked structure) of the second curable resin composition. The cured product of the second curable resin composition preferably contains a (meth)acrylic component and a urethane component. The proportion of the cured product of the second curable resin composition is, for example, 70% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass, based on the total resin components constituting the primer layer.

[0074] The second curable resin composition may be, for example, a thermosetting resin composition. The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a composition that is cured by heating. The thermosetting resin composition preferably contains at least a urethane (meth)acrylic resin as a thermosetting resin. The second curable resin composition may further contain at least one of a (meth)acrylic resin, a urethane resin, a phenolic resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicone resin as a thermosetting resin in addition to the urethane (meth)acrylic resin. The thermosetting resin composition may further contain a curing agent such as an isocyanate curing agent or an epoxy curing agent.

[0075] In addition, when the second curable resin composition contains a urethane (meth)acrylic resin, the urethane (meth)acrylic resin is preferably a urethane (meth)acrylic copolymer, more preferably a polycarbonate-based urethane (meth)acrylic copolymer. The polycarbonate-based urethane (meth)acrylic copolymer is a resin obtained by radically polymerizing a (meth)acrylic monomer with a polycarbonate-based polyurethane polymer obtained by reacting a polycarbonate diol with a (di)isocyanate.

[0076] Examples of the (di)isocyanate include aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 1,5-naphthalene diisocyanate, n-isocyanate phenylsulfonyl isocyanate, o-isocyanate phenylsulfonyl isocyanate, and p-isocyanate phenylsulfonyl isocyanate; aliphatic isocyanates such as 1,6-hexamethylene diisocyanate; and alicyclic isocyanates such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.

[0077] Examples of the (meth)acrylic monomer include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.

[0078] In the polycarbonate-based urethane (meth)acrylic copolymer, the mass ratio of the urethane component to the total of the (meth)acrylic component and the urethane component ([urethane component] / ([(meth)acrylic component]+[urethane component]) is, for example, 65% by mass or more and 95% by mass or less, and may be 70% by mass or more and 90% by mass or less. By setting the mass ratio to 65% by mass or more, the proportion of the polycarbonate structure in the polycarbonate-based urethane (meth)acrylic copolymer can be increased, and the structure of the polycarbonate-based urethane acrylic copolymer becomes more rigid. Therefore, the indentation hardness of the cross section of the primer layer can be adjusted to a predetermined value or more. Furthermore, by setting the mass ratio to 95% by mass or less, the indentation hardness of the cross section of the primer layer can be adjusted to a predetermined value or less.

[0079] The primer layer may contain a weathering agent. When both the protective layer and the primer layer contain a weathering agent, high weather resistance can be imparted while maintaining the properties required for the protective layer (e.g., surface properties such as scratch resistance and abrasion resistance) and the properties required for the primer layer (e.g., adhesion).

[0080] Examples of weather resistance agents include ultraviolet absorbers and light stabilizers. The primer layer preferably contains at least one of an ultraviolet absorber and a light stabilizer. The preferred types and modes of the weather resistance agent are the same as those described in "2. Protective layer" above, and therefore will not be described here. In particular, the primer layer preferably contains a triazine-based ultraviolet absorber. The primer layer preferably contains a hindered amine-based light stabilizer.

[0081] The content of the ultraviolet absorber in the primer layer is, for example, 0.1 parts by mass or more and 50 parts by mass or less, or may be 3 parts by mass or more and 40 parts by mass or less, or may be 10 parts by mass or more and 35 parts by mass or less, relative to 100 parts by mass of the resin component. The content of the ultraviolet absorber in the primer layer (content relative to 100 parts by mass of the resin component) may be greater than the content of the ultraviolet absorber in the protective layer (content relative to 100 parts by mass of the resin component).

[0082] The content of the light stabilizer in the primer layer is, for example, 0.1 to 15 parts by mass, or 1 to 15 parts by mass, or 3 to 10 parts by mass, relative to 100 parts by mass of the resin component. The content of the light stabilizer in the primer layer (content relative to 100 parts by mass of the resin component) may be greater than the content of the light stabilizer in the protective layer (content relative to 100 parts by mass of the resin component).

[0083] The primer layer may contain additives such as a silicone compound, a polymerization inhibitor, a crosslinking agent, an antistatic agent, an adhesion improver, an antioxidant, a leveling agent, a thixotropy imparting agent, a coupling agent, a plasticizer, an antifouling agent, an antifoaming agent, a filler, and an antiblocking agent.

[0084] The thickness of the primer layer is, for example, 2 μm or more and 10 μm or less, may be 3 μm or more and 8 μm or less, or may be 3 μm or more and 5 μm or less. If the primer layer is thin, the adhesion (particularly initial adhesion) with the protective layer may be low. On the other hand, if the primer layer is thick, the movement of the primer layer becomes large in an environment where temperature changes are repeated, and good weather-resistant adhesion may not be obtained.

[0085] (c) Adhesive layer The transfer sheet in the present disclosure may have an adhesive layer on the side opposite to the protective layer of the decorative layer, but it is preferable that it does not have an adhesive layer. The thickness of the transfer layer can be reduced, and the hardness peculiar to the fiber-reinforced resin substrate can be utilized, making it easier to obtain scratch resistance. The transfer sheet in the present disclosure can be integrated with the prepreg without an adhesive layer.

[0086] (2) Transfer layer (a) Thickness The thickness of the transfer layer is, for example, 60 μm or less, preferably 50 μm or less, and particularly preferably 45 μm or less. By making the thickness of the transfer layer within the above range, the hardness specific to the fiber-reinforced resin substrate can be utilized, and scratch resistance can be easily obtained. On the other hand, the thickness of the transfer layer is, for example, 5 μm or more, may be 8 μm or more, may be 15 μm or more, or may be 20 μm or more.

[0087] (b) Concealment rate The transfer layer in the present disclosure preferably has a high hiding rate in order to suppress the influence of the color and fiber pattern of the fiber-reinforced resin substrate. Specifically, the transfer layer preferably has a hiding rate of 85% or more, and may have a hiding rate of 90% or more, as measured in accordance with JIS K 5600-4-1. On the other hand, the hiding rate is, for example, 100% or less.

[0088] The hiding ratio of the transfer layer in the present disclosure is measured as follows. 1) Cut the transfer sheet to the specified size for the area where you want to measure the coverage rate. 2) Apply tape to the top edge of the transfer surface (the surface on the decorative layer side) of the cut transfer sheet, and peel the transfer layer from the release film. Then, remove the tape to obtain a single transfer layer. 3) The transfer layer is placed on a single layer on a hiding ratio test paper conforming to JIS K 5600-4-1, and the tristimulus values ​​YW and YB are measured using a spectrophotometer (Konica Minolta spectrophotometer CM-3700A), and the hiding ratio YB / YW is calculated as a percentage.

[0089] 4.Release film The transfer sheet in the present disclosure has a release film (first release film) on the side of the protective layer opposite the decorative layer. The release film and the protective layer may be arranged so as to be in direct contact with each other, or may be arranged via another layer.

[0090] The release film preferably contains a resin film, for example, an ester resin, an olefin resin, a styrene resin, a vinyl resin, a (meth)acrylic resin, an amide resin, an imide resin, or a carbonate resin.

[0091] The resin film preferably contains an ester-based resin or an olefin-based resin. Examples of ester-based resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyethylene terephthalate-isophthalate copolymers. Among these, PET or PBT is preferred, and PET is more preferred, from the viewpoint of being less susceptible to thermal shrinkage during the production of the transfer sheet and shrinkage due to irradiation with ionizing radiation.

[0092] Examples of olefin resins include polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, and ethylene-propylene-butene copolymer. Among these, polypropylene is preferred from the viewpoint of being less susceptible to thermal shrinkage during the production of the transfer sheet and shrinkage due to irradiation with ionizing radiation.

[0093] The resin film may be a stretched film or an unstretched film. The stretch ratio in the machine direction (MD) of the stretched film is, for example, 5 times or more and 30 times or less. The stretch ratio in the width direction (TD) of the stretched film is, for example, 5 times or more and 30 times or less. The thickness of the release film is, for example, 10 μm or more and 200 μm or less, may be 15 μm or more and 150 μm or less, or may be 20 μm or more and 100 μm or less.

[0094] The release film in the present disclosure may be a mirror film or a low gloss film, depending on the desired surface shape of the protective layer.

[0095] The release film in the present disclosure is not particularly limited, and may be a single layer or may have a multi-layer structure. When the release film is a low-gloss film, for example, it is preferable that the release film has a film layer and a matte layer disposed on the surface of the film layer on the transfer layer side.

[0096] The film layer is preferably the resin film described above. The matte layer contains, for example, a resin component and particles as a matte agent. Hereinafter, the matte layer containing the resin component and particles as a matte agent is referred to as a first matte layer. The resin component in the first matte layer is typically a cured product (crosslinked structure) of a curable resin. On the other hand, the resin component may be a thermoplastic resin. In particular, the first matte layer preferably contains a cured product of a curable resin. When the first matte layer contains a cured product of a curable resin, the releasability from the protective layer becomes good.

[0097] Examples of the curable resin include ionizing radiation curable resins and thermosetting resins. Examples of the ionizing radiation curable resin include electron beam curable resins and ultraviolet ray curable resins.

[0098] Examples of the particles include inorganic particles and synthetic resin particles. Examples of the inorganic particles include silica, alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and kaolin. Examples of the synthetic resin particles include acrylic beads, urethane beads, nylon beads, silicone beads, silicone rubber beads, polycarbonate beads, and polyolefin wax (e.g., polypropylene wax, polyethylene wax).

[0099] The average particle size of the particles is preferably 1.0 μm or more and 10 μm or less, and more preferably 2.0 μm or more and 8.0 μm or less.

[0100] The content of the particles in the first mat layer is preferably 3 parts by mass or more and 80 parts by mass or less, and more preferably 5 parts by mass or more and 60 parts by mass or less, based on 100 parts by mass of the resin component.

[0101] The first matte layer may contain additives such as a release agent, an ultraviolet absorber, an infrared absorber, a light stabilizer, a polymerization inhibitor, a crosslinking agent, an antistatic agent, an antioxidant, a leveling agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a thermal radical generator, an aluminum chelating agent, etc. The thickness of the first matte layer is not particularly limited, but is, for example, 0.1 μm or more and 10 μm or less.

[0102] The first matte layer can be obtained, for example, by applying a matte layer-forming ink containing a curable resin onto one surface of the film layer and curing the ink.

[0103] The mat layer may be, for example, a layer (second mat layer) having an uneven shape formed by irregular wrinkles on one side. The material and forming method of the release layer described in JP 2022-149930 A can be used as the material and forming method of such a second mat layer.

[0104] The first matte layer and the second matte layer may be formed on the entire surface of one side of the film layer, or may be formed on a partial area of ​​one side of the film layer. The entire surface of one side of the film layer refers to 90% or more of the area of ​​one side of the film layer. The matte layer may be arranged so as to cover 95% or more of one side of the film layer, or may be arranged so as to cover 100%. On the other hand, the matte layer may be arranged so as to cover 50% or less of one side of the film layer, or may be arranged so as to cover 40% or less, or may be arranged so as to cover 30% or less.

[0105] In addition, the low gloss film is not limited to the structure having the film layer and the matte layer as described above, but may be a single layer. For example, a matte film in which the particles exemplified in the first matte layer are kneaded can be used.

[0106] The transfer sheet in the present disclosure may have a second release film on the side opposite to the protective layer of the decorative layer. For example, when the transfer sheet is wound into a roll, the occurrence of blocking can be suppressed. The second release film is usually peeled off from the transfer sheet before the integration process described later. Details of the second release film are the same as those described for the first release film described later, so the description here is omitted.

[0107] 5. Manufacturing method of transfer sheet FIG. 2 is a schematic cross-sectional view illustrating a method for producing a transfer sheet in the present disclosure. First, as shown in FIG. 2(a), a release film 1 is prepared. Next, as shown in FIG. 2(b), a first composition containing a first curable resin composition is applied to the surface of the release film 1 and cured to form a protective layer 2 (protective layer forming step). Next, as shown in FIG. 2(c), a decorative layer 3 is formed on the surface of the protective layer 2 opposite to the release film 1 (decorative layer forming step). Thereby, the release film 1, the protective layer 2, and the decorative layer 3 are arranged in a thickness direction D. T In this order, a transfer sheet 10 having the above-mentioned layers is obtained. In FIG.

[0108] (1) Protective layer formation process The protective layer forming step in the present disclosure is a step of applying a first composition containing the first curable resin composition to the surface of the release film, curing the composition, and forming the protective layer. The first composition is a composition for forming a protective layer. The first composition may contain a weathering agent. The first curable resin composition and the weathering agent are the same as those described in "A. Transfer sheet" above, and therefore will not be described here.

[0109] Examples of the method for applying the first composition include gravure printing, bar coating, roll coating, reverse roll coating, and comma coating. The first coating layer is obtained by applying the first composition. Examples of the method for curing the first coating layer include a method of irradiating with ionizing radiation such as electron beams and ultraviolet rays, and a method of applying heat.

[0110] (2) Decorative layer formation process The protective layer forming step in the present disclosure is a step of forming a decorative layer on the surface of the protective layer opposite to the release film. When the decorative layer has a solid layer and a pattern layer, it is preferable to form the pattern layer on the surface of the protective layer opposite to the release film, and then form the solid layer.

[0111] The decorative layer may be formed, for example, by coating the surface of the protective layer opposite to the release film with an ink containing a colorant, a binder resin, and a solvent. Coating methods for forming the decorative layer include, for example, various coating methods such as roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, and dip coating, and various printing methods such as gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing.

[0112] (3) Other processes The method for producing the transfer sheet preferably includes a primer layer forming step after the protective layer forming step and before the decorative layer forming step. The primer layer forming step is a step of applying a second composition containing the second curable resin composition to the surface of the protective layer opposite to the release film, curing the composition, and forming the primer layer. The second composition is a composition for forming a primer layer. The second composition may contain a weathering agent. The second curable resin composition and the weathering agent are the same as those described in "A. Transfer sheet" above, so the description here is omitted.

[0113] Examples of the method for applying the second composition include gravure printing, bar coating, roll coating, reverse roll coating, and comma coating. By applying the second composition, a second coating layer is obtained. Examples of the method for curing the second coating layer include a method of applying heat.

[0114] The method for producing the transfer sheet preferably includes a permeation suppression layer forming step after the decorative layer forming step. The permeation suppression layer forming step is a step of applying a third composition containing the third curable resin composition to the surface of the decorative layer opposite to the protective layer, curing the composition, and forming a permeation suppression layer. Examples of the method for applying the third composition include gravure printing, bar coating, roll coating, reverse roll coating, and comma coating. The third composition is applied to obtain a third coating layer. Examples of the method for curing the third coating layer include a method of applying heat.

[0115] The transfer sheet obtained by each of the above-mentioned steps is the same as that described above in "A. Transfer sheet", so the description here is omitted.

[0116] 6.Applications The transfer sheet in the present disclosure is a transfer sheet for producing a decorated molded article by transferring a transfer layer to a fiber-reinforced resin substrate. The fiber-reinforced resin substrate will be described later.

[0117] B. Method for manufacturing decorated molded body 3 is a schematic cross-sectional view illustrating a method for manufacturing a decorated molded body according to the present disclosure. First, as shown in FIG. 3(a), the above-mentioned transfer sheet 10 is prepared (preparation step). The transfer sheet 10 shown in FIG. 3(a) is a sheet including a release film 1, a protective layer 2, a primer layer 5, a decorative layer 3, and a permeation prevention layer 4, which are arranged in a thickness direction D. T In this order:

[0118] Next, as shown in FIG. 3(b) and FIG. 3(c), the surface of the transfer sheet 10 on the transfer layer X side is opposed to the prepreg 20 in which the reinforcement fiber is impregnated with the matrix resin, and the two are pressed together to harden the matrix resin, thereby obtaining a fiber-reinforced resin substrate 30 from the prepreg 20, and integrating the transfer sheet 10 and the fiber-reinforced resin substrate 30 (integration process). The "surface of the transfer sheet 10 on the transfer layer X side" refers to the surface of the transfer sheet 10 located on the transfer layer X side when the release film 1 is used as a reference. Since the transfer sheet 10 shown in FIG. 3(a) has a permeation prevention layer 4, the "surface of the transfer sheet 10 on the transfer layer X side" corresponds to the surface of the permeation prevention layer 4.

[0119] Next, the release film 1 of the transfer sheet 10 is peeled off (peeling step). As a result, the protective layer 2, the primer layer 5, the decorative layer 3, the permeation prevention layer 4, and the fiber reinforced resin substrate 30 are peeled off in the thickness direction D T A decorated molded body 100 having the above-mentioned steps in this order is obtained.

[0120] According to the present disclosure, by using the above-mentioned transfer sheet, the transfer layer can be transferred satisfactorily to the fiber-reinforced resin substrate. Specifically, when the release film is peeled off, the release film can be peeled off at the interface between the release film and the transfer layer, and it is possible to prevent the release film from being broken or the protective layer from remaining on the release film side.

[0121] 1. Preparation process The transfer sheet prepared in this step is the same as that described above in "A. Transfer sheet," and so a description thereof will be omitted here.

[0122] 2.Integration process In this process, the surface of the transfer sheet 10 on the transfer layer X side and the prepreg 20 in which the reinforcing fibers are impregnated with the matrix resin are placed opposite each other and pressed together to harden the matrix resin. For example, it is preferable to apply heat and pressure while the two are in close contact with each other. This process allows the integrated molding and the hardening of the matrix resin to proceed simultaneously, thereby improving productivity.

[0123] In the present disclosure, when the indentation hardness of the cross section of the decorative layer in the transfer sheet is equal to or greater than a predetermined value, the matrix resin is less likely to seep into the protective layer side of the transfer sheet.

[0124] A prepreg is a member in which reinforcing fibers are impregnated with a matrix resin, and has a laminated structure in which a single layer or multiple layers are laminated. Examples of the matrix resin include thermosetting resins and thermoplastic resins. Examples of the thermosetting resin include epoxy resins, unsaturated polyester resins, phenolic resins, silicone resins, urethane resins, and polyimide resins. Examples of the thermoplastic resin include polysulfone, polyethersulfone, polyetherimide, polyimide, polycarbonate, polypropylene, and polyamide. Only one type of matrix resin may be used, or two or more types may be used.

[0125] The reinforcing fibers constituting the prepreg are not particularly limited, and for example, carbon fibers, glass fibers, aramid fibers, boron fibers, steel fibers, etc. can be used. Among them, carbon fibers are preferable because they have good mechanical properties after molding. Examples of carbon fibers include polyacrylonitrile (PAN)-based carbon fibers and pitch-based carbon fibers. The form and arrangement of the reinforcing fibers are not particularly limited, and examples include sheets, cloths (woven fabrics), tows, mats, knits, and sleeves in which long fibers are aligned in one direction. The long fibers refer to continuous single fibers or fiber bundles of, for example, 10 mm or more.

[0126] Specific examples of the pressure-bonding method in the above integration step include press molding, autoclave molding, bagging molding, wrapping tape, and internal pressure molding. From the viewpoint of increasing the adhesion between the prepreg and the transfer sheet, the press molding method is preferred. The heating temperature may be appropriately selected depending on the selected matrix resin. For example, in the case of an epoxy resin composition, the temperature is usually 60°C or higher and 220°C or lower, depending on the type of curing agent contained. If the heating temperature is too low, sufficient rapid curing may not be obtained. On the other hand, if the heating temperature is too high, warping due to thermal distortion may easily occur. The pressure varies depending on the thickness of the prepreg, but is preferably 0.1 MPa or higher and 10 MPa or lower. If the pressure is too low, a problem of insufficient adhesive strength with the fiber-reinforced resin substrate may occur, or voids may remain. If the pressure is too high, the resin may flow out to the surroundings before curing, and voids may occur in the fiber-reinforced resin substrate.

[0127] The fiber reinforced resin substrate is integrated with the transfer sheet. The fiber reinforced resin substrate has, for example, a three-dimensional fine woven pattern. The thickness of the fiber reinforced resin substrate is, for example, 0.3 mm or more and 50 mm or less.

[0128] 3. Peeling process In this step, the release film 1 of the transfer sheet 10 is peeled off. Since the penetration of the matrix resin into the protective layer side of the transfer sheet is suppressed in the above-mentioned integration step, in this step, the release film can be peeled off at the interface between the release film and the protective layer.

[0129] 4.Decorative molding The above steps provide a decorated molded body having a protective layer, a decorative layer, and a fiber-reinforced resin substrate in this order in the thickness direction. The decorated molded body is the same as that described in "C. Decorative molded body" below.

[0130] C. Decorative Molding 4A is a schematic cross-sectional view illustrating a decorative molded body according to the present disclosure. As shown in FIG. 4A, the decorative molded body 100 according to the present disclosure is a laminate including a protective layer 2, a decorative layer 3, and a fiber-reinforced resin substrate 30 arranged in a thickness direction D. T 4(b), the decorative molded body 100 may have a primer layer 5 between the protective layer 2 and the decorative layer 3, and may have a permeation prevention layer 4 between the decorative layer 3 and the fiber-reinforced resin substrate 30.

[0131] The decorative molded body in the present disclosure has an indentation hardness of the cross section of the decorative layer that is equal to or greater than a predetermined value. Such a decorative molded body is obtained by transferring a transfer layer to a fiber-reinforced resin substrate using a transfer sheet having a transfer layer including a decorative layer having an indentation hardness of equal to or greater than a predetermined value. Therefore, for the above-mentioned reasons, during the integration process in which the transfer sheet and the prepreg are pressure-bonded, the matrix resin is prevented from seeping into the protective layer, and the transfer layer is transferred well in the peeling process. Therefore, a decorative molded body in which peeling of the protective layer is suppressed is obtained.

[0132] 1.Decorative layer The decorative molded body in the present disclosure has a decorative layer. The indentation hardness of the decorative layer in the cross section of the decorative molded body is usually 100 MPa or more, may be 150 MPa or more, or may be 160 MPa or more. If the indentation hardness of the decorative layer in the cross section of the decorative molded body is within the above range, the decorative molded body is one in which peeling of the protective layer is suppressed. In addition, the hardness unique to the fiber-reinforced resin substrate can be utilized, and scratch resistance is easily obtained.

[0133] On the other hand, the indentation hardness of the decorative layer in a cross section is, for example, 400 MPa or less, may be 350 MPa or less, or may be 300 MPa or less. If the indentation hardness of the decorative layer in a cross section is within the above range, for example, good adhesion can be obtained between the decorative layer and the protective layer.

[0134] Due to the influence of soaking of the matrix resin and thermal compression during transfer, the indentation hardness of the cross section of the decorative layer in the decorated molded body may be greater than the indentation hardness of the cross section of the decorative layer in the transfer sheet.

[0135] The method for adjusting the indentation hardness of the cross section of the decorative layer is the same as that described above in "A. Transfer sheet."

[0136] The indentation hardness of the decorative layer in the decorated molded article was a value obtained by measuring a cross-sectional sample piece prepared using a resin embedding method and a microtome according to the following method. (Method of preparing cross-sectional sample pieces for measurement) The decorated molded body is cut to an arbitrary size to prepare a cut sample. The cut sample is embedded in resin (a room temperature curing type two-component epoxy resin) and left to harden at room temperature for 24 hours or more to prepare an embedded sample in which the cut sample is embedded in resin (resin embedding method). The embedded sample is cut vertically using a microtome to expose the cross section of the layer to be measured, thereby preparing a cross-sectional sample piece for indentation hardness measurement. The cutting method for the embedded sample is the same as that described above in "A. Transfer sheet".

[0137] The configuration, thickness and material of the decorative layer are the same as those described above in “A. Transfer sheet.” The decorative layer may contain a cured product of the above-mentioned matrix resin.

[0138] 2.Protective layer The decorative molded body in the present disclosure has a protective layer. The protective layer contributes to improving the surface properties (e.g., scratch resistance, abrasion resistance, etc.) of the decorative molded body. The protective layer may be the outermost layer of the decorative molded body. The indentation hardness and the adjustment method thereof, resin components, weathering agents, additives, and thickness of the protective layer are the same as those described above in "A. Transfer sheet". In addition, the method for measuring the indentation hardness of the protective layer in the decorative molded body is the same as the method described for the decorative layer in the above-mentioned decorative molded body.

[0139] 3. Fiber-reinforced resin substrate The decorative molded article according to the present disclosure has a fiber-reinforced resin substrate. The fiber-reinforced resin substrate is the same as that described above in "B. Method for producing the decorative molded article."

[0140] 4. Other layers The decorated molded body in the present disclosure may have layers other than the decorative layer, the protective layer, and the fiber-reinforced resin substrate. Examples of the other layers include a primer layer and a permeation prevention layer. Details of the primer layer and the permeation prevention layer are the same as those described in "A. Transfer sheet" above.

[0141] 5.Applications The uses of the decorative molded body in the present disclosure are not particularly limited, but examples thereof include architectural components such as walls, ceilings, floors, roofs, eaves, fences, and gates; fittings or fixtures such as window frames, doors, handrails, skirting boards, moldings, and other building components; general furniture such as chests of drawers, shelves, and desks; kitchen furniture such as dining tables and sinks; various furniture used around water such as kitchens, toilets, bathrooms, and washbasins; surface decorative panels such as cabinets for home appliances and office automation equipment; and interior or exterior components for vehicles. The decorative molded body in the present disclosure may be a component used outdoors (exterior component) or a component used indoors (interior component).

[0142] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits similar effects is included in the technical scope of the present disclosure. EXAMPLES

[0143] [Example 1] (Production of transfer sheets) The following composition 1 for forming a protective layer was applied to one side of a release film (polyethylene terephthalate having a thickness of 50 μm) and dried. Then, the film was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a protective layer having a thickness of 5 μm. <Composition 1 for forming protective layer> ·Ionizing radiation curable resin composition: 100 parts by mass (Urethane acrylate: 30 parts by weight) (Hydroxyl-containing acrylate): 70 parts by mass) Triazine-based UV absorber: 2 parts by weight Light stabilizer having a reactive functional group: 2 parts by weight

[0144] Next, the following ink composition 1 for decorative layer was applied to the surface of the obtained protective layer and dried to form a decorative layer (solid layer and pattern layer) having a thickness of 3 μm. This resulted in a transfer sheet having a release film, a protective layer, and a decorative layer in this order in the thickness direction. <Ink composition for decorative layer 1> Ink resin component (acrylic polyol resin) 100 parts by weight Pigments (organic and inorganic pigments) 30 parts by weight

[0145] (Manufacturing of Decorative Molded Products) The transfer layer side of the transfer sheet obtained above was placed face-to-face with the prepreg, and in this state where the two were in close contact with each other, they were pressed in a vacuum press at 160°C and 3 kg / cm 2 Heating and pressing were performed for 1 hour under the condition of 150 μm, which was made by impregnating unidirectionally woven carbon fibers with matrix resin (epoxy resin). As a result, the matrix resin hardened, and a fiber-reinforced resin substrate was obtained from the prepreg, and the transfer sheet and the fiber-reinforced resin substrate were integrated. After gradual cooling, the release film was peeled off to obtain a decorated molded body.

[0146] [Example 2] (Production of transfer sheets) The above-mentioned composition 1 for forming a protective layer was applied to one side of a release film (polyethylene terephthalate having a thickness of 50 μm) and dried. Then, the composition was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a protective layer having a thickness of 5 μm.

[0147] Next, the following ink composition 2 for decorative layer was applied to the surface of the obtained protective layer and dried to form a decorative layer (solid layer and pattern layer) having a thickness of 3 μm. This resulted in a transfer sheet having a release film, a protective layer, and a decorative layer in this order in the thickness direction. <Ink composition for decorative layer 2> Ink resin component (acrylic polyol resin) 100 parts by weight Pigments (organic and inorganic pigments) 30 parts by weight Hardener (HDI nurate) 4 parts by weight

[0148] (Manufacturing of Decorative Molded Products) The transfer layer side of the transfer sheet obtained above was placed face-to-face with the prepreg, and in this state where the two were in close contact with each other, they were pressed in a vacuum press at 160°C and 3 kg / cm 2 Heating and pressure were applied for 1 hour. This caused the matrix resin to harden, obtaining a fiber-reinforced resin substrate from the prepreg, and integrating the transfer sheet and the fiber-reinforced resin substrate. After slow cooling, the release film was peeled off to obtain a decorated molded body.

[0149] [Example 3] (Production of transfer sheets) The above-mentioned composition 1 for forming a protective layer was applied to one side of a release film (polyethylene terephthalate having a thickness of 50 μm) and dried. Then, the composition was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a protective layer having a thickness of 5 μm.

[0150] Next, the above-mentioned ink composition 1 for decorative layer was applied to the surface of the obtained protective layer, and dried to form a decorative layer (solid layer and pattern layer) with a thickness of 3 μm. Next, the following composition for permeation prevention layer was applied to the surface of the obtained decorative layer, and cured to form a permeation prevention layer with a thickness of 20 μm. This resulted in a transfer sheet having a release film, a protective layer, a decorative layer, and a permeation prevention layer in this order in the thickness direction. <Composition for penetration prevention layer> Acrylic main chain hydroxyl group-containing resin 100 parts by weight Hardener (XDI type) 5 parts by weight

[0151] (Manufacturing of Decorative Molded Products) The transfer layer side of the transfer sheet obtained above was placed face-to-face with the prepreg, and in this state where the two were in close contact with each other, they were pressed in a vacuum press at 160°C and 3 kg / cm 2 Heating and pressure were applied for 1 hour. This caused the matrix resin to harden, obtaining a fiber-reinforced resin substrate from the prepreg, and integrating the transfer sheet and the fiber-reinforced resin substrate. After slow cooling, the release film was peeled off to obtain a decorated molded body.

[0152] [Example 4] (Production of transfer sheets) The above-mentioned composition 1 for forming a protective layer was applied to one side of a release film (polyethylene terephthalate having a thickness of 50 μm) and dried. Then, the composition was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a protective layer having a thickness of 15 μm.

[0153] Next, the following composition 1 for forming a primer layer was applied to the surface of the obtained protective layer and dried to form a primer layer having a thickness of 5 μm. <Composition 1 for forming primer layer> Polycarbonate-based urethane acrylic copolymer: 100 parts by weight (urethane to acrylic ratio is 9:1) Hydroxyphenyltriazine-based UV absorber: 17 parts by weight Hindered amine light stabilizer: 8 parts by weight (product name: TINUVIN 123, BASF) Anti-blocking agent: 9 parts by weight (silica particles, average particle size 3 μm) Hardener: 25 parts by weight (hexamethylene diisocyanate)

[0154] Next, the ink composition 1 for decorative layer was applied to the surface of the obtained primer layer and dried to form a decorative layer (solid layer and pattern layer) having a thickness of 3 μm. This resulted in a transfer sheet having a release film, a protective layer, a primer layer, and a decorative layer in this order in the thickness direction.

[0155] (Manufacturing of Decorative Molded Products) The transfer layer side of the transfer sheet obtained above was placed face-to-face with the prepreg, and in this state where the two were in close contact with each other, they were pressed in a vacuum press at 160°C and 3 kg / cm 2 Heating and pressure were applied for 1 hour. This caused the matrix resin to harden, obtaining a fiber-reinforced resin substrate from the prepreg, and integrating the transfer sheet and the fiber-reinforced resin substrate. After slow cooling, the release film was peeled off to obtain a decorated molded body.

[0156] [Example 5] (Production of transfer sheets) The above-mentioned composition 1 for forming a protective layer was applied to one side of a release film (polyethylene terephthalate having a thickness of 50 μm) and dried. Then, the composition was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a protective layer having a thickness of 15 μm.

[0157] Next, the primer layer forming composition 1 was applied to the surface of the obtained protective layer and dried to form a primer layer having a thickness of 5 μm. Next, the decorative layer ink composition 1 was applied to the surface of the obtained primer layer and dried to form a decorative layer (solid layer and pattern layer) having a thickness of 3 μm.

[0158] Next, the above-mentioned permeation prevention layer composition was applied to the surface of the obtained decorative layer and cured to form a permeation prevention layer having a thickness of 20 μm. This resulted in a transfer sheet having a release film, a protective layer, a primer layer, a decorative layer, and a permeation prevention layer in this order in the thickness direction.

[0159] (Manufacturing of Decorative Molded Products) The transfer layer side of the transfer sheet obtained above was placed face-to-face with the prepreg, and in this state where the two were in close contact with each other, they were pressed in a vacuum press at 160°C and 3 kg / cm 2 Heating and pressure were applied for 1 hour. This caused the matrix resin to harden, obtaining a fiber-reinforced resin substrate from the prepreg, and integrating the transfer sheet and the fiber-reinforced resin substrate. After slow cooling, the release film was peeled off to obtain a decorated molded body.

[0160] [Example 6] (Production of transfer sheets) The following composition 2 for forming a protective layer was applied to one side of a release film (polyethylene terephthalate having a thickness of 50 μm) and dried. Then, the film was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a protective layer having a thickness of 5 μm. <Composition 2 for forming protective layer> Ionizing radiation curable resin composition (urethane acrylic copolymer): 100 parts by mass Triazine-based UV absorber: 30 parts by weight Light stabilizer having a reactive functional group: 8 parts by weight

[0161] Next, the ink composition 1 for decorative layer was applied to the surface of the obtained protective layer and dried to form a decorative layer (solid layer and pattern layer) having a thickness of 3 μm. This resulted in a transfer sheet having a release film, a protective layer, and a decorative layer in this order in the thickness direction.

[0162] (Manufacturing of Decorative Molded Products) The transfer layer side of the transfer sheet obtained above was placed face-to-face with the prepreg, and in this state where the two were in close contact with each other, they were pressed in a vacuum press at 160°C and 3 kg / cm 2 Heating and pressure were applied for 1 hour. This caused the matrix resin to harden, obtaining a fiber-reinforced resin substrate from the prepreg, and integrating the transfer sheet and the fiber-reinforced resin substrate. After slow cooling, the release film was peeled off to obtain a decorated molded body.

[0163] [Example 7] (Production of transfer sheets) The above-mentioned composition 1 for forming a protective layer was applied to one side of a release film (polyethylene terephthalate having a thickness of 50 μm) and dried. Then, the composition was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a protective layer having a thickness of 5 μm.

[0164] Next, the above-mentioned ink composition 1 for decorative layer was applied to the surface of the obtained protective layer, and dried to form a decorative layer (solid layer and pattern layer) with a thickness of 3 μm. Next, the following adhesive layer composition was applied to the surface of the obtained decorative layer, and dried to form a base layer with a thickness of 50 μm. This resulted in a transfer sheet having a release film, a protective layer, a decorative layer, and an adhesive layer in this order in the thickness direction. <Adhesive layer composition> Polyester adhesive 100 parts by weight Hardener (HDI nurate) 10 parts by weight

[0165] (Manufacturing of Decorative Molded Products) The transfer layer side of the transfer sheet obtained above was placed face-to-face with the prepreg 1, and in this state where the two were in close contact with each other, they were pressed in a vacuum press at 160°C and 3 kg / cm 2 Heating and pressure were applied for 1 hour. This caused the matrix resin to harden, obtaining a fiber-reinforced resin substrate from the prepreg, and integrating the transfer sheet and the fiber-reinforced resin substrate. After slow cooling, the release film was peeled off to obtain a decorated molded body.

[0166] [Comparative Example] (Production of transfer sheets) The above-mentioned composition 1 for forming a protective layer was applied to one side of a release film (polyethylene terephthalate having a thickness of 50 μm) and dried. Then, the composition was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a protective layer having a thickness of 5 μm.

[0167] Next, the following ink composition 3 for decorative layer was applied to the surface of the obtained protective layer and dried to form a decorative layer (solid layer and pattern layer) having a thickness of 3 μm. This resulted in a transfer sheet having a release film, a protective layer, and a decorative layer in this order in the thickness direction. <Ink composition for decorative layer 3> Ink resin component (urethane resin) 100 parts by weight Pigments (organic and inorganic pigments) 30 parts by weight

[0168] (Manufacturing of Decorative Molded Products) The transfer layer side of the transfer sheet obtained above was placed face-to-face with the prepreg, and in this state where the two were in close contact with each other, they were pressed in a vacuum press at 160°C and 3 kg / cm 2 Heating and pressure were applied for 1 hour. This caused the matrix resin to harden, obtaining a fiber-reinforced resin substrate from the prepreg, and integrating the transfer sheet and the fiber-reinforced resin substrate. After slow cooling, the release film was peeled off to obtain a decorated molded body.

[0169] [Reference example] Without using a transfer sheet, the prepreg alone was pressed in a vacuum press at 160°C and 3 kg / cm 2 Heating and pressure were applied for 1 hour, whereby the matrix resin was cured to obtain a fiber-reinforced resin substrate (molded body).

[0170] [Indentation hardness measurement] The indentation hardness of the transfer sheet and the protective layer and decorative layer of the decorated molded article obtained above was measured by the method described above. The results are shown in Table 1.

[0171] [Transferability evaluation] The obtained molded article was visually observed and evaluated according to the following evaluation criteria. <Evaluation criteria> A: There is no damage to the release film, and more than 95% of the area has been transferred successfully. B: The release film is broken and normal transfer is not possible, or there are areas where the transfer layer remains on the release film side, and the area of ​​the area where the transfer is normal is less than 95%.

[0172] [Scratch resistance evaluation] Pencil hardness test The surface of the protective layer side of the obtained molded product was subjected to the pencil hardness test specified in JIS K5600-5-4 (1999) at a pencil hardness of 3H, an angle of 45°, a load of 750 g, a speed of 0.5 mm / sec to 1 mm / sec, and a temperature of 23±2°C. It was visually confirmed whether the decorative layer had been removed, and the results were evaluated according to the following criteria. The evaluation results are shown in Table 1. <Evaluation criteria> A: No decorative layer is removed B: The decorative layer has been removed

[0173] Steel wool resistance test The surface of the above-mentioned molded product on the protective layer side was subjected to a load of 300 g / cm using steel wool (Bonstar, #0000). 2 The surface condition was checked by rubbing five times with a brush and evaluated according to the following criteria. The evaluation results are shown in Table 1. <Evaluation criteria> A: Almost no change in appearance was observed. B: Significant scratches and gloss changes were observed.

[0174] [Table 1]

[0175] As shown in Table 1, the transfer sheets of Examples 1 to 7 were confirmed to have good transferability compared to the comparative examples. Example 1 was confirmed to have excellent scratch resistance compared to Example 6, in which the indentation hardness of the protective layer was low. Also, Example 1 was confirmed to have excellent scratch resistance (pencil hardness test) compared to Example 7, in which the transfer layer was thick. This is presumably because when the transfer layer was thick, it was difficult to obtain the scratch resistance effect (pencil hardness) due to the hardness specific to the fiber-reinforced resin substrate. Also, Examples 1 to 5 and Example 7, in which the indentation hardness of the protective layer was 100 MPa or more, had good scratch resistance (steel wool resistance) compared to Example 6 and the Reference Example.

[0176] Thus, in the present disclosure, for example, the following inventions are provided:

[0177] [1] A transfer sheet for transferring a transfer layer to a fiber reinforced resin substrate, The transfer sheet has a release film and the transfer layer disposed on one surface of the release film, The transfer layer has a protective layer and a decorative layer in this order in a thickness direction from the release film side, A transfer sheet, wherein the indentation hardness of the cross section of the decorative layer is 100 MPa or more.

[0178] [2] The transfer sheet according to [1], wherein the indentation hardness of the cross section of the decorative layer is 400 MPa or less.

[0179] [3] The transfer sheet according to [1] or [2], wherein the indentation hardness of the cross section of the protective layer is 100 MPa or more.

[0180] [4] The transfer sheet according to any one of [1] to [3], wherein the indentation hardness of the cross section of the protective layer is 400 MPa or less.

[0181] [5] The transfer sheet according to any one of [1] to [4], wherein the thickness of the transfer layer is 50 μm or less.

[0182] [6] The transfer sheet according to any one of [1] to [5], wherein the protective layer contains a cured product of a first curable resin composition.

[0183] [7] The transfer sheet according to [6], wherein the first curable resin composition is an ionizing radiation curable resin composition.

[0184] [8] The transfer sheet according to [6] or [7], wherein the first curable resin composition is an electron beam curable resin composition.

[0185] [9] The transfer sheet according to any one of [6] to [8], wherein the first curable resin composition contains a urethane (meth)acrylate.

[0186]

[10] The transfer sheet according to any one of [1] to [9], wherein the protective layer contains a weather resistance agent.

[0187]

[11] The transfer sheet according to

[10] , wherein the protective layer contains at least one of an ultraviolet absorbing agent and a light stabilizer as the weather resistance agent.

[0188]

[12] At least one of the ultraviolet absorber and the light stabilizer has a reactive functional group.

[0189]

[13] A transfer sheet described in any one of [1] to

[12] , which has a permeation prevention layer on the side of the decorative layer opposite the protective layer.

[0190]

[14] The transfer sheet according to

[13] , wherein the permeation prevention layer contains a cured product of a thermosetting resin.

[0191]

[15] The transfer sheet according to

[13] or

[14] , wherein the thickness of the permeation prevention layer is 1 μm or more and 50 μm or less.

[0192]

[16] The transfer sheet according to any one of [1] to

[15] , further comprising a primer layer between the protective layer and the decorative layer.

[0193]

[17] The transfer sheet according to any one of [1] to

[16] , wherein the decorative layer includes a solid layer.

[0194]

[18] The transfer sheet according to any one of [1] to

[17] , wherein the transfer layer has a concealing rate of 85% or more.

[0195]

[19] A preparation step of preparing a transfer sheet according to any one of [1] to

[18] ; An integration process in which the transfer layer side of the transfer sheet and a prepreg in which reinforcement fibers are impregnated with a matrix resin are opposed to each other, and the two are pressure-bonded to each other, and the matrix resin is cured to obtain the fiber-reinforced resin substrate from the prepreg, and the transfer sheet and the fiber-reinforced resin substrate are integrated; a peeling step of peeling off the release film from the transfer sheet; The method for producing a decorated molded body comprising the steps of:

[0196]

[20] A decorated molded body having a protective layer, a decorative layer, and a fiber-reinforced resin substrate in this order in a thickness direction, A decorated molded body, wherein the indentation hardness of the cross section of the decorative layer is 100 MPa or more.

[0197] [twenty one] The decorated molded body according to

[20] , wherein the indentation hardness of the cross section of the decorative layer is 150 MPa or more. [Explanation of symbols]

[0198] 1 ... Release film 2…protective layer 3 … Decorative layer 4 … Penetration prevention layer 5 … Primer layer 10 ... Transfer sheet 20 ... Prepreg 30 … Fiber-reinforced resin substrate 100 … Decorative molding

Claims

1. A transfer sheet for transferring a transfer layer to a fiber reinforced resin substrate, The transfer sheet has a release film and the transfer layer disposed on one surface of the release film, The transfer layer has a protective layer and a decorative layer in this order in a thickness direction from the release film side, A transfer sheet, wherein the indentation hardness of the cross section of the decorative layer is 100 MPa or more.

2. The transfer sheet according to claim 1 , wherein the decorative layer has an indentation hardness of 400 MPa or less in a cross section.

3. The transfer sheet according to claim 1 , wherein the protective layer has an indentation hardness of 100 MPa or more in a cross section.

4. The transfer sheet according to claim 1 , wherein the protective layer has an indentation hardness of 400 MPa or less in a cross section.

5. The transfer sheet according to claim 1 , wherein the transfer layer has a thickness of 50 μm or less.

6. The transfer sheet according to claim 1 , wherein the protective layer contains a cured product of a first curable resin composition.

7. The transfer sheet according to claim 6 , wherein the first curable resin composition is an ionizing radiation curable resin composition.

8. The transfer sheet according to claim 6 , wherein the first curable resin composition is an electron beam curable resin composition.

9. The transfer sheet according to claim 6 , wherein the first curable resin composition contains a urethane (meth)acrylate.

10. The transfer sheet according to claim 1 , wherein the protective layer contains a weathering agent.

11. The transfer sheet according to claim 10 , wherein the protective layer contains at least one of an ultraviolet absorbing agent and a light stabilizer as the weather resistance agent.

12. The transfer sheet according to claim 11 , wherein at least one of the ultraviolet absorbing agent and the light stabilizer has a reactive functional group.

13. The transfer sheet according to claim 1 , further comprising a permeation prevention layer on a surface of the decorative layer opposite to the protective layer.

14. The transfer sheet according to claim 13 , wherein the permeation prevention layer comprises a cured product of a thermosetting resin.

15. The transfer sheet according to claim 13, wherein the permeation prevention layer has a thickness of 1 μm or more and 50 μm or less.

16. The transfer sheet according to claim 1 , further comprising a primer layer between the protective layer and the decorative layer.

17. The transfer sheet according to claim 1 , wherein the decorative layer comprises a solid layer.

18. The transfer sheet according to claim 1 , wherein the transfer layer has a concealing ratio of 85% or more.

19. A preparation step of preparing a transfer sheet according to any one of claims 1 to 18; An integration process in which the transfer layer side of the transfer sheet and a prepreg in which reinforcement fibers are impregnated with a matrix resin are opposed to each other, and the two are pressure-bonded to each other, and the matrix resin is cured to obtain the fiber-reinforced resin substrate from the prepreg, and the transfer sheet and the fiber-reinforced resin substrate are integrated; a peeling step of peeling off the release film from the transfer sheet; The method for producing a decorated molded body comprising the steps of:

20. A decorated molded body having a protective layer, a decorative layer, and a fiber-reinforced resin substrate in this order in a thickness direction, A decorated molded body, wherein the indentation hardness of the cross section of the decorative layer is 100 MPa or more.

21. The decorated molded body according to claim 20 , wherein the indentation hardness of the cross section of the decorative layer is 150 MPa or more.

Images