Laminated film, molded body and method for producing the same

Abstract

To provide a laminated film excellent in formability and releasability from a mold.SOLUTION: A laminated film comprises: a transparent support base material; and a coating layer arranged on at least one main face of the transparent support base material. The coating material includes an active energy ray-curable resin composition, a thickness of the coating layer is more than 2 μm, an indentation hardness HB100 by a nanoindentation method in an indentation depth 100 nm of the coating layer is 0.30 GPa or more and 0.65 GPa or less, an indentation hardness HB2000 by a nanoindentation method in an indentation depth 2,000 nm of the coating layer is 0.15 GPa or more and 0.35 GPa or less, and the indentation hardness HB2000 is smaller than the indentation hardness HB100.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

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

[0003] The information display portion of a display is usually protected by a protective material. The protective material may be provided with fine irregularities to improve anti-glare properties. Patent Document 1 discloses a film having convex portions with a height of 100 nm or more and 250 nm or less.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In recent years, there has been a demand for a protective material with a design in which a plurality of regions having different surface properties such as texture are seamlessly formed (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 realize 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 realizing a seamless design and has excellent formability and releasability from a mold.

Means for Solving the Problems

[0006] To solve the above problems, the present invention provides the following aspects. [1] A transparent support substrate, and a coating layer disposed on at least one main surface of the transparent support substrate, wherein the coating layer contains a resin composition curable by active energy rays, the thickness of the coating layer is more than 2 μm, the indentation hardness HB at an indentation depth of 100 nm of the coating layer measured by nanoindentation 100 is 0.30 GPa or more and 0.65 GPa or less, the indentation hardness HB at an indentation depth of 2000 nm of the coating layer measured by nanoindentation 2000 is 0.15 GPa or more and 0.35 GPa or less, the indentation hardness HB 2000 is smaller than the indentation hardness HB 100 A laminated film.

[0007] [2] The difference between the polymerization rate PB of the resin composition and the polymerization rate PA of the resin composition in the coating layer after irradiation with 1500 mJ / cm 2 of active energy rays is 15% or more. The laminated film according to [1] above.

[0008] [3] The pencil hardness of the surface of the coating layer after irradiation with 1500 mJ / cm 2 of active energy rays is H or more. The laminated film according to [1] or [2] above.

[0009] [4] The elongation at 160 °C is 5% or more. The laminated film according to any one of [1] to [3] above.

[0010] [5] The thickness of the coating layer is 3 μm or more and 20 μm or less. The laminated film according to any one of [1] to [4] above.

[0011] [6] The laminated film according to any one of [1] to [5] above, wherein the thickness of the transparent support substrate is 75 μm or more and 500 μm or less.

[0012] [7] A coating step of applying an active energy ray curable resin composition to at least one main surface of the transparent support substrate, 5 mJ / cm 2 or more and 150 mJ / cm 2 or less of active energy rays to obtain a coating layer, and a first irradiation step, The thickness of the coating layer is more than 2 μm, The indentation hardness HB by nanoindentation method at an indentation depth of 100 nm of the coating layer 100 is 0.30 GPa or more and 0.65 GPa or less, The indentation hardness HB by nanoindentation method at an indentation depth of 2000 nm of the coating layer 2000 is 0.15 GPa or more and 0.35 GPa or less, The indentation hardness HB 2000 is smaller than the indentation hardness HB 100 A method for manufacturing a laminated film.

[0013] [8] A transparent support substrate, and a cured resin layer disposed on at least one main surface of the transparent support substrate, The main surface of the cured resin layer opposite to the transparent support substrate includes a first region with unevenness 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. A molded body.

[0014] [9] The cured resin layer is disposed on one main surface of the transparent support substrate, The molded body according to the above [8], further comprising a decorative layer disposed on the other main surface of the transparent support substrate.

[0015]

[10] The cured resin layer is disposed on one main surface of the transparent support substrate, The molded body according to the above [8] or [9], further comprising a molded resin layer disposed on the other main surface of the transparent support substrate.

[0016]

[11] An unevenness forming step of bringing the coating layer of the laminated film according to any one of the above [1] to [6] into contact with a mold having unevenness to form unevenness in a part of the coating layer; A method for manufacturing a molded body, comprising: a second irradiation step of irradiating the coating layer with active energy rays after the unevenness forming step to obtain a cured resin layer.

[0017]

[12] In the second irradiation step, the active energy rays are irradiated so that the pencil hardness of the surface of the cured coating layer becomes H or more. The method for manufacturing a molded body according to the above

[11] .

[0018]

[13] In the laminated film, the coating layer is disposed on one main surface of the transparent support substrate, A method for manufacturing a molded body according to the above

[11] or

[12] , wherein a decorative layer is disposed on the other main surface of the transparent support substrate.

[0019]

[14] In the laminated film, the coating layer is disposed on one main surface of the transparent support substrate, In the unevenness forming step, the coating layer is opposed to the mold, and molding resin is injected toward the transparent support substrate, so that a molded resin layer is formed on the coating layer together with the unevenness. The method for manufacturing a molded body according to any one of the above

[11] to

[13] .

[0020]

[15] The mold imparts a three-dimensional shape to the laminated film, Furthermore, after the preparation step and before the concavo-convex formation step, a preform step of shaping the laminated film into a shape along the three-dimensional shape is provided, and the method for manufacturing a molded body according to the above

[14] .

Advantages of the Invention

[0021] According to the present invention, a laminated film excellent in formability and releasability from a mold can be provided.

Brief Description of the Drawings

[0022]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Modes for Carrying Out the Invention

[0023] Normally, a layer containing a cured resin (hereinafter sometimes referred to as a cured resin layer) is disposed on the outermost part of the protective material. In order to achieve a seamless design, in this cured resin layer, for example, a region corresponding to the information display part of the display and a region corresponding to the bezel need to be integrally formed. That is, on the surface of the cured resin layer, a region having unevenness and a region having a different texture (texture), for example, a glossy feeling, must be formed. However, it is difficult to impart unevenness to the hard cured resin layer. Therefore, it is conceivable to form the unevenness before the resin is completely cured.

[0024] The region having unevenness and the region having a different texture are formed, for example, by pressing a mold having uneven portions and flat portions against a cured resin layer (coating layer) that is neither completely uncured nor completely cured. If the tackiness of the coating layer is large, when peeling from the mold, the surface of the coating layer that was in close contact with the flat portion in particular becomes rough or whitened, and it is difficult to obtain the desired texture. The tackiness of the coating layer is affected by the hardness of the coating layer in the vicinity of the surface.

[0025] On the other hand, the ease of forming the unevenness is affected by the hardness inside the coating layer. For example, if the hardness inside the coating layer is excessively low, the recovery rate becomes high and it becomes difficult to form the unevenness. In particular, the hardness at a position inside the coating layer that is about the same as the height of the convex portion to be imparted has a great influence on the ease of forming the unevenness.

[0026] This embodiment focuses on the hardness near the surface and inside of the coating layer, and provides a laminated film including a coating layer that satisfies specific ranges and relationships. Such a coating layer is neither fully uncured nor fully cured. Therefore, the coating layer has both a hardness that allows unevenness to be transferred and a low tackiness that enables easy peeling from the mold. Thus, a plurality of regions having different textures, for example, an uneven region and a smooth region, can be simultaneously formed on the coating layer. Furthermore, since the coating layer to be formed into a three-dimensional shape (for example, preformed) can be in an uncured or semi-cured state, it is easy to stretch. Therefore, it is also possible to form the laminated film into a complex three-dimensional shape. In addition, after imparting unevenness and, if necessary, a three-dimensional shape, by completely curing the coating layer, these shapes are retained in the long term.

[0027] By using the laminated film according to this embodiment, a seamless design is realized. That is, the laminated film according to this embodiment is suitable as a material for a molded article having a seamless design. In recent years, for example, in in-vehicle applications, panels having a seamless design in which the bezel portion is expanded to also serve as an instrument panel and / or a center cluster panel have been proposed. Such panels are very large and have a complex three-dimensional shape. The laminated film according to this embodiment is particularly suitable as a material for a large molded article having the above-described seamless design.

[0028] Laminated film The laminated film according to this embodiment includes a transparent support substrate and a coating layer disposed on at least one main surface of the transparent support substrate. The thickness of the coating layer is more than 2 μm. The coating layer contains an active energy ray curable resin composition.

[0029] (Indentation hardness) Indentation hardness HB by nanoindentation method at an indentation depth of 100 nm of the coating layer 100is 0.30 GPa or more and 0.65 GPa or less. The indentation hardness HB by the nanoindentation method at the indentation depth of 2000 nm of the coating layer 2000 is 0.15 GPa or more and 0.35 GPa or less. The indentation hardness HB 2000 is the indentation hardness HB 100 is smaller. Such a coating layer can be said to be in a state that is neither fully cured nor fully uncured (hereinafter referred to as semi-cured or semi-cured state).

[0030] The indentation hardness HB 100 indicates the hardness near the surface of the coating layer (hereinafter sometimes referred to as surface hardness). The indentation hardness HB 2000 indicates the hardness inside the coating layer (hereinafter sometimes referred to as internal hardness). The inside of the coating layer is the region on the side of the transparent support substrate of the coating layer. The higher the indentation hardness, the higher the hardness. The hardness of the coating layer may decrease from the surface toward the transparent support substrate.

[0031] When relatively high protrusions of about 300 nm or more and 4000 nm or less are provided on the coating layer, the ease of forming irregularities is dominated by the internal hardness of the coating layer. When the internal hardness is low, the coating layer can be easily deformed along the irregularities of the pressed mold. However, if the hardness of the coating layer is excessively low, when the laminated film is removed from the mold, the coating layer tends to return to its original shape. This tendency is remarkable when the protrusions are high.

[0032] In the present embodiment, the coating layer has an internal hardness such that the irregularities are transferred and maintained. On the other hand, the surface hardness of the coating layer is high, showing low tackiness and being difficult to deform. That is, the deformation of the irregularities when peeled off from the mold is suppressed by the high surface hardness of the coating layer. Therefore, desired irregularities can be easily formed on the laminated film according to the present embodiment. In the present embodiment, it is assumed that relatively high protrusions as described above are provided on the coating layer, and attention is paid to the hardness at a depth of 2000 nm of the coating layer.

[0033] When small convex portions with a height of about several hundred nm are provided as in Patent Document 1, the ease of forming unevenness is dominated by the surface hardness of the coating layer. In this case, the coating layer in the vicinity of the surface needs to have a hardness that allows the unevenness to be transferred. Therefore, in Patent Document 1, a parameter α related to the ratio of the elastic component to the viscous component is defined to be 80 or more and 94 or less. This numerical value indicates that the recovery rate is high when a indenter is pressed into the coating layer. A high recovery rate means that at least the coating layer in the vicinity of the surface has low hardness and high elasticity. The inside of the coating layer is usually less hard than the surface. That is, the inside of the coating layer has higher elasticity. Thus, it is difficult to accurately form high convex portions of 300 nm or more on a coating layer that is highly elastic both on the surface and inside and has a high recovery rate.

[0034] Indentation hardness HB 100 When it is 0.30 GPa or more, the surface of the coating layer exhibits low tackiness and is difficult to deform. Therefore, the coating layer can be easily peeled off from the mold. That is, the laminated film can be peeled off while maintaining the pattern of the mold transferred to the surface of the coating layer with high precision. Indentation hardness HB 100 When it is 0.65 GPa or less, it becomes easy to stretch the laminated film. Therefore, the laminated film can be formed into a complex three-dimensional shape while suppressing the generation of cracks.

[0035] Indentation hardness HB 2000 When it is 0.15 GPa or more and 0.35 GPa or less, the coating layer has a hardness such that unevenness can be easily shaped. That is, the coating layer has excellent formability. Therefore, a desired pattern can be imparted to the coating layer.

[0036] Indentation hardness HB 2000 is the indentation hardness HB 100By being smaller, near the surface and inside the coating layer, each can exhibit its respective function. That is, the coating layer exhibits excellent mold release properties and shapeability.

[0037] After the coating layer imparts fine irregularities and, if necessary, a three-dimensional shape to the laminated film, it can be completely cured. As a result, the imparted irregularities and three-dimensional shape are retained in the long term. That is, the obtained molded body has excellent shape retention.

[0038] Indentation hardness HB 100 and indentation hardness HB 2000 The measurement targets of are the laminated film immediately before the formation of the above-mentioned fine irregularities. The coating layer in the measurement target laminated film is in a semi-cured state. Within a range that does not affect the above-mentioned indentation hardness, after the measurement of the above-mentioned indentation hardness and before the formation of irregularities, the laminated film may be subjected to heat treatment, decoration, or preforming. After heat treatment, decoration, or preforming, indentation hardness HB 100 and indentation hardness HB 2000 may be measured.

[0039] The indentation hardness H by the nanoindentation method is obtained, for example, by the continuous stiffness measurement method using a nanoindentation device. In the continuous stiffness measurement method, a minute load (alternating current (AC) load) is applied to the sample in addition to a quasi-static test load (direct current (DC) load). As a result, the force applied to the sample vibrates slightly. From the vibration component of the displacement generated as a result and the phase difference between the displacement and the load, the stiffness with respect to the depth is calculated. Thereby, a continuous hardness profile with respect to the depth can be obtained. The hardness at a depth of 100 nm in this profile is the indentation hardness HB 100 or HA to be described later 100 and the hardness at 2000 nm is the indentation hardness HB 2000 or HA to be described later 2000 is.

[0040] For the continuous rigidity measurement method, for example, the Advanced Dynamic E and H.NMT methods can be used. As the nanoindentation device, the iMicro Nanoindenter manufactured by NANOMECHANICS, INC. can be used. In this case, the dedicated iMicro software can be used for the calculation of load and stiffness. A load is applied to the sample by the indenter until a maximum load of 50 mN is reached. As the indenter, for example, a Berkovich-type diamond indenter is used. For the measurement and calculation of stiffness, appropriate values can be set as appropriate for the Poisson's ratio and load of the coating layer.

[0041] (Elongation rate) The elongation rate of the laminated film at 160°C is preferably 5.0% or more. In this case, the laminated film exhibits a sufficient elongation 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 preform process described later, damage to the laminated film is easily suppressed. The above elongation rate is more preferably 8.0% or more, and particularly preferably 10% or more. The above elongation rate may be 500% or less, and may be 200% or less. Forming in this specification is a concept including molding by a preform process and an uneven formation process.

[0042] The elongation rate is measured in accordance with JIS K 7127. Specifically, a test piece obtained by cutting the laminated film into a length of 200 mm and a width of 10 mm, and a tensile testing machine with a chuck distance of 150 mm are used. Under the conditions of an atmosphere of 160°C and a tensile speed of 300 mm / min, the long side of the test piece is stretched by 2.5%. Then, the test piece is observed with a microscope having a magnification of 1000 times or more to confirm the presence or absence of cracks having a size exceeding 1 mm in length. If no crack occurs, a new test piece is cut out, and next, the long side is stretched by 5%. Then, the observation of crack generation is carried out in the same procedure. This procedure is repeated, and the elongation rate at the time when a crack having the above size is confirmed for the first time is defined as the elongation rate of the laminated film. The elongation rate may be increased, for example, by 2.5% each time and the above procedure may be repeated.

[0043] Hereinafter, the elements constituting the laminated film according to the present embodiment will be described in detail. [Transparent support substrate] The transparent support substrate is a substrate that supports the coating layer. The transparent support substrate is not particularly limited as long as it is transparent. Specifically, being 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 a method in accordance with JIS K 7361-1.

[0044] A transparent support substrate known in the art is used without particular limitation. The transparent support substrate may be colorless or colored.

[0045] The transparent support substrate is appropriately selected according to the application. Examples of the transparent support substrate include polyester films such as polycarbonate (PC) - based films, polyethylene terephthalate, and polyethylene naphthalate; cellulose - based films such as diacetyl cellulose and triacetyl cellulose; acrylic 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, polyolefins having a cyclic or norbornene structure, and ethylene - propylene copolymers; and amide - based films such as nylon and aromatic polyamides. Further, the transparent support substrate may be a film containing resins such as polyimide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polyvinyl alcohol, polyvinylidene chloride, polyvinyl butyral, polyarylate, polyoxymethylene, and epoxy resins, or may be a film containing a mixture of these polymers.

[0046] The transparent support substrate may be a laminate of a plurality of films. For example, the transparent support substrate may be a laminate of an acrylic film and a polycarbonate - based film.

[0047] The transparent support substrate may have optical anisotropy or may have optical isotropy. The magnitude of the birefringence of the optically anisotropic transparent support substrate is not particularly limited. The retardation of the anisotropic transparent support substrate may be 1 / 4 (λ / 4) of the wavelength or may be 1 / 2 (λ / 2) of the wavelength.

[0048] The thickness of the transparent support substrate is appropriately set according to the application of the laminated film and / or molded article, the manufacturing method, etc. From the viewpoints of strength and handleability, the thickness of the transparent support substrate is preferably 30 μm or more, more preferably 75 μm or more, and particularly preferably 200 μm or more. From the viewpoint of stretchability, the thickness of the transparent support substrate is preferably 500 μm or less, more preferably 400 μm or less. In one aspect, the thickness of the transparent support substrate is 75 μm or more and 500 μm or less.

[0049] The transparent support substrate desirably has stretchability at the temperature at which the laminated film is formed into a three-dimensional shape. For example, the transparent support substrate desirably has stretchability at the forming temperature in the preform process. The forming temperature in the preform 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.

[0050] [Coating layer] The coating layer contains a resin composition curable by active energy rays. However, the coating layer is not completely cured and is not completely uncured either. The coating layer is in a semi-cured state. After various shapes such as unevenness are imparted to the laminated film, the shape is retained over a long period by completely curing the coating layer.

[0051] The semi-cured resin composition (coating layer) can be formed, for example, by irradiating the resin composition with active energy rays of 5 mJ / cm 2 or more and 150 mJ / cm 2 or less. The integrated light amount of the active energy rays for semi-curing the resin composition is not limited to this and is appropriately set according to the composition of the resin composition and the like. In the present embodiment, considering the composition of the resin composition and the like, and further, the indentation hardness HB 100 and the indentation hardness HB 2000 of the coating layer, the active energy rays are irradiated so as to satisfy the above ranges and relationships.

[0052] The resin composition irradiated with 1500 mJ / cm 2 of active energy rays can generally be said to be completely cured. The cured resin layer (for example, the hard coat layer and / or the functional layer) in the molded body according to the present embodiment described later is also completely cured. That is, 1500 mJ / cm 2The physical properties of the resin composition irradiated with active energy rays can be regarded as the physical properties of the cured resin layer in the molded body. The pencil hardness of the resin composition in a completely cured state (cured resin layer) is, for example, H or higher.

[0053] The resin composition that has not been exposed to active energy rays or has been exposed to active energy rays of less than 5 mJ / cm 2 can be regarded as being completely uncured.

[0054] The coating layer may be a single layer or may include two or more layers. As long as the resin composition forming each layer contains an active energy ray curable resin, they may be the same or different from each other. Regardless of the number of laminated layers, by satisfying the hardness at the indentation depths of 100 nm and 2000 nm within the above ranges and relationships, a laminated film excellent in formability and releasability from the mold can be obtained.

[0055] The coating layer preferably includes at least a semi-cured hard coat layer, and typically includes a semi-cured hard coat layer and a semi-cured functional layer. The hard coat layer is mainly provided to impart scratch resistance and high hardness to the molded body. The functional layer may be an optical interference layer. The optical interference layer is disposed outside the hard coat layer mainly to reduce the reflectance.

[0056] The optical interference layer may be a single layer or may be provided with a plurality of layers. The optical interference layer includes, for example, at least one of a layer having a high refractive index (hereinafter sometimes referred to as a high refractive index layer or an HR layer), a layer having a medium refractive index (hereinafter sometimes referred to as a medium refractive index layer or an MR layer), and a layer having a low refractive index (hereinafter sometimes referred to as a low refractive index layer or an LR layer). The refractive index of the HR layer may be 1.55 or more and 2.00 or less. The refractive index of the MR layer may be 1.45 or more and 1.60 or less. The refractive index of the LR layer may be 1.35 or more and 1.50 or less.

[0057] The functional layer may be other layers than the optical interference layer, and may include other layers together with the optical interference layer. Examples of the other layers include an antibacterial / antiviral layer and an antifouling layer. The antibacterial / antiviral layer and the antifouling layer are disposed, for example, outside the hard coat layer (and further, the optical interference layer).

[0058] <Polymerization rate> The difference (=|PB - PA|) between the polymerization rate PB of the resin composition in the coating layer, that is, the resin composition in the semi-cured state, and the polymerization rate PA of the resin composition after irradiation with active energy rays of 1500 mJ / cm 2 is, for example, 15% or more. When |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| may be 60% or less, preferably 50% or less. When |PB - PA| is 15% or more and 60% or less, it can be said that the coating layer is in a semi-cured state. The indentation hardness H of the coating layer and the hard coat layer can be controlled by the polymerization rate.

[0059] The polymerization rate can be obtained, for example, based on the infrared absorption spectrum obtained by infrared spectroscopy (IR: Infrared Spectroscopy) according to the following procedure.

[0060] First, the uncured coating layer is analyzed with a Fourier transform infrared spectrophotometer (FT-IR) from the surface opposite to the transparent support substrate of the coating layer. On the spectral chart where the horizontal axis represents the wave number (cm -1 ) and the vertical axis represents the absorbance, a baseline between 690 cm -1 and 2015 cm -1 is determined. Using this baseline, the peak heights I -1 near 810 cm -1 and 1440 cm NC1 derived from the carbon-carbon double bond (C = C) of the (meth)acryloyl group and I NC2are calculated respectively. Similarly, using the above baseline, the peak height I -1 near the wave number 1730 cm derived from the carbon-oxygen bond (C=O) of the ester bond NO is calculated. The peak height I NC1 and I NC2 are each divided by the peak height I NO to obtain the initial values r 01 and r 02 .

[0061] Next, the semi-cured coating layer is analyzed by FT-IR in the same manner as above, and the peak heights I -1 near 810 cm and 1440 cm -1 near the wave number derived from the C=C of the (meth)acryloyl group BC1 and I BC2 , and the peak height I -1 near the wave number 1730 cm derived from the C=O of the ester bond BO are calculated. The peak heights I BC1 and I BC2 are each divided by the peak height I BO to obtain r B1 and r B2 .

[0062] The ratio of r 01 to the initial value r B1 (= r B1 / r 01 ) and the ratio of r 02 to the initial value r B2 (= r B2 / r 02 ) each 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 indicators of 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.

[0063] Furthermore, a fully cured coating layer was analyzed by FT-IR in the same manner as above, and the peak heights I -1 near the wavenumber 810 cm -1 derived from the C=C of the (meth)acryloyl group and I AC1 near 1440 cm AC2 were calculated. Also, the peak height I -1 near the wavenumber 1730 cm AO derived from the C=O of the ester bond was calculated. The values obtained by dividing the peak heights I AC1 and I AC2 by the peak height I AO were defined as r A1 and r A2 . The polymerization rate PA (%) of the cured resin composition was calculated by (1 - r A1 / r 01 ) × 100, or (1 - r B2 / r 02 ) × 100.

[0064] 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.

[0065] 〈Indentation hardness〉 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.

[0066] The indentation hardness HB 100and the indentation hardness HA by nanoindentation method at an indentation depth of 100 nm of the coating layer after irradiation with active energy rays of 1500 mJ / cm 2 100 The difference from it (= |HB 100 - HA 100 |) is not particularly limited. From the viewpoint of shape retention, |HB 100 - HA 100 | may be 0.05 GPa or more. When |HB 100 - HA 100 | is within this range, the shape retention is also likely to be improved. |HB 100 - HA 100 | may be 0.30 GPa or less. According to this embodiment, |HB 100 - HA 100 | can satisfy the above range.

[0067] 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.

[0068] The indentation hardness HB 2000 and the indentation hardness HA by nanoindentation method at an indentation depth of 2000 nm of the coating layer after irradiation with active energy rays of 1500 mJ / cm 2 2000 The difference from it (= |HB 2000 - HA 2000 |) is not particularly limited. From the viewpoint of formability, |HB 2000 - HA 2000 | is preferably 0.05 GPa or more. When |HB 2000 - HA 2000 | is within this range, the shape retention is also likely to be improved. |HB 2000 - HA 2000 | may be 0.30 GPa or less. According to this embodiment, |HB 2000 - HA 2000 | can satisfy the above range.

[0069] ​​ Indentation hardness HB 100 and the indentation hardness HB 2000 The difference from (= |HB 100 -HB 2000 |) is not particularly limited. From the viewpoints of formability and releasability, |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.

[0070] The coating layer preferably has stretchability at the temperature when the laminated film is formed into a three-dimensional shape. The coating layer preferably has stretchability, for example, at the molding temperature in the preform process described later. The molding temperature in the preform process is usually 180°C or lower. From the viewpoint of moldability, the Tg of the resin composition in the coating layer is preferably at or below the molding temperature, that is, 180°C or lower.

[0071] The coating layer is required to be easily peeled off from the mold used for forming unevenness. The temperature of the mold used for forming unevenness is usually 50°C or higher. From the viewpoint of releasability, the Tg of the resin composition in the coating layer is preferably 50°C or higher, more preferably 60°C or higher. The glass transition temperature is measured by a differential scanning calorimeter (DSC) conforming to JIS K 7121. The Tg of the resin composition in the coating layer is related to the degree of curing of the coating layer. By controlling the Tg, the formability and releasability of the coating layer can be improved.

[0072] 〈Pencil hardness〉 In terms of being more likely to further improve scratch resistance, the pencil hardness of the surface of the coating layer after irradiating with active energy rays of 1500 mJ / cm 2 is preferably H or higher, more preferably 2H or higher. The pencil hardness is measured in accordance with JIS K 5600-5-4.

[0073] <Visual reflectance> A laminated film containing an uncured optical interference layer has particularly excellent antireflection performance. For example, the visual reflectance including specularly reflected light in the wavelength range 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. In addition to the first region, the second region of the molded body obtained by curing the laminated film also has excellent antireflection properties. Therefore, there is little reflection of external light on the molded body, and the molded body has good display characteristics and good visibility. The visual reflectance in the second region of the molded body can similarly be 0.1% or more and 4.0% or less.

[0074] The visual reflectance of the laminated film and the molded body is preferably 0.1% or more and 3.0% or less, and more preferably 0.1% or more and 2.5% or less.

[0075] The above visual reflectance is obtained by measuring all reflected light including specularly reflected light. That is, the above visual reflectance is measured by a so-called SCI (Specular Component Include) method. Since this method is hardly affected by the surface state of the object to be measured, the visual reflectance of the uncured layer can be measured.

[0076] Specifically, the visual reflectance of the laminated film can be measured by the following method. On the surface of the transparent support substrate opposite to the coating layer, a black paint (for example, product name: CZ-805 BLACK (manufactured by Nichihiro Bix Co., Ltd.)) is applied using a bar coater so that the dry film thickness is 3 μm or more and 6 μm or less. Then, it is left to dry at room temperature for 5 hours to create an evaluation sample M.

[0077] From the coating layer side of the obtained evaluation sample M, using a spectrocolorimeter (for example, SD7000 manufactured by Nippon Denshoku Industries Co., Ltd.), the visual reflectance by the SCI method in the wavelength range of 380 nm or more and 780 nm or less is measured.

[0078] The visual reflectance of the molded body can be measured as follows. To the evaluation sample M created above, active energy rays of an integrated light amount of 150 mJ / cm 2 ultra (for example, an integrated light amount of 1500 mJ / cm 2 ) are irradiated to create an evaluation sample N. From the coating layer side of the obtained evaluation sample N, the visual reflectance is measured in the same manner as above.

[0079] 〈Thickness〉 The thickness of the coating layer is not particularly limited as long as it is more than 2 μm. In terms of being easily able to form relatively high convex portions, the thickness of the coating layer is preferably 3 μm or more, more preferably 5 μm or more. In terms of being easily cured, the thickness of the coating layer is preferably 20 μm or less, more preferably 15 μm or less. The thickness of the coating layer is, for example, 3 μm or more and 20 μm or less. When the coating layer includes a plurality of layers, the thickness of the coating layer is the sum of these thicknesses.

[0080] The thickness of the hard coat layer can be in the same range as the thickness of the above coating layer. The thickness per layer of the functional layer is, for example, 5 nm or more and 300 nm or less, and 10 nm or more and 200 nm or less.

[0081] The thickness of the coating layer is determined from its cross-section. Specifically, a 10 mm × 10 mm test piece is cut out from the laminated film. Using a microtome, a section for observing the cross-section is created from the test piece. The obtained section is observed with a laser microscope or a transmission electron microscope, and the thickness of the coating layer at any 10 points is measured. These average values are taken as the thickness of the coating layer. The thickness of the transparent support substrate is also determined 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.

[0082] (Resin composition) The resin composition contains at least one selected from the group consisting of active energy ray curable monomers, oligomers, and polymers. The active energy ray is not particularly limited and may be an ionizing radiation such as ultraviolet rays, electron beams, α-rays, β-rays, γ-rays, etc. 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 layer and the cured resin layer can be controlled by the resin composition.

[0083] When the coating layer includes a plurality of layers, the resin components forming each layer may be the same or different. Among them, it is preferable that each layer contains the same or the same type of resin component. This is because the adhesion of each layer is improved and delamination between the layers is less likely to occur.

[0084] In one aspect, the resin composition contains a polymerizable polymer. The polymerizable polymer tends to impart low tackiness as well as curability to the coating layer.

[0085] In another aspect, the resin composition contains at least one of polymerizable and non-polymerizable polymers (hereinafter may be collectively referred to as polymers), and at least one of polymerizable monomers and oligomers. The polymer tends to impart low tackiness to the coating layer. Also, the formability is likely to be improved. By blending the polymer together with at least one of the polymerizable monomers and oligomers, it becomes easier to adjust so that the difference in polymerization rate (=|PB - PA|) is 15.0% or more. As a result, the shape retention is more likely to be further improved. In terms of easy control of tackiness, it is preferable that the resin composition contains both a polymerizable polymer and a non-polymerizable polymer, and at least one of polymerizable monomers and oligomers.

[0086] 〈Non-polymerizable polymer〉 The non-polymerizable polymer is a polymer that does not contain a polymerizable unsaturated group. The weight-average molecular weight of the non-polymerizable polymer is 5,000 or more. From the perspective of tackiness, 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, and more preferably 80,000 or less.

[0087] Examples of the non-polymerizable polymer include urethane resins, acrylic resins, polyester resins, and epoxy resins. From the perspectives of transparency, tackiness, physical properties, and durability, acrylic resins are preferred.

[0088] 〈Polymerizable Polymer〉 The polymerizable polymer is a polymer containing a polymerizable unsaturated group. The weight-average molecular weight of the polymerizable polymer is 5,000 or more. From the perspective of tackiness, 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, and more preferably 80,000 or less.

[0089] 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 a polymerizable unsaturated group as a side chain or a terminal group. From the perspective of transparency, a polymer chain containing a carbon-carbon bond is preferred. From the perspective of formability, a polymer chain containing a urethane bond is preferred.

[0090] The polymerizable unsaturated group is preferably contained in an amount of 2 or more, more preferably 3 or more, and particularly preferably 5 or more. The polymerizable unsaturated group is not particularly limited. Among them, acryloyl groups and methacryloyl groups are preferred as the polymerizable unsaturated group.

[0091] Specific examples of the preferred polymerizable polymer include urethane (meth)acrylate polymers and acrylic (meth)acrylate polymers.

[0092] The urethane (meth)acrylate polymer can be prepared, for example, by (1) adding a compound having a hydroxyl group and an acryloyl group (or a methacryloyl group) to a polyisocyanate compound having a terminal isocyanate group in the molecule, or (2) reacting a polyurethane polyol obtained by reacting a polyisocyanate compound and a polyol with an isocyanate group-containing (meth)acrylate monomer.

[0093] 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, or a diisocyanate compound obtained by hydrogenating aromatic isocyanates among these diisocyanate compounds (for example, diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate), divalent or trivalent polyisocyanate compounds such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate, and burette type adducts and isocyanurate ring type adducts of these diisocyanates.

[0094] 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 alkylene oxide-modified or lactone-modified compounds obtained by adding ethylene oxide, propylene oxide, ε-caprolactone, γ-butyrolactone, etc. thereto.

[0095] Examples of the polyol in the above method (2) include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol, polycaprolactone diol, polyester polyol, and polyether polyol.

[0096] Examples of the isocyanate group-containing (meth)acrylate monomer in the above method (2) include isocyanate ethyl acrylate, isocyanate propyl acrylate, and unsaturated compounds obtained by adding a polyisocyanate compound such as hexamethylene diisocyanate to an active hydrogen-containing polymerizable monomer such as hydroxyethyl acrylate.

[0097] 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 combination with the polyol in the above method (2).

[0098] An acrylic (meth)acrylate polymer is an acrylic polymer containing an acryloyl group and / or a methacryloyl group. Specifically, compounds obtained by adding (meth)acrylic acid to an acrylic resin copolymerized with glycidyl methacrylate, compounds obtained by adding 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol tri(meth)acrylate, etc. to an acrylic resin copolymerized with 2-acryloyloxyethyl isocyanate, and resins obtained by adding 2-acryloyloxyethyl isocyanate to an acrylic resin copolymerized with a hydroxyl group-containing monomer can be mentioned.

[0099] The polymer is used alone or in combination of two or more.

[0100] In a resin composition for forming a hard coat layer (hereinafter sometimes referred to as 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 with respect to 100 parts by mass of the solid content of the resin composition HC. 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. The blending ratio of the polymerizable polymer and the non-polymerizable polymer is not particularly limited.

[0101] In a resin composition for forming an optical interference layer (hereinafter sometimes referred to as 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 with respect to 100 parts by mass of the solid content of the resin composition R. 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. The blending ratio of the polymerizable polymer and the non-polymerizable polymer is not particularly limited.

[0102] 〈Polymerizable oligomer〉 The polymerizable oligomer is an oligomer containing polymerizable unsaturated groups. 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 may be 2,000 or more.

[0103] The polymerizable oligomer has the same structure as the polymerizable polymer except for the molecular weight. The polymerizable 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 preferable. From the viewpoint of moldability, an oligomer chain containing a urethane bond is preferable.

[0104] Preferably, 2 or more, more preferably 3 or more, and particularly preferably 5 or more polymerizable unsaturated groups are contained. The polymerizable unsaturated group is not particularly limited. Among them, acryloyl group and methacryloyl group are preferable as the polymerizable unsaturated group.

[0105] Specific examples of the preferable polymerizable oligomer include urethane (meth) acrylate oligomer and acrylic (meth) acrylate oligomer.

[0106] The above urethane (meth) acrylate oligomer and acrylic (meth) acrylate oligomer are each prepared in the same manner as the urethane (meth) acrylate polymer and acrylic (meth) acrylate polymer.

[0107] The polymerizable oligomer is used alone or in combination of two or more.

[0108] As the coincident oligomer or polymerizable polymer, commercially available products may be used. Examples of commercially available urethane (meth) acrylate oligomers or polymers include 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 Ornex 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. can be used.;

[0109] Examples of commercially available acrylic (meth)acrylate oligomers or polymers include, for example, Unidic V-6840, Unidic V-6841, Unidic V-6850, Unidic EMS-635, Unidic WHV-649 manufactured by DIC Corporation; Hitroid 7975, Hitroid 7977, Hitroid 7988, Hitroid 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. can be used.

[0110] 〈Polymerizable monomer〉 The polymerizable monomer is a monomer containing a polymerizable unsaturated group. The molecular weight of the polymerizable monomer is not particularly limited. The polymerizable unsaturated group equivalent of the polymerizable monomer may be 50 g / eq. or more and may be 200 g / eq. or less.

[0111] The polymerizable monomer preferably has two or more, more preferably three or more, and particularly preferably five or more polymerizable unsaturated groups. Examples of the polymerizable unsaturated group preferably include an acryloyl group and a methacryloyl group. A preferred polymerizable monomer is a polyfunctional (meth)acrylate monomer.

[0112] The polyfunctional (meth)acrylate monomer can be prepared by a dehydration reaction between a polyhydric alcohol and (meth)acrylic acid, or by a transesterification reaction between a polyhydric alcohol and a (meth)acrylate ester.

[0113] Examples of the polyfunctional (meth)acrylate monomer having a coincidence unsaturated group equivalent 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 glycol 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 glycerin 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, ditrimethylolpropane 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 hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate and the like can be mentioned.;

[0114] The polymerizable monomer is used alone or in combination of two or more kinds.;

[0115] 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.;

[0116] 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, and 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.

[0117] 〈Light-transmitting fine particles〉 The resin composition may contain light-transmitting fine particles as required. The light-transmitting fine particles can more easily improve the antiglare property and hardness of the cured coating layer (cured resin layer). The average particle diameter of the light-transmitting fine particles is, for example, 1.0 μm or more and 10 μm or less, and may be 0.5 μm or more and 10 μm or less. The average particle diameter refers to the particle diameter (D50) at which the volume-converted integration measured by a laser diffraction particle size distribution analyzer is 50%. The light-transmitting fine particles are transparent or translucent. Specifically, being translucent means that the total light transmittance measured by a method conforming to JIS K 7361-1 is 30% or more and less than 40%.

[0118] The light-transmitting fine particles may be organic fine particles or inorganic fine particles. Commercially available products may be used as the light-transmitting fine particles. Examples of commercially available light-transmitting fine particles include, for example, Tech Polymer SSX series (styrene-acrylic copolymer fine particles) manufactured by Sekisui Chemical Co., Ltd., Chemisnow SX series (styrene polymer fine particles) manufactured by Soken Chemical & Engineering Co., Ltd., Chemisnow MX series (acrylic polymer fine particles), Sea Hostar KE-P, KE-S series (silica fine particles) manufactured by Nippon Shokubai Co., Ltd., Solioster RA (silicone-acrylic copolymer fine particles), Epostar S12 (melamine polymer fine particles), Epostar MA series (styrene-acrylic copolymer fine particles), acrylic copolymer fine particles, MSP series, NH series (silicone fine particles) manufactured by Nikko Rika Co., Ltd., AZ series, AY series (alumina fine particles) manufactured by Shin Nippon Sumitomo Metals Materials Co., Ltd. Among them, Tech Polymer SSX series (styrene-acrylic copolymer fine particles), Chemisnow SX series (styrene polymer fine particles), and Epostar MA series (styrene-acrylic copolymer fine particles) are preferable.

[0119] 〈Filler〉 The resin composition contains a filler as required. The filler relaxes the volume shrinkage due to the curing of the coating layer. The filler improves the scratch resistance of the cured coating layer.

[0120] From the viewpoints of transparency and stability, the primary particle diameter 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 diameter is measured using image processing software from an image of a cross-sectional electron microscope.

[0121] The filler may be organic fine particles or inorganic fine particles. Among them, inorganic fine particles are preferable. Examples of the inorganic fine particles include, for example, silica (SiO 2)Examples of the filler include particles, alumina particles, titania particles, tin oxide particles, antimony-doped tin oxide (abbreviation: ATO) particles, phosphorus-doped tin oxide particles, zinc oxide particles, particles with silver supported on titanium oxide, particles with silver supported on silica-alumina particles, particles with double metal (silver / zinc / copper) ions supported on glass, and copper iodide particles. Among these, silica particles and alumina particles are more preferable from the viewpoints of cost and stability. The surface of the filler is preferably modified with an unsaturated group such as a (meth)acryloyl group.

[0122] Commercially available products may be used as the filler. 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 and Chemicals Ltd., and NANOBYK-3605 manufactured by BYK Japan K.K. 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 Japan K.K.

[0123] Examples of commercially available indium tin oxide particles include HX-204 IP manufactured by Nissan Chemical Industries, Ltd. and PTOPGM15WT%-N09 manufactured by CIK Nanotech Co., Ltd. Examples of particles with silver supported on titanium oxide include ATOMY BALL-(S) manufactured by JGC Catalysts & Chemicals Ltd. Examples of particles with silver supported on silica-alumina particles include ATOMY BALL-(UA), ELCOM NU-1023SIV, and ELCOM NU-1024SIV manufactured by JGC Catalysts & Chemicals Ltd. Examples of particles with silver supported on silica particles include Ionpure ZAF HS manufactured by Ishizuka Glass Co., Ltd. Examples of copper iodide particles include Cufitec BE4-ANA01, AA1-ANA01, BB2-ANA01, and BD3-ANA01 manufactured by NBC Mesh Tech Co., Ltd.

[0124] In the resin composition HC, the filler content 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 filler content 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 filler content in the resin composition HC is, for example, 0.1 part by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition HC.

[0125] In the resin composition R, the filler content 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 with respect to 100 parts by mass of the solid content of the resin composition R. The filler content is preferably 90 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition R. The filler content in the resin composition R is, for example, 1 part by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition R.

[0126] <Photoinitiator> The resin composition contains a photoinitiator as required. The blending amount of the photoinitiator is preferably 0.01 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, based on 100 parts by mass of the solid content of the resin composition.

[0127] Examples of the photoinitiator include alkylphenone-based photoinitiators, acylphosphine oxide-based photoinitiators, titanocene-based photoinitiators, and oxime ester-based polymerization initiators.

[0128] Examples of the alkylphenone-based photoinitiator include 2,2-dimethoxy-1,2-diphenylethan-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-1-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.

[0129] Examples of the acylphosphine oxide-based photoinitiator include monoacylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4,6-triethylbenzoyldiphenylphosphine oxide, 2,4,6-triphenylbenzoyldiphenylphosphine oxide; bisacylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0130] Examples of titanocene-based photoinitiators include bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium. Examples of oxime ester-based polymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxyim)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(0-acetoxyim), oxyphenylacetic acid, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester, and 2-(2-hydroxyethoxy)ethyl ester.

[0131] The photoinitiator is used alone or in combination of two or more.

[0132] Among them, photoinitiators having an absorption wavelength in the long wavelength region, for example, a wavelength region of 370 nm or more, are preferred. Examples of such photoinitiators include the above-mentioned acylphosphine oxide-based photoinitiators. 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.

[0133] When the active energy rays are irradiated under mild curing conditions such that the coating layer is semi-cured, the curing reaction hardly proceeds inside the coating layer, so that it is difficult to obtain a desired hardness. By using a photoinitiator having an absorption wavelength in the long wavelength region, the curing reaction inside the coating layer is promoted.

[0134] <Solvent> The resin composition contains a solvent as needed. The solvent is not particularly limited and is appropriately selected in a timely manner according to the components contained in the composition, the type of substrate to be coated, the coating method of the composition, etc. Examples of the solvent include 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 isobutyl alcohol; and halogen solvents such as dichloromethane and chloroform. 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.

[0135] 〈Refractive index lowering component〉 The resin composition R preferably contains a refractive index lowering component that lowers the refractive index of the optical interference layer. The refractive index lowering component is, for example, particulate (hereinafter may be referred to as refractive index lowering particles).

[0136] 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 optical interference layer. The hollow silica fine particles have a structure filled with gas 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 compared to the original refractive index of the silica fine particles. Examples of the hollow silica fine particles include Thruia 4320 (manufactured by JGC Catalysts and Chemicals Ltd.).

[0137] As the refractive index reducing component, silica fine particles having a nanoporous structure formed on at least a part of the inside and / or surface may be used. The nanoporous structure is formed according to the form, structure, aggregation state of the silica fine particles, and the dispersion state inside the coating film. As the refractive index reducing component, hollow acrylic fine particles may be used. Examples of the hollow acrylic fine particles include XX-5952Z, XX-5966Z, and XX-6061Z manufactured by Sekisui Chemical Co., Ltd.

[0138] 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.

[0139] 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, with respect to 100 parts by mass of the solid content of the resin composition R. Thereby, the cured optical interference layer is likely to exhibit excellent antireflection properties. The content of the refractive index reducing component is, for example, 35 parts by mass or more and 75 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition R.

[0140] <Others> The resin composition contains various additives as required. Examples of the additives include an antistatic agent, a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, a surface conditioner, a leveling agent, and a light stabilizer (e.g., a hindered amine light stabilizer (HALS)), an antibacterial agent, an antifungal agent, an antiviral agent, and an antifouling agent. In particular, it is desirable that the antibacterial agent, the antifungal agent, the antiviral agent, and the antifouling agent be contained in the resin composition forming the outermost layer (e.g., resin composition R).

[0141] [Protective Film] The laminated film may have a protective film on the outer surface side of the coating layer. The protective film protects the coating layer and the laminated film and 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 surface to which the resin composition R is applied.

[0142] A protective film known in the art is used without particular limitation. The protective film may be colorless or colored. The protective film may be transparent.

[0143] The thickness of the protective film is not particularly limited. The thickness of the protective film may be 20 μm or more and 100 μm or less. Thereby, the protective effect on the coating layer is likely to be enhanced. The thickness of the protective film is preferably 25 μm or more, more preferably 30 μm or more, still more preferably 33 μm or more, and particularly preferably 35 μm or more. The thickness of the protective film is preferably 85 μm or less, more preferably 80 μm or less, and still more preferably 65 μm or less. The thickness of the protective film is a value excluding the thickness of the adhesive layer.

[0144] The protective film is made of, for example, resin. Examples of the resin film include 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 adding further functions, polyester films such as polyethylene terephthalate, polycarbonate, and polylactic acid, polystyrene films, polystyrene-based resin films such as AS resin films and ABS resin films, nylon films, polyamide films, polyvinyl chloride films and polyvinylidene chloride films, and polymethylpentene films.

[0145] Among them, at least one selected from polyethylene films, polystyrene films, modified polyolefin films, polymethylpentene films, OPP films, and CPP films is preferable. In particular, at least one selected from polyethylene films, polystyrene films, modified polyolefin films, polymethylpentene films, OPP films, and CPP films with a thickness of 30 μm or more and 100 μm or less is preferable.

[0146] Additives such as antistatic agents and ultraviolet ray inhibitors may be added to the resin film as necessary. The surface of the resin film may be subjected to corona treatment or low-temperature plasma treatment.

[0147] FIG. 1 is a cross-sectional view schematically showing the laminated film according to the present embodiment. The laminated film 10 includes a transparent support substrate 11 and a coating layer 12 disposed on one main surface thereof.

[0148] Method for manufacturing a laminated film The laminated film according to the present embodiment includes, for example, a coating step of applying an active energy ray-curable resin composition to at least one main surface of a transparent support substrate, and irradiating the resin composition with 5 mJ / cm 2 or more and 150 mJ / cm 2It is manufactured by a method comprising a first irradiation step of irradiating the following active energy rays to obtain a coating layer formed of a resin composition in a semi-cured state. FIG. 2 is a flowchart showing a method for manufacturing a laminated film according to the present embodiment.

[0149] (1) Coating step (S11) An active energy ray-curable resin composition (for example, the above resin composition HC) is applied to at least one main surface of a transparent support substrate. Thereby, an uncured coating layer is formed.

[0150] 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 shaker, a mixer, or a disperser.

[0151] The coating method of the resin composition is appropriately selected according to the properties of the resin composition and the like. Examples of the coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a bar coating method, a die coating method, an inkjet method, a gravure coating method, or an extrusion coating method.

[0152] The coating amount of the resin composition is not particularly limited. The resin composition is applied so that the thickness of the coating layer is more than 2 μm, for example, 3 μm or more and 20 μm or less.

[0153] (2) Drying step (S12) After the coating step (1) and before the first irradiation step (3), the applied resin composition may be dried. By the drying step, at least a part of the solvent component contained in the resin composition is removed, the handleability is improved, and the degree of curing is easily controlled. The drying conditions are not particularly limited and are appropriately set according to the coating amount, the type of solvent, and the like.

[0154] (3) First irradiation step (S13) 5 mJ / cm is applied to the resin composition 2 or more and 150 mJ / cm2 Irradiate with the following active energy rays. Through the first irradiation step, the resin composition becomes in a semi-cured state, and the above coating layer is obtained. The polymerization rate of the resin composition and thus the indentation hardness H of the coating layer can be controlled by the integrated light quantity in the first irradiation step. The first irradiation step may be performed before the unevenness formation step described later, may be before the preform step, or may be after that.

[0155] The integrated light quantity in this step may be 10 mJ / cm 2 or more, and may be 20 mJ / cm 2 or more. The integrated light quantity in this step may be 130 mJ / cm 2 or less, and may be 100 mJ / cm 2 or less. The irradiation of the active energy rays may be performed from the coating layer side or may be performed from the transparent support substrate side. The irradiation of the active energy rays may be performed in an air atmosphere or may be performed in a nitrogen atmosphere.

[0156] In the coating layer, the indentation hardness HB 2000 is smaller than the indentation hardness HB 100 . Further, the indentation hardness HB 2000 is 0.15 GPa or more and 0.35 GPa or less. Therefore, the coating layer has excellent formability. Thus, a desired pattern can be imparted to the coating layer. The indentation hardness HB 100 is 0.30 GPa or more and 0.65 GPa or less. Therefore, the laminated film can be peeled off from the mold while the pattern of the mold transferred to the surface of the coating layer is maintained with high precision.

[0157] The type of the active energy rays is not particularly limited. The active energy rays are appropriately selected according to the type of the polymerizable monomer or oligomer. The active energy rays are not particularly limited and may be ionizing radiations such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Among them, ultraviolet rays are preferable. The ultraviolet rays are irradiated, for example, using a high-pressure mercury lamp or an ultra-high-pressure mercury lamp.

[0158] Method for manufacturing a laminated film having a coating layer including a plurality of layers A coating layer including a plurality of layers (typically, a semi-cured hard coat layer and a semi-cured light interference layer) is formed by a lamination method or a coating method. The first irradiation step (3) may be performed a plurality of times.

[0159] (Lamination method) In the lamination method, according to the coating step (1), a plurality of layers formed on different base materials are bonded together. The drying step (2) is optionally performed before bonding the layers together. The first irradiation step (3) may be performed on each layer before bonding the layers together, or may be performed collectively after bonding. According to the lamination method, even when the layers are uncured, phase mixing is likely to be suppressed.

[0160] (Coating method) In the coating method, a resin composition for forming another layer is applied onto a layer formed on a transparent support substrate according to the coating step (1). The drying step (2) is optionally performed before the other resin composition is applied. From the viewpoint of suppressing phase mixing, the first irradiation step (3) is preferably performed on the layer formed on the transparent support substrate before the other resin composition is applied. After the other resin composition is applied, the first irradiation step (3) is then performed on the other resin composition.

[0161] FIG. 3 is a flowchart showing the method for manufacturing the laminated film according to the present embodiment. FIG. 3 shows an embodiment in which the first irradiation step is performed after the uncured hard coat layer and the uncured light interference layer are laminated by the lamination method.

[0162] Formed body The molded body according to this embodiment includes the above-described transparent support substrate and a cured resin layer (coating layer after curing) disposed on at least one main surface of the transparent support substrate. The main surface of the cured resin layer opposite to the transparent support substrate includes 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 higher. The molded body may have a three-dimensional shape (three-dimensional shape) together with fine unevenness.

[0163] The molded body is formed by partially imparting unevenness to the coating layer of the laminated film according to this embodiment and curing it. The cured resin layer has the same physical properties as the coating layer irradiated with active energy rays of 1500 mJ / cm 2

[0164] [Cured resin layer] The cured resin layer includes a first region with fine unevenness formed thereon and a second region other than that. A plurality of first regions and / or second regions may be arranged.

[0165] The cured resin layer may be a single layer or may include two or more layers. The cured resin layer includes at least a hard coat layer. In one aspect, the cured resin layer includes a hard coat layer and one or more functional layers (typically, an optical interference layer).

[0166] The molded body is used, for example, as a protective material for a display. In this case, the first region is arranged so as to correspond to the display. The first region can be understood as the display portion of the molded body. The anti-glare property is improved by the unevenness. The first region may be arranged so as to correspond to the operation display portion. The second region is arranged so as to correspond to, for example, a region (bezel) surrounding the periphery of the display. The second region can be understood as the bezel portion of the molded body. The second region has a different texture from the first region, for example, a glossy texture. Therefore, the design of the bezel portion is improved.

[0167] 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 a single cured resin layer. Therefore, by using this molded body, a seamless design can be realized.

[0168] The pencil hardness of the surface of the cured resin layer is H or higher. That is, the cured resin layer has a high hardness. Therefore, the molded body is excellent in scratch resistance, and the unevenness is retained over a long period. The pencil hardness of the surface of the cured resin layer is preferably 2H or higher. The pencil hardness of the surface of the cured resin layer is measured in a region where no unevenness is imparted (for example, the second region). Alternatively, it is measured on the surface of a smooth cured resin layer created for measurement, on which no unevenness is imparted.

[0169] The height of the convex portion is not particularly limited. From the viewpoint of antiglare properties, the height of the convex portion may be, for example, 0.3 μm or more and 4.0 μm or less, or may be 1.0 μm or more and 2.0 μm or less. The height of the convex portion is calculated from a cross-section in the thickness direction of the cured resin layer. The height of the convex portion is the average value at any five 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.

[0170] From the viewpoint of antiglare properties, the ten-point average roughness Rz of the first region JIS is preferably 0.2 μm or more and 1.0 μm or less. The ten-point average roughness Rz JIS is determined, for example, using a laser microscope in accordance with the provisions of JIS B0601; 2001. The ten-point average roughness Rz JIS is specifically the sum of the average of the heights of the five highest peaks from the highest peak (convex portion) and the average of the depths of the five deepest valleys from the deepest valley (concave portion) in the roughness curve of the reference length obtained by applying a cut-off value phase compensation band-pass filter.

[0171] [Decorative layer] The shaped body may further include a decorative layer. For example, the shaped 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 gives the shaped body decorations such as patterns, characters, or metallic luster. The decorative layer enhances the design property of the shaped body. For example, the decorative layer is disposed so as to face the second region. At this time, the decorative layer is visually recognized through the second region.

[0172] Examples of the decorative layer include at least one of a printing layer and a vapor deposition layer. The printing layer and the vapor deposition layer are each one or more layers, and may include a plurality of layers. The thickness of the decorative layer is not particularly limited and is appropriately set according to design properties and the like.

[0173] For example, a wood grain pattern, a stone grain pattern, a cloth grain pattern, a sand grain pattern, a geometric pattern, characters, or a solid color are drawn on the printing layer. The printing layer is formed, for example, with a colored ink containing a binder resin and a colorant. The binder resin is not particularly limited. Examples of the binder resin include polyvinyl resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, cellulose ester resins, alkyd resins, and chlorinated polyolefin resins.

[0174] The colorant is not particularly limited, and examples include known pigments or dyes. Examples of yellow pigments include azo pigments such as polyazo, organic pigments such as isoindolinone, or inorganic pigments such as titanium nickel antimonate. Examples of red pigments include azo pigments such as polyazo, organic pigments such as quinacridone, or inorganic pigments such as cinnabar. Examples of blue pigments include organic pigments such as phthalocyanine blue or inorganic pigments such as cobalt blue. Examples of black pigments include organic pigments such as aniline black. Examples of white pigments include inorganic pigments such as titanium dioxide.

[0175] The vapor deposition layer is formed of at least one metal selected from the group consisting of, for example, aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead, zinc, etc., or an alloy or compound thereof.

[0176] [Molded resin layer] The molded body may further include a molded resin layer. The molded resin layer supports the cured resin layer together with the transparent support substrate. The molded body includes, for example, a transparent support substrate, a cured resin layer disposed on one main surface of the transparent support substrate, and a molded resin layer disposed on the other main surface of the transparent support substrate. The shape of the molded resin layer is not limited. Therefore, the degree of freedom in the design of the molded body is increased.

[0177] The resin forming the molded resin layer is not particularly limited. The molded resin layer includes, for example, a thermosetting resin and / or a thermoplastic resin. Examples of the thermosetting resin include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester, and 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, and liquid crystal polymer.

[0178] 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 molded resin layer. The decorative layer is disposed, for example, so as to be sandwiched between the cured resin layer and the molded resin layer, or on the surface of the molded resin layer opposite to the cured resin layer.

[0179] The molded body is particularly suitable as a protective material for a display. Examples of the display include a liquid crystal display, an organic EL display, and a plasma display. The molded body is particularly suitable as a protective material for an in-vehicle touch panel display. The molded body is arranged such that the first region faces the information display portion of the display. The molded body is arranged such that the hard coat layer faces outward. The molded body is also particularly suitable as an instrument panel and / or a center cluster panel that also serves as a protective material for the display.

[0180] FIG. 4 is a cross-sectional view schematically showing the molded body according to the present 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.

[0181] FIG. 5 is a cross-sectional view schematically showing another molded body according to the present 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 molded resin layer 24. The decorative layer 23 is disposed so as to face the second region 222 and be sandwiched between the cured resin layer 22 and the molded resin layer 24.

[0182] FIG. 6 is a cross-sectional view schematically showing another molded body according to the present 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 molded resin layer 24. The decorative layer 23 is disposed so as to face the second region 222 and on the side opposite to the cured resin layer 22 of the molded resin layer 24.

[0183] FIG. 7 is a perspective view schematically showing still 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 molded 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 a car 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 an operation display portion. The second region 222 corresponds to a bezel surrounding the display.

[0184] Method for manufacturing a formed body The molded body according to the present embodiment is obtained by forming irregularities in the coating layer of the laminated film and then performing irradiation with active energy rays (second irradiation step). Thereby, a plurality of regions having different textures, for example, an uneven region and a smooth region, can be simultaneously formed in the coating layer. As described above, the coating layer is curable by active energy rays, and is obtained, for example, by performing the first irradiation step on an uncured resin composition.

[0185] A molded body including a decorative layer is obtained by forming a decorative layer on a laminated body (hereinafter referred to as a precursor of the laminated film) including a laminated film, a transparent support substrate, and an uncured resin composition layer, or on a molded body. The step of forming the decorative layer (decorative step) may be performed before the first irradiation step, may be performed after the second irradiation step, or may be performed between the first irradiation step and the second irradiation step.

[0186] A molded body having a three-dimensional shape is obtained by injection molding a laminated film. The injection molding step is performed before, after, or in parallel with the unevenness forming step. Among these, it is preferable that the injection molding step and the unevenness forming step are performed in parallel, that is, fine unevenness and a three-dimensional shape are formed in one step.

[0187] Before the injection molding process, it is desirable to perform a preform process. In the preform process, a laminated film or a precursor of the laminated film is preformed into a shape close to a three-dimensional shape in advance. Thereby, in injection molding, a desired three-dimensional shape can be obtained more easily.

[0188] In one aspect, the method for manufacturing a molded body includes a concavo-convex forming step on a laminated film and a second irradiation step. FIG. 8 is a flowchart showing the method for manufacturing a molded body according to the present embodiment.

[0189] In one aspect, the method for manufacturing a molded body includes a decorating step on a laminated film, a preform step, a concavo-convex forming step (and an injection molding step), and a second irradiation step. FIG. 9 is a flowchart showing the method for manufacturing a molded body according to the present embodiment.

[0190] In one aspect, the method for manufacturing a molded body includes a decorating step on a precursor of a laminated film, a preform step, a first irradiation step, a concavo-convex forming step (and an injection molding step), and a second irradiation step. FIG. 10 is a flowchart showing the method for manufacturing a molded body according to the present embodiment. Hereinafter, each step will be described.

[0191] (i) Preparation of laminated film For example, the laminated film produced as described above is prepared.

[0192] (ii) Production of precursor of laminated film For example, a precursor of a laminated film produced by a method including the above coating step (1) and drying step (2) is prepared.

[0193] (iii) First irradiation step (S25) In this step, in the same manner as the first irradiation step (3) of the method for manufacturing a laminated film, the resin composition is irradiated with actinic energy rays of 5 mJ / cm 2 or more and 150 mJ / cm 2 or less.

[0194] In the first irradiation step, the resin composition is semi-cured to form a coating layer. The indentation hardness H 100 of the coating layer is 0.30 GPa or more and 0.65 GPa or less. The indentation hardness HB 2000 of the coating layer is 0.15 GPa or more and 0.35 GPa or less. The indentation hardness HB 2000 is the indentation hardness HB 100 and is smaller.

[0195] (iv) Decoration step (S23) In this step, the above-described decoration layer is formed on the other main surface of the transparent support substrate or the surface of the molded resin layer opposite to the cured resin layer.

[0196] The method for forming the printing layer is not particularly limited. Examples of the method for forming the printing layer include an offset printing method, a gravure printing method, a screen printing method, a roll coating method, and a spray coating method. The method for forming the vapor deposition layer is also not particularly limited. Examples of the method for forming the vapor deposition layer include a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plating method.

[0197] (v) Preform step (S24) In this step, a shape along a desired three-dimensional shape is formed on the laminated film or its precursor. After the preform step, a trimming step of removing unnecessary portions of the laminated film or its precursor may be performed.

[0198] The method for preforming is not particularly limited. The preform is performed, for example, by a vacuum forming method, a pressure air forming method, or a vacuum pressure air forming method. In the preform, the first mold and the laminated film or its precursor are installed in the same processing chamber. The laminated film or its precursor is installed such that the transparent support substrate faces the first mold. The laminated film or its precursor is heated to a temperature equal to or higher than the Tg of the resin composition, and the processing chamber is brought into a vacuum state and / or a pressurized state. Thereby, the laminated film or its precursor is deformed along the first mold. Next, the laminated film or its precursor is cooled and removed from the first mold.

[0199] The material of the first mold is not particularly limited. The first mold may be made of resin or metal.

[0200] The resin composition to be subjected to the preform process is in an uncured or semi-cured state. Therefore, the laminated film or its precursor can be easily deformed along the first mold without generating cracks. Thus, a complex three-dimensional shape is realized. The resin composition after the preform process is still in an uncured or semi-cured state.

[0201] (vi) Concavo-convex forming step (S21) In this step, a coating layer containing a semi-cured resin composition is brought into contact with a mold (second mold) having concavo-convexities to form concavo-convexities in a part of the coating layer.

[0202] The indentation hardness HB by nanoindentation method at an indentation depth of 100 nm of the coating layer 100 is 0.30 GPa or more and 0.65 GPa or less. The indentation hardness HB by nanoindentation method at an indentation depth of 2000 nm of the coating layer 2000 is 0.15 GPa or more and 0.35 GPa or less. The indentation hardness HB 2000 is the indentation hardness HB 100 is smaller. Therefore, the coating layer exhibits excellent mold release property and shapeability.

[0203] The material of the second mold is not particularly limited. The second mold may be made of resin or metal. Regardless of the material of the mold, the coating layer can be easily peeled off from the mold.

[0204] In this step, a three-dimensional shape may be imparted together with the concavo-convexities. In this case, a second mold having a desired three-dimensional shape together with the concavo-convexities is used.

[0205] When the coating layer is disposed on one main surface of the transparent support substrate, the unevenness may be imparted by an injection molding method (for example, an insert molding method). In injection molding, for example, the coating layer is opposed to a second mold having unevenness partially, and a molding resin is injected toward the transparent support substrate. Thereby, unevenness is formed in a part of the coating layer, and a molded resin layer is formed on the other main surface of the transparent support substrate.

[0206] The laminated film includes a coating layer in a semi-cured state. Therefore, the laminated film can follow molds of various shapes. Further, even when there is a dimensional difference between the three-dimensional shape formed by the preform and the second mold used in this step, the occurrence of cracks is suppressed.

[0207] (vii) Second irradiation step (S22) In this step, the coating layer is irradiated with active energy rays. Thereby, the coating layer is completely cured to form a cured resin layer.

[0208] The active energy rays are irradiated so that, for example, the pencil hardness of the cured resin layer becomes H or more. The integrated light quantity of the active energy rays in this step is 150 mJ / cm 2 or more, and for example, 300 mJ / cm 2 or more and 2000 mJ / cm 2 or less.

[0209] In the method for manufacturing a molded body according to the present embodiment, an unevenness forming step is performed on a laminated film including a coating layer in a semi-cured state. Therefore, dense unevenness can be imparted to the laminated film with high precision. Further, the laminated film can be molded into various three-dimensional shapes without generating cracks. Then, after the unevenness forming step is completed, the resin composition is cured. Therefore, the imparted shape is maintained over a long period of time.

Example

[0210] The present invention will be described in more detail by the following examples, but the present invention is not limited thereto. In the examples, "parts" and "%" are based on mass unless otherwise specified. The number of mixing parts is the mass of the solid content in each case.

[0211] Each component used in the examples and comparative examples in this specification is as follows. (Non-polymerizable polymer) Acrylic polymer A: Mw 60,000 (Polymerizable polymer) Acrylic polymer B: Mw 20,000

[0212] Acrylic polymers A and B were prepared as follows. [Preparation of acrylic polymer A] A mixture consisting of 30 parts of n-butyl methacrylate, 70 parts of methyl methacrylate, and 0.8 part of t-butyl peroxy-2-ethylhexanoate was prepared. Separately, 40 parts of toluene was charged into a 500 ml reaction vessel equipped with a stirring blade, a nitrogen inlet tube, a cooling tube, and a dropping funnel, and heated to 110°C. While stirring the inside of this reaction vessel, the above mixture was dropped at a constant rate over 2 hours under a nitrogen atmosphere. After the dropping was completed, the reaction was carried out at a temperature of 110°C for 1 hour. Then, a mixed solution of 1 part of t-butyl peroxy-2-ethylhexanoate and 25 parts of toluene was dropped into the above reaction vessel over 1 hour. Next, the inside of the reaction vessel was heated to 145°C and further reacted for 2 hours. Subsequently, the inside of the reaction vessel was cooled to 110°C or lower, and 59 parts of toluene was further added. Thereby, acrylic polymer A having a weight average molecular weight of 60,000 was obtained.

[0213] [Preparation of acrylic polymer B] A mixture consisting of 30 parts of 2,3-epoxypropyl methacrylate, 70 parts of methyl methacrylate, and 10 parts of t-butyl peroxy-2-ethylhexanoate was prepared. Separately, 40 parts of toluene was charged into a 500 ml reaction vessel equipped with a stirring blade, a nitrogen inlet tube, a cooling tube, and a dropping funnel, and heated to 110°C. While stirring the inside of this reaction vessel, the above mixture was dropped at a constant rate over 2 hours under a nitrogen atmosphere. After completion of the dropping, the reaction was carried out for 1 hour under the temperature condition of 110°C. Then, a mixed solution of 1 part of t-butyl peroxy-2-ethylhexanoate and 25 parts of toluene was dropped into the above reaction vessel over 1 hour. Next, the inside of the reaction vessel was heated to 145°C and reacted for another 2 hours. Subsequently, the inside of the reaction vessel was cooled to 110°C or lower, and 59 parts of toluene was further added to obtain precursor B1.

[0214] In another reaction vessel of the same shape as 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 respectively charged, air was blown in, and while stirring, it was heated to 90°C. Under the temperature condition of 90°C, a mixed solution of 3 parts of toluene and 0.81 part of tetrabutylammonium bromide was further added to this reaction vessel and reacted for 1 hour. Subsequently, it was heated to 105°C and the reaction was carried out under the temperature condition of 105°C until the acid value of the solid content in the reaction solution became 8 or less. Then, 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. Subsequently, a mixed solution of 10.1 parts of Karenz MOI (manufactured by Showa Denko K.K., 2-methacryloyloxyethyl isocyanate), 5.0 parts of toluene, and 0.043 part of dibutyltin dilaurate was added and reacted for 2 hours under the temperature condition of 70°C. Then, it was cooled to 60°C or lower, and a mixed solution of 2 parts of methanol and 10 parts of toluene was added. Thereby, an acrylic polymer B having a weight average molecular weight of 20,000 was obtained.

[0215] The acid value was measured by titrating the above reaction solution with 0.1 N potassium hydroxide (KOH) solution in accordance with JIS K5601-2-1, and calculated according to the following formula: acid value = {(the amount of KOH solution dropped [ml]) × (molar concentration of KOH solution [mol / L])} / (mass of solid content [g]).

[0216] (Violet light UV-AF305A) Fluorine-containing polyfunctional silicone urethane acrylate oligomer Manufactured by Mitsubishi Chemical Corporation (KRM-8452) Polyfunctional urethane acrylate oligomer Manufactured by Daicel Ornex Co., Ltd. Mw3,884

[0217] (CN-9893) Bifunctional urethane acrylate oligomer Manufactured by Sartomer Company (Aronix M-402) Polyfunctional acrylic monomer Manufactured by Toagosei Co., Ltd. (Aronix M-315) Trifunctional acrylic monomer Manufactured by Toagosei Co., Ltd. (Art Resin H-7M40) Tetrafunctional urethane acrylate oligomer Manufactured by Negami Kogyo Co., Ltd. Mw = 1000~1500 (Art Resin UN-904M) Decafunctional urethane acrylate oligomer Manufactured by Negami Kogyo Co., Ltd. Mw = 4900

[0218] (ELCOM V-8802) Filler (silica fine particles, primary particle diameter of about 10 nm) Manufactured by JGC Catalysts & Chemicals Ltd. (HX-204 IP) Filler (rhodium-doped tin oxide sol, primary particle diameter of 5 nm to 20 nm) Manufactured by Nissan Chemical Industries, Ltd. (Through Lia 4320) Refractive index lowering particles (hollow silica fine particles, volume average particle diameter 55 nm) Manufactured by Nichi Asahi Catalyst Kasei Co., Ltd.

[0219] (Omnirad 184) Photoinitiator Manufactured by IGM Resins B.V. (Omnirad TPO H) Photoinitiator Manufactured by IGM Resins B.V.

[0220] [Example 1] (1) Preparation of resin composition HC1 In a container charged 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 with respect to a total of 100 parts of the above resin components and Elcom V-8802, and 3.9 parts of Omnirad TPO H with respect to a total of 100 parts of the above resin components and Elcom V-8802 were mixed to produce a transparent resin composition HC1 with a solid content concentration of 35%.

[0221] (2) Preparation of laminated film On the PMMA surface of a transparent support substrate (a two-layer film composed of PMMA and PC, trade name: AW-10U, manufactured by Shine Tech Co., Ltd., total thickness 250 μm, PMMA layer thickness 35 μm, PC layer thickness 215 μm), the resin composition HC1 was applied by a bar coater and dried at 80°C for 1 minute to volatilize the solvent. Subsequently, the coating film was irradiated with active energy rays (ultraviolet rays) having an integrated light amount of 35 mJ / cm 2 to obtain a laminated film A1 having a semi-cured coating layer (hard coat layer). The film thickness of the coating layer was 8 μm.

[0222] (3) Preparation of molded article (3-1) Formation of printing layer On the main surface of the fabricated laminated film A1 opposite to the coating layer 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 for the formation of the printing layer.

[0223] (3-2) Preform The laminated film provided with the printing layer was heated to 160 °C, and a preform was formed by a vacuum pressure molding method. Subsequently, trimming was performed.

[0224] (3-3) Formation of unevenness Insert molding was performed using a mold having unevenness in part. The mold was heated to 80 °C. As the molding resin, a polycarbonate resin was used. The maximum height of the convex portion of the mold was 2.0 μm, and the ten-point average roughness Rz JIS was 1.5 μm.

[0225] (3-4) Irradiation with active energy rays The coating layer was irradiated with active energy rays (ultraviolet rays) having an integrated light quantity of 1500 mJ / cm 2 . As a result, a molded body X1 including a transparent support substrate, a cured resin layer (hard coat layer) disposed on one main surface of the transparent support substrate, a printing layer disposed on the other main surface of the transparent support substrate, and a molding resin layer was obtained. The surface of the cured resin layer included a first region formed by transferring the unevenness of the mold and a smooth second region.

[0226] [Evaluation] The following evaluations were performed on the laminated film A1 or the molded body X1. The results are shown in Table 1.

[0227] (a) Release property The second region of the cured resin layer of the molded body was visually observed and evaluated according to the following criteria. Best: No roughness and whitening generated during mold peeling are confirmed on the surface. Good: Slight roughness and whitening generated during mold peeling are confirmed on the surface, but there is no significant deterioration in texture. Acceptable: Roughness and whitening occurred during mold release can be confirmed on the surface, but there is no significant reduction in texture. Defective: Roughness and whitening occurred during mold release can be confirmed on the surface, and a significant reduction in texture is observed.

[0228] (b) Shapeability The first region of the cured resin layer of the molded body was visually observed and evaluated according to the following criteria. Best: Sufficient anti-glare property is obtained, and it can be determined that the height of the convex part is 80% or more of the maximum height of the convex part of the mold. Good: Practically sufficient anti-glare property is obtained, and it can be determined that the height of the convex part is 50% or more and less than 80% of the maximum height of the convex part of the mold. Defective: The anti-glare property is insufficient, and it can be determined that the height of the convex part is less than 50% of the maximum height of the convex part of the mold.

[0229] (c) Shape retention 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, it was evaluated according to the same criteria as in shapeability (b).

[0230] (d) Indentation hardness It was measured by the continuous stiffness measurement method (used method: Advanced Dynamic E and H.NMT) using an iMicro Nanoindenter manufactured by NANOMECHANICS, INC.

[0231] Specifically, a minute AC load was superimposed on a quasi-static test load and applied to the surface of the laminated film. The load was applied until it reached a maximum load of 50 mN. As the indenter, a Berkovich-type diamond indenter (tip radius of curvature 20 nm) was used. From the vibration component of the generated displacement and the phase difference between the displacement and the load, the continuous stiffness with respect to the depth was calculated to obtain the hardness profile with respect to the depth. The hardness at a depth of 100 nm in this profile was defined as the indentation hardness HB 100 and the hardness at 2000 nm was defined as the indentation hardness HB 2000It was set as such. iMicro dedicated software was used for the calculation of load and stiffness. When calculating the stiffness, the Poisson's ratio of the coating layer was set to 0.35. The load was controlled such that the strain rate (∂P / ∂t) / P was 0.2. When performing analysis with the iMicro dedicated software, as the surface position of the coating layer, the point tentatively defined on the iMicro dedicated software during measurement (the point where d(Force) / d(Disp) is approximately 500 N / m) was set as it is.

[0232] (e) Polymerization rate For the uncured laminated film and the semi-cured laminated film, FT-IR analysis was performed according to the above method, and the infrared absorption spectra of each were obtained. From the infrared absorption spectra, the polymerization rates PB and PA were calculated according to the above method.

[0233] (f) Elongation rate It was measured in accordance with JIS K 7127. Specifically, a test piece with a length of 200 mm × width of 10 mm was cut out from the laminated film. This test piece was set in a tensile testing machine with a chuck distance of 150 mm, and the test piece was stretched by 2.5% under the conditions of an atmosphere of 160°C and a tensile speed of 300 mm / min. Then, the test piece was observed with a microscope at a magnification of 1000 times or more to confirm the presence or absence of cracks with a size exceeding 1 mm in length. If no cracks occurred, a new test piece was cut out and next the long side was stretched by 5%. And the observation of crack generation was carried out in the same procedure. This procedure was repeated while increasing the elongation rate by 2.5% each time. The elongation rate when the cracks of the above size were confirmed for the first time was taken as the elongation rate of the laminated film. Three test pieces were made from the same laminated film, and the average value of the elongation rates calculated for each was taken as the elongation rate of the laminated film.

[0234] (g) Pencil hardness In accordance with JIS K 5600-5-4 (1999) Scratch hardness (pencil method), the pencil hardness in the second region of the cured resin layer of the molded body was measured.

[0235] [Example 2] In the production of the laminated film (2), a laminated film A2 was obtained in the same manner as in Example 1, except that the film thickness of the coating layer was set to 6 μm. Using the laminated film A2, a molded body X2 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film A2 and the molded body X2. The results are shown in Table 1.

[0236] [Example 3] In the production of the laminated film (2), a laminated film A3 was obtained in the same manner as in Example 1, except that the film thickness of the coating layer was set to 10 μm. Using the laminated film A3, a molded body X3 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film A3 and the molded body X3. The results are shown in Table 1.

[0237] [Example 4] In the production of the laminated film (2), a laminated film A4 was obtained in the same manner as in Example 1, except that the active energy rays were irradiated in a nitrogen atmosphere. Using the laminated film A4, a molded body X4 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film A4 and the molded body X4. The results are shown in Table 1.

[0238] [Example 5] In the production of the laminated film (2), a laminated film A5 was obtained in the same manner as in Example 1, except that the active energy rays were irradiated so that the integrated light quantity became 7.5 mJ / cm 2 . Using the laminated film A5, a molded body X5 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film A5 and the molded body X5. The results are shown in Table 1.

[0239] [Example 6] In the production of the laminated film (2), a laminated film A6 was obtained in the same manner as in Example 1, except that the active energy rays were irradiated so that the integrated light quantity became 100 mJ / cm 2 . Using the laminated film A6, a molded body X6 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film A6 and the molded body X6. The results are shown in Table 1.

[0240] [Comparative Example 1] In the production of the laminated film (2), a laminated film B1 was obtained in the same manner as in Example 1, except that the active energy ray was not irradiated. Using the laminated film B1, a molded body Y1 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film B1 and the molded body Y1. The results are shown in Table 1.

[0241] [Comparative Example 2] In the production of the laminated film (2), a laminated film B2 was obtained in the same manner as in Example 1, except that the active energy ray was irradiated so that the integrated light quantity became 200 mJ / cm 2 . Using the laminated film B2, a molded body Y2 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film B2 and the molded body Y2. The results are shown in Table 1.

[0242] [Comparative Example 3] In the production of the laminated film (2), a laminated film B3 was obtained in the same manner as in Example 1, except that the active energy ray was irradiated so that the integrated light quantity became 500 mJ / cm 2 . Using the laminated film B3, a molded body Y3 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film B3 and the molded body Y3. The results are shown in Table 1.

[0243] [Comparative Example 4] In the production of the laminated film (2), a laminated film B4 was obtained in the same manner as in Example 1, except that the active energy ray was irradiated so that the integrated light quantity became 1500 mJ / cm 2 . Using the laminated film B4, a molded body Y4 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film B4 and the molded body Y4. The results are shown in Table 1.

[0244]

Table 1

[0245] All of the molded articles of Examples 1 to 6 were excellent in mold release properties and shapeability. Furthermore, the shape retention was also high. Also, no visible cracks were confirmed in these molded articles. Comparative Example 1 is an example in which both the indentation hardness HB 100 and also HB 2000 are small. In this example, the mold release properties and shapeability are low. Comparative Examples 2 to 4 are examples in which the indentation hardness HB 2000 is large. Also in these examples, the shapeability is low. In Comparative Examples 3 and 4, the shape retention was also low.

[0246] [Example 7] (1) Preparation of Resin Composition HC2 Into a container containing propylene glycol monomethyl ether, 43 parts of acrylic polymer A, 42 parts of Allnex M-402, 15 parts of ELCOM V-8802, 2.9 parts of Omnirad184 with respect to 100 parts in total of the above resin components and ELCOM V-8802, and 3.9 parts of Omnirad TPO H with respect to 100 parts in total of the above resin components and ELCOM V-8802 were mixed to produce a transparent resin composition HC2 having a solid content concentration of 35%.

[0247] (2) Production of Laminated Film A laminated film A7 was obtained in the same manner as in Example 6, except that resin composition HC2 was used instead of resin composition HC1. (3) Production of Molded Article Using the laminated film A7, a molded article X7 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film A7 and the molded article X7. The results are shown in Table 2.

[0248] [Example 8] (1) Preparation of Resin Composition HC3 Into 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 with respect to 100 parts of the above resin components, and 3.9 parts of Omnirad TPO H with respect 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%.

[0249] (2) Preparation of laminated film A laminated film A8 was obtained in the same manner as in Example 6, except that resin composition HC3 was used instead of resin composition HC1. (3) Preparation of molded body Using the laminated film A8, a molded body X8 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film A8 and the molded body X8. The results are shown in Table 2.

[0250] [Example 9] (1) Preparation of resin composition HC4 Into a container containing propylene glycol monomethyl ether, 73 parts of acrylic polymer B, 12 parts of Violet UV-AF305A, 15 parts of ELCOM V-8802, 2.9 parts of Omnirad 184 with respect to a total of 100 parts of the above resin components and ELCOM V-8802, and 3.9 parts of Omnirad TPO H with respect 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%.

[0251] (2) Preparation of laminated film A laminated film A9 was obtained in the same manner as in Example 6, except that resin composition HC4 was used instead of resin composition HC1. (3) Preparation of molded body Using the laminated film A9, a molded body X9 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film A9 and the molded body X9. The results are shown in Table 2.

[0252] [Example 10] (1) Preparation of resin composition HC5 Into a container containing propylene glycol monomethyl ether, 85 parts of acrylic polymer B, 15 parts of ELCOM V-8802, 2.9 parts of Omnirad184 with respect to 100 parts in total of the above resin components and ELCOM V-8802, and 3.9 parts of Omnirad TPO H with respect to 100 parts in total 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%.

[0253] (2) Preparation of laminated film A laminated film A10 was obtained in the same manner as in Example 6, except that resin composition HC5 was used instead of resin composition HC1. (3) Preparation of molded body Using the laminated film A10, a molded body X10 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film A10 and the molded body X10. The results are shown in Table 2.

[0254] [Example 11] (1) Preparation of resin composition HC6 Into a container containing propylene glycol monomethyl ether, 100 parts of acrylic polymer B, 2.9 parts of Omnirad184 with respect to 100 parts of the above resin components, and 3.9 parts of Omnirad TPO H with respect to 100 parts of the above resin components were mixed to produce a transparent resin composition HC6 with a solid content concentration of 35%.

[0255] (2) Preparation of laminated film A laminated film A11 was obtained in the same manner as in Example 6, except that resin composition HC6 was used instead of resin composition HC1. (3) Preparation of molded body Using the laminated film A11, a molded body X11 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film A11 and the molded body X11. The results are shown in Table 2.

[0256] [Example 12] (1) Preparation of resin composition HC7 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 with respect to 100 parts of the above resin components, and 3.9 parts of Omnirad TPO H with respect to 100 parts of the above resin components were mixed to produce a transparent resin composition HC7 with a solid content concentration of 35%.

[0257] (2) Preparation of laminated film Except that resin composition HC7 was used instead of resin composition HC1, the film thickness of the coating layer was made 3 μm, and the active energy ray was irradiated so that the integrated light amount became 150 mJ / cm 2 A laminated film A12 was obtained in the same manner as in Example 1. (3) Preparation of molded body Using the laminated film A12, a molded body X12 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film A12 and the molded body X12. The results are shown in Table 2.

[0258] [Example 13] (1) Preparation of resin composition HC8 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 with respect to 100 parts of the above resin components, and 3.9 parts of Omnirad TPO H with respect to 100 parts of the above resin components were mixed to produce a transparent resin composition HC8 with a solid content concentration of 35%.

[0259] (2) Preparation of laminated film Except that resin composition HC8 was used instead of resin composition HC1, the film thickness of the coating layer was made 3 μm, and the active energy ray was irradiated so that the integrated light amount became 150 mJ / cm 2 A laminated film A13 was obtained in the same manner as in Example 1. (3) Preparation of molded body Using the laminated film A13, a molded article X13 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film A13 and the molded article X13. The results are shown in Table 2.

[0260] [Comparative Example 5] (1) Preparation of Resin Composition HC9 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 with respect to a total of 100 parts of the above resin components and ELCOM V-8802, and 3.9 parts of Omnirad TPO H with respect 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%.

[0261] (2) Production of Laminated Film A laminated film B5 was obtained in the same manner as in Example 6, except that the resin composition HC9 was used instead of the resin composition HC1. (3) Production of Molded Article Using the laminated film B5, a molded article Y5 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film B5 and the molded article Y5. The results are shown in Table 2.

[0262] [Comparative Example 6] (1) Preparation of Resin Composition HC10 In a container containing propylene glycol monomethyl ether, 100 parts of Violet UV-AF305A, 2.9 parts of Omnirad184 with respect to 100 parts of the above resin components, and 3.9 parts of Omnirad TPO H with respect to 100 parts of the above resin components were mixed to produce a transparent resin composition HC10 with a solid content concentration of 35%.

[0263] (2) Production of Laminated Film A laminated film B5 was obtained in the same manner as in Example 6, except that the resin composition HC10 was used instead of the resin composition HC1. (3) Production of Molded Article Using the laminated film B5, a molded body Y6 was obtained in the same manner as in Example 1. The above evaluations were performed on the laminated film B6 and the molded body Y6. The results are shown in Table 2.

[0264]

Table 2

[0265] All of the molded bodies of Examples 7 to 13 are excellent in releasability and formability. No visible cracks were confirmed in the molded bodies of Examples 7 to 12. In the molded bodies of Examples 7 to 11, furthermore, the shape retention is also high. Comparative Example 5 is an example where the indentation hardness HB 2000 is excessively large. In this example, the formability is low. In addition, the shape retention was also low. Comparative Example 6 is an example where the indentation hardness HB 2000 is large. In this example, the formability is low.

[0266] [Example 14] (1) Preparation of Resin Composition LR In a container into which propylene glycol monomethyl ether was charged, 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 Light UV-AF305A, and 4.8 parts by mass of Omnirad 184 were mixed. Further, 43.8 parts by mass of Throughia 4320 was mixed. Thereby, 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 by the resin composition LR was 1.20 or more and 1.55 or less.

[0267] (2) Production of Laminated Film (2-1) Formation of Uncured Optical Interference Layer (Low Refractive Index Layer) The resin composition LR was applied to an OPP film (protective film) with a bar coater so that the thickness after drying was 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.

[0268] (2-2) Formation of an uncured hard coat layer In the same manner as in Example 1, an uncured hard coat layer with a thickness of 12 μm after drying was formed on a transparent support substrate.

[0269] (2-3) Lamination of the uncured hard coat layer and the low refractive index layer The surface of the uncured hard coat layer supported by the transparent support substrate was bonded to the surface of the uncured low refractive index layer of the transfer film C-1. Subsequently, the protective film was peeled off.

[0270] (2-4) Irradiation with active energy rays Subsequently, the obtained laminate was irradiated with active energy rays (ultraviolet rays) having an integrated light quantity of 35 mJ / cm 2 . As a result, a laminated film A14 having a transparent support substrate, a semi-cured hard coat layer, and a semi-cured low refractive index layer in this order was produced.

[0271] (3) Production of a molded body A molded body X14 including a transparent support substrate, a hard coat layer disposed on one main surface of the transparent support substrate, a low refractive index layer disposed on the hard coat layer, a printing layer disposed on the other main surface of the transparent support substrate, and a molding resin layer was obtained in the same manner as in Example 1, except that the uncured laminated film A14 was used instead of the laminated film A1. The above evaluations were performed on the laminated film A14 and the molded body X14. The results are shown in Table 3.

[0272] [Example 15] (1) Preparation of resin composition HR In a container into which propylene glycol monomethyl ether was introduced, 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. Further, 86.5 parts by mass of HX-204 IP was mixed. Thereby, 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 by the resin composition HR was more than 1.55 and 2.00 or less.

[0273] (2) Preparation of laminated film (2-1) Formation of uncured optical interference layer (high refractive index layer) Resin composition R2 was applied to an OPP film (protective film) using a bar coater so that the thickness after drying was 95 nm. Then, it was dried at 80°C for 1 minute to volatilize the solvent, and a transfer film C-2 with an uncured high refractive index layer formed thereon was obtained.

[0274] (2-2) Formation of uncured hard coat layer In the same manner as in Example 1, an uncured hard coat layer with a thickness of 8 μm after drying was formed on a transparent support substrate.

[0275] (2-3) Formation of uncured low refractive index layer In the same manner as in Example 14, a transfer film C-1 with an uncured low refractive index layer formed thereon was obtained.

[0276] (2-4) Lamination of uncured hard coat layer, low refractive index layer and high refractive index layer 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 layer supported by a transparent support substrate.

[0277] Next, the protective film of the transfer film C-2 was peeled off to expose the uncured high refractive index layer. Subsequently, 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, the laminate was irradiated with active energy rays (ultraviolet rays) having an integrated light quantity of 35 mJ / cm 2 to obtain a laminated film A15 having an uncured hard coat layer, a high refractive index layer and a low refractive index layer in this order.

[0278] (3) Preparation of molded body A molded body X15 was obtained in the same manner as in Example 14, except that the laminated film A15 was used instead of the laminated film A14. The above evaluations were performed on the laminated film A15 and the molded body X15. The results are shown in Table 3.

[0279] In Examples 14 and 15, the visual reflectance of the obtained molded article was further evaluated. (h) Visual reflectance On the surface of the transparent support substrate of the laminated film opposite to the hard coat layer, a black paint (product name: CZ-805 BLACK (manufactured by Nichihiro Bix Co., Ltd.)) was applied using a bar coater so that the dry film thickness was 3 μm or more and 6 μm or less. Next, the laminated film coated with the black paint was left to stand at room temperature for 5 hours for drying. Subsequently, an evaluation sample cured by irradiating active energy rays with an integrated light quantity of 1500 mJ / cm 2 was prepared.

[0280] The visual reflectance by the SCI method was measured and evaluated from the light interference layer side of the evaluation sample. For the measurement, SD7000 manufactured by Nippon Denshoku Industries Co., Ltd. was used, and the measurement wavelength range was set to 380 nm or more and 780 nm or less.

[0281] [Table 3]

[0282] Both of the molded articles of Examples 14 and 15 are excellent in releasability, formability, and shape retention. Furthermore, no visible cracks were confirmed in these molded articles. In addition, it can be seen that the visual reflectance of the molded article is small and has excellent antireflection performance.

Industrial Applicability

[0283] According to the present invention, a laminated film excellent in formability and releasability of fine irregularities can be provided. Therefore, this laminated film is preferably used particularly for manufacturing a protective material for a display having a seamless design.

[0284] This application claims priority based on Japanese Patent Application No. 2020-088300 filed in Japan on May 20, 2020, and all of the descriptions thereof are incorporated herein by reference.

Explanation of Reference Numerals

[0285] 10 laminated film 11 transparent support substrate 12 coating layer 20A, 20B, 20C, 20D shaped body 22 cured resin layer 221 first region 222 second region 23 decorative layer 24 shaped resin layer

Claims

1. A transparent support substrate; A coating layer disposed on at least one main surface of the transparent support substrate, The coating layer contains an active energy ray-curable resin composition, The thickness of the coating layer is greater than 2 μm; Indentation hardness HB of the coating layer at an indentation depth of 100 nm measured by nanoindentation method １００ is 0.30 GPa or more and 0.65 GPa or less, Indentation hardness HB of the coating layer at an indentation depth of 2000 nm measured by nanoindentation method ２０００ is 0.15 GPa or more and 0.35 GPa or less, The indentation hardness HB ２０００ is the indentation hardness HB １００ Smaller, laminated film.

2. The polymerization rate PB of the resin composition and the active energy ray of 1500 mJ / cm ２ The laminated film according to claim 1 , wherein a difference between a polymerization rate PA of the resin composition in the coating layer after irradiation and a polymerization rate PA of the resin composition in the coating layer after irradiation is 15% or more.

3. Active energy rays at 1500 mJ / cm ２ 3. The laminated film according to claim 1, wherein the surface of the coating layer after irradiation has a pencil hardness of H or more.

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

5. The laminate film according to any one of claims 1 to 4, wherein the coating layer has a thickness of 3 µm or more and 20 µm or less.

6. The laminate film according to any one of claims 1 to 5, wherein the transparent supporting substrate has a thickness of 75 µm or more and 500 µm or less.

7. A coating step of coating at least one main surface of a transparent support substrate with an active energy ray-curable resin composition; 5 mJ / cm ２ More than 150mJ / cm ２ A first irradiation step of irradiating the coating layer with the following active energy rays, The thickness of the coating layer is greater than 2 μm; Indentation hardness HB of the coating layer at an indentation depth of 100 nm measured by nanoindentation method １００ is 0.30 GPa or more and 0.65 GPa or less, Indentation hardness HB of the coating layer at an indentation depth of 2000 nm measured by nanoindentation method ２０００ is 0.15 GPa or more and 0.35 GPa or less, The indentation hardness HB ２０００ is the indentation hardness HB １００ A method for manufacturing smaller laminated films.

8. A transparent support substrate; A cured resin layer is disposed on at least one main surface of the transparent support substrate, a main surface of the cured resin layer opposite to the transparent support substrate includes a first region having projections and recesses and a second region other than the first region; The first region and the second region are integrally formed, The molded product, wherein the pencil hardness of the surface of the cured resin layer is H or more.

9. the cured resin layer is disposed on one main surface of the transparent support substrate, The molded article according to claim 8 , further comprising a decorative layer disposed on the other main surface of the transparent support substrate.

10. the cured resin layer is disposed on one main surface of the transparent support substrate, The molded article according to claim 8 or 9, further comprising a molded resin layer disposed on the other main surface of the transparent supporting substrate.

11. A step of contacting the coating layer of the laminated film according to any one of claims 1 to 6 with a mold having projections and recesses to form projections and recesses in a part of the coating layer; a second irradiation step of irradiating the coating layer with active energy rays after the unevenness forming step to obtain a cured resin layer.

12. The method for producing a molded body according to claim 11 , wherein in the second irradiation step, the active energy rays are irradiated so that a pencil hardness of the surface of the cured resin layer becomes H or more.

13. In the laminate film, the coating layer is disposed on one main surface of the transparent support substrate, The method for producing a molded article according to claim 11 or 12, wherein a decorative layer is disposed on the other main surface of the transparent support substrate.

14. In the laminate film, the coating layer is disposed on one main surface of the transparent support substrate, The method for producing a molded body according to any one of claims 11 to 13, wherein in the unevenness forming step, the coating layer is opposed to the metal mold, and a molding resin is injected toward the transparent support substrate to form a molded resin layer together with the unevenness on the coating layer.

15. The mold imparts a three-dimensional shape to the laminate film, The method for producing a molded article according to claim 14, further comprising a preforming step of molding the laminated film into a shape that conforms to the three-dimensional shape before the unevenness forming step.

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