Stacked film and molded body, and method for producing the same

Abstract

The present invention provides a laminated film having excellent formability and releasability from a mold. A laminated film includes a transparent support substrate and a coating disposed on at least one main surface of the transparent support substrate, the coating containing an energy ray curable resin composition, the thickness of the coating exceeding 2 μ μm, the indentation hardness HB of the coating based on nanoindentation method at an indentation depth of 100 nm 100 being 0.30 GPa or more and 0.65 GPa or less, the indentation hardness HB of the coating based on nanoindentation method at an indentation depth of 2000 nm 2000 being 0.15 GPa or more and 0.35 GPa or less, and the indentation hardness HB 2000 being less than the indentation hardness HB 100 .

Description

Technical Field

[0001] The present invention relates to a laminated film and a molded body, and methods for manufacturing them. Background Art

[0002] Displays are used in various electrical components such as computers, televisions, mobile phones, portable information terminal devices (tablet computers, mobile devices, electronic notebooks, etc.), and in-vehicle devices.

[0003] The information display portion of a display is usually protected with a protective material. The protective material sometimes has fine irregularities on its surface to improve anti-glare properties. In Patent Document 1, a film having convex portions with a height of 100 nm or more and 250 nm or less is disclosed.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2018-12279 Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] In recent years, there has been a demand for a design in which multiple regions having different surface properties such as texture are formed without seams (hereinafter referred to as a seamless design), for example, a design in which the information display portion of a display and the bezel portion surrounding it are integrally formed. However, it is difficult to achieve a seamless design using the film described in Patent Document 1. An object of the present invention is to provide a laminated film that is suitable for achieving a seamless design and has excellent formability and mold releasability.

[0009] Means for Solving the Problems

[0010] To solve the above problems, the present invention provides the following solutions.

[0011] [1] A laminated film comprising:

[0012] a transparent support substrate; and

[0013] a coating disposed on at least one main surface of the transparent support substrate,

[0014] wherein the coating contains an energy ray curable resin composition,

[0015] the thickness of the coating exceeds 2 μ μm,

[0016] the indentation hardness HB of the coating at an indentation depth of 100 nm based on nanoindentation 100is 0.30 GPa or more and 0.65 GPa or less,

[0017] The indentation hardness HB of the above coating based on nanoindentation method at an indentation depth of 2000 nm 2000 is 0.15 GPa or more and 0.35 GPa or less,

[0018] The above indentation hardness HB 2000 is less than the above indentation hardness HB 100 .

[0019] [2] The laminated film according to [1] above, wherein the difference between the polymerization rate PB of the above resin composition and the polymerization rate PA of the above resin composition in the above coating after irradiation with active energy rays of 1500 mJ / cm 2 is 15% or more.

[0020] [3] The laminated film according to [1] or [2] above, wherein the pencil hardness of the surface of the above coating after irradiation with active energy rays of 1500 mJ / cm 2 is H or more.

[0021] [4] The laminated film according to any one of [1] to [3] above, wherein the elongation rate of the laminated film at 160 °C is 5% or more.

[0022] [5] The laminated film according to any one of [1] to [4] above, wherein the thickness of the above coating is 3 μ μm or more and 20 μ μm or less.

[0023] [6] The laminated film according to any one of [1] to [5] above, wherein the thickness of the above transparent support substrate is 75 μ μm or more and 500 μ μm or less.

[0024] [7] A method for manufacturing a laminated film, the manufacturing method comprising the following steps:

[0025] A coating step of coating an active energy ray curable resin composition on at least one main surface of a transparent support substrate; and

[0026] A first irradiation step of irradiating the above resin composition with active energy rays of 5 mJ / cm 2 or more and 150 mJ / cm 2 or less to obtain a coating,

[0027] The thickness of the above coating exceeds 2 μ μm,

[0028] The indentation hardness HB of the above coating based on nanoindentation method at an indentation depth of 100 nm100 is above 0.30 GPa and below 0.65 GPa,

[0029] The indentation hardness HB based on the nanoindentation method at an indentation depth of 2000 nm of the above-mentioned coating 2000 is above 0.15 GPa and below 0.35 GPa,

[0030] The above-mentioned indentation hardness HB 2000 is less than the above-mentioned indentation hardness HB 100 .

[0031] [8] A molded body, comprising:

[0032] A transparent support substrate; and

[0033] A cured resin layer provided on at least one main surface of the above-mentioned transparent support substrate,

[0034] The main surface of the above-mentioned cured resin layer on the opposite side of the above-mentioned transparent support substrate has a first region formed with unevenness and a second region other than this,

[0035] The above-mentioned first region and the above-mentioned second region are integrally formed,

[0036] The pencil hardness of the surface of the above-mentioned cured resin layer is H or more.

[0037] [9] The molded body according to [8] above, wherein the above-mentioned cured resin layer is provided on one main surface of the above-mentioned transparent support substrate,

[0038] It further includes a decorative layer disposed on the other main surface of the above-mentioned transparent support substrate.

[0039]

[10] The molded body according to [8] or [9] above, wherein,

[0040] The above-mentioned cured resin layer is provided on one main surface of the above-mentioned transparent support substrate,

[0041] It further includes a molded resin layer provided on the other main surface of the above-mentioned transparent support substrate.

[0042]

[11] A method for manufacturing a molded body, the manufacturing method comprising the following steps:

[0043] An unevenness forming step of bringing the coating of the above-mentioned laminated film according to any one of [1] to [6] into contact with a mold having unevenness and forming unevenness on a part of the above-mentioned coating; and

[0044] A second irradiation step of irradiating the above-mentioned coating with active energy rays after the above-mentioned unevenness forming step to obtain a cured resin layer.

[0045]

[12] The method for manufacturing the molded body described in

[11] above, wherein in the second irradiation step, the active energy ray is irradiated so that the pencil hardness of the surface of the cured coating is H or more.

[0046]

[13] The method for manufacturing the molded body described in

[11] or

[12] above, wherein

[0047] In the laminate film, the coating is disposed on one main surface of the transparent support substrate,

[0048] and a decorative layer is disposed on the other main surface of the transparent support substrate.

[0049]

[14] The method for manufacturing the molded body according to any one of

[11] to

[13] above, wherein

[0050] In the laminate film, the coating is disposed on one main surface of the transparent support substrate,

[0051] In the unevenness forming step, while making the coating face the mold, the injection molding resin is directed toward the transparent support substrate, and the unevenness and the molding resin layer are simultaneously formed on the coating.

[0052]

[15] The method for manufacturing the molded body described in

[14] above, wherein

[0053] The mold imparts a three-dimensional shape to the laminate film,

[0054] and, after the preparation step and before the unevenness forming step, a pre-forming step of forming the laminate film into a shape along the three-dimensional shape is provided.

[0055] Advantages of the Invention

[0056] According to the present invention, a laminate film excellent in formability and mold releasability can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 is a cross-sectional view schematically showing a laminate film according to an embodiment of the present invention.

[0058] Figure 2 is a flowchart showing a method for manufacturing a laminate film according to an embodiment of the present invention.

[0059] Figure 3 is a flowchart showing a method for manufacturing a laminate film according to another embodiment of the present invention.

[0060] Figure 4 is a cross-sectional view schematically showing a molded body according to an embodiment of the present invention.​​​​

[0061] Figure 5 is a cross-sectional view schematically showing a molded body according to another embodiment of the present invention.

[0062] Figure 6 is a perspective view schematically showing a molded body according to yet another embodiment of the present invention.

[0063] Figure 7 is a perspective view schematically showing a molded body according to yet another embodiment of the present invention.

[0064] Figure 8 is a flowchart showing a method for manufacturing a molded body according to one embodiment of the present invention.

[0065] Figure 9 is a flowchart showing a method for manufacturing a molded body according to another embodiment of the present invention.

[0066] Figure 10 is a flowchart showing a method for manufacturing a molded body according to yet another embodiment of the present invention. Detailed Embodiments

[0067] Generally, a layer containing a cured resin (hereinafter, sometimes referred to as a cured resin layer) is disposed on the outermost part of a protective material. In order to achieve a seamless design, for example, the region corresponding to the information display part of the display and the region corresponding to the frame need to be integrally formed on the cured resin layer. That is, a region having irregularities and a region having a texture (grain) different from that of this region, such as a glossiness, must be formed on the surface of the cured resin layer. However, it is difficult to impart irregularities to the hard cured resin layer. Therefore, it is considered to form irregularities before the resin is completely cured.

[0068] The region having irregularities and the region having a texture different from that of this region can be formed, for example, by pressing a mold having concave and convex portions and flat portions against a cured resin layer (coating) that is neither completely uncured nor completely cured. If the viscosity of the coating is high, when peeling from the mold, in particular, the surface of the coating that is in close contact with the flat portion becomes rough or whitened, and it is difficult to obtain the desired texture. The viscosity of the coating is affected by the hardness of the coating near the surface.

[0069] On the other hand, the ease of forming irregularities is affected by the hardness inside the coating. For example, if the hardness inside the coating is too low, the recovery rate becomes high and it is difficult to form irregularities. In particular, the hardness at a position inside the coating that is about the same as the height of the convex portion imparted has a great influence on the ease of forming irregularities.

[0070] ​​​​​​This embodiment focuses on the hardness near the surface and inside of the coating, and provides a laminated film having a coating with the above hardness satisfying a specific range and relationship. Such a coating is neither completely uncured nor completely cured. Therefore, the coating has both the hardness to transfer unevenness and the low adhesiveness that can be easily peeled off from the mold. Thus, a plurality of regions having different textures, such as uneven regions and smooth regions, can be formed on the coating at the same time. Moreover, since the coating formed into a three-dimensional shape by molding (e.g., pre-molding) can be in an uncured or semi-cured state, it is easy to stretch. Thus, the laminated film can also be formed into a complex three-dimensional shape. In addition, after unevenness and, if necessary, a three-dimensional shape are imparted, these shapes are maintained for a long time by completely curing the coating.

[0071] By using the laminated film according to this embodiment, a seamless design can be achieved. That is, the laminated film according to this embodiment is suitable as a material for a molded body having a seamless design. In recent years, for example, in in-vehicle applications, a panel having a seamless design has been proposed, in which the border part is enlarged to include both the instrument panel and / or the center cluster panel. Such a panel is very large and has a complex three-dimensional shape. The laminated film according to this embodiment is particularly suitable as a material for a large molded body having the seamless design as described above.

[0072] laminated film

[0073] The laminated film according to this embodiment includes a transparent support substrate and a coating disposed on at least one main surface of the transparent support substrate. The thickness of the coating exceeds 2 μ μm. The coating contains an active energy ray curable resin composition.

[0074] (Indentation hardness)

[0075] The indentation hardness HB of the coating based on nanoindentation at an indentation depth of 100 nm 100 is 0.30 GPa or more and 0.65 GPa or less. The indentation hardness HB of the coating based on nanoindentation at an indentation depth of 2000 nm 2000 is 0.15 GPa or more and 0.35 GPa or less. The indentation hardness HB 2000 is less than the indentation hardness HB 100 . Such a coating can be said to be in a state that is neither completely uncured nor completely cured (hereinafter, referred to as semi-cured or semi-cured state).

[0076] The indentation hardness HB 100 represents the hardness near the surface of the coating (hereinafter, sometimes referred to as surface hardness). The indentation hardness HB 2000Indicates the hardness of the interior of the coating (hereinafter, sometimes referred to as internal hardness). The interior of the coating refers to the area on the transparent support substrate side of the coating. The greater the indentation hardness, the higher the hardness. The hardness of the coating can decrease from the surface toward the transparent support substrate.

[0077] In the case of giving the coating a relatively high convex portion of about 300 nm or more and about 4000 nm or less, the internal hardness of the coating is a dominant factor in the ease of forming the concavoconvex. If the internal hardness is low, the coating can easily deform along the concavoconvex of the pressed mold. However, if the hardness of the coating is too low, when the laminated film is removed from the mold, the coating easily returns to its original shape. In the case of a high convex portion, this tendency is significant.

[0078] In the present embodiment, the coating has an internal hardness to the extent that the concavoconvex is transferred and maintained. On the other hand, the surface hardness of the coating is high, showing low viscosity and not easily deformed. That is, the deformation of the concavoconvex when peeling off from the mold is suppressed because the surface hardness of the coating is high. Therefore, the desired concavoconvex can be easily formed on the laminated film involved in the present embodiment. In the present embodiment, it is envisaged that the coating is given a higher convex portion as described above, focusing on the hardness of the depth 2000nm of the coating.

[0079] In the case of a small convex portion with a height of about hundreds of nm as in Patent Document 1, the surface hardness of the coating is the dominant factor of the ease of concavoconvex formation. In this case, the coating near the surface needs to have a hardness that can transfer concavoconvex. Therefore, in Patent Document 1, the relevant parameter α of the ratio of the elastic component to the viscous component is specified to be more than 80 and less than 94. This numerical value represents a high recovery rate when the indenter is pressed into the coating. The high recovery rate means that the coating hardness near at least the surface is low and has high elasticity. Usually the hardness inside the coating is lower than the surface. That is, the inside of the coating has higher elasticity. In this way, the elasticity of the surface and the inside is high, and it is difficult to form a high convex portion of more than 300nm with high precision on a coating with a high recovery rate.

[0080] If the indentation hardness is HB 100 If the hardness HB is above 0.30 GPa, the surface of the coating shows low viscosity and is not easily deformed. Therefore, the coating is easily peeled off from the mold. That is, the laminated film can be peeled off with high precision while maintaining the pattern of the mold transferred to the surface of the coating unchanged. 100 When the pressure is 0.65 GPa or less, the laminated film can be easily stretched, so that the laminated film can be molded into a complex three-dimensional shape while suppressing cracks from occurring in the laminated film.

[0081] If the indentation hardness is HB 2000 When the hardness is 0.15 GPa or more and 0.35 GPa or less, the coating layer has a hardness that is easy to be given a concavoconvex shape. That is, the coating layer has excellent shape-imparting properties. Therefore, the coating layer can be given a desired pattern.

[0082] By making the indentation hardness HB 2000 less than the indentation hardness HB 100 , the functions of the vicinity of the surface and the interior of the coating can be exerted respectively. That is, the coating exhibits excellent mold release properties and shape forming properties.

[0083] After imparting fine irregularities and, if necessary, a three-dimensional shape to the laminated film, the coating can be completely cured. Thereby, the imparted irregularities and three-dimensional shape are maintained for a long time. That is, the obtained molded body has excellent shape retention.

[0084] Indentation hardness HB 100 and the indentation hardness HB 2000 are measured for the laminated film before the formation of the above-mentioned fine irregularities. The coating in the measured laminated film is in a semi-cured state. Heat treatment, decoration, or pre-forming can be performed on the laminated film before the formation of the irregularities after the measurement of the indentation hardness within a range that does not affect the above-mentioned indentation hardness. The indentation hardness HB 100 and the indentation hardness HB 2000 can be measured after the heat treatment, decoration, or pre-forming.

[0085] The indentation hardness H based on the nanoindentation method is obtained using a nanoindentation device, for example, by the Continuous Stiffness Measurement method. In the Continuous Stiffness Measurement method, in addition to applying a quasi-static test load (DC load) to the sample, a small load (AC load) is also applied. Thereby, the force applied to the sample vibrates slightly. Based on the vibration component of the displacement resulting therefrom and the phase difference between the displacement and the load, the stiffness with respect to the depth is calculated. Thereby, a continuous hardness distribution can be obtained for the depth. The hardness at a depth of 100 nm in this distribution is the indentation hardness HB 100 or HA described later 100 , and the hardness at 2000 nm is the indentation hardness HB 2000 or HA described later 2000 .

[0086] In the continuous rigidity measurement method, for example, the Advanced Dynamic E and H. NMT method can be adopted. As a nanoindentation device, an iMicro Nanoindenter manufactured by NANOMECHANICS, INC. can be used. In this case, iMicr dedicated software can be used in the calculation of load and rigidity. A load is applied to the sample through the indenter until the maximum load reaches 50 mN. As the indenter, for example, a verkovich type diamond indenter can be used. In the measurement and calculation of rigidity, appropriate and accurate values can be set for the Poisson's ratio and load of the coating, etc.

[0087] (Tensile rate)

[0088] The tensile rate of the laminated film at 160 °C is preferably 5.0% or more. In this case, the laminated film shows a sufficient tensile rate at a molding temperature of 180 °C or lower. Therefore, the laminated film is easily formed into a three-dimensional shape. In particular, in the pre-forming process described later, damage to the laminated film is easily suppressed. The above-mentioned tensile rate is more preferably 8.0% or more, and particularly preferably 10.0% or more. The above-mentioned tensile rate can be 500% or less, or can also be 200% or less. Forming in this specification is a concept including molding using a pre-forming process and a concavo-convex forming process.

[0089] The tensile rate is measured according to JIS K 7127. Specifically, a test piece with a length of 200 mm × a width of 10 mm cut from the laminated film and a tensile testing machine with a distance between chucks of 150 mm are used. Under the condition of an atmosphere of 160 °C and a tensile speed of 300 mm / minute, the long side of the test piece is stretched by 2.5%. Then, a microscope with a magnification of 1000 times or higher is used to observe the test piece to confirm whether there are cracks with a size exceeding 1 mm in length. If no cracks are generated, a new test piece is cut, and then the long side is stretched by 5%. Then, the generation of cracks is observed according to the same procedure. This step is repeated, and the tensile rate at the time when cracks of the above-mentioned size are first confirmed is used as the tensile rate of the laminated film. For example, the above-mentioned step can be repeated while increasing the tensile rate by 2.5% each time.

[0090] Hereinafter, the elements constituting the laminated film according to the present embodiment will be described in detail.

[0091] [Transparent support substrate]

[0092] The transparent support substrate is a substrate that supports the coating. The transparent support substrate only needs to be transparent and is not particularly limited. Specifically, transparent means that the total light transmittance is 40% or more. The total light transmittance of the transparent support substrate is preferably 90% or more. The total light transmittance can be measured by the method according to JIS K 7361-1.

[0093] The known transparent support substrates in this field can be used without particular limitation. The transparent support substrate can be colorless or colored.

[0094] The transparent support substrate is appropriately selected according to the use. Examples of the transparent support substrate include: polycarbonate (PC)-based films, polyester-based films such as polyethylene terephthalate and polyethylene naphthalate; cellulose-based films such as diacetate cellulose and triacetate cellulose; acrylic-based films such as polymethyl methacrylate (PMMA); styrene-based films such as polystyrene and acrylonitrile / styrene copolymers; olefin-based films such as polyvinyl chloride, polyethylene, polypropylene, cyclic or polyolefins having a norbornene structure, and ethylene / propylene copolymers; amide-based films such as nylon and aromatic polyamides. In addition, the transparent support substrate can be a film containing resins such as polyimide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polyvinyl alcohol, polyvinylidene chloride, polyvinyl butyral, polyarylate, polyoxymethylene, and epoxy resin, or a film containing a mixture of these polymers.

[0095] The transparent support substrate can be a laminate of multiple films. For example, the transparent support substrate can be a laminate of an acrylic-based film and a polycarbonate-based film.

[0096] The transparent support substrate can be anisotropic or isotropic in terms of optical properties. There is no particular limitation on the magnitude of birefringence of the transparent support substrate having anisotropy in optical properties. The retardation of the transparent support substrate having anisotropy can be 1 / 4 (λ / 4) of the wavelength or 1 / 2 (λ / 2) of the wavelength.

[0097] The thickness of the transparent support substrate is appropriately set according to the use, manufacturing method, etc. of the laminated film and / or molded body. From the viewpoints of strength and operability, the thickness of the transparent support substrate is preferably 30 μ μm or more, more preferably 75 μ μm or more, particularly preferably 200 μ μm or more. From the viewpoint of stretchability, the thickness of the transparent support substrate is preferably 500 μ μm or less, more preferably 400 μ μm or less. In one embodiment, the thickness of the transparent support substrate is 75 μ μm or more and 500 μ μm or less.

[0098] It is desired that the transparent support substrate has stretchability at the temperature when the laminated film is formed into a three-dimensional shape. For example, it is desired that the transparent support substrate has stretchability at the forming temperature in the preforming process. The forming temperature in the preforming process is usually 180°C or lower. From the viewpoint of formability, the glass transition temperature (Tg) of the material constituting the transparent support substrate is preferably at or below the forming temperature, that is, 180°C or lower.

[0099] [Coating]

[0100] The coating contains a radiation curable resin composition. However, the coating is neither completely cured nor completely uncured. The coating is in a semi-cured state. After various shapes such as concavities and convexities are imparted to the laminated film, the shape can be maintained for a long time by completely curing the coating.

[0101] The semi-cured resin composition (coating) can be formed, for example, by irradiating the resin composition with radiation of 5 mJ / cm 2 or more and 150 mJ / cm 2 or less. The cumulative light amount of the radiation used to semi-cure the resin composition is not limited to this, and is appropriately set according to the composition of the resin composition, etc. In the present embodiment, in consideration of the composition of the resin composition, etc., the coating is further irradiated with radiation so that the indentation hardness HB 100 and the indentation hardness HB 2000 satisfy the above ranges and relationships.

[0102] The resin composition irradiated with 1500 mJ / cm 2 of radiation is generally regarded as completely cured. The cured resin layer (for example, a hard coat and / or a functional layer) in the molded article according to the present embodiment described later is also completely cured. That is, the physical properties of the resin composition irradiated with 1500 mJ / cm 2 of radiation can be regarded as the physical properties of the cured resin layer in the molded article. The pencil hardness of the completely cured resin composition (cured resin layer) is, for example, H or higher.

[0103] The resin composition that is not exposed to radiation or is exposed to less than 5 mJ / cm 2 of radiation can be regarded as completely uncured.

[0104] The coating can be a single layer or can include two or more layers. As long as the resin composition forming each layer contains a radiation curable resin, they can be the same or different from each other. Regardless of the number of layers laminated, by making the hardness at indentation depths of 100 nm and 2000 nm satisfy the above ranges and relationships, a laminated film excellent in formability and releasability from a mold can be obtained.

[0105] The coating preferably contains at least a semi-cured hard coat, and typically, it contains a semi-cured hard coat and a semi-cured functional layer. The hard coat is mainly provided to impart scratch resistance or high hardness to the molded body. The functional layer can be an optical interference layer. The optical interference layer is mainly disposed on the outer side of the hard coat to reduce the reflectance.

[0106] The optical interference layer can be a single layer or can have multiple layers. For example, the optical interference layer has at least one of: a layer with a high refractive index (hereinafter, sometimes referred to as a high refractive index layer or HR layer), a layer with a medium refractive index (hereinafter, sometimes referred to as a medium refractive index layer or MR layer), and a layer with a low refractive index (hereinafter, sometimes referred to as a low refractive index layer or LR layer). The refractive index of the HR layer can be 1.55 or more and 2.00 or less. The refractive index of the MR layer can be 1.45 or more and 1.60 or less. The refractive index of the LR layer can be 1.35 or more and 1.50 or less.

[0107] The functional layer can be other layers than the optical interference layer, and can have both the optical interference layer and other layers at the same time. As other layers, for example, an antibacterial / antiviral layer and an antifouling layer can be cited. The antibacterial / antiviral layer and the antifouling layer are, for example, disposed on the outer side of the hard coat (and thus the optical interference layer).

[0108] <Polymerization rate>

[0109] The difference (=|PB - PA|) between the polymerization rate PB of the resin composition in the coating, that is, the resin composition in the semi-cured state, and the polymerization rate PA of the resin composition after irradiation with 1500 mJ / cm 2 of the active energy ray, that is, the resin composition in the fully cured state, is, for example, 15% or more. If |PB - PA| is within this range, the shape retention is further improved. |PB - PA| is preferably 18% or more, more preferably 20% or more. |PB - PA| can be 60% or less, preferably 50% or less. When |PB - PA| is 15% or more and 60% or less, the coating can be said to be in a semi-cured state. The indentation hardness H of the coating and the hard coat can be controlled by the polymerization rate.

[0110] The polymerization rate can be obtained, for example, according to the infrared absorption spectrum obtained by infrared spectroscopy (IR: Infrared Spectroscopy) through the following steps.

[0111] First, starting from the surface on the opposite side of the transparent support substrate of the coating, the uncured coating is analyzed using a Fourier transform infrared spectrometer (FT-IR). On the spectrogram with the wavenumber (cm -1 ) on the horizontal axis and the absorbance on the vertical axis, determine 690 cm -1 ~2015 cm -1The baseline between them. Using this baseline, the wave numbers of the carbon-carbon double bond (C=C) from (meth)acryloyl are calculated to be around 810 cm -1 and around 1440 cm -1 for the peak heights I NC1 and I NC2 . Similarly, using the above baseline, the wave number of the carbon-oxygen bond (C=O) from the ester bond is calculated to be around 1730 cm -1 for the peak height I NO . Divide the peak height I NC1 and I NC2 by the peak height I NO respectively, and use the obtained values as the initial values r 01 and r 02 .

[0112] Next, perform the same operation as above. Use FT-IR to analyze the semi-cured coating, and calculate the wave numbers of the C=C from (meth)acryloyl to be around 810 cm -1 and around 1440 cm -1 for the peak heights I BC1 and I BC2 , and the wave number of the C=O from the ester bond to be around 1730 cm -1 for the peak height I BO . Divide the peak height I BC1 and I BC2 by the peak height I BO respectively, and use the obtained values as r B1 and r B2 .

[0113] r B1 The ratio to the initial value r 01 (= r B1 / r 01 ) and the ratio of r B2 to the initial value r 02 (= r B2 / r 02 ) respectively represent the reduction rate of C=C. C=C decreases due to the polymerization reaction. Therefore, the values obtained by subtracting r B1 / r 01 from 1 and the values obtained by subtracting r B2 / r 02 from 1 can be used as indicators representing the polymerization rate. The polymerization rate PB (%) of the semi-cured resin composition is calculated by (1 - r B1 / r 01 ) × 100 or (1 - r B2 / r 02 ) × 100.

[0114] Further, the same operation as above was performed, and the coating in the completely cured state was analyzed by FT-IR. The wave numbers of C=C from (meth)acryloyl were calculated to be around 810 cm -1 and around 1440 cm -1 The peak heights I AC1 and I AC2 , and the wave number of C=O from the ester bond was around 1730 cm -1 The peak height I AO . Using the peak height I AC1 and I AC2 divided by the peak height I AO respectively, the obtained values were taken as r A1 and r A2 . The polymerization rate PA (%) of the resin composition in the cured state was calculated by (1 - r A1 / r 01 ) × 100 or (1 - r B2 / r 02 ) × 100.

[0115] In this embodiment, the difference in polymerization rate (= |PB - PA|) being 15% or more means that at least one of |(1 - r A1 / r 01 ) × 100 - (1 - r B1 / r 01 ) × 100| and |(1 - r A2 / r 02 ) × 100 - (1 - r B2 / r 02 ) × 100| is 15% or more.

[0116] <Indentation hardness>

[0117] The indentation hardness HB 100 is 0.30 GPa or more and 0.65 GPa or less. The indentation hardness HB 100 is preferably 0.40 GPa or more, more preferably 0.45 GPa or more. The indentation hardness HB 100 is preferably 0.60 GPa or less, more preferably 0.55 GPa or less, and particularly preferably 0.50 GPa or less.

[0118] There is no particular limitation on the difference between the indentation hardness HB 100 and the indentation hardness HA 100 (= |HB 100 - HA 100 |). The above indentation hardness HA 100 is irradiated with 1500 mJ / cm 2The hardness based on nanoindentation method at an indentation depth of 100 nm of the coating after irradiation with active energy rays. From the viewpoint of shape retention, |HB 100 -HA 100 | can be 0.05 GPa or more. If |HB 100 -HA 100 | is in this range, the shape retention is also likely to be improved. |HB 100 -HA 100 | can be 0.30 GPa or less. According to this embodiment, |HB 100 -HA 100 | can satisfy the above range.

[0119] The indentation hardness HB 2000 is 0.15 GPa or more and 0.35 GPa or less. The indentation hardness HB 2000 is preferably 0.20 GPa or more. The indentation hardness HB 2000 is preferably 0.33 GPa or less.

[0120] There is no particular limitation on the difference between the indentation hardness HB 2000 and the indentation hardness HA 2000 (=|HB 2000 -HA 2000 |). The above hardness HA 2000 is the hardness based on nanoindentation method at an indentation depth of 2000 nm of the coating after irradiation with 1500 mJ / cm 2 of active energy rays. From the viewpoint of formability, |HB 2000 -HA 2000 | is preferably 0.05 GPa or more. If |HB 2000 -HA 2000 | is in this range, the shape retention is also likely to be improved. |HB 2000 -HA 2000 | can be 0.30 GPa or less. According to this embodiment, |HB 2000 -HA 2000 | can satisfy the above range.

[0121] There is no particular limitation on the difference between the indentation hardness HB 100 and the indentation hardness HB 2000 (=|HB 100 -HB 2000 |). From the viewpoints of formability and demolding property, |HB 100 -HB 2000 | is preferably 0.15 GPa or more, more preferably 0.17 GPa or more. |HB 100 -HB 2000 | is preferably 0.30 GPa or less, more preferably 0.25 GPa or less.

[0122] It is desired that the coating has stretchability at the temperature when the laminated film is formed into a three-dimensional shape. For example, it is desired that the coating has stretchability at the forming temperature in the preforming process described below. The forming temperature in the preforming process is usually 180°C or lower. From the viewpoint of formability, the Tg of the resin composition in the coating is preferably at or below the forming temperature, that is, 180°C or lower.

[0123] It is required that the coating can be easily peeled off from the mold for forming unevenness. The temperature of the mold for forming unevenness is usually 50°C or higher. From the viewpoint of releasability, the Tg of the resin composition in the coating is preferably 50°C or higher, more preferably 60°C or higher. The glass transition temperature is measured by a differential scanning calorimeter (DSC) according to JIS K 7121. The Tg of the resin composition in the coating is related to the degree of curing of the coating. By suppressing Tg, the formability and releasability of the coating can be improved.

[0124] <Pencil hardness>

[0125] In terms of being easily further improved in scratch resistance, the pencil hardness of the coating surface after irradiating active energy rays of 1500 mJ / cm 2 is preferably H or higher, more preferably 2H or higher. The pencil hardness is measured according to JIS K 5600-5-4.

[0126] <Visual reflectance>

[0127] The laminated film containing an uncured optical interference layer has particularly excellent antireflection performance. For example, the visual reflectance including specular reflected light in the wavelength region of 380 nm or more and 780 nm or less measured from the optical interference layer side of the laminated film is 0.1% or more and 4.0% or less. Except for the first region of the molded body obtained by curing the laminated film, the second region also has excellent antireflection properties. Therefore, there is less reflection of external light in the molded body, and the molded body has good display characteristics and good visibility. The above visual reflectance of the second region of the molded body can also be 0.1% or more and 4.0% or less.

[0128] The above visual reflectance of the laminated film and the molded body is preferably 0.1% or more and 3.0% or less, more preferably 0.1% or more and 2.5% or less.

[0129] The above visual reflectance is obtained by measuring all reflected light including specular reflected light. That is, the above visual reflectance is measured by the so-called SCI (Specular Component Include) method. This method is less affected by the surface state of the object to be measured, so the visual reflectance of the uncured layer can be measured.

[0130] Specifically, the above-mentioned visual reflectance of the laminated film can be measured by the following method.

[0131] Using a bar coater, apply a black coating (for example, product name: CZ-805 BLACK (manufactured by Nikkō BICS Co., Ltd.)) on the surface opposite to the coating side of the transparent support substrate so that the dry film thickness reaches 3 μ m or more and 6 μ m or less. Then, leave it to dry at room temperature for 5 hours to produce an evaluation sample M.

[0132] Using a spectrophotometer (for example, SD7000 manufactured by Nippon Denshoku Industries Co., Ltd.), measure the visual reflectance based on the SCI method in the wavelength range of 380 nm or more and 780 nm or less from the coating side of the obtained evaluation sample M.

[0133] The above-mentioned visual reflectance of the molded body can be measured as follows.

[0134] Irradiate the evaluation sample M produced above with actinic rays having an accumulated light amount exceeding 150 mJ / cm 2 (for example, the accumulated light amount is 1500 mJ / cm 2 ) to produce an evaluation sample N. From the coating side of the obtained evaluation sample N, perform the same operation as above to measure the visual reflectance.

[0135] <Thickness>

[0136] The thickness of the coating only needs to exceed 2 μ m, and there is no particular limitation. From the perspective of easily forming higher protrusions, the thickness of the coating is preferably 3 μ m or more, more preferably 5 μ m or more. From the perspective of easy curing, the thickness of the coating is preferably 20 μ m or less, more preferably 15 μ m or less. The thickness of the coating is, for example, 3 μ m or more and 20 μ m or less. In the case where the coating includes multiple layers, the thickness of the coating is the total of the thicknesses of these layers.

[0137] The thickness of the hard coat can be in the same range as the thickness of the above-mentioned coating. The thickness of each layer of the functional layer is, for example, 5 nm or more and 300 nm or less, 10 nm or more and 200 nm or less.

[0138] The thickness of the coating can be determined from its cross-section. Specifically, a test piece of 10 mm × 10 mm is cut from the laminated film. A microtome is used to prepare a cross-section slice from the test piece for observation. The obtained slice is observed under a laser microscope or a transmission electron microscope, and the thickness of the coating at arbitrarily selected 10 points is measured. The average value of them is taken as the thickness of the coating. The thickness of the transparent support substrate is obtained in the same manner. As the microtome, for example, RM2265 manufactured by Leica Microsystems is used. As the laser microscope, for example, VK8700 manufactured by KEYENCE is used.

[0139] (Resin composition)

[0140] The resin composition contains at least one selected from active energy ray curable monomers, oligomers, and polymers. There is no particular limitation on the active energy ray, and it can be ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. Hereinafter, the active energy ray curable monomers, oligomers, and polymers may be collectively referred to as resin components. The polymerization rate, and the indentation hardness H of the coating and the cured resin layer can be controlled by the resin composition.

[0141] When the coating has multiple layers, the resin components forming each layer may be the same or different. Among them, each layer preferably contains the same or the same kind of resin component. This is because: the adhesion between each layer is improved, and delamination between layers is less likely to occur.

[0142] In one aspect, the resin composition contains a polymerizable polymer. By the polymerizable polymer, curability and low tack can be easily imparted to the coating at the same time.

[0143] In another aspect, the resin composition contains at least one of a polymerizable and a non-polymerizable polymer (hereinafter sometimes collectively referred to as a polymer), and at least one of a polymerizable monomer and an oligomer. By the polymer, low tack can be easily imparted to the coating. In addition, the formability is easily improved. By simultaneously blending at least one of a polymerizable monomer and an oligomer with the polymer, the polymerization rate difference (=|PB - PA|) can be easily adjusted to 15.0% or more. As a result, the shape retention can be further easily improved. From the viewpoint of easily controlling the tack, the resin composition preferably contains both a polymerizable polymer and a non-polymerizable polymer, and at least one of a polymerizable monomer and an oligomer.

[0144] <Non-polymerizable polymer>

[0145] The non-polymerizable polymer is a polymer that does not contain a polymerizable unsaturated group.

[0146] The weight-average molecular weight of the non-polymerizable polymer is 5,000 or more. From the viewpoint of viscosity, the weight-average molecular weight of the non-polymerizable polymer is preferably 10,000 or more. The weight-average molecular weight of the non-polymerizable polymer may be 200,000 or less, preferably 100,000 or less, more preferably 80,000 or less.

[0147] Examples of the non-polymerizable polymer include urethane resins, acrylic resins, polyester resins, and epoxy resins. From the viewpoints of transparency, viscosity, physical properties, and durability, an acrylic resin is preferred.

[0148] <Polymerizable polymer>

[0149] The polymerizable polymer is a polymer containing polymerizable unsaturated groups.

[0150] The weight-average molecular weight of the polymerizable polymer is 5,000 or more. From the viewpoint of viscosity, the weight-average molecular weight of the polymerizable polymer is preferably 10,000 or more. The weight-average molecular weight of the non-polymerizable polymer may be 200,000 or less, preferably 100,000 or less, more preferably 80,000 or less.

[0151] The polymerizable polymer contains a polymer chain containing a carbon-carbon bond, an ether bond, a urea bond, an ester bond, a urethane bond, etc. as the main chain, and contains polymerizable unsaturated groups as side chains or terminal groups. From the viewpoint of transparency, a polymer chain containing a carbon-carbon bond is preferred. From the viewpoint of formability, a polymer chain containing a urethane bond is preferred.

[0152] The polymerizable unsaturated groups preferably contain 2 or more, more preferably 3 or more, particularly preferably 5 or more. There is no particular limitation on the polymerizable unsaturated groups. Among them, as the polymerizable unsaturated groups, acryloyl and methacryloyl are preferred.

[0153] Specifically, examples of the preferred polymerizable polymer include urethane (meth)acrylate polymers and acrylic (meth)acrylate polymers.

[0154] The urethane (meth)acrylate polymer can be prepared, for example, by the following methods: Method (1), an addition reaction of a compound having a hydroxyl group and an acryloyl group (or methacryloyl group) with a polyisocyanate compound having a terminal isocyanate group in the molecule; or Method (2), for a polyurethane polyol obtained by reacting a polyisocyanate compound with a polyol, reacting an isocyanate group-containing (meth)acrylate monomer therewith.

[0155] Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and diisocyanate compounds obtained by hydrogenating aromatic isocyanates in these diisocyanate compounds (for example, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc.), polyisocyanate compounds having a valence of 2 or 3 such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate, and biuret-type adducts or isocyanurate ring-type adducts of these diisocyanates.

[0156] Examples of the compound having a hydroxyl group and an acryloyl group (or methacryloyl group) in the above method (1) include pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycerol di(meth)acrylate, and compounds modified with an alkylene oxide or a lactone obtained by adding ethylene oxide, propylene oxide, ε-caprolactone, γ-butyrolactone, etc. to them.

[0157] Examples of the polyol in the above method (2) include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, polycaprolactone diol, polyester polyol, and polyether polyol.

[0158] Examples of the isocyanate group-containing (meth)acrylate monomer in the above method (2) include ethyl isocyanate acrylate, propyl isocyanate acrylate, and unsaturated compounds formed by adding a polyisocyanate compound such as hexamethylene diisocyanate to a polymerizable monomer having an active hydrogen such as 2-hydroxyethyl acrylate.

[0159] The urethane (meth)acrylate polymer may be a urethane urea (meth)acrylate polymer having a urea bond. The urethane urea (meth)acrylate polymer can be prepared, for example, by using a polyamine in addition to the polyol in the above method (2).

[0160] The acrylic (meth)acrylate polymer is an acrylic polymer containing an acryloyl group and / or a methacryloyl group. Specifically, examples thereof include: a compound obtained by adding (meth)acrylic acid to an acrylic resin obtained by copolymerizing glycidyl methacrylate; a compound obtained by adding 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate, pentaerythritol tri(meth)acrylate, etc. to an acrylic resin obtained by copolymerizing 2-acryloyloxyethyl isocyanate; a resin obtained by adding 2-acryloyloxyethyl isocyanate to an acrylic resin obtained by copolymerizing a hydroxyl group-containing monomer.

[0161] The polymer can be used alone or in combination of two or more.

[0162] In the resin composition for forming a hard coat (hereinafter sometimes referred to as resin composition HC), with respect to 100 parts by mass of the solid content of the resin composition HC, the content of the polymer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and particularly preferably 15 parts by mass or more. In the resin composition HC, the content of the polymer is preferably 85 parts by mass or less, more preferably 60 parts by mass or less, and particularly preferably 45 parts by mass or less. The content of the polymer in the resin composition HC is, for example, more than 5 parts by mass and 85 parts by mass or less. There is no particular limitation on the blending ratio of the polymerizable polymer and the non-polymerizable polymer.

[0163] In the resin composition for forming an optical interference layer (hereinafter sometimes referred to as resin composition R), with respect to 100 parts by mass of the solid content of the resin composition R, the content of the polymer is preferably more than 5 parts by mass, more preferably 10 parts by mass or more, and particularly preferably 15 parts by mass or more. With respect to 100 parts by mass of the solid content of the resin composition R, the content of the polymer is preferably 85 parts by mass or less, more preferably 60 parts by mass or less, and particularly preferably 25 parts by mass or less. The content of the polymer in the resin composition R is, for example, more than 5 parts by mass and 85 parts by mass or less. There is no particular limitation on the blending ratio of the polymerizable polymer and the non-polymerizable polymer.

[0164] <Polymerizable oligomer>

[0165] The polymerizable oligomer is an oligomer containing a polymerizable unsaturated group.

[0166] The weight average molecular weight of the polymerizable oligomer is 500 or more and less than 5,000. The weight average molecular weight of the polymerizable oligomer can be 2,000 or more.

[0167] The polymeric oligomer has the same composition as the polymeric polymer except for the molecular weight. The polymeric oligomer contains an oligomer chain containing a carbon-carbon bond, an ether bond, a urea bond, an ester bond, a urethane bond, etc. as the main chain, and contains a polymerizable unsaturated group as a side chain or a terminal group. From the viewpoint of transparency, an oligomer chain containing a carbon-carbon bond is preferred. From the viewpoint of formability, an oligomer chain containing a urethane bond is preferred.

[0168] The polymerizable unsaturated group preferably contains 2 or more, more preferably 3 or more, and particularly preferably 5 or more. There is no particular limitation on the polymerizable unsaturated group. Among them, as the polymerizable unsaturated group, an acryloyl group and a methacryloyl group are preferred.

[0169] As preferred polymeric oligomers, specifically, urethane (meth)acrylate oligomers and acrylic (meth)acrylate oligomers can be cited.

[0170] The above-mentioned urethane (meth)acrylate oligomers and acrylic (meth)acrylate oligomers are prepared by the same operations as urethane (meth)acrylate polymers and acrylic (meth)acrylate polymers, respectively.

[0171] The polymeric oligomer can be used alone or in combination of two or more.

[0172] As the aggregative oligomer or aggregative polymer, commercially available products can be used. As the commercially available urethane (meth)acrylate oligomer or polymer, for example, the following can be used: DPHA-40H, UX-5000, UX-5102D20, UX-5103D, UX-5005, UX-3204, UX-4101, UXT-6100, UX-6101, UX-8101, UX-0937, UXF-4001-M35, UXF-4002 manufactured by Nippon Kayaku Co., Ltd.; UF-8001G, UA-510H manufactured by Kyoeisha Chemical Co., Ltd.; EBECRYL 244, EBECRYL 284, EBECRYL 8402, EBECRYL 8807, EBECRYL 264, EBECRYL 265, EBECRYL 9260, EBECRYL 8701, EBECRYL 8405, EBECRYL 1290, EBECRYL 5129, EBECRYL 220, KRM 8200, KRM 7804, KRM 8452 manufactured by DAICEL-ALLNEX Co., Ltd.; UV-1700B, UV-6300B, UV-7600B, UV-7640B, UV-7650B, UV-3520EA, UV-7000B, Violet UV-AF305A manufactured by Mitsubishi Chemical Corporation; CN-9001, CN-9004, CN-9005, CN-965, CN-9178, CN-9893, CN-9782, CN-964, CN-9013, CN-9010 manufactured by Arkema; U-10PA, U-10HA, UA-33A, UA-53H, UA-32P, U-15HA, UA-122P, UA-160TM, UA-31F, UA-7100, UA-4200, UA-4400 manufactured by Shin-Nakamura Chemical Co., Ltd.;ART RESIN UN-3320HA, ART RESIN UN-3320HB, ART RESIN UN-3320HC, ART RESIN UN-3320HS, ART RESIN H-7M40, ART RESIN UN-904, ART RESIN UN-904M, ART RESIN UN-901T, ART RESIN UN-905, ART RESIN UN-951, ART RESIN UN-952, ART RESIN UN-953, ART RESIN UN-954, ART RESIN UN-906, ART RESIN UN-906S, ART RESIN UN-907, ART RESIN UN-908, ART RESIN UN-333, ART RESIN UN-5507, ART RESIN UN-6300, ART RESIN UN-6301, ART RESIN UN-7600, ART RESIN UN-7700, ART RESIN UN-9000PEP, ART RESIN UN-9200, ART RESIN UN-904UREA, ART RESIN UN-H7UREA, etc., manufactured by Negami Kogyo Co., Ltd.;

[0173] As commercially available acrylic (meth)acrylate oligomers or polymers, for example, the following can be used: UNIDIC V-6840, UNIDIC V-6841, UNIDIC V-6850, UNIDIC EMS-635, UNIDIC WHV-649 manufactured by DIC Corporation; Hitaroid 7975, Hitaroid 7977, Hitaroid 7988, Hitaroid 7975D manufactured by Hitachi Chemical Co., Ltd.; ART CURE RA-3969MP, ART CURE RA-3960PG, ART CURE RA-3602MI, ART CURE OAP-5000, ART CURE OAP-2511, ART CURE AHC-9202MI80, ART CURE RA-3704MB, ART CURE RA-3953MP, ART CURE RA-4101, ART CURE MAP-4000, ART CURE MAP2801, etc., manufactured by Negami Kogyo Co., Ltd.

[0174] <Polymerizable monomer>

[0175] The polymerizable monomer is a monomer containing a polymerizable unsaturated group.

[0176] There is no particular limitation on the molecular weight of the polymerizable monomer. The polymerizable unsaturated group equivalent of the polymerizable monomer may be 50 g / eq. or more, or may be 200 g / eq. or less.

[0177] The polymerizable monomer preferably has two or more, more preferably three or more, and particularly preferably five or more polymerizable unsaturated groups. As the polymerizable unsaturated group, acryloyl and methacryloyl can be preferably exemplified. Preferred polymerizable monomers are polyfunctional (meth)acrylate monomers.

[0178] The polyfunctional (meth)acrylate monomer can be prepared by a dehydration reaction of a polyol with (meth)acrylic acid or a transesterification reaction of a polyol with a (meth)acrylate.

[0179] Examples of the polyfunctional (meth)acrylate monomer having an equivalent weight of the polymerizable unsaturated group of 50 g / eq. or more and 200 g / eq. or less include bifunctional (meth)acrylate monomers such as ethylene glycol di(meth)acrylate, 1,6 - hexanediol di(meth)acrylate, polyethylene glycol(200) di(meth)acrylate, allyl (meth)acrylate, 1,4 - butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dioxane diol di(meth)acrylate, ethoxylated(2) bisphenol A di(meth)acrylate, ethoxylated(3) bisphenol A di(meth)acrylate, ethoxylated(4) bisphenol A di(meth)acrylate, ethoxylated(10) bisphenol A di(meth)acrylate, propoxylated(3) bisphenol A di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 9,9 - bis[4-(2 - hydroxyethoxy)phenyl]fluorene di(meth)acrylate; trifunctional (meth)acrylate monomers such as glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated(3) trimethylolpropane triacrylate, ethoxylated(6) trimethylolpropane triacrylate, ethoxylated(9) trimethylolpropane triacrylate, propoxylated(3) trimethylolpropane triacrylate, propoxylated(6) trimethylolpropane triacrylate, propoxylated(9) trimethylolpropane triacrylate, pentaerythritol tri(meth)acrylate, ethoxylated(4) pentaerythritol tri(meth)acrylate, ethoxylated(8) pentaerythritol tri(meth)acrylate, tris(2 - hydroxyethyl)isocyanurate tri(meth)acrylate, caprolactone - modified(1) tris(2 - hydroxyethyl)isocyanurate tri(meth)acrylate, caprolactone - modified(3) tris(2 - hydroxyethyl)isocyanurate tri(meth)acrylate; tetrafunctional (meth)acrylate monomers such as pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, tripentaerythritol tetra(meth)acrylate, bis - trimethylolpropane tetra(meth)acrylate, ethoxylated(4) pentaerythritol tetra(meth)acrylate, ethoxylated(8) pentaerythritol tetra(meth)acrylate; pentafunctional (meth)acrylate monomers such as dipentaerythritol penta(meth)acrylate, tripentaerythritol penta(meth)acrylate; hexafunctional (meth)acrylate monomers such as dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate; (meth)acrylate monomers having 7 or more functional groups such as tripentaerythritol penta(meth)acrylate, tripentaerythritol octa(meth)acrylate.

[0180] The polymerizable monomer may be used alone or in combination of two or more.

[0181] In the resin composition HC, the content of the polymerizable oligomer is, for example, 5 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition HC. The content of the polymerizable monomer is, for example, 5 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition HC. The total content of the polymerizable monomer and / or the polymerizable oligomer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the solid content of the resin composition HC. The total content of the polymerizable monomer and / or the polymerizable oligomer is preferably 95 parts by mass or less, more preferably 70 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition HC. The total content of the polymerizable monomer and / or the polymerizable oligomer in the resin composition HC is, for example, 5 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition HC.

[0182] In the resin composition R, the content of the polymerizable oligomer is, for example, 5 parts by mass or more and 85 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition R. The content of the polymerizable monomer is, for example, 5 parts by mass or more and 85 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition R. The total content of the polymerizable monomer and / or the polymerizable oligomer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, particularly preferably 13 parts by mass or more with respect to 100 parts by mass of the solid content of the resin composition R. The total content of the polymerizable monomer and / or the polymerizable oligomer is preferably 85 parts by mass or less, more preferably 60 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition R. The total content of the polymerizable monomer and / or the polymerizable oligomer in the resin composition R is, for example, 5 parts by mass or more and 85 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition R.

[0183] <Light-transmitting fine particles>

[0184] The resin composition may contain light-transmitting fine particles as needed. By the light-transmitting fine particles, it is easier to improve the antiglare property and hardness of the cured coating (cured resin layer). The average particle size of the light-transmitting fine particles is, for example, 1.0 μ μm or more and 10 μ μm or less, and may be 0.5 μ μm or more and 10 μ μm or less. The average particle size means the particle size (D50) at which the cumulative volume conversion measured by a laser diffraction particle size distribution analyzer is 50%. The light-transmitting fine particles are transparent or translucent. Specifically, translucent means that the total light transmittance measured by the method according to JIS K 7361-1 is 30% or more and less than 40%.

[0185] The light-transmissive fine particles can be organic fine particles or inorganic fine particles. As the light-transmissive fine particles, commercially available products can be used. Examples of commercially available light-transmissive fine particles include: TECHPOLYMER SSX series (styrene-acrylic copolymer fine particles) manufactured by Sekisui Chemical Co., Ltd.; Chemisnow SX series (styrene polymer fine particles), Chemisnow MX series (acrylic polymer fine particles) manufactured by Soken Chemical & Engineering Co., Ltd.; SEAHOSTAR KE-P, KE-S series (silica fine particles), SOLIOSTAR RA (silicon-acrylic copolymer fine particles), EPOSTAR S12 (melamine polymer fine particles), EPOSTAR MA series (styrene-acrylic copolymer fine particles), acrylic copolymer fine particles manufactured by Nippon Catalyst Co., Ltd.; MSP series, NH series (organosilicon fine particles) manufactured by Nisshin RICA Co., Ltd.; AZ series, AY series (aluminum oxide fine particles) manufactured by Nippon Steel & Sumikin Materials Co., Ltd. Among them, TECHPOLYMER SSX series (styrene-acrylic copolymer fine particles), Chemisnow SX series (styrene polymer fine particles), and EPOSTAR MA series (styrene-acrylic copolymer fine particles) are preferred.

[0186] <Filler>

[0187] The resin composition contains a filler as needed. By means of the filler, the volume shrinkage caused by the curing of the coating is alleviated. By means of the filler, the scratch resistance of the cured coating is improved.

[0188] From the viewpoints of transparency and stability, the primary particle size of the filler is preferably 5 nm or more and 1,000 nm or less, more preferably 500 nm or less, and particularly preferably 100 nm or less. The primary particle size is measured using image processing software based on a cross-sectional electron microscope image.

[0189] The filler can be organic fine particles or inorganic fine particles. Among them, inorganic fine particles are preferred. Examples of the inorganic fine particles include: silica (SiO2) particles, alumina particles, titanium oxide particles, tin oxide particles, antimony-doped tin oxide (abbreviated as ATO) particles, phosphorus-doped tin oxide particles, zinc oxide particles, particles obtained by supporting silver on titanium oxide, particles obtained by supporting silver on silica / alumina particles, particles obtained by supporting multi-metal (silver / zinc / copper) ions on glass, and copper iodide particles. Among them, from the viewpoints of cost and stability, silica particles and alumina particles are more preferred. The surface of the filler is preferably modified with unsaturated groups such as (meth)acryloyl groups.

[0190] As the filler, commercially available products can be used. Examples of commercially available silica particles (colloidal silica) include IPA-ST, MEK-STM, IBK-ST, PGM-ST, XBA-ST, MEK-AC-2101, MEK-AC-2202, MEK-AC-4101, and MIBK-SD manufactured by Nissan Chemical Industries, Ltd.; PL-1-IPA, PL-1-TOL, PL-2-IPA, PL-2-MEK, and PL-3-TOL manufactured by Fuso Chemical Industry Co., Ltd.; OSCAL series and ELECOM series manufactured by JGC Catalysts & Chemicals Ltd.; and NANOBYK-3605 manufactured by BYK-Chemie Japan. Examples of commercially available alumina particles include AS-150I and AS-150T manufactured by Sumitomo Osaka Cement Co., Ltd.; and NANOBYK-3601, NANOBYK-3602, and NANOBYK-3610 manufactured by BYK-Chemie Japan.

[0191] Examples of commercially available phosphorus-doped tin oxide particles include HX-204 IP manufactured by Nissan Chemical Corporation and PTOPGM15WT%-N09 manufactured by CIK-Nano Tek. Examples of particles obtained by supporting silver on titanium oxide include ATOMY BALL-(S) manufactured by JGC Catalysts & Chemicals Ltd. Examples of particles obtained by supporting silver on silica-alumina particles include ATOMY BALL-(UA), ELCOM NU-1023SIV, and ELCOM NU-1024SIV manufactured by JGC Catalysts & Chemicals Ltd. Examples of particles obtained by supporting silver on silica particles include ION PURE ZAF HS manufactured by Ishizuka Glass Co., Ltd. Examples of copper iodide particles include CufitecBE4-ANA01, AA1-ANA01, BB2-ANA01, and BD3-ANA01 manufactured by NBC Meshtec.

[0192] In the resin composition HC, with respect to 100 parts by mass of the solid content of the resin composition HC, the content of the filler is preferably 60 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 15 parts by mass or less. With respect to 100 parts by mass of the solid content of the resin composition HC, the content of the filler is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and particularly preferably 3 parts by mass or more. With respect to 100 parts by mass of the solid content of the resin composition HC, the content of the filler in the resin composition HC is, for example, 0.1 part by mass or more and 60 parts by mass or less.

[0193] In the resin composition R, relative to 100 parts by mass of the solid content of the resin composition R, the content of the filler is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and particularly preferably 7 parts by mass or more. Relative to 100 parts by mass of the solid content of the resin composition R, the content of the filler is preferably 90 parts by mass or less. Relative to 100 parts by mass of the solid content of the resin composition R, the content of the filler in the resin composition R is, for example, 1 part by mass or more and 90 parts by mass or less.

[0194] <Photoinitiator>

[0195] The resin composition may contain a photoinitiator as needed. Relative to 100 parts by mass of the solid content of the resin composition, the blending amount of the photoinitiator is preferably 0.01 part by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less.

[0196] Examples of the photoinitiator include: alkylbenzophenone-based photoinitiators, acylphosphine oxide-based photoinitiators, titanocene-based photoinitiators, and oxime ester-based polymerization initiators.

[0197] Examples of the alkylbenzophenone-based photoinitiator include: 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.

[0198] Examples of the acylphosphine oxide-based photoinitiator include: monoacylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-oxide, 2,4,6-triethylbenzoyldiphenyl oxide, 2,4,6-triphenylbenzoyldiphenyl oxide; bisacylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)-phenyl oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl oxide.

[0199] As the titanocene-based photopolymerization initiator, for example, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium can be cited. As the oxime ester-based polymerization initiator, for example, 1.2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)], acetophenone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyl oxime), hydroxybenzene acetate, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl acetate, 2-(2-hydroxyethoxy)ethyl acetate can be cited.

[0200] The photopolymerization initiator can be used alone or in combination of two or more.

[0201] Among them, a photopolymerization initiator having an absorption wavelength in the long wavelength region, for example, a wavelength region of 370 nm or more, is preferably used. As such a photopolymerization initiator, for example, the above-mentioned acylphosphine oxide-based photopolymerization initiator can be cited. 2,4,6-Trimethylbenzoyldiphenylphosphine oxide is commercially available from IGM Resins B.V. as Omnirad TPO H. Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is commercially available from IGM Resins B.V. as Omnirad 819.

[0202] When irradiating active energy rays under stable curing conditions such that the coating is semi-cured, it is difficult to carry out the curing reaction inside the coating, so it is difficult to obtain the desired hardness. By using a photopolymerization initiator having an absorption wavelength in the long wavelength region, the curing reaction inside the coating is promoted.

[0203] <Solvent>

[0204] The resin composition contains a solvent as needed. There is no particular limitation on the solvent, and it is appropriately selected according to the components contained in the composition, the type of the substrate to be coated, the coating method of the composition, etc. As the solvent, for example, aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol, and isobutanol; halogen solvents such as dichloromethane and chloroform can be cited. These can be used alone or in combination of two or more. Among them, ester solvents, ether solvents, alcohol solvents, and ketone solvents are preferred.

[0205] <Refractive index reducing component>

[0206] The resin composition R preferably contains a refractive index reducing component that reduces the refractive index of the light interference layer. The refractive index reducing component is, for example, particulate (hereinafter sometimes referred to as refractive index reducing particles).

[0207] Examples of the refractive index reducing component include hollow silica fine particles. The hollow silica fine particles can reduce the refractive index while maintaining the strength of the light interference layer. The hollow silica fine particles are a structure with gas filled inside and / or a porous structure containing gas. The refractive index decreases in inverse proportion to the occupancy of the gas. Therefore, the hollow silica fine particles have a lower refractive index than the original refractive index of the silica fine particles. Examples of the hollow silica fine particles include THRULYA 4320 (manufactured by JGC Catalysts and Chemicals Ltd.).

[0208] As the refractive index reducing component, silica fine particles that form a nanoporous structure on at least a part of the inside and / or surface can be used. The nanoporous structure is formed according to the morphology, structure, aggregation state, and dispersion state inside the coating film of the silica fine particles. As the refractive index reducing component, hollow acrylic fine particles can be used. Examples of the hollow acrylic fine particles include XX-5952Z, XX-5966Z, and XX-6061Z manufactured by Sekisui Chemical Co., Ltd.

[0209] The volume average particle diameter of the refractive index reducing particles is preferably 50 nm or more and 200 nm or less. The volume average particle diameter is the primary particle diameter.

[0210] With respect to 100 parts by mass of the solid content of the resin composition R, the content of the refractive index reducing component is preferably 35 parts by mass or more, more preferably 37.5 parts by mass or more. With respect to 100 parts by mass of the solid content of the resin composition R, the content of the refractive index reducing component is preferably 75 parts by mass or less, more preferably 60 parts by mass or less. Thereby, the cured light interference layer can easily exhibit excellent antireflectivity. With respect to 100 parts by mass of the solid content of the resin composition R, the content of the refractive index reducing component is, for example, 35 parts by mass or more and 75 parts by mass or less.

[0211] <Others>

[0212] The resin composition contains various additives as required. Examples of the additives include antistatic agents, plasticizers, surfactants, antioxidants, ultraviolet absorbers, surface modifiers, homogenizers, and light stabilizers (e.g., hindered amine light stabilizers (HALS)), antibacterial agents, mildewproof agents, antiviral agents, and antifouling agents. It is particularly desirable to include antibacterial agents, mildewproof agents, antiviral agents, and antifouling agents in the resin composition (e.g., resin composition R) that forms the outermost layer.

[0213] [Protective film]

[0214] The laminated film may have a protective film on the outer surface side of the coating. While protecting the coating and the laminated film, the protective film functions as a release paper for forming the resin composition R into a film shape. The protective film may have an adhesive layer or a release layer on the side coated with the resin composition R.

[0215] The protective films known in the art can be used without particular limitation. The protective film can be colorless or colored. The protective film can be transparent.

[0216] There is no particular limitation on the thickness of the protective film. The thickness of the protective film can be 20 μ μm or more and 100 μ μm or less. Thus, the protective effect of the coating is easily improved. The thickness of the protective film is preferably 25 μ μm or more, more preferably 30 μ μm or more, further preferably 33 μ μm or more, particularly preferably 35 μ μm or more. The thickness of the protective film is preferably 85 μ μm or less, more preferably 80 μ μm or less, further preferably 65 μ μm or less. The thickness of the protective film refers to the value excluding the thickness of the adhesive layer.

[0217] The protective film is made of resin, for example. As the resin film, the following can be cited: polyolefin films such as polyethylene films and polypropylene films (including unstretched polypropylene films (CPP films) and biaxially stretched polypropylene films (OPP films)); modified polyolefin films obtained by modifying these polyolefins and further imparting functions; polyester films such as polyethylene terephthalate, polycarbonate, and polylactic acid; polystyrene-based resin films such as polystyrene films, AS resin films, and ABS resin films; nylon films, polyamide films, polyvinyl chloride films, polyvinylidene chloride films, and polymethylpentene films.

[0218] Among them, at least one selected from polyethylene films, polystyrene films, modified polyolefin films, polymethylpentene films, OPP films, and CPP films is preferred. In particular, at least one selected from polyethylene films, polystyrene films, modified polyolefin films, polymethylpentene films, OPP films, and CPP films having a thickness of 30 μ μm or more and 100 μ μm or less is preferred.

[0219] Additives such as antistatic agents and ultraviolet ray inhibitors can be added to the resin film as needed. The surface of the resin film can be subjected to corona treatment or low-temperature plasma treatment.

[0220] Figure 1It is a cross-sectional view schematically showing the laminated film according to this embodiment. The laminated film 10 includes a transparent support substrate 11 and a coating 12 disposed on one main surface of the substrate 11.

[0221] Manufacturing method of laminated film

[0222] The laminated film according to this embodiment is manufactured, for example, by a method having the following steps: a coating step of coating a radiation curable resin composition on at least one main surface of a transparent support substrate; and a first irradiation step of irradiating the resin composition with radiation of 5 mJ / cm 2 or more and 150 mJ / cm 2 or less to obtain a coating formed of a semi-cured resin composition.

[0223] Figure 2 It is a flowchart showing the manufacturing method of the laminated film according to this embodiment.

[0224] (1) Coating step (S11)

[0225] A radiation curable resin composition (for example, the above resin composition HC) is coated on at least one main surface of a transparent support substrate. Thereby, an uncured coating is formed.

[0226] The resin composition is prepared by a known method. The resin composition is prepared, for example, by mixing each component using a commonly used mixing device such as a paint stirrer, a mixer, or a disperser.

[0227] The coating method of the resin composition is appropriately selected according to the properties of the resin composition and the like. As the coating method, for example, dip coating method, air knife coating method, curtain coating method, roll coating method, bar coating method, die coating method, inkjet method, gravure coating method, or extrusion coating method can be cited.

[0228] There is no particular limitation on the coating amount of the resin composition. The resin composition is coated so that the coating thickness is more than 2 μ μm, for example, 3 μ μm or more and 20 μ μm or less.

[0229] (2) Drying step (S12)

[0230] After the coating step (1) and before the first irradiation step (3), the coated resin composition can be dried. By the drying step, at least a part of the solvent component contained in the resin composition is removed, the operability is improved, and at the same time, the degree of curing is easily controlled. There is no particular limitation on the drying conditions, and they are appropriately set according to the coating amount, the type of solvent, and the like.

[0231] (3) First irradiation step (S13)

[0232] Irradiate the resin composition with 5 mJ / cm 2 or more and 150 mJ / cm 2 or less of actinic energy rays. Through the first irradiation step, the resin composition becomes in a semi-cured state, and the above-mentioned coating is obtained. By the cumulative light amount in the first irradiation step, the polymerization rate of the resin composition can be controlled, and further the indentation hardness H of the coating can be controlled. The first irradiation step only needs to be carried out before the uneven formation step described later, and can be carried out before or after the preforming step.

[0233] The cumulative light amount in this step can be 10 mJ / cm 2 or more, or can be 20 mJ / cm 2 or more. The cumulative light amount in this step can be 130 mJ / cm 2 or less, or can be 100 mJ / cm 2 or less. The irradiation of the actinic energy rays can be carried out from the coating side or from the transparent support substrate side. The irradiation of the actinic energy rays can be carried out in an air atmosphere or in a nitrogen atmosphere.

[0234] In the coating, the indentation hardness HB 2000 is less than the indentation hardness HB 100 . Moreover, the indentation hardness HB 2000 is 0.15 GPa or more and 0.35 GPa or less. Therefore, the coating has excellent formability. Thus, a desired pattern can be imparted to the coating. The indentation hardness HB 100 is 0.30 GPa or more and 0.65 GPa or less. Therefore, the pattern of the mold transferred to the coating surface can be maintained with high precision without change, and the laminated film can be peeled off from the mold.

[0235] There is no particular limitation on the type of actinic energy rays. The actinic energy rays are appropriately selected according to the type of polymerizable monomer or oligomer. There is no particular limitation on the actinic energy rays, and they can be ionizing radiations such as ultraviolet rays, electron rays, α rays, β rays, γ rays, etc. Among them, ultraviolet rays are preferred. For example, ultraviolet rays are irradiated using a high-pressure mercury lamp or an ultra-high-pressure mercury lamp.

[0236] [Manufacturing method of a laminated film having a coating including multiple layers]

[0237] A coating including multiple layers (representatively, a semi-cured hard coating and a semi-cured light interference layer) is formed by a lamination method or a coating method. The first irradiation step (3) can be carried out multiple times.

[0238] (Lamination method)

[0239] In the lamination method, according to the coating step (1), a plurality of layers formed on other substrates are laminated respectively. The drying step (2) is optionally carried out before the layers are laminated to each other. The first irradiation step (3) can be carried out on each layer before the layers are laminated to each other, or can be carried out together after the lamination. According to the lamination method, even between uncured layers, it is easy to suppress phase mixing.

[0240] (Coating method)

[0241] In the coating method, a resin composition for forming other layers is coated on the layer formed on the transparent support substrate according to the coating step (1). The drying step (2) is optionally carried out before coating the other resin composition. From the viewpoint of suppressing phase mixing, the first irradiation step (3) is preferably carried out on the layer formed on the transparent support substrate before coating the other resin composition. After coating the other resin composition, the first irradiation step (3) is carried out on the other resin composition this time.

[0242] Figure 3 is a flowchart showing the manufacturing method of the laminated film according to the present embodiment. Figure 3 Shows an embodiment in which an uncured hard coat and an uncured optical interference layer are laminated by a lamination method and then the first irradiation step is carried out.

[0243] formed body

[0244] The molded body according to the present embodiment includes: the above-mentioned transparent support substrate and a cured resin layer (cured coating) disposed on at least one main surface of the transparent support substrate. The main surface on the opposite side of the transparent support substrate of the cured resin layer has a first region formed with irregularities and a second region other than that. The first region and the second region are integrally formed. The pencil hardness of the surface of the cured resin layer is H or more. The molded body can have fine irregularities and a three-dimensional shape (three-dimensional shape) at the same time.

[0245] The molded body is formed by partially imparting irregularities to the coating of the laminated film according to the present embodiment and curing it. The cured resin layer has the same physical properties as the coating after being irradiated with actinic energy rays of 1500 mJ / cm 2 2.

[0246] [Cured resin layer]

[0247] The cured resin layer has a first region formed with fine irregularities and a second region other than that. A plurality of the first regions and / or the second regions can be arranged.

[0248] The cured resin layer can be one layer, or can include two or more layers. The cured resin layer at least includes a hard coat. In one aspect, the cured resin layer includes a hard coat and one or more functional layers (representatively an optical interference layer).

[0249] The molded body is used, for example, as a protective material for a display. In this case, the first region is configured to correspond to the display. The first region can be understood as the display portion of the molded body. The antiglare property is improved by the unevenness. The first region can be configured to correspond to the operation display unit. The second region is configured, for example, to correspond to the region (border) surrounding the display. The second region can be understood as the border portion of the molded body. The second region has a texture different from that of the first region, such as a glossiness. Therefore, the design of the border portion is improved.

[0250] The first region and the second region are integrally formed. That is, both the first region and the second region are disposed on the surface of one cured resin layer. Therefore, a seamless design can be achieved by using this molded body.

[0251] The pencil hardness of the surface of the cured resin layer is H or more. That is, the cured resin layer has a high hardness. Therefore, the molded body has excellent scratch resistance, and the unevenness is maintained for a long time. The pencil hardness of the surface of the cured resin layer is preferably 2H or more. The pencil hardness of the surface of the cured resin layer is measured in a region where no unevenness is given (for example, the second region). Or, it is measured on the surface of a smooth cured resin layer made for measurement purposes where no unevenness is given.

[0252] There is no particular limitation on the height of the convex portion. From the viewpoint of antiglare property, the height of the convex portion can be, for example, 0.3 μ m or more and 4.0 μ m or less, or can be 1.0 μ m or more and 2.0 μ m or less. The height of the convex portion is calculated from the cross section in the thickness direction of the cured resin layer. The height of the convex portion is the average of any 5 points of the distance from the lowest point of the concave portion formed in the first region to the highest point of the convex portion.

[0253] From the viewpoint of antiglare property, the ten-point average roughness Rz of the first region JIS is preferably 0.2 μ m or more and 1.0 μ m or less. The ten-point average roughness Rz JIS is obtained, for example, using a laser microscope in accordance with the provisions of JIS B0601; 2001. Specifically, the ten-point average roughness Rz JIS means the sum of the average of the peak heights from the highest peak (convex portion) to the fifth in descending order and the average of the valley depths from the deepest valley (concave portion) to the fifth in ascending order in the roughness curve of the reference length obtained by applying the cut-off value phase compensation band-pass filter.

[0254] [Decorative layer]

[0255] The molded body may further include a decorative layer. For example, the molded body includes a transparent support substrate, a cured resin layer disposed on one main surface of the transparent support substrate, and a decorative layer disposed on the other main surface of the transparent support substrate. The decorative layer may be provided on a part of the other main surface of the transparent support substrate. The decorative layer is a layer that imparts decorations such as patterns, letters, or metallic luster to the molded body. Through the decorative layer, the designability of the molded body is improved. For example, the decorative layer is disposed opposite to the second region. At this time, the decorative layer is recognized through the second region.

[0256] As the decorative layer, for example, at least one of a printed layer and a vapor deposition layer can be cited. The printed layer and the vapor deposition layer are each one or more layers and may include multiple layers. There is no particular limitation on the thickness of the decorative layer, and it is appropriately set according to designability and the like.

[0257] In the printed layer, for example, a wood grain pattern, a stone grain pattern, a cloth grain pattern, a sand grain pattern, a geometric pattern, letters, or solid color printing is depicted. The printed layer is formed of, for example, colored ink containing an adhesive resin and a colorant. There is no particular limitation on the adhesive resin. As the adhesive resin, for example, polyvinyl-based resins such as vinyl chloride / vinyl acetate copolymer, polyamide-based resins, polyester-based resins, polyacrylic-based resins, polyurethane-based resins, polyvinyl acetal-based resins, polyester urethane-based resins, cellulose ester-based resins, alkyd resins, and chlorinated polyolefin-based resins can be cited.

[0258] There is no particular limitation on the colorant, and known pigments or dyes can be cited. As the yellow pigment, for example, azo-based pigments such as polyazo, organic pigments such as isoindolinone, or inorganic pigments such as titanium nickel antimony oxide can be cited. As the red pigment, for example, azo-based pigments such as polyazo, organic pigments such as quinacridone, or inorganic pigments such as iron oxide red can be cited. As the blue pigment, for example, organic pigments such as phthalocyanine blue or inorganic pigments such as cobalt blue can be cited. As the black pigment, for example, organic pigments such as aniline black can be cited. As the white pigment, for example, inorganic pigments such as titanium dioxide can be cited.

[0259] The vapor deposition layer is formed of, for example, at least one metal selected from aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, etc., or an alloy or compound thereof.

[0260] [Forming resin layer]

[0261] The molded body may further include a forming resin layer. The forming resin layer supports the cured resin layer together with the transparent support substrate. For example, the molded body includes a transparent support substrate, a cured resin layer disposed on one main surface of the transparent support substrate, and a forming resin layer disposed on the other main surface of the transparent support substrate. There is no limitation on the shape of the forming resin layer. Thus, the design freedom of the molded body is improved.

[0262] There is no particular limitation on the resin for forming the formed resin layer. The formed resin layer contains, for example, a thermosetting resin and / or a thermoplastic resin. Examples of the thermosetting resin include: phenolic resin, epoxy resin, melamine resin, urea resin, unsaturated polyester, thermosetting polyimide. Examples of the thermoplastic resin include: so-called engineering plastics. Examples of the engineering plastics include: polyamide, polyacetal, polycarbonate, ultra-high molecular weight polyethylene, polysulfone, polyethersulfone, polyphenylene sulfide, liquid crystal polymer.

[0263] The molded body may include a transparent support substrate, a cured resin layer disposed on one main surface of the transparent support substrate, a decorative layer disposed on the other main surface of the transparent support substrate, and a formed resin layer. The decorative layer is disposed, for example, so as to be sandwiched between the cured resin layer and the formed resin layer, or on the surface on the opposite side of the cured resin layer disposed on the formed resin layer.

[0264] The molded body is particularly suitable as a protective material for a display. Examples of the display include: liquid crystal display, organic EL display, plasma display. The molded body is particularly suitable as a protective material for an in-vehicle touch panel display. The molded body is disposed such that the first region faces the information display portion of the display. The molded body is disposed with the hard coat facing outward. In addition, the molded body is particularly suitable as an instrument panel and / or a center cluster panel that also serves as a display protective material.

[0265] Figure 4 It is a cross-sectional view schematically showing the molded body according to this embodiment. The molded body 20A includes: a transparent support substrate 11 and a cured resin layer 22 disposed on one main surface thereof. The cured resin layer 22 includes: a first region 221 having fine irregularities and a smooth second region 222.

[0266] Figure 5 It is a cross-sectional view schematically showing another molded body according to this embodiment. The molded body 20B includes: a transparent support substrate 11, a cured resin layer 22 disposed on one main surface thereof, a decorative layer 23, and a formed resin layer 24. The decorative layer 23 is disposed so as to face the second region 222 and is sandwiched between the cured resin layer 22 and the formed resin layer 24.

[0267] Figure 6 It is a cross-sectional view schematically showing yet another molded body according to this embodiment. The molded body 20C includes: a transparent support substrate 11, a cured resin layer 22 disposed on one main surface thereof, a decorative layer 23, and a formed resin layer 24. The decorative layer 23 is disposed so as to face the second region 222 and is disposed on the side opposite to the cured resin layer 22 of the formed resin layer 24.

[0268] Figure 7It is a perspective view schematically showing another molded body according to the present embodiment. The molded body 20D includes: a transparent support substrate 11, a cured resin layer 22 disposed on one main surface thereof, a decorative layer 23, and a molding resin layer 24. The molded body 20D has a three-dimensional shape. The molded body 20D is, for example, a protective material for a display of an automotive navigation system. The cured resin layer 22 includes: a plurality of first regions 221 and a second region 222 surrounding these first regions 221. One first region 221 corresponds to an information display portion of the display, and the other first regions 221 face the operation display portion. The second region 222 corresponds to a frame surrounding the display.

[0269] Manufacturing method of formed body

[0270] The molded body according to the present embodiment is obtained by forming irregularities on the coating of the above-described laminated film and then irradiating active energy rays (second irradiation step). Thereby, a plurality of regions having different textures, such as an irregularity region and a smooth region, can be formed on the coating at the same time. As described above, the coating is curable by active energy rays. For example, it is obtained by performing the first irradiation step on the uncured resin composition.

[0271] The molded body having a decorative layer is obtained by forming a decorative layer on a laminated film, a laminate including a transparent support substrate and an uncured resin composition layer (hereinafter referred to as a laminated film precursor), or a molded body. The step of forming the decorative layer (decorative step) can be performed before the first irradiation step, after the second irradiation step, or between the first irradiation step and the second irradiation step.

[0272] The molded body having a three-dimensional shape is obtained by injection molding the laminated film. The injection molding step can be performed before, after, or simultaneously with the irregularity forming step. Among them, it is preferable that the injection molding step is performed simultaneously with the irregularity forming step, that is, it is preferable to form fine irregularities and a three-dimensional shape by one step.

[0273] It is desirable to perform a preforming step before the injection molding step. In the preforming step, the laminated film or the precursor of the laminated film is preformed into a shape close to a three-dimensional shape. Thereby, in injection molding, it is easier to obtain a desired three-dimensional shape.

[0274] In one aspect, the manufacturing method of the molded body includes: an irregularity forming step and a second irradiation step for the laminated film. Figure 8 It is a flowchart showing the manufacturing method of the molded body according to the present embodiment.

[0275] In one aspect, the manufacturing method of the molded body includes: a decorative step, a preforming step, an irregularity forming step (and an injection molding step), and a second irradiation step for the laminated film. Figure 9It is a flowchart showing the manufacturing method of the molded body according to the present embodiment.

[0276] In one aspect, the manufacturing method of the molded body includes: a decoration process, a preforming process, a first irradiation process, an uneven formation process (and an injection molding process), and a second irradiation process for the laminate film precursor. Figure 10 It is a flowchart showing the manufacturing method of the molded body according to the present embodiment.

[0277] Hereinafter, each process will be described.

[0278] (i) Preparation of the laminate film

[0279] For example, prepare the laminate film produced by the above operations.

[0280] (ii) Production of the laminate film precursor

[0281] For example, prepare the laminate film precursor produced by a method including the above coating process (1) and drying process (2).

[0282] (iii) First irradiation process (S25)

[0283] In this process, the resin composition is irradiated with actinic energy rays of 5 mJ / cm 2 or more and 150 mJ / cm 2 or less in the same manner as the first irradiation process (3) of the laminate film manufacturing method.

[0284] By the first irradiation process, the resin composition is semi-cured to form a coating. The indentation hardness H 100 of the coating is 0.30 GPa or more and 0.65 GPa or less. The indentation hardness HB 2000 of the coating is 0.15 GPa or more and 0.35 GPa or less. The indentation hardness HB 2000 is less than the indentation hardness HB 100 .

[0285] (iv) Decoration process (S23)

[0286] In this process, the above-mentioned decorative layer is formed on the other main surface of the transparent support substrate or on the surface opposite to the cured resin layer of the molding resin layer.

[0287] There is no particular limitation on the method for forming the printing layer. As the method for forming the printing layer, for example, lithography, gravure printing, screen printing, roll coating, and spraying can be cited. There is also no particular limitation on the method for forming the vapor deposition layer. As the method for forming the vapor deposition layer, for example, vacuum evaporation, sputtering, ion plating, and gold plating can be cited.

[0288] (v) Preforming process (S24)

[0289] In this process, a shape along a desired three-dimensional shape is formed on the laminated film or its precursor. After the preforming process, a trimming process of removing unnecessary portions of the laminated film or its precursor may be performed.

[0290] There is no particular limitation on the preforming method. The preforming is performed, for example, by a vacuum forming method, a pressure air forming method, or a vacuum pressure air forming method. In the preforming, the first mold and the laminated film or its precursor are set in the same processing chamber. The laminated film or its precursor is set in such a manner that the transparent support substrate faces the first mold. The laminated film or its precursor is heated to a temperature above the Tg of the resin composition, and the processing chamber is brought into a vacuum state and / or a pressurized state. As a result, the laminated film or its precursor is deformed along the first mold. Then, the laminated film or its precursor is cooled and removed from the first mold.

[0291] There is no particular limitation on the material of the first mold. The first mold may be made of resin or metal.

[0292] The resin composition supplied to the preforming process is in an uncured or semi-cured state. Therefore, the laminated film or its precursor does not crack and can be easily deformed along the first mold. Thus, a complex three-dimensional shape is achieved. The resin composition after the preforming process is still in an uncured or semi-cured state.

[0293] (vi) Concavo-convex forming process (S21)

[0294] In this process, a coating containing a semi-cured resin composition is brought into contact with a mold having concavo-convexities (second mold), and concavo-convexities are formed on a part of the coating.

[0295] The indentation hardness HB of the coating based on nanoindentation method at an indentation depth of 100 nm 100 is 0.30 GPa or more and 0.65 GPa or less. The indentation hardness HB of the coating based on nanoindentation method at an indentation depth of 2000 nm 2000 is 0.15 GPa or more and 0.35 GPa or less. The indentation hardness HB 2000 is less than the indentation hardness HB 100 . Therefore, the coating exhibits excellent releasability and formability.

[0296] There is no particular limitation on the material of the second mold. The second mold may be made of resin or metal. Regardless of the material of the mold, the coating is easily peeled off from the mold.

[0297] In this process, concavo-convexities and a three-dimensional shape are imparted simultaneously. In this case, a second mold having both concavo-convexities and a desired three-dimensional shape is used.

[0298] When the coating is disposed on one major surface of the transparent support substrate, unevenness can be imparted by an injection molding method (e.g., insert molding method). In injection molding, for example, the coating is opposed to a second mold partially having unevenness, and at the same time, an injection molding resin is injected toward the transparent support substrate. Thereby, unevenness is formed on a part of the coating, and at the same time, a molded resin layer is formed on the other major surface of the transparent support substrate.

[0299] The laminated film has a coating in a semi-cured state. Therefore, the laminated film can follow molds of various shapes. Moreover, even when there is a dimensional difference between the three-dimensional shape formed by preforming and the second mold used in this step, generation of cracks can be suppressed.

[0300] (vii) Second irradiation step (S22)

[0301] In this step, the coating is irradiated with active energy rays. Thereby, the coating is completely cured to form a cured resin layer.

[0302] The active energy rays are irradiated, for example, such that the pencil hardness of the cured resin layer reaches H or more. The cumulative light amount of the active energy rays in this step exceeds 150 mJ / cm 2 , for example, is 300 mJ / cm 2 or more and 2000 mJ / cm 2 or less.

[0303] In the method for manufacturing a molded article according to this embodiment, an unevenness forming step is performed on the laminated film having a coating in a semi-cured state. Therefore, dense unevenness can be imparted to the laminated film with high precision. Moreover, the laminated film can be molded into various three-dimensional shapes without generating cracks. Moreover, after the unevenness forming step is completed, the resin composition is cured. Therefore, the imparted shape is maintained for a long time. Examples

[0304] The present invention will be further specifically described by the following examples, but the present invention is not limited to these. In the examples, unless otherwise specified, "parts" and "%" are based on mass basis. The mixing parts are all the mass of the solid components.

[0305] The respective components used in the examples and comparative examples in this specification are as follows.

[0306] (Non-polymeric polymer)

[0307] Acrylic polymer A: Mw 60,000;

[0308] (Polymeric polymer)

[0309] Acrylic polymer B: Mw 20,000.

[0310] Acrylic polymers A and B are prepared as follows.

[0311] [Preparation of acrylic polymer A]

[0312] A mixture consisting of 30 parts of n-butyl methacrylate, 70 parts of methyl methacrylate, and 0.8 part of tert-butyl peroxy-2-ethylhexanoate was prepared. Additionally, 40 parts of toluene were charged into a 500 ml reaction vessel equipped with a stirring paddle, a nitrogen inlet tube, a condenser, and a dropping funnel, and heated to 110 °C. While stirring the inside of the reaction vessel, the above mixture was added dropwise at a constant rate over 2 hours under a nitrogen atmosphere. After the addition was completed, the reaction was carried out at 110 °C for 1 hour. Then, a mixed solution of 1 part of tert-butyl peroxy-2-ethylhexanoate and 25 parts of toluene was added dropwise to the reaction vessel over 1 hour. Subsequently, the inside of the reaction vessel was heated to 145 °C and reacted for another 2 hours. Then, the inside of the reaction vessel was cooled to below 110 °C, and 59 parts of toluene were added. Thus, acrylic polymer A with a weight-average molecular weight of 60,000 was obtained.

[0313] [Preparation of acrylic polymer B]

[0314] A mixture consisting of 30 parts of glycidyl methacrylate, 70 parts of methyl methacrylate, and 10 parts of tert-butyl peroxy-2-ethylhexanoate was prepared. Additionally, 40 parts of toluene were charged into a 500 ml reaction vessel equipped with a stirring paddle, a nitrogen inlet tube, a condenser, and a dropping funnel, and heated to 110 °C. While stirring the inside of the reaction vessel, the above mixture was added dropwise at a constant rate over 2 hours under a nitrogen atmosphere. After the addition was completed, the reaction was carried out at 110 °C for 1 hour. Then, a mixed solution of 1 part of tert-butyl peroxy-2-ethylhexanoate and 25 parts of toluene was added dropwise to the reaction vessel over 1 hour. Subsequently, the inside of the reaction vessel was heated to 145 °C and reacted for another 2 hours. Then, the inside of the reaction vessel was cooled to below 110 °C, and 59 parts of toluene were added to obtain precursor B1.

[0315] In another reaction vessel having the same shape as described above, 306.5 parts of precursor B1, 15.66 parts of acrylic acid, 0.43 part of hydroquinone monomethyl ether, and 56 parts of toluene were charged respectively. While blowing air and stirring, it was heated to 90 °C. At a temperature of 90 °C, a mixed solution of 3 parts of toluene and 0.81 part of tetrabutylammonium bromide was further added to the reaction vessel, and the reaction was carried out for 1 hour. Then, it was heated to 105 °C, and the reaction was carried out at a temperature of 105 °C until the acid value of the solid component in the reaction solution reached 8 or less. Thereafter, a mixed solution of 0.43 part of hydroquinone monomethyl ether and 3 parts of toluene was added to the above reaction solution, and the temperature was set to 75 °C. Then, 10.1 parts of Karenz MOI (manufactured by Showa Denko K.K., 2-methacryloyloxyethyl isocyanate), a mixed solution of 5.0 parts of toluene and 0.043 part of dibutyltin dilaurate were added, and the reaction was carried out at a temperature of 70 °C for 2 hours. Thereafter, it was cooled to 60 °C or less, and a mixed solution of 2 parts of methanol and 10 parts of toluene was added. Thus, an acrylic polymer B having a weight average molecular weight of 20,000 was obtained.

[0316] The acid value was measured as follows: According to JIS K5601-2-1, the above reaction solution was titrated with a 0.1N potassium hydroxide (KOH) solution, and calculated according to the following formula: acid value = {(the amount of KOH solution added [ml]) × (molar concentration of KOH solution [mol / L])} / (mass of solid component [g]).

[0317] (Violet light UV-AF305A)

[0318] Fluorine-containing polyfunctional organosilicone urethane acrylate oligomer

[0319] Manufactured by Mitsubishi Chemical Corporation;

[0320] (KRM-8452)

[0321] Polyfunctional urethane acrylate oligomer

[0322] DAICEL ALLNEX

[0323] Mw 3,884;

[0324] (CN-9893)

[0325] Bifunctional urethane acrylate oligomer

[0326] Manufactured by SARTOMER;

[0327] (ARONIX M-402)

[0328] Polyfunctional acrylic monomer

[0329] Manufactured by Toagosei Co., Ltd.;

[0330] (ARONIX M-315)

[0331] 3-functional acrylic monomer

[0332] Manufactured by Toagosei Co., Ltd.;

[0333] (ART RESIN H-7M40)

[0334] 4-functional urethane acrylate oligomer

[0335] Manufactured by Negami Kogyo Co., Ltd

[0336] Mw = 1000 - 1500;

[0337] (ART RESIN UN-904M)

[0338] 10-functional urethane acrylate oligomer

[0339] Manufactured by Negami Kogyo Co., Ltd

[0340] Mw = 4900;

[0341] (ELCOM V-8802)

[0342] Filler (silica particles, primary particle size of about 10 nm)

[0343] Manufactured by JGC Catalysts & Chemicals Ltd.;

[0344] (HX-204 IP)

[0345] Filler (phosphorus-doped tin oxide sol, primary particle size of 5 nm - 20 nm)

[0346] Manufactured by Nissan Chemical Industries, Ltd.;

[0347] (THRULYA 4320)

[0348] Refractive index reducing particles (hollow silica particles, volume average particle size of 55 nm)

[0349] Manufactured by JGC Catalysts & Chemicals Ltd.;

[0350] (Omnirad 184)

[0351] Photoinitiator

[0352] Manufactured by IGM Resins B.V.;

[0353] (Omnirad TPO H)

[0354] Photoinitiator

[0355] Manufactured by IGM Resins B.V.

[0356] [Example 1]

[0357] (1) Preparation of Resin Composition HC1

[0358] In a container filled with propylene glycol monomethyl ether, 37 parts of acrylic polymer A, 35 parts of ARONIX M-402, 12 parts of Violet UV-AF305A, 15 parts of ELCOM V-8802, 2.9 parts of Omnirad184 (relative to a total of 100 parts of the above resin components and ELCOM V-8802), and 3.9 parts of Omnirad TPO H (relative to a total of 100 parts of the above resin components and ELCOM V-8802) were mixed to prepare a transparent resin composition HC1 with a solid content concentration of 35%.

[0359] (2) Preparation of laminated film

[0360] Using a bar coater, the resin composition HC1 was coated on the PMMA surface of a transparent support substrate (a double-layer film composed of PMMA and PC, trade name: AW-10U, manufactured by SHINE TECHNO Co., Ltd., total thickness 250 μ μm, PMMA layer thickness 35 μ μm, PC layer thickness 215 μ μm), and dried at 80°C for 1 minute to volatilize the solvent. Then, the coated film was irradiated with actinic rays (ultraviolet rays) with an accumulated light amount of 35 mJ / cm 2 to obtain a laminated film A1 having a semi-cured state coating (hard coating). The film thickness of the coating was 8 μ μm.

[0361] (3) Preparation of molded article

[0362] (3-1) Formation of printing layer

[0363] On the main surface of the laminated film A1 opposite to the coating of the transparent support substrate, a printing layer was formed by screen printing and dried at a drying temperature of 80°C for 10 minutes. This printing process was repeated 5 times, and then dried at 90°C for 1 hour. Aniline black was used in the formation of the printing layer.

[0364] (3-2) Preforming

[0365] The laminated film with the printing layer was heated to 160°C and preformed by vacuum pressure forming method. Then, trimming was carried out.

[0366] (3-3) Formation of concavities and convexities

[0367] Insert molding was performed using a mold partially having concavities and convexities. The mold was heated to 80 °C. Polycarbonate resin was used as the molding resin. The maximum height of the convex part of the mold was 2.0 μ m, and the ten-point average roughness Rz JIS was 1.5 μ m.

[0368] (3-4) Irradiation with active energy rays

[0369] The coating was irradiated with active energy rays (ultraviolet rays) having an accumulated light quantity of 1500 mJ / cm 2 . As a result, a molded body X1 having a transparent support substrate, a cured resin layer (hard coat) disposed on one main surface of the transparent support substrate, a printed layer and a molded resin layer disposed on the other main surface of the transparent support substrate was obtained. The surface of the cured resin layer has: a first region formed with the concavities and convexities of the transfer mold and a smooth second region.

[0370] [Evaluation]

[0371] The following evaluations were performed on the laminated film A1 or the molded body X1. The results are shown in Table 1.

[0372] (a) Demolding property

[0373] The second region of the cured resin layer of the molded body was visually observed and evaluated according to the following criteria.

[0374] Optimal: No roughness and whitening caused by peeling the mold were confirmed on the surface;

[0375] Good: Slight roughness and whitening caused by peeling the mold were confirmed on the surface, but the texture was not significantly reduced;

[0376] Fair: Roughness and whitening caused by peeling the mold were confirmed on the surface, but the texture was not significantly reduced;

[0377] Poor: Roughness and whitening caused by peeling the mold were confirmed on the surface, and a significant reduction in texture was visible.

[0378] (b) Shapeability

[0379] The first region of the cured resin layer of the molded body was visually observed and evaluated according to the following criteria.

[0380] Optimal: Sufficient antiglare property was obtained, and it could be judged that the height of the convex part was 80% or more of the maximum height of the convex part of the mold;

[0381] Good: Sufficient anti-glare property in practical use is obtained, and it can be judged that the height of the convex portion is more than 50% and less than 80% of the maximum height of the mold convex portion;

[0382] Poor: The anti-glare property is insufficient, and it can be judged that the height of the convex portion is less than 50% of the maximum height of the mold convex portion.

[0383] (c) Shape retention

[0384] The molded body was left standing in a thermo-hygrostat chamber at a relative humidity of 85% and a temperature of 85 °C for 250 hours. After this accelerated test, evaluation was carried out according to the same criteria as in (b) formability.

[0385] (d) Indentation hardness

[0386] Measurement was carried out using an iMicro Nanoindenter manufactured by NANOMECHANICS, INC. by the continuous stiffness measurement method (measurement method: Advanced Dynamic E and H. NMT).

[0387] Specifically, a minute AC load was superimposed on the quasi-static test load and applied to the surface of the laminated film. The load was applied until the maximum load reached 50 mN. As the indenter, a Berkovich-type diamond indenter (front-end curvature radius: 20 nm) was used. Based on the vibration component of the displacement generated and the phase difference between the displacement and the load, the stiffness with respect to the depth was calculated, and the hardness distribution with respect to the depth was obtained. The hardness at a depth of 100 nm in this distribution was defined as the indentation hardness HB 100 and the hardness at 2000 nm was defined as the indentation hardness HB 2000 . The load and stiffness were calculated using iMicro dedicated software. When calculating the stiffness, the Poisson's ratio of the coating was set to 0.35. The load was controlled so that the strain rate (∂P / ∂t) / P reached 0.2. When analyzing using iMicro dedicated software, the point temporarily defined on the iMicro dedicated software (the point where d(Force) / d(Disp) is approximately 500 N / m) was directly set as the surface position of the coating during measurement.

[0388] (e) Polymerization rate

[0389] For the uncured laminated film and the semi-cured laminated film, FT-IR analysis was carried out according to the above method, and the infrared absorption spectra of each were obtained. Based on the infrared absorption spectra, the polymerization rates PB and PA were calculated according to the above method.

[0390] (f) Elongation rate

[0391] Measurement was carried out in accordance with JIS K 7127.

[0392] Specifically, a test piece with a length of 200 mm and a width of 10 mm is cut from the laminated film. This test piece is placed in a tensile testing machine with a chuck distance of 150 mm, and the test piece is stretched by 2.5% under the conditions of an atmosphere at 160°C and a stretching speed of 300 mm / min. Thereafter, the test piece is observed using a microscope with a magnification of 1000 times or higher to confirm whether there are cracks with a size exceeding 1 mm in length. If no cracks are generated, a new test piece is cut, and then the long side is stretched by 5%. Then, the observation of crack generation is carried out in the same manner. This step is repeated while increasing the stretching rate by 2.5% each time. The stretching rate at which cracks of the above size are first confirmed is taken as the stretching rate of the laminated film. Three test pieces are made from the same laminated film, and the average value of the stretching rates calculated for each of them is taken as the stretching rate of the laminated film.

[0393] (g) Pencil hardness

[0394] In accordance with JIS K 5600-5-4 (1999) scratch hardness (pencil method), the pencil hardness of the second region of the cured resin layer of the molded body is measured.

[0395] [Example 2]

[0396] In the production (2) of the laminated film, except that the film thickness of the coating is set to 6 μ μm, the operation is carried out in the same manner as in Example 1 to obtain a laminated film A2. Using the laminated film A2, the operation is carried out in the same manner as in Example 1 to obtain a molded body X2. The above evaluations are carried out on the laminated film A2 and the molded body X2. The results are shown in Table 1.

[0397] [Example 3]

[0398] In the production (2) of the laminated film, except that the film thickness of the coating is set to 10 μ μm, the operation is carried out in the same manner as in Example 1 to obtain a laminated film A3. Using the laminated film A3, the operation is carried out in the same manner as in Example 1 to obtain a molded body X3. The above evaluations are carried out on the laminated film A3 and the molded body X3. The results are shown in Table 1.

[0399] [Example 4]

[0400] In the production (2) of the laminated film, except that active energy rays are irradiated in a nitrogen atmosphere, the operation is carried out in the same manner as in Example 1 to obtain a laminated film A4. Using the laminated film A4, the operation is carried out in the same manner as in Example 1 to obtain a molded body X4. The above evaluations are carried out on the laminated film A4 and the molded body X4. The results are shown in Table 1.

[0401] [Example 5]

[0402] In the production (2) of the laminated film, except for irradiating active energy rays so that the cumulative light quantity is 7.5 mJ / cm 2 other than this, the operation was carried out in the same manner as in Example 1 to obtain a laminated film A5. Using the laminated film A5, the operation was carried out in the same manner as in Example 1 to obtain a molded body X5. The above evaluations were performed on the laminated film A5 and the molded body X5. The results are shown in Table 1.

[0403] [Example 6]

[0404] In the production (2) of the laminated film, except for irradiating active energy rays so that the cumulative light quantity is 100 mJ / cm 2 other than this, the operation was carried out in the same manner as in Example 1 to obtain a laminated film A6. Using the laminated film A6, the operation was carried out in the same manner as in Example 1 to obtain a molded body X6. The above evaluations were performed on the laminated film A6 and the molded body X6. The results are shown in Table 1.

[0405] [Comparative Example 1]

[0406] In the production (2) of the laminated film, except for not irradiating active energy rays, the operation was carried out in the same manner as in Example 1 to obtain a laminated film B1. Using the laminated film B1, the operation was carried out in the same manner as in Example 1 to obtain a molded body Y1. The above evaluations were performed on the laminated film B1 and the molded body Y1. The results are shown in Table 1.

[0407] [Comparative Example 2]

[0408] In the production (2) of the laminated film, except for irradiating active energy rays so that the cumulative light quantity is 200 mJ / cm 2 other than this, the operation was carried out in the same manner as in Example 1 to obtain a laminated film B2. Using the laminated film B2, the operation was carried out in the same manner as in Example 1 to obtain a molded body Y2. The above evaluations were performed on the laminated film B2 and the molded body Y2. The results are shown in Table 1.

[0409] [Comparative Example 3]

[0410] In the production (2) of the laminated film, except for irradiating active energy rays so that the cumulative light quantity is 500 mJ / cm 2 other than this, the operation was carried out in the same manner as in Example 1 to obtain a laminated film B3. Using the laminated film B3, the operation was carried out in the same manner as in Example 1 to obtain a molded body Y3. The above evaluations were performed on the laminated film B3 and the molded body Y3. The results are shown in Table 1.

[0411] [Comparative Example 4]

[0412] In the production (2) of the laminated film, except for irradiating active energy rays so that the cumulative light quantity is 1500 mJ / cm 2Except for this, the operation was carried out in the same manner as in Example 1 to obtain a laminated film B4. Using the laminated film B4, the operation was carried out in the same manner as in Example 1 to obtain a molded body Y4. The above evaluations were performed on the laminated film B4 and the molded body Y4. The results are shown in Table 1. [Table 1]

[0413]

[0414] The releasability and shapeability of the molded bodies of Examples 1 to 6 were both excellent. Moreover, the shape retention was also high. In addition, no visually observable cracks were confirmed in these molded bodies.

[0415] Comparative Example 1 is an example where the indentation hardness HB 100 and HB 2000 are both small. In this example, the releasability and shapeability are low.

[0416] Comparative Examples 2 to 4 are examples where the indentation hardness HB 2000 is large. In these examples, the shapeability is also low. In Comparative Examples 3 and 4, the shape retention is also low.

[0417] [Example 7]

[0418] (1) Preparation of resin composition HC2

[0419] 43 parts of acrylic polymer A, 42 parts of ARONIX M-402, 15 parts of ELCOM V-8802, 2.9 parts of Omnirad184 (relative to 100 parts in total of the above resin components and ELCOM V-8802), and 3.9 parts of Omnirad TPO H (relative to 100 parts in total of the above resin components and ELCOM V-8802) were mixed in a container containing propylene glycol monomethyl ether to produce a transparent resin composition HC2 with a solid content concentration of 35%.

[0420] (2) Production of laminated film

[0421] Except for using the resin composition HC2 instead of the resin composition HC1, the operation was carried out in the same manner as in Example 6 to obtain a laminated film A7.

[0422] (3) Production of molded body

[0423] Using the laminated film A7, the operation was carried out in the same manner as in Example 1 to obtain a molded body X7. The above evaluations were performed on the laminated film A7 and the molded body X7. The results are shown in Table 2.

[0424] [Example 8]

[0425] (1) Preparation of resin composition HC3

[0426] In a container containing propylene glycol monomethyl ether, 51 parts of acrylic polymer A, 49 parts of ARONIX M-402, 2.9 parts of Omnirad 184 (relative to 100 parts of the above resin components), and 3.9 parts of Omnirad TPO H (relative to a total of 100 parts of the above resin components) were mixed to produce a transparent resin composition HC3 with a solid content concentration of 35%.

[0427] (2) Production of the laminated film

[0428] Except for using the resin composition HC3 instead of the resin composition HC1, the operation was carried out in the same manner as in Example 6 to obtain a laminated film A8.

[0429] (3) Production of the molded body

[0430] Using the laminated film A8, the operation was carried out in the same manner as in Example 1 to obtain a molded body X8. The above evaluations were performed on the laminated film A8 and the molded body X8. The results are shown in Table 2.

[0431] [Example 9]

[0432] (1) Preparation of the resin composition HC4

[0433] In a container containing propylene glycol monomethyl ether, 73 parts of acrylic polymer B, 12 parts of violet light UV-AF305A, 15 parts of ELCOM V-8802, 2.9 parts of Omnirad 184 (relative to a total of 100 parts of the above resin components and ELCOM V-8802), and 3.9 parts of Omnirad TPO H (relative to a total of 100 parts of the above resin components and ELCOM V-8802) were mixed to produce a transparent resin composition HC4 with a solid content concentration of 35%.

[0434] (2) Production of the laminated film

[0435] Except for using the resin composition HC4 instead of the resin composition HC1, the operation was carried out in the same manner as in Example 6 to obtain a laminated film A9.

[0436] (3) Production of the molded body

[0437] Using the laminated film A9, the operation was carried out in the same manner as in Example 1 to obtain a molded body X9. The above evaluations were performed on the laminated film A9 and the molded body X9. The results are shown in Table 2.

[0438] [Example 10]

[0439] (1) Preparation of the resin composition HC5

[0440] In a container containing propylene glycol monomethyl ether, 85 parts of acrylic polymer B, 15 parts of ELCOM V-8802, 2.9 parts of Omnirad 184 (relative to a total of 100 parts of the above resin components and ELCOM V-8802), and 3.9 parts of Omnirad TPOH (relative to a total of 100 parts of the above resin components and ELCOM V-8802) were mixed to produce a transparent resin composition HC5 with a solid content concentration of 35%.

[0441] (2) Production of the laminated film

[0442] Except that the resin composition HC5 was used instead of the resin composition HC1, the operation was carried out in the same manner as in Example 6 to obtain a laminated film A10.

[0443] (3) Production of the molded body

[0444] Using the laminated film A10, the operation was carried out in the same manner as in Example 1 to obtain a molded body X10. The above evaluations were performed on the laminated film A10 and the molded body X10. The results are shown in Table 2.

[0445] [Example 11]

[0446] (1) Preparation of the resin composition HC6

[0447] In a container containing propylene glycol monomethyl ether, 100 parts of acrylic polymer B, 2.9 parts of Omnirad 184 (relative to 100 parts of the above resin components), and 3.9 parts of Omnirad TPOH (relative to 100 parts of the above resin components) were mixed to produce a transparent resin composition HC6 with a solid content concentration of 35%.

[0448] (2) Production of the laminated film

[0449] Except that the resin composition HC6 was used instead of the resin composition HC1, the operation was carried out in the same manner as in Example 6 to obtain a laminated film A11.

[0450] (3) Production of the molded body

[0451] Using the laminated film A11, the operation was carried out in the same manner as in Example 1 to obtain a molded body X11. The above evaluations were performed on the laminated film A11 and the molded body X11. The results are shown in Table 2.

[0452] [Example 12]

[0453] (1) Preparation of the resin composition HC7

[0454] In a container containing propylene glycol monomethyl ether, 67.5 parts of CN-9893, 22.5 parts of ARONIX M-315, 5.0 parts of ART RESIN H-7M40, 5.0 parts of ART RESIN UN-904M, 2.9 parts of Omnirad184 (relative to 100 parts of the above resin components), and 3.9 parts of Omnirad TPO H (relative to 100 parts of the above resin components) were mixed to produce a transparent resin composition HC7 with a solid component concentration of 35%.

[0455] (2) Production of the laminated film

[0456] Except for using the resin composition HC7 instead of the resin composition HC1, setting the film thickness of the coating to 3 μ m, and irradiating active energy rays to make the cumulative light amount 150 mJ / cm 2 Other than that, the operation was carried out in the same manner as in Example 1 to obtain a laminated film A12.

[0457] (3) Production of the molded body

[0458] Using the laminated film A12, the operation was carried out in the same manner as in Example 1 to obtain a molded body X12. The above evaluations were performed on the laminated film A12 and the molded body X12. The results are shown in Table 2.

[0459] [Example 13]

[0460] (1) Preparation of the resin composition HC8

[0461] In a container containing propylene glycol monomethyl ether, 50 parts of ART RESIN H-7M40, 50 parts of ART RESIN UN-904M, 2.9 parts of Omnirad184 (relative to 100 parts of the above resin components), and 3.9 parts of Omnirad TPO H (relative to 100 parts of the above resin components) were mixed to produce a transparent resin composition HC8 with a solid component concentration of 35%.

[0462] (2) Production of the laminated film

[0463] Except for using the resin composition HC8 instead of the resin composition HC1, setting the film thickness of the coating to 3 μ m, and irradiating active energy rays to make the cumulative light amount 150 mJ / cm 2 Other than that, the operation was carried out in the same manner as in Example 1 to obtain a laminated film A13.

[0464] (3) Production of the molded body

[0465] Using the laminated film A13, the operation was carried out in the same manner as in Example 1 to obtain the molded body X13. The above evaluations were performed on the laminated film A13 and the molded body X13. The results are shown in Table 2.

[0466] [Comparative Example 5]

[0467] (1) Preparation of the resin composition HC9

[0468] In a container containing propylene glycol monomethyl ether, 85 parts of Violet UV-AF305A, 15 parts of ELCOM V-8802, 2.9 parts of Omnirad184 (relative to a total of 100 parts of the above resin components and ELCOM V-8802), and 3.9 parts of Omnirad TPOH (relative to a total of 100 parts of the above resin components and ELCOM V-8802) were mixed to produce a transparent resin composition HC9 with a solid content concentration of 35%.

[0469] (2) Production of the laminated film

[0470] Except for using the resin composition HC9 instead of the resin composition HC1, the operation was carried out in the same manner as in Example 6 to obtain the laminated film B5.

[0471] (3) Production of the molded body

[0472] Using the laminated film B5, the operation was carried out in the same manner as in Example 1 to obtain the molded body Y5. The above evaluations were performed on the laminated film B5 and the molded body Y5. The results are shown in Table 2.

[0473] [Comparative Example 6]

[0474] (1) Preparation of the resin composition HC10

[0475] In a container containing propylene glycol monomethyl ether, 100 parts of Violet UV-AF305A, 2.9 parts of Omnirad184 (relative to 100 parts of the above resin components), and 3.9 parts of Omnirad TPO H (relative to 100 parts of the above resin components) were mixed to produce a transparent resin composition HC10 with a solid content concentration of 35%.

[0476] (2) Production of the laminated film

[0477] Except for using the resin composition HC10 instead of the resin composition HC1, the operation was carried out in the same manner as in Example 6 to obtain the laminated film B5.

[0478] (3) Production of the molded body

[0479] Using the laminated film B5, the operation was carried out in the same manner as in Example 1 to obtain the molded body Y6. The laminated film B6 and the molded body Y6 were evaluated as described above. The results are shown in Table 2.

[0480] [Table 2]

[0481]

[0482] The releasability and formability of the molded bodies of Examples 7 to 13 were both excellent. No visually observable cracks were confirmed in the molded bodies of Examples 7 to 12. Moreover, the shape retention was also high in the molded bodies of Examples 7 to 11.

[0483] Comparative Example 5 is an example where the indentation hardness HB 2000 is too large. In this example, the formability is low. In addition, the shape retention is also low.

[0484] Comparative Example 6 is an example where the indentation hardness HB 2000 is large. In this example, the formability is low.

[0485] [Example 14]

[0486] (1) Preparation of the resin composition LR

[0487] In a container charged with propylene glycol monomethyl ether, 14.8 parts by mass of acrylic polymer A, 10 parts by mass of ARONIX M-402, 13.3 parts by mass of KRM-8452, 13.3 parts by mass of violet UV-AF305A, and 4.8 parts by mass of Omnirad184 were mixed. Then, 43.8 parts by mass of THRULYA 4320 was further mixed. Thus, a milky white resin composition LR for a low refractive index layer with a solid content concentration of 3% was prepared. The refractive index of the layer formed from the resin composition LR was 1.20 or more and 1.55 or less.

[0488] (2) Production of the laminated film

[0489] (2-1) Formation of the uncured optical interference layer (low refractive index layer)

[0490] The resin composition LR was coated on an OPP film (protective film) using a bar coater to a dried thickness of 95 nm. Then, it was dried at 80 °C for 1 minute to volatilize the solvent, and a transfer film C-1 having an uncured low refractive index layer formed thereon was obtained.

[0491] (2-2) Formation of the uncured hard coat

[0492] The operation was carried out in the same manner as in Example 1 to form an uncured hard coat with a dried thickness of 12 μ μm on the transparent support substrate.

[0493] (2 - 3) Lamination of uncured hard coat and low refractive index layer

[0494] The surface of the uncured hard coat supported by a transparent support substrate was bonded to the surface of the uncured low refractive index layer of the transfer film C - 1. Then, the protective film was peeled off.

[0495] (2 - 4) Irradiation with active energy rays

[0496] Next, the obtained laminate was irradiated with active energy rays (ultraviolet rays) having an accumulated light amount of 35 mJ / cm 2 . Thus, a laminated film A14 having a transparent support substrate, a semi - cured hard coat, and a semi - cured low refractive index layer in this order was manufactured.

[0497] (3) Production of molded body

[0498] Except for using the uncured laminated film A14 instead of the laminated film A1, the same operations as in Example 1 were carried out, and a molded body X14 having a transparent support substrate, a hard coat disposed on one main surface of the transparent support substrate, a low refractive index layer disposed on the hard coat, a printing layer disposed on the other main surface of the transparent support substrate, and a molding resin layer was obtained. The above evaluations were performed on the laminated film A14 and the molded body X14. The results are shown in Table 3.

[0499] [Example 15]

[0500] (1) Preparation of resin composition HR

[0501] 8.9 parts by mass of acrylic polymer A, 2.7 parts by mass of KRM - 8452, and 1.8 parts by mass of Omnirad184 were mixed in a container into which propylene glycol monomethyl ether was introduced. Then, 86.5 parts by mass of HX - 204 IP was further mixed. Thus, a milky white resin composition HR for a high refractive index layer with a solid content concentration of 3% was prepared. The refractive index of the layer formed from the resin composition HR exceeds 1.55 and is 2.00 or less.

[0502] (2) Production of laminated film

[0503] (2 - 1) Formation of uncured optical interference layer (high refractive index layer)

[0504] The resin composition R2 was coated on an OPP film (protective film) using a bar coater to a dried thickness of 95 nm. Then, it was dried at 80°C for 1 minute to volatilize the solvent, and a transfer film C - 2 having an uncured high refractive index layer formed thereon was obtained.

[0505] (2 - 2) Formation of uncured hard coat

[0506] The same operation as in Example 1 was carried out, and an uncured hard coat with a thickness of 8 μ μm was formed on the transparent support substrate.

[0507] (2-3) Formation of uncured low refractive index layer

[0508] The same operation as in Example 14 was carried out to obtain a transfer film C-1 having an uncured low refractive index layer formed thereon.

[0509] (2-4) Lamination of uncured hard coat, low refractive index layer and high refractive index layer

[0510] First, the surface of the uncured high refractive index layer of the transfer film C-2 was bonded to the surface of the uncured hard coat supported by the transparent support substrate.

[0511] Then, the protective film of the transfer film C-2 was peeled off to expose the uncured high refractive index layer. Next, the low refractive index layer of the transfer film C-1 was bonded to the high refractive index layer. After peeling off the protective film, actinic rays (ultraviolet rays) with an accumulated light amount of 35 mJ / cm 2 were irradiated. A laminated film A15 having a semi-cured hard coat, a high refractive index layer and a low refractive index layer in this order was obtained.

[0512] (3) Production of molded body

[0513] The same operation as in Example 14 was carried out except that the laminated film A15 was used instead of the laminated film A14 to obtain a molded body X15. The above evaluations were carried out on the laminated film A15 and the molded body X15. The results are shown in Table 3.

[0514] In Examples 14 and 15, the visual reflectance of the obtained molded bodies was also evaluated.

[0515] (h) Visual reflectance

[0516] For the surface on the opposite side of the hard coat in the transparent support substrate of the laminated film, a black coating (product name: CZ-805 BLACK (manufactured by Nihon BICS Co., Ltd.)) was applied using a bar coater so that the dry film thickness was 3 μ μm or more and 6 μ μm or less. Then, the laminated film coated with the black coating was left at room temperature for 5 hours for drying. Next, actinic rays with an accumulated light amount of 1500 mJ / cm 2 were irradiated to produce a cured evaluation sample.

[0517] From the side of the optical interference layer of the evaluation sample, the visual reflectance based on the SCI method is measured for evaluation. During the measurement, SD7000 manufactured by Nippon Denshoku Industries Co., Ltd. is used, and the measurement wavelength range is set to 380 nm or more and 780 nm or less.

[0518] [Table 3]

[0519]

[0520] The mold release property, shape conformability, and shape retention property of the molded bodies of Examples 14 and 15 are all excellent. Moreover, no visually observable cracks could be confirmed in these molded bodies. In addition, the visual reflectance of the molded bodies is small, and it can be known that they have excellent antireflection performance.

[0521] Industrial Applicability

[0522] According to the present invention, a laminated film with excellent shape conformability and mold release property of fine irregularities can be provided. Therefore, this laminated film is particularly preferably used for manufacturing a protective material for a display having a seamless design.

[0523] This application claims the priority of Japanese Patent Application No. 2020-088300 filed on May 20, 2020, and all of its descriptions are incorporated herein by reference.

[0524] Symbol Explanation

[0525] 10: Laminated film;

[0526] 11: Transparent support substrate;

[0527] 12: Coating;

[0528] 20A, 20B, 20C, 20D: Molded bodies;

[0529] 22: Cured resin layer;

[0530] 221: First region;

[0531] 222: Second region;

[0532] 23: Decorative layer;

[0533] 24: Molded resin layer.

Claims

1. A laminated film, comprising: A transparent support substrate; and A coating disposed on at least one main surface of the transparent support substrate, The coating contains an energy ray curable resin composition, The thickness of the coating exceeds 2 μm, The indentation hardness HB based on nanoindentation method at an indentation depth of 100 nm of the above coating 100 is 0.30 GPa or more and 0.65 GPa or less, The indentation hardness HB based on nanoindentation method at an indentation depth of 2000 nm for the above coating 2000 is not less than 0.15 GPa and not more than 0.35 GPa, The above indentation hardness HB 2000 Less than the above indentation hardness HB 100 , The difference between the polymerization rate PB of the above resin composition and the polymerization rate PA of the above resin composition in the above coating after irradiation with actinic energy rays of 1500 mJ / cm 2 is 15% or more.

2. The laminated film according to claim 1, wherein, The pencil hardness of the coating surface after irradiation with actinic rays of 1500 mJ / cm 2 is H or more.

3. The laminated film according to claim 1, wherein the elongation rate of the laminated film at 160 °C is 5% or more.

4. The laminated film according to claim 1, wherein, The thickness of the coating is 3 μm or more and 20 μm or less.

5. The laminated film according to any one of claims 1 to 4, wherein, The thickness of the transparent support substrate is 75 μm or more and 500 μm or less.

6. A method for manufacturing a laminated film, the manufacturing method comprising the following steps: A coating step of coating an energy ray curable resin composition on at least one main surface of a transparent support substrate; and First irradiation step: irradiate the above resin composition with active energy rays of 5 mJ / cm 2 or more and 150 mJ / cm 2 or less to obtain a coating film, The thickness of the coating exceeds 2 μm, The indentation hardness HB based on nanoindentation method at an indentation depth of 100 nm of the above coating 100 is 0.30 GPa or more and 0.65 GPa or less, The indentation hardness HB based on nanoindentation method at an indentation depth of 2000 nm of the above coating 2000 is 0.15 GPa or more and 0.35 GPa or less, The above indentation hardness HB 2000 Less than the above indentation hardness HB 100 , The difference between the polymerization rate PB of the above resin composition and the polymerization rate PA of the above resin composition in the above coating after irradiation with actinic energy rays of 1500 mJ / cm 2 is 15% or more.

7. A molded article, which is a molded article formed by partially imparting unevenness to the coating of the laminated film according to any one of claims 1 to 5 and curing it, and comprises: A transparent support substrate; and A cured resin layer provided on at least one main surface of the transparent support substrate, The main surface of the cured resin layer on the opposite side of the transparent support substrate has a first region with unevenness formed thereon and a second region other than that, The first region and the second region are integrally formed, The pencil hardness of the surface of the cured resin layer is H or more.

8. The molded body according to claim 7, wherein, The cured resin layer is provided on one main surface of the transparent support substrate, It further comprises a decorative layer disposed on the other main surface of the transparent support substrate.

9. The molded article according to claim 7 or 8, wherein The cured resin layer is provided on one main surface of the transparent support substrate, It further comprises a molded resin layer provided on the other main surface of the transparent support substrate.

10. A method for manufacturing a molded article, the manufacturing method comprising the following steps: An unevenness forming step of bringing the coating of the laminated film according to any one of claims 1 to 5 into contact with a mold having unevenness to form unevenness on a part of the coating; and A second irradiation step of irradiating the coating with energy rays after the unevenness forming step to obtain a cured resin layer.

11. The method for manufacturing a molded body according to claim 10, wherein, In the second irradiation step, the energy rays are irradiated to make the pencil hardness of the surface of the cured resin layer H or more.

12. The method for manufacturing a molded article according to claim 10, wherein In the laminated film, the coating is disposed on one main surface of the transparent support substrate, A decorative layer is disposed on the other main surface of the transparent support substrate.

13. The method for manufacturing a molded article according to any one of claims 10 to 12, wherein In the laminated film, the coating is disposed on one main surface of the transparent support substrate, In the unevenness forming step, while bringing the coating into contact with the mold, an injection molding resin is injected toward the transparent support substrate to simultaneously form the unevenness and the molded resin layer on the coating.

14. The method for manufacturing a molded article according to claim 13, wherein The mold imparts a three-dimensional shape to the laminated film, Moreover, before the unevenness forming step, it comprises a preforming step of forming the laminated film into a shape along the three-dimensional shape.

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