WO2021235493A1

WO2021235493A1 - Multilayer film, molded body, method for producing multilayer film, and method for producing molded body

Info

Publication number: WO2021235493A1
Application number: PCT/JP2021/019013
Authority: WO
Inventors: 慶滝川; 武喜細川; 純平高橋; 剛司中出; 和人小林
Original assignee: 日本ペイント・オートモーティブコーティングス株式会社
Priority date: 2020-05-20
Filing date: 2021-05-19
Publication date: 2021-11-25
Also published as: JP2023126785A; KR20230013242A; CN115515789A; JPWO2021235493A1; JP7297156B2; TW202200381A

Abstract

The present invention provides a multilayer film which has excellent shapability and excellent releasability from a mold. A multilayer film according to the present invention, which is provided with a transparent supporting base material and a coating layer that is arranged on at least one main surface of the transparent supporting base material, wherein: the coating layer contains an active energy ray-curable resin composition; the coating layer has a thickness of more than 2 μm; the coating layer has an indentation hardness HB100 of from 0.30 GPa to 0.65 GPa at an indentation depth of 100 nm as determined by a nanoindentation method; the coating layer has an indentation hardness HB2000 of from 0.15 GPa to 0.35 GPa at an indentation depth of 2,000 nm as determined by a nanoindentation method; and the indentation hardness HB2000 is lower than the indentation hardness HB100.

Description

Laminated films and molded bodies, and methods for manufacturing them.

The present invention relates to a laminated film and a molded product, and a method for producing these.

The display is used for various electrical components such as computers, televisions, mobile phones, personal digital assistants (tablet personal computers, mobile devices, electronic organizers, etc.), in-vehicle devices, and the like.

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

Japanese Unexamined Patent Publication No. 2018-12279

In recent years, the protective material has a design in which a plurality of areas having different surface textures such as textures are seamlessly formed (hereinafter referred to as seamless design), for example, an information display part of a display and a bezel part surrounding the information display part are integrated. There is a need for a specifically formed design. However, it is difficult to realize a seamless design by using the film described in Patent Document 1. An object of the present invention is to provide a laminated film having excellent shapeability and mold releasability, which is suitable for realizing a seamless design.

In order to solve the above problems, the present invention provides the following aspects.
[1]
With a transparent support base material,
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 and contains.
The thickness of the coating layer is more than 2 μm.
_{The indentation hardness HB 100} by the nanoindentation method at an indentation depth of 100 nm of the coating layer is 0.30 GPa or more and 0.65 GPa or less.
_{The indentation hardness HB 2000} by the nanoindentation method at an indentation depth of 2000 nm of the coating layer is 0.15 GPa or more and 0.35 GPa or less.
The indentation hardness HB ₂₀₀₀ is a laminated film smaller than the indentation hardness HB _100.

[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 ^{active energy rays at 1500 mJ / cm 2 is 15% or more, according to the above [1].} The laminated film described.

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

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

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

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

[7]
A coating step of applying an active energy ray-curable resin composition to at least one main surface of the transparent supporting substrate, and
The resin composition is provided with a first irradiation step of irradiating the ^{resin composition with active energy rays of 5 mJ / cm 2} or more and 150 mJ / cm ^{2 or less to obtain a coating layer.}
The thickness of the coating layer is more than 2 μm.
_{The indentation hardness HB 100} by the nanoindentation method at an indentation depth of 100 nm of the coating layer is 0.30 GPa or more and 0.65 GPa or less.
_{The indentation hardness HB 2000} by the nanoindentation method at an indentation depth of 2000 nm of the coating layer is 0.15 GPa or more and 0.35 GPa or less.
The indentation hardness HB ₂₀₀₀ is a method for producing a laminated film, which is smaller than the indentation hardness HB _100.

[8]
With a transparent support base material,
A cured resin layer disposed on at least one main surface of the transparent support substrate.
The main surface of the cured resin layer on the opposite side of the transparent supporting base material includes a first region in which irregularities are formed and a second region other than that.
The first region and the second region are integrally formed.
A molded product having a pencil hardness on the surface of the cured resin layer of H or higher.

[9]
The cured resin layer is arranged on one main surface of the transparent supporting base material, and is arranged on one main surface.
The molded product according to the above [8], further comprising a decorative layer arranged on the other main surface of the transparent support base material.

[10]
The cured resin layer is arranged on one main surface of the transparent supporting base material, and is arranged on one main surface.
The molded product according to the above [8] or [9], further comprising a molding resin layer arranged on the other main surface of the transparent supporting base material.

[11]
The unevenness forming step of contacting the coating layer of the laminated film according to any one of claims 1 to 6 with a mold having unevenness to form unevenness on a part of the coating layer.
A method for producing a molded product, comprising a second irradiation step of irradiating the coating layer with active energy rays to obtain a cured resin layer after the unevenness forming step.

[12]
The method for producing a molded product according to the above [11], wherein in the second irradiation step, the active energy rays are irradiated so that the pencil hardness of the surface of the coating layer after curing becomes H or more.

[13]
In the laminated film, the coating layer is arranged on one main surface of the transparent supporting base material.
The method for producing a molded product according to the above [11] or [12], wherein the decorative layer is arranged on the other main surface of the transparent support base material.

[14]
In the laminated film, the coating layer is arranged on one main surface of the transparent supporting base material.
In the unevenness forming step, the coating layer is opposed to the mold, and the molding resin is injected toward the transparent support base material to form the molding resin layer together with the unevenness on the coating layer. The method for producing a molded product according to any one of [11] to [13].

[15]
The mold imparts a three-dimensional shape to the laminated film and gives the laminated film a three-dimensional shape.
The method for producing a molded product according to the above [14], further comprising a preform step of molding the laminated film into a shape along the three-dimensional shape after the preparation step and before the unevenness forming step.

According to the present invention, it is possible to provide a laminated film having excellent shapeability and mold releasability.

It is sectional drawing which shows typically the laminated film which concerns on one Embodiment of this invention. It is a flowchart which shows the manufacturing method of the laminated film which concerns on one Embodiment of this invention. It is a flowchart which shows the manufacturing method of the laminated film which concerns on other embodiment of this invention. It is sectional drawing which shows typically the molded body which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the molded body which concerns on other embodiment of this invention. It is a perspective view which shows typically the molded body which concerns on still another Embodiment of this invention. It is a perspective view which shows typically the molded body which concerns on still another Embodiment of this invention. It is a flowchart which shows the manufacturing method of the molded body which concerns on one Embodiment of this invention. It is a flowchart which shows the manufacturing method of the molded article which concerns on other embodiment of this invention. It is a flowchart which shows the manufacturing method of the molded article which concerns on still another Embodiment of this invention.

A layer containing a cured resin (hereinafter, may be referred to as a cured resin layer) is usually arranged on the outermost side of the protective material. In order to realize a seamless design, for example, a region corresponding to an information display portion of a display and a region corresponding to a bezel need to be integrally formed on this cured resin layer. 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 irregularities before the resin is completely cured.

The region having unevenness and the region having a texture different from this are formed by, for example, pressing a mold having an uneven portion and a flat portion against a cured resin layer (coating layer) that is neither completely uncured nor completely cured. Will be done. If the tackiness of the coating layer is large, the surface of the coating layer, which is particularly in close contact with the flat portion, becomes rough or whitened when peeled from the mold, and it is difficult to obtain a desired texture. The tackiness of the coating layer is affected by the hardness of the coating layer in the vicinity of the surface.

On the other hand, the ease of forming irregularities is affected by the hardness inside the coating layer. For example, if the hardness inside the coating layer is excessively low, the restoration rate becomes high and unevenness is difficult to form. In particular, the hardness at the internal position of the coating layer to the same extent as the height of the applied convex portion has a great influence on the easiness of forming the unevenness.

The present embodiment focuses on the hardness near and inside the surface of the coating layer, and provides a laminated film having a coating layer in which these satisfy a specific range and relationship. Such a coating layer is neither completely uncured nor completely cured. Therefore, the coating layer has both hardness that allows unevenness to be transferred and low tackiness that can be easily peeled off from the mold. Therefore, it is possible to simultaneously form a plurality of regions having different textures on the coating layer, for example, an uneven region and a smooth region. Further, since the coating layer formed into a three-dimensional shape (for example, preformed) can be uncured or semi-cured, it is easy to stretch. Therefore, it is also possible to form the laminated film into a complicated three-dimensional shape. In addition, these shapes are retained for a long period of time by completely curing the coating layer after imparting irregularities and, if necessary, three-dimensional shapes.

A seamless design is realized by using the laminated film according to this embodiment. That is, the laminated film according to this embodiment is suitable as a material for a molded product 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 serve as an instrument panel and / or a center cluster panel have also been proposed. Such panels are very large and have a complex three-dimensional shape. The laminated film according to the present embodiment is particularly suitable as a material for a large molded body having the above-mentioned seamless design.

Laminated Film The laminated film according to the present embodiment includes a transparent support base material and a coating layer arranged on at least one main surface of the transparent support base material. The thickness of the coating layer is more than 2 μm. The coating layer contains an active energy ray-curable resin composition.

(Pushing hardness)
_{The indentation hardness HB 100} by the nanoindentation method at an indentation depth of 100 nm of the coating layer is 0.30 GPa or more and 0.65 GPa or less. _{The indentation hardness HB 2000} by the nanoindentation method at an indentation depth of 2000 nm of the coating layer 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. It can be said that such a coating layer is in a state of neither completely uncured nor completely cured (hereinafter, referred to as semi-cured or semi-cured state).

The indentation hardness HB ₁₀₀ indicates the hardness in the vicinity of the surface of the coating layer (hereinafter, may be referred to as surface hardness). The indentation hardness HB ₂₀₀₀ indicates the hardness inside the coating layer (hereinafter, may be referred to as internal hardness). The inside of the coating layer is a region of the coating layer on the transparent support base material side. The greater the indentation hardness, the higher the hardness. The hardness of the coating layer may decrease from the surface toward the transparent supporting substrate.

When the coating layer is provided with relatively high convex portions of about 300 nm or more and 4000 nm or less, the internal hardness of the coating layer is dominant in the ease of forming irregularities. If the internal hardness is low, the coating layer can be easily deformed along the unevenness of the pressed mold. However, if the hardness of the coating layer is excessively low, the coating layer tends to return to its original shape when the laminated film is removed from the mold. This tendency is remarkable when the convex part is high.

In the present embodiment, the coating layer has an internal hardness sufficient to transfer and maintain the unevenness. On the other hand, the surface hardness of the coating layer is high, and it exhibits low tackiness and is not easily deformed. That is, the deformation of the unevenness when peeled from the mold is suppressed by the high surface hardness of the coating layer. Therefore, desired unevenness can be easily formed on the laminated film according to the present embodiment. In this embodiment, it is assumed that the coating layer is provided with the relatively high convex portion as described above, and the hardness of the coating layer at a depth of 2000 nm is focused on.

When a small convex portion having a height of about several hundred nm is provided as in Patent Document 1, the surface hardness of the coating layer is dominant in the ease of forming the unevenness. 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, Patent Document 1 defines the parameter α related to the ratio of the elastic component to the viscous component to be 80 or more and 94 or less. This value indicates that the restoration rate is high when the indenter is pushed into the coating layer. A high recovery rate means that the coating layer, at least in the vicinity of the surface, has a 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. As described above, it is difficult to accurately form a convex portion having a high elasticity of 300 nm or more on a coating layer having high elasticity both on the surface and inside and a high restoration rate.

When the indentation hardness HB ₁₀₀ is 0.30 GPa or more, the surface of the coating layer exhibits low tackiness and is not easily deformed. Therefore, the coating layer is 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 accuracy. When the indentation hardness HB ₁₀₀ is 0.65 GPa or less, it becomes easy to stretch the laminated film. Therefore, the laminated film can be formed into a complicated three-dimensional shape while suppressing the occurrence of cracks.

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

Since the indentation hardness HB ₂₀₀₀ is smaller than the indentation hardness HB _{100, the} vicinity of the surface and the inside of the coating layer can exert their respective functions. That is, the coating layer exhibits excellent releasability and formability.

The coating layer can be completely cured after giving the laminated film fine irregularities and, if necessary, a three-dimensional shape. As a result, the imparted unevenness and three-dimensional shape are maintained for a long period of time. That is, the obtained molded product has excellent shape retention.

The measurement target of the indentation hardness HB ₁₀₀ and the indentation hardness HB ₂₀₀₀ is the laminated film immediately before the fine irregularities are formed. The coating layer in the laminated film to be measured is in a semi-cured state. To the extent that the indentation hardness is not affected, the laminated film after the indentation hardness is measured and before the unevenness is formed may be heat-treated, decorated, or preformed. After heat treatment, decoration, and preformation, the indentation hardness HB ₁₀₀ and the indentation hardness HB ₂₀₀₀ may be measured.

The indentation hardness H by the nanoindentation method is determined by, for example, continuous stiffness measurement 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. The stiffness with respect to the depth is calculated from the vibration component of the resulting displacement and the phase difference between the displacement and the load. This makes it possible to obtain a continuous profile of hardness with respect to the depth. In this profile, the hardness at a depth of 100 nm is the indentation hardness HB ₁₀₀ or HA ₁₀₀ described later, and the hardness at 2000 nm is the indentation hardness HB ₂₀₀₀ or HA ₂₀₀₀ described later.

The continuous rigidity measurement method includes, for example, Advanced Dynamic E and H. NMT methods can be used. Examples of the nanoindentation device include NANOMECHANICS, INC. IMicro Nanoindenter made by the company can be used. In this case, iMicro dedicated software may be used to calculate the load and stiffness. The sample is loaded by an indenter until a maximum load of 50 mN is reached. As the indenter, for example, a verkovic type diamond indenter is used. In the measurement and the calculation of the stiffness, the Poisson's ratio, the load, etc. of the coating layer may be appropriately set to appropriate values.

(Extend 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 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 step described later, damage to the laminated film is easily suppressed. The elongation rate is more preferably 8.0% or more, and particularly preferably 10% or more. The elongation rate may be 500% or less, and may be 200% or less. Forming in the present specification is a concept including molding by a preform step and an unevenness forming step.

The elongation rate is measured according to JIS K7127. Specifically, a test piece obtained by cutting a laminated film into a length of 200 mm and a width of 10 mm and a tensile tester having a chuck-to-chuck distance of 150 mm are used. The long side of the test piece is stretched by 2.5% under the condition of a tensile speed of 300 mm / min in an atmosphere of 160 ° C. 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 length exceeding 1 mm. If no cracks occur, a new test piece is cut out, and then the long side is stretched by 5%. Then, the crack generation is observed by the same procedure. This procedure is repeated, and the elongation rate when a crack having the above size is first confirmed is defined as the elongation rate of the laminated film. The above procedure may be repeated by increasing the elongation rate by, for example, 2.5%.

Hereinafter, the elements constituting the laminated film according to the present embodiment will be described in detail.
[Transparent support base material]
The transparent support base material is a base material that supports the coating layer. The transparent supporting base material is not particularly limited as long as it is transparent. "Transparent" specifically means that the total light transmittance is 40% or more. The total light transmittance of the transparent supporting substrate is preferably 90% or more. The total light transmittance can be measured by a method according to JIS K 7631-1.

A transparent supporting base material known in the art is used without particular limitation. The transparent supporting substrate may be colorless or colored.

The transparent support base material is appropriately selected according to the application. Examples of the transparent supporting base material include a polycarbonate (PC) -based film, a polyester-based film such as polyethylene terephthalate and polyethylene naphthalate; a cellulose-based film such as diacetyl cellulose and triacetyl cellulose; and an acrylic-based film such as polymethyl methacrylate (PMMA). Films; styrene films such as polystyrene and acrylonitrile / styrene copolymers; olefin films such as polyvinyl chloride, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, ethylene / propylene copolymers, etc .; nylon, aromatic polyamides, etc. Amid-based film can be mentioned. The transparent supporting base material is a film containing resins such as polyimide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polyvinyl alcohol, polyvinylidene chloride, polyvinylbutyral, polyallylate, polyoxymethylene, and epoxy resin. It may be a film containing a mixture of these polymers.

The transparent support base material may be a laminate of a plurality of films. The transparent support base material may be, for example, a laminate of an acrylic film and a polycarbonate film.

The transparent supporting substrate may be optically anisotropic or isotropic. The magnitude of birefringence of the optically anisotropic transparent supporting substrate is not particularly limited. The phase difference of the transparent supporting substrate having anisotropy may be 1/4 (λ / 4) of the wavelength and may be 1/2 (λ / 2) of the wavelength.

The thickness of the transparent support base material is appropriately set according to the use and manufacturing method of the laminated film and / or the molded product. The thickness of the transparent supporting base material is preferably 30 μm or more, more preferably 75 μm or more, and particularly preferably 200 μm or more from the viewpoint of strength and handleability. The thickness of the transparent supporting base material is preferably 500 μm or less, more preferably 400 μm or less, from the viewpoint of extensibility. In one embodiment, the thickness of the transparent supporting substrate is 75 μm or more and 500 μm or less.

It is desirable that the transparent support base material has extensibility at the temperature at which the laminated film is formed into a three-dimensional shape. It is desirable that the transparent support substrate has, for example, extensibility at the molding temperature in the preform process. The molding temperature in the preform step is usually 180 ° C. or lower. From the viewpoint of moldability, the glass transition temperature (Tg) of the material constituting the transparent supporting base material is preferably not more than the molding temperature, that is, 180 ° C. or less.

[Coating layer]
The coating layer contains an active energy ray-curable resin composition. However, the coating layer is neither completely cured nor completely uncured. The coating layer is in a semi-cured state. After various shapes such as unevenness are given to the laminated film, the shape is maintained for a long period of time by completely curing the coating layer.

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 depending on the composition of the resin composition and the like. In the present embodiment, the active energy rays are irradiated so that _{the indentation hardness HB 100} and the indentation hardness HB _{2000 of} the coating layer satisfy the above range and relationship in consideration of the composition of the resin composition and the like. ..

It can be said that the resin composition irradiated with the active energy ray of 1500 mJ / cm ^{2 is usually completely cured.} The cured resin layer (for example, the hard coat layer and / or the functional layer) in the molded product according to the present embodiment described later is also completely cured. That is, the ^{physical characteristics of the resin composition irradiated with the active energy rays of 1500 mJ / cm 2} can be regarded as the physical characteristics of the cured resin layer in the molded product. The pencil hardness of the completely cured resin composition (cured resin layer) is, for example, H or more.

A resin composition in which the resin composition 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 considered to be completely uncured.

The coating layer may be one layer or may include two or more layers. The resin composition forming each layer may be the same or different as long as it contains an active energy ray-curable resin. Regardless of the number of layers, when the hardness at the indentation depths of 100 nm and 2000 nm satisfies the above range and relationship, a laminated film having excellent shapeability and mold releasability can be obtained.

The coating layer preferably contains 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 product. The functional layer may be an optical interference layer. The optical interference layer is arranged outside the hard coat layer mainly to reduce the reflectance.

The optical interference layer may be one layer and may include a plurality of layers. The optical interference layer is, for example, a layer having a high refractive index (hereinafter, may be referred to as a high refractive index layer or an HR layer), a layer having a medium refractive index (hereinafter, referred to as a medium refractive index layer or an MR layer). There is) and at least one layer having a low refractive index (hereinafter, may be 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.

The functional layer may be a layer other than the optical interference layer, and may be provided with another layer together with the optical interference layer. Examples of the other layer include an antibacterial / antiviral layer and an antifouling layer. The antibacterial / antiviral layer and the antifouling layer are arranged, for example, outside the hard coat layer (further, the optical interference layer).

<Polymerization rate>
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 at 1500 mJ / cm 2} , that is, the resin composition in the completely cured state. The difference (= | PB-PA |) is, for example, 15% or more. When | PB-PA | is in 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.

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

First, the uncured coating layer is analyzed by a Fourier transform infrared spectrophotometer (FT-IR) from the surface of the coating layer opposite to the transparent supporting substrate. The horizontal axis indicates the wave number (cm ^-1 ), and the vertical axis indicates the absorbance. On the spectral chart, the baseline ^{between 690 cm -1} and 2015 cm ^-1 is determined. Using this baseline, (meth) carbon acryloyl groups - double bond (C = C) respectively a peak height _{I NC1} and _{I NC2} near and 1440cm around ^-1 wavenumber 810 cm ^-1 derived from the carbon-carbon calculate. Similarly, using the above baseline, carbon ester bond - calculating the peak height _{I NO} near the wave number 1730 cm ^-1 derived from an oxygen bond (C = O). The divided by the peak height _{I NC1} and peak _{I NC2} respectively height _{I NO} to the initial value _{r 01} and _{r 02.}

Then, the coating layer in a semi-cured state, in the same manner as described above, was analyzed by FT-IR, (meth) peak height in the vicinity of and 1440cm around ^-1 wavenumber 810 cm ^-1 derived from the C = C acryloyl groups I _BC1 and _{I BC2,} calculates a peak height _{I BO} near wave number 1730 cm ^-1 derived from the C = O of ester bonds. The values obtained by dividing the peak heights I _BC1 and I _BC2 by the peak heights I _BO _{are defined as r B1} and r _B2 , respectively.

The ratio of r _{B1 to} the initial value r ₀₁ (= r _B1 / r ₀₁ ) and the ratio of r _{B2 to} the initial value r ₀₂ (= r _B2 / r ₀₂ ) represent the reduction rate of C = C, respectively. C = C decreases due to the polymerization reaction. Therefore, _{the value obtained by subtracting r B1} / r ₀₁ from 1 and the value obtained by subtracting r _B2 / r ₀₂ from 1 can be indicators of the polymerization rate. The polymerization rate PB (%) of the resin composition in the semi-cured state is _{calculated by (1-r B1} / r ₀₁ ) × 100 or (1-r _B2 / r ₀₂ ) × 100.

Further, the coating layer completely cured, in the same manner as described above, FT-IR in analyzes, (meth) near the wave number 810 cm ^-1 derived from the C = C of acryloyl group and 1440cm peak height at around ^-1 I _AC1 and _{I AC2,} calculates a peak height _{I AO} near wave number 1730 cm ^-1 derived from the C = O of ester bonds. The values obtained by dividing the peak heights I _AC1 and I _AC2 by the peak height I _AO _{are defined as r A1} and r _A2 , respectively. The polymerization rate PA (%) of the cured resin composition is _{calculated by (1-r A1} / r ₀₁ ) × 100 or (1-r _B2 / r ₀₂ ) × 100.

<Pushing 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.

The difference between the indentation hardness HB ₁₀₀ _{and the indentation hardness HA 100} by the nanoindentation method at an indentation depth of 100 nm of the coating layer after irradiation with active energy rays at 1500 mJ / cm ² (= | HB _100- HA ₁₀₀ |) , 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 in this range, shape retention is likely to be improved. | HB _100- HA ₁₀₀ | may be 0.30 GPa or less. According to the present embodiment, | HB _100- HA ₁₀₀ | can satisfy the above range.

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.

The difference between the indentation hardness HB ₂₀₀₀ _{and the indentation hardness HA 2000} by the nanoindentation method at the indentation depth of 2000 nm of the coating layer after irradiation with active energy rays at 1500 mJ / cm ² (= | HB _2000- HA ₂₀₀₀ |) , 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 in this range, shape retention is 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.

The difference between the indentation hardness HB ₁₀₀ and the indentation hardness HB ₂₀₀₀ _{(= | HB 100} _{-HB 2000} |) is not particularly limited. From the viewpoint of formability and releasability, | HB _100- _{HB 2000} | is preferably 0.15 GPa or more, and 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.

It is desirable that the coating layer has extensibility at the temperature at which the laminated film is formed into a three-dimensional shape. It is desirable that the coating layer has extensibility, for example, at the molding temperature in the preform step described later. The molding temperature in the preform step is usually 180 ° C. or lower. From the viewpoint of moldability, the Tg of the resin composition in the coating layer is preferably not more than the molding temperature, that is, 180 ° C. or less.

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 the 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 K7121. The Tg of the resin composition in the coating layer is related to the degree of curing of the coating layer. By controlling Tg, the shapeability and releasability of the coating layer can be improved.

<Pencil hardness>
The pencil hardness of the surface of the coating layer after irradiation with active energy rays at 1500 mJ / cm ² is preferably H or higher, and more preferably 2H or higher, in that scratch resistance is more likely to be improved. Pencil hardness is measured according to JIS K 5600-5-4.

<Visual reflectance>
Laminated films containing uncured optical interference layers have particularly excellent antireflection performance. For example, the visual reflectance including the specularly reflected light in the wavelength region of 380 nm or more and 780 nm or less measured from the optical interference layer side of the laminated film is 0.1% or more and 4.0% or less. In addition to the first region of the molded product obtained by curing the laminated film, the second region also has excellent antireflection properties. Therefore, the molded body has less reflection due to external light, and the molded body has good display characteristics and good visibility. Similarly, the visual reflectance in the second region of the molded product can be 0.1% or more and 4.0% or less.

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

The above-mentioned visual reflectance is obtained by measuring all reflected light including specular reflected light. That is, the specular reflectance is measured by a so-called SCI (Specular Component Include) method. Since this method is not easily affected by the surface condition of the object to be measured, the visual reflectance of the uncured layer can be measured.

Specifically, the visual reflectance of the laminated film can be measured by the following method.
A black paint (for example, product name: CZ-805 BLACK (manufactured by Nikko Bics Co., Ltd.)) is applied to the surface of the transparent support substrate opposite to the coating layer using a bar coater, and the dry film thickness is 3 μm or more and 6 μm or less. Apply so that Then, the evaluation sample M is prepared by leaving it to dry in a room temperature environment for 5 hours.

From the coating layer side of the obtained evaluation sample M, a spectrocolorimeter (for example, SD7000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) is used to measure the visual reflectance by the SCI method in the wavelength region of 380 nm or more and 780 nm or less.

The visual reflectance of the molded product can be measured as follows.
The evaluation sample N is prepared by irradiating the evaluation sample M prepared above with ^{an active energy ray having an integrated light amount of more than 150 mJ / cm 2} (for example, an integrated light amount of 1500 mJ / cm ^2). The visual reflectance is measured from the coating layer side of the obtained evaluation sample N in the same manner as described above.

<thickness>
The thickness of the coating layer is not particularly limited as long as it is more than 2 μm. The thickness of the coating layer is preferably 3 μm or more, more preferably 5 μm or more, in that relatively high convex portions can be easily formed. The thickness of the coating layer is preferably 20 μm or less, more preferably 15 μm or less in that it is easily cured. The thickness of the coating layer is, for example, 3 μm or more and 20 μm or less. If the coating layer contains more than one layer, the thickness of the coating layer is the sum of these thicknesses.

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

The thickness of the coating layer can be obtained from its cross section. Specifically, a 10 mm × 10 mm test piece is cut out from the laminated film. A section for observing a cross section is prepared from a test piece using a microtom. 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. The average value of these is taken as the thickness of the coating layer. The thickness of the transparent supporting base material is also obtained in the same manner. As the microtome, for example, RM2265 manufactured by Leica Microsystems is used. As the laser microscope, for example, VK8700 manufactured by KEYENCE is used.

(Resin composition)
The resin composition comprises 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 ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Hereinafter, active energy ray-curable monomers, oligomers and polymers may be collectively referred to as resin components. The resin composition can control the polymerization rate and the indentation hardness H of the coating layer and the cured resin layer.

When the coating layer includes a plurality of layers, the resin components forming each layer may be the same or different. Above all, it is preferable that each layer contains the same or the same kind of resin component. This is because the adhesion of each layer is improved and peeling between layers is less likely to occur.

In one embodiment, the resin composition comprises a polymerizable polymer. The polymerizable polymer facilitates the coating layer to be imparted with curability as well as low tackiness.

In another embodiment, the resin composition comprises at least one of a polymerizable and non-polymerizable polymer (hereinafter, may be collectively referred to as a polymer) and at least one of a polymerizable monomer and an oligomer. The polymer makes it easier to impart low tackiness to the coating layer. In addition, the formability is easily improved. By blending the polymer together with at least one of the polymerizable monomer and oligomer, it becomes easy to adjust the difference in polymerization rate (= | PB-PA |) to be 15.0% or more. As a result, the shape retention is more likely to be improved. The resin composition preferably contains both a polymerizable polymer and a non-polymerizable polymer, and at least one of a polymerizable monomer and an oligomer, from the viewpoint of facilitating the control of tackiness.

<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 viewpoint 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.

Examples of the non-polymerizable polymer include urethane resin, acrylic resin, polyester resin, and epoxy resin. Acrylic resin is preferable from the viewpoint of transparency, tackiness, physical properties, and durability.

<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 viewpoint 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.

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 a main chain, and a polymerizable unsaturated group as a side chain or a terminal group. From the viewpoint of transparency, a polymer chain containing a carbon-carbon bond is preferable. From the viewpoint of formability, a polymer chain containing a urethane bond is preferable.

The polymerizable unsaturated group is preferably 2 or more, more preferably 3 or more, and particularly preferably 5 or more. The polymerizable unsaturated group is not particularly limited. Of these, acryloyl group and methacryloyl group are preferable as the polymerizable unsaturated group.

Specific examples of the preferable polymerizable polymer include urethane (meth) acrylate polymer and acrylic (meth) acrylate polymer.

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

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-naphthalenedi isocyanate, and m. -Phenylene diisocyanate, p-phenylenediisocyanate, diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyldiisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate , 2,4,4-trimethylhexamethylene diisocyanate or diisocyanate compounds obtained by hydrogenating aromatic isocyanates among these diisocyanate compounds (for example, diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate). Examples thereof include divalent or trivalent polyisocyanate compounds such as triphenylmethane triisocyanate and dimethylene triphenyl triisocyanate, and bullet-type adducts and isocyanurate ring-type adducts of these diisocyanates.

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, and 2-hydroxyethyl (meth) acrylate. Examples thereof include glycerol di (meth) acrylates and alkylene oxide-modified or lactone-modified compounds obtained by adding ethylene oxide, propylene oxide, ε-caprolactone, γ-butyrolactone and the like to these.

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 poly. Examples include ether polyol.

As the isocyanate group-containing (meth) acrylate monomer in the above method (2), for example, an active hydrogen-containing polymerizable monomer such as isocyanate ethyl acrylate, isocyanate propyl acrylate, and hydroxyethyl acrylate is mixed with a polyisocyanate compound such as hexamethylene diisocyanate. Examples thereof include unsaturated compounds formed by addition.

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).

The acrylic (meth) acrylate polymer is an acrylic polymer containing an acryloyl group and / or a methacryloyl group. Specifically, a compound obtained by adding (meth) acrylic acid to an acrylic resin copolymerized with glycidyl methacrylate, or 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl to an acrylic resin copolymerized with 2-acryloyloxyethyl isocyanate. Examples thereof include a compound to which (meth) acrylate and pentaerythritol tri (meth) acrylate are added, and a resin obtained by adding 2-acryloyloxyethyl isocyanate to an acrylic resin copolymerized with a hydroxyl group-containing monomer.

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

In the resin composition forming the hard coat layer (hereinafter, may be referred to as resin composition HC), the polymer content is 5 parts by mass or more with respect to 100 parts by mass of the solid content of the resin composition HC. Preferably, 10 parts by mass or more is more preferable, and 15 parts by mass or more is particularly preferable. In the resin composition HC, the polymer content 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 compounding ratio of the polymerizable polymer and the non-polymerizable polymer is not particularly limited.

In the resin composition forming the optical interference layer (hereinafter, may be referred to as resin composition R), the content of the polymer is more than 5 parts by mass with respect to 100 parts by mass of the solid content of the resin composition R. It is preferable, 10 parts by mass or more is more preferable, and 15 parts by mass or more is particularly preferable. 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 compounding ratio of the polymerizable polymer and the non-polymerizable polymer is not particularly limited.

<Polymerizable oligomer>
The polymerizable oligomer is an oligomer containing a polymerizable unsaturated group.
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.

The polymerizable oligomer has the same composition 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 and the like as a main chain, and 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 formability, an oligomer chain containing a urethane bond is preferable.

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

The urethane (meth) acrylate oligomer and the acrylic (meth) acrylate oligomer are prepared in the same manner as the urethane (meth) acrylate polymer and the acrylic (meth) acrylate polymer, respectively.

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

Commercially available products may be used as the polymerizable oligomer or the polymerizable polymer. Examples of commercially available urethane (meth) acrylate oligomers or polymers include DPHA-40H, UX-5000, UX-5102D20, UX-5103D, UX-5005, UX-3204, and UX- manufactured by Nippon Kayaku Co., Ltd. 4101, UXT-6100, UX-6101, UX-8101, UX-0937, UXF-4001-M35, UXF-402; UF-8001G, UA-510H manufactured by Kyoeisha Chemical Co., Ltd .; EBECRYL manufactured by Daicel Ornex Co., Ltd. 244, EBECRYL 284, EBECRYL 8402, EBECRYL 8807, EBECRYL 264, EBECRYL 265, EBECRYL 9260, EBECRYL 8701, EBECRYL 8405, EBECRYL 8405, EBECRYL 1290, EBECRYL UV-1700B, UV-6300B, UV-7600B, UV-7640B, UV-7650B, UV-3520EA, UV-7000B, Purple UV-AF305A; Alchema CN-9001, CN-9004, CN-9005, CN -965, CN-9178, CN-9893, CN-9782, CN-964, CN-9913, CN-9010; U-10PA, U-10HA, UA-33A, UA-53H manufactured by Shin-Nakamura Chemical Industry Co., Ltd. , UA-32P, U-15HA, UA-122P, UA-160TM, UA-31F, UA-7100, UA-4200, UA-4400; Art Resin UN-3320HA, Art Resin UN-3320HB manufactured by Negami Kogyo Co., Ltd. , 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 Regis UN-9000PEP, Art Resin UN-9200, Art Resin UN-904UREA, Art Resin UN-H7UREA, and the like can be used.

Examples of commercially available acrylic (meth) acrylate oligomers or polymers include Unidick V-6840, Unidick V-6841, Unidick V-6850, Unidick EMS-635, and Unidick WHV- manufactured by DIC Co., Ltd. 649; Hitachi Kasei Co., Ltd., Hitaroid 7975, Hitaroid 7977, Hitaroid 7988, Hitaroid 7975D; Negami Kogyo Co., Ltd., Art Cure RA-3769MP, 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 and the like can be used.

<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 is 50 g / eq. The above may be sufficient, and 200 g / eq. It may be:

The polymerizable monomer preferably has 2 or more, more preferably 3 or more, and particularly preferably 5 or more polymerizable unsaturated groups. Acryloyl group and methacryloyl group are preferably exemplified as the polymerizable unsaturated group. Preferred polymerizable monomers are polyfunctional (meth) acrylate monomers.

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

Polymerizable unsaturated group equivalent is 50 g / eq. More than 200 g / eq. Examples of the polyfunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol (200) di (meth) acrylate, and allyl (meth) acrylate. , 1,4-Butandiol 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, tricyclodecanedimethanol Bifunctional (meth) acrylate monomers such as di (meth) acrylate, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluororange (meth) acrylate; glycerintri (meth) acrylate, trimethylolpropane tri ( Meta) acrylate, ethoxylated (3) trimethylolpropane triacrylate, ethoxylated (6) trimethylolpropane triacrylate, ethoxylated (9) trimethylolpropane triacrylate, propoxydated (3) trimethylolpropane triacrylate, propoxylated (6) Trimethylolpropane triacrylate, propoxylation (9) Trimethylolpropanetriacrylate, pentaerythritol tri (meth) acrylate, ethoxylated (4) pentaerythritol tri (meth) acrylate, ethoxylated (8) pentaerythritol tri (8) pentaerythritol tri (8) Meta) acrylate, Tris (2-hydroxyethyl) isocyanuratetri (meth) acrylate, caprolactone modification (1) Tris (2-hydroxyethyl) isocyanuratetri (meth) acrylate, caprolactone-modified (3) Tris (2-hydroxyethyl) ) Trifunctional (meth) acrylate monomers such as isocyanurate tri (meth) acrylate; pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate, trimethylolpropane tetra (meth) acrylate. ) Acrylate, ethoxylated (4) Pentaerythritol tetra (meth) acrylate, Tetra-functional (meth) acrylate monomer such as ethoxylated (8) pentaerythritol tetra (meth) acrylate; pentafunctional (meth) acrylate monomer such as dipentaerythritol penta (meth) acrylate and tripentaerythritol penta (meth) acrylate; Six-functional (meth) acrylate monomers such as pentaerythritol hexa (meth) acrylate and tripentaerythritol hexa (meth) acrylate; Meta) Acrylate monomer can be mentioned.

The polymerizable monomer is used alone or in combination of two or more.

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, based on 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, based on 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.

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 13 parts by mass or more with respect to 100 parts by mass of the solid content of the resin composition R. Especially preferable. 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, based on 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.

<Translucent fine particles>
The resin composition contains translucent fine particles, if necessary. The translucent fine particles make it easier to improve the antiglare property and hardness of the coated layer (cured resin layer) after curing. The average particle size of the translucent fine particles may be, 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 size refers to the particle size (D50) at which the cumulative volume conversion measured by the laser diffraction type particle size distribution meter is 50%. Translucent fine particles are transparent or translucent. Translucent means that the total light transmittance measured by a method conforming to JIS K 7631-1 is 30% or more and less than 40%.

The translucent fine particles may be organic fine particles or inorganic fine particles. Commercially available products may be used as the translucent fine particles. Examples of commercially available translucent fine particles include Techpolymer SSX series (styrene-acrylic copolymer fine particles) manufactured by Sekisui Kasei Kogyo Co., Ltd., Chemisnow SX series (styrene polymer fine particles) manufactured by Soken Kagaku Co., Ltd. Chemisnow MX series (acrylic polymer fine particles), Seahoster KE-P manufactured by Nippon Catalyst Co., Ltd., KE-S series (silica fine particles), Soliostar RA (silicon-acrylic copolymer fine particles), Epostal S12 (melamine polymer fine particles) , Epostal MA series (styrene-acrylic copolymer fine particles), acrylic copolymer fine particles, MSP series manufactured by Nikko Rika Co., Ltd., NH series (silicone fine particles), AZ series manufactured by Shin Nihon Sumikin Materials Co., Ltd., AY series (alumina) Fine particles). Of these, the techpolymer SSX series (styrene-acrylic copolymer fine particles) Chemisnow SX series (styrene polymer fine particles) and the Epostal MA series (styrene-acrylic copolymer fine particles) are preferable.

<Filler>
The resin composition contains a filler, if necessary. The filler alleviates volume shrinkage due to curing of the coating layer. The filler improves the scratch resistance of the coating layer after curing.

The primary particle size of the filler is preferably 5 nm or more and 1,000 nm or less, more preferably 500 nm or less, and particularly preferably 100 nm or less from the viewpoint of transparency and stability. The primary particle size is measured from an image of a cross-sectional electron microscope using image processing software.

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

A commercially available product may be used as the filler. Examples of commercially available silica particles (coloidal silica) include IPA-ST, MEK-STM, IBK-ST, PGM-ST, XBA-ST, MEK-AC-2101, and MEK- manufactured by Nissan Chemical Industries, Ltd. AC-2202, MEK-AC-4101 and MIBK-SD, PL-1-IPA, PL-1-TL, PL-2-IPA, PL-2-MEK and PL-3-TL manufactured by Fuso Chemical Industry Co., Ltd. , OSCAL series and ELECOM series manufactured by JGC Catalysts and Chemicals Co., Ltd., and NANOBYK-3605 manufactured by Big Chemie Japan. Examples of commercially available alumina particles include AS-150I and AS-150T manufactured by Sumitomo Osaka Cement Co., Ltd., NANOBYK-3601, NANOBYK-3602, and NANOBYK-3610 manufactured by Big Chemie Japan.

Examples of commercially available phosphorus-doped tin oxide particles include HX-204 IP manufactured by Nissan Chemical Industries, Ltd. and PTOPGM15WT% -N09 manufactured by CIK Nanotech. Examples of the particles in which silver is supported on titanium oxide include ATOMY BALL- (S) manufactured by JGC Catalysts and Chemicals Co., Ltd. Examples of the particles in which silver is supported on the silica-alumina particles include ATOMY BALL- (UA), ELCOM NU-1023SIV, and ELCOM NU-1024SIV manufactured by JGC Catalysts and Chemicals. Examples of the silver-supported particles on the silica particles include Ion Pure ZAF HS manufactured by Ishizuka Glass Co., Ltd. Examples of the copper iodide particles include Cufitec BE4-ANA01, AA1-ANA01, BB2-ANA01, and BD3-ANA01 manufactured by NBC Meshtec Inc.

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

In the resin composition R, the content of the filler is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and particularly preferably 7 parts by mass or more with respect to 100 parts by mass of the solid content of the resin composition R. The content of the filler is preferably 90 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition R. The content of the filler in the resin composition R is, for example, 1 part by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition R.

<Photopolymerization initiator>
The resin composition contains a photopolymerization initiator, if necessary. The blending amount of the photopolymerization initiator is preferably 0.01 part by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the solid content of the resin composition.

Examples of the photopolymerization initiator include an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a titanosen-based photopolymerization initiator, and an oxime ester-based polymerization initiator.

Examples of the alkylphenone-based photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-. Propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hirodoxy-1- {4- [4- ( 2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone.

Examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphinoxide, 2,4,6-triethylbenzoyldiphenylphosphine oxide, and 2,4,6-triphenyl. Monoacylphosphine oxides such as benzoyldiphenylphosphine oxide; bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphos Examples thereof include bisacylphosphine oxides such as fin oxides.

Examples of the titanosen-based photopolymerization initiator include bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium. Can be mentioned. Examples of the oxime ester-based polymerization initiator include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, 2- (2- (2-) Hydroxyethoxy) ethyl ester can be mentioned.

The photopolymerization initiator is used alone or in combination of two or more.

Among them, a photopolymerization initiator having an absorption wavelength in a long wavelength region, for example, a wavelength region of 370 nm or more is preferable. Examples of such a photopolymerization initiator include the above-mentioned acylphosphine oxide-based photopolymerization initiator. 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.

When the active energy rays are irradiated under mild curing conditions such as semi-curing the coating layer, it is difficult to obtain the desired hardness because the curing reaction does not easily proceed inside the coating layer. By using a photopolymerization initiator having an absorption wavelength in the long wavelength region, the curing reaction inside the coating layer is promoted.

<solvent>
The resin composition contains a solvent, if necessary. The solvent is not particularly limited, and is appropriately selected depending on the components contained in the composition, the type of the substrate to be applied, the method of applying the composition, and the like. 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; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and ethylene glycol diethyl ether. Ethereal solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol diacetate; dimethylformamide, diethylformamide, N-methylpyrrolidone Amid-based solvents such as; cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol-based solvents such as methanol, ethanol, propanol, isopropyl alcohol, butanol, and isobutyl alcohol; halogen-based solvents such as dichloromethane and chloroform. These may be used alone or in combination of two or more. Of these, ester-based solvents, ether-based solvents, alcohol-based solvents and ketone-based solvents are preferable.

<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, in the form of particles (hereinafter, may be referred to as refractive index lowering particles).

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

As the refractive index lowering component, silica fine particles having a nanoporous structure formed inside and / or at least a part of the surface may be used. The nanoporous structure is formed according to the morphology, structure, aggregated state, and dispersed state inside the coating film of the silica fine particles. Hollow acrylic fine particles may be used as the refractive index lowering component. Examples of the hollow acrylic fine particles include XX-5952Z, XX-5966Z, and XX-6061Z manufactured by Sekisui Plastics Co., Ltd.

The volume average particle size of the particles having a reduced refractive index is preferably 50 nm or more and 200 nm or less. The volume average particle size is the primary particle size.

The content of the refractive index lowering component is preferably 35 parts by mass or more, and 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 lowering component is preferably 75 parts by mass or less, more preferably 60 parts by mass or less, based on 100 parts by mass of the solid content of the resin composition R. As a result, the cured optical interference layer tends to exhibit excellent antireflection properties. The content of the refractive index lowering 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.

<others>
The resin composition contains various additives as required. Additives include, for example, antistatic agents, plasticizers, surfactants, antioxidants, ultraviolet absorbers, surface modifiers, leveling agents and light stabilizers (eg, hindered amine light stabilizers (HALS)), antibacterial agents. Examples include agents, antifungal agents, antiviral agents, and antifouling agents. In particular, it is desirable that the antibacterial agent, antifungal agent, antiviral agent, and antifouling agent are contained in the resin composition (for example, resin composition R) forming the outermost layer.

[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 paper pattern for forming the resin composition R into a film. The protective film may have an adhesive layer or a release layer on the surface to which the resin composition R is applied.

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.

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. This tends to enhance the protective effect of the coating layer. The thickness of the protective film is preferably 25 μm or more, more preferably 30 μm or more, further 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, still more preferably 65 μm or less. The thickness of the protective film is a value that does not include the thickness of the adhesive layer.

The protective film is made of resin, for example. Examples of the resin film include a polyolefin film such as a polyethylene film and a polypropylene film (including a non-stretched polypropylene film (CPP film) and a biaxially stretched polypropylene film (OPP film)), and a modification obtained by modifying these polyolefins to add further functions. Polyethylene film, polyethylene terephthalate, polyester film such as polycarbonate and polylactic acid, polystyrene film, polystyrene resin film such as AS resin film and ABS resin film, nylon film, polyamide film, polyvinyl chloride film and polyvinylidene chloride film, polymethyl Penten film can be mentioned.

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

Additives such as an antistatic agent and an ultraviolet ray inhibitor may be added to the resin film, if necessary. The surface of the resin film may be subjected to corona treatment or low temperature plasma treatment.

FIG. 1 is a cross-sectional view schematically showing a laminated film according to this embodiment. The laminated film 10 includes a transparent support base material 11 and a coating layer 12 arranged on one of the main surfaces thereof.

Method for Producing Laminated Film The laminated film according to this embodiment has, for example, a coating step of applying an active energy ray-curable resin composition to at least one main surface of a transparent support base material, and 5 mJ / J / to the resin composition. It is produced by a method comprising a first irradiation step of irradiating an active energy ray of cm ² or more and 150 mJ / cm ^{2 or less to obtain a coating layer formed of a semi-cured resin composition.}
FIG. 2 is a flowchart showing a method for manufacturing a laminated film according to the present embodiment.

(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 the transparent supporting substrate. This forms an uncured coating layer.

The resin composition is prepared by a known method. The resin composition is prepared by mixing each component using a commonly used mixing device such as a paint shaker, a mixer, and a disper.

The method for applying 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.

The amount of the resin composition applied 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.

(2) Drying step (S12)
After the coating step (1) and before the first irradiation step (3), the coated 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.

(3) First irradiation step (S13)
The resin composition is irradiated with active energy rays of ^{5 mJ / cm 2} or more and 150 mJ / cm ^{2 or less.} By the first irradiation step, the resin composition is in a semi-cured state, and the above-mentioned 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 amount in the first irradiation step. The first irradiation step may be performed before the unevenness forming step described later, and may be before or after the preform step.

Integrated light quantity in this step may be at 10 mJ / cm ² or more, may be at 20 mJ / cm ² or more. Integrated light quantity in this step may be at 130 mJ / cm ² or less, may be at 100 mJ / cm ² or less. The irradiation of the active energy rays may be performed from the coating layer side or the transparent support base material side. The irradiation of the active energy rays may be performed in an atmospheric atmosphere or in a nitrogen atmosphere.

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. Therefore, 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 accuracy.

The type of active energy ray is not particularly limited. The active energy ray is appropriately selected depending on the type of the polymerizable monomer or oligomer. The active energy ray is not particularly limited, and may be ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Of these, ultraviolet rays are preferable. Ultraviolet rays are irradiated using, for example, a high-pressure mercury lamp or an ultra-high pressure mercury lamp.

[Manufacturing method of a laminated film including a coating layer including a plurality of layers]
A coating layer containing a plurality of layers (typically a semi-cured hard coat layer and a semi-cured optical interference layer) is formed by a laminating method or a coating method. The first irradiation step (3) may be performed a plurality of times.

(Laminating method)
In the laminating method, a plurality of layers formed on different substrates are bonded together according to the coating step (1). The drying step (2) is arbitrarily performed before the layers are bonded together. The first irradiation step (3) may be performed on each layer before the layers are bonded to each other, or may be performed collectively after the layers are bonded. According to the laminating method, multiphase flow is easily suppressed even between uncured layers.

(Coating method)
In the coating method, the resin composition forming another layer is applied onto the layer formed on the transparent supporting 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, it is preferable that the first irradiation step (3) is performed on the layer formed on the transparent supporting substrate before the other resin composition is applied. After the application of the other resin composition, the first irradiation step (3) is performed on the other resin composition.

FIG. 3 is a flowchart showing a method for manufacturing a 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 optical interference layer are laminated by the laminating method.

Molded body The molded body according to the present embodiment includes the above-mentioned transparent support base material and a cured resin layer (coating layer after curing) arranged on at least one main surface of the transparent support base material. The main surface of the cured resin layer on the opposite side to the transparent supporting base material includes a first region in which irregularities are formed and a second region other than that. The first region and the second region are integrally formed. The pencil hardness on the surface of the cured resin layer is H or more. The molded body may have a three-dimensional shape (three-dimensional shape) as well as fine irregularities.

The molded body is formed by partially imparting unevenness to the coating layer of the laminated film according to the present embodiment and curing it. The cured resin layer has the same physical characteristics as the coating layer irradiated with ^{1500 mJ / cm 2 active energy rays.}

[Curing resin layer]
The cured resin layer includes a first region in which fine irregularities are formed and a second region other than the first region. A plurality of first and / or second regions may be arranged.

The cured resin layer may be one layer or may include two or more layers, and the cured resin layer includes at least a hard coat layer. In one embodiment, the cured resin layer includes a hard coat layer and one or more functional layers (typically, a light interference layer).

The molded body is used, for example, as a protective material for a display. In this case, the first area is arranged so as to correspond to the display. The first region can be understood as the display portion of the molded body. The unevenness improves anti-glare properties. The first area may be arranged so as to correspond to the operation display unit. The second area is arranged so as to correspond to, for example, an area (bezel) surrounding the display. The second region can be understood as the bezel portion of the molded body. The second region has a texture different from that of the first region, for example, a glossy feeling. Therefore, the design of the bezel portion is improved.

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

The pencil hardness on the surface of the cured resin layer is H or higher. That is, the cured resin layer has a high hardness. Therefore, the molded product has excellent scratch resistance, and the unevenness is maintained for a long period of time. The pencil hardness on the surface of the cured resin layer is preferably 2H or more. The pencil hardness of the surface of the cured resin layer is measured in a region where unevenness is not imparted (for example, a second region). Alternatively, it is measured on the surface of a smooth cured resin layer without irregularities created for measurement.

The height of the convex part is not particularly limited. From the viewpoint of anti-glare property, the height of the convex portion may be, for example, 0.3 μm or more and 4.0 μm or less, and may be 1.0 μm or more and 2.0 μm or less. The height of the convex portion is calculated from the cross section of the cured resin layer in the thickness direction. The height of the convex portion is an 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.

From the viewpoint of anti-glare property, the ten-point average roughness Rz _JIS of the first region is preferably 0.2 μm or more and 1.0 μm or less. The ten-point average roughness Rz _JIS is determined in accordance with the provisions of JIS B0601; 2001, for example, using a laser microscope. The ten-point average roughness Rz _JIS is specifically, in the roughness curve of the reference length obtained by applying the cutoff value phase compensation band passage filter, from the highest peak (convex part) to the fifth from the highest. It is the sum of the average of the mountain heights and the average of the valley depths from the deepest valley bottom (recess) to the fifth in the order of depth.

[Decorative layer]
The molded body may further include a decorative layer. The molded body includes, for example, a transparent support base material, a cured resin layer arranged on one main surface of the transparent support base material, and a decorative layer arranged on the other main surface of the transparent support base material. .. The decorative layer may be provided on a part of the other main surface of the transparent supporting substrate. The decorative layer is a layer that gives the molded body decoration such as a pattern, letters, or metallic luster. The decorative layer enhances the design of the molded product. The decorative layer is arranged, for example, so as to face the second region. At this time, the decorative layer is visually recognized through the second region.

Examples of the decorative layer include at least one of a printing layer and a thin-film deposition layer. The print 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 the design and the like.

For example, wood grain pattern, stone grain pattern, cloth grain pattern, sand grain pattern, geometric pattern, characters, and solid surface are drawn on the print layer. The print layer is formed of, for example, a colored ink containing a binder resin and a colorant. The binder resin is not particularly limited. Examples of the binder resin include polyvinyl chloride resins such as vinyl chloride / vinyl acetate copolymers, polyamide resins, polyester resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, and celluloses. Examples thereof include ester-based resins, alkyd resins, and chlorinated polyolefin-based resins.

The colorant is not particularly limited, and examples thereof include known pigments or dyes. Examples of the yellow pigment include azo pigments such as polyazo, organic pigments such as isoindolinone, and inorganic pigments such as titanium nickel antimon oxide. Examples of the red pigment include azo pigments such as polyazo, organic pigments such as quinacridone, and inorganic pigments such as valve stems. Examples of the blue pigment include organic pigments such as phthalocyanine blue and inorganic pigments such as cobalt blue. Examples of the black pigment include organic pigments such as aniline black. Examples of the white pigment include inorganic pigments such as titanium dioxide.

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

[Molding resin layer]
The molded body may further include a molding resin layer. The molded resin layer supports the cured resin layer together with the transparent supporting base material. The molded body includes, for example, a transparent support base material, a cured resin layer arranged on one main surface of the transparent support base material, and a molding resin layer arranged on the other main surface of the transparent support base material. .. The shape of the molded resin layer is not limited. Therefore, the degree of freedom in designing the molded body is increased.

The resin forming the molding resin layer is not particularly limited. The molded resin layer contains, 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 engineering plastics include polyamide, polyacetal, polycarbonate, ultra-high molecular weight polyethylene, polysulfone, polyether sulfone, polyphenylene sulfide, and liquid crystal polymer.

The molded body includes a transparent support base material, a cured resin layer arranged on one main surface of the transparent support base material, a decorative layer arranged on the other main surface of the transparent support base material, and a molding resin layer. , May be provided. The decorative layer is arranged so as to be sandwiched between the cured resin layer and the molded resin layer, or is arranged on the surface of the molded resin layer opposite to the cured resin layer.

The molded product 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 so that the first region faces the information display portion of the display. The molded body is arranged so 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.

FIG. 4 is a cross-sectional view schematically showing a molded body according to the present embodiment. The molded body 20A includes a transparent support base material 11 and a cured resin layer 22 arranged on one of the main surfaces thereof. The cured resin layer 22 includes a first region 221 having fine irregularities and a smooth second region 222.

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 base material 11, a cured resin layer 22 arranged on one of the main surfaces thereof, a decorative layer 23, and a molded resin layer 24. The decorative layer 23 is arranged so as to face the second region 222 and to be sandwiched between the cured resin layer 22 and the molding resin layer 24.

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 base material 11, a cured resin layer 22 arranged on one of the main surfaces thereof, a decorative layer 23, and a molded resin layer 24. The decorative layer 23 is arranged so as to face the second region 222 and on the side opposite to the cured resin layer 22 of the molding resin layer 24.

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 base material 11, a cured resin layer 22 arranged on one of the main surfaces 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 the first regions 221. One first area 221 corresponds to the information display portion of the display, and the other first area 221 faces the operation display unit. The second area 222 corresponds to the bezel surrounding the display.

Method for Manufacturing a Molded Body The molded product according to the present embodiment is obtained by forming irregularities on the coating layer of the above-mentioned laminated film and then irradiating with active energy rays (second irradiation step). This makes it possible to simultaneously form a plurality of regions having different textures on the coating layer, for example, an uneven region and a smooth region. As described above, the coating layer is active energy ray-curable and can be obtained, for example, by performing the first irradiation step on the uncured resin composition.

The molded body provided with the decorative layer is a laminated film, a laminated body having a transparent support base material and an uncured resin composition layer (hereinafter referred to as a precursor of a laminated film), or a molded body having a decorative layer. Obtained by forming. The step of forming the decorative layer (decoration step) may be performed before the first irradiation step or after the second irradiation step, and may be performed between the first irradiation step and the second irradiation step. May be done.

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

It is desirable that the preform process be performed before the injection molding process. In the preform step, the laminated film or the precursor of the laminated film is formed in advance into a shape close to a three-dimensional shape. This makes it easier to obtain the desired three-dimensional shape in injection molding.

In one embodiment, the method for manufacturing the molded product includes a step of forming irregularities on the laminated film and a second irradiation step. FIG. 8 is a flowchart showing a method for manufacturing a molded product according to the present embodiment.

In one embodiment, the method for manufacturing the molded body includes a decoration step on the laminated film, a preform step, an unevenness forming step (and an injection molding step), and a second irradiation step. FIG. 9 is a flowchart showing a method of manufacturing a molded product according to the present embodiment.

In one embodiment, the method for producing the molded product includes a decoration step on the precursor of the laminated film, a preform step, a first irradiation step, an unevenness forming step (and an injection molding step), and a second irradiation step. , Equipped with. FIG. 10 is a flowchart showing a method for manufacturing a molded product according to the present embodiment.
Hereinafter, each step will be described.

(I) Preparation of laminated film For example, the laminated film produced as described above is prepared.

(Ii) Preparation of Precursor for Laminated Film For example, a precursor for a laminated film prepared by a method including the above-mentioned coating step (1) and drying step (2) is prepared.

(Iii) First irradiation step (S25)
In this step, the resin composition is irradiated with active energy rays of ^{5 mJ / cm 2} or more and 150 mJ / cm ² or less in the same manner as in the first irradiation step (3) of the method for producing a laminated film.

The resin composition is semi-cured by the first irradiation step 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 smaller than the indentation hardness HB _100.

(Iv) Decoration process (S23)
In this step, the above-mentioned decorative layer is formed on the other main surface of the transparent support base material or the surface of the molding resin layer opposite to the cured resin layer.

The method of forming the print layer is not particularly limited. Examples of the method for forming the print 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 thin-film deposition layer is also not particularly limited. Examples of the method for forming the thin-film deposition layer include a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plating method.

(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 may be performed to remove unnecessary portions of the laminated film or its precursor.

The preform method is not particularly limited. The preform is performed by, for example, a vacuum forming method, a compressed air forming method, or a vacuum 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 so that the transparent supporting base material faces the first mold. The laminated film or its precursor is heated to a temperature equal to or higher than Tg of the resin composition to put the treatment chamber in a vacuum state and / or a pressurized state. As a result, the laminated film or its precursor is deformed along the first mold. The laminated film or its precursor is then cooled and removed from the first mold.

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

The resin composition used in 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 causing cracks. Therefore, a complicated three-dimensional shape is realized. The resin composition after the preform step is still in an uncured or semi-cured state.

(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 having irregularities (second mold) to form irregularities on a part of the coating layer.

_{The indentation hardness HB 100} by the nanoindentation method at an indentation depth of 100 nm of the coating layer is 0.30 GPa or more and 0.65 GPa or less. _{The indentation hardness HB 2000} by the nanoindentation method at an indentation depth of 2000 nm of the coating layer 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. Therefore, the coating layer exhibits excellent releasability and formability.

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 is easily stripped from the mold.

In this step, a three-dimensional shape may be imparted along with the unevenness. In this case, a second mold having a desired three-dimensional shape as well as unevenness is used.

When the coating layer is arranged on one main surface of the transparent supporting base material, 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 the second mold having partial irregularities, and the molding resin is injected toward the transparent support base material. As a result, unevenness is formed on a part of the coating layer, and a molding resin layer is formed on the other main surface of the transparent supporting base material.

The laminated film has a semi-cured coating layer. Therefore, the laminated film can follow the molds having 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 generation of cracks is suppressed.

(Vii) Second irradiation step (S22)
In this step, the coating layer is irradiated with active energy rays. As a result, the coating layer is completely cured to form a cured resin layer.

The active energy rays are irradiated so that the pencil hardness of the cured resin layer is H or higher, for example. Integrated light quantity of the active energy ray in the present step is 150 mJ / cm ^2, such as more than, at 300 mJ / cm ² or more 2000 mJ / cm ² or less.

In the method for manufacturing a molded product according to the present embodiment, an unevenness forming step is performed on a laminated film provided with a coating layer in a semi-cured state. Therefore, it is possible to impart fine unevenness to the laminated film with high accuracy. Further, the laminated film can be formed into various three-dimensional shapes without causing cracks. Then, after the unevenness forming step is completed, the resin composition is cured. Therefore, the imparted shape is retained for a long period of time.

The present invention will be described in more detail with reference to 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 mixed copies is the mass of the solid content.

The components used in the examples and comparative examples in the present specification are as follows.
(Non-polymerizable polymer)
Acrylic polymer A: Mw60,000
(Polymerizable polymer)
Acrylic polymer B: Mw20,000

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 parts of t-butylperoxy-2-ethylhexanoate was prepared. Separately, 40 parts of toluene was put into a 500 ml reaction vessel equipped with a stirring blade, a nitrogen introduction tube, a cooling tube and a dropping funnel, and heated to 110 ° C. While stirring the inside of the reaction vessel, the above mixture was added dropwise at a constant velocity 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-butylperoxy-2-ethylhexanoate and 25 parts of toluene was added dropwise to the reaction vessel over 1 hour. Then, 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. As a result, an acrylic polymer A having a weight average molecular weight of 60,000 was obtained.

[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-butylperoxy-2-ethylhexanoate was prepared. Separately, 40 parts of toluene was put into a 500 ml reaction vessel equipped with a stirring blade, a nitrogen introduction tube, a cooling tube and a dropping funnel, and heated to 110 ° C. While stirring the inside of the reaction vessel, the above mixture was added dropwise at a constant velocity 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-butylperoxy-2-ethylhexanoate and 25 parts of toluene was added dropwise to the reaction vessel over 1 hour. Then, 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.

In another reaction vessel having the same shape as above, 306.5 parts of precursor B1, 15.66 parts of acrylic acid, 0.43 parts of hydroquinone monomethyl ether, 56 parts of toluene were charged, and air was blown into the reaction vessel to stir. While heating 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 the mixture was reacted for 1 hour. Subsequently, the mixture 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 adjusted to 75 ° C. Subsequently, a mixed solution of 10.1 parts of Karenz MOI (2-methacryloyloxyethyl isocyanate manufactured by Showa Denko KK), 5.0 parts of toluene and 0.043 parts of dibutyltin dilaurate was added, and the temperature was 70 ° C. The reaction was carried out under the conditions for 2 hours. Then, the temperature was cooled to 60 ° C. or lower, and a mixed solution of 2 parts of methanol and 10 parts of toluene was added. As a result, an acrylic polymer B having a weight average molecular weight of 20,000 was obtained.

To measure the acid value, the above reaction solution is titrated with a 0.1 N potassium hydroxide (KOH) solution according to JIS K5601-2-1, and the following formula acid value = {(KOH solution dropping amount [ml] ]) × (Molar concentration of KOH solution [mol / L]} / (mass of solid content [g]).

(Purple UV-AF305A)
Fluorine-containing polyfunctional silicone urethane acrylate oligomer manufactured by Mitsubishi Chemical Corporation (KRM-8452)
Polyfunctional Urethane Acrylate Oligomer Dycel Ornex Mw3,884

(CN-9893)
Bifunctional Urethane Acrylate Oligomer Made by Sartmer (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)
4-Functional Urethane Acrylate Oligomer Made by Negami Kogyo Co., Ltd. Mw = 1000-1500
(Art Resin UN-904M)
10 Functional Urethane Acrylate Oligomer Made by Negami Kogyo Co., Ltd. Mw = 4900

(ELCOM V-8802)
Filler (silica fine particles, primary particle diameter about 10 nm)
Made by JGC Catalysts and Chemicals Co., Ltd. (HX-204 IP)
Filler (lin-doped tin oxide sol, primary particle size 5 nm to 20 nm)
Made by Nissan Chemical Industries, Ltd. (Thruria 4320)
Refractive index reduced particles (hollow silica fine particles, volume average particle diameter 55 nm)
Made by JGC Catalysts and Chemicals Co., Ltd.

(Omnirad 184)
Photopolymerization Initiator IGM Resins B.V. (Omnirad TPO H)
Photopolymerization Initiator IGM Resins B.V.

[Example 1]
(1) Preparation of Resin Composition HC1 In a container filled with propylene glycol monomethyl ether, 37 parts of acrylic polymer A, 35 parts of Aronix M-402, 12 parts of purple light UV-AF305A, and 15 parts of ELCOM V-8802. 2.9 parts for a total of 100 parts of the above resin component and ELCOM V-8802, and 3.9 parts of Omnirad TPO H for a total of 100 parts of the above resin component and ELCOM V-8802. The parts were mixed to produce a transparent resin composition HC1 having a solid content concentration of 35%.

(2) Preparation of laminated film PMMA of transparent support base material (two-layer film consisting of PMMA and PC, trade name: AW-10U, manufactured by Shine Techno Co., Ltd., total thickness 250 μm, PMMA layer thickness 35 μm, PC layer thickness 215 μm) The resin composition HC1 was applied to the surface of the film with 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 provided with a coating layer (hard coat layer) in a semi-cured state. The film thickness of the coating layer was 8 μm.

(3) Preparation of molded product (3-1) Formation of print layer A print layer is formed by screen printing on the main surface of the produced laminated film 1 opposite to the coating layer of the transparent support base material, and the drying temperature is increased. It was dried at 80 ° C. for 10 minutes. This printing step was repeated 5 times and then dried at 90 ° C. for 1 hour. Aniline black was used to form the print layer.

(3-2) Preform The laminated film provided with the print layer was heated to 160 ° C., and preform was carried out by a vacuum compressed air molding method. Subsequently, trimming was performed.

(3-3) Formation of unevenness Insert molding was performed using a mold having unevenness in a part. The mold was heated to 80 ° C. A polycarbonate resin was used as the molding resin. 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.

(3-4) Irradiation of active energy rays The coating layer was irradiated with active energy rays (ultraviolet rays) having ^{an integrated light amount of 1500 mJ / cm 2.} As a result, the transparent support base material, the cured resin layer (hard coat layer) arranged on one main surface of the transparent support base material, and the printing layer arranged on the other main surface of the transparent support base material are molded. A molded product X1 comprising a resin layer was obtained. The surface of the cured resin layer had a first region formed by transferring the unevenness of the mold and a smooth second region.

[evaluation]
The following evaluation was performed on the laminated film A1 or the molded product X1. The results are shown in Table 1.

(A) Releasability The second region of the cured resin layer of the molded product was visually observed and evaluated according to the following criteria.
Best: Roughness and whitening caused by peeling the mold are not confirmed on the surface Good: Roughness and whitening caused by peeling the mold are slightly confirmed on the surface, but the texture is not significantly deteriorated. Yes Yes: Roughness and whitening caused by peeling the mold are confirmed on the surface, but there is no significant deterioration of the texture. Defect: Roughness and whitening caused by peeling the mold are confirmed on the surface. , Significant deterioration of texture is seen

(B) Formability The first region of the cured resin layer of the molded product was visually observed and evaluated according to the following criteria.
Best: Sufficient anti-glare property is obtained, and it can be judged that the height of the convex part is 80% or more of the maximum height of the convex part of the mold. Good: Sufficient anti-glare property is obtained for practical use. , It can be judged 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. It can be judged that it is less than 50% of the maximum height of the part.

(C) Shape retention The molded product was allowed to stand in a constant temperature and humidity chamber having a relative humidity of 85% and a temperature of 85 ° C. for 250 hours. After this accelerated test, it was evaluated by the same criteria as the formability (b).

(D) Indentation hardness NANOMECHANICS, INC. It was measured by a continuous rigidity measurement method (method used: Advanced Dynamic Eand H. NMT) using an iMicro Nanoindenter manufactured by M...

Specifically, a minute AC load was superposed on the surface of the laminated film on a quasi-static test load. The load was applied until the maximum load of 50 mN was reached. As an indenter, a Berkovich-type diamond indenter (tip radius of curvature of 20 nm) was used. The continuous stiffness with respect to the depth was calculated from the vibration component of the generated displacement and the phase difference between the displacement and the load, and the hardness profile with respect to the depth was obtained. 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 ₂₀₀₀ . IMicro dedicated software was used to calculate the load and stiffness. In calculating the stiffness, the Poisson's ratio of the coating layer was set to 0.35. The load was controlled so that the strain rate (∂P / ∂t) / P was 0.2. In the analysis with the iMicro dedicated software, the point tentatively defined on the iMicro dedicated software at the time of measurement (the point where d (Force) / d (Disp) becomes about 500 N / m) was set as it is as the surface position of the coating layer. ..

(E) Polymerization rate The uncured laminated film and the semi-cured laminated film were subjected to FT-IR analysis according to the above method to obtain infrared absorption spectra thereof. From the infrared absorption spectrum, the polymerization rates PB and PA were calculated according to the above method.

(F) Stretch rate Measured according to JIS K 7127.
Specifically, a test piece having a length of 200 mm and a width of 10 mm was cut out from the laminated film. This test piece was set in a tensile tester having a chuck-to-chuck distance of 150 mm, and the test piece was stretched by 2.5% under the condition of a tensile speed of 300 mm / min under an atmosphere of 160 ° C. Then, the test piece was observed with a microscope having a magnification of 1000 times or more to confirm the presence or absence of cracks having a length exceeding 1 mm. If no cracks were generated, a new test piece was cut out, and then the long side was extended by 5%. Then, the occurrence of cracks was observed by the same procedure. This procedure was repeated while increasing the elongation rate by 2.5%. The elongation rate when a crack of the above size was first confirmed was defined as the elongation rate of the laminated film. Three test pieces were prepared 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.

(G) Pencil hardness JIS K 5600-5-4 (1999) The pencil hardness in the second region of the cured resin layer of the molded product was measured according to the scratch hardness (pencil method).

[Example 2]
In the preparation of the laminated film (2), the 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 product X2 was obtained in the same manner as in Example 1. The laminated film A2 and the molded product X2 were evaluated as described above. The results are shown in Table 1.

[Example 3]
In the preparation of the laminated film (2), the 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 product X3 was obtained in the same manner as in Example 1. The laminated film A3 and the molded product X3 were evaluated as described above. The results are shown in Table 1.

[Example 4]
In the preparation of the laminated film (2), the 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 product X4 was obtained in the same manner as in Example 1. The laminated film A4 and the molded product X4 were evaluated as described above. The results are shown in Table 1.

[Example 5]
In the preparation of the laminated film (2), the 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 amount was 7.5 mJ / cm 2.} Using the laminated film A5, a molded product X5 was obtained in the same manner as in Example 1. The laminated film A5 and the molded product X5 were evaluated as described above. The results are shown in Table 1.

[Example 6]
In the preparation of the laminated film (2), the 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 amount was 100 mJ / cm 2.} Using the laminated film A6, a molded product X6 was obtained in the same manner as in Example 1. The laminated film A6 and the molded product X6 were evaluated as described above. The results are shown in Table 1.

[Comparative Example 1]
A laminated film B1 was obtained in the same manner as in Example 1 except that the laminated film was not irradiated with active energy rays in the preparation (2). Using the laminated film B1, a molded body Y1 was obtained in the same manner as in Example 1. The laminated film B1 and the molded body Y1 were evaluated as described above. The results are shown in Table 1.

[Comparative Example 2]
In the preparation of the laminated film (2), the laminated film B2 was obtained in the same manner as in Example 1 except ^{that the active energy rays were irradiated so that the integrated light amount was 200 mJ / cm 2.} Using the laminated film B2, a molded product Y2 was obtained in the same manner as in Example 1. The laminated film B2 and the molded body Y2 were evaluated as described above. The results are shown in Table 1.

[Comparative Example 3]
In the preparation of the laminated film (2), the laminated film B3 was obtained in the same manner as in Example 1 except ^{that the active energy rays were irradiated so that the integrated light amount was 500 mJ / cm 2.} Using the laminated film B3, a molded product Y3 was obtained in the same manner as in Example 1. The laminated film B3 and the molded body Y3 were evaluated as described above. The results are shown in Table 1.

[Comparative Example 4]
In the preparation of the laminated film (2), the laminated film B4 was obtained in the same manner as in Example 1 except ^{that the active energy rays were irradiated so that the integrated light amount was 1500 mJ / cm 2.} Using the laminated film B4, a molded product Y4 was obtained in the same manner as in Example 1. The laminated film B4 and the molded body Y4 were evaluated as described above. The results are shown in Table 1.

All of the molded products of Examples 1 to 6 are excellent in mold releasability and shapeability. Furthermore, the shape retention was also high. In addition, no visible cracks could be confirmed in these molded bodies.
Comparative Example 1 is an example in which the indentation hardness HB ₁₀₀ and the _{indentation hardness HB 2000} are both small. In this example, the releasability and formability are low.
Comparative Examples 2 to 4 are examples in which the indentation hardness HB ₂₀₀₀ is large. Even in these examples, the formability is low. In Comparative Example 3 and Comparative Example 4, the shape retention was also low.

[Example 7]
(1) Preparation of Resin Composition HC2 In a container containing propylene glycol monomethyl ether, 43 parts of acrylic polymer A, 42 parts of Aronix M-402, 15 parts of ELCOM V-8802, and Omnirad 184 are the above resin components and ELCOM V. 2.9 parts for a total of 100 parts of -8802 and 3.9 parts of Omnirad TPO H for a total of 100 parts of the above resin component and ELCOM V-8802 were mixed to obtain a solid content concentration of 35%. A transparent resin composition HC2 was produced.

(2) Preparation of Laminated Film A laminated film A7 was obtained in the same manner as in Example 6 except that the resin composition HC2 was used instead of the resin composition HC1.
(3) Preparation of Molded Body Using the laminated film A7, a molded body X7 was obtained in the same manner as in Example 1. The laminated film A7 and the molded product X7 were evaluated as described above. The results are shown in Table 2.

[Example 8]
(1) Preparation of Resin Composition HC3 In a container containing propylene glycol monomethyl ether, 51 parts of acrylic polymer A, 49 parts of Aronix M-402, 2.9 parts of Omnirad 184 with respect to 100 parts of the above resin component, Omnirad. 3.9 parts of TPO H was mixed with a total of 100 parts of the above resin components to produce a transparent resin composition HC3 having a solid content concentration of 35%.

(2) Preparation of Laminated Film A laminated film A8 was obtained in the same manner as in Example 6 except that the resin composition HC3 was used instead of the 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 laminated film A8 and the molded product X8 were evaluated as described above. The results are shown in Table 2.

[Example 9]
(1) Preparation of resin composition HC4 In a container containing propylene glycol monomethyl ether, 73 parts of n-acrylic polymer B, 12 parts of purple light UV-AF305A, 15 parts of ELCOM V-8802, and Omnirad 184 are the above resin components and ELCOM. 2.9 parts for a total of 100 parts with V-8802 and 3.9 parts for a total of 100 parts with the above resin component and ELCOM V-8802 were mixed, and the solid content concentration was 35%. The transparent resin composition HC4 of the above was produced.

(2) Preparation of Laminated Film A laminated film A9 was obtained in the same manner as in Example 6 except that the resin composition HC4 was used instead of the 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 laminated film A9 and the molded product X9 were evaluated as described above. The results are shown in Table 2.

[Example 10]
(1) Preparation of Resin Composition HC5 In a container containing propylene glycol monomethyl ether, 85 parts of acrylic polymer B, 15 parts of ELCOM V-8802, and Omnirad 184 in a total of 100 parts of the above resin component and ELCOM V-8802. On the other hand, 2.9 parts and 3.9 parts of Omnirad TPO H were mixed with 100 parts in total of the above resin component and ELCOM V-8802 to produce a transparent resin composition HC5 having a solid content concentration of 35%. bottom.

(2) Preparation of Laminated Film A laminated film A10 was obtained in the same manner as in Example 6 except that the resin composition HC5 was used instead of the 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 laminated film A10 and the molded product X10 were evaluated as described above. The results are shown in Table 2.

[Example 11]
(1) Preparation of Resin Composition HC6 In a container containing propylene glycol monomethyl ether, 100 parts of acrylic polymer B, 2.9 parts of Omnirad 184 with respect to 100 parts of the above resin component, and 100 parts of Omnirad TPO H with respect to the above resin component 100. 3.9 parts were mixed with respect to the parts to produce a transparent resin composition HC6 having a solid content concentration of 35%.

(2) Preparation of Laminated Film A laminated film A11 was obtained in the same manner as in Example 6 except that the resin composition HC6 was used instead of the 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 laminated film A11 and the molded product X11 were evaluated as described above. The results are shown in Table 2.

[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, and Art Resin 5.0 parts of UN-904M, 2.9 parts of Omnirad 184 with respect to 100 parts of the above resin component, and 3.9 parts of Omnirad TPO H with respect to 100 parts of the above resin component were mixed, and the solid content concentration was 35. %% Transparent resin composition HC7 was produced.

(2) Preparation of laminated film The resin composition HC7 was used instead of the resin composition HC1, the film thickness of the coating layer was set to 3 μm, and the integrated light intensity of the active energy rays was 150 mJ / cm ² . A laminated film A12 was obtained in the same manner as in Example 1 except that the film was irradiated in this manner.
(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 laminated film A12 and the molded product X12 were evaluated as described above. The results are shown in Table 2.

[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, and Omnirad 184 are 2.9 with respect to 100 parts of the above resin component. 3.9 parts of Omnirad TPO H was mixed with 100 parts of the above resin component to produce a transparent resin composition HC8 having a solid content concentration of 35%.

(2) Preparation of laminated film The resin composition HC8 was used instead of the resin composition HC1, the film thickness of the coating layer was set to 3 μm, and the integrated light intensity of the active energy rays was 150 mJ / cm ^2. A laminated film A13 was obtained in the same manner as in Example 1 except that the film was irradiated so as to be.
(3) Preparation of Molded Body Using the laminated film A13, a molded body X13 was obtained in the same manner as in Example 1. The laminated film A13 and the molded product X13 were evaluated as described above. The results are shown in Table 2.

[Comparative Example 5]
(1) Preparation of resin composition HC9 In a container containing propylene glycol monomethyl ether, 85 parts of purple light UV-AF305A, 15 parts of ELCOM V-8802, and Omnirad 184 are 100 parts in total of the above resin component and ELCOM V-8802. 2.9 parts of Omnirad TPO H was mixed with 3.9 parts of a total of 100 parts of the above resin component and ELCOM V-8802 to obtain a transparent resin composition HC9 having a solid content concentration of 35%. Manufactured.

(2) Preparation 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) Preparation of Molded Body Using the laminated film B5, a molded body Y5 was obtained in the same manner as in Example 1. The laminated film B5 and the molded body Y5 were evaluated as described above. The results are shown in Table 2.

[Comparative Example 6]
(1) Preparation of Resin Composition HC10 In a container containing propylene glycol monomethyl ether, 100 parts of purple light UV-AF305A, 2.9 parts of Omnirad 184 with respect to 100 parts of the above resin component, and Omnirad TPO H of the above resin component. 3.9 parts were mixed with 100 parts to produce a transparent resin composition HC10 having a solid content concentration of 35%.

(2) Preparation 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 1.
(3) Preparation of Molded Body Using the laminated film B5, a molded body Y6 was obtained in the same manner as in Example 1. The laminated film B6 and the molded body Y6 were evaluated as described above. The results are shown in Table 2.

All of the molded products of Examples 7 to 13 are excellent in mold releasability and shapeability. No visible cracks could be confirmed in the molded products of Examples 7 to 12. In the molded products of Examples 7 to 11, the shape retention is also high.
Comparative Example 5 is an example in which the indentation hardness HB ₂₀₀₀ is excessively large. In this example, the formability is low. In addition, the shape retention was low.
Comparative Example 6 is an example in which the indentation hardness HB ₂₀₀₀ is large. In this example, the formability is low.

[Example 14]
(1) Preparation of Resin Composition LR In a container containing propylene glycol monomethyl ether, 14.8 parts by mass of acrylic polymer A, 10 parts by mass of Aronix M-402, 13.3 parts by mass of KRM-8452, and so on. 13.3 parts by mass of purple light UV-AF305A and 4.8 parts by mass of Polymerd 184 were mixed. Further, the thru rear 4320 was mixed in an amount of 43.8 parts by mass. Thereby, a milky white resin composition LR for a low refractive index layer having 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.

(2) Preparation of laminated film (2-1) Formation of uncured optical interference layer (low refractive index layer) The resin composition LR is applied to the OPP film (protective film) with a bar coater to increase the thickness after drying. It was applied so as to be 95 nm. Then, it was dried at 80 ° C. for 1 minute to volatilize the solvent to obtain a transfer film C-1 on which an uncured low refractive index layer was formed.

(2-2) Formation of Uncured Hard Coat Layer In the same manner as in Example 1, an uncured hard coat layer having a thickness of 12 μm after drying was formed on the transparent supporting substrate.

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

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

(3) Preparation of Molded Body In the same manner as in Example 1, except that the uncured laminated film A14 was used instead of the laminated film A1, the transparent support base material and the transparent support base material were placed on one main surface of the transparent support base material. A molded body X14 comprising an arranged hard coat layer, a low refractive index layer arranged on the hard coat layer, a printing layer arranged on the other main surface of the transparent support base material, and a molding resin layer. Obtained. The laminated film A14 and the molded product X14 were evaluated as described above. The results are shown in Table 3.

[Example 15]
(1) Adjustment of Resin Composition HR In a container containing propylene glycol monomethyl ether, 8.9 parts by mass of acrylic polymer A, 2.7 parts by mass of KRM-8452, and 1.8 parts by mass of Omnirad 184 were added. , 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 having 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.

(2) Preparation of laminated film (2-1) Formation of uncured optical interference layer (high refractive index layer) The resin composition R2 is added to the OPP film (protective film) by a bar coater to increase the thickness after drying. It was applied so as to be 95 nm. Then, it was dried at 80 ° C. for 1 minute to volatilize the solvent to obtain a transfer film C-2 on which an uncured high refractive index layer was formed.

(2-2) Formation of Uncured Hard Coat Layer In the same manner as in Example 1, an uncured hard coat layer having a thickness of 8 μm after drying was formed on the transparent supporting substrate.

(2-3) Formation of Uncured Low Refractive Index Layer In the same manner as in Example 14, a transfer film C-1 on which an uncured low refractive index layer was formed was obtained.

(2-4) Laminating an uncured hard coat layer, a low refractive index layer, and a high refractive index layer First, the transfer film C-2 is supported by the uncured high refractive index layer surface and a transparent supporting base material. It was bonded to the surface of the uncured hard coat layer.

Then, 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. The protective film was peeled off, and the laminated body was irradiated with active energy rays (ultraviolet rays) having an ^{integrated light amount of 35 mJ / cm 2.} A laminated film A15 having a semi-cured hard coat layer, a high refractive index layer, and a low refractive index layer in this order was obtained.

(3) Preparation of 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 laminated film A15 and the molded product X15 were evaluated as described above. The results are shown in Table 3.

In Examples 14 and 15, the visual reflectance of the obtained molded product was also evaluated.
(H) Visual reflectance A black paint (product name: CZ-805 BLACK (manufactured by Nikko Bics Co., Ltd.)) is applied to the surface of the transparent support base material of the laminated film opposite to the hard coat layer using a bar coater. The film was applied 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 in a room temperature environment for 5 hours to dry. Subsequently, the integrated light amount was 1500 mJ / cm ^2. A cured evaluation sample was prepared by irradiating with active energy rays of.

The visual reflectance by the SCI method was measured and evaluated from the optical interference layer side of the evaluation sample. SD7000 manufactured by Nippon Denshoku Kogyo Co., Ltd. was used for the measurement, and the measurement wavelength region was set to 380 nm or more and 780 nm or less.

Both the molded bodies of Examples 14 and 15 are excellent in releasability, shapeability and shape retention. Furthermore, no visible cracks could be confirmed in these molded bodies. In addition, it can be seen that the molded product has a small visual reflectance and has excellent antireflection performance.

According to the present invention, it is possible to provide a laminated film having excellent shapeability and releasability of fine irregularities. Therefore, this laminated film is particularly preferably used for producing a protective material for a display having a seamless design.

This application claims priority based on Japanese Patent Application No. 2020-088300 filed in Japan on May 20, 2020, the entire contents of which are incorporated herein by reference.

10 Laminated film 11 Transparent support base material 12

Coating layer

20A, 20B, 20C, 20D Molded product 22 Cured resin layer 221 First region 222 Second region 23 Decorative layer 24 Molded resin layer

Claims

With a transparent support base material,
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 and contains.
The thickness of the coating layer is more than 2 μm.
The indentation hardness HB 100 by the nanoindentation method at an indentation depth of 100 nm of the coating layer is 0.30 GPa or more and 0.65 GPa or less.
The indentation hardness HB 2000 by the nanoindentation method at an indentation depth of 2000 nm of the coating layer is 0.15 GPa or more and 0.35 GPa or less.
The indentation hardness HB 2000 is a laminated film smaller than the indentation hardness HB 100.
The first aspect of the present invention, wherein 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 active energy rays at 1500 mJ / cm 2 is 15% or more. Laminated film.
The laminated film according to claim 1 or 2, wherein the pencil hardness of the surface of the coating layer after irradiation with active energy rays at 1500 mJ / cm 2 is H or more.
The laminated film according to any one of claims 1 to 3, wherein the elongation rate at 160 ° C. is 5% or more.
The laminated film according to any one of claims 1 to 4, wherein the thickness of the coating layer is 3 μm or more and 20 μm or less.
The laminated film according to any one of claims 1 to 5, wherein the thickness of the transparent supporting base material is 75 μm or more and 500 μm or less.
A coating step of applying an active energy ray-curable resin composition to at least one main surface of the transparent supporting substrate, and
The resin composition is provided with a first irradiation step of irradiating the resin composition with active energy rays of 5 mJ / cm 2 or more and 150 mJ / cm 2 or less to obtain a coating layer.
The thickness of the coating layer is more than 2 μm.
The indentation hardness HB 100 by the nanoindentation method at an indentation depth of 100 nm of the coating layer is 0.30 GPa or more and 0.65 GPa or less.
The indentation hardness HB 2000 by the nanoindentation method at an indentation depth of 2000 nm of the coating layer is 0.15 GPa or more and 0.35 GPa or less.
The indentation hardness HB 2000 is a method for producing a laminated film, which is smaller than the indentation hardness HB 100.
With a transparent support base material,
A cured resin layer disposed on at least one main surface of the transparent support substrate.
The main surface of the cured resin layer on the opposite side of the transparent supporting base material includes a first region in which irregularities are formed and a second region other than that.
The first region and the second region are integrally formed.
A molded product having a pencil hardness on the surface of the cured resin layer of H or higher.
The cured resin layer is arranged on one main surface of the transparent supporting base material, and is arranged on one main surface.
The molded product according to claim 8, further comprising a decorative layer arranged on the other main surface of the transparent support base material.
The cured resin layer is arranged on one main surface of the transparent supporting base material, and is arranged on one main surface.
The molded product according to claim 8 or 9, further comprising a molding resin layer arranged on the other main surface of the transparent supporting base material.
The unevenness forming step of contacting the coating layer of the laminated film according to any one of claims 1 to 6 with a mold having unevenness to form unevenness on a part of the coating layer.
A method for producing a molded product, comprising a second irradiation step of irradiating the coating layer with active energy rays to obtain a cured resin layer after the unevenness forming step.
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 the pencil hardness on the surface of the cured resin layer becomes H or more.
In the laminated film, the coating layer is arranged on one main surface of the transparent supporting base material.
The method for producing a molded product according to claim 11 or 12, wherein a decorative layer is arranged on the other main surface of the transparent support base material.
In the laminated film, the coating layer is arranged on one main surface of the transparent supporting base material.
In the uneven forming step, the coating layer is opposed to the mold, and the molding resin is injected toward the transparent support base material to form the molding resin layer together with the unevenness on the coating layer. Item 6. The method for producing a molded product according to any one of Items 11 to 13.
The mold imparts a three-dimensional shape to the laminated film and gives the laminated film a three-dimensional shape.
The method for manufacturing a molded product according to claim 14, further comprising a preform step of molding the laminated film into a shape along the three-dimensional shape before the unevenness forming step.